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WO2018155309A1 - Polymer composition containing modified chlorinated polyolefin and method for producing same - Google Patents

Polymer composition containing modified chlorinated polyolefin and method for producing same Download PDF

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Publication number
WO2018155309A1
WO2018155309A1 PCT/JP2018/005329 JP2018005329W WO2018155309A1 WO 2018155309 A1 WO2018155309 A1 WO 2018155309A1 JP 2018005329 W JP2018005329 W JP 2018005329W WO 2018155309 A1 WO2018155309 A1 WO 2018155309A1
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WIPO (PCT)
Prior art keywords
parts
chlorinated polyolefin
group
compound
meth
Prior art date
Application number
PCT/JP2018/005329
Other languages
French (fr)
Japanese (ja)
Inventor
小畑　政示
Original Assignee
関西ペイント株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2017222648A external-priority patent/JP6937668B2/en
Application filed by 関西ペイント株式会社 filed Critical 関西ペイント株式会社
Priority to US16/488,483 priority Critical patent/US10968304B2/en
Priority to CN201880013006.9A priority patent/CN110325563B/en
Publication of WO2018155309A1 publication Critical patent/WO2018155309A1/en

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    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • C08F255/023—On to modified polymers, e.g. chlorinated polymers
    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/12—Polymers provided for in subclasses C08C or C08F
    • C08F290/122—Polymers of hydrocarbons as defined in group C08F10/00
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    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
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    • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
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    • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F216/14—Monomers containing only one unsaturated aliphatic radical
    • C08F216/1416—Monomers containing oxygen in addition to the ether oxygen, e.g. allyl glycidyl ether
    • C08F216/1425—Monomers containing side chains of polyether groups
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    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
    • C08G18/633—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto polymers of compounds having carbon-to-carbon double bonds
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or halogen-containing compounds
    • C08L23/286—Chlorinated polyethene
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    • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
    • C09D123/26—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers modified by chemical after-treatment
    • C09D123/28—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
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    • C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
    • C09D125/02—Homopolymers or copolymers of hydrocarbons
    • C09D125/04—Homopolymers or copolymers of styrene
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    • C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
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    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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    • C09D155/00—Coating compositions based on homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C09D123/00 - C09D153/00
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Definitions

