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WO2018155309A1 - Composition polymère contenant une polyoléfine chlorée modifiée et son procédé de production - Google Patents

Composition polymère contenant une polyoléfine chlorée modifiée et son procédé de production 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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Prior art keywords
parts
chlorinated polyolefin
group
compound
meth
Prior art date
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PCT/JP2018/005329
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English (en)
Japanese (ja)
Inventor
小畑　政示
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Kansai Paint Co Ltd
Original Assignee
Kansai Paint Co Ltd
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/ja
Application filed by Kansai Paint Co Ltd filed Critical Kansai Paint Co Ltd
Priority to CN201880013006.9A priority Critical patent/CN110325563B/zh
Priority to US16/488,483 priority patent/US10968304B2/en
Publication of WO2018155309A1 publication Critical patent/WO2018155309A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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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    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
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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
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    • 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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    • C08F216/12—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
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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
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    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
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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
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    • C08F8/14—Esterification
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
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    • 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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    • C08G18/06—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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    • C08G18/06—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
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    • 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
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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
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    • C—CHEMISTRY; METALLURGY
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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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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Paints Or Removers (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne : un procédé de production d'une composition polymère contenant une polyoléfine chlorée modifiée, qui présente une excellente stabilité de production ; et un matériau de revêtement la contenant. La composition polymère contenant une polyoléfine chlorée modifiée selon l'invention est obtenue par copolymérisation de monomères polymérisables comprenant (b) une polyoléfine chlorée ayant un groupe allyloxy et (c) un ou plusieurs composés choisis parmi les esters d'acides (méth)acryliques, les acides (méth)acryliques et le styrène en présence de (a) un composé ayant un groupe allyloxy et un groupe hydroxyle.
PCT/JP2018/005329 2017-02-24 2018-02-15 Composition polymère contenant une polyoléfine chlorée modifiée et son procédé de production Ceased WO2018155309A1 (fr)

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