  • the present invention relates to a polymer composition containing a modified chlorinated polyolefin, a method for producing the same, and a coating composition containing the composition.
  • polyolefin-based resins such as polypropylene resins are materials having many excellent properties and are economical. Widely used as a substrate for films and the like. However, since the polyolefin-based substrate is low in polarity, it is inferior in the adhesiveness of the coating film formed at the time of coating. Therefore, in the coating to such a plastic substrate such as polyolefin, the polyolefin-based substrate A composition containing a modified chlorinated polyolefin, such as an acrylic-modified chlorinated polyolefin, which is compatible with the adhesion to the base material and other resin components used together, is used as a paint or a primer. Yes.
  • a modified chlorinated polyolefin such as an acrylic-modified chlorinated polyolefin
  • Patent Document 3 as a method for improving the above production stability, a chlorinated polyolefin having an acid anhydride group is modified with a hydroxyl group-containing (meth) acrylic acid ester and an alcohol, and the resulting esterified chlorination is obtained.
  • a method for producing a modified chlorinated polyolefin resin composition in which a polymerizable vinyl monomer is copolymerized in an organic solvent in the presence of polyolefin is described.
  • the modified chlorinated polyolefin resin composition obtained by the production method sometimes has insufficient curability in a composition used in combination with a crosslinking agent having reactivity with a hydroxyl group.
  • production stability may be insufficient.
  • JP-A-8-59757 JP 2002-309161 A Japanese Patent Laid-Open No. 2015-3991
  • the present invention is a method for obtaining a polymer composition containing a modified chlorinated polyolefin, and is intended to provide a method having excellent production stability. Furthermore, in one aspect of the present invention, there is provided a method for obtaining a polymer composition containing a modified chlorinated polyolefin, which can obtain a composition having excellent curability when used in combination with a crosslinking agent having reactivity with a hydroxyl group. It is something to be offered.
  • the present invention provides a polymer composition containing a modified chlorinated polyolefin by copolymerizing a polymerizable monomer such as an acrylic monomer with a chlorinated polyolefin having an allyloxy group in the presence of a compound having an allyloxy group and a hydroxyl group.
  • a polymerizable monomer such as an acrylic monomer
  • a chlorinated polyolefin having an allyloxy group in the presence of a compound having an allyloxy group and a hydroxyl group.
  • a polymerizable monomer such as an acrylic monomer
  • a chlorinated polyolefin having an allyloxy group in the presence of a compound having an allyloxy group and a hydroxyl group as in the present invention.
  • the polymer composition containing the modified chlorinated polyolefin produced by the production method of the present invention can be used in combination with a crosslinking agent having reactivity with a hydroxyl group to obtain a composition having excellent curability. I was found.
  • R 1 and R 2 each independently represents an alkylene group having 2 or 3 carbon atoms which may be branched
  • m and n are each independently a real number of 0 to 50, and (The sum of n represents a real number equal to or greater than 1, and may be a block structure or a random structure.
  • the addition reaction product of allyl alcohol and lactone the addition reaction product of the compound represented by formula (I) and lactone, and the like.
  • the compounds represented by the above general formula (I) are preferable because they are easily available.
  • Specific examples of the compound contained in the general formula (I) include allyloxyethanol, ethylene glycol monoallyl ether, diethylene glycol monoallyl ether, and the like.
  • 2-allyloxyethanol also known as ethylene glycol monoallyl ether.
  • Diethylene glycol monoallyl ether 1,2-allyloxy-2-propanol (also known as propylene glycol monoallyl ether, dipropylene glycol monoallyl ether, polyethylene glycol monoallyl ether, polypropylene glycol monoallyl ether, polypropylene glycol (2-allyloxyethyl) ) Ether, allyl alcohol and ethylene oxide and propylene oxide addition reaction products, etc.
  • 2-allyloxyethanol Le. Alka: ethylene glycol monoallyl ether
  • diethylene glycol monoallyl ether are particularly preferably used among them, allyloxy ethanol is more preferable because industrially easily available.
  • allyl alcohol can be reacted with ethylene oxide and / or propylene oxide, or ethylene glycol, diethylene glycol, propylene glycol, di- It can be obtained by reacting one or more selected from propylene glycol, polyethylene glycol and polypropylene glycol with allyl chloride or allyl alcohol.
  • a basic compound or an acidic compound may be allowed to coexist as necessary, and these compounds may be neutralized or removed after completion of the reaction.
  • the chlorinated polyolefin (b) having an allyloxy group can be obtained, for example, by introducing an allyloxy group by modifying the chlorinated polyolefin with a compound having an allyloxy group.
  • a method for introducing an allyloxy group into a chlorinated polyolefin specifically, for example, a chlorinated polyolefin having an acid group is reacted with a compound having an allyloxy group and a hydroxyl group, and an ester condensation reaction between the acid group and the hydroxyl group is performed.
  • a method of adding a compound having an allyloxy group and a hydroxyl group to a chlorinated polyolefin through an addition reaction with chlorinated polyolefin can be used.
  • Examples of the chlorinated polyolefin having an acid group include those obtained by modifying a polyolefin with an organic carboxylic acid such as maleic acid or itaconic acid and introducing an acid group, or by chlorinating a polyolefin.
  • a modified polyolefin is preferably used by introducing an acid group by modifying it with an organic carboxylic acid such as maleic acid or itaconic acid. These modification and chlorination can be carried out by known methods.
  • the chlorinated polyolefin (d) having the above acid anhydride group the polyolefin is modified with an anhydride of an organic carboxylic acid such as maleic acid or itaconic acid, and then chlorinated after introducing the acid anhydride group.
  • a chlorinated polyolefin obtained by chlorinating a polyolefin is preferably modified with an anhydride of an organic carboxylic acid such as maleic acid or itaconic acid and introduced with an acid anhydride group. Chlorination can be performed by known methods.
  • the polyolefin used as a raw material is not particularly limited. For example, at least one selected from ⁇ -olefins having 2 to 10 carbon atoms such as ethylene, propylene, 1-butene, and 1-octene is homopolymerized or copolymerized. Those obtained by copolymerizing these ⁇ -olefins with other polymerizable monomers such as vinyl acetate are preferred.
  • a Ziegler-Natta catalyst, a metallocene catalyst, and / or a radical generator can be used for these polymerizations.
  • the polymerization form may be one-stage polymerization or multi-stage polymerization. It may be a static polymerization.
  • These polyolefins can be mixed and used as raw materials in order to adjust compatibility, crystallinity, hardness, liquid stability, adhesion, and the like.
  • chlorinated polyolefin (d) having such an acid anhydride group examples include “Super Clone 892L”, “Super Clone 892LS”, “Super Clone 822”, “Super Clone 822S”, “Super Clone 930”, “Super Clone 930S”, “ “Super Clon 842LM” “Super Clon 851L” "Super Clon 3228S” "Super Clone 3221S” “Super Clon 2319S” (trade name, manufactured by Nippon Paper Industries Co., Ltd., maleic anhydride modified chlorinated polyolefin), “Hardlen CY-9122P” "CY-9124P” "Hardren HM-21P” “Hardren CY-1321P” “Hardren CY-2121P” “Hardren CY-2129P” “Hardren F-225P” “Hardren F-7P” "Hardren M 28P "” HARDLEN F-2P "" HARDLEN F-6P “” HARDLEN CY-1132 "(trade name,
  • chlorinated polyolefin (d) having an acid anhydride group is used alone or in combination of two or more in order to adjust compatibility, crystallinity, hardness, liquid stability, adhesion, and the like. be able to.
  • the chlorine content of the chlorinated polyolefin (d) having an acid anhydride group is preferably 10 to 35% by mass.
  • the production method of the present invention has high production stability even when the chlorine content of the chlorinated polyolefin (d) having an acid anhydride group is relatively high. Therefore, in the production method of the present invention, the chlorine content of the chlorinated polyolefin (d) having an acid anhydride group is 10 to 35% by mass, preferably 19 to 32% by mass, more preferably 20 to 28% by mass. When it is within the range, it can be particularly preferably used. If the chlorine content exceeds 35% by mass, the adhesion to a plastic substrate may be lowered, and if it is less than 10%, the solution stability may be lowered.
  • the amount of the acid anhydride introduced in the chlorinated polyolefin (d) having an acid anhydride group is 0.1 to 8 parts by mass with respect to 100 parts by mass of the chlorinated polyolefin (d) having an acid anhydride group. It is preferably 0.5 to 3 parts by mass.
  • the amount of the introduced acid anhydride is less than 0.1 parts by mass, the adhesion between the layers may be reduced when used for a multilayer coating film. Adhesion may be reduced.
  • a compound having an allyloxy group and a hydroxyl group is reacted with a chlorinated polyolefin (d) having an acid anhydride group, the compound having an allyloxy group and a hydroxyl group is added to the acid anhydride group, and the chlorinated polyolefin having an allyloxy group ( b) can be obtained.
  • a compound (a) having an allyloxy group and a hydroxyl group as represented by the general formula (I) can be used as represented by the general formula (I) can be used.
  • the amount of the compound having an allyloxy group and a hydroxyl group used for the reaction with the chlorinated polyolefin (d) having an acid anhydride group is preferably in the range of 0.2 to 300 mol with respect to 1 mol of the acid anhydride group. Furthermore, the range of 0.5 to 150 mol is preferable.
  • the amount of the compound having an allyloxy group and a hydroxyl group is less than 0.2 mol, the curability of the polymer composition containing the modified chlorinated polyolefin may be lowered, and when it exceeds 300 mol, a part of the polymer composition remains after copolymerization.
  • the amount of the unreacted allyloxy group and the compound having a hydroxyl group may be too large, and the stability of the polymer composition containing the modified chlorinated polyolefin may be lowered.
  • the reaction between the chlorinated polyolefin (d) having an acid anhydride group and the compound having an allyloxy group and a hydroxyl group is not particularly limited, and may be performed according to a usual method of reacting an acid anhydride group and a hydroxyl group. it can.
  • the chlorinated polyolefin (d) having an acid anhydride group and the compound having an allyloxy group and a hydroxyl group are about 20 to 160 ° C., preferably about 60 to 120 ° C., more preferably 80 to
  • the heating can be performed at about 110 ° C. for about 0.5 to 72 hours.
  • the reaction may be carried out at a high temperature and thereafter kept at a low temperature.
  • a catalyst for promoting the reaction can be used.
  • the catalyst include Lewis acidic metal compounds such as dibutyltin oxide, dibutyltin dilaurate, antimony trioxide, zinc acetate, manganese acetate, cobalt acetate, calcium acetate, lead acetate, tetrabutyl titanate, and tetraisopropyl titanate;
  • Known catalysts such as onium salts such as tetrabutylammonium bromide and tetraphenylphosphonium chloride; basic nitrogen-containing compounds such as triethylamine and triazole can be used.
  • a polymerization inhibitor can be used in the case of the said reaction.
  • polymerization inhibitor examples include phenolic hydroxyl group-containing compounds such as di-t-butylhydroxytoluene and methoxyphenol; carbonyl group-containing aromatic compounds such as benzoquinone; nitroso skeleton-containing compounds; N-oxyl skeleton-containing compounds Known polymerization inhibitors such as compounds can be used.
  • the chlorinated polyolefin (b) having an allyloxy group undergoes an addition reaction between the chlorinated polyolefin (d) having an acid anhydride group and the compound (a) having the allyloxy group and the hydroxyl group represented by the general formula (I).
  • a hydroxyl group-containing compound other than the compound (a) having the allyloxy group and the hydroxyl group may be added as necessary.
  • the hydroxyl group-containing compound other than the compound (a) having an allyloxy group and a hydroxyl group include alcohols, compounds having a (meth) acryloyl group and a hydroxyl group, and the like.
  • alcohols examples include alkyl alcohols such as methanol, ethanol, propanol, butanol and 2-ethylhexanol; ether group-containing alcohols such as ethylene glycol monobutyl ether, propylene glycol monopropyl ether and diethylene glycol monomethyl ether; benzyl alcohol Aromatic alcohols such as carbonyl group-containing alcohols such as diacetone alcohol; polyols such as diethylene glycol, tripropylene glycol, 1,6-hexanediol, and trimethylolpropane.
  • alkyl alcohols such as methanol, ethanol, propanol, butanol and 2-ethylhexanol
  • ether group-containing alcohols such as ethylene glycol monobutyl ether, propylene glycol monopropyl ether and diethylene glycol monomethyl ether
  • benzyl alcohol Aromatic alcohols such as carbonyl group-containing alcohols such as diacetone alcohol
  • Examples of the compound having a (meth) acryloyl group and a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl ( Monoesterified product of (meth) acrylic acid such as (meth) acrylate and dihydric alcohol having 2 to 8 carbon atoms; ⁇ - of monoesterified product of (meth) acrylic acid and dihydric alcohol having 2 to 8 carbon atoms Examples include modified caprolactone.
  • the chlorinated polyolefin (d) having the acid anhydride group is added to a compound (a) having an allyloxy group and a hydroxyl group represented by the general formula (I) and a hydroxyl group other than the compound (a) having the allyloxy group and the hydroxyl group.
  • the compound (a) having an allyloxy group and a hydroxyl group is added to the chlorinated polyolefin (d) having an acid anhydride group, and then the compound (a) other than the compound (a) having an allyloxy group and a hydroxyl group.
  • a compound (a) having an allyloxy group and a hydroxyl group and a compound (a) having an allyloxy group and a hydroxyl group may be added to the chlorinated polyolefin (d) having an acid anhydride group.
  • An addition reaction may be performed by adding a mixture of a hydroxyl group-containing compound in advance, or a chlorinated polyol having an acid anhydride group.
  • Compound (a) other than hydroxyl group-containing compound having an aryloxy group and a hydroxyl group in the fins (d) is reacted, it may be further addition reaction compound having aryloxy group and a hydroxyl group (a).
  • the hydroxyl group-containing compound other than the compound (a) having an allyloxy group and a hydroxyl group is added to the chlorinated polyolefin (d) having an acid anhydride group
  • the hydroxyl group-containing compound other than the compound (a) having an allyloxy group and a hydroxyl group is added.
  • the amount used is not particularly limited with respect to 1 mol of the acid anhydride group of the chlorinated polyolefin (d) having an acid anhydride group, but is preferably 500 mol or less, and more preferably 300 mol or less. . If it exceeds 500 moles, the stability of the polymer composition containing the modified chlorinated polyolefin may be lowered.
  • a hydroxyl group-containing compound other than the compound (a) having an allyloxy group and a hydroxyl group includes a compound having a (meth) acryloyl group and a hydroxyl group
  • the amount of the compound having a (meth) acryloyl group and a hydroxyl group is used as an acid anhydride.
  • the amount is preferably 10 mol or less, more preferably 5 mol or less, per 1 mol of the acid anhydride group of the chlorinated polyolefin (d) having a group. If it exceeds 10 mol, the system may be easily gelled in the copolymerization step.
  • (meth) acrylic acid is “acrylic acid or methacrylic acid”
  • (meth) acrylic acid ester is “acrylic acid ester or methacrylic acid ester”
  • (meth) acryloyl is “Acryloyl or methacryloyl” means “(meth) acrylate” means “acrylate or methacrylate”.
  • the (meth) acrylic acid ester used in the present invention is not particularly limited.
  • Styrene may be substituted, and in that case, alkyl group-substituted styrenes such as methylstyrene and ethylstyrene are exemplified.
  • alkyl group-substituted styrenes such as methylstyrene and ethylstyrene are exemplified.
  • These polymerizable monomers can be used alone or in combination of two or more in order to adjust the molecular weight, hardness, polarity, adhesion, solution viscosity, solution stability, compatibility, etc. of the polymer composition. .
  • compound (a), chlorinated polyolefin (b) having an allyloxy group, and (meth) acrylic acid ester, (meth) acrylic acid, and one or more compounds (c) selected from styrene are included.
  • the amount of each polymerizable monomer used is preferably in the following range based on 100 parts by mass of the total solid content of the components (a) to (c).
  • Compound (a) having an allyloxy group and a hydroxyl group 0.05 to 40 parts by mass, preferably 0.1 to 30 parts by mass, more preferably 0.2 to 20 parts by mass, Chlorinated polyolefin having an allyloxy group (b): 1 to 89.95 parts by mass, preferably 5 to 60 parts by mass, more preferably 10 to 35 parts by mass,
  • the chlorinated polyolefin (b) having an allyloxy group in the presence of the compound (a) having an allyloxy group and a hydroxyl group, from the chlorinated polyolefin (b) having an allyloxy group, (meth) acrylic acid ester, (meth) acrylic acid and styrene.
  • a copolymer component other than (meth) acrylic acid ester, (meth) acrylic acid and styrene may be added.
  • examples of such other copolymer components include aliphatic carboxylates such as vinyl acetate, vinyl octoate, and vinyl decanoate.
  • one or more selected from chlorinated polyolefins having no allyloxy group and chlorinated polyolefins having no acid anhydride group are allowed to coexist.
  • copolymerization may be performed.
  • a chlorinated polyolefin (b) having an allyloxy group (hereinafter simply referred to as “(”) in the presence of a compound (a) having an allyloxy group and a hydroxyl group (hereinafter sometimes simply referred to as “(a)”).
  • a polymerizable monomer containing one or more compounds (c) selected from (meth) acrylic acid ester, (meth) acrylic acid and styrene hereinafter simply referred to as" (c)
  • c) a polymerizable monomer containing one or more compounds (c) selected from (meth) acrylic acid ester, (meth) acrylic acid and styrene
  • reaction vessel First added, then polymerized while adding (b); previously added (b) and (c) to the reaction vessel, and then polymerized while adding a polymerizable monomer containing compound (c); reaction (B) and (c) are added to the tank first, and then polymerization is performed while adding (b) and (c); polymerization is performed while adding (b) and (c) to the reaction tank; c) is added first and then polymerized while adding (b); (c) is first added to the reaction vessel and then polymerized while adding (b) and (c); A method may be used. Further, the polymerization process may be performed in multiple stages and these methods may be used in combination.
  • the step of adding (b) and (c) to the reaction vessel in the first stage and then performing batch polymerization and the step of polymerizing while adding (b) and / or (c) to the reaction vessel in the second stage are combined.
  • the polymerization may be performed while adding (b) and (c) to the reaction tank in the first stage, and the polymerization may be performed while adding (b) and / or (c) to the reaction tank in the second stage. You may combine a process.
  • each composition of (b) and / or (c) used at each process may be the same, or may differ.
  • the chlorinated polyolefin (d) having an acid anhydride group When the chlorinated polyolefin (d) having an acid anhydride group, the compound (a) having an allyloxy group and a hydroxyl group are mixed and subjected to an addition reaction to obtain the chlorinated polyolefin (b) having an allyloxy group, the addition By not completing the reaction or by increasing the number of moles of the compound (a) having an allyloxy group and a hydroxyl group to be mixed as compared with the number of moles of the acid anhydride group, the chlorinated polyolefin (b) having an allyloxy group is unreacted. It can be obtained as a mixture coexisting with the compound (a) having an allyloxy group and a hydroxyl group in the reaction.
  • the chlorinated polyolefin (b) having an allyloxy group in the coexistence of the compound (a) having an allyloxy group and a hydroxyl group by copolymerizing this mixture with a polymerizable monomer containing the compound (c), And the polymerizable monomer containing 1 or more types of compounds (c) chosen from (meth) acrylic acid ester, (meth) acrylic acid, and styrene can be copolymerized.
  • the chlorinated polyolefin (b) having an allyloxy group and the compound (c) when copolymerizing the polymerizable monomer containing the chlorinated polyolefin (b) having an allyloxy group and the compound (c), the chlorinated polyolefin (b) having an allyloxy group, the compound (a) having an allyloxy group and a hydroxyl group Or a compound having an allyloxy group and a hydroxyl group (a) by mixing a polymerizable monomer containing the compound (c) with a compound (a) having an allyloxy group and a hydroxyl group in advance ( a polymerizable monomer containing a chlorinated polyolefin (b) having an allyloxy group in the presence of a) and one or more compounds (c) selected from (meth) acrylic acid ester, (meth) acrylic acid and styrene; It can be copolymerized.
  • chlorinated polyolefin (b) having an allyloxy group in the coexistence of a compound (a) having an allyloxy group and a hydroxyl group is selected from (b), (meth) acrylic acid ester, (meth) acrylic acid and styrene.
  • the method for copolymerizing the polymerizable monomer containing one or more compounds (c) is not particularly limited, and a known copolymerization method can be used, but in particular in an organic solvent.
  • a solution polymerization method in which polymerization is performed in the presence of a polymerization initiator can be preferably used.
  • organic solvent used in the solution polymerization method examples include aromatic solvents such as toluene, xylene, and “Swazole 1000” (trade name, high-boiling petroleum solvent) manufactured by Cosmo Oil; cyclohexane, methylcyclohexane, and the like.
  • Aliphatic solvents such as hexane and heptane; ethyl acetate, butyl acetate, 3-methoxybutyl acetate, butyl propionate, ethyl-3-ethoxypropionate, ethylene glycol monoethyl ether acetate, Ester solvents such as propylene glycol monomethyl ether acetate; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and methyl pentyl ketone; butanol, 2-ethylhexanol, ethylene glycol monobutyl ether, dipropylene glycol monomethyl It may be mentioned alcohol solvents such as ether or the like.
  • the amount of the organic solvent used in the polymerization reaction is not particularly limited, but may be appropriately adjusted in order to adjust the stability of the polymer composition containing the modified chlorinated polyolefin. From the viewpoint of increasing the production efficiency, it is usually 500 parts by mass or less, preferably 50 to 400 parts by mass, more preferably 100 to 100 parts by mass based on 100 parts by mass of the total solid content of the components (a) to (c). It is preferable to be within the range of 300 parts by mass.
  • the organic solvent may be added after the copolymerization reaction. Further, the solvent may be removed after the copolymerization reaction.
  • ketone peroxides such as methyl ethyl ketone peroxide and acetylacetone peroxide
  • di (tert-hexylperoxy) cyclohexane di (tert-butylperoxide) Peroxyketals such as oxy) cyclohexane
  • hydroperoxides such as p-menthane hydroperoxide
  • di-tert-butyl peroxide di (2-tert-butylperoxyisopropyl) benzene, dicumyl peroxide, etc.
  • Dialkyl peroxides diacyl peroxides such as diisobutyryl peroxide, di (3,5,5-trimethylhexanoyl) peroxide, dilauroyl peroxide; di (2-ethylhexyl) Peroxydicarbonates such as peroxydicarbonate, diisopropylperoxydicarbonate, di (4-tert-butylcyclohexyl) peroxydicarbonate; tert-butylperoxyisopropylcarbonate, tert-butylperoxy-2-ethylhexyl carbonate, etc.
  • diacyl peroxides such as diisobutyryl peroxide, di (3,5,5-trimethylhexanoyl) peroxide, dilauroyl peroxide
  • di (2-ethylhexyl) Peroxydicarbonates such as peroxydicarbonate, diisopropylperoxydicarbonate, di (4-
  • Peroxycarbonates tert-butyl peroxypivalate, tert-butyl peroxylaurate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxyacetate, tert-butyl peroxybenzoate
  • Peroxyesters such as 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, di-tert-butylperoxyhexahydroterephthalate Azobisisobutyronitrile, azobis (2,4-dimethylvaleronitrile), azobis (2-methylpropionitrile), azobis (2-methylbutyronitrile), 4,4′-azobis (4-cyano Pentanoic acid), dimethylazobis (2-methylpropionate), azobis [2-methyl-N- (2-hydroxyethyl) -propionamide], azobis ⁇ 2-methyl-N- [2- (1-hydroxy Butyl
  • the polymerization initiator may be monofunctional or polyfunctional with respect to the radicals generated. These polymerization initiators can be used alone or in combination of two or more. Moreover, it is good also as a redox initiator by using reducing agents, such as saccharide
  • reducing agents such as saccharide
  • the amount of the polymerization initiator used is usually 0.1 to 10 parts by weight, preferably 0.5 to 8 parts by weight, based on 100 parts by weight of the total solid content of the components (a) to (c). It is preferably within the range of 1 to 6 parts by mass.
  • the molecular weight of the polymer composition containing the modified chlorinated polyolefin can be changed by changing the amount of the polymerization initiator used.
  • the molecular weight is easily produced in a weight average molecular weight of about 10,000 to 1,000,000, and is preferably about 30,000 to 400,000 in order to improve the solution stability and compatibility of the polymer composition. More preferably, it is about 70,000 to 200,000.
  • the weight average molecular weight is the retention time (retention capacity) of a standard polystyrene having a known molecular weight measured under the same conditions as the retention time (retention capacity) measured using a gel permeation chromatograph (GPC). Is a value obtained by converting to a molecular weight of polystyrene.
  • GPC gel permeation chromatograph
  • G2000HXL (trade name, all manufactured by Tosoh Corporation), using a differential refractometer as the detector, mobile phase: tetrahydrofuran, measurement temperature: 40 ° C, flow rate: 1 mL / min Can be measured below.
  • the method for adding the polymerization initiator is not particularly limited, and can be appropriately selected according to the type and amount thereof. For example, it may be previously contained in the monomer mixture or solvent, or may be added all at once during the polymerization, or may be added dropwise. Further, the copolymerization reaction can be carried out usually within a range of 20 to 170 ° C., preferably 70 to 130 ° C., more preferably 80 to 120 ° C. Moreover, you may add antioxidant after the said copolymerization reaction. Examples of the antioxidant include phenolic hydroxyl group-containing compounds such as di-t-butylhydroxytoluene and methoxyphenol; and carbonyl group-containing aromatic compounds such as benzoquinone.
  • the polymer composition containing the modified chlorinated polyolefin of the present invention can contain a crosslinking agent as required. Any crosslinking agent can be used as long as it can be combined with the polymer composition containing the modified chlorinated polyolefin to form a curable composition, but is usually included in the modified chlorinated polyolefin.
  • a crosslinking agent having reactivity with a hydroxyl group is preferably used. As such a crosslinking agent having reactivity with a hydroxyl group, for example, a polyisocyanate compound, a blocked polyisocyanate compound, an amino resin, or the like can be suitably used.
  • the crosslinking agents can be used alone or in combination of two or more.
  • the polyisocyanate compound is a compound having at least two isocyanate groups in one molecule, and includes, for example, an aliphatic polyisocyanate, an alicyclic polyisocyanate, an araliphatic polyisocyanate, an aromatic polyisocyanate, and the polyisocyanate. And the like.
  • aliphatic polyisocyanate examples include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3.
  • Aliphatic diisocyanates such as butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, dimer diisocyanate, methyl 2,6-diisocyanatohexanoate (common name: lysine diisocyanate); 2 , 6-Diisocyanatohexanoic acid 2-isocyanatoethyl, 1,6-diisocyanato-3-isocyanatomethylhexane, 1,4,8-triisocyanatooctane, 1,6 11-triisocyanatoundecane, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-triisocyanatohexane, 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyl Examples thereof include aliphatic triisocyanates such as octane.
  • alicyclic polyisocyanate examples include 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (common name) : Isophorone diisocyanate), 4-methyl-1,3-cyclohexylene diisocyanate (common name: hydrogenated TDI), 2-methyl-1,3-cyclohexylene diisocyanate, 1,3- or 1,4-bis (isocyanato) Methyl) cyclohexane (common name: hydrogenated xylylene diisocyanate) or a mixture thereof, alicyclic diisols such as methylenebis (4,1-cyclohexanediyl) diisocyanate (common name: hydrogenated MDI), norbornane diisocyanate 1,3,5-triiso
  • araliphatic polyisocyanate examples include methylene bis (4,1-phenylene) diisocyanate (common name: MDI), 1,3- or 1,4-xylylene diisocyanate, or a mixture thereof, ⁇ , ⁇ ′-diisocyanato- Aromatic aliphatic diisocyanates such as 1,4-diethylbenzene, 1,3- or 1,4-bis (1-isocyanato-1-methylethyl) benzene (common name: tetramethylxylylene diisocyanate) or mixtures thereof; 1,3 And araliphatic triisocyanates such as 5-triisocyanatomethylbenzene.
  • MDI methylene bis (4,1-phenylene) diisocyanate
  • 1,3- or 1,4-xylylene diisocyanate or a mixture thereof
  • ⁇ , ⁇ ′-diisocyanato- Aromatic aliphatic diisocyanates such as 1,4
  • aromatic polyisocyanate examples include m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 2,4-tolylene diisocyanate (common name: 2,4- TDI) or 2,6-tolylene diisocyanate (common name: 2,6-TDI) or a mixture thereof, aromatic diisocyanates such as 4,4′-toluidine diisocyanate, 4,4′-diphenyl ether diisocyanate; , 4 ′, 4 ′′ -triisocyanate, 1,3,5-triisocyanatobenzene, 2,4,6-triisocyanatotoluene and the like; 4,4′-diphenylmethane-2,2 ′ Fragrance such as 5,5'-tetraisocyanate Mention may be made of tetra-isocyanate, and the like.
  • polyisocyanate derivatives examples include dimer, trimer, biuret, allophanate, uretdione, uretoimine, isocyanurate, oxadiazine trione, polymethylene polyphenyl polyisocyanate (crude MDI, polymeric MDI). And Crude TDI.
  • polyisocyanates and derivatives thereof may be used alone or in combination of two or more. Of these polyisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, and derivatives thereof are preferred. Further, as the polyisocyanate compound, a prepolymer obtained by reacting the polyisocyanate and a derivative thereof with a compound capable of reacting with the polyisocyanate under conditions of excess isocyanate groups may be used. Examples of the compound capable of reacting with the polyisocyanate include compounds having an active hydrogen group such as a hydroxyl group and an amino group. Specifically, for example, polyhydric alcohol, low molecular weight polyester resin, amine, water, etc. Can be used.
  • the polyisocyanate compound may be a polymer of an isocyanate group-containing polymerizable unsaturated monomer, or a polymerizable unsaturated monomer other than the isocyanate group-containing polymerizable unsaturated monomer and the isocyanate group-containing polymerizable unsaturated monomer.
  • a copolymer may be used.
  • the polyisocyanate compound usually has an equivalent ratio (NCO / OH) of the isocyanate group in the polyisocyanate compound and the hydroxyl group in the resin component in the polymer composition containing the modified chlorinated polyolefin from the viewpoint of curability and the like. It is preferable to use it in a proportion within the range of 0.5 to 2.5, particularly 0.8 to 1.9.
  • the blocked polyisocyanate compound is a compound obtained by blocking the isocyanate group of the polyisocyanate compound with a blocking agent.
  • the blocking agent include phenols such as phenol, cresol, xylenol, nitrophenol, ethylphenol, hydroxydiphenyl, butylphenol, isopropylphenol, nonylphenol, octylphenol, and hydroxybenzoic acid methyl; ⁇ -caprolactam, ⁇ -valerolactam, Lactams such as ⁇ -butyrolactam and ⁇ -propiolactam; aliphatic alcohols such as methanol, ethanol, propyl alcohol, butyl alcohol, amyl alcohol, lauryl alcohol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono Butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene Ethers such as glycol monomethyl
  • azole compounds examples include pyrazole, 3,5-dimethylpyrazole, 3-methylpyrazole, 4-benzyl-3,5-dimethylpyrazole, 4-nitro-3,5-dimethylpyrazole, 4-bromo-3, Pyrazole or pyrazole derivatives such as 5-dimethylpyrazole and 3-methyl-5-phenylpyrazole; Imidazole or imidazole derivatives such as imidazole, benzimidazole, 2-methylimidazole, 2-ethylimidazole and 2-phenylimidazole; 2-methylimidazoline And imidazoline derivatives such as 2-phenylimidazoline.
  • preferable blocking agents include oxime-based blocking agents, malonic acid diester-based or acetyl group-containing compound-based blocking agents having an active methylene position, pyrazole or pyrazole derivatives.
  • solvents used for the blocking reaction are preferably those that are not reactive with isocyanate groups.
  • ketones such as acetone and methyl ethyl ketone
  • esters such as ethyl acetate
  • NMP N-methyl-2-pyrrolidone
  • the catalyst of a normal urethanation reaction can be used as a catalyst.
  • the catalyst include tin octylate, dibutyltin diacetate, dibutyltin di (2-ethylhexanoate), dibutyltin dilaurate, dioctyltin diacetate, dioctyltin di (2-ethylhexanoate), and dibutyl.
  • the catalyst amount is within the range of 0.0001 to 1% by mass, particularly 0.0005 to 0.5% by mass, based on the total solid content of the polymer composition. preferable.
  • the polymer composition contains the catalyst
  • the polymer composition is acetic acid, propionic acid, butyric acid, isopentanoic acid, hexanoic acid, 2-ethylbutyric acid, naphthenic acid, octyl from the viewpoints of storage stability and curability.
  • Acid nonanoic acid, decanoic acid, 2-ethylhexanoic acid, isooctanoic acid, isononanoic acid, lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid, neodecanoic acid, versatic acid, isobutyric anhydride, itaconic anhydride, anhydrous Organic acids such as acetic acid, citraconic anhydride, propionic anhydride, maleic anhydride, butyric anhydride, citric anhydride, trimellitic anhydride, pyromellitic anhydride, phthalic anhydride; inorganic acids such as hydrochloric acid and phosphoric acid; acetylacetone, imidazole A metal coordination compound such as a compound may be contained.
  • the partial methylolation amino resin or complete methylolation amino resin obtained by reaction of an amino component and an aldehyde component can be used.
  • the amino component include melamine, urea, benzoguanamine, acetoguanamine, steroguanamine, spiroguanamine, dicyandiamide and the like.
  • the aldehyde component include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde and the like.
  • what methylated the methylol group of the said methylolated amino resin partially or completely with suitable alcohol can also be used.
  • Examples of the alcohol used for etherification include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, 2-ethylbutanol, 2-ethylhexanol and the like.
  • a melamine resin is preferable.
  • the melamine resin for example, an alkyl etherified melamine resin obtained by partially or completely etherifying a methylol group of a partially or completely methylolated melamine resin with the above alcohol can be used.
  • alkyl etherified melamine resin examples include a methyl ether melamine resin obtained by partially or fully etherifying a methylol group of a partially or completely methylolated melamine resin with methyl alcohol; a methylol group of a partially or completely methylolated melamine resin; Butyl etherified melamine resin partially or fully etherified with butyl alcohol; methyl-butyl mixed etherification wherein methylol groups of partially or fully methylolated melamine resin are partially or fully etherified with methyl alcohol and butyl alcohol A melamine resin etc. can be used conveniently.
  • a commercially available product can be used as the melamine resin.
  • Examples of commercially available product names include “Cymel 202”, “Cymel 203”, “Cymel 238”, “Cymel 251”, “Cymel 303”, “Cymel 323”, “Cymel 324”, “Cymel 325”, “Cymel 327”, “Cymel 350”, “Cymel 385”, “Cymel 1156”, “Cymel 1158”, “Cymel 1116”, “Cymel 1130” (manufactured by Ornex Japan), “Uban 120”, “ Examples include “Uban 20HS”, “Uban 20SE60”, “Uban 2021”, “Uban 2028”, “Uban 28-60” (all manufactured by Mitsui Chemicals, Inc.).
  • the melamine resins described above can be used alone or in combination of two or more.
  • a melamine resin is used as a crosslinking agent
  • sulfonic acids such as p-toluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid; monobutyl phosphoric acid, dibutyl phosphoric acid, mono 2-ethylhexyl phosphoric acid, di-2- Alkyl phosphate esters such as ethylhexyl phosphate; salts of these acids with amine compounds, etc. can be used as catalysts.
  • the polymer composition containing the modified chlorinated polyolefin of the present invention obtained by copolymerizing the polymerizable monomer containing (c) can be suitably used as a curable composition or a coating composition.
  • the polymer composition containing the modified chlorinated polyolefin of the present invention is used as a coating composition, it preferably contains a crosslinking agent having reactivity with the hydroxyl group.
  • the coating composition can be applied to coating resins such as epoxy resins, acrylic resins, polyester resins, urethane resins, chlorinated polyolefins, various pigments, viscosity modifiers, pigment dispersants, antifoaming agents, and UV absorbers as necessary.
  • resins such as epoxy resins, acrylic resins, polyester resins, urethane resins, chlorinated polyolefins, various pigments, viscosity modifiers, pigment dispersants, antifoaming agents, and UV absorbers as necessary.
  • Various additives used in the paint field such as an agent can be blended.
  • the coating composition according to the present invention can be applied using various known coating methods.
  • the object to be coated is not particularly limited, but can be suitably used for plastic substrates such as molded articles and films.
  • Example 1 In a four-necked flask equipped with a condenser, 100 parts of “Super Clone 822S” (trade name, manufactured by Nippon Paper Industries Co., Ltd., maleic anhydride-modified chlorinated polyolefin, chlorine content 24.5%), 221 parts of toluene, di-t -0.05 part of butylhydroxytoluene (abbreviation: BHT) was added and stirred while blowing air into the liquid phase, and the temperature was raised to about 95 ° C to obtain a solution.
  • “Super Clone 822S” trade name, manufactured by Nippon Paper Industries Co., Ltd., maleic anhydride-modified chlorinated polyolefin, chlorine content 24.5%
  • BHT butylhydroxytoluene
  • the modified chlorinated polyolefin was Polymer composition having (P-1) was obtained.
  • the obtained polymer composition (P-1) containing the modified chlorinated polyolefin had a solid content of about 46%, and the composition contained about 45 parts of 2-allyloxyethanol.
  • the hydroxyl value of the resin solid content was approximately 11 mgKOH / g.
  • the component ratio of the chlorinated polyolefin skeleton and the acrylic resin skeleton obtained by copolymerizing a part of 2-allyloxyethanol in the composition was about 20/80.
  • Example 2 In a four-necked flask with a condenser tube, “Super Clone 822S” (trade name, manufactured by Nippon Paper Industries Co., Ltd., maleic anhydride modified chlorinated polyolefin, chlorine content 24.5%) 100 parts, toluene 70 parts, di-t -0.05 part of butylhydroxytoluene (abbreviation: BHT) was added and stirred while blowing air into the liquid phase, and the temperature was raised to about 95 ° C to obtain a solution. To this, 23 parts of 2-allyloxyethanol and 0.1 part of tetrabutylammonium bromide were added, and stirring was continued while reacting 2-allyloxyethanol with the acid anhydride group.
  • BHT butylhydroxytoluene
  • the ratio of the absorbance of the absorbance and about 1460 cm -1 to about 1770 cm -1 in the infrared absorption analysis of the solids in the solution to lower the temperature to about 90 ° C. at a stage where almost no change, 150 parts of toluene and 2-allyloxy
  • the concentration of chlorinated polyolefin (b) having an allyloxy group is about 27%, including about 55 parts of 2-allyloxyethanol, which is a compound (a) having an allyloxy group and a hydroxyl group.
  • a solution was obtained. Next, air blowing into the liquid phase is stopped, stirring is continued at about 90 ° C.
  • a mixed solution of 5 parts of perbutyl PV and 70 parts of toluene was dropped over about 1 hour, and stirring was continued for about 1 hour, followed by cooling to room temperature, and a polymer composition containing a modified chlorinated polyolefin (P-2) Got.
  • the obtained polymer composition (P-2) containing the modified chlorinated polyolefin had a solid content of about 46%, and the composition contained about 45 parts of 2-allyloxyethanol.
  • the hydroxyl value of the resin solid content was approximately 11 mgKOH / g.
  • the component ratio of the chlorinated polyolefin skeleton and the acrylic resin skeleton obtained by copolymerizing a part of 2-allyloxyethanol in the composition was about 20/80.
  • Example 3 In a four-necked flask with a condenser tube, “Super Clon 3228S” (trade name, manufactured by Nippon Paper Industries Co., Ltd., maleic anhydride-modified chlorinated polyolefin, chlorine content 28%) 100 parts, 210 parts toluene, 11 parts butyl acetate, 0.05 part of di-t-butylhydroxytoluene (abbreviation: BHT) was added and stirred while blowing air into the liquid phase, and the temperature was raised to about 95 ° C. to obtain a solution.
  • BHT di-t-butylhydroxytoluene
  • a mixed solution of 5 parts of perbutyl PV and 70 parts of toluene was dropped over about 1 hour, and stirring was continued for about 1 hour, followed by cooling to room temperature and a polymer composition containing modified chlorinated polyolefin (P -3) was obtained.
  • the resulting polymer composition (P-3) containing the modified chlorinated polyolefin had a solid content of about 46%, and the composition contained about 45 parts of 2-allyloxyethanol.
  • the hydroxyl value of the resin solid content was approximately 11 mgKOH / g.
  • the component ratio of the chlorinated polyolefin skeleton and the acrylic resin skeleton obtained by copolymerizing a part of 2-allyloxyethanol in the composition was about 20/80.
  • Example 4 In a four-necked flask with a condenser tube, "Hardlen F-6P" (trade name, manufactured by Toyobo, maleic anhydride-modified chlorinated polyolefin, chlorine content 20%), 214 parts of toluene, di-t-butyl 0.05 part of hydroxytoluene (abbreviation: BHT) was added and stirred while blowing air into the liquid phase, and the temperature was raised to about 95 ° C. to obtain a solution. To this, 65 parts of 2-allyloxyethanol and 0.1 part of tetrabutylammonium bromide were added, and stirring was continued while reacting 2-allyloxyethanol with the acid anhydride group.
  • BHT hydroxytoluene
  • the ratio of the absorbance of the absorbance and about 1460 cm -1 to about 1770 cm -1 in the infrared absorption analysis of the solids in the solution to lower the temperature to about 90 ° C. at a stage where almost no change, a compound having an aryloxy group and a hydroxyl group ( A solution containing about 64 parts of 2-allyloxyethanol as a) and having a concentration of chlorinated polyolefin (b) having an allyloxy group of about 16% was obtained. Next, air blowing into the liquid phase is stopped, stirring is continued at about 90 ° C.
  • a solution containing 5 parts of perbutyl PV and 70 parts of toluene was added dropwise over about 1 hour, and stirring was continued for about 1 hour, followed by cooling to room temperature, and a polymer containing a modified chlorinated polyolefin.
  • a composition (P-4) was obtained.
  • the resulting polymer composition (P-4) containing the modified chlorinated polyolefin had a solid content of about 46%, and the composition contained about 52 parts of 2-allyloxyethanol.
  • the hydroxyl value of the resin solid content was approximately 12 mgKOH / g.
  • the component ratio of the chlorinated polyolefin skeleton and the acrylic resin skeleton obtained by copolymerizing a part of 2-allyloxyethanol in the composition was about 10/90.
  • Example 5 In a four-necked flask equipped with a condenser tube, 100 parts of “Superclone 822S”, 221 parts of toluene, 0.05 part of di-t-butylhydroxytoluene (abbreviation: BHT) are added and stirred while blowing air into the liquid phase. The temperature was raised to about 95 ° C. to obtain a solution. To this, 82.5 parts of diethylene glycol monoallyl ether and 0.1 part of tetrabutylammonium bromide were added, and stirring was continued while reacting diethylene glycol monoallyl ether and acid anhydride groups.
  • BHT di-t-butylhydroxytoluene
  • the ratio of the absorbance of the absorbance and about 1460 cm -1 to about 1770 cm -1 in the infrared absorption analysis of the solids in the solution to lower the temperature to about 90 ° C. at a stage where almost no change, a compound having an aryloxy group and a hydroxyl group ( A solution containing about 79 parts of diethylene glycol monoallyl ether as a) and having a concentration of chlorinated polyolefin (b) having an allyloxy group of about 25% was obtained. Next, air blowing into the liquid phase is stopped, stirring is continued at about 90 ° C.
  • a composition (P-5) was obtained.
  • the obtained polymer composition (P-5) containing the modified chlorinated polyolefin had a solid content of about 47%, and the composition contained about 65 parts of diethylene glycol monoallyl ether.
  • the hydroxyl value of the resin solid content was approximately 15 mg KOH / g.
  • the component ratio of the acrylic resin skeleton obtained by copolymerizing a part of the chlorinated polyolefin skeleton and diethylene glycol monoallyl ether in the composition was about 19/81.
  • Example 6 In a four-necked flask equipped with a condenser tube, 100 parts of “Supercron 822S”, 228 parts of toluene and 0.05 part of di-t-butylhydroxytoluene (abbreviation: BHT) are added and stirred while blowing air into the liquid phase. The temperature was raised to about 95 ° C. to obtain a solution. To this, 46 parts of 2-allyloxyethanol, 4 parts of butanol and 0.1 part of tetrabutylammonium bromide were added, and stirring was continued while reacting 2-allyloxyethanol, butanol and acid anhydride groups. It was.
  • BHT di-t-butylhydroxytoluene
  • the ratio of the absorbance of the absorbance and about 1460 cm -1 to about 1770 cm -1 in the infrared absorption analysis of the solids in the solution to lower the temperature to about 90 ° C. at a stage where almost no change, a compound having an aryloxy group and a hydroxyl group (
  • a solution containing about 44 parts of 2-allyloxyethanol as a) and having a concentration of chlorinated polyolefin (b) having an allyloxy group of about 27% was obtained.
  • the approximate molar ratio of 2-allyloxyethanol and butanol reacted with the acid anhydride group was 0.8 / 0.2.
  • air blowing into the liquid phase is stopped, stirring is continued at about 90 ° C.
  • a solution containing 5 parts of perbutyl PV and 70 parts of toluene was added dropwise over about 1 hour, and stirring was continued for about 1 hour, followed by cooling to room temperature, and a polymer containing a modified chlorinated polyolefin.
  • a composition (P-6) was obtained.
  • the obtained polymer composition (P-6) containing the modified chlorinated polyolefin had a solid content of about 46%, and the composition contained about 36 parts of 2-allyloxyethanol.
  • the hydroxyl value of the resin solid content was approximately 9 mgKOH / g.
  • the component ratio of the chlorinated polyolefin skeleton and the acrylic resin skeleton obtained by copolymerizing a part of 2-allyloxyethanol in the composition was about 20/80.
  • Example 7 In a four-necked flask equipped with a condenser tube, 100 parts of “Superclone 822S”, 70 parts of toluene and 0.05 part of di-t-butylhydroxytoluene (abbreviation: BHT) are added and stirred while blowing air into the liquid phase. The temperature was raised to about 95 ° C. to obtain a solution. To this, 11.5 parts of 2-allyloxyethanol, 17 parts of butanol and 0.1 part of tetrabutylammonium bromide were added, and stirred while reacting 2-allyloxyethanol, butanol and acid anhydride groups. Continued.
  • BHT di-t-butylhydroxytoluene
  • the ratio of the absorbance of the absorbance and about 1460 cm -1 to about 1770 cm -1 in the infrared absorption analysis of the solids in the solution to lower the temperature to about 90 ° C. at a stage where almost no change, 140 parts of 2-ants of toluene
  • the approximate molar ratio of 2-allyloxyethanol and butanol reacted with the anhydride group was 0.2 / 0.8.
  • a mixed solution of 5 parts of perbutyl PV and 70 parts of toluene was dropped over about 1 hour, and stirring was continued for about 1 hour, followed by cooling to room temperature and a polymer composition containing modified chlorinated polyolefin (P -7) was obtained.
  • the resulting polymer composition (P-7) containing the modified chlorinated polyolefin had a solid content of about 46%, and the composition contained about 42 parts of 2-allyloxyethanol.
  • the hydroxyl value of the resin solid content was approximately 10 mg KOH / g.
  • the component ratio of the chlorinated polyolefin skeleton and the acrylic resin skeleton obtained by copolymerizing a part of 2-allyloxyethanol in the composition was about 20/80.
  • Example 8 In a four-necked flask equipped with a condenser tube, 100 parts of “Superclon 3228S”, 70 parts of toluene and 0.05 part of di-t-butylhydroxytoluene (abbreviation: BHT) were added and stirred while blowing air into the liquid phase. The temperature was raised to about 95 ° C. to obtain a solution. To this, 11.5 parts of 2-allyloxyethanol, 16 parts of butanol, 1 part of 2-ethylhexanol and 0.1 part of tetrabutylammonium bromide were added, and 2-allyloxyethanol, butanol, 2-ethylhexanol were added.
  • BHT di-t-butylhydroxytoluene
  • a solution containing 5 parts of perbutyl PV and 70 parts of toluene was added dropwise over about 1 hour, and stirring was continued for about 1 hour, followed by cooling to room temperature, and a polymer containing a modified chlorinated polyolefin.
  • a composition (P-8) was obtained.
  • the resulting polymer composition (P-8) containing the modified chlorinated polyolefin had a solid content of about 46%, and the composition contained about 41 parts of 2-allyloxyethanol.
  • the hydroxyl value of the resin solid content was approximately 10 mg KOH / g.
  • the component ratio of the chlorinated polyolefin skeleton and the acrylic resin skeleton obtained by copolymerizing a part of 2-allyloxyethanol in the composition was about 20/80.
  • Example 9 In a four-necked flask equipped with a condenser tube, 100 parts of “Superclone 822S”, 70 parts of toluene and 0.05 part of di-t-butylhydroxytoluene (abbreviation: BHT) are added and stirred while blowing air into the liquid phase. The temperature was raised to about 95 ° C. to obtain a solution. To this, 11.5 parts of 2-allyloxyethanol, 1 part of 4-hydroxybutyl acrylate and 0.1 part of tetrabutylammonium bromide were added, and 2-allyloxyethanol, 4-hydroxybutyl acrylate and acid were added. Stirring was continued while the anhydride group was reacted.
  • BHT di-t-butylhydroxytoluene
  • the ratio of the absorbance of the absorbance and about 1460 cm -1 to about 1770 cm -1 in the infrared absorption analysis of the solids in the solution to lower the temperature to about 90 ° C. at a stage where almost no change, further 156 parts of 2-ants toluene
  • the approximate molar ratio of 2-allyloxyethanol reacted with acid anhydride groups to 4-hydroxybutyl acrylate was 0.9 / 0.1.
  • a mixture of 70 parts of toluene and 70 parts of toluene was added dropwise over about 1 hour, and stirring was continued for about 1 hour, followed by cooling to room temperature to obtain a polymer composition (P-9) containing a modified chlorinated polyolefin.
  • the resulting polymer composition (P-9) containing the modified chlorinated polyolefin had a solid content of about 46%, and the composition contained about 39 parts of 2-allyloxyethanol.
  • the hydroxyl value of the resin solid content was approximately 10 mg KOH / g.
  • the component ratio of the chlorinated polyolefin skeleton and the acrylic resin skeleton obtained by copolymerizing a part of 2-allyloxyethanol in the composition was about 20/80.
  • Example 10 In a four-necked flask equipped with a condenser tube, 50 parts of “Hardylene F-6P”, 70 parts of toluene and 0.05 part of di-t-butylhydroxytoluene (abbreviation: BHT) are placed and stirred while blowing air into the liquid phase. The temperature was raised to about 95 ° C. to obtain a solution. To this, 1.3 parts of 2-allyloxyethanol, 3 parts of 2-hydroxyethyl methacrylate, 4 parts of butanol and 0.1 part of tetrabutylammonium bromide were added, and 2-allyloxyethanol, 2-hydroxyethyl methacrylate was added.
  • BHT di-t-butylhydroxytoluene
  • a mixed solution of 5 parts of perbutyl PV and 70 parts of toluene was dropped over about 1 hour, and stirring was continued for about 1 hour, followed by cooling to room temperature and a polymer composition containing a modified chlorinated polyolefin (P-10) Got.
  • the obtained polymer composition (P-10) containing the modified chlorinated polyolefin had a solid content of about 46%, and the composition contained about 49 parts of 2-allyloxyethanol.
  • the hydroxyl value of the resin solid content was approximately 14 mg KOH / g.
  • the component ratio of the chlorinated polyolefin skeleton and the acrylic resin skeleton obtained by copolymerizing a part of 2-allyloxyethanol in the composition was about 10/90.
  • Example 11 In a four-necked flask with a condenser tube, 100 parts of “Superclon 3228S”, 221 parts of toluene, 0.05 part of di-t-butylhydroxytoluene (abbreviation: BHT) are placed and stirred while blowing air into the liquid phase. The temperature was raised to about 95 ° C. to obtain a solution. To this, 40 parts of 2-allyloxyethanol, 15 parts of butanol and 0.1 part of tetrabutylammonium bromide were added, and stirring was continued while reacting 2-allyloxyethanol, butanol and acid anhydride groups. It was.
  • BHT di-t-butylhydroxytoluene
  • the ratio of the absorbance of the absorbance and about 1460 cm -1 to about 1770 cm -1 in the infrared absorption analysis of the solids in the solution to lower the temperature to about 90 ° C. at a stage where almost no change, a compound having an aryloxy group and a hydroxyl group (
  • a solution containing about 39 parts of 2-allyloxyethanol as a) and having a concentration of chlorinated polyolefin (b) having an allyloxy group of about 27% was obtained.
  • the approximate molar ratio of 2-allyloxyethanol and butanol reacted with the acid anhydride group was 0.5 / 0.5.
  • air blowing into the liquid phase is stopped, stirring is continued at about 90 ° C.
  • a polymer composition (P-11) containing a modified chlorinated polyolefin was obtained.
  • the resulting polymer composition (P-11) containing the modified chlorinated polyolefin had a solid content of about 46%, and the composition contained about 32 parts of 2-allyloxyethanol.
  • the hydroxyl value of the resin solid content was approximately 42 mgKOH / g.
  • the component ratio of the chlorinated polyolefin skeleton and the acrylic resin skeleton obtained by copolymerizing a part of 2-allyloxyethanol in the composition was about 20/80.
  • Example 12 In a four-necked flask equipped with a condenser tube, 100 parts of “Superclone 822S”, 70 parts of toluene and 0.05 part of di-t-butylhydroxytoluene (abbreviation: BHT) are added and stirred while blowing air into the liquid phase. The temperature was raised to about 95 ° C. to obtain a solution. To this, 30 parts of 2-allyloxyethanol and 0.1 part of tetrabutylammonium bromide were added, and stirring was continued while reacting 2-allyloxyethanol and the acid anhydride group.
  • BHT di-t-butylhydroxytoluene
  • the polymer composition (P-12) containing the obtained modified chlorinated polyolefin had a solid content of about 46%, and the composition contained about 23 parts of 2-allyloxyethanol.
  • the hydroxyl value of the resin solid content was approximately 15 mg KOH / g.
  • the component ratio of the chlorinated polyolefin skeleton and the acrylic resin skeleton obtained by copolymerizing a part of 2-allyloxyethanol in the composition was about 20/80.
  • Example 13 In a four-necked flask equipped with a condenser tube, 100 parts of “Hardylene F-6P”, 70 parts of toluene, 0.05 part of di-t-butylhydroxytoluene (abbreviation: BHT) are added and stirred while blowing air into the liquid phase. The temperature was raised to about 95 ° C. to obtain a solution. To this, 11.5 parts of 2-allyloxyethanol, 3 parts of 2-hydroxyethyl methacrylate and 0.1 part of tetrabutylammonium bromide were added, and 2-allyloxyethanol, 2-hydroxyethyl methacrylate and acid were added. Stirring was continued while the anhydride group was reacted.
  • “Hardylene F-6P” 70 parts of toluene
  • BHT di-t-butylhydroxytoluene
  • the ratio of the absorbance of the absorbance and about 1460 cm -1 to about 1770 cm -1 in the infrared absorption analysis of the solids in the solution to lower the temperature to about 90 ° C. at a stage where almost no change, further added 193 parts of toluene,
  • a solution containing about 9 parts of 2-allyloxyethanol which is a compound (a) having an allyloxy group and a hydroxyl group and having a concentration of about 27% of the chlorinated polyolefin (b) having an allyloxy group was obtained.
  • the approximate molar ratio of 2-allyloxyethanol reacted with the acid anhydride group to 2-hydroxyethyl methacrylate was 0.9 / 0.1.
  • the mixture After stirring for about 1 hour, the mixture is cooled to room temperature and contains a modified chlorinated polyolefin.
  • a polymer composition (P-13) was obtained.
  • the resulting polymer composition (P-13) containing the modified chlorinated polyolefin had a solid content of about 45%, and the composition contained about 8 parts of 2-allyloxyethanol.
  • the hydroxyl value of the resin solid content was approximately 26 mg KOH / g.
  • the component ratio of the chlorinated polyolefin skeleton and the acrylic resin skeleton obtained by copolymerizing a part of 2-allyloxyethanol in the composition was about 20/80.
  • Example 14 In a four-necked flask equipped with a condenser tube, 150 parts of “Supercron 822S”, 105 parts of toluene, and 0.05 parts of di-t-butylhydroxytoluene (abbreviation: BHT) are placed and stirred while blowing air into the liquid phase. The temperature was raised to about 95 ° C. to obtain a solution. To this, 18 parts of 2-allyloxyethanol, 3 parts of butanol and 0.1 part of tetrabutylammonium bromide were added, and stirring was continued while reacting 2-allyloxyethanol, butanol and acid anhydride groups. It was.
  • BHT di-t-butylhydroxytoluene
  • the solution was added dropwise over about 4 hours, and a mixed solution of 5 parts perbutyl PV and 70 parts of toluene was added dropwise over about 1 hour. After stirring for about 1 hour, the mixture was cooled to room temperature and contained modified chlorinated polyolefin.
  • a polymer composition (P-14) was obtained.
  • the obtained polymer composition (P-14) containing the modified chlorinated polyolefin had a solid content of about 45%, and the composition contained about 12 parts of 2-allyloxyethanol.
  • the hydroxyl value of the resin solid content was approximately 22 mg KOH / g.
  • the component ratio of the chlorinated polyolefin skeleton and the acrylic resin skeleton obtained by copolymerizing a part of 2-allyloxyethanol in the composition was about 30/70.
  • Example 15 In a four-necked flask equipped with a condenser tube, 100 parts of “Superclone 822S”, 70 parts of toluene and 0.05 part of di-t-butylhydroxytoluene (abbreviation: BHT) are added and stirred while blowing air into the liquid phase. The temperature was raised to about 95 ° C. to obtain a solution. To this, 23 parts of 2-allyloxyethanol and 0.1 part of tetrabutylammonium bromide were added, and stirring was continued while reacting 2-allyloxyethanol with the acid anhydride group.
  • BHT di-t-butylhydroxytoluene
  • the ratio of the absorbance of the absorbance and about 1460 cm -1 to about 1770 cm -1 in the infrared absorption analysis of the solids in the solution to lower the temperature to about 90 ° C. at a stage where almost no change, 150 parts of toluene and 2-allyloxy
  • the concentration of chlorinated polyolefin (b) having an allyloxy group is about 27%, including about 55 parts of 2-allyloxyethanol, which is a compound (a) having an allyloxy group and a hydroxyl group.
  • a solution was obtained. Next, air blowing into the liquid phase is stopped, stirring is continued at about 90 ° C.
  • the resulting polymer composition (P-15) containing the modified chlorinated polyolefin had a solid content of about 46%, and the composition contained about 45 parts of 2-allyloxyethanol.
  • the hydroxyl value of the resin solid content was approximately 11 mgKOH / g.
  • the component ratio of the chlorinated polyolefin skeleton and the acrylic resin skeleton obtained by copolymerizing a part of 2-allyloxyethanol in the composition was about 20/80.
  • Example 16 In a four-necked flask equipped with a condenser tube, 100 parts of “Superclone 822S”, 70 parts of toluene and 0.05 part of di-t-butylhydroxytoluene (abbreviation: BHT) are added and stirred while blowing air into the liquid phase. The temperature was raised to about 95 ° C. to obtain a solution. To this, 23 parts of 2-allyloxyethanol and 0.1 part of tetrabutylammonium bromide were added, and stirring was continued while reacting 2-allyloxyethanol with the acid anhydride group.
  • BHT di-t-butylhydroxytoluene
  • the ratio of the absorbance of the absorbance and about 1460 cm -1 to about 1770 cm -1 in the infrared absorption analysis of the solids in the solution to lower the temperature to about 90 ° C. at a stage where almost no change, 150 parts of toluene and 2-allyloxy
  • the concentration of chlorinated polyolefin (b) having an allyloxy group is about 27%, including about 55 parts of 2-allyloxyethanol, which is a compound (a) having an allyloxy group and a hydroxyl group.
  • a solution was obtained. Next, air blowing into the liquid phase is stopped, stirring is continued at about 90 ° C.
  • the mixture was cooled to room temperature to obtain a polymer composition (P-16) containing a modified chlorinated polyolefin.
  • the resulting polymer composition (P-16) containing the modified chlorinated polyolefin had a solid content of about 46%, and the composition contained about 45 parts of 2-allyloxyethanol.
  • the hydroxyl value of the resin solid content was approximately 11 mgKOH / g.
  • the component ratio of the chlorinated polyolefin skeleton and the acrylic resin skeleton obtained by copolymerizing a part of 2-allyloxyethanol in the composition was about 20/80.
  • Example 17 In a four-necked flask equipped with a condenser tube, 100 parts of “Superclone 822S”, 67 parts of toluene, 3 parts of methylcyclohexane, 0.05 part of di-t-butylhydroxytoluene (abbreviation: BHT) are placed in the liquid phase. The mixture was stirred while blowing and heated to about 95 ° C. to obtain a solution. To this, 23 parts of 2-allyloxyethanol and 0.1 part of tetrabutylammonium bromide were added, and stirring was continued while reacting 2-allyloxyethanol with the acid anhydride group.
  • BHT di-t-butylhydroxytoluene
  • the ratio of the absorbance of the absorbance and about 1460 cm -1 to about 1770 cm -1 in the infrared absorption analysis of the solids in the solution to lower the temperature to about 90 ° C. at a stage where almost no change, 145 parts of toluene, methylcyclohexane 5 parts Further, 34.5 parts of 2-allyloxyethanol are further added, so that about 55 parts of 2-allyloxyethanol, which is a compound (a) having an allyloxy group and a hydroxyl group, is contained, and A solution having a concentration of about 27% was obtained. Next, air blowing into the liquid phase is stopped, stirring is continued at about 90 ° C.
  • the resulting polymer composition (P-17) containing the modified chlorinated polyolefin had a solid content of about 46%, and the composition contained about 45 parts of 2-allyloxyethanol.
  • the hydroxyl value of the resin solid content was approximately 11 mgKOH / g.
  • the component ratio of the chlorinated polyolefin skeleton and the acrylic resin skeleton obtained by copolymerizing a part of 2-allyloxyethanol in the composition was about 20/80.
  • Example 18 In a four-necked flask equipped with a condenser tube, 100 parts of “Superclone 822S”, 70 parts of toluene and 0.05 part of di-t-butylhydroxytoluene (abbreviation: BHT) are added and stirred while blowing air into the liquid phase. The temperature was raised to about 95 ° C. to obtain a solution. To this, 23 parts of 2-allyloxyethanol and 0.1 part of tetrabutylammonium bromide were added, and stirring was continued while reacting 2-allyloxyethanol with the acid anhydride group.
  • BHT di-t-butylhydroxytoluene
  • the ratio of the absorbance of the absorbance and about 1460 cm -1 to about 1770 cm -1 in the infrared absorption analysis of the solids in the solution to lower the temperature to about 90 ° C. at a stage where almost no change, 150 parts of toluene and 2-allyloxy
  • the concentration of chlorinated polyolefin (b) having an allyloxy group is about 27%, including about 55 parts of 2-allyloxyethanol, which is a compound (a) having an allyloxy group and a hydroxyl group.
  • a solution was obtained. Next, air blowing into the liquid phase is stopped, stirring is continued at about 90 ° C.
  • a polymer composition (P-18) containing a modified chlorinated polyolefin was obtained.
  • the resulting polymer composition (P-18) containing the modified chlorinated polyolefin had a solid content of about 46%, and the composition contained about 45 parts of 2-allyloxyethanol.
  • the hydroxyl value of the resin solid content was approximately 11 mgKOH / g.
  • the component ratio of the chlorinated polyolefin skeleton and the acrylic resin skeleton obtained by copolymerizing a part of 2-allyloxyethanol in the composition was about 20/80.
  • Comparative Example 1 In a four-necked flask equipped with a condenser tube, 100 parts of “Superclone 822S”, 221 parts of toluene, 0.05 part of di-t-butylhydroxytoluene (abbreviation: BHT) are added and stirred while blowing air into the liquid phase. The temperature was raised to about 95 ° C. to obtain a solution. To this, 57.5 parts of 2-hydroxyethyl methacrylate and 0.1 part of tetrabutylammonium bromide were added, and stirring was continued while reacting 2-hydroxyethyl methacrylate and acid anhydride groups.
  • BHT di-t-butylhydroxytoluene
  • the ratio of the absorbance of the absorbance and about 1460 cm -1 to about 1770 cm -1 in the infrared absorption analysis of the solids in the solution to lower the temperature to about 90 ° C. at a stage where almost no change, further added 180 parts of toluene, A solution having a concentration of chlorinated polyolefin (b) having no allyloxy group of about 27% was obtained.
  • the approximate molar ratio of 2-hydroxyethyl methacrylate and butanol reacted with the acid anhydride group was 0.1 / 0.9.
  • air blowing into the liquid phase is stopped, stirring is continued at about 90 ° C.
  • a solution containing 5 parts of perbutyl PV and 70 parts of toluene was added dropwise over about 1 hour, and stirring was continued for about 1 hour, followed by cooling to room temperature, and a polymer containing a modified chlorinated polyolefin.
  • a composition (P-22) was obtained.
  • the obtained polymer composition (P-22) containing the modified chlorinated polyolefin had a solid content of about 46%, and the hydroxyl value of the resin solid content was about 9 mgKOH / g.
  • the component ratio of the chlorinated polyolefin skeleton to the acrylic resin skeleton in the composition was about 20/80.
  • the ratio of the absorbance of the absorbance and about 1460 cm -1 to about 1770 cm -1 in the infrared absorption analysis of the solids in the solution to lower the temperature to about 90 ° C. at a stage where almost no change, 172 parts of toluene and 2-hydroxyethyl 6.8 parts of ethyl methacrylate was added to obtain a solution having a concentration of about 27% of the chlorinated polyolefin (b) having no allyloxy group.
  • the approximate molar ratio of 2-hydroxyethyl methacrylate and butanol reacted with the acid anhydride group was 0.1 / 0.9.
  • air blowing into the liquid phase is stopped, stirring is continued at about 90 ° C.
  • a mixed solution of 5 parts of perbutyl PV and 70 parts of toluene was dropped over about 1 hour, and stirring was continued for about 1 hour, followed by cooling to room temperature and a polymer composition containing modified chlorinated polyolefin (P -23) was obtained.
  • the obtained polymer composition (P-23) containing the modified chlorinated polyolefin had a solid content of about 46%, and the hydroxyl value of the resin solid content was about 15 mgKOH / g.
  • the component ratio of the chlorinated polyolefin skeleton to the acrylic resin skeleton in the composition was about 20/80.
  • Comparative Example 6 In a four-necked flask equipped with a condenser tube, 50 parts of “Hardylene F-6P”, 70 parts of toluene and 0.05 part of di-t-butylhydroxytoluene (abbreviation: BHT) are placed and stirred while blowing air into the liquid phase. The temperature was raised to about 95 ° C. to obtain a solution.
  • BHT di-t-butylhydroxytoluene
  • a solution containing 5 parts of perbutyl PV and 70 parts of toluene was added dropwise over about 1 hour, and stirring was continued for about 1 hour, followed by cooling to room temperature, and a polymer containing a modified chlorinated polyolefin.
  • a composition (P-24) was obtained.
  • the obtained polymer composition (P-24) containing the modified chlorinated polyolefin had a solid content of about 46%, and the hydroxyl value of the resin solid content was about 9 mgKOH / g.
  • the component ratio of the chlorinated polyolefin skeleton to the acrylic resin skeleton in the composition was about 10/90.
  • Example 19 100 parts of a polymer composition (P-1) containing the modified chlorinated polyolefin obtained in Example 1 and “Sumidule N3300” (trade name, manufactured by Sumika Covestro Urethane Co., Ltd., isocyanurate of hexamethylene diisocyanate, solid Viscosity by adding 0.15 part of dibutyltin dilaurate as a catalyst and further adding toluene and butyl acetate to a blended composition in which 3.2 parts of a uniform content of 100% and isocyanate content of 21.6 wt% were mixed uniformly.
  • the equivalent ratio (NCO / OH) of the isocyanate group in the “Sumidule N3300” to the hydroxyl group in the resin component in the polymer composition (P-1) containing the modified chlorinated polyolefin is about 1.8. Met.
  • Example 19 the Ford Cup No. 20 at 20 ° C. was used in the same manner as in Example 19 except that the composition of the polymer composition containing the modified chlorinated polyolefin and the polyisocyanate compound was as shown in Table 1 below. 4 with a viscosity of 30 seconds according to each coating composition No. 2-24 were obtained.
  • Comparative Examples 7 to 9 a polymer composition (“P-19” to “P-21”) containing modified chlorinated polyolefin as a raw material could not be produced, and thus a coating composition was not produced.
  • Test method Production stability The case where the polymer composition containing the modified chlorinated polyolefin could be produced was marked with ⁇ , and the case where the polymer composition could not be produced was marked with x.
  • Gel fraction (mass%) (Wb / Wa) ⁇ 100 A: Gel fraction is 70% or more B: Gel fraction is 60% or more and less than 70% C: Gel fraction is 50% or more and less than 60% D: Gel fraction is 30% or more and less than 50% E: Gel fraction Is less than 30%

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Abstract

Provided are: a method for producing a polymer composition containing a modified chlorinated polyolefin, which exhibits excellent production stability; and a coating material which contains a polymer composition containing a modified chlorinated polyolefin. According to the present invention, a polymer composition containing a modified chlorinated polyolefin is obtained by copolymerizing polymerizable monomers including (b) a chlorinated polyolefin having an allyloxy group and (c) one or more compounds selected from among (meth)acrylic acid esters, (meth)acrylic acids and styrene in the coexistence of (a) a compound having an allyloxy group and a hydroxyl group.

Description

変性塩素化ポリオレフィンを含有するポリマー組成物及びその製造方法Polymer composition containing modified chlorinated polyolefin and method for producing the same
　本発明は、変性塩素化ポリオレフィンを含有するポリマー組成物、及びその製造方法、並びに同組成物を含有する塗料組成物に関する。 The present invention relates to a polymer composition containing a modified chlorinated polyolefin, a method for producing the same, and a coating composition containing the composition.
　今日、プラスチック材料はさまざまな各種産業分野において用いられており、なかでもポリプロピレン樹脂等のポリオレフィン系樹脂は、多くの優れた性質を有する材料であって、かつ経済的であることから、成型物品、フィルム等の基材として広範囲に使用されている。しかしながら、ポリオレフィン系の基材はその極性が低いために、塗装時に形成される塗膜の付着性に劣り、このため、このようなポリオレフィン等のプラスチック基材への塗装においては、該ポリオレフィン系の基材への付着性と、併用される他の樹脂成分との相容性の両立を図ったアクリル変性塩素化ポリオレフィン等の変性塩素化ポリオレフィンを含有する組成物が、塗料又はプライマーとして用いられている。 Today, plastic materials are used in various industrial fields. Among them, polyolefin-based resins such as polypropylene resins are materials having many excellent properties and are economical. Widely used as a substrate for films and the like. However, since the polyolefin-based substrate is low in polarity, it is inferior in the adhesiveness of the coating film formed at the time of coating. Therefore, in the coating to such a plastic substrate such as polyolefin, the polyolefin-based substrate A composition containing a modified chlorinated polyolefin, such as an acrylic-modified chlorinated polyolefin, which is compatible with the adhesion to the base material and other resin components used together, is used as a paint or a primer. Yes.
　従来、このような変性塩素化ポリオレフィンを含有する組成物を得る方法としては、例えば、酸無水物基を有する塩素化ポリオレフィンに水酸基含有重合性不飽和単量体を反応させて重合性不飽和基を導入し、該重合性不飽和基に重合性不飽和単量体を重合させる方法等が開示されている（特許文献１、特許文献２）。
　しかしながら、このような従来技術においては、製造安定性が不十分な場合がある場合があるという問題があった。
　また、特許文献３には、上記製造安定性を向上させる方法として、酸無水物基を有する塩素化ポリオレフィンをヒドロキシル基含有（メタ）アクリル酸エステル及びアルコールで変性し、得られたエステル化塩素化ポリオレフィンの存在下で重合性ビニル系単量体を有機溶剤中で共重合する変性塩素化ポリオレフィン樹脂組成物の製造方法が記載されている。しかしながら、該製造方法によって得られた変性塩素化ポリオレフィン樹脂組成物は、水酸基との反応性を有する架橋剤と併用する組成物において、硬化性が不十分な場合があった。また、該製造方法においても製造安定性が不十分な場合があった。 Conventionally, as a method for obtaining a composition containing such a modified chlorinated polyolefin, for example, a hydroxyl group-containing polymerizable unsaturated monomer is reacted with a chlorinated polyolefin having an acid anhydride group to form a polymerizable unsaturated group. And a method of polymerizing a polymerizable unsaturated monomer on the polymerizable unsaturated group is disclosed (Patent Document 1, Patent Document 2).
However, such a conventional technique has a problem that manufacturing stability may be insufficient in some cases.
In Patent Document 3, as a method for improving the above production stability, a chlorinated polyolefin having an acid anhydride group is modified with a hydroxyl group-containing (meth) acrylic acid ester and an alcohol, and the resulting esterified chlorination is obtained. A method for producing a modified chlorinated polyolefin resin composition in which a polymerizable vinyl monomer is copolymerized in an organic solvent in the presence of polyolefin is described. However, the modified chlorinated polyolefin resin composition obtained by the production method sometimes has insufficient curability in a composition used in combination with a crosslinking agent having reactivity with a hydroxyl group. In addition, even in the production method, production stability may be insufficient.
特開平８－５９７５７号公報JP-A-8-59757 特開２００２－３０９１６１号公報JP 2002-309161 A 特開２０１５－３９９１号公報Japanese Patent Laid-Open No. 2015-3991
　本発明は、変性塩素化ポリオレフィンを含有するポリマー組成物を得る方法であって、製造安定性に優れた方法が提供しようとするものである。さらに、本発明の一態様では、水酸基との反応性を有する架橋剤と併用する場合に、硬化性に優れた組成物を得ることができる変性塩素化ポリオレフィンを含有するポリマー組成物を得る方法を提供しようとするものである。 The present invention is a method for obtaining a polymer composition containing a modified chlorinated polyolefin, and is intended to provide a method having excellent production stability. Furthermore, in one aspect of the present invention, there is provided a method for obtaining a polymer composition containing a modified chlorinated polyolefin, which can obtain a composition having excellent curability when used in combination with a crosslinking agent having reactivity with a hydroxyl group. It is something to be offered.
　すなわち、本発明は、アリロキシ基と水酸基を有する化合物の共存下で、アリロキシ基を有する塩素化ポリオレフィンに、アクリル系モノマー等の重合性モノマーを共重合させて、変性塩素化ポリオレフィンを含有するポリマー組成物を得るものである。 That is, the present invention provides a polymer composition containing a modified chlorinated polyolefin by copolymerizing a polymerizable monomer such as an acrylic monomer with a chlorinated polyolefin having an allyloxy group in the presence of a compound having an allyloxy group and a hydroxyl group. To get things.
　本発明のように、アリロキシ基と水酸基を有する化合物の共存下で、アリロキシ基を有する塩素化ポリオレフィンに、アクリル系モノマー等の重合性モノマーを共重合させて、変性塩素化ポリオレフィンを含有するポリマー組成物を得る場合には、製造安定性が優れることが見い出された。さらに、本発明の製造方法によって製造される変性塩素化ポリオレフィンを含有するポリマー組成物は、水酸基との反応性を有する架橋剤と併用することにより、硬化性に優れた組成物を得られることが見い出された。 A polymer composition containing a modified chlorinated polyolefin by copolymerizing a polymerizable monomer such as an acrylic monomer with a chlorinated polyolefin having an allyloxy group in the presence of a compound having an allyloxy group and a hydroxyl group as in the present invention. In the case of obtaining a product, it has been found that the production stability is excellent. Furthermore, the polymer composition containing the modified chlorinated polyolefin produced by the production method of the present invention can be used in combination with a crosslinking agent having reactivity with a hydroxyl group to obtain a composition having excellent curability. I was found.
　以下、本発明を実施するための形態について詳細に説明する。 Hereinafter, embodiments for carrying out the present invention will be described in detail.
［アリロキシ基と水酸基を有する化合物（ａ）］
　本発明では、アリロキシ基と水酸基とを有する化合物（ａ）の共存下において、アリロキシ基を有する塩素化ポリオレフィン（ｂ）、及び、（メタ）アクリル酸エステル、（メタ）アクリル酸及びスチレンから選ばれる１種以上の化合物（ｃ）を含む重合性モノマーを共重合させる。本発明で用いられるアリロキシ基と水酸基を有する化合物（ａ）は、１分子中にアリロキシ基と水酸基を有するものであり、例えば、一般式（Ｉ） [Compound having an allyloxy group and a hydroxyl group (a)]
In the present invention, in the presence of the compound (a) having an allyloxy group and a hydroxyl group, the chlorinated polyolefin (b) having an allyloxy group, (meth) acrylic acid ester, (meth) acrylic acid, and styrene are selected. A polymerizable monomer containing at least one compound (c) is copolymerized. The compound (a) having an allyloxy group and a hydroxyl group used in the present invention has an allyloxy group and a hydroxyl group in one molecule. For example, the compound represented by the general formula (I)
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
（式中、Ｒ１及びＲ２はそれぞれ独立して炭素数２又は３の分岐していてもよいアルキレン基を示し、ｍ、ｎはそれぞれ独立して０～５０の実数で、かつ、ｍとｎの和は１以上である実数を示し、ブロック構造でもランダム構造であってもよい。）
で表される化合物；アリルアルコールとラクトンの付加反応物；一般式（Ｉ）で表される化合物とラクトンの付加反応物等が挙げられる。なかでも、上記一般式（Ｉ）で表される化合物が入手しやすく好適である。上記一般式（Ｉ）に含まれる化合物の具体例としては、アリロキシエタノール、エチレングリコールモノアリルエーテル、ジエチレングリコールモノアリルエーテル等が挙げられ、例えば、２－アリロキシエタノール（別称：エチレングリコールモノアリルエーテル）、ジエチレングリコールモノアリルエーテル、１－アリロキシ－２－プロパノール（別称：プロピレングリコールモノアリルエーテル、ジプロピレングリコールモノアリルエーテル、ポリエチレングリコールモノアリルエーテル、ポリプロピレングリコールモノアリルエーテル、ポリプロピレングリコール（２－アリロキシエチル）エーテル、アリルアルコールとエチレンオキシド及びプロピレンオキシドの付加反応生成物等が挙げられる。この中でも２－アリロキシエタノール（別称：エチレングリコールモノアリルエーテル）、ジエチレングリコールモノアリルエーテルが特に好適に用いられる。中でも、アリロキシエタノールが工業的に入手しやすいのでより好ましい。 (Wherein R 1 and R 2 each independently represents an alkylene group having 2 or 3 carbon atoms which may be branched, m and n are each independently a real number of 0 to 50, and (The sum of n represents a real number equal to or greater than 1, and may be a block structure or a random structure.)
And the addition reaction product of allyl alcohol and lactone; the addition reaction product of the compound represented by formula (I) and lactone, and the like. Among these, the compounds represented by the above general formula (I) are preferable because they are easily available. Specific examples of the compound contained in the general formula (I) include allyloxyethanol, ethylene glycol monoallyl ether, diethylene glycol monoallyl ether, and the like. For example, 2-allyloxyethanol (also known as ethylene glycol monoallyl ether). ), Diethylene glycol monoallyl ether, 1-allyloxy-2-propanol (also known as propylene glycol monoallyl ether, dipropylene glycol monoallyl ether, polyethylene glycol monoallyl ether, polypropylene glycol monoallyl ether, polypropylene glycol (2-allyloxyethyl) ) Ether, allyl alcohol and ethylene oxide and propylene oxide addition reaction products, etc. Among them, 2-allyloxyethanol Le. (Aka: ethylene glycol monoallyl ether), diethylene glycol monoallyl ether are particularly preferably used among them, allyloxy ethanol is more preferable because industrially easily available.
　一般式（Ｉ）で表される化合物の製造方法としては、公知の方法を用いることができ、例えば、アリルアルコールにエチレンオキシド及び／又はプロピレンオキシドを反応させたり、エチレングリコール、ジエチレングリコール、プロピレングリコール、ジプロピレングリコール、ポリエチレングリコール及びポリプロピレングリコールから選ばれる１種以上を塩化アリル又はアリルアルコールと反応させたりすることで得ることができる。これらの反応において、必要に応じて塩基性化合物や酸性化合物を共存させてもよく、これら化合物は、反応終了後に中和したり除去したりしてもよい。 As a method for producing the compound represented by the general formula (I), a known method can be used. For example, allyl alcohol can be reacted with ethylene oxide and / or propylene oxide, or ethylene glycol, diethylene glycol, propylene glycol, di- It can be obtained by reacting one or more selected from propylene glycol, polyethylene glycol and polypropylene glycol with allyl chloride or allyl alcohol. In these reactions, a basic compound or an acidic compound may be allowed to coexist as necessary, and these compounds may be neutralized or removed after completion of the reaction.
［アリロキシ基を有する塩素化ポリオレフィン（ｂ）］
　アリロキシ基を有する塩素化ポリオレフィン（ｂ）は、例えば、塩素化ポリオレフィンをアリロキシ基を有する化合物により変性してアリロキシ基を導入することによって得ることができる。塩素化ポリオレフィンへのアリロキシ基の導入方法としては、具体的には、例えば、酸基を有する塩素化ポリオレフィンとアリロキシ基と水酸基を有する化合物を反応させ、酸基と水酸基とのエステル縮合反応を介してアリロキシ基と水酸基を有する化合物を塩素化ポリオレフィンに付加させる方法、また、酸無水物基を有する塩素化ポリオレフィン（ｄ）に、アリロキシ基と水酸基を有する化合物を反応させ、酸無水物基と水酸基との付加反応を介してアリロキシ基と水酸基を有する化合物を塩素化ポリオレフィンに付加させる方法を用いることができる。 [Chlorinated polyolefin having an allyloxy group (b)]
The chlorinated polyolefin (b) having an allyloxy group can be obtained, for example, by introducing an allyloxy group by modifying the chlorinated polyolefin with a compound having an allyloxy group. As a method for introducing an allyloxy group into a chlorinated polyolefin, specifically, for example, a chlorinated polyolefin having an acid group is reacted with a compound having an allyloxy group and a hydroxyl group, and an ester condensation reaction between the acid group and the hydroxyl group is performed. A method of adding a compound having an allyloxy group and a hydroxyl group to a chlorinated polyolefin, or reacting a compound having an allyloxy group and a hydroxyl group with a chlorinated polyolefin (d) having an acid anhydride group, thereby reacting the acid anhydride group and the hydroxyl group. A method of adding a compound having an allyloxy group and a hydroxyl group to a chlorinated polyolefin through an addition reaction with chlorinated polyolefin can be used.
　上記の酸基を有する塩素化ポリオレフィンとしては、ポリオレフィンをマレイン酸、イタコン酸等の有機カルボン酸で変性して酸基を導入した後に塩素化したものや、あるいは、ポリオレフィンを塩素化して得られる塩素化ポリオレフィンをマレイン酸、イタコン酸等の有機カルボン酸で変性して酸基を導入したものが好適に用いられ、これらの変性や塩素化は既知の方法によって行うことができる。また、上記の酸無水物基を有する塩素化ポリオレフィン（ｄ）としては、ポリオレフィンをマレイン酸、イタコン酸等の有機カルボン酸の無水物で変性して酸無水物基を導入した後に塩素化したものや、あるいは、ポリオレフィンを塩素化して得られる塩素化ポリオレフィンをマレイン酸、イタコン酸等の有機カルボン酸の無水物で変性して酸無水物基を導入したものが好適に用いられ、これらの変性や塩素化は既知の方法によって行うことができる。原料となるポリオレフィンは、特に限定はされないが、例えば、エチレン、プロピレン、１－ブテン、１－オクテン等の炭素数２～１０のα－オレフィンから選ばれる１種以上を単独重合又は共重合させたもの、また、これらα－オレフィンと酢酸ビニル等の他の重合性モノマーを共重合させたもの等が好ましい。これらの重合にはチーグラーナッタ系触媒、メタロセン系触媒及び／又はラジカル発生剤を用いることができ、重合形態としては、１段重合的であっても多段重合的であっても、また、リアクターゴム的重合であってもよい。これらポリオレフィンは、相容性、結晶性、硬度、液安定性や付着性などを調整するために、混合して原料として利用することもできる。このような酸無水物基を有する塩素化ポリオレフィン（ｄ）として、例えば、「スーパークロン８９２Ｌ」「スーパークロン８９２ＬＳ」「スーパークロン８２２」「スーパークロン８２２Ｓ」「スーパークロン９３０」「スーパークロン９３０Ｓ」「スーパークロン８４２ＬＭ」「スーパークロン８５１Ｌ」「スーパークロン３２２８Ｓ」「スーパークロン３２２１Ｓ」「スーパークロン２３１９Ｓ」（商品名、日本製紙社製、無水マレイン酸変性塩素化ポリオレフィン）、「ハードレンＣＹ－９１２２Ｐ」「ハードレンＣＹ－９１２４Ｐ」「ハードレンＨＭ－２１Ｐ」「ハードレンＣＹ－１３２１Ｐ」「ハードレンＣＹ－２１２１Ｐ」「ハードレンＣＹ－２１２９Ｐ」「ハードレンＦ－２２５Ｐ」「ハードレンＦ－７Ｐ」「ハードレンＭ－２８Ｐ」「ハードレンＦ－２Ｐ」「ハードレンＦ－６Ｐ」「ハードレンＣＹ－１１３２」（商品名、東洋紡社製、無水マレイン酸変性塩素化ポリオレフィン）等の市販品を用いることもできる。これらは、溶液品であっても固形品であってもよい。また、上記酸無水物基を有する塩素化ポリオレフィン（ｄ）は、相容性、結晶性、硬度、液安定性や付着性などを調整するために、それぞれ単独で又は２種以上組み合わせて使用することができる。また、上記酸無水物基を有する塩素化ポリオレフィン（ｄ）の塩素含有率は好ましくは１０～３５質量％である。 Examples of the chlorinated polyolefin having an acid group include those obtained by modifying a polyolefin with an organic carboxylic acid such as maleic acid or itaconic acid and introducing an acid group, or by chlorinating a polyolefin. A modified polyolefin is preferably used by introducing an acid group by modifying it with an organic carboxylic acid such as maleic acid or itaconic acid. These modification and chlorination can be carried out by known methods. In addition, as the chlorinated polyolefin (d) having the above acid anhydride group, the polyolefin is modified with an anhydride of an organic carboxylic acid such as maleic acid or itaconic acid, and then chlorinated after introducing the acid anhydride group. Alternatively, a chlorinated polyolefin obtained by chlorinating a polyolefin is preferably modified with an anhydride of an organic carboxylic acid such as maleic acid or itaconic acid and introduced with an acid anhydride group. Chlorination can be performed by known methods. The polyolefin used as a raw material is not particularly limited. For example, at least one selected from α-olefins having 2 to 10 carbon atoms such as ethylene, propylene, 1-butene, and 1-octene is homopolymerized or copolymerized. Those obtained by copolymerizing these α-olefins with other polymerizable monomers such as vinyl acetate are preferred. A Ziegler-Natta catalyst, a metallocene catalyst, and / or a radical generator can be used for these polymerizations. The polymerization form may be one-stage polymerization or multi-stage polymerization. It may be a static polymerization. These polyolefins can be mixed and used as raw materials in order to adjust compatibility, crystallinity, hardness, liquid stability, adhesion, and the like. Examples of the chlorinated polyolefin (d) having such an acid anhydride group include “Super Clone 892L”, “Super Clone 892LS”, “Super Clone 822”, “Super Clone 822S”, “Super Clone 930”, “Super Clone 930S”, “ "Super Clon 842LM" "Super Clon 851L" "Super Clon 3228S" "Super Clone 3221S" "Super Clon 2319S" (trade name, manufactured by Nippon Paper Industries Co., Ltd., maleic anhydride modified chlorinated polyolefin), "Hardlen CY-9122P" "CY-9124P" "Hardren HM-21P" "Hardren CY-1321P" "Hardren CY-2121P" "Hardren CY-2129P" "Hardren F-225P" "Hardren F-7P" "Hardren M 28P "" HARDLEN F-2P "" HARDLEN F-6P "" HARDLEN CY-1132 "(trade name, manufactured by Toyobo Co., Ltd., maleic anhydride-modified chlorinated polyolefin) may also be used commercially available products such as. These may be solution products or solid products. In addition, the chlorinated polyolefin (d) having an acid anhydride group is used alone or in combination of two or more in order to adjust compatibility, crystallinity, hardness, liquid stability, adhesion, and the like. be able to. The chlorine content of the chlorinated polyolefin (d) having an acid anhydride group is preferably 10 to 35% by mass.
　なお、本発明の製造方法は、上記酸無水物基を有する塩素化ポリオレフィン（ｄ）の塩素含有率が比較的高い場合においても、高い製造安定性を有する。したがって、本発明の製造方法は、上記酸無水物基を有する塩素化ポリオレフィン（ｄ）の塩素含有率が１０～３５質量％、好ましくは１９～３２質量％、より好ましくは２０～２８質量％の範囲内である場合に特に好適に使用することができる。塩素含有率が３５質量％を超えると、プラスチック基材への付着性等が低下する場合があり、１０％未満になると溶液安定性が低下する場合があるので好ましくない。 The production method of the present invention has high production stability even when the chlorine content of the chlorinated polyolefin (d) having an acid anhydride group is relatively high. Therefore, in the production method of the present invention, the chlorine content of the chlorinated polyolefin (d) having an acid anhydride group is 10 to 35% by mass, preferably 19 to 32% by mass, more preferably 20 to 28% by mass. When it is within the range, it can be particularly preferably used. If the chlorine content exceeds 35% by mass, the adhesion to a plastic substrate may be lowered, and if it is less than 10%, the solution stability may be lowered.
　酸無水物基を有する塩素化ポリオレフィン（ｄ）において導入されている酸無水物の量は、酸無水物基を有する塩素化ポリオレフィン（ｄ）１００質量部に対して、０．１～８質量部が好ましく、さらに好ましくは、０．５～３質量部である。導入されている酸無水物の量が、０．１質量部未満になると複層塗膜に使用した場合の層間の付着性が低下する場合があり、８質量部を超えるとプラスチック基材への付着が低下する場合がある。 The amount of the acid anhydride introduced in the chlorinated polyolefin (d) having an acid anhydride group is 0.1 to 8 parts by mass with respect to 100 parts by mass of the chlorinated polyolefin (d) having an acid anhydride group. It is preferably 0.5 to 3 parts by mass. When the amount of the introduced acid anhydride is less than 0.1 parts by mass, the adhesion between the layers may be reduced when used for a multilayer coating film. Adhesion may be reduced.
　酸無水物基を有する塩素化ポリオレフィン（ｄ）にアリロキシ基と水酸基を有する化合物を反応させると、アリロキシ基と水酸基を有する化合物が酸無水物基に付加されて、アリロキシ基を有する塩素化ポリオレフィン（ｂ）を得ることができる。アリロキシ基と水酸基を有する化合物としては、例えば上記一般式（Ｉ）で表されるようなアリロキシ基と水酸基を有する化合物（ａ）を用いることができる。 When a compound having an allyloxy group and a hydroxyl group is reacted with a chlorinated polyolefin (d) having an acid anhydride group, the compound having an allyloxy group and a hydroxyl group is added to the acid anhydride group, and the chlorinated polyolefin having an allyloxy group ( b) can be obtained. As the compound having an allyloxy group and a hydroxyl group, for example, a compound (a) having an allyloxy group and a hydroxyl group as represented by the general formula (I) can be used.
　酸無水物基を有する塩素化ポリオレフィン（ｄ）との反応に用いられるアリロキシ基と水酸基を有する化合物の量は、酸無水物基１モルに対して、０．２～３００モルの範囲が好ましく、さらに、０．５～１５０モルの範囲が好ましい。アリロキシ基と水酸基を有する化合物の量が０．２モル未満になると変性塩素化ポリオレフィンを含有するポリマー組成物の硬化性が低下する場合があり、また３００モルを超えると共重合後に一部残存する未反応のアリロキシ基と水酸基を有する化合物の量が多くなりすぎ変性塩素化ポリオレフィンを含有するポリマー組成物の安定性が低下する場合がある。 The amount of the compound having an allyloxy group and a hydroxyl group used for the reaction with the chlorinated polyolefin (d) having an acid anhydride group is preferably in the range of 0.2 to 300 mol with respect to 1 mol of the acid anhydride group. Furthermore, the range of 0.5 to 150 mol is preferable. When the amount of the compound having an allyloxy group and a hydroxyl group is less than 0.2 mol, the curability of the polymer composition containing the modified chlorinated polyolefin may be lowered, and when it exceeds 300 mol, a part of the polymer composition remains after copolymerization. The amount of the unreacted allyloxy group and the compound having a hydroxyl group may be too large, and the stability of the polymer composition containing the modified chlorinated polyolefin may be lowered.
　酸無水物基を有する塩素化ポリオレフィン（ｄ）と、アリロキシ基と水酸基を有する化合物との反応は、特に限定されるものではなく、酸無水物基と水酸基を反応させる通常の方法に従って行うことができる。具体的には例えば、前記酸無水物基を有する塩素化ポリオレフィン（ｄ）と、アリロキシ基と水酸基を有する化合物とを、２０～１６０℃程度、好ましくは６０～１２０℃程度、さらに好ましくは８０～１１０℃程度で、０．５～７２時間程度加熱する方法により行うことができる。反応の進行度を高めるために、高温で反応させてからその後で低温で保持してもよい。 The reaction between the chlorinated polyolefin (d) having an acid anhydride group and the compound having an allyloxy group and a hydroxyl group is not particularly limited, and may be performed according to a usual method of reacting an acid anhydride group and a hydroxyl group. it can. Specifically, for example, the chlorinated polyolefin (d) having an acid anhydride group and the compound having an allyloxy group and a hydroxyl group are about 20 to 160 ° C., preferably about 60 to 120 ° C., more preferably 80 to The heating can be performed at about 110 ° C. for about 0.5 to 72 hours. In order to increase the degree of progress of the reaction, the reaction may be carried out at a high temperature and thereafter kept at a low temperature.
　また、上記反応の際には、反応を促進させるための触媒を使用することができる。該触媒としては、例えば、ジブチル錫オキサイド、ジブチル錫ジラウレート、三酸化アンチモン、酢酸亜鉛、酢酸マンガン、酢酸コバルト、酢酸カルシウム、酢酸鉛、テトラブチルチタネート、テトライソプロピルチタネート等のルイス酸性金属化合物類；臭化テトラブチルアンモニウム、塩化テトラフェニルホスホニウム等のオニウム塩類；トリエチルアミン、トリアゾール等の塩基性窒素含有化合物類等のそれ自体既知の触媒を使用することができる。
　また、上記反応の際には、重合禁止剤を使用することができる。該重合禁止剤としては、例えば、ジ－ｔ－ブチルヒドロキシトルエン、メトキシフェノール等のフェノール性水酸基含有化合物類；ベンゾキノン等のカルボニル基含有芳香族化合物類；ニトロソ骨格含有化合物類；Ｎ－オキシル骨格含有化合物類等のそれ自体既知の重合禁止剤を使用することができる。 In the above reaction, a catalyst for promoting the reaction can be used. Examples of the catalyst include Lewis acidic metal compounds such as dibutyltin oxide, dibutyltin dilaurate, antimony trioxide, zinc acetate, manganese acetate, cobalt acetate, calcium acetate, lead acetate, tetrabutyl titanate, and tetraisopropyl titanate; Known catalysts such as onium salts such as tetrabutylammonium bromide and tetraphenylphosphonium chloride; basic nitrogen-containing compounds such as triethylamine and triazole can be used.
Moreover, a polymerization inhibitor can be used in the case of the said reaction. Examples of the polymerization inhibitor include phenolic hydroxyl group-containing compounds such as di-t-butylhydroxytoluene and methoxyphenol; carbonyl group-containing aromatic compounds such as benzoquinone; nitroso skeleton-containing compounds; N-oxyl skeleton-containing compounds Known polymerization inhibitors such as compounds can be used.
　また、アリロキシ基を有する塩素化ポリオレフィン（ｂ）が、酸無水基を有する塩素化ポリオレフィン（ｄ）に上記一般式（Ｉ）で表わされるアリロキシ基と水酸基を有する化合物（ａ）を付加反応させて得られるものである場合は、アリロキシ基と水酸基を有する化合物（ａ）の他に、必要に応じて、上記アリロキシ基と水酸基を有する化合物（ａ）以外の水酸基含有化合物を付加させてもよい。該アリロキシ基と水酸基を有する化合物（ａ）以外の水酸基含有化合物としては、例えば、アルコール、（メタ）アクリロイル基と水酸基を有する化合物等が挙げられる。 In addition, the chlorinated polyolefin (b) having an allyloxy group undergoes an addition reaction between the chlorinated polyolefin (d) having an acid anhydride group and the compound (a) having the allyloxy group and the hydroxyl group represented by the general formula (I). When it is obtained, in addition to the compound (a) having an allyloxy group and a hydroxyl group, a hydroxyl group-containing compound other than the compound (a) having the allyloxy group and the hydroxyl group may be added as necessary. Examples of the hydroxyl group-containing compound other than the compound (a) having an allyloxy group and a hydroxyl group include alcohols, compounds having a (meth) acryloyl group and a hydroxyl group, and the like.
　このようなアルコールとしては、例えばメタノール、エタノール、プロパノール、ブタノール、２－エチルヘキサノール等のアルキルアルコール類；エチレングリコールモノブチルエーテル、プロピレングリコールモノプロピルエーテル、ジエチレングリコールモノメチルエーテル等のエーテル基含有アルコール類；ベンジルアルコール等の芳香族アルコール類；ダイアセトンアルコール等のカルボニル基含有アルコール類；ジエチレングリコール、トリプロピレングリコール、１，６－ヘキサンジオール、トリメチロールプロパン等のポリオール類等が挙げられる。 Examples of such alcohols include alkyl alcohols such as methanol, ethanol, propanol, butanol and 2-ethylhexanol; ether group-containing alcohols such as ethylene glycol monobutyl ether, propylene glycol monopropyl ether and diethylene glycol monomethyl ether; benzyl alcohol Aromatic alcohols such as carbonyl group-containing alcohols such as diacetone alcohol; polyols such as diethylene glycol, tripropylene glycol, 1,6-hexanediol, and trimethylolpropane.
　また、上記（メタ）アクリロイル基と水酸基を有する化合物としては、例えば、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、３－ヒドロキシプロピル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート等の（メタ）アクリル酸と炭素数２～８の２価アルコールとのモノエステル化物；該（メタ）アクリル酸と炭素数２～８の２価アルコールとのモノエステル化物のε－カプロラクトン変性体等が挙げられる。 Examples of the compound having a (meth) acryloyl group and a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl ( Monoesterified product of (meth) acrylic acid such as (meth) acrylate and dihydric alcohol having 2 to 8 carbon atoms; ε- of monoesterified product of (meth) acrylic acid and dihydric alcohol having 2 to 8 carbon atoms Examples include modified caprolactone.
　また、上記酸無水基を有する塩素化ポリオレフィン（ｄ）に、前記一般式（Ｉ）で表わされるアリロキシ基と水酸基を有する化合物（ａ）と該アリロキシ基と水酸基を有する化合物（ａ）以外の水酸基含有化合物とを付加させる場合、該酸無水物基を有する塩素化ポリオレフィン（ｄ）にアリロキシ基と水酸基を有する化合物（ａ）を付加反応させてから、アリロキシ基と水酸基を有する化合物（ａ）以外の水酸基含有化合物をさらに付加反応させてもよいし、酸無水基を有する塩素化ポリオレフィン（ｄ）に、アリロキシ基と水酸基を有する化合物（ａ）とアリロキシ基と水酸基を有する化合物（ａ）以外の水酸基含有化合物とをあらかじめ混合したものを添加して付加反応させてもよいし、あるいは、酸無水物基を有する塩素化ポリオレフィン（ｄ）にアリロキシ基と水酸基を有する化合物（ａ）以外の水酸基含有化合物を反応させてから、アリロキシ基と水酸基を有する化合物（ａ）をさらに付加反応させてもよい。酸無水物基を有する塩素化ポリオレフィン（ｄ）にアリロキシ基と水酸基を有する化合物（ａ）以外の水酸基含有化合物も付加させる場合は、アリロキシ基と水酸基を有する化合物（ａ）以外の水酸基含有化合物の使用量は、酸無水基を有する塩素化ポリオレフィン（ｄ）の酸無水物基１モルに対して、特には限定されないが５００モル以下であることが好ましく、さらに、３００モル以下であることが好ましい。５００モルを超えると変性塩素化ポリオレフィンを含有するポリマー組成物の安定性が低下する場合がある。また、アリロキシ基と水酸基を有する化合物（ａ）以外の水酸基含有化合物が（メタ）アクリロイル基と水酸基を有する化合物を含む場合においては、（メタ）アクリロイル基と水酸基を有する化合物の使用量は酸無水基を有する塩素化ポリオレフィン（ｄ）の酸無水物基１モルに対して１０モル以下であることが好ましく、さらに好ましくは５モル以下である。１０モルを超えると共重合の工程で系がゲル化しやすくなる場合がある。 In addition, the chlorinated polyolefin (d) having the acid anhydride group is added to a compound (a) having an allyloxy group and a hydroxyl group represented by the general formula (I) and a hydroxyl group other than the compound (a) having the allyloxy group and the hydroxyl group. In the case of adding a compound containing the compound, the compound (a) having an allyloxy group and a hydroxyl group is added to the chlorinated polyolefin (d) having an acid anhydride group, and then the compound (a) other than the compound (a) having an allyloxy group and a hydroxyl group. Or a compound (a) having an allyloxy group and a hydroxyl group and a compound (a) having an allyloxy group and a hydroxyl group may be added to the chlorinated polyolefin (d) having an acid anhydride group. An addition reaction may be performed by adding a mixture of a hydroxyl group-containing compound in advance, or a chlorinated polyol having an acid anhydride group. After Compound (a) other than hydroxyl group-containing compound having an aryloxy group and a hydroxyl group in the fins (d) is reacted, it may be further addition reaction compound having aryloxy group and a hydroxyl group (a). When a hydroxyl group-containing compound other than the compound (a) having an allyloxy group and a hydroxyl group is added to the chlorinated polyolefin (d) having an acid anhydride group, the hydroxyl group-containing compound other than the compound (a) having an allyloxy group and a hydroxyl group is added. The amount used is not particularly limited with respect to 1 mol of the acid anhydride group of the chlorinated polyolefin (d) having an acid anhydride group, but is preferably 500 mol or less, and more preferably 300 mol or less. . If it exceeds 500 moles, the stability of the polymer composition containing the modified chlorinated polyolefin may be lowered. In the case where a hydroxyl group-containing compound other than the compound (a) having an allyloxy group and a hydroxyl group includes a compound having a (meth) acryloyl group and a hydroxyl group, the amount of the compound having a (meth) acryloyl group and a hydroxyl group is used as an acid anhydride. The amount is preferably 10 mol or less, more preferably 5 mol or less, per 1 mol of the acid anhydride group of the chlorinated polyolefin (d) having a group. If it exceeds 10 mol, the system may be easily gelled in the copolymerization step.
［（メタ）アクリル酸エステル、（メタ）アクリル酸及びスチレンから選ばれる１種以上の化合物（ｃ）を含む重合性モノマー］
　本明細書において、「（メタ）アクリル酸」は「アクリル酸又はメタクリル酸」を、「（メタ）アクリル酸エステル」は「アクリル酸エステル又はメタクリル酸エステル」を、「（メタ）アクリロイル」は「アクリロイル又はメタクリロイル」を、「（メタ）アクリレート」は「アクリレート又はメタクリレート」を意味する。本発明で用いられる(メタ）アクリル酸エステルとしては、特に限定はないが、例えば、(メタ）アクリル酸メチル、(メタ）アクリル酸エチル、(メタ）アクリル酸ｎ－プロピル、(メタ）アクリル酸ｉ－プロピル、(メタ）アクリル酸ｎ－ブチル、(メタ）アクリル酸ｉ－ブチル、(メタ）アクリル酸ｔ－ブチル、(メタ）アクリル酸２－エチルヘキシル、(メタ）アクリル酸ラウリル、(メタ)アクリル酸シクロヘキシル、(メタ）アクリル酸イソボルニル等の(メタ）アクリル酸のアルキルエステル；(メタ）アクリル酸ヒドロキシエチル、(メタ）アクリル酸ヒドロキシプロピル、(メタ）アクリル酸ヒドロキシブチル等のヒドロキシ基含有(メタ）アクリル酸エステル；エチレングリコールジ(メタ）アクリレート等のジ(メタ）アクリレート類；アリル（メタ）アクリレート等のアリル基含有（メタ）アクリル酸エステル類；グリシジル（メタ）アクリレート等のエポキシ基含有（メタ）アクリル酸エステル類；リン酸２－（（メタ）アクリロイルオキシ）エチル、アシッドホスホキシポリオキシエチレングリコールモノ（メタ）アクリレート、アシッドホスホキシポリオキシプロピレングリコールモノ（メタ）アクリレート等のリン酸基含有(メタ）アクリル酸エステル等が例示される。また、スチレンは置換されていてもよく、その場合は、メチルスチレン、エチルスチレン等のアルキル基置換型スチレン類が例示される。これらの重合性モノマーは、ポリマー組成物の分子量、硬度、極性、付着性、溶液粘度、溶液安定性や相容性などを調整するために、それぞれ単独でもしくは２種以上組み合わせて用いることができる。 [Polymerizable monomer containing at least one compound (c) selected from (meth) acrylic acid ester, (meth) acrylic acid and styrene]
In the present specification, “(meth) acrylic acid” is “acrylic acid or methacrylic acid”, “(meth) acrylic acid ester” is “acrylic acid ester or methacrylic acid ester”, and “(meth) acryloyl” is “ “Acryloyl or methacryloyl” means “(meth) acrylate” means “acrylate or methacrylate”. The (meth) acrylic acid ester used in the present invention is not particularly limited. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, (meth) acrylic acid i-propyl, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, (meth) Alkyl esters of (meth) acrylic acid such as cyclohexyl acrylate and isobornyl (meth) acrylate; hydroxy groups such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate ( (Meth) acrylic acid ester; di (meth) acrylates such as ethylene glycol di (meth) acrylate; allyl ( ) Allyl group-containing (meth) acrylic acid esters such as acrylate; Epoxy group-containing (meth) acrylic acid esters such as glycidyl (meth) acrylate; 2-((meth) acryloyloxy) ethyl phosphate, acid phosphoxy Examples thereof include phosphoric acid group-containing (meth) acrylic acid esters such as polyoxyethylene glycol mono (meth) acrylate and acid phosphoxypolyoxypropylene glycol mono (meth) acrylate. Styrene may be substituted, and in that case, alkyl group-substituted styrenes such as methylstyrene and ethylstyrene are exemplified. These polymerizable monomers can be used alone or in combination of two or more in order to adjust the molecular weight, hardness, polarity, adhesion, solution viscosity, solution stability, compatibility, etc. of the polymer composition. .
［化合物（ａ）の共存下での、アリロキシ基を有する塩素化ポリオレフィン（ｂ）と化合物（ｃ）を含む重合性モノマーの共重合］
　本発明では、アリロキシ基と水酸基を有する化合物（ａ）の共存下で、アリロキシ基を有する塩素化ポリオレフィン（ｂ）、及び、（メタ）アクリル酸エステル、（メタ）アクリル酸及びスチレンから選ばれる１種以上の化合物（ｃ）を含む重合性モノマーを共重合させて、変性塩素化ポリオレフィンを生成させる。共重合にあたっての、化合物（ａ）、アリロキシ基を有する塩素化ポリオレフィン（ｂ）、及び、（メタ）アクリル酸エステル、（メタ）アクリル酸及びスチレンから選ばれる１種以上の化合物（ｃ）を含む重合性モノマーのそれぞれの使用量は、上記成分（ａ）～（ｃ）の合計固形分１００質量部を基準として、以下の範囲内であることが好適である。
　アリロキシ基と水酸基を有する化合物（ａ）：０．０５～４０質量部、好ましくは０．１～３０質量部、さらに好ましくは０．２～２０質量部、
　アリロキシ基を有する塩素化ポリオレフィン（ｂ）：１～８９．９５質量部、好ましくは５～６０質量部、さらに好ましくは１０～３５質量部、
　（メタ）アクリル酸エステル、（メタ）アクリル酸及びスチレンから選ばれる１種以上の化合物（ｃ）：１０～９８．９５質量部、好ましくは３５～９５質量部、さらに好ましくは６５～９０質量部。 [Copolymerization of polymerizable monomer containing chlorinated polyolefin (b) having allyloxy group and compound (c) in the presence of compound (a)]
In the present invention, in the presence of the compound (a) having an allyloxy group and a hydroxyl group, 1 selected from chlorinated polyolefin (b) having an allyloxy group, (meth) acrylic acid ester, (meth) acrylic acid and styrene. A polymerizable monomer containing at least one kind of compound (c) is copolymerized to produce a modified chlorinated polyolefin. In the copolymerization, compound (a), chlorinated polyolefin (b) having an allyloxy group, and (meth) acrylic acid ester, (meth) acrylic acid, and one or more compounds (c) selected from styrene are included. The amount of each polymerizable monomer used is preferably in the following range based on 100 parts by mass of the total solid content of the components (a) to (c).
Compound (a) having an allyloxy group and a hydroxyl group: 0.05 to 40 parts by mass, preferably 0.1 to 30 parts by mass, more preferably 0.2 to 20 parts by mass,
Chlorinated polyolefin having an allyloxy group (b): 1 to 89.95 parts by mass, preferably 5 to 60 parts by mass, more preferably 10 to 35 parts by mass,
One or more compounds (c) selected from (meth) acrylic acid ester, (meth) acrylic acid and styrene: 10 to 98.95 parts by mass, preferably 35 to 95 parts by mass, more preferably 65 to 90 parts by mass .
　また、本発明においては、アリロキシ基と水酸基を有する化合物（ａ）の共存下で、アリロキシ基を有する塩素化ポリオレフィン（ｂ）、及び、（メタ）アクリル酸エステル、（メタ）アクリル酸及びスチレンから選ばれる１種以上の化合物（ｃ）を含む重合性モノマーを共重合させるに際して、さらに（メタ）アクリル酸エステル、（メタ）アクリル酸及びスチレン以外の共重合成分を加えてもよい。このような他の共重合成分としては、例えば、酢酸ビニル、オクタン酸ビニル、デカン酸ビニル等の脂肪族カルボン酸ビニル類等が挙げられる。また、ポリマー組成物の分子量、液安定性や相容性などを調整するために、アリロキシ基を有しない塩素化ポリオレフィン及び酸無水物基を有しない塩素化ポリオレフィンから選ばれる１種以上を共存させながら、共重合を行ってもよい。 In the present invention, in the presence of the compound (a) having an allyloxy group and a hydroxyl group, from the chlorinated polyolefin (b) having an allyloxy group, (meth) acrylic acid ester, (meth) acrylic acid and styrene. When the polymerizable monomer containing one or more selected compounds (c) is copolymerized, a copolymer component other than (meth) acrylic acid ester, (meth) acrylic acid and styrene may be added. Examples of such other copolymer components include aliphatic carboxylates such as vinyl acetate, vinyl octoate, and vinyl decanoate. In addition, in order to adjust the molecular weight, liquid stability and compatibility of the polymer composition, one or more selected from chlorinated polyolefins having no allyloxy group and chlorinated polyolefins having no acid anhydride group are allowed to coexist. However, copolymerization may be performed.
　本発明において、アリロキシ基と水酸基を有する化合物（ａ）（以下、単に「（ａ）」ということがある。）の共存下で、アリロキシ基を有する塩素化ポリオレフィン（ｂ）（以下、単に「（ｂ）」ということがある。）、及び、（メタ）アクリル酸エステル、（メタ）アクリル酸及びスチレンから選ばれる１種以上の化合物（ｃ）を含む重合性モノマー（以下、単に「（ｃ）」ということがある。）を共重合させるに際して、ポリマー組成物の分子量、液安定性や相容性などを調整するために、反応槽に（ｂ）を先に加えておき、次いで（ｃ）を加えながら重合させる；反応槽に（ｂ）を先に加えておき、次いで（ｂ）と（ｃ）を加えながら重合させる；反応槽に（ｂ）と（ｃ）を加え、次いで一括重合させる；反応槽に（ｂ）と（ｃ）を先に加えておき、次いで（ｂ）を加えながら重合させる；反応槽に（ｂ）と（ｃ）を先に加えておき、次いで化合物（ｃ）を含む重合性モノマーを加えながら重合させる；反応槽に（ｂ）と（ｃ）を先に加えておき、次いで（ｂ）と（ｃ）を加えながら重合させる；反応槽に（ｂ）と（ｃ）を加えながら重合させる；反応槽に（ｃ）を先に加えておき、次いで（ｂ）を加えながら重合させる；反応槽に（ｃ）を先に加えておき、次いで（ｂ）と（ｃ）を加えながら重合させる；等のいずれの方法を用いてもよい。また、重合工程を多段階にして、これらの方法を組み合わせて用いてもよい。例えば、第１段階で反応槽に（ｂ）と（ｃ）を加えて次いで一括重合させる工程と、第２段階で（ｂ）及び／又は（ｃ）を反応槽に加えながら重合させる工程を組み合わせてもよいし、或いは、第１段階で反応槽に（ｂ）と（ｃ）を加えながら重合させる工程と、第２段階で（ｂ）及び／又は（ｃ）を反応槽に加えながら重合させる工程を組み合わせてもよい。また重合工程を多段階にする場合は、それぞれの工程で用いる（ｂ）及び／又は（ｃ）のそれぞれの組成は同じであっても異なっていてもよい。 In the present invention, a chlorinated polyolefin (b) having an allyloxy group (hereinafter simply referred to as “(”) in the presence of a compound (a) having an allyloxy group and a hydroxyl group (hereinafter sometimes simply referred to as “(a)”). b) "), and a polymerizable monomer containing one or more compounds (c) selected from (meth) acrylic acid ester, (meth) acrylic acid and styrene (hereinafter simply referred to as" (c) ") In order to adjust the molecular weight, liquid stability, compatibility, etc. of the polymer composition, (b) is first added to the reaction vessel, and then (c) (B) is added to the reaction tank first, and then polymerization is performed while adding (b) and (c); (b) and (c) are added to the reaction tank, and then batch polymerization is performed. ; (B) and (c) in the reaction vessel First added, then polymerized while adding (b); previously added (b) and (c) to the reaction vessel, and then polymerized while adding a polymerizable monomer containing compound (c); reaction (B) and (c) are added to the tank first, and then polymerization is performed while adding (b) and (c); polymerization is performed while adding (b) and (c) to the reaction tank; c) is added first and then polymerized while adding (b); (c) is first added to the reaction vessel and then polymerized while adding (b) and (c); A method may be used. Further, the polymerization process may be performed in multiple stages and these methods may be used in combination. For example, the step of adding (b) and (c) to the reaction vessel in the first stage and then performing batch polymerization and the step of polymerizing while adding (b) and / or (c) to the reaction vessel in the second stage are combined. Alternatively, the polymerization may be performed while adding (b) and (c) to the reaction tank in the first stage, and the polymerization may be performed while adding (b) and / or (c) to the reaction tank in the second stage. You may combine a process. Moreover, when making a polymerization process multistage, each composition of (b) and / or (c) used at each process may be the same, or may differ.
　また、酸無水物基を有する塩素化ポリオレフィン（ｄ）とアリロキシ基と水酸基を有する化合物（ａ）を混合し付加反応させてアリロキシ基を有する塩素化ポリオレフィン（ｂ）を得る場合には、前記付加反応を完結させなかったり、混合するアリロキシ基と水酸基を有する化合物（ａ）のモル数を酸無水基のモル数より多くしたりすることによって、アリロキシ基を有する塩素化ポリオレフィン（ｂ）を、未反応のアリロキシ基と水酸基を有する化合物（ａ）と共存した混合物として得ることとができる。このような場合、この混合物を化合物（ｃ）を含む重合性モノマーと共重合させることによって、アリロキシ基と水酸基を有する化合物（ａ）の共存下で、アリロキシ基を有する塩素化ポリオレフィン（ｂ）、及び、（メタ）アクリル酸エステル、（メタ）アクリル酸及びスチレンから選ばれる１種以上の化合物（ｃ）を含む重合性モノマーを共重合させることができる。また、アリロキシ基を有する塩素化ポリオレフィン（ｂ）と化合物（ｃ）を含む重合性モノマーを共重合させる場合に、アリロキシ基を有する塩素化ポリオレフィン（ｂ）とアリロキシ基と水酸基を有する化合物（ａ）をあらかじめ混合しておいたり、また、化合物（ｃ）を含む重合性モノマーとアリロキシ基と水酸基を有する化合物（ａ）をあらかじめ混合しておいたりすることによっても、アリロキシ基と水酸基を有する化合物（ａ）の共存下でアリロキシ基を有する塩素化ポリオレフィン（ｂ）、及び、（メタ）アクリル酸エステル、（メタ）アクリル酸及びスチレンから選ばれる１種以上の化合物（ｃ）を含む重合性モノマーを共重合させることができる。 When the chlorinated polyolefin (d) having an acid anhydride group, the compound (a) having an allyloxy group and a hydroxyl group are mixed and subjected to an addition reaction to obtain the chlorinated polyolefin (b) having an allyloxy group, the addition By not completing the reaction or by increasing the number of moles of the compound (a) having an allyloxy group and a hydroxyl group to be mixed as compared with the number of moles of the acid anhydride group, the chlorinated polyolefin (b) having an allyloxy group is unreacted. It can be obtained as a mixture coexisting with the compound (a) having an allyloxy group and a hydroxyl group in the reaction. In such a case, the chlorinated polyolefin (b) having an allyloxy group in the coexistence of the compound (a) having an allyloxy group and a hydroxyl group by copolymerizing this mixture with a polymerizable monomer containing the compound (c), And the polymerizable monomer containing 1 or more types of compounds (c) chosen from (meth) acrylic acid ester, (meth) acrylic acid, and styrene can be copolymerized. Moreover, when copolymerizing the polymerizable monomer containing the chlorinated polyolefin (b) having an allyloxy group and the compound (c), the chlorinated polyolefin (b) having an allyloxy group, the compound (a) having an allyloxy group and a hydroxyl group Or a compound having an allyloxy group and a hydroxyl group (a) by mixing a polymerizable monomer containing the compound (c) with a compound (a) having an allyloxy group and a hydroxyl group in advance ( a polymerizable monomer containing a chlorinated polyolefin (b) having an allyloxy group in the presence of a) and one or more compounds (c) selected from (meth) acrylic acid ester, (meth) acrylic acid and styrene; It can be copolymerized.
　本発明において、アリロキシ基と水酸基を有する化合物（ａ）の共存下での、アリロキシ基を有する塩素化ポリオレフィン（ｂ）、及び、（メタ）アクリル酸エステル、（メタ）アクリル酸及びスチレンから選ばれる１種以上の化合物（ｃ）を含む重合性モノマーの共重合の方法としては、特に限定されるものではなく、それ自体既知の共重合方法を用いることができるが、なかでも有機溶剤中にて、重合開始剤の存在下で重合を行なう溶液重合法を好適に用いることができる。 In the present invention, chlorinated polyolefin (b) having an allyloxy group in the coexistence of a compound (a) having an allyloxy group and a hydroxyl group is selected from (b), (meth) acrylic acid ester, (meth) acrylic acid and styrene. The method for copolymerizing the polymerizable monomer containing one or more compounds (c) is not particularly limited, and a known copolymerization method can be used, but in particular in an organic solvent. A solution polymerization method in which polymerization is performed in the presence of a polymerization initiator can be preferably used.
　上記溶液重合法において使用される有機溶剤としては、例えば、トルエン、キシレン、「スワゾール１０００」（コスモ石油社製、商品名、高沸点石油系溶剤）等の芳香族系溶剤；シクロヘキサン、メチルシクロヘキサン等の脂環族系溶剤；ヘキサン、ヘプタン等の脂肪族系溶剤；酢酸エチル、酢酸ブチル、３－メトキシブチルアセテート、ブチルプロピオネート、エチル－３－エトキシプロピオネート、エチレングリコールモノエチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート等のエステル系溶剤；メチルエチルケトン、メチルイソブチルケトン、メチルペンチルケトン等のケトン系溶剤；ブタノール、２－エチルヘキサノール、エチレングリコールモノブチルエーテル、ジプロピレングリコールモノメチルエーテル等のアルコール系溶剤等を挙げることができる。これらは２種以上を混合して用いてもよい。
　重合反応時における上記有機溶剤の使用量は、特には限定されないが、変性塩素化ポリオレフィンを含有するポリマー組成物の安定性調整等のために適宜調整してもよい。また、製造効率を高める観点からは、前記成分（ａ）～（ｃ）の合計固形分１００質量部を基準として、通常、５００質量部以下、好ましくは５０～４００質量部、さらに好ましくは１００～３００質量部の範囲内であることが好適である。
　また、上記有機溶剤は前記共重合反応後に加えてもよい。また、該共重合反応後に脱溶剤を行ってもよい。 Examples of the organic solvent used in the solution polymerization method include aromatic solvents such as toluene, xylene, and “Swazole 1000” (trade name, high-boiling petroleum solvent) manufactured by Cosmo Oil; cyclohexane, methylcyclohexane, and the like. Aliphatic solvents such as hexane and heptane; ethyl acetate, butyl acetate, 3-methoxybutyl acetate, butyl propionate, ethyl-3-ethoxypropionate, ethylene glycol monoethyl ether acetate, Ester solvents such as propylene glycol monomethyl ether acetate; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and methyl pentyl ketone; butanol, 2-ethylhexanol, ethylene glycol monobutyl ether, dipropylene glycol monomethyl It may be mentioned alcohol solvents such as ether or the like. You may use these in mixture of 2 or more types.
The amount of the organic solvent used in the polymerization reaction is not particularly limited, but may be appropriately adjusted in order to adjust the stability of the polymer composition containing the modified chlorinated polyolefin. From the viewpoint of increasing the production efficiency, it is usually 500 parts by mass or less, preferably 50 to 400 parts by mass, more preferably 100 to 100 parts by mass based on 100 parts by mass of the total solid content of the components (a) to (c). It is preferable to be within the range of 300 parts by mass.
The organic solvent may be added after the copolymerization reaction. Further, the solvent may be removed after the copolymerization reaction.
　また、前記重合開始剤としては、既知の化合物を用いることができ、例えば、メチルエチルケトンパーオキサイド、アセチルアセトンパーオキサイドなどのケトンパーオキサイド類；ジ（ｔｅｒｔ－ヘキシルパーオキシ）シクロヘキサン、ジ（ｔｅｒｔ－ブチルパーオキシ）シクロヘキサンなどのパーオキシケタール類；ｐ－メンタンヒドロパーオキサイドなどのヒドロパーオキサイド類；ジ－ｔｅｒｔ－ブチルパーオキサイド、ジ（２－ｔｅｒｔ－ブチルパーオキシイソプロピル）ベンゼン、ジクミルパーオキサイドなどのジアルキルパーオキサイド類；ジイソブチリルパーオキサイド、ジ（３，５，５－トリメチルヘキサノイル）パーオキサイド、ジラウロイルパーオキサイドなどのジアシルパーオキサイド類；ジ（２－エチルヘキシル）パーオキシジカーボネート、ジイソプロピルパーオキシジカーボネート、ジ（４－ｔｅｒｔ－ブチルシクロヘキシル）パーオキシジカーボネートなどのパーオキシジカーボネート類；ｔｅｒｔ－ブチルパーオキシイソプロピルカーボネート、ｔｅｒｔ－ブチルパーオキシ２－エチルヘキシルカーボネートなどのパーオキシカーボネート類；ｔｅｒｔ－ブチルパーオキシピバレート、ｔｅｒｔ－ブチルパーオキシラウレート、ｔｅｒｔ－ブチルパーオキシ－２－エチルヘキサノエート、ｔｅｒｔ－ブチルパーオキシアセテート、ｔｅｒｔ－ブチルパーオキシベンソエート、２，５－ジメチル－２，５－ジ（２－エチルヘキサノイルパーオキシ）ヘキサン、ジ－ｔｅｒｔ－ブチルパーオキシヘキサヒドロテレフタレートなどのパーオキシエステル類；アゾビスイソブチロニトリル、アゾビス（２，４－ジメチルバレロニトリル）、アゾビス（２－メチルプロピオニトリル）、アゾビス（２－メチルブチロニトリル）、４、４'－アゾビス（４－シアノペンタン酸）、ジメチルアゾビス（２－メチルプロピオネート）、アゾビス［２－メチル－Ｎ－（２－ヒドロキシエチル）－プロピオンアミド］、アゾビス｛２－メチル－Ｎ－［２－（１－ヒドロキシブチル）］－プロピオンアミド｝等のアゾ化合物類；過硫酸カリウム、過硫酸アンモニウム、過硫酸ナトリウム等の過硫酸塩類等が挙げられる。重合開始剤は、生成するラジカルに関して単官能型であっても多官能型であってもよい。
　これらの重合開始剤はそれぞれ単独でもしくは２種以上組み合わせて用いることができる。また、上記重合開始剤に、必要に応じて、例えば、糖、ナトリウムホルムアルデヒドスルホキシレート、鉄錯体等の還元剤を併用してレドックス開始剤としてもよい。 As the polymerization initiator, known compounds can be used. For example, ketone peroxides such as methyl ethyl ketone peroxide and acetylacetone peroxide; di (tert-hexylperoxy) cyclohexane, di (tert-butylperoxide) Peroxyketals such as oxy) cyclohexane; hydroperoxides such as p-menthane hydroperoxide; di-tert-butyl peroxide, di (2-tert-butylperoxyisopropyl) benzene, dicumyl peroxide, etc. Dialkyl peroxides; diacyl peroxides such as diisobutyryl peroxide, di (3,5,5-trimethylhexanoyl) peroxide, dilauroyl peroxide; di (2-ethylhexyl) Peroxydicarbonates such as peroxydicarbonate, diisopropylperoxydicarbonate, di (4-tert-butylcyclohexyl) peroxydicarbonate; tert-butylperoxyisopropylcarbonate, tert-butylperoxy-2-ethylhexyl carbonate, etc. Peroxycarbonates: tert-butyl peroxypivalate, tert-butyl peroxylaurate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxyacetate, tert-butyl peroxybenzoate Peroxyesters such as 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, di-tert-butylperoxyhexahydroterephthalate Azobisisobutyronitrile, azobis (2,4-dimethylvaleronitrile), azobis (2-methylpropionitrile), azobis (2-methylbutyronitrile), 4,4′-azobis (4-cyano Pentanoic acid), dimethylazobis (2-methylpropionate), azobis [2-methyl-N- (2-hydroxyethyl) -propionamide], azobis {2-methyl-N- [2- (1-hydroxy Butyl)]-propionamide} and the like; and persulfates such as potassium persulfate, ammonium persulfate, and sodium persulfate. The polymerization initiator may be monofunctional or polyfunctional with respect to the radicals generated.
These polymerization initiators can be used alone or in combination of two or more. Moreover, it is good also as a redox initiator by using reducing agents, such as saccharide | sugar, sodium formaldehyde sulfoxylate, and an iron complex, for example as needed to the said polymerization initiator.
　上記重合開始剤の使用量は、前記成分（ａ）～（ｃ）の合計固形分１００質量部を基準として、通常、０．１～１０質量部、好ましくは０．５～８質量部、さらに好ましくは１～６質量部の範囲内であることが好適である。重合開始剤の使用量を変えることにより、変性塩素化ポリオレフィンを含有するポリマー組成物の分子量を変えることができる。分子量は、重量平均分子量で１０，０００～１，０００，０００程度が製造しやすく、ポリマー組成物の溶液安定性や相容性などを高めるためには３０，０００～４００，０００程度が好ましく、さらに好ましくは７０，０００～２００，０００程度である。 The amount of the polymerization initiator used is usually 0.1 to 10 parts by weight, preferably 0.5 to 8 parts by weight, based on 100 parts by weight of the total solid content of the components (a) to (c). It is preferably within the range of 1 to 6 parts by mass. The molecular weight of the polymer composition containing the modified chlorinated polyolefin can be changed by changing the amount of the polymerization initiator used. The molecular weight is easily produced in a weight average molecular weight of about 10,000 to 1,000,000, and is preferably about 30,000 to 400,000 in order to improve the solution stability and compatibility of the polymer composition. More preferably, it is about 70,000 to 200,000.
　なお、本明細書において、重量平均分子量は、ゲルパーミエーションクロマトグラフ（ＧＰＣ）を用いて測定した保持時間（保持容量）を、同一条件で測定した分子量既知の標準ポリスチレンの保持時間（保持容量）によりポリスチレンの分子量に換算して求めた値である。具体的には、ゲルパーミエーションクロマトグラフ装置として、「ＨＬＣ－８１２０ＧＰＣ」（商品名、東ソー社製）を使用し、カラムとして、「ＴＳＫｇｅｌ　Ｇ４０００ＨＸＬ」、「ＴＳＫｇｅｌ　Ｇ３０００ＨＸＬ」、「ＴＳＫｇｅｌ　Ｇ２５００ＨＸＬ」及び「ＴＳＫｇｅｌ　Ｇ２０００ＨＸＬ」（商品名、いずれも東ソー社製）の計４本を使用し、検出器として、示差屈折率計を使用し、移動相：テトラヒドロフラン、測定温度：４０℃、流速：１ｍＬ／ｍｉｎの条件下で測定することができる。 In this specification, the weight average molecular weight is the retention time (retention capacity) of a standard polystyrene having a known molecular weight measured under the same conditions as the retention time (retention capacity) measured using a gel permeation chromatograph (GPC). Is a value obtained by converting to a molecular weight of polystyrene. Specifically, “HLC-8120GPC” (trade name, manufactured by Tosoh Corporation) is used as a gel permeation chromatograph, and “TSKgel G4000HXL”, “TSKgel G3000HXL”, “TSKgel G2500HXL” and “TSKgel” are used as columns. G2000HXL "(trade name, all manufactured by Tosoh Corporation), using a differential refractometer as the detector, mobile phase: tetrahydrofuran, measurement temperature: 40 ° C, flow rate: 1 mL / min Can be measured below.
　該重合開始剤の添加方法は、特に制限されるものではなく、その種類及び量等に応じて適宜選択することができる。例えば、予めモノマー混合物又は溶媒に含ませてもよく、或いは重合時に一括して添加してもよく又は滴下してもよい。
　また、前記共重合反応は、通常、２０～１７０℃、好ましくは７０～１３０℃、さらに好ましくは８０～１２０℃の範囲内で行うことができる。
　また、上記共重合反応後に酸化防止剤を添加してもよい。該酸化防止剤としては、例えば、ジ－ｔ－ブチルヒドロキシトルエン、メトキシフェノール等のフェノール性水酸基含有化合物類；ベンゾキノン等のカルボニル基含有芳香族化合物類を使用することができる。 The method for adding the polymerization initiator is not particularly limited, and can be appropriately selected according to the type and amount thereof. For example, it may be previously contained in the monomer mixture or solvent, or may be added all at once during the polymerization, or may be added dropwise.
Further, the copolymerization reaction can be carried out usually within a range of 20 to 170 ° C., preferably 70 to 130 ° C., more preferably 80 to 120 ° C.
Moreover, you may add antioxidant after the said copolymerization reaction. Examples of the antioxidant include phenolic hydroxyl group-containing compounds such as di-t-butylhydroxytoluene and methoxyphenol; and carbonyl group-containing aromatic compounds such as benzoquinone.
［変性塩素化ポリオレフィンを含有するポリマー組成物］
　本発明の変性塩素化ポリオレフィンを含有するポリマー組成物には、必要に応じて架橋剤を含有させることができる。架橋剤としては、前記変性塩素化ポリオレフィンを含有するポリマー組成物と組み合わせて硬化性組成物とすることができるものであれば任意のものが使用できるが、通常、上記変性塩素化ポリオレフィン等に含まれる水酸基との反応性を有する架橋剤が好適に用いられる。このような水酸基との反応性を有する架橋剤としては、例えば、ポリイソシアネート化合物、ブロック化ポリイソシアネート化合物、アミノ樹脂等を好適に用いることできる。架橋剤は、それぞれ単独でもしくは２種以上組み合わせて使用することができる。 [Polymer composition containing modified chlorinated polyolefin]
The polymer composition containing the modified chlorinated polyolefin of the present invention can contain a crosslinking agent as required. Any crosslinking agent can be used as long as it can be combined with the polymer composition containing the modified chlorinated polyolefin to form a curable composition, but is usually included in the modified chlorinated polyolefin. A crosslinking agent having reactivity with a hydroxyl group is preferably used. As such a crosslinking agent having reactivity with a hydroxyl group, for example, a polyisocyanate compound, a blocked polyisocyanate compound, an amino resin, or the like can be suitably used. The crosslinking agents can be used alone or in combination of two or more.
　前記ポリイソシアネート化合物は、１分子中に少なくとも２個のイソシアネート基を有する化合物であって、例えば、脂肪族ポリイソシアネート、脂環族ポリイソシアネート、芳香脂肪族ポリイソシアネート、芳香族ポリイソシアネート、該ポリイソシアネートの誘導体等を挙げることができる。 The polyisocyanate compound is a compound having at least two isocyanate groups in one molecule, and includes, for example, an aliphatic polyisocyanate, an alicyclic polyisocyanate, an araliphatic polyisocyanate, an aromatic polyisocyanate, and the polyisocyanate. And the like.
　上記脂肪族ポリイソシアネートとしては、例えば、トリメチレンジイソシアネート、テトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート、ペンタメチレンジイソシアネート、１，２－プロピレンジイソシアネート、１，２－ブチレンジイソシアネート、２，３－ブチレンジイソシアネート、１，３－ブチレンジイソシアネート、２，４，４－又は２，２，４－トリメチルヘキサメチレンジイソシアネート、ダイマー酸ジイソシアネート、２，６－ジイソシアナトヘキサン酸メチル（慣用名：リジンジイソシアネート）等の脂肪族ジイソシアネート；２，６－ジイソシアナトヘキサン酸２－イソシアナトエチル、１，６－ジイソシアナト－３－イソシアナトメチルヘキサン、１，４，８－トリイソシアナトオクタン、１，６，１１－トリイソシアナトウンデカン、１，８－ジイソシアナト－４－イソシアナトメチルオクタン、１，３，６－トリイソシアナトヘキサン、２，５，７－トリメチル－１，８－ジイソシアナト－５－イソシアナトメチルオクタン等の脂肪族トリイソシアネート等を挙げることができる。 Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3. Aliphatic diisocyanates such as butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, dimer diisocyanate, methyl 2,6-diisocyanatohexanoate (common name: lysine diisocyanate); 2 , 6-Diisocyanatohexanoic acid 2-isocyanatoethyl, 1,6-diisocyanato-3-isocyanatomethylhexane, 1,4,8-triisocyanatooctane, 1,6 11-triisocyanatoundecane, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-triisocyanatohexane, 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyl Examples thereof include aliphatic triisocyanates such as octane.
　前記脂環族ポリイソシアネートとしては、例えば、１，３－シクロペンテンジイソシアネート、１，４－シクロヘキサンジイソシアネート、１，３－シクロヘキサンジイソシアネート、３－イソシアナトメチル－３，５，５－トリメチルシクロヘキシルイソシアネート（慣用名：イソホロンジイソシアネート）、４－メチル－１，３－シクロヘキシレンジイソシアネート（慣用名：水添ＴＤＩ）、２－メチル－１，３－シクロヘキシレンジイソシアネート、１，３－もしくは１，４－ビス（イソシアナトメチル）シクロヘキサン（慣用名：水添キシリレンジイソシアネート）もしくはその混合物、メチレンビス（４，１－シクロヘキサンジイル）ジイソシアネート（慣用名：水添ＭＤＩ）、ノルボルナンジイソシアネート等の脂環族ジイソシアネート；１，３，５－トリイソシアナトシクロヘキサン、１，３，５－トリメチルイソシアナトシクロヘキサン、２－（３－イソシアナトプロピル）－２，５－ジ（イソシアナトメチル）－ビシクロ（２．２．１）ヘプタン、２－（３－イソシアナトプロピル）－２，６－ジ（イソシアナトメチル）－ビシクロ（２．２．１）ヘプタン、３－（３－イソシアナトプロピル）－２，５－ジ（イソシアナトメチル）－ビシクロ（２．２．１）ヘプタン、５－（２－イソシアナトエチル）－２－イソシアナトメチル－３－（３－イソシアナトプロピル）－ビシクロ（２．２．１）ヘプタン、６－（２－イソシアナトエチル）－２－イソシアナトメチル－３－（３－イソシアナトプロピル）－ビシクロ（２．２．１）ヘプタン、５－（２－イソシアナトエチル）－２－イソシアナトメチル－２－（３－イソシアナトプロピル）－ビシクロ（２．２．１）－ヘプタン、６－（２－イソシアナトエチル）－２－イソシアナトメチル－２－（３－イソシアナトプロピル）－ビシクロ（２．２．１）ヘプタン等の脂環族トリイソシアネート等を挙げることができる。 Examples of the alicyclic polyisocyanate include 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (common name) : Isophorone diisocyanate), 4-methyl-1,3-cyclohexylene diisocyanate (common name: hydrogenated TDI), 2-methyl-1,3-cyclohexylene diisocyanate, 1,3- or 1,4-bis (isocyanato) Methyl) cyclohexane (common name: hydrogenated xylylene diisocyanate) or a mixture thereof, alicyclic diisols such as methylenebis (4,1-cyclohexanediyl) diisocyanate (common name: hydrogenated MDI), norbornane diisocyanate 1,3,5-triisocyanatocyclohexane, 1,3,5-trimethylisocyanatocyclohexane, 2- (3-isocyanatopropyl) -2,5-di (isocyanatomethyl) -bicyclo (2.2 .1) Heptane, 2- (3-isocyanatopropyl) -2,6-di (isocyanatomethyl) -bicyclo (2.2.1) heptane, 3- (3-isocyanatopropyl) -2,5- Di (isocyanatomethyl) -bicyclo (2.2.1) heptane, 5- (2-isocyanatoethyl) -2-isocyanatomethyl-3- (3-isocyanatopropyl) -bicyclo (2.2.1) ) Heptane, 6- (2-isocyanatoethyl) -2-isocyanatomethyl-3- (3-isocyanatopropyl) -bicyclo (2.2.1) heptane, 5- (2-isocyanate) Natoethyl) -2-isocyanatomethyl-2- (3-isocyanatopropyl) -bicyclo (2.2.1) -heptane, 6- (2-isocyanatoethyl) -2-isocyanatomethyl-2- (3 And alicyclic triisocyanates such as -isocyanatopropyl) -bicyclo (2.2.1) heptane.
　前記芳香脂肪族ポリイソシアネートとしては、例えば、メチレンビス（４，１－フェニレン）ジイソシアネート（慣用名：ＭＤＩ）、１，３－もしくは１，４－キシリレンジイソシアネート又はその混合物、ω，ω'－ジイソシアナト－１，４－ジエチルベンゼン、１，３－又は１，４－ビス（１－イソシアナト－１－メチルエチル）ベンゼン（慣用名：テトラメチルキシリレンジイソシアネート）もしくはその混合物等の芳香脂肪族ジイソシアネート；１，３，５－トリイソシアナトメチルベンゼン等の芳香脂肪族トリイソシアネート等を挙げることができる。 Examples of the araliphatic polyisocyanate include methylene bis (4,1-phenylene) diisocyanate (common name: MDI), 1,3- or 1,4-xylylene diisocyanate, or a mixture thereof, ω, ω′-diisocyanato- Aromatic aliphatic diisocyanates such as 1,4-diethylbenzene, 1,3- or 1,4-bis (1-isocyanato-1-methylethyl) benzene (common name: tetramethylxylylene diisocyanate) or mixtures thereof; 1,3 And araliphatic triisocyanates such as 5-triisocyanatomethylbenzene.
　前記芳香族ポリイソシアネートとしては、例えば、ｍ－フェニレンジイソシアネート、ｐ－フェニレンジイソシアネート、４，４'－ジフェニルジイソシアネート、１，５－ナフタレンジイソシアネート、２，４－トリレンジイソシアネート（慣用名：２，４－ＴＤＩ）もしくは２，６－トリレンジイソシアネート（慣用名：２，６－ＴＤＩ）もしくはその混合物、４，４'－トルイジンジイソシアネート、４，４'－ジフェニルエーテルジイソシアネート等の芳香族ジイソシアネート；トリフェニルメタン－４，４'，４''－トリイソシアネート、１，３，５－トリイソシアナトベンゼン、２，４，６－トリイソシアナトトルエン等の芳香族トリイソシアネート；４，４'－ジフェニルメタン－２，２'，５，５'－テトライソシアネート等の芳香族テトライソシアネート等を挙げることができる。 Examples of the aromatic polyisocyanate include m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 2,4-tolylene diisocyanate (common name: 2,4- TDI) or 2,6-tolylene diisocyanate (common name: 2,6-TDI) or a mixture thereof, aromatic diisocyanates such as 4,4′-toluidine diisocyanate, 4,4′-diphenyl ether diisocyanate; , 4 ′, 4 ″ -triisocyanate, 1,3,5-triisocyanatobenzene, 2,4,6-triisocyanatotoluene and the like; 4,4′-diphenylmethane-2,2 ′ Fragrance such as 5,5'-tetraisocyanate Mention may be made of tetra-isocyanate, and the like.
　また、前記ポリイソシアネートの誘導体としては、例えば、上記したポリイソシアネートのダイマー、トリマー、ビウレット、アロファネート、ウレトジオン、ウレトイミン、イソシアヌレート、オキサジアジントリオン、ポリメチレンポリフェニルポリイソシアネート（クルードＭＤＩ、ポリメリックＭＤＩ）、クルードＴＤＩ等を挙げることができる。 Examples of the polyisocyanate derivatives include dimer, trimer, biuret, allophanate, uretdione, uretoimine, isocyanurate, oxadiazine trione, polymethylene polyphenyl polyisocyanate (crude MDI, polymeric MDI). And Crude TDI.
　上記ポリイソシアネート及びその誘導体は、それぞれ単独で用いてもよく又は２種以上併用してもよい。また、これらポリイソシアネートのうち、脂肪族ジイソシアネート、脂環族ジイソシアネート及びこれらの誘導体が好ましい。
　また、前記ポリイソシアネート化合物としては、上記ポリイソシアネート及びその誘導体と、該ポリイソシアネートと反応し得る化合物とを、イソシアネート基過剰の条件で反応させてなるプレポリマーを使用してもよい。該ポリイソシアネートと反応し得る化合物としては、例えば、水酸基、アミノ基等の活性水素基を有する化合物が挙げられ、具体的には、例えば、多価アルコール、低分子量ポリエステル樹脂、アミン、水等を使用することができる。 The above polyisocyanates and derivatives thereof may be used alone or in combination of two or more. Of these polyisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, and derivatives thereof are preferred.
Further, as the polyisocyanate compound, a prepolymer obtained by reacting the polyisocyanate and a derivative thereof with a compound capable of reacting with the polyisocyanate under conditions of excess isocyanate groups may be used. Examples of the compound capable of reacting with the polyisocyanate include compounds having an active hydrogen group such as a hydroxyl group and an amino group. Specifically, for example, polyhydric alcohol, low molecular weight polyester resin, amine, water, etc. Can be used.
　また、前記ポリイソシアネート化合物としては、イソシアネート基含有重合性不飽和モノマーの重合体、又は該イソシアネート基含有重合性不飽和モノマーと該イソシアネート基含有重合性不飽和モノマー以外の重合性不飽和モノマーとの共重合体を使用してもよい。 The polyisocyanate compound may be a polymer of an isocyanate group-containing polymerizable unsaturated monomer, or a polymerizable unsaturated monomer other than the isocyanate group-containing polymerizable unsaturated monomer and the isocyanate group-containing polymerizable unsaturated monomer. A copolymer may be used.
　ポリイソシアネート化合物は、硬化性等の観点から、該ポリイソシアネート化合物中のイソシアネート基と前記変性塩素化ポリオレフィンを含有するポリマー組成物中の樹脂成分中の水酸基との当量比（ＮＣＯ／ＯＨ）が通常０．５～２．５、特に０．８～１．９の範囲内となる割合で使用することが好適である。 The polyisocyanate compound usually has an equivalent ratio (NCO / OH) of the isocyanate group in the polyisocyanate compound and the hydroxyl group in the resin component in the polymer composition containing the modified chlorinated polyolefin from the viewpoint of curability and the like. It is preferable to use it in a proportion within the range of 0.5 to 2.5, particularly 0.8 to 1.9.
　前記ブロック化ポリイソシアネート化合物は、上記ポリイソシアネート化合物のイソシアネート基を、ブロック剤でブロックした化合物である。
　上記ブロック剤としては、例えば、フェノール、クレゾール、キシレノール、ニトロフェノール、エチルフェノール、ヒドロキシジフェニル、ブチルフェノール、イソプロピルフェノール、ノニルフェノール、オクチルフェノール、ヒドロキシ安息香酸メチル等のフェノール系；ε－カプロラクタム、δ－バレロラクタム、γ－ブチロラクタム、β－プロピオラクタム等のラクタム系；メタノール、エタノール、プロピルアルコール、ブチルアルコール、アミルアルコール、ラウリルアルコール等の脂肪族アルコール系；エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテル、メトキシメタノール等のエーテル系；ベンジルアルコール、グリコール酸、グリコール酸メチル、グリコール酸エチル、グリコール酸ブチル、乳酸、乳酸メチル、乳酸エチル、乳酸ブチル、メチロール尿素、メチロールメラミン、ジアセトンアルコール、２－ヒドロキシエチルアクリレート、２－ヒドロキシエチルメタクリレート等のアルコール系；ホルムアミドオキシム、アセトアミドオキシム、アセトオキシム、メチルエチルケトオキシム、ジアセチルモノオキシム、ベンゾフェノンオキシム、シクロヘキサンオキシム等のオキシム系；マロン酸ジメチル、マロン酸ジエチル、マロン酸エチルメチル、マロン酸ジ（２－メトキシ－１－メチルエチル）などの活性メチレン位を有するマロン酸ジエステル系、アセト酢酸エチル、アセト酢酸メチル、アセチルアセトン等の活性メチレン位を有するアセチル基含有化合物系；ブチルメルカプタン、ｔ－ブチルメルカプタン、ヘキシルメルカプタン、ｔ－ドデシルメルカプタン、２－メルカプトベンゾチアゾール、チオフェノール、メチルチオフェノール、エチルチオフェノール等のメルカプタン系；アセトアニリド、アセトアニシジド、アセトトルイド、アクリルアミド、メタクリルアミド、酢酸アミド、ステアリン酸アミド、ベンズアミド等の酸アミド系；コハク酸イミド、フタル酸イミド、マレイン酸イミド等のイミド系；ジフェニルアミン、フェニルナフチルアミン、キシリジン、Ｎ－フェニルキシリジン、カルバゾール、アニリン、ナフチルアミン、ブチルアミン、ジブチルアミン、ブチルフェニルアミン等アミン系；イミダゾール、２－エチルイミダゾール等のイミダゾール系；尿素、チオ尿素、エチレン尿素、エチレンチオ尿素、ジフェニル尿素等の尿素系；Ｎ－フェニルカルバミン酸フェニル等のカルバミン酸エステル系；エチレンイミン、プロピレンイミン等のイミン系；重亜硫酸ソーダ、重亜硫酸カリ等の亜硫酸塩系；アゾール系の化合物等が挙げられる。上記アゾール系の化合物としては、ピラゾール、３，５－ジメチルピラゾール、３－メチルピラゾール、４－ベンジル－３，５－ジメチルピラゾール、４－ニトロ－３，５－ジメチルピラゾール、４－ブロモ－３，５－ジメチルピラゾール、３－メチル－５－フェニルピラゾール等のピラゾール又はピラゾール誘導体；イミダゾール、ベンズイミダゾール、２－メチルイミダゾール、２－エチルイミダゾール、２－フェニルイミダゾール等のイミダゾール又はイミダゾール誘導体；２－メチルイミダゾリン、２－フェニルイミダゾリン等のイミダゾリン誘導体等が挙げられる。
　なかでも、好ましいブロック剤としては、オキシム系のブロック剤、活性メチレン位を有するマロン酸ジエステル系又はアセチル基含有化合物系のブロック剤、ピラゾール又はピラゾール誘導体が挙げられる。 The blocked polyisocyanate compound is a compound obtained by blocking the isocyanate group of the polyisocyanate compound with a blocking agent.
Examples of the blocking agent include phenols such as phenol, cresol, xylenol, nitrophenol, ethylphenol, hydroxydiphenyl, butylphenol, isopropylphenol, nonylphenol, octylphenol, and hydroxybenzoic acid methyl; ε-caprolactam, δ-valerolactam, Lactams such as γ-butyrolactam and β-propiolactam; aliphatic alcohols such as methanol, ethanol, propyl alcohol, butyl alcohol, amyl alcohol, lauryl alcohol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono Butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene Ethers such as glycol monomethyl ether and methoxymethanol; benzyl alcohol, glycolic acid, methyl glycolate, ethyl glycolate, butyl glycolate, lactic acid, methyl lactate, ethyl lactate, butyl lactate, methylol urea, methylol melamine, diacetone alcohol Alcohols such as 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate; oximes such as formamide oxime, acetamide oxime, acetoxime, methyl ethyl ketoxime, diacetyl monooxime, benzophenone oxime, cyclohexane oxime; dimethyl malonate, diethyl malonate , Malonic acid diesters having an active methylene position such as ethyl methyl malonate and di (2-methoxy-1-methylethyl) malonate , An acetyl group-containing compound system having an active methylene position such as ethyl acetoacetate, methyl acetoacetate, acetylacetone; butyl mercaptan, t-butyl mercaptan, hexyl mercaptan, t-dodecyl mercaptan, 2-mercaptobenzothiazole, thiophenol, methylthio Mercaptans such as phenol and ethylthiophenol; acid amides such as acetanilide, acetanisid, acetolide, acrylamide, methacrylamide, acetic acid amide, stearamide, benzamide; imides such as succinimide, phthalimide, and maleic imide Diphenylamine, phenylnaphthylamine, xylidine, N-phenylxylidine, carbazole, aniline, naphthylamine, butylamine, dibutylamine, buty Amines such as phenylamine; Imidazoles such as imidazole and 2-ethylimidazole; Ureas such as urea, thiourea, ethyleneurea, ethylenethiourea and diphenylurea; Carbamate esters such as phenyl N-phenylcarbamate; Ethyleneimine And imine compounds such as propyleneimine; sulfite compounds such as sodium bisulfite and potassium bisulfite; and azole compounds. Examples of the azole compounds include pyrazole, 3,5-dimethylpyrazole, 3-methylpyrazole, 4-benzyl-3,5-dimethylpyrazole, 4-nitro-3,5-dimethylpyrazole, 4-bromo-3, Pyrazole or pyrazole derivatives such as 5-dimethylpyrazole and 3-methyl-5-phenylpyrazole; Imidazole or imidazole derivatives such as imidazole, benzimidazole, 2-methylimidazole, 2-ethylimidazole and 2-phenylimidazole; 2-methylimidazoline And imidazoline derivatives such as 2-phenylimidazoline.
Among these, preferable blocking agents include oxime-based blocking agents, malonic acid diester-based or acetyl group-containing compound-based blocking agents having an active methylene position, pyrazole or pyrazole derivatives.
　ブロック化を行なう（ブロック剤を反応させる）にあたっては、必要に応じて溶剤を添加して行なうことができる。ブロック化反応に用いる溶剤としてはイソシアネート基に対して反応性でないものが良く、例えば、アセトン、メチルエチルケトンのようなケトン類、酢酸エチルのようなエステル類、Ｎ－メチル－２－ピロリドン（ＮＭＰ）のような溶剤を挙げることができる。 In performing the blocking (reacting the blocking agent), a solvent can be added as necessary. Solvents used for the blocking reaction are preferably those that are not reactive with isocyanate groups. For example, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate, and N-methyl-2-pyrrolidone (NMP) Such solvents can be mentioned.
　架橋剤として、上記ポリイソシアネート化合物及び／又はブロック化ポリイソシアネート化合物を使用する場合、触媒として、通常のウレタン化反応の触媒を使用することができる。該触媒としては、例えば、オクチル酸錫、ジブチル錫ジアセテート、ジブチル錫ジ（２－エチルヘキサノエート）、ジブチル錫ジラウレート、ジオクチル錫ジアセテート、ジオクチル錫ジ（２－エチルヘキサノエート）、ジブチル錫オキサイド、ジブチル錫サルファイト、ジオクチル錫オキサイド、ジブチル錫脂肪酸塩、２－エチルヘキサン酸鉛、オクチル酸亜鉛、ナフテン酸亜鉛、脂肪酸亜鉛類、オクタン酸ビスマス、２－エチルヘキサン酸ビスマス、オレイン酸ビスマス、ネオデカン酸ビスマス、バーサチック酸ビスマス、ナフテン酸ビスマス、ナフテン酸コバルト、オクチル酸カルシウム、ナフテン酸銅、テトラ（２－エチルヘキシル）チタネート等の有機金属化合物；第三級アミン等が挙げられ、これらはそれぞれ単独でもしくは２種以上組み合せて使用することができる。
　また、触媒を使用する場合、触媒量としては、前記ポリマー組成物の固形分総量に対して、０．０００１～１質量％、特に０．０００５～０．５質量％の範囲内であることが好ましい。 When using the said polyisocyanate compound and / or blocked polyisocyanate compound as a crosslinking agent, the catalyst of a normal urethanation reaction can be used as a catalyst. Examples of the catalyst include tin octylate, dibutyltin diacetate, dibutyltin di (2-ethylhexanoate), dibutyltin dilaurate, dioctyltin diacetate, dioctyltin di (2-ethylhexanoate), and dibutyl. Tin oxide, dibutyltin sulfite, dioctyltin oxide, dibutyltin fatty acid salt, lead 2-ethylhexanoate, zinc octylate, zinc naphthenate, zinc fatty acids, bismuth octoate, bismuth 2-ethylhexanoate, bismuth oleate , Bismuth neodecanoate, bismuth versatate, bismuth naphthenate, cobalt naphthenate, calcium octylate, copper naphthenate, tetra (2-ethylhexyl) titanate, etc .; tertiary amines, etc. Alone or 2 It can be used in combination or more.
When a catalyst is used, the catalyst amount is within the range of 0.0001 to 1% by mass, particularly 0.0005 to 0.5% by mass, based on the total solid content of the polymer composition. preferable.
　上記ポリマー組成物が上記触媒を含有する場合、該ポリマー組成物は貯蔵安定性、硬化性等の観点から、酢酸、プロピオン酸、酪酸、イソペンタン酸、ヘキサン酸、２－エチル酪酸、ナフテン酸、オクチル酸、ノナン酸、デカン酸、２－エチルヘキサン酸、イソオクタン酸、イソノナン酸、ラウリル酸、パルミチン酸、ステアリン酸、オレイン酸、リノール酸、ネオデカン酸、バーサチック酸、無水イソ酪酸、無水イタコン酸、無水酢酸、無水シトラコン酸、無水プロピオン酸、無水マレイン酸、無水酪酸、無水クエン酸、無水トリメリト酸、無水ピロメリット酸、無水フタル酸等の有機酸；塩酸、リン酸等の無機酸；アセチルアセトン、イミダゾール系化合物等の金属配位性化合物等を含有してもよい。 When the polymer composition contains the catalyst, the polymer composition is acetic acid, propionic acid, butyric acid, isopentanoic acid, hexanoic acid, 2-ethylbutyric acid, naphthenic acid, octyl from the viewpoints of storage stability and curability. Acid, nonanoic acid, decanoic acid, 2-ethylhexanoic acid, isooctanoic acid, isononanoic acid, lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid, neodecanoic acid, versatic acid, isobutyric anhydride, itaconic anhydride, anhydrous Organic acids such as acetic acid, citraconic anhydride, propionic anhydride, maleic anhydride, butyric anhydride, citric anhydride, trimellitic anhydride, pyromellitic anhydride, phthalic anhydride; inorganic acids such as hydrochloric acid and phosphoric acid; acetylacetone, imidazole A metal coordination compound such as a compound may be contained.
　前記アミノ樹脂としては、アミノ成分とアルデヒド成分との反応によって得られる部分メチロール化アミノ樹脂又は完全メチロール化アミノ樹脂を使用することができる。アミノ成分としては、例えば、メラミン、尿素、ベンゾグアナミン、アセトグアナミン、ステログアナミン、スピログアナミン、ジシアンジアミド等が挙げられる。アルデヒド成分としては、ホルムアルデヒド、パラホルムアルデヒド、アセトアルデヒド、ベンズアルデヒド等が挙げられる。
　また、上記メチロール化アミノ樹脂のメチロール基を、適当なアルコールによって、部分的に又は完全にエーテル化したものも使用することができる。エーテル化に用いられるアルコールとしては、例えば、メチルアルコール、エチルアルコール、ｎ－プロピルアルコール、イソプロピルアルコール、ｎ－ブチルアルコール、イソブチルアルコール、２－エチルブタノール、２－エチルヘキサノール等が挙げられる。 As said amino resin, the partial methylolation amino resin or complete methylolation amino resin obtained by reaction of an amino component and an aldehyde component can be used. Examples of the amino component include melamine, urea, benzoguanamine, acetoguanamine, steroguanamine, spiroguanamine, dicyandiamide and the like. Examples of the aldehyde component include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde and the like.
Moreover, what methylated the methylol group of the said methylolated amino resin partially or completely with suitable alcohol can also be used. Examples of the alcohol used for etherification include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, 2-ethylbutanol, 2-ethylhexanol and the like.
　アミノ樹脂としては、メラミン樹脂が好ましい。メラミン樹脂としては、例えば、部分又は完全メチロール化メラミン樹脂のメチロール基を上記アルコールで部分的に又は完全にエーテル化したアルキルエーテル化メラミン樹脂を使用することができる。
　上記アルキルエーテル化メラミン樹脂としては、例えば、部分又は完全メチロール化メラミン樹脂のメチロール基をメチルアルコールで部分的に又は完全にエーテル化したメチルエーテル化メラミン樹脂；部分又は完全メチロール化メラミン樹脂のメチロール基をブチルアルコールで部分的に又は完全にエーテル化したブチルエーテル化メラミン樹脂；部分又は完全メチロール化メラミン樹脂のメチロール基をメチルアルコール及びブチルアルコールで部分的に又は完全にエーテル化したメチル－ブチル混合エーテル化メラミン樹脂等を好適に使用することができる。 As the amino resin, a melamine resin is preferable. As the melamine resin, for example, an alkyl etherified melamine resin obtained by partially or completely etherifying a methylol group of a partially or completely methylolated melamine resin with the above alcohol can be used.
Examples of the alkyl etherified melamine resin include a methyl ether melamine resin obtained by partially or fully etherifying a methylol group of a partially or completely methylolated melamine resin with methyl alcohol; a methylol group of a partially or completely methylolated melamine resin; Butyl etherified melamine resin partially or fully etherified with butyl alcohol; methyl-butyl mixed etherification wherein methylol groups of partially or fully methylolated melamine resin are partially or fully etherified with methyl alcohol and butyl alcohol A melamine resin etc. can be used conveniently.
　メラミン樹脂としては市販品を使用できる。市販品の商品名としては、例えば、「サイメル２０２」、「サイメル２０３」、「サイメル２３８」、「サイメル２５１」、「サイメル３０３」、「サイメル３２３」、「サイメル３２４」、「サイメル３２５」、「サイメル３２７」、「サイメル３５０」、「サイメル３８５」、「サイメル１１５６」、「サイメル１１５８」、「サイメル１１１６」、「サイメル１１３０」（以上、オルネクスジャパン社製）、「ユーバン１２０」、「ユーバン２０ＨＳ」、「ユーバン２０ＳＥ６０」、「ユーバン２０２１」、「ユーバン２０２８」、「ユーバン２８－６０」（以上、三井化学社製）等が挙げられる。
　以上に述べたメラミン樹脂は、それぞれ単独で又は２種以上組み合わせて使用することができる。
　また、架橋剤として、メラミン樹脂を使用する場合は、パラトルエンスルホン酸、ドデシルベンゼンスルホン酸、ジノニルナフタレンスルホン酸等のスルホン酸；モノブチルリン酸、ジブチルリン酸、モノ２－エチルヘキシルリン酸、ジ２－エチルヘキシルリン酸等のアルキルリン酸エステル；これらの酸とアミン化合物との塩等を触媒として使用することができる。 A commercially available product can be used as the melamine resin. Examples of commercially available product names include “Cymel 202”, “Cymel 203”, “Cymel 238”, “Cymel 251”, “Cymel 303”, “Cymel 323”, “Cymel 324”, “Cymel 325”, “Cymel 327”, “Cymel 350”, “Cymel 385”, “Cymel 1156”, “Cymel 1158”, “Cymel 1116”, “Cymel 1130” (manufactured by Ornex Japan), “Uban 120”, “ Examples include “Uban 20HS”, “Uban 20SE60”, “Uban 2021”, “Uban 2028”, “Uban 28-60” (all manufactured by Mitsui Chemicals, Inc.).
The melamine resins described above can be used alone or in combination of two or more.
When a melamine resin is used as a crosslinking agent, sulfonic acids such as p-toluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid; monobutyl phosphoric acid, dibutyl phosphoric acid, mono 2-ethylhexyl phosphoric acid, di-2- Alkyl phosphate esters such as ethylhexyl phosphate; salts of these acids with amine compounds, etc. can be used as catalysts.
　アリロキシ基と水酸基を有する化合物（ａ）の共存下で、アリロキシ基を有する塩素化ポリオレフィン（ｂ）、及び、（メタ）アクリル酸エステル、（メタ）アクリル酸及びスチレンから選ばれる１種以上の化合物（ｃ）を含む重合性モノマーを共重合させて得られる、本発明の変性塩素化ポリオレフィンを含有するポリマー組成物は、硬化性組成物、塗料用組成物として好適に用いることができる。本発明の変性塩素化ポリオレフィンを含有するポリマー組成物を塗料用組成物として使用する場合は、前記水酸基との反応性を有する架橋剤を含有することが好ましい。また、該塗料組成物は、必要に応じてエポキシ樹脂、アクリル樹脂、ポリエステル樹脂、ウレタン樹脂、塩素化ポリオレフィン等の塗料用樹脂、各種顔料、粘度調整剤、顔料分散剤、消泡剤、紫外線吸収剤等の塗料分野で用いられる各種添加剤等を配合することができる。
　本発明に係る塗料組成物は、既知のさまざまな塗装方法を用いて塗装することができる。また、塗装対象物は、特に限定されるものではないが、例えば成型物品、フィルム等のプラスチック基材に好適に用いることができる。 One or more compounds selected from chlorinated polyolefin (b) having an allyloxy group and (meth) acrylic acid ester, (meth) acrylic acid and styrene in the presence of a compound (a) having an allyloxy group and a hydroxyl group The polymer composition containing the modified chlorinated polyolefin of the present invention obtained by copolymerizing the polymerizable monomer containing (c) can be suitably used as a curable composition or a coating composition. When the polymer composition containing the modified chlorinated polyolefin of the present invention is used as a coating composition, it preferably contains a crosslinking agent having reactivity with the hydroxyl group. In addition, the coating composition can be applied to coating resins such as epoxy resins, acrylic resins, polyester resins, urethane resins, chlorinated polyolefins, various pigments, viscosity modifiers, pigment dispersants, antifoaming agents, and UV absorbers as necessary. Various additives used in the paint field such as an agent can be blended.
The coating composition according to the present invention can be applied using various known coating methods. The object to be coated is not particularly limited, but can be suitably used for plastic substrates such as molded articles and films.
　以下、製造例、実施例及び比較例を挙げて、本発明をさらに具体的に説明する。ただし、本発明はこれらにより限定されるものではない。各例において、「部」及び「％」は、特記しない限り質量基準による。また、塗膜の膜厚は硬化塗膜に基づく。
変性塩素化ポリオレフィンを含有するポリマー組成物の製造 Hereinafter, the present invention will be described more specifically with reference to production examples, examples and comparative examples. However, the present invention is not limited to these. In each example, “parts” and “%” are based on mass unless otherwise specified. Moreover, the film thickness of a coating film is based on a cured coating film.
Production of polymer compositions containing modified chlorinated polyolefins
実施例１
　冷却管のついた４つ口フラスコに「スーパークロン８２２Ｓ」（商品名、日本製紙社製、無水マレイン酸変性塩素化ポリオレフィン、塩素含有率２４．５％）１００部、トルエン２２１部、ジ－ｔ－ブチルヒドロキシトルエン（略称：ＢＨＴ）０．０５部を入れ液相に空気を吹きこみながら撹拌し約９５℃に昇温し溶液とした。これに、２－アリロキシエタノール５７．５部と臭化テトラブチルアンモニウム０．１部を加え、２－アリロキシエタノールと酸無水物基を反応させながら撹拌を続けた。溶液中の固形分の赤外吸光分析において約１７７０cm－１の吸光度と約１４６０cm－１の吸光度の比がほぼ変化しなくなった段階で約９０℃に温度を下げ、アリロキシ基と水酸基を有する化合物（ａ）である２－アリロキシエタノール約５５部を含み、アリロキシ基を有する塩素化ポリオレフィン（ｂ）の濃度が約２７％である溶液を得た。次に、液相への空気吹き込みをやめ、気相へ窒素を流しながら約９０℃で撹拌を続け、（メタ）アクリル酸エステル、（メタ）アクリル酸及びスチレンから選ばれる１種以上の化合物（ｃ）として、メチルメタクリレート１９７部、シクロヘキシルメタクリレート１８９部、スチレン１０部、アクリル酸２部、エチレングリコールジメタクリレート２部、さらに、パーブチルＰＶ（商品名、日油社製、ｔ－ブチルパーオキシピバレートの７０％炭化水素溶液）５部（有効成分３．５部）、トルエン１８９．５部、酢酸ブチル６３部の混合液を約４時間かけて滴下し、さらにパーブチルＰＶ５部（有効成分３．５部）、トルエン７０部の混合液を約１時間かけて滴下し、約１時間撹拌を続けたのち、室温に冷却し、変性塩素化ポリオレフィンを含有するポリマー組成物（Ｐ－１）を得た。得られた変性塩素化ポリオレフィンを含有するポリマー組成物（Ｐ－１）の固形分は約４６％であり、組成物中には約４５部の２－アリロキシエタノールが含まれていた。樹脂固形分の水酸基価はおよそ１１ｍｇＫＯＨ／ｇであった。また、組成物中の塩素化ポリオレフィン骨格と２－アリロキシエタノールの一部が共重合されたアクリル樹脂骨格の成分比は、約２０／８０であった。 Example 1
In a four-necked flask equipped with a condenser, 100 parts of “Super Clone 822S” (trade name, manufactured by Nippon Paper Industries Co., Ltd., maleic anhydride-modified chlorinated polyolefin, chlorine content 24.5%), 221 parts of toluene, di-t -0.05 part of butylhydroxytoluene (abbreviation: BHT) was added and stirred while blowing air into the liquid phase, and the temperature was raised to about 95 ° C to obtain a solution. To this, 57.5 parts of 2-allyloxyethanol and 0.1 part of tetrabutylammonium bromide were added, and stirring was continued while reacting 2-allyloxyethanol with the acid anhydride group. The ratio of the absorbance of the absorbance and about 1460 cm -1 to about 1770 cm -1 in the infrared absorption analysis of the solids in the solution to lower the temperature to about 90 ° C. at a stage where almost no change, a compound having an aryloxy group and a hydroxyl group ( A solution containing about 55 parts of 2-allyloxyethanol as a) and having a concentration of about 27% of the chlorinated polyolefin (b) having an allyloxy group was obtained. Next, air blowing into the liquid phase is stopped, stirring is continued at about 90 ° C. while flowing nitrogen into the gas phase, and one or more compounds selected from (meth) acrylic acid ester, (meth) acrylic acid and styrene ( c), methyl methacrylate 197 parts, cyclohexyl methacrylate 189 parts, styrene 10 parts, acrylic acid 2 parts, ethylene glycol dimethacrylate 2 parts, and perbutyl PV (trade name, manufactured by NOF Corporation, t-butyl peroxypivalate) 70 parts hydrocarbon solution) 5 parts (3.5 parts active ingredient), 189.5 parts toluene, 63 parts butyl acetate are added dropwise over about 4 hours, and further 5 parts perbutyl PV (3.5 active ingredient 3.5 parts). Part), and a mixture of 70 parts of toluene was added dropwise over about 1 hour. After stirring for about 1 hour, the mixture was cooled to room temperature, and the modified chlorinated polyolefin was Polymer composition having (P-1) was obtained. The obtained polymer composition (P-1) containing the modified chlorinated polyolefin had a solid content of about 46%, and the composition contained about 45 parts of 2-allyloxyethanol. The hydroxyl value of the resin solid content was approximately 11 mgKOH / g. The component ratio of the chlorinated polyolefin skeleton and the acrylic resin skeleton obtained by copolymerizing a part of 2-allyloxyethanol in the composition was about 20/80.
実施例２
　冷却管のついた４つ口フラスコに「スーパークロン８２２Ｓ」（商品名、日本製紙社製、無水マレイン酸変性塩素化ポリオレフィン、塩素含有率２４．５％）１００部、トルエン７０部、ジ－ｔ－ブチルヒドロキシトルエン（略称：ＢＨＴ）０．０５部を入れ液相に空気を吹きこみながら撹拌し約９５℃に昇温し溶液とした。これに、２－アリロキシエタノール２３部と臭化テトラブチルアンモニウム０．１部を加え、２－アリロキシエタノールと酸無水物基を反応させながら撹拌を続けた。溶液中の固形分の赤外吸光分析において約１７７０cm－１の吸光度と約１４６０cm－１の吸光度の比がほぼ変化しなくなった段階で約９０℃に温度を下げ、トルエン１５０部及び２－アリロキシエタノール３４．５部をさらに加えることで、アリロキシ基と水酸基を有する化合物（ａ）である２－アリロキシエタノール約５５部を含み、アリロキシ基を有する塩素化ポリオレフィン（ｂ）の濃度が約２７％である溶液を得た。次に、液相への空気吹き込みをやめ、気相へ窒素を流しながら約９０℃で撹拌を続け、（メタ）アクリル酸エステル、（メタ）アクリル酸及びスチレンから選ばれる１種以上の化合物（ｃ）として、メチルメタクリレート１９７部、シクロヘキシルメタクリレート１９１部、スチレン１０部、アクリル酸２部、さらに、パーブチルＰＶ５部、トルエン１８９．５部、酢酸ブチル６３部の混合液を約４時間かけて滴下し、さらにパーブチルＰＶ５部、トルエン７０部の混合液を約１時間かけて滴下し、約１時間撹拌を続けたのち、室温に冷却し、変性塩素化ポリオレフィンを含有するポリマー組成物（Ｐ－２）を得た。得られた変性塩素化ポリオレフィンを含有するポリマー組成物（Ｐ－２）の固形分は約４６％であり、組成物中には約４５部の２－アリロキシエタノールが含まれていた。樹脂固形分の水酸基価はおよそ１１ｍｇＫＯＨ／ｇであった。また、組成物中の塩素化ポリオレフィン骨格と２－アリロキシエタノールの一部が共重合されたアクリル樹脂骨格の成分比は、約２０／８０であった。 Example 2
In a four-necked flask with a condenser tube, “Super Clone 822S” (trade name, manufactured by Nippon Paper Industries Co., Ltd., maleic anhydride modified chlorinated polyolefin, chlorine content 24.5%) 100 parts, toluene 70 parts, di-t -0.05 part of butylhydroxytoluene (abbreviation: BHT) was added and stirred while blowing air into the liquid phase, and the temperature was raised to about 95 ° C to obtain a solution. To this, 23 parts of 2-allyloxyethanol and 0.1 part of tetrabutylammonium bromide were added, and stirring was continued while reacting 2-allyloxyethanol with the acid anhydride group. The ratio of the absorbance of the absorbance and about 1460 cm -1 to about 1770 cm -1 in the infrared absorption analysis of the solids in the solution to lower the temperature to about 90 ° C. at a stage where almost no change, 150 parts of toluene and 2-allyloxy By further adding 34.5 parts of ethanol, the concentration of chlorinated polyolefin (b) having an allyloxy group is about 27%, including about 55 parts of 2-allyloxyethanol, which is a compound (a) having an allyloxy group and a hydroxyl group. A solution was obtained. Next, air blowing into the liquid phase is stopped, stirring is continued at about 90 ° C. while flowing nitrogen into the gas phase, and one or more compounds selected from (meth) acrylic acid ester, (meth) acrylic acid and styrene ( c) As a mixture of 197 parts of methyl methacrylate, 191 parts of cyclohexyl methacrylate, 10 parts of styrene, 2 parts of acrylic acid, 5 parts of perbutyl PV, 189.5 parts of toluene, and 63 parts of butyl acetate are dropped over about 4 hours. Further, a mixed solution of 5 parts of perbutyl PV and 70 parts of toluene was dropped over about 1 hour, and stirring was continued for about 1 hour, followed by cooling to room temperature, and a polymer composition containing a modified chlorinated polyolefin (P-2) Got. The obtained polymer composition (P-2) containing the modified chlorinated polyolefin had a solid content of about 46%, and the composition contained about 45 parts of 2-allyloxyethanol. The hydroxyl value of the resin solid content was approximately 11 mgKOH / g. The component ratio of the chlorinated polyolefin skeleton and the acrylic resin skeleton obtained by copolymerizing a part of 2-allyloxyethanol in the composition was about 20/80.
実施例３
　冷却管のついた４つ口フラスコに「スーパークロン３２２８Ｓ」（商品名、日本製紙社製、無水マレイン酸変性塩素化ポリオレフィン、塩素含有率２８％）１００部、トルエン２１０部、酢酸ブチル１１部、ジ－ｔ－ブチルヒドロキシトルエン（略称：ＢＨＴ）０．０５部を入れ液相に空気を吹きこみながら撹拌し約９５℃に昇温し溶液とした。これに、２－アリロキシエタノール５７．５部と臭化テトラブチルアンモニウム０．１部を加え、２－アリロキシエタノールと酸無水物基を反応させながら撹拌を続けた。溶液中の固形分の赤外吸光分析において約１７７０cm－１の吸光度と約１４６０cm－１の吸光度の比がほぼ変化しなくなった段階で約９０℃に温度を下げ、アリロキシ基と水酸基を有する化合物（ａ）である２－アリロキシエタノール約５５部を含み、アリロキシ基を有する塩素化ポリオレフィン（ｂ）の濃度が約２７％である溶液を得た。次に、液相への空気吹き込みをやめ、気相へ窒素を流しながら約９０℃で撹拌を続け、（メタ）アクリル酸エステル、（メタ）アクリル酸及びスチレンから選ばれる１種以上の化合物（ｃ）として、メチルメタクリレート２０５部、シクロヘキシルメタクリレート１８３部、メタクリル酸８部、エチレングリコールジメタクリレート４部、さらに、パーブチルＰＶ５部、トルエン１８９．５部、酢酸ブチル６３部の混合液を約４時間かけて滴下し、さらにパーブチルＰＶ５部、トルエン７０部の混合液を約１時間かけて滴下し、約１時間撹拌を続けたのち、室温に冷却し、変性塩素化ポリオレフィンを含有するポリマー組成物（Ｐ－３）を得た。得られた変性塩素化ポリオレフィンを含有するポリマー組成物（Ｐ－３）の固形分は約４６％であり、組成物中には約４５部の２－アリロキシエタノールが含まれていた。樹脂固形分の水酸基価はおよそ１１ｍｇＫＯＨ／ｇであった。また、組成物中の塩素化ポリオレフィン骨格と２－アリロキシエタノールの一部が共重合されたアクリル樹脂骨格の成分比は、約２０／８０であった。 Example 3
In a four-necked flask with a condenser tube, “Super Clon 3228S” (trade name, manufactured by Nippon Paper Industries Co., Ltd., maleic anhydride-modified chlorinated polyolefin, chlorine content 28%) 100 parts, 210 parts toluene, 11 parts butyl acetate, 0.05 part of di-t-butylhydroxytoluene (abbreviation: BHT) was added and stirred while blowing air into the liquid phase, and the temperature was raised to about 95 ° C. to obtain a solution. To this, 57.5 parts of 2-allyloxyethanol and 0.1 part of tetrabutylammonium bromide were added, and stirring was continued while reacting 2-allyloxyethanol with the acid anhydride group. The ratio of the absorbance of the absorbance and about 1460 cm -1 to about 1770 cm -1 in the infrared absorption analysis of the solids in the solution to lower the temperature to about 90 ° C. at a stage where almost no change, a compound having an aryloxy group and a hydroxyl group ( A solution containing about 55 parts of 2-allyloxyethanol as a) and having a concentration of about 27% of the chlorinated polyolefin (b) having an allyloxy group was obtained. Next, air blowing into the liquid phase is stopped, stirring is continued at about 90 ° C. while flowing nitrogen into the gas phase, and one or more compounds selected from (meth) acrylic acid ester, (meth) acrylic acid and styrene ( c) As a mixture of 205 parts of methyl methacrylate, 183 parts of cyclohexyl methacrylate, 8 parts of methacrylic acid, 4 parts of ethylene glycol dimethacrylate, 5 parts of perbutyl PV, 189.5 parts of toluene and 63 parts of butyl acetate, it takes about 4 hours. Further, a mixed solution of 5 parts of perbutyl PV and 70 parts of toluene was dropped over about 1 hour, and stirring was continued for about 1 hour, followed by cooling to room temperature and a polymer composition containing modified chlorinated polyolefin (P -3) was obtained. The resulting polymer composition (P-3) containing the modified chlorinated polyolefin had a solid content of about 46%, and the composition contained about 45 parts of 2-allyloxyethanol. The hydroxyl value of the resin solid content was approximately 11 mgKOH / g. The component ratio of the chlorinated polyolefin skeleton and the acrylic resin skeleton obtained by copolymerizing a part of 2-allyloxyethanol in the composition was about 20/80.
実施例４
　冷却管のついた４つ口フラスコに「ハードレンＦ－６Ｐ」（商品名、東洋紡社製、無水マレイン酸変性塩素化ポリオレフィン、塩素含有率２０％）５０部、トルエン２１４部、ジ－ｔ－ブチルヒドロキシトルエン（略称：ＢＨＴ）０．０５部を入れ液相に空気を吹きこみながら撹拌し約９５℃に昇温し溶液とした。これに、２－アリロキシエタノール６５部と臭化テトラブチルアンモニウム０．１部を加え、２－アリロキシエタノールと酸無水物基を反応させながら撹拌を続けた。溶液中の固形分の赤外吸光分析において約１７７０cm－１の吸光度と約１４６０cm－１の吸光度の比がほぼ変化しなくなった段階で約９０℃に温度を下げ、アリロキシ基と水酸基を有する化合物（ａ）である２－アリロキシエタノール約６４部を含み、アリロキシ基を有する塩素化ポリオレフィン（ｂ）の濃度が約１６％である溶液を得た。次に、液相への空気吹き込みをやめ、気相へ窒素を流しながら約９０℃で撹拌を続け、（メタ）アクリル酸エステル、（メタ）アクリル酸及びスチレンから選ばれる１種以上の化合物（ｃ）として、メチルメタクリレート２１４部、シクロヘキシルメタクリレート２２２部、スチレン１０部、アクリル酸２部、エチレングリコールジメタクリレート２部、さらに、パーブチルＰＶ５部、トルエン１８９．５部、酢酸ブチル６３部の混合液を約４時間かけて滴下し、さらにパーブチルＰＶ５部、トルエン７０部の混合液を約１時間かけて滴下し、約１時間撹拌を続けたのち、室温に冷却し、変性塩素化ポリオレフィンを含有するポリマー組成物（Ｐ－４）を得た。得られた変性塩素化ポリオレフィンを含有するポリマー組成物（Ｐ－４）の固形分は約４６％であり、組成物中には約５２部の２－アリロキシエタノールが含まれていた。樹脂固形分の水酸基価はおよそ１２ｍｇＫＯＨ／ｇであった。また、組成物中の塩素化ポリオレフィン骨格と２－アリロキシエタノールの一部が共重合されたアクリル樹脂骨格の成分比は、約１０／９０であった。 Example 4
In a four-necked flask with a condenser tube, "Hardlen F-6P" (trade name, manufactured by Toyobo, maleic anhydride-modified chlorinated polyolefin, chlorine content 20%), 214 parts of toluene, di-t-butyl 0.05 part of hydroxytoluene (abbreviation: BHT) was added and stirred while blowing air into the liquid phase, and the temperature was raised to about 95 ° C. to obtain a solution. To this, 65 parts of 2-allyloxyethanol and 0.1 part of tetrabutylammonium bromide were added, and stirring was continued while reacting 2-allyloxyethanol with the acid anhydride group. The ratio of the absorbance of the absorbance and about 1460 cm -1 to about 1770 cm -1 in the infrared absorption analysis of the solids in the solution to lower the temperature to about 90 ° C. at a stage where almost no change, a compound having an aryloxy group and a hydroxyl group ( A solution containing about 64 parts of 2-allyloxyethanol as a) and having a concentration of chlorinated polyolefin (b) having an allyloxy group of about 16% was obtained. Next, air blowing into the liquid phase is stopped, stirring is continued at about 90 ° C. while flowing nitrogen into the gas phase, and one or more compounds selected from (meth) acrylic acid ester, (meth) acrylic acid and styrene ( c) As a mixture of 214 parts of methyl methacrylate, 222 parts of cyclohexyl methacrylate, 10 parts of styrene, 2 parts of acrylic acid, 2 parts of ethylene glycol dimethacrylate, 5 parts of perbutyl PV, 189.5 parts of toluene, and 63 parts of butyl acetate. A solution containing 5 parts of perbutyl PV and 70 parts of toluene was added dropwise over about 1 hour, and stirring was continued for about 1 hour, followed by cooling to room temperature, and a polymer containing a modified chlorinated polyolefin. A composition (P-4) was obtained. The resulting polymer composition (P-4) containing the modified chlorinated polyolefin had a solid content of about 46%, and the composition contained about 52 parts of 2-allyloxyethanol. The hydroxyl value of the resin solid content was approximately 12 mgKOH / g. The component ratio of the chlorinated polyolefin skeleton and the acrylic resin skeleton obtained by copolymerizing a part of 2-allyloxyethanol in the composition was about 10/90.
実施例５
　冷却管のついた４つ口フラスコに「スーパークロン８２２Ｓ」１００部、トルエン２２１部、ジ－ｔ－ブチルヒドロキシトルエン（略称：ＢＨＴ）０．０５部を入れ液相に空気を吹きこみながら撹拌し約９５℃に昇温し溶液とした。これに、ジエチレングリコールモノアリルエーテル８２．５部と臭化テトラブチルアンモニウム０．１部を加え、ジエチレングリコールモノアリルエーテルと酸無水物基を反応させながら撹拌を続けた。溶液中の固形分の赤外吸光分析において約１７７０cm－１の吸光度と約１４６０cm－１の吸光度の比がほぼ変化しなくなった段階で約９０℃に温度を下げ、アリロキシ基と水酸基を有する化合物（ａ）であるジエチレングリコールモノアリルエーテル約７９部を含み、アリロキシ基を有する塩素化ポリオレフィン（ｂ）の濃度が約２５％である溶液を得た。次に、液相への空気吹き込みをやめ、気相へ窒素を流しながら約９０℃で撹拌を続け、（メタ）アクリル酸エステル、（メタ）アクリル酸及びスチレンから選ばれる１種以上の化合物（ｃ）として、メチルメタクリレート１８７部、シクロヘキシルメタクリレート１８９部、スチレン２０部、アクリル酸２部、エチレングリコールジメタクリレート２部、さらに、パーブチルＰＶ５部、トルエン１８９．５部、酢酸ブチル３９部の混合液を約４時間かけて滴下し、さらにパーブチルＰＶ５部、トルエン７０部の混合液を約１時間かけて滴下し、約１時間撹拌を続けたのち、室温に冷却し、変性塩素化ポリオレフィンを含有するポリマー組成物（Ｐ－５）を得た。得られた変性塩素化ポリオレフィンを含有するポリマー組成物（Ｐ－５）の固形分は約４７％であり、組成物中には約６５部のジエチレングリコールモノアリルエーテル含まれていた。樹脂固形分の水酸基価はおよそ１５ｍｇＫＯＨ／ｇであった。また、組成物中の塩素化ポリオレフィン骨格とジエチレングリコールモノアリルエーテルの一部が共重合されたアクリル樹脂骨格の成分比は、約１９／８１であった。 Example 5
In a four-necked flask equipped with a condenser tube, 100 parts of “Superclone 822S”, 221 parts of toluene, 0.05 part of di-t-butylhydroxytoluene (abbreviation: BHT) are added and stirred while blowing air into the liquid phase. The temperature was raised to about 95 ° C. to obtain a solution. To this, 82.5 parts of diethylene glycol monoallyl ether and 0.1 part of tetrabutylammonium bromide were added, and stirring was continued while reacting diethylene glycol monoallyl ether and acid anhydride groups. The ratio of the absorbance of the absorbance and about 1460 cm -1 to about 1770 cm -1 in the infrared absorption analysis of the solids in the solution to lower the temperature to about 90 ° C. at a stage where almost no change, a compound having an aryloxy group and a hydroxyl group ( A solution containing about 79 parts of diethylene glycol monoallyl ether as a) and having a concentration of chlorinated polyolefin (b) having an allyloxy group of about 25% was obtained. Next, air blowing into the liquid phase is stopped, stirring is continued at about 90 ° C. while flowing nitrogen into the gas phase, and one or more compounds selected from (meth) acrylic acid ester, (meth) acrylic acid and styrene ( c) As a mixture of 187 parts methyl methacrylate, 189 parts cyclohexyl methacrylate, 20 parts styrene, 2 parts acrylic acid, 2 parts ethylene glycol dimethacrylate, 5 parts perbutyl PV, 189.5 parts toluene, and 39 parts butyl acetate. A solution containing 5 parts of perbutyl PV and 70 parts of toluene was added dropwise over about 1 hour, and stirring was continued for about 1 hour, followed by cooling to room temperature, and a polymer containing a modified chlorinated polyolefin. A composition (P-5) was obtained. The obtained polymer composition (P-5) containing the modified chlorinated polyolefin had a solid content of about 47%, and the composition contained about 65 parts of diethylene glycol monoallyl ether. The hydroxyl value of the resin solid content was approximately 15 mg KOH / g. The component ratio of the acrylic resin skeleton obtained by copolymerizing a part of the chlorinated polyolefin skeleton and diethylene glycol monoallyl ether in the composition was about 19/81.
実施例６
　冷却管のついた４つ口フラスコに「スーパークロン８２２Ｓ」１００部、トルエン２２８部、ジ－ｔ－ブチルヒドロキシトルエン（略称：ＢＨＴ）０．０５部を入れ液相に空気を吹きこみながら撹拌し約９５℃に昇温し溶液とした。これに、２－アリロキシエタノール４６部、ブタノール４部、及び、臭化テトラブチルアンモニウム０．１部を加え、２－アリロキシエタノール、ブタノール、及び、酸無水物基を反応させながら撹拌を続けた。溶液中の固形分の赤外吸光分析において約１７７０cm－１の吸光度と約１４６０cm－１の吸光度の比がほぼ変化しなくなった段階で約９０℃に温度を下げ、アリロキシ基と水酸基を有する化合物（ａ）である２－アリロキシエタノール約４４部を含み、アリロキシ基を有する塩素化ポリオレフィン（ｂ）の濃度が約２７％である溶液を得た。酸無水物基と反応した２－アリロキシエタノールとブタノールの概算モル比は、０．８／０．２であった。次に、液相への空気吹き込みをやめ、気相へ窒素を流しながら約９０℃で撹拌を続け、（メタ）アクリル酸エステル、（メタ）アクリル酸及びスチレンから選ばれる１種以上の化合物（ｃ）として、メチルメタクリレート１９７部、シクロヘキシルメタクリレート１８９部、スチレン１０部、アクリル酸２部、エチレングリコールジメタクリレート２部、さらに、パーブチルＰＶ５部、トルエン１８９．５部、酢酸ブチル６３部の混合液を約４時間かけて滴下し、さらにパーブチルＰＶ５部、トルエン７０部の混合液を約１時間かけて滴下し、約１時間撹拌を続けたのち、室温に冷却し、変性塩素化ポリオレフィンを含有するポリマー組成物（Ｐ－６）を得た。得られた変性塩素化ポリオレフィンを含有するポリマー組成物（Ｐ－６）の固形分は約４６％であり、組成物中には約３６部の２－アリロキシエタノールが含まれていた。樹脂固形分の水酸基価はおよそ９ｍｇＫＯＨ／ｇであった。また、組成物中の塩素化ポリオレフィン骨格と２－アリロキシエタノールの一部が共重合されたアクリル樹脂骨格の成分比は、約２０／８０であった。 Example 6
In a four-necked flask equipped with a condenser tube, 100 parts of “Supercron 822S”, 228 parts of toluene and 0.05 part of di-t-butylhydroxytoluene (abbreviation: BHT) are added and stirred while blowing air into the liquid phase. The temperature was raised to about 95 ° C. to obtain a solution. To this, 46 parts of 2-allyloxyethanol, 4 parts of butanol and 0.1 part of tetrabutylammonium bromide were added, and stirring was continued while reacting 2-allyloxyethanol, butanol and acid anhydride groups. It was. The ratio of the absorbance of the absorbance and about 1460 cm -1 to about 1770 cm -1 in the infrared absorption analysis of the solids in the solution to lower the temperature to about 90 ° C. at a stage where almost no change, a compound having an aryloxy group and a hydroxyl group ( A solution containing about 44 parts of 2-allyloxyethanol as a) and having a concentration of chlorinated polyolefin (b) having an allyloxy group of about 27% was obtained. The approximate molar ratio of 2-allyloxyethanol and butanol reacted with the acid anhydride group was 0.8 / 0.2. Next, air blowing into the liquid phase is stopped, stirring is continued at about 90 ° C. while flowing nitrogen into the gas phase, and one or more compounds selected from (meth) acrylic acid ester, (meth) acrylic acid and styrene ( c) As a mixture of 197 parts of methyl methacrylate, 189 parts of cyclohexyl methacrylate, 10 parts of styrene, 2 parts of acrylic acid, 2 parts of ethylene glycol dimethacrylate, 5 parts of perbutyl PV, 189.5 parts of toluene, and 63 parts of butyl acetate. A solution containing 5 parts of perbutyl PV and 70 parts of toluene was added dropwise over about 1 hour, and stirring was continued for about 1 hour, followed by cooling to room temperature, and a polymer containing a modified chlorinated polyolefin. A composition (P-6) was obtained. The obtained polymer composition (P-6) containing the modified chlorinated polyolefin had a solid content of about 46%, and the composition contained about 36 parts of 2-allyloxyethanol. The hydroxyl value of the resin solid content was approximately 9 mgKOH / g. The component ratio of the chlorinated polyolefin skeleton and the acrylic resin skeleton obtained by copolymerizing a part of 2-allyloxyethanol in the composition was about 20/80.
実施例７
　冷却管のついた４つ口フラスコに「スーパークロン８２２Ｓ」１００部、トルエン７０部、ジ－ｔ－ブチルヒドロキシトルエン（略称：ＢＨＴ）０．０５部を入れ液相に空気を吹きこみながら撹拌し約９５℃に昇温し溶液とした。これに、２－アリロキシエタノール１１．５部、ブタノール１７部、及び、臭化テトラブチルアンモニウム０．１部を加え、２－アリロキシエタノール、ブタノール、及び、酸無水物基を反応させながら撹拌を続けた。溶液中の固形分の赤外吸光分析において約１７７０cm－１の吸光度と約１４６０cm－１の吸光度の比がほぼ変化しなくなった段階で約９０℃に温度を下げ、さらにトルエン１４０部及び２－アリロキシエタノール３９部を添加し、アリロキシ基と水酸基を有する化合物（ａ）である２－アリロキシエタノール約５０部を含み、アリロキシ基を有する塩素化ポリオレフィン（ｂ）の濃度が約２７％である溶液を得た。酸無水物基と反応した２－アリロキシエタノールとブタノールの概算モル比は、０．２／０．８であった。次に、液相への空気吹き込みをやめ、気相へ窒素を流しながら約９０℃で撹拌を続け、（メタ）アクリル酸エステル、（メタ）アクリル酸及びスチレンから選ばれる１種以上の化合物（ｃ）として、メチルメタクリレート２０６部、シクロヘキシルメタクリレート１８９部、メタクリル酸３部、エチレングリコールジメタクリレート２部、さらに、パーブチルＰＶ５部、トルエン１８９．５部、酢酸ブチル６３部の混合液を約４時間かけて滴下し、さらにパーブチルＰＶ５部、トルエン７０部の混合液を約１時間かけて滴下し、約１時間撹拌を続けたのち、室温に冷却し、変性塩素化ポリオレフィンを含有するポリマー組成物（Ｐ－７）を得た。得られた変性塩素化ポリオレフィンを含有するポリマー組成物（Ｐ－７）の固形分は約４６％であり、組成物中には約４２部の２－アリロキシエタノールが含まれていた。樹脂固形分の水酸基価はおよそ１０ｍｇＫＯＨ／ｇであった。また、組成物中の塩素化ポリオレフィン骨格と２－アリロキシエタノールの一部が共重合されたアクリル樹脂骨格の成分比は、約２０／８０であった。 Example 7
In a four-necked flask equipped with a condenser tube, 100 parts of “Superclone 822S”, 70 parts of toluene and 0.05 part of di-t-butylhydroxytoluene (abbreviation: BHT) are added and stirred while blowing air into the liquid phase. The temperature was raised to about 95 ° C. to obtain a solution. To this, 11.5 parts of 2-allyloxyethanol, 17 parts of butanol and 0.1 part of tetrabutylammonium bromide were added, and stirred while reacting 2-allyloxyethanol, butanol and acid anhydride groups. Continued. The ratio of the absorbance of the absorbance and about 1460 cm -1 to about 1770 cm -1 in the infrared absorption analysis of the solids in the solution to lower the temperature to about 90 ° C. at a stage where almost no change, 140 parts of 2-ants of toluene A solution containing about 50 parts of 2-allyloxyethanol, which is a compound (a) having an allyloxy group and a hydroxyl group, to which 39 parts of roxyethanol are added, and the concentration of the chlorinated polyolefin (b) having an allyloxy group is about 27% Got. The approximate molar ratio of 2-allyloxyethanol and butanol reacted with the anhydride group was 0.2 / 0.8. Next, air blowing into the liquid phase is stopped, stirring is continued at about 90 ° C. while flowing nitrogen into the gas phase, and one or more compounds selected from (meth) acrylic acid ester, (meth) acrylic acid and styrene ( c) As a mixture of 206 parts of methyl methacrylate, 189 parts of cyclohexyl methacrylate, 3 parts of methacrylic acid, 2 parts of ethylene glycol dimethacrylate, 5 parts of perbutyl PV, 189.5 parts of toluene and 63 parts of butyl acetate, it takes about 4 hours. Further, a mixed solution of 5 parts of perbutyl PV and 70 parts of toluene was dropped over about 1 hour, and stirring was continued for about 1 hour, followed by cooling to room temperature and a polymer composition containing modified chlorinated polyolefin (P -7) was obtained. The resulting polymer composition (P-7) containing the modified chlorinated polyolefin had a solid content of about 46%, and the composition contained about 42 parts of 2-allyloxyethanol. The hydroxyl value of the resin solid content was approximately 10 mg KOH / g. The component ratio of the chlorinated polyolefin skeleton and the acrylic resin skeleton obtained by copolymerizing a part of 2-allyloxyethanol in the composition was about 20/80.
実施例８
　冷却管のついた４つ口フラスコに「スーパークロン３２２８Ｓ」１００部、トルエン７０部、ジ－ｔ－ブチルヒドロキシトルエン（略称：ＢＨＴ）０．０５部を入れ液相に空気を吹きこみながら撹拌し約９５℃に昇温し溶液とした。これに、２－アリロキシエタノール１１．５部、ブタノール１６部、２－エチルヘキサノール１部、及び、臭化テトラブチルアンモニウム０．１部を加え、２－アリロキシエタノール、ブタノール、２－エチルヘキサノール、及び、酸無水物基を反応させながら撹拌を続けた。溶液中の固形分の赤外吸光分析において約１７７０cm－１の吸光度と約１４６０cm－１の吸光度の比がほぼ変化しなくなった段階で約９０℃に温度を下げ、さらにトルエン１４０部及び２－アリロキシエタノール３９部を添加し、アリロキシ基と水酸基を有する化合物（ａ）である２－アリロキシエタノール約５０部を含み、アリロキシ基を有する塩素化ポリオレフィン（ｂ）の濃度が約２７％である溶液を得た。酸無水物基と反応した２－アリロキシエタノールとそれ以外のアルコールの概算モル比は、０．２／０．８であった。次に、液相への空気吹き込みをやめ、気相へ窒素を流しながら約９０℃で撹拌を続け、（メタ）アクリル酸エステル、（メタ）アクリル酸及びスチレンから選ばれる１種以上の化合物（ｃ）として、メチルメタクリレート２０６部、シクロヘキシルメタクリレート１８０部、スチレン１０部、アクリル酸２部、エチレングリコールジメタクリレート２部、さらに、パーブチルＰＶ５部、トルエン１８９．５部、酢酸ブチル６３部の混合液を約４時間かけて滴下し、さらにパーブチルＰＶ５部、トルエン７０部の混合液を約１時間かけて滴下し、約１時間撹拌を続けたのち、室温に冷却し、変性塩素化ポリオレフィンを含有するポリマー組成物（Ｐ－８）を得た。得られた変性塩素化ポリオレフィンを含有するポリマー組成物（Ｐ－８）の固形分は約４６％であり、組成物中には約４１部の２－アリロキシエタノールが含まれていた。樹脂固形分の水酸基価はおよそ１０ｍｇＫＯＨ／ｇであった。また、組成物中の塩素化ポリオレフィン骨格と２－アリロキシエタノールの一部が共重合されたアクリル樹脂骨格の成分比は、約２０／８０であった。 Example 8
In a four-necked flask equipped with a condenser tube, 100 parts of “Superclon 3228S”, 70 parts of toluene and 0.05 part of di-t-butylhydroxytoluene (abbreviation: BHT) were added and stirred while blowing air into the liquid phase. The temperature was raised to about 95 ° C. to obtain a solution. To this, 11.5 parts of 2-allyloxyethanol, 16 parts of butanol, 1 part of 2-ethylhexanol and 0.1 part of tetrabutylammonium bromide were added, and 2-allyloxyethanol, butanol, 2-ethylhexanol were added. And stirring was continued while the acid anhydride group was reacted. The ratio of the absorbance of the absorbance and about 1460 cm -1 to about 1770 cm -1 in the infrared absorption analysis of the solids in the solution to lower the temperature to about 90 ° C. at a stage where almost no change, 140 parts of 2-ants of toluene A solution containing about 50 parts of 2-allyloxyethanol, which is a compound (a) having an allyloxy group and a hydroxyl group, to which 39 parts of roxyethanol are added, and the concentration of the chlorinated polyolefin (b) having an allyloxy group is about 27% Got. The approximate molar ratio of 2-allyloxyethanol reacted with the acid anhydride group to the other alcohol was 0.2 / 0.8. Next, air blowing into the liquid phase is stopped, stirring is continued at about 90 ° C. while flowing nitrogen into the gas phase, and one or more compounds selected from (meth) acrylic acid ester, (meth) acrylic acid and styrene ( c) As a mixture of 206 parts methyl methacrylate, 180 parts cyclohexyl methacrylate, 10 parts styrene, 2 parts acrylic acid, 2 parts ethylene glycol dimethacrylate, 5 parts perbutyl PV, 189.5 parts toluene, 63 parts butyl acetate. A solution containing 5 parts of perbutyl PV and 70 parts of toluene was added dropwise over about 1 hour, and stirring was continued for about 1 hour, followed by cooling to room temperature, and a polymer containing a modified chlorinated polyolefin. A composition (P-8) was obtained. The resulting polymer composition (P-8) containing the modified chlorinated polyolefin had a solid content of about 46%, and the composition contained about 41 parts of 2-allyloxyethanol. The hydroxyl value of the resin solid content was approximately 10 mg KOH / g. The component ratio of the chlorinated polyolefin skeleton and the acrylic resin skeleton obtained by copolymerizing a part of 2-allyloxyethanol in the composition was about 20/80.
実施例９
　冷却管のついた４つ口フラスコに「スーパークロン８２２Ｓ」１００部、トルエン７０部、ジ－ｔ－ブチルヒドロキシトルエン（略称：ＢＨＴ）０．０５部を入れ液相に空気を吹きこみながら撹拌し約９５℃に昇温し溶液とした。これに、２－アリロキシエタノール１１．５部、４－ヒドロキシブチルアクリレート１部、及び、臭化テトラブチルアンモニウム０．１部を加え、２－アリロキシエタノール、４－ヒドロキシブチルアクリレート、及び、酸無水物基を反応させながら撹拌を続けた。溶液中の固形分の赤外吸光分析において約１７７０cm－１の吸光度と約１４６０cm－１の吸光度の比がほぼ変化しなくなった段階で約９０℃に温度を下げ、さらにトルエン１５６部及び２－アリロキシエタノール３９部を添加し、アリロキシ基と水酸基を有する化合物（ａ）である２－アリロキシエタノール約４８部を含み、アリロキシ基を有する塩素化ポリオレフィン（ｂ）の濃度が約２７％である溶液を得た。酸無水物基と反応した２－アリロキシエタノールと４－ヒドロキシブチルアクリレートの概算モル比は、０．９／０．１であった。次に、液相への空気吹き込みをやめ、気相へ窒素を流しながら約９０℃で撹拌を続け、（メタ）アクリル酸エステル、（メタ）アクリル酸及びスチレンから選ばれる１種以上の化合物（ｃ）として、メチルメタクリレート３０３部、シクロヘキシルメタクリレート９６部、アクリル酸１部、さらに、パーブチルＰＶ５部、トルエン１８９．５部、酢酸ブチル６３部の混合液を約４時間かけて滴下し、さらにパーブチルＰＶ５部、トルエン７０部の混合液を約１時間かけて滴下し、約１時間撹拌を続けたのち、室温に冷却し、変性塩素化ポリオレフィンを含有するポリマー組成物（Ｐ－９）を得た。得られた変性塩素化ポリオレフィンを含有するポリマー組成物（Ｐ－９）の固形分は約４６％であり、組成物中には約３９部の２－アリロキシエタノールが含まれていた。樹脂固形分の水酸基価はおよそ１０ｍｇＫＯＨ／ｇであった。また、組成物中の塩素化ポリオレフィン骨格と２－アリロキシエタノールの一部が共重合されたアクリル樹脂骨格の成分比は、約２０／８０であった。 Example 9
In a four-necked flask equipped with a condenser tube, 100 parts of “Superclone 822S”, 70 parts of toluene and 0.05 part of di-t-butylhydroxytoluene (abbreviation: BHT) are added and stirred while blowing air into the liquid phase. The temperature was raised to about 95 ° C. to obtain a solution. To this, 11.5 parts of 2-allyloxyethanol, 1 part of 4-hydroxybutyl acrylate and 0.1 part of tetrabutylammonium bromide were added, and 2-allyloxyethanol, 4-hydroxybutyl acrylate and acid were added. Stirring was continued while the anhydride group was reacted. The ratio of the absorbance of the absorbance and about 1460 cm -1 to about 1770 cm -1 in the infrared absorption analysis of the solids in the solution to lower the temperature to about 90 ° C. at a stage where almost no change, further 156 parts of 2-ants toluene A solution containing about 48 parts of 2-allyloxyethanol, which is a compound (a) having an allyloxy group and a hydroxyl group, to which 39 parts of roxyethanol are added, and the concentration of the chlorinated polyolefin (b) having an allyloxy group is about 27% Got. The approximate molar ratio of 2-allyloxyethanol reacted with acid anhydride groups to 4-hydroxybutyl acrylate was 0.9 / 0.1. Next, air blowing into the liquid phase is stopped, stirring is continued at about 90 ° C. while flowing nitrogen into the gas phase, and one or more compounds selected from (meth) acrylic acid ester, (meth) acrylic acid and styrene ( c) As a mixture, 303 parts of methyl methacrylate, 96 parts of cyclohexyl methacrylate, 1 part of acrylic acid, 5 parts of perbutyl PV, 189.5 parts of toluene, and 63 parts of butyl acetate were added dropwise over about 4 hours. A mixture of 70 parts of toluene and 70 parts of toluene was added dropwise over about 1 hour, and stirring was continued for about 1 hour, followed by cooling to room temperature to obtain a polymer composition (P-9) containing a modified chlorinated polyolefin. The resulting polymer composition (P-9) containing the modified chlorinated polyolefin had a solid content of about 46%, and the composition contained about 39 parts of 2-allyloxyethanol. The hydroxyl value of the resin solid content was approximately 10 mg KOH / g. The component ratio of the chlorinated polyolefin skeleton and the acrylic resin skeleton obtained by copolymerizing a part of 2-allyloxyethanol in the composition was about 20/80.
実施例１０
　冷却管のついた４つ口フラスコに「ハードレンＦ－６Ｐ」５０部、トルエン７０部、ジ－ｔ－ブチルヒドロキシトルエン（略称：ＢＨＴ）０．０５部を入れ液相に空気を吹きこみながら撹拌し約９５℃に昇温し溶液とした。これに、２－アリロキシエタノール１．３部、２－ヒドロキシエチルメタクリレート３部、ブタノール４部、及び、臭化テトラブチルアンモニウム０．１部を加え、２－アリロキシエタノール、２－ヒドロキシエチルメタクリレート、ブタノール、及び、酸無水物基を反応させながら撹拌を続けた。溶液中の固形分の赤外吸光分析において約１７７０cm－１の吸光度と約１４６０cm－１の吸光度の比がほぼ変化しなくなった段階で約９０℃に温度を下げ、さらにトルエン１４０部及び２－アリロキシエタノール６０部を添加し、アリロキシ基と水酸基を有する化合物（ａ）である２－アリロキシエタノール約６１部を含み、アリロキシ基を有する塩素化ポリオレフィン（ｂ）の濃度が約１６％である溶液を得た。酸無水物基と反応した２－アリロキシエタノールと２－ヒドロキシエチルメタクリレートとブタノールの概算モル比は、０．１／０．１／０．８であった。次に、液相への空気吹き込みをやめ、気相へ窒素を流しながら約９０℃で撹拌を続け、（メタ）アクリル酸エステル、（メタ）アクリル酸及びスチレンから選ばれる１種以上の化合物（ｃ）として、メチルメタクリレート９０部、シクロヘキシルメタクリレート３５２部、スチレン５部、アクリル酸３部、さらに、パーブチルＰＶ５部、トルエン１８９．５部、酢酸ブチル６３部の混合液を約４時間かけて滴下し、さらにパーブチルＰＶ５部、トルエン７０部の混合液を約１時間かけて滴下し、約１時間撹拌を続けたのち、室温に冷却し、変性塩素化ポリオレフィンを含有するポリマー組成物（Ｐ－１０）を得た。得られた変性塩素化ポリオレフィンを含有するポリマー組成物（Ｐ－１０）の固形分は約４６％であり、組成物中には約４９部の２－アリロキシエタノールが含まれていた。樹脂固形分の水酸基価はおよそ１４ｍｇＫＯＨ／ｇであった。また、組成物中の塩素化ポリオレフィン骨格と２－アリロキシエタノールの一部が共重合されたアクリル樹脂骨格の成分比は、約１０／９０であった。 Example 10
In a four-necked flask equipped with a condenser tube, 50 parts of “Hardylene F-6P”, 70 parts of toluene and 0.05 part of di-t-butylhydroxytoluene (abbreviation: BHT) are placed and stirred while blowing air into the liquid phase. The temperature was raised to about 95 ° C. to obtain a solution. To this, 1.3 parts of 2-allyloxyethanol, 3 parts of 2-hydroxyethyl methacrylate, 4 parts of butanol and 0.1 part of tetrabutylammonium bromide were added, and 2-allyloxyethanol, 2-hydroxyethyl methacrylate was added. Stirring was continued while reacting butanol and acid anhydride groups. The ratio of the absorbance of the absorbance and about 1460 cm -1 to about 1770 cm -1 in the infrared absorption analysis of the solids in the solution to lower the temperature to about 90 ° C. at a stage where almost no change, 140 parts of 2-ants of toluene A solution containing about 61 parts of 2-allyloxyethanol, which is a compound (a) having an allyloxy group and a hydroxyl group, to which 60 parts of roxyethanol is added, and the concentration of the chlorinated polyolefin (b) having an allyloxy group is about 16% Got. The approximate molar ratio of 2-allyloxyethanol, 2-hydroxyethyl methacrylate and butanol reacted with acid anhydride groups was 0.1 / 0.1 / 0.8. Next, air blowing into the liquid phase is stopped, stirring is continued at about 90 ° C. while flowing nitrogen into the gas phase, and one or more compounds selected from (meth) acrylic acid ester, (meth) acrylic acid and styrene ( c) As a mixture, 90 parts of methyl methacrylate, 352 parts of cyclohexyl methacrylate, 5 parts of styrene, 3 parts of acrylic acid, 5 parts of perbutyl PV, 189.5 parts of toluene, and 63 parts of butyl acetate are dropped over about 4 hours. Further, a mixed solution of 5 parts of perbutyl PV and 70 parts of toluene was dropped over about 1 hour, and stirring was continued for about 1 hour, followed by cooling to room temperature and a polymer composition containing a modified chlorinated polyolefin (P-10) Got. The obtained polymer composition (P-10) containing the modified chlorinated polyolefin had a solid content of about 46%, and the composition contained about 49 parts of 2-allyloxyethanol. The hydroxyl value of the resin solid content was approximately 14 mg KOH / g. The component ratio of the chlorinated polyolefin skeleton and the acrylic resin skeleton obtained by copolymerizing a part of 2-allyloxyethanol in the composition was about 10/90.
実施例１１
　冷却管のついた４つ口フラスコに「スーパークロン３２２８Ｓ」１００部、トルエン２２１部、ジ－ｔ－ブチルヒドロキシトルエン（略称：ＢＨＴ）０．０５部を入れ液相に空気を吹きこみながら撹拌し約９５℃に昇温し溶液とした。これに、２－アリロキシエタノール４０部、ブタノール１５部、及び、臭化テトラブチルアンモニウム０．１部を加え、２－アリロキシエタノール、ブタノール、及び、酸無水物基を反応させながら撹拌を続けた。溶液中の固形分の赤外吸光分析において約１７７０cm－１の吸光度と約１４６０cm－１の吸光度の比がほぼ変化しなくなった段階で約９０℃に温度を下げ、アリロキシ基と水酸基を有する化合物（ａ）である２－アリロキシエタノール約３９部を含み、アリロキシ基を有する塩素化ポリオレフィン（ｂ）の濃度が約２７％である溶液を得た。酸無水物基と反応した２－アリロキシエタノールとブタノールの概算モル比は、０．５／０．５であった。次に、液相への空気吹き込みをやめ、気相へ窒素を流しながら約９０℃で撹拌を続け、（メタ）アクリル酸エステル、（メタ）アクリル酸及びスチレンから選ばれる１種以上の化合物（ｃ）として、メチルメタクリレート１６２部、ｎ－ブチルアクリレート５６部、イソボルニルアクリレート１４４部、２－ヒドロキシエチルアクリレート３６部、エチレングリコールジメタクリレート２部、さらに、パーブチルＰＶ５部、トルエン１８９．５部、酢酸ブチル３０部、ブタノール３３部の混合液を約４時間かけて滴下し、さらにパーブチルＰＶ５部、トルエン７０部の混合液を約１時間かけて滴下し、約１時間撹拌を続けたのち、室温に冷却し、変性塩素化ポリオレフィンを含有するポリマー組成物（Ｐ－１１）を得た。得られた変性塩素化ポリオレフィンを含有するポリマー組成物（Ｐ－１１）の固形分は約４６％であり、組成物中には約３２部の２－アリロキシエタノールが含まれていた。樹脂固形分の水酸基価はおよそ４２ｍｇＫＯＨ／ｇであった。また、組成物中の塩素化ポリオレフィン骨格と２－アリロキシエタノールの一部が共重合されたアクリル樹脂骨格の成分比は、約２０／８０であった。 Example 11
In a four-necked flask with a condenser tube, 100 parts of “Superclon 3228S”, 221 parts of toluene, 0.05 part of di-t-butylhydroxytoluene (abbreviation: BHT) are placed and stirred while blowing air into the liquid phase. The temperature was raised to about 95 ° C. to obtain a solution. To this, 40 parts of 2-allyloxyethanol, 15 parts of butanol and 0.1 part of tetrabutylammonium bromide were added, and stirring was continued while reacting 2-allyloxyethanol, butanol and acid anhydride groups. It was. The ratio of the absorbance of the absorbance and about 1460 cm -1 to about 1770 cm -1 in the infrared absorption analysis of the solids in the solution to lower the temperature to about 90 ° C. at a stage where almost no change, a compound having an aryloxy group and a hydroxyl group ( A solution containing about 39 parts of 2-allyloxyethanol as a) and having a concentration of chlorinated polyolefin (b) having an allyloxy group of about 27% was obtained. The approximate molar ratio of 2-allyloxyethanol and butanol reacted with the acid anhydride group was 0.5 / 0.5. Next, air blowing into the liquid phase is stopped, stirring is continued at about 90 ° C. while flowing nitrogen into the gas phase, and one or more compounds selected from (meth) acrylic acid ester, (meth) acrylic acid and styrene ( c), 162 parts methyl methacrylate, 56 parts n-butyl acrylate, 144 parts isobornyl acrylate, 36 parts 2-hydroxyethyl acrylate, 2 parts ethylene glycol dimethacrylate, 5 parts perbutyl PV, 189.5 parts toluene, A mixture of 30 parts of butyl acetate and 33 parts of butanol was added dropwise over about 4 hours, a mixture of 5 parts of perbutyl PV and 70 parts of toluene was added dropwise over about 1 hour, and stirring was continued for about 1 hour. And a polymer composition (P-11) containing a modified chlorinated polyolefin was obtained. The resulting polymer composition (P-11) containing the modified chlorinated polyolefin had a solid content of about 46%, and the composition contained about 32 parts of 2-allyloxyethanol. The hydroxyl value of the resin solid content was approximately 42 mgKOH / g. The component ratio of the chlorinated polyolefin skeleton and the acrylic resin skeleton obtained by copolymerizing a part of 2-allyloxyethanol in the composition was about 20/80.
実施例１２
　冷却管のついた４つ口フラスコに「スーパークロン８２２Ｓ」１００部、トルエン７０部、ジ－ｔ－ブチルヒドロキシトルエン（略称：ＢＨＴ）０．０５部を入れ液相に空気を吹きこみながら撹拌し約９５℃に昇温し溶液とした。これに、２－アリロキシエタノール３０部、及び、臭化テトラブチルアンモニウム０．１部を加え、２－アリロキシエタノール、及び、酸無水物基を反応させながら撹拌を続けた。溶液中の固形分の赤外吸光分析において約１７７０cm－１の吸光度と約１４６０cm－１の吸光度の比がほぼ変化しなくなった段階で約９０℃に温度を下げ、さらにトルエン１７８部を添加し、アリロキシ基と水酸基を有する化合物（ａ）である２－アリロキシエタノール約２８部を含み、アリロキシ基を有する塩素化ポリオレフィン（ｂ）の濃度が約２７％である溶液を得た。次に、液相への空気吹き込みをやめ、気相へ窒素を流しながら約９０℃で撹拌を続け、（メタ）アクリル酸エステル、（メタ）アクリル酸及びスチレンから選ばれる１種以上の化合物（ｃ）として、シクロヘキシルメタクリレート３０３部、ｎ－ブチルアクリレート８４部、２－ヒドロキシエチルアクリレート１０部、メタクリル酸３部、さらに、パーブチルＰＶ５部、トルエン１８９．５部、酢酸ブチル４５部、ブタノール１８部の混合液を約４時間かけて滴下し、さらにパーブチルＰＶ５部、トルエン７０部の混合液を約１時間かけて滴下し、約１時間撹拌を続けたのち、室温に冷却し、変性塩素化ポリオレフィンを含有するポリマー組成物（Ｐ－１２）を得た。得られた変性塩素化ポリオレフィンを含有するポリマー組成物（Ｐ－１２）の固形分は約４６％であり、組成物中には約２３部の２－アリロキシエタノールが含まれていた。樹脂固形分の水酸基価はおよそ１５ｍｇＫＯＨ／ｇであった。また、組成物中の塩素化ポリオレフィン骨格と２－アリロキシエタノールの一部が共重合されたアクリル樹脂骨格の成分比は、約２０／８０であった。 Example 12
In a four-necked flask equipped with a condenser tube, 100 parts of “Superclone 822S”, 70 parts of toluene and 0.05 part of di-t-butylhydroxytoluene (abbreviation: BHT) are added and stirred while blowing air into the liquid phase. The temperature was raised to about 95 ° C. to obtain a solution. To this, 30 parts of 2-allyloxyethanol and 0.1 part of tetrabutylammonium bromide were added, and stirring was continued while reacting 2-allyloxyethanol and the acid anhydride group. The ratio of the absorbance of the absorbance and about 1460 cm -1 to about 1770 cm -1 in the infrared absorption analysis of the solids in the solution to lower the temperature to about 90 ° C. at a stage where almost no change, further added 178 parts of toluene, A solution containing about 28 parts of 2-allyloxyethanol which is a compound (a) having an allyloxy group and a hydroxyl group and having a concentration of about 27% of the chlorinated polyolefin (b) having an allyloxy group was obtained. Next, air blowing into the liquid phase is stopped, stirring is continued at about 90 ° C. while flowing nitrogen into the gas phase, and one or more compounds selected from (meth) acrylic acid ester, (meth) acrylic acid and styrene ( c): 303 parts of cyclohexyl methacrylate, 84 parts of n-butyl acrylate, 10 parts of 2-hydroxyethyl acrylate, 3 parts of methacrylic acid, 5 parts of perbutyl PV, 189.5 parts of toluene, 45 parts of butyl acetate and 18 parts of butanol The mixed solution was dropped over about 4 hours, and a mixed solution of 5 parts of perbutyl PV and 70 parts of toluene was added dropwise over about 1 hour. After stirring for about 1 hour, the mixture was cooled to room temperature, A containing polymer composition (P-12) was obtained. The polymer composition (P-12) containing the obtained modified chlorinated polyolefin had a solid content of about 46%, and the composition contained about 23 parts of 2-allyloxyethanol. The hydroxyl value of the resin solid content was approximately 15 mg KOH / g. The component ratio of the chlorinated polyolefin skeleton and the acrylic resin skeleton obtained by copolymerizing a part of 2-allyloxyethanol in the composition was about 20/80.
実施例１３
　冷却管のついた４つ口フラスコに「ハードレンＦ－６Ｐ」１００部、トルエン７０部、ジ－ｔ－ブチルヒドロキシトルエン（略称：ＢＨＴ）０．０５部を入れ液相に空気を吹きこみながら撹拌し約９５℃に昇温し溶液とした。これに、２－アリロキシエタノール１１．５部、２－ヒドロキシエチルメタクリレート３部、及び、臭化テトラブチルアンモニウム０．１部を加え、２－アリロキシエタノール、２－ヒドロキシエチルメタクリレート、及び、酸無水物基を反応させながら撹拌を続けた。溶液中の固形分の赤外吸光分析において約１７７０cm－１の吸光度と約１４６０cm－１の吸光度の比がほぼ変化しなくなった段階で約９０℃に温度を下げ、さらにトルエン１９３部を添加し、アリロキシ基と水酸基を有する化合物（ａ）である２－アリロキシエタノール約９部を含み、アリロキシ基を有する塩素化ポリオレフィン（ｂ）の濃度が約２７％である溶液を得た。酸無水物基と反応した２－アリロキシエタノールと２－ヒドロキシエチルメタクリレートの概算モル比は、０．９／０．１であった。次に、液相への空気吹き込みをやめ、気相へ窒素を流しながら約９０℃で撹拌を続け、（メタ）アクリル酸エステル、（メタ）アクリル酸及びスチレンから選ばれる１種以上の化合物（ｃ）として、メチルメタクリレート１７５部、シクロヘキシルメタクリレート１９５部、２－ヒドロキシエチルメタクリレート２６部、アクリル酸４部、さらに、パーブチルＰＶ５部、トルエン１８９．５部、酢酸ブチル３３部、ブタノール３０部の混合液を約４時間かけて滴下し、さらにパーブチルＰＶ５部、トルエン７０部の混合液を約１時間かけて滴下し、約１時間撹拌を続けたのち、室温に冷却し、変性塩素化ポリオレフィンを含有するポリマー組成物（Ｐ－１３）を得た。得られた変性塩素化ポリオレフィンを含有するポリマー組成物（Ｐ－１３）の固形分は約４５％であり、組成物中には約８部の２－アリロキシエタノールが含まれていた。樹脂固形分の水酸基価はおよそ２６ｍｇＫＯＨ／ｇであった。また、組成物中の塩素化ポリオレフィン骨格と２－アリロキシエタノールの一部が共重合されたアクリル樹脂骨格の成分比は、約２０／８０であった。 Example 13
In a four-necked flask equipped with a condenser tube, 100 parts of “Hardylene F-6P”, 70 parts of toluene, 0.05 part of di-t-butylhydroxytoluene (abbreviation: BHT) are added and stirred while blowing air into the liquid phase. The temperature was raised to about 95 ° C. to obtain a solution. To this, 11.5 parts of 2-allyloxyethanol, 3 parts of 2-hydroxyethyl methacrylate and 0.1 part of tetrabutylammonium bromide were added, and 2-allyloxyethanol, 2-hydroxyethyl methacrylate and acid were added. Stirring was continued while the anhydride group was reacted. The ratio of the absorbance of the absorbance and about 1460 cm -1 to about 1770 cm -1 in the infrared absorption analysis of the solids in the solution to lower the temperature to about 90 ° C. at a stage where almost no change, further added 193 parts of toluene, A solution containing about 9 parts of 2-allyloxyethanol which is a compound (a) having an allyloxy group and a hydroxyl group and having a concentration of about 27% of the chlorinated polyolefin (b) having an allyloxy group was obtained. The approximate molar ratio of 2-allyloxyethanol reacted with the acid anhydride group to 2-hydroxyethyl methacrylate was 0.9 / 0.1. Next, air blowing into the liquid phase is stopped, stirring is continued at about 90 ° C. while flowing nitrogen into the gas phase, and one or more compounds selected from (meth) acrylic acid ester, (meth) acrylic acid and styrene ( c), a mixed solution of 175 parts of methyl methacrylate, 195 parts of cyclohexyl methacrylate, 26 parts of 2-hydroxyethyl methacrylate, 4 parts of acrylic acid, 5 parts of perbutyl PV, 189.5 parts of toluene, 33 parts of butyl acetate and 30 parts of butanol Is added dropwise over about 4 hours, and a mixture of 5 parts of perbutyl PV and 70 parts of toluene is added dropwise over about 1 hour. After stirring for about 1 hour, the mixture is cooled to room temperature and contains a modified chlorinated polyolefin. A polymer composition (P-13) was obtained. The resulting polymer composition (P-13) containing the modified chlorinated polyolefin had a solid content of about 45%, and the composition contained about 8 parts of 2-allyloxyethanol. The hydroxyl value of the resin solid content was approximately 26 mg KOH / g. The component ratio of the chlorinated polyolefin skeleton and the acrylic resin skeleton obtained by copolymerizing a part of 2-allyloxyethanol in the composition was about 20/80.
実施例１４
　冷却管のついた４つ口フラスコに「スーパークロン８２２Ｓ」１５０部、トルエン１０５部、ジ－ｔ－ブチルヒドロキシトルエン（略称：ＢＨＴ）０．０５部を入れ液相に空気を吹きこみながら撹拌し約９５℃に昇温し溶液とした。これに、２－アリロキシエタノール１８部、ブタノール３部、及び、臭化テトラブチルアンモニウム０．１部を加え、２－アリロキシエタノール、ブタノール、及び、酸無水物基を反応させながら撹拌を続けた。溶液中の固形分の赤外吸光分析において約１７７０cm－１の吸光度と約１４６０cm－１の吸光度の比がほぼ変化しなくなった段階で約９０℃に温度を下げ、さらにトルエン２５５部を添加し、アリロキシ基と水酸基を有する化合物（ａ）である２－アリロキシエタノール約１４部を含み、アリロキシ基を有する塩素化ポリオレフィン（ｂ）の濃度が約２９％である溶液を得た。酸無水物基と反応した２－アリロキシエタノールとブタノールの概算モル比は、０．７／０．３であった。次に、液相への空気吹き込みをやめ、気相へ窒素を流しながら約９０℃で撹拌を続け、（メタ）アクリル酸エステル、（メタ）アクリル酸及びスチレンから選ばれる１種以上の化合物（ｃ）として、シクロヘキシルメタクリレート２５０部、イソボルニルアクリレート４８部、２－ヒドロキシエチルメタクリレート２２部、スチレン３０部、さらに、パーブチルＰＶ５部、トルエン８２．５部、酢酸ブチル３８部、ブタノール２７部の混合液を約４時間かけて滴下し、さらにパーブチルＰＶ５部、トルエン７０部の混合液を約１時間かけて滴下し、約１時間撹拌を続けたのち、室温に冷却し、変性塩素化ポリオレフィンを含有するポリマー組成物（Ｐ－１４）を得た。得られた変性塩素化ポリオレフィンを含有するポリマー組成物（Ｐ－１４）の固形分は約４５％であり、組成物中には約１２部の２－アリロキシエタノールが含まれていた。樹脂固形分の水酸基価はおよそ２２ｍｇＫＯＨ／ｇであった。また、組成物中の塩素化ポリオレフィン骨格と２－アリロキシエタノールの一部が共重合されたアクリル樹脂骨格の成分比は、約３０／７０であった。 Example 14
In a four-necked flask equipped with a condenser tube, 150 parts of “Supercron 822S”, 105 parts of toluene, and 0.05 parts of di-t-butylhydroxytoluene (abbreviation: BHT) are placed and stirred while blowing air into the liquid phase. The temperature was raised to about 95 ° C. to obtain a solution. To this, 18 parts of 2-allyloxyethanol, 3 parts of butanol and 0.1 part of tetrabutylammonium bromide were added, and stirring was continued while reacting 2-allyloxyethanol, butanol and acid anhydride groups. It was. The ratio of the absorbance of the absorbance and about 1460 cm -1 to about 1770 cm -1 in the infrared absorption analysis of the solids in the solution to lower the temperature to about 90 ° C. at a stage where almost no change, further added 255 parts of toluene, A solution containing about 14 parts of 2-allyloxyethanol which is a compound (a) having an allyloxy group and a hydroxyl group and having a concentration of about 29% of the chlorinated polyolefin (b) having an allyloxy group was obtained. The approximate molar ratio of 2-allyloxyethanol reacted with acid anhydride groups to butanol was 0.7 / 0.3. Next, air blowing into the liquid phase is stopped, stirring is continued at about 90 ° C. while flowing nitrogen into the gas phase, and one or more compounds selected from (meth) acrylic acid ester, (meth) acrylic acid and styrene ( c) As a mixture of 250 parts of cyclohexyl methacrylate, 48 parts of isobornyl acrylate, 22 parts of 2-hydroxyethyl methacrylate, 30 parts of styrene, 5 parts of perbutyl PV, 82.5 parts of toluene, 38 parts of butyl acetate and 27 parts of butanol. The solution was added dropwise over about 4 hours, and a mixed solution of 5 parts perbutyl PV and 70 parts of toluene was added dropwise over about 1 hour. After stirring for about 1 hour, the mixture was cooled to room temperature and contained modified chlorinated polyolefin. A polymer composition (P-14) was obtained. The obtained polymer composition (P-14) containing the modified chlorinated polyolefin had a solid content of about 45%, and the composition contained about 12 parts of 2-allyloxyethanol. The hydroxyl value of the resin solid content was approximately 22 mg KOH / g. The component ratio of the chlorinated polyolefin skeleton and the acrylic resin skeleton obtained by copolymerizing a part of 2-allyloxyethanol in the composition was about 30/70.
実施例１５
　冷却管のついた４つ口フラスコに「スーパークロン８２２Ｓ」１００部、トルエン７０部、ジ－ｔ－ブチルヒドロキシトルエン（略称：ＢＨＴ）０．０５部を入れ液相に空気を吹きこみながら撹拌し約９５℃に昇温し溶液とした。これに、２－アリロキシエタノール２３部と臭化テトラブチルアンモニウム０．１部を加え、２－アリロキシエタノールと酸無水物基を反応させながら撹拌を続けた。溶液中の固形分の赤外吸光分析において約１７７０cm－１の吸光度と約１４６０cm－１の吸光度の比がほぼ変化しなくなった段階で約９０℃に温度を下げ、トルエン１５０部及び２－アリロキシエタノール３４．５部をさらに加えることで、アリロキシ基と水酸基を有する化合物（ａ）である２－アリロキシエタノール約５５部を含み、アリロキシ基を有する塩素化ポリオレフィン（ｂ）の濃度が約２７％である溶液を得た。次に、液相への空気吹き込みをやめ、気相へ窒素を流しながら約９０℃で撹拌を続け、（メタ）アクリル酸エステル、（メタ）アクリル酸及びスチレンから選ばれる１種以上の化合物（ｃ）として、メチルメタクリレート１９７部、シクロヘキシルメタクリレート１９１部、スチレン１０部、アクリル酸２部、さらに、パーヘキサ２５Ｏ（商品名、日油社製、２，５－ジメチル－２，５－ジ（２－エチルヘキサノイルパーオキシ）ヘキサンの５０％炭化水素溶液）１２部（有効成分６部）、トルエン１８９．５部、酢酸ブチル６３部の混合液を約４時間かけて滴下し、さらにパーヘキサ２５Ｏ６部、トルエン７０部の混合液を約１時間かけて滴下し、約１時間撹拌を続けたのち、室温に冷却し、変性塩素化ポリオレフィンを含有するポリマー組成物（Ｐ－１５）を得た。得られた変性塩素化ポリオレフィンを含有するポリマー組成物（Ｐ－１５）の固形分は約４６％であり、組成物中には約４５部の２－アリロキシエタノールが含まれていた。樹脂固形分の水酸基価はおよそ１１ｍｇＫＯＨ／ｇであった。また、組成物中の塩素化ポリオレフィン骨格と２－アリロキシエタノールの一部が共重合されたアクリル樹脂骨格の成分比は、約２０／８０であった。 Example 15
In a four-necked flask equipped with a condenser tube, 100 parts of “Superclone 822S”, 70 parts of toluene and 0.05 part of di-t-butylhydroxytoluene (abbreviation: BHT) are added and stirred while blowing air into the liquid phase. The temperature was raised to about 95 ° C. to obtain a solution. To this, 23 parts of 2-allyloxyethanol and 0.1 part of tetrabutylammonium bromide were added, and stirring was continued while reacting 2-allyloxyethanol with the acid anhydride group. The ratio of the absorbance of the absorbance and about 1460 cm -1 to about 1770 cm -1 in the infrared absorption analysis of the solids in the solution to lower the temperature to about 90 ° C. at a stage where almost no change, 150 parts of toluene and 2-allyloxy By further adding 34.5 parts of ethanol, the concentration of chlorinated polyolefin (b) having an allyloxy group is about 27%, including about 55 parts of 2-allyloxyethanol, which is a compound (a) having an allyloxy group and a hydroxyl group. A solution was obtained. Next, air blowing into the liquid phase is stopped, stirring is continued at about 90 ° C. while flowing nitrogen into the gas phase, and one or more compounds selected from (meth) acrylic acid ester, (meth) acrylic acid and styrene ( c), methyl methacrylate 197 parts, cyclohexyl methacrylate 191 parts, styrene 10 parts, acrylic acid 2 parts, perhexa 25O (trade name, manufactured by NOF Corporation, 2,5-dimethyl-2,5-di (2- Ethylhexanoylperoxy) hexane 50% hydrocarbon solution) 12 parts (6 parts active ingredient), 189.5 parts toluene, 63 parts butyl acetate was added dropwise over about 4 hours, and further 6 parts perhexa25O, A mixture of 70 parts of toluene was added dropwise over about 1 hour, and stirring was continued for about 1 hour, followed by cooling to room temperature and a polymer containing a modified chlorinated polyolefin. Was obtained Narubutsu the (P-15). The resulting polymer composition (P-15) containing the modified chlorinated polyolefin had a solid content of about 46%, and the composition contained about 45 parts of 2-allyloxyethanol. The hydroxyl value of the resin solid content was approximately 11 mgKOH / g. The component ratio of the chlorinated polyolefin skeleton and the acrylic resin skeleton obtained by copolymerizing a part of 2-allyloxyethanol in the composition was about 20/80.
実施例１６
　冷却管のついた４つ口フラスコに「スーパークロン８２２Ｓ」１００部、トルエン７０部、ジ－ｔ－ブチルヒドロキシトルエン（略称：ＢＨＴ）０．０５部を入れ液相に空気を吹きこみながら撹拌し約９５℃に昇温し溶液とした。これに、２－アリロキシエタノール２３部と臭化テトラブチルアンモニウム０．１部を加え、２－アリロキシエタノールと酸無水物基を反応させながら撹拌を続けた。溶液中の固形分の赤外吸光分析において約１７７０cm－１の吸光度と約１４６０cm－１の吸光度の比がほぼ変化しなくなった段階で約９０℃に温度を下げ、トルエン１５０部及び２－アリロキシエタノール３４．５部をさらに加えることで、アリロキシ基と水酸基を有する化合物（ａ）である２－アリロキシエタノール約５５部を含み、アリロキシ基を有する塩素化ポリオレフィン（ｂ）の濃度が約２７％である溶液を得た。次に、液相への空気吹き込みをやめ、気相へ窒素を流しながら約９０℃で撹拌を続け、（メタ）アクリル酸エステル、（メタ）アクリル酸及びスチレンから選ばれる１種以上の化合物（ｃ）として、メチルメタクリレート１９７部、シクロヘキシルメタクリレート１９１部、スチレン１０部、アクリル酸２部、さらに、Ｖ－６５（商品名、和光純薬社製、アゾビス（２，４－ジメチルバレロニトリル））５部、トルエン１８９．５部、酢酸ブチル６３部の混合液を約４時間かけて滴下し、さらにパーブチルＰＶ５部、トルエン７０部の混合液を約１時間かけて滴下し、約１時間撹拌を続けたのち、室温に冷却し、変性塩素化ポリオレフィンを含有するポリマー組成物（Ｐ－１６）を得た。得られた変性塩素化ポリオレフィンを含有するポリマー組成物（Ｐ－１６）の固形分は約４６％であり、組成物中には約４５部の２－アリロキシエタノールが含まれていた。樹脂固形分の水酸基価はおよそ１１ｍｇＫＯＨ／ｇであった。また、組成物中の塩素化ポリオレフィン骨格と２－アリロキシエタノールの一部が共重合されたアクリル樹脂骨格の成分比は、約２０／８０であった。 Example 16
In a four-necked flask equipped with a condenser tube, 100 parts of “Superclone 822S”, 70 parts of toluene and 0.05 part of di-t-butylhydroxytoluene (abbreviation: BHT) are added and stirred while blowing air into the liquid phase. The temperature was raised to about 95 ° C. to obtain a solution. To this, 23 parts of 2-allyloxyethanol and 0.1 part of tetrabutylammonium bromide were added, and stirring was continued while reacting 2-allyloxyethanol with the acid anhydride group. The ratio of the absorbance of the absorbance and about 1460 cm -1 to about 1770 cm -1 in the infrared absorption analysis of the solids in the solution to lower the temperature to about 90 ° C. at a stage where almost no change, 150 parts of toluene and 2-allyloxy By further adding 34.5 parts of ethanol, the concentration of chlorinated polyolefin (b) having an allyloxy group is about 27%, including about 55 parts of 2-allyloxyethanol, which is a compound (a) having an allyloxy group and a hydroxyl group. A solution was obtained. Next, air blowing into the liquid phase is stopped, stirring is continued at about 90 ° C. while flowing nitrogen into the gas phase, and one or more compounds selected from (meth) acrylic acid ester, (meth) acrylic acid and styrene ( c), methyl methacrylate 197 parts, cyclohexyl methacrylate 191 parts, styrene 10 parts, acrylic acid 2 parts, and V-65 (trade name, manufactured by Wako Pure Chemical Industries, Ltd., azobis (2,4-dimethylvaleronitrile)) 5 A mixture of 189.5 parts of toluene and 63 parts of butyl acetate was added dropwise over about 4 hours, and a mixture of 5 parts of perbutyl PV and 70 parts of toluene was added dropwise over about 1 hour, and stirring was continued for about 1 hour. Thereafter, the mixture was cooled to room temperature to obtain a polymer composition (P-16) containing a modified chlorinated polyolefin. The resulting polymer composition (P-16) containing the modified chlorinated polyolefin had a solid content of about 46%, and the composition contained about 45 parts of 2-allyloxyethanol. The hydroxyl value of the resin solid content was approximately 11 mgKOH / g. The component ratio of the chlorinated polyolefin skeleton and the acrylic resin skeleton obtained by copolymerizing a part of 2-allyloxyethanol in the composition was about 20/80.
実施例１７
　冷却管のついた４つ口フラスコに「スーパークロン８２２Ｓ」１００部、トルエン６７部、メチルシクロヘキサン３部、ジ－ｔ－ブチルヒドロキシトルエン（略称：ＢＨＴ）０．０５部を入れ液相に空気を吹きこみながら撹拌し約９５℃に昇温し溶液とした。これに、２－アリロキシエタノール２３部と臭化テトラブチルアンモニウム０．１部を加え、２－アリロキシエタノールと酸無水物基を反応させながら撹拌を続けた。溶液中の固形分の赤外吸光分析において約１７７０cm－１の吸光度と約１４６０cm－１の吸光度の比がほぼ変化しなくなった段階で約９０℃に温度を下げ、トルエン１４５部、メチルシクロヘキサン５部及び２－アリロキシエタノール３４．５部をさらに加えることで、アリロキシ基と水酸基を有する化合物（ａ）である２－アリロキシエタノール約５５部を含み、アリロキシ基を有する塩素化ポリオレフィン（ｂ）の濃度が約２７％である溶液を得た。次に、液相への空気吹き込みをやめ、気相へ窒素を流しながら約９０℃で撹拌を続け、（メタ）アクリル酸エステル、（メタ）アクリル酸及びスチレンから選ばれる１種以上の化合物（ｃ）として、メチルメタクリレート１９７部、シクロヘキシルメタクリレート１９１部、スチレン１０部、アクリル酸２部、さらに、パーブチルＰＶ５部、トルエン１７１．５部、メチルシクロヘキサン１８部、酢酸ブチル６３部の混合液を約４時間かけて滴下し、さらにパーブチルＰＶ５部、トルエン６３部、メチルシクロヘキサン７部の混合液を約１時間かけて滴下し、約１時間撹拌を続けたのち、室温に冷却し、変性塩素化ポリオレフィンを含有するポリマー組成物（Ｐ－１７）を得た。得られた変性塩素化ポリオレフィンを含有するポリマー組成物（Ｐ－１７）の固形分は約４６％であり、組成物中には約４５部の２－アリロキシエタノールが含まれていた。樹脂固形分の水酸基価はおよそ１１ｍｇＫＯＨ／ｇであった。また、組成物中の塩素化ポリオレフィン骨格と２－アリロキシエタノールの一部が共重合されたアクリル樹脂骨格の成分比は、約２０／８０であった。 Example 17
In a four-necked flask equipped with a condenser tube, 100 parts of “Superclone 822S”, 67 parts of toluene, 3 parts of methylcyclohexane, 0.05 part of di-t-butylhydroxytoluene (abbreviation: BHT) are placed in the liquid phase. The mixture was stirred while blowing and heated to about 95 ° C. to obtain a solution. To this, 23 parts of 2-allyloxyethanol and 0.1 part of tetrabutylammonium bromide were added, and stirring was continued while reacting 2-allyloxyethanol with the acid anhydride group. The ratio of the absorbance of the absorbance and about 1460 cm -1 to about 1770 cm -1 in the infrared absorption analysis of the solids in the solution to lower the temperature to about 90 ° C. at a stage where almost no change, 145 parts of toluene, methylcyclohexane 5 parts Further, 34.5 parts of 2-allyloxyethanol are further added, so that about 55 parts of 2-allyloxyethanol, which is a compound (a) having an allyloxy group and a hydroxyl group, is contained, and A solution having a concentration of about 27% was obtained. Next, air blowing into the liquid phase is stopped, stirring is continued at about 90 ° C. while flowing nitrogen into the gas phase, and one or more compounds selected from (meth) acrylic acid ester, (meth) acrylic acid and styrene ( c) As a mixture of about 197 parts of methyl methacrylate, 191 parts of cyclohexyl methacrylate, 10 parts of styrene, 2 parts of acrylic acid, 5 parts of perbutyl PV, 171.5 parts of toluene, 18 parts of methylcyclohexane and 63 parts of butyl acetate. The mixture was added dropwise over a period of time, and a mixture of 5 parts of perbutyl PV, 63 parts of toluene, and 7 parts of methylcyclohexane was added dropwise over about 1 hour. After stirring for about 1 hour, the mixture was cooled to room temperature, A polymer composition (P-17) containing was obtained. The resulting polymer composition (P-17) containing the modified chlorinated polyolefin had a solid content of about 46%, and the composition contained about 45 parts of 2-allyloxyethanol. The hydroxyl value of the resin solid content was approximately 11 mgKOH / g. The component ratio of the chlorinated polyolefin skeleton and the acrylic resin skeleton obtained by copolymerizing a part of 2-allyloxyethanol in the composition was about 20/80.
実施例１８
　冷却管のついた４つ口フラスコに「スーパークロン８２２Ｓ」１００部、トルエン７０部、ジ－ｔ－ブチルヒドロキシトルエン（略称：ＢＨＴ）０．０５部を入れ液相に空気を吹きこみながら撹拌し約９５℃に昇温し溶液とした。これに、２－アリロキシエタノール２３部と臭化テトラブチルアンモニウム０．１部を加え、２－アリロキシエタノールと酸無水物基を反応させながら撹拌を続けた。溶液中の固形分の赤外吸光分析において約１７７０cm－１の吸光度と約１４６０cm－１の吸光度の比がほぼ変化しなくなった段階で約９０℃に温度を下げ、トルエン１５０部及び２－アリロキシエタノール３４．５部をさらに加えることで、アリロキシ基と水酸基を有する化合物（ａ）である２－アリロキシエタノール約５５部を含み、アリロキシ基を有する塩素化ポリオレフィン（ｂ）の濃度が約２７％である溶液を得た。次に、液相への空気吹き込みをやめ、気相へ窒素を流しながら約９０℃で撹拌を続け、（メタ）アクリル酸エステル、（メタ）アクリル酸及びスチレンから選ばれる１種以上の化合物（ｃ）として、メチルメタクリレート１９７部、シクロヘキシルメタクリレート１９１部、スチレン１０部、アクリル酸２部、さらに、パーブチルＰＶ５部、トルエン１７１．５部、シクロヘキサン９部、メチルシクロヘキサン９部、酢酸ブチル６３部の混合液を約４時間かけて滴下し、さらにパーブチルＰＶ５部、トルエン６３部、シクロヘキサン３部、メチルシクロヘキサン４部の混合液を約１時間かけて滴下し、約１時間撹拌を続けたのち、室温に冷却し、変性塩素化ポリオレフィンを含有するポリマー組成物（Ｐ－１８）を得た。得られた変性塩素化ポリオレフィンを含有するポリマー組成物（Ｐ－１８）の固形分は約４６％であり、組成物中には約４５部の２－アリロキシエタノールが含まれていた。樹脂固形分の水酸基価はおよそ１１ｍｇＫＯＨ／ｇであった。また、組成物中の塩素化ポリオレフィン骨格と２－アリロキシエタノールの一部が共重合されたアクリル樹脂骨格の成分比は、約２０／８０であった。 Example 18
In a four-necked flask equipped with a condenser tube, 100 parts of “Superclone 822S”, 70 parts of toluene and 0.05 part of di-t-butylhydroxytoluene (abbreviation: BHT) are added and stirred while blowing air into the liquid phase. The temperature was raised to about 95 ° C. to obtain a solution. To this, 23 parts of 2-allyloxyethanol and 0.1 part of tetrabutylammonium bromide were added, and stirring was continued while reacting 2-allyloxyethanol with the acid anhydride group. The ratio of the absorbance of the absorbance and about 1460 cm -1 to about 1770 cm -1 in the infrared absorption analysis of the solids in the solution to lower the temperature to about 90 ° C. at a stage where almost no change, 150 parts of toluene and 2-allyloxy By further adding 34.5 parts of ethanol, the concentration of chlorinated polyolefin (b) having an allyloxy group is about 27%, including about 55 parts of 2-allyloxyethanol, which is a compound (a) having an allyloxy group and a hydroxyl group. A solution was obtained. Next, air blowing into the liquid phase is stopped, stirring is continued at about 90 ° C. while flowing nitrogen into the gas phase, and one or more compounds selected from (meth) acrylic acid ester, (meth) acrylic acid and styrene ( c) As a mixture of 197 parts methyl methacrylate, 191 parts cyclohexyl methacrylate, 10 parts styrene, 2 parts acrylic acid, 5 parts perbutyl PV, 171.5 parts toluene, 9 parts cyclohexane, 9 parts methylcyclohexane, 63 parts butyl acetate The solution was added dropwise over about 4 hours, and a mixture of 5 parts of perbutyl PV, 63 parts of toluene, 3 parts of cyclohexane, and 4 parts of methylcyclohexane was added dropwise over about 1 hour, and the stirring was continued for about 1 hour. After cooling, a polymer composition (P-18) containing a modified chlorinated polyolefin was obtained. The resulting polymer composition (P-18) containing the modified chlorinated polyolefin had a solid content of about 46%, and the composition contained about 45 parts of 2-allyloxyethanol. The hydroxyl value of the resin solid content was approximately 11 mgKOH / g. The component ratio of the chlorinated polyolefin skeleton and the acrylic resin skeleton obtained by copolymerizing a part of 2-allyloxyethanol in the composition was about 20/80.
比較例１
　冷却管のついた４つ口フラスコに「スーパークロン８２２Ｓ」１００部、トルエン２２１部、ジ－ｔ－ブチルヒドロキシトルエン（略称：ＢＨＴ）０．０５部を入れ液相に空気を吹きこみながら撹拌し約９５℃に昇温し溶液とした。これに、２－ヒドロキシエチルメタクリレート５７．５部、及び、臭化テトラブチルアンモニウム０．１部を加え、２－ヒドロキシエチルメタクリレート、及び、酸無水物基を反応させながら撹拌を続けた。溶液中の固形分の赤外吸光分析において約１７７０cm－１の吸光度と約１４６０cm－１の吸光度の比がほぼ変化しなくなった段階で約９０℃に温度を下げ、アリロキシ基を有さない塩素化ポリオレフィン（ｂ）の濃度が約２７％である溶液を得た。次に、液相への空気吹き込みをやめ、気相へ窒素を流しながら約９０℃で撹拌を続け、（メタ）アクリル酸エステル、（メタ）アクリル酸及びスチレンから選ばれる１種以上の化合物（ｃ）として、メチルメタクリレート１９７部、シクロヘキシルメタクリレート１８９部、スチレン１０部、エチレングリコールジメタクリレート２部、アクリル酸２部、さらに、パーブチルＰＶ５部、トルエン１８９．５部、酢酸ブチル６３部の混合液を滴下したところ、滴下開始後約１時間で反応系がゲル化したため、変性塩素化ポリオレフィンを含有するポリマー組成物の製造を中止した。 Comparative Example 1
In a four-necked flask equipped with a condenser tube, 100 parts of “Superclone 822S”, 221 parts of toluene, 0.05 part of di-t-butylhydroxytoluene (abbreviation: BHT) are added and stirred while blowing air into the liquid phase. The temperature was raised to about 95 ° C. to obtain a solution. To this, 57.5 parts of 2-hydroxyethyl methacrylate and 0.1 part of tetrabutylammonium bromide were added, and stirring was continued while reacting 2-hydroxyethyl methacrylate and acid anhydride groups. The ratio of the absorbance of the absorbance and about 1460 cm -1 to about 1770 cm -1 in the infrared absorption analysis of the solids in the solution to lower the temperature to about 90 ° C. at a stage where almost no change, chlorinated without a allyloxy group A solution having a concentration of polyolefin (b) of about 27% was obtained. Next, air blowing into the liquid phase is stopped, stirring is continued at about 90 ° C. while flowing nitrogen into the gas phase, and one or more compounds selected from (meth) acrylic acid ester, (meth) acrylic acid and styrene ( c) As a mixed solution of 197 parts methyl methacrylate, 189 parts cyclohexyl methacrylate, 10 parts styrene, 2 parts ethylene glycol dimethacrylate, 2 parts acrylic acid, 5 parts perbutyl PV, 189.5 parts toluene, and 63 parts butyl acetate. When the solution was added dropwise, the reaction system gelled about 1 hour after the start of the addition, so the production of the polymer composition containing the modified chlorinated polyolefin was stopped.
比較例２
　冷却管のついた４つ口フラスコに「スーパークロン３２２８Ｓ」１００部、トルエン７０部、ジ－ｔ－ブチルヒドロキシトルエン（略称：ＢＨＴ）０．０５部を入れ液相に空気を吹きこみながら撹拌し約９５℃に昇温し溶液とした。これに、２－ヒドロキシエチルメタクリレート２３部、及び、臭化テトラブチルアンモニウム０．１部を加え、２－ヒドロキシエチルメタクリレート２３部、及び、酸無水物基を反応させながら撹拌を続けた。約４０分後に突然系が発熱し重合が始まったため、変性塩素化ポリオレフィンを含有するポリマー組成物の製造を中止した。 Comparative Example 2
In a four-necked flask equipped with a condenser tube, 100 parts of “Superclon 3228S”, 70 parts of toluene and 0.05 part of di-t-butylhydroxytoluene (abbreviation: BHT) were added and stirred while blowing air into the liquid phase. The temperature was raised to about 95 ° C. to obtain a solution. To this, 23 parts of 2-hydroxyethyl methacrylate and 0.1 part of tetrabutylammonium bromide were added, and stirring was continued while reacting 23 parts of 2-hydroxyethyl methacrylate and an acid anhydride group. After about 40 minutes, the system suddenly exothermed and polymerization started, and production of the polymer composition containing the modified chlorinated polyolefin was discontinued.
比較例３
　冷却管のついた４つ口フラスコに「スーパークロン８２２Ｓ」１００部、トルエン２１８部、ジ－ｔ－ブチルヒドロキシトルエン（略称：ＢＨＴ）０．０５部を入れ液相に空気を吹きこみながら撹拌し約９５℃に昇温し溶液とした。これに、２－ヒドロキシエチルメタクリレート５７．５部、ブタノール２部、及び、臭化テトラブチルアンモニウム０．１部を加え、２－ヒドロキシエチルメタクリレート、ブタノール、及び、酸無水物基を反応させながら撹拌を続けた。溶液中の固形分の赤外吸光分析において約１７７０cm－１の吸光度と約１４６０cm－１の吸光度の比がほぼ変化しなくなった段階で約９０℃に温度を下げ、アリロキシ基を有さない塩素化ポリオレフィン（ｂ）の濃度が約２７％である溶液を得た。酸無水物基と反応した２－ヒドロキシエチルメタクリレートとブタノールの概算モル比は、０．８／０．２であった。次に、液相への空気吹き込みをやめ、気相へ窒素を流しながら約９０℃で撹拌を続け、（メタ）アクリル酸エステル、（メタ）アクリル酸及びスチレンから選ばれる１種以上の化合物（ｃ）として、メチルメタクリレート１９７部、シクロヘキシルメタクリレート１８６部、２－ヒドロキシエチルアクリレート６部、スチレン１０部、アクリル酸１部、さらに、パーブチルＰＶ５部、トルエン１８９．５部、酢酸ブチル６３部の混合液を滴下したところ、滴下開始後約１時間で反応系がゲル化したため、変性塩素化ポリオレフィンを含有するポリマー組成物の製造を中止した。 Comparative Example 3
In a four-necked flask equipped with a condenser tube, 100 parts of “Superclone 822S”, 218 parts of toluene and 0.05 part of di-t-butylhydroxytoluene (abbreviation: BHT) are added and stirred while blowing air into the liquid phase. The temperature was raised to about 95 ° C. to obtain a solution. To this was added 57.5 parts of 2-hydroxyethyl methacrylate, 2 parts of butanol, and 0.1 part of tetrabutylammonium bromide, and the mixture was stirred while reacting 2-hydroxyethyl methacrylate, butanol, and acid anhydride groups. Continued. The ratio of the absorbance of the absorbance and about 1460 cm -1 to about 1770 cm -1 in the infrared absorption analysis of the solids in the solution to lower the temperature to about 90 ° C. at a stage where almost no change, chlorinated without a allyloxy group A solution having a concentration of polyolefin (b) of about 27% was obtained. The approximate molar ratio of 2-hydroxyethyl methacrylate and butanol reacted with acid anhydride groups was 0.8 / 0.2. Next, air blowing into the liquid phase is stopped, stirring is continued at about 90 ° C. while flowing nitrogen into the gas phase, and one or more compounds selected from (meth) acrylic acid ester, (meth) acrylic acid and styrene ( c) As a mixed solution of 197 parts of methyl methacrylate, 186 parts of cyclohexyl methacrylate, 6 parts of 2-hydroxyethyl acrylate, 10 parts of styrene, 1 part of acrylic acid, 5 parts of perbutyl PV, 189.5 parts of toluene, and 63 parts of butyl acetate Was dropped, the reaction system gelled about 1 hour after the start of dropping, and the production of the polymer composition containing the modified chlorinated polyolefin was stopped.
比較例４
　冷却管のついた４つ口フラスコに「スーパークロン８２２Ｓ」１００部、トルエン７０部、ジ－ｔ－ブチルヒドロキシトルエン（略称：ＢＨＴ）０．０５部を入れ液相に空気を吹きこみながら撹拌し約９５℃に昇温し溶液とした。これに、２－ヒドロキシエチルメタクリレート１１．５部、ブタノール１７部、及び、臭化テトラブチルアンモニウム０．１部を加え、２－ヒドロキシエチルメタクリレート、ブタノール及び、酸無水物基を反応させながら撹拌を続けた。溶液中の固形分の赤外吸光分析において約１７７０cm－１の吸光度と約１４６０cm－１の吸光度の比がほぼ変化しなくなった段階で約９０℃に温度を下げ、さらにトルエン１８０部を添加し、アリロキシ基を有さない塩素化ポリオレフィン（ｂ）の濃度が約２７％である溶液を得た。酸無水物基と反応した２－ヒドロキシエチルメタクリレートとブタノールの概算モル比は、０．１／０．９であった。次に、液相への空気吹き込みをやめ、気相へ窒素を流しながら約９０℃で撹拌を続け、（メタ）アクリル酸エステル、（メタ）アクリル酸及びスチレンから選ばれる１種以上の化合物（ｃ）として、メチルメタクリレート１９７部、シクロヘキシルメタクリレート１８９部、エチレングリコールジメタクリレート２部、スチレン１０部、アクリル酸２部、さらに、パーブチルＰＶ５部、トルエン１８９．５部、酢酸ブチル６３部の混合液を約４時間かけて滴下し、さらにパーブチルＰＶ５部、トルエン７０部の混合液を約１時間かけて滴下し、約１時間撹拌を続けたのち、室温に冷却し、変性塩素化ポリオレフィンを含有するポリマー組成物（Ｐ－２２）を得た。得られた変性塩素化ポリオレフィンを含有するポリマー組成物（Ｐ－２２）の固形分は約４６％であり、樹脂固形分の水酸基価はおよそ９ｍｇＫＯＨ／ｇであった。また、組成物中の塩素化ポリオレフィン骨格とアクリル樹脂骨格の成分比は、約２０／８０であった。 Comparative Example 4
In a four-necked flask equipped with a condenser tube, 100 parts of “Superclone 822S”, 70 parts of toluene and 0.05 part of di-t-butylhydroxytoluene (abbreviation: BHT) are added and stirred while blowing air into the liquid phase. The temperature was raised to about 95 ° C. to obtain a solution. To this, 11.5 parts of 2-hydroxyethyl methacrylate, 17 parts of butanol and 0.1 part of tetrabutylammonium bromide were added, and the mixture was stirred while reacting 2-hydroxyethyl methacrylate, butanol and an acid anhydride group. Continued. The ratio of the absorbance of the absorbance and about 1460 cm -1 to about 1770 cm -1 in the infrared absorption analysis of the solids in the solution to lower the temperature to about 90 ° C. at a stage where almost no change, further added 180 parts of toluene, A solution having a concentration of chlorinated polyolefin (b) having no allyloxy group of about 27% was obtained. The approximate molar ratio of 2-hydroxyethyl methacrylate and butanol reacted with the acid anhydride group was 0.1 / 0.9. Next, air blowing into the liquid phase is stopped, stirring is continued at about 90 ° C. while flowing nitrogen into the gas phase, and one or more compounds selected from (meth) acrylic acid ester, (meth) acrylic acid and styrene ( c) As a mixed solution of 197 parts of methyl methacrylate, 189 parts of cyclohexyl methacrylate, 2 parts of ethylene glycol dimethacrylate, 10 parts of styrene, 2 parts of acrylic acid, 5 parts of perbutyl PV, 189.5 parts of toluene, and 63 parts of butyl acetate. A solution containing 5 parts of perbutyl PV and 70 parts of toluene was added dropwise over about 1 hour, and stirring was continued for about 1 hour, followed by cooling to room temperature, and a polymer containing a modified chlorinated polyolefin. A composition (P-22) was obtained. The obtained polymer composition (P-22) containing the modified chlorinated polyolefin had a solid content of about 46%, and the hydroxyl value of the resin solid content was about 9 mgKOH / g. The component ratio of the chlorinated polyolefin skeleton to the acrylic resin skeleton in the composition was about 20/80.
比較例５
　冷却管のついた４つ口フラスコに「スーパークロン８２２Ｓ」１００部、トルエン７０部、ジ－ｔ－ブチルヒドロキシトルエン（略称：ＢＨＴ）０．０５部を入れ液相に空気を吹きこみながら撹拌し約９５℃に昇温し溶液とした。これに、２－ヒドロキシエチルメタクリレート１１．５部、ブタノール１７部、及び、臭化テトラブチルアンモニウム０．１部を加え、２－ヒドロキシエチルメタクリレート、ブタノール及び、酸無水物基を反応させながら撹拌を続けた。溶液中の固形分の赤外吸光分析において約１７７０cm－１の吸光度と約１４６０cm－１の吸光度の比がほぼ変化しなくなった段階で約９０℃に温度を下げ、さらにトルエン１７２部及び２－ヒドロキシエチルメタクリレート６．８部を添加し、アリロキシ基を有さない塩素化ポリオレフィン（ｂ）の濃度が約２７％である溶液を得た。酸無水物基と反応した２－ヒドロキシエチルメタクリレートとブタノールの概算モル比は、０．１／０．９であった。次に、液相への空気吹き込みをやめ、気相へ窒素を流しながら約９０℃で撹拌を続け、（メタ）アクリル酸エステル、（メタ）アクリル酸及びスチレンから選ばれる１種以上の化合物（ｃ）として、メチルメタクリレート２０６部、シクロヘキシルメタクリレート１８９部、エチレングリコールジメタクリレート２部、メタクリル酸３部、さらに、パーブチルＰＶ５部、トルエン１８９．５部、酢酸ブチル６３部の混合液を約４時間かけて滴下し、さらにパーブチルＰＶ５部、トルエン７０部の混合液を約１時間かけて滴下し、約１時間撹拌を続けたのち、室温に冷却し、変性塩素化ポリオレフィンを含有するポリマー組成物（Ｐ－２３）を得た。得られた変性塩素化ポリオレフィンを含有するポリマー組成物（Ｐ－２３）の固形分は約４６％であり、樹脂固形分の水酸基価はおよそ１５ｍｇＫＯＨ／ｇであった。また、組成物中の塩素化ポリオレフィン骨格とアクリル樹脂骨格の成分比は、約２０／８０であった。 Comparative Example 5
In a four-necked flask equipped with a condenser tube, 100 parts of “Superclone 822S”, 70 parts of toluene and 0.05 part of di-t-butylhydroxytoluene (abbreviation: BHT) are added and stirred while blowing air into the liquid phase. The temperature was raised to about 95 ° C. to obtain a solution. To this, 11.5 parts of 2-hydroxyethyl methacrylate, 17 parts of butanol and 0.1 part of tetrabutylammonium bromide were added, and the mixture was stirred while reacting 2-hydroxyethyl methacrylate, butanol and an acid anhydride group. Continued. The ratio of the absorbance of the absorbance and about 1460 cm -1 to about 1770 cm -1 in the infrared absorption analysis of the solids in the solution to lower the temperature to about 90 ° C. at a stage where almost no change, 172 parts of toluene and 2-hydroxyethyl 6.8 parts of ethyl methacrylate was added to obtain a solution having a concentration of about 27% of the chlorinated polyolefin (b) having no allyloxy group. The approximate molar ratio of 2-hydroxyethyl methacrylate and butanol reacted with the acid anhydride group was 0.1 / 0.9. Next, air blowing into the liquid phase is stopped, stirring is continued at about 90 ° C. while flowing nitrogen into the gas phase, and one or more compounds selected from (meth) acrylic acid ester, (meth) acrylic acid and styrene ( c) As a mixture of 206 parts of methyl methacrylate, 189 parts of cyclohexyl methacrylate, 2 parts of ethylene glycol dimethacrylate, 3 parts of methacrylic acid, and 5 parts of perbutyl PV, 189.5 parts of toluene and 63 parts of butyl acetate, it takes about 4 hours. Further, a mixed solution of 5 parts of perbutyl PV and 70 parts of toluene was dropped over about 1 hour, and stirring was continued for about 1 hour, followed by cooling to room temperature and a polymer composition containing modified chlorinated polyolefin (P -23) was obtained. The obtained polymer composition (P-23) containing the modified chlorinated polyolefin had a solid content of about 46%, and the hydroxyl value of the resin solid content was about 15 mgKOH / g. The component ratio of the chlorinated polyolefin skeleton to the acrylic resin skeleton in the composition was about 20/80.
比較例６
　冷却管のついた４つ口フラスコに「ハードレンＦ－６Ｐ」５０部、トルエン７０部、ジ－ｔ－ブチルヒドロキシトルエン（略称：ＢＨＴ）０．０５部を入れ液相に空気を吹きこみながら撹拌し約９５℃に昇温し溶液とした。これに、２－ヒドロキシエチルメタクリレート１１．５部、ブタノール１６部、２－エチルヘキサノール１部及び、臭化テトラブチルアンモニウム０．１部を加え、２－ヒドロキシエチルメタクリレート、ブタノール、２－エチルヘキサノール及び、酸無水物基を反応させながら撹拌を続けた。溶液中の固形分の赤外吸光分析において約１７７０cm－１の吸光度と約１４６０cm－１の吸光度の比がほぼ変化しなくなった段階で約９０℃に温度を下げ、さらにトルエン１８０部を添加し、アリロキシ基を有さない塩素化ポリオレフィン（ｂ）の濃度が約１６％である溶液を得た。酸無水物基と反応した２－ヒドロキシエチルメタクリレートとそれ以外のアルコールの概算モル比は、０．１／０．９であった。次に、液相への空気吹き込みをやめ、気相へ窒素を流しながら約９０℃で撹拌を続け、（メタ）アクリル酸エステル、（メタ）アクリル酸及びスチレンから選ばれる１種以上の化合物（ｃ）として、メチルメタクリレート２１４部、シクロヘキシルメタクリレート２２２部、スチレン１０部、エチレングリコールジメタクリレート２部、アクリル酸２部、さらに、パーブチルＰＶ５部、トルエン１８９．５部、酢酸ブチル６３部の混合液を約４時間かけて滴下し、さらにパーブチルＰＶ５部、トルエン７０部の混合液を約１時間かけて滴下し、約１時間撹拌を続けたのち、室温に冷却し、変性塩素化ポリオレフィンを含有するポリマー組成物（Ｐ－２４）を得た。得られた変性塩素化ポリオレフィンを含有するポリマー組成物（Ｐ－２４）の固形分は約４６％であり、樹脂固形分の水酸基価はおよそ９ｍｇＫＯＨ／ｇであった。また、組成物中の塩素化ポリオレフィン骨格とアクリル樹脂骨格の成分比は、約１０／９０であった。
塗料組成物の製造 Comparative Example 6
In a four-necked flask equipped with a condenser tube, 50 parts of “Hardylene F-6P”, 70 parts of toluene and 0.05 part of di-t-butylhydroxytoluene (abbreviation: BHT) are placed and stirred while blowing air into the liquid phase. The temperature was raised to about 95 ° C. to obtain a solution. To this, 11.5 parts of 2-hydroxyethyl methacrylate, 16 parts of butanol, 1 part of 2-ethylhexanol and 0.1 part of tetrabutylammonium bromide were added, and 2-hydroxyethyl methacrylate, butanol, 2-ethylhexanol and Stirring was continued while the acid anhydride group was reacted. The ratio of the absorbance of the absorbance and about 1460 cm -1 to about 1770 cm -1 in the infrared absorption analysis of the solids in the solution to lower the temperature to about 90 ° C. at a stage where almost no change, further added 180 parts of toluene, A solution having a concentration of chlorinated polyolefin (b) having no allyloxy group of about 16% was obtained. The approximate molar ratio of 2-hydroxyethyl methacrylate reacted with the acid anhydride group to the other alcohol was 0.1 / 0.9. Next, air blowing into the liquid phase is stopped, stirring is continued at about 90 ° C. while flowing nitrogen into the gas phase, and one or more compounds selected from (meth) acrylic acid ester, (meth) acrylic acid and styrene ( c) As a mixture of 214 parts of methyl methacrylate, 222 parts of cyclohexyl methacrylate, 10 parts of styrene, 2 parts of ethylene glycol dimethacrylate, 2 parts of acrylic acid, 5 parts of perbutyl PV, 189.5 parts of toluene, and 63 parts of butyl acetate. A solution containing 5 parts of perbutyl PV and 70 parts of toluene was added dropwise over about 1 hour, and stirring was continued for about 1 hour, followed by cooling to room temperature, and a polymer containing a modified chlorinated polyolefin. A composition (P-24) was obtained. The obtained polymer composition (P-24) containing the modified chlorinated polyolefin had a solid content of about 46%, and the hydroxyl value of the resin solid content was about 9 mgKOH / g. The component ratio of the chlorinated polyolefin skeleton to the acrylic resin skeleton in the composition was about 10/90.
Manufacture of paint compositions
実施例１９
　実施例１で得た変性塩素化ポリオレフィンを含有するポリマー組成物（Ｐ－１）１００部及び「スミジュールＮ３３００」（商品名、住化コベストロウレタン社製、ヘキサメチレンジイソシアネートのイソシアヌレート体、固形分含有率１００％、イソシアネート含有量２１．６ｗｔ％）３．２部を均一に混合した配合組成に、触媒としてジブチル錫ジラウレート０．１５部を添加してさらにトルエンと酢酸ブチルを添加して粘度を調整し、２０℃におけるフォードカップＮｏ．４による粘度が約３０秒の塗料組成物Ｎｏ．１を得た。なお、上記「スミジュールＮ３３００」中のイソシアネート基と上記変性塩素化ポリオレフィンを含有するポリマー組成物（Ｐ－１）中の樹脂成分中の水酸基との当量比（ＮＣＯ／ＯＨ）は約１．８であった。 Example 19
100 parts of a polymer composition (P-1) containing the modified chlorinated polyolefin obtained in Example 1 and “Sumidule N3300” (trade name, manufactured by Sumika Covestro Urethane Co., Ltd., isocyanurate of hexamethylene diisocyanate, solid Viscosity by adding 0.15 part of dibutyltin dilaurate as a catalyst and further adding toluene and butyl acetate to a blended composition in which 3.2 parts of a uniform content of 100% and isocyanate content of 21.6 wt% were mixed uniformly. Ford cup No. 20 at 20 ° C. No. 4 coating composition No. having a viscosity of about 30 seconds. 1 was obtained. The equivalent ratio (NCO / OH) of the isocyanate group in the “Sumidule N3300” to the hydroxyl group in the resin component in the polymer composition (P-1) containing the modified chlorinated polyolefin is about 1.8. Met.
実施例２０～３６及び比較例７～１２
　実施例１９において、変性塩素化ポリオレフィンを含有するポリマー組成物とポリイソシアネート化合物の配合組成を後記の表１に示すものとする以外は、実施例１９と同様にして、２０℃におけるフォードカップＮｏ．４による粘度が３０秒の各塗料組成物Ｎｏ．２～２４を得た。また、比較例７～９は原料である変性塩素化ポリオレフィンを含有するポリマー組成物（「Ｐ－１９」～「Ｐ－２１」）が製造できなかったため、塗料組成物は製造しなかった。 Examples 20 to 36 and Comparative Examples 7 to 12
In Example 19, the Ford Cup No. 20 at 20 ° C. was used in the same manner as in Example 19 except that the composition of the polymer composition containing the modified chlorinated polyolefin and the polyisocyanate compound was as shown in Table 1 below. 4 with a viscosity of 30 seconds according to each coating composition No. 2-24 were obtained. In Comparative Examples 7 to 9, a polymer composition (“P-19” to “P-21”) containing modified chlorinated polyolefin as a raw material could not be produced, and thus a coating composition was not produced.
　上記で得られた各塗料組成物について、下記の試験方法により評価を行なった。評価結果を塗料組成と併せて表１に示す。 Each coating composition obtained above was evaluated by the following test method. The evaluation results are shown in Table 1 together with the paint composition.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
試験方法
　製造安定性：変性塩素化ポリオレフィンを含有するポリマー組成物が製造できた場合を○とし、製造できなかった場合を×とした。
　硬化性（ゲル分率）：ガラス板上に各塗料組成物を乾燥膜厚が４０μｍとなるように塗装し、９０℃で３０分間加熱乾燥する。次に、該ガラス板上の塗膜を回収し、質量（Ｗａ）を測定する。その後、該塗膜を２００メッシュのステンレススチール製の網状容器に入れ、約５６℃に加温したアセトン中で１時間還流させながら抽出し、１００℃で１時間乾燥した後の塗膜質量（Ｗｂ）を測定し、以下の式に従って算出される不溶塗膜残存率（質量％）をゲル分率とし、下記基準で硬化性を評価した。
ゲル分率（質量％）＝（Ｗｂ／Ｗａ）×１００
　Ａ：ゲル分率が７０％以上
　Ｂ：ゲル分率が６０％以上７０％未満
　Ｃ：ゲル分率が５０％以上６０％未満
　Ｄ：ゲル分率が３０％以上５０％未満
　Ｅ：ゲル分率が３０％未満 Test method Production stability: The case where the polymer composition containing the modified chlorinated polyolefin could be produced was marked with ◯, and the case where the polymer composition could not be produced was marked with x.
Curability (gel fraction): Each coating composition is applied onto a glass plate so that the dry film thickness is 40 μm, and is dried by heating at 90 ° C. for 30 minutes. Next, the coating film on this glass plate is collect | recovered and mass (Wa) is measured. Thereafter, the coating film was placed in a 200-mesh stainless steel mesh container, extracted while refluxing in acetone heated to about 56 ° C. for 1 hour, and dried at 100 ° C. for 1 hour. ) Was measured, and the insoluble coating film residual ratio (mass%) calculated according to the following formula was used as the gel fraction, and the curability was evaluated according to the following criteria.
Gel fraction (mass%) = (Wb / Wa) × 100
A: Gel fraction is 70% or more B: Gel fraction is 60% or more and less than 70% C: Gel fraction is 50% or more and less than 60% D: Gel fraction is 30% or more and less than 50% E: Gel fraction Is less than 30%

Claims (8)

  1. 　アリロキシ基と水酸基とを有する化合物（ａ）の共存下で、アリロキシ基を有する塩素化ポリオレフィン（ｂ）、及び、（メタ）アクリル酸エステル、（メタ）アクリル酸及びスチレンから選ばれる１種以上の化合物（ｃ）を含む重合性モノマーを共重合させて、変性塩素化ポリオレフィンを得る工程を含む、変性塩素化ポリオレフィンを含有するポリマー組成物の製造方法。 In the coexistence of the compound (a) having an allyloxy group and a hydroxyl group, the chlorinated polyolefin (b) having an allyloxy group and one or more selected from (meth) acrylic acid ester, (meth) acrylic acid and styrene A method for producing a polymer composition containing a modified chlorinated polyolefin, comprising a step of copolymerizing a polymerizable monomer containing the compound (c) to obtain a modified chlorinated polyolefin.
  2. 　前記アリロキシ基と水酸基を有する化合物（ａ）が、下記一般式（Ｉ）
    Figure JPOXMLDOC01-appb-C000001
     （式中、Ｒ１及びＲ２はそれぞれ独立して炭素数２又は３の分岐していてもよいアルキレン基を示し、ｍ、ｎはそれぞれ独立して０～５０の実数で、かつ、ｍとｎの和は１以上である実数を示し、ブロック構造でもランダム構造であってもよい。）
    で表される化合物である、請求項１記載の方法。     The compound (a) having an allyloxy group and a hydroxyl group is represented by the following general formula (I):
    Figure JPOXMLDOC01-appb-C000001
     (Wherein R 1 and R 2 each independently represents an alkylene group having 2 or 3 carbon atoms which may be branched, m and n are each independently a real number of 0 to 50, and (The sum of n represents a real number equal to or greater than 1, and may be a block structure or a random structure.)
    The method of Claim 1 which is a compound represented by these.
  3. 　前記アリロキシ基を有する塩素化ポリオレフィン（ｂ）が、酸無水物基を有する塩素化ポリオレフィン（ｄ）と前記一般式（Ｉ）で表わされるアリロキシ基と水酸基を有する化合物（ａ）を付加反応させて得られる、請求項１又は２に記載の方法。 The chlorinated polyolefin (b) having an allyloxy group is subjected to an addition reaction between the chlorinated polyolefin (d) having an acid anhydride group and the compound (a) having an allyloxy group and a hydroxyl group represented by the general formula (I). The method according to claim 1 or 2, which is obtained.
  4. 　前記アリロキシ基と水酸基を有する化合物（ａ）が、アリロキシエタノールである、請求項１～３のいずれか一項に記載の方法。 The method according to any one of claims 1 to 3, wherein the compound (a) having an allyloxy group and a hydroxyl group is allyloxyethanol.
  5. 　アリロキシ基と水酸基とを有する化合物（ａ）の共存下で、アリロキシ基を有する塩素化ポリオレフィン（ｂ）、及び、（メタ）アクリル酸エステル、（メタ）アクリル酸及びスチレンから選ばれる１種以上の化合物（ｃ）を含む重合性モノマーを共重合させて得られる、変性塩素化ポリオレフィンを含有するポリマー組成物。 In the coexistence of the compound (a) having an allyloxy group and a hydroxyl group, the chlorinated polyolefin (b) having an allyloxy group and one or more selected from (meth) acrylic acid ester, (meth) acrylic acid and styrene A polymer composition containing a modified chlorinated polyolefin obtained by copolymerizing a polymerizable monomer containing the compound (c).
  6. 　請求項５に記載のポリマー組成物と、水酸基との反応性を有する架橋剤とを含む、硬化性組成物。 A curable composition comprising the polymer composition according to claim 5 and a crosslinking agent having reactivity with a hydroxyl group.
  7. 　請求項５に記載のポリマー組成物を含む、塗料組成物。 A coating composition comprising the polymer composition according to claim 5.
  8. 　水酸基との反応性を有する架橋剤をさらに含む、請求項７に記載の塗料組成物。 The coating composition according to claim 7, further comprising a crosslinking agent having reactivity with a hydroxyl group.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019082903A1 (en) * 2017-10-25 2019-05-02 日本製紙株式会社 Modified polyolefin resin composition and production method therefor

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111906871B (en) * 2020-08-14 2022-01-14 潍坊恒远新材料科技有限公司 Wood reinforcing, toughening and flame-retardant modifier and preparation method thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5996136A (en) * 1982-11-25 1984-06-02 Dainippon Ink & Chem Inc Resin composition for paint
JPH04161334A (en) * 1990-10-25 1992-06-04 Mitsubishi Petrochem Co Ltd Manufacture of laminate
JPH06199918A (en) * 1992-12-28 1994-07-19 Nippon Paper Ind Co Ltd Aqueous resin composition
JPH0859757A (en) * 1994-08-22 1996-03-05 Kansai Paint Co Ltd Resin composition for aqueous coating material
JP2002309161A (en) * 2001-04-11 2002-10-23 Toyo Kasei Kogyo Co Ltd Coating composition for polyolefinic resin and its manufacturing method
JP2015003991A (en) * 2013-06-20 2015-01-08 東レ・ファインケミカル株式会社 Coating modified chlorinated polyolefin resin composition and method for producing the same
JP2015059182A (en) * 2013-09-19 2015-03-30 新中村化学工業株式会社 Resin composition, adhesive, and method for producing resin composition

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6392041B1 (en) * 1999-02-25 2002-05-21 Ciba Specialty Chemicals Corporation Hydroxy-substituted N-alkoxy hindered amines and compositions stabilized therewith
JP4508635B2 (en) * 2003-12-26 2010-07-21 リンテック株式会社 Hard coat film for image display device
EP1801086A1 (en) * 2005-11-25 2007-06-27 Synthacon GmbH Synthesis of carbon acid amides
CN101402704A (en) * 2008-11-14 2009-04-08 沂源瑞丰高分子材料有限公司 Uses of allyloxy hydroxide sodium dimercaptosulphanate in PVC processing aid
CN103333571B (en) * 2013-06-24 2015-12-02 广州慧谷化学有限公司 For the waterborne antibacterial mildew-proof hydrophilic coating of heat exchanger fin surfaces process
CN105693939B (en) * 2014-11-28 2019-03-29 合众（佛山）化工有限公司 A kind of preparation method of the SMA modified cation acrylic acid ester emulsion of priming paint
CN105111361B (en) * 2015-09-10 2018-05-25 江南大学 A kind of preparation method for drawing timber-used Nano-grade latex mill base

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5996136A (en) * 1982-11-25 1984-06-02 Dainippon Ink & Chem Inc Resin composition for paint
JPH04161334A (en) * 1990-10-25 1992-06-04 Mitsubishi Petrochem Co Ltd Manufacture of laminate
JPH06199918A (en) * 1992-12-28 1994-07-19 Nippon Paper Ind Co Ltd Aqueous resin composition
JPH0859757A (en) * 1994-08-22 1996-03-05 Kansai Paint Co Ltd Resin composition for aqueous coating material
JP2002309161A (en) * 2001-04-11 2002-10-23 Toyo Kasei Kogyo Co Ltd Coating composition for polyolefinic resin and its manufacturing method
JP2015003991A (en) * 2013-06-20 2015-01-08 東レ・ファインケミカル株式会社 Coating modified chlorinated polyolefin resin composition and method for producing the same
JP2015059182A (en) * 2013-09-19 2015-03-30 新中村化学工業株式会社 Resin composition, adhesive, and method for producing resin composition

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019082903A1 (en) * 2017-10-25 2019-05-02 日本製紙株式会社 Modified polyolefin resin composition and production method therefor
JPWO2019082903A1 (en) * 2017-10-25 2020-09-24 日本製紙株式会社 Modified polyolefin resin composition and method for producing the same
US11518838B2 (en) 2017-10-25 2022-12-06 Nippon Paper Industries Co., Ltd. Modified polyolefin resin composition and method for producing the same
JP7265483B2 (en) 2017-10-25 2023-04-26 日本製紙株式会社 Modified polyolefin resin composition and method for producing the same

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