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WO2006038493A1 - Composition hydrofuge et oléorésistante contenant du fluor - Google Patents

Composition hydrofuge et oléorésistante contenant du fluor Download PDF

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Publication number
WO2006038493A1
WO2006038493A1 PCT/JP2005/017739 JP2005017739W WO2006038493A1 WO 2006038493 A1 WO2006038493 A1 WO 2006038493A1 JP 2005017739 W JP2005017739 W JP 2005017739W WO 2006038493 A1 WO2006038493 A1 WO 2006038493A1
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Prior art keywords
polymer
fluorine
monomer
group
water
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PCT/JP2005/017739
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English (en)
Japanese (ja)
Inventor
Hitoharu Hachisuka
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Daikin Industries, Ltd.
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Publication date
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Priority to JP2006539231A priority Critical patent/JP4930058B2/ja
Publication of WO2006038493A1 publication Critical patent/WO2006038493A1/fr

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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • 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
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C09D133/16—Homopolymers or copolymers of esters containing halogen atoms

Definitions

  • the present invention relates to a water / oil repellent composition capable of imparting excellent water / oil repellency to an object to be treated.
  • an addition-polymerizable monomer containing a polyfluoroalkyl group (hereinafter, polyfluoroalkyl group is referred to as R f group) (hereinafter, the addition-polymerizable monomer is simply referred to as monomer).
  • R f group polyfluoroalkyl group
  • monomer the addition-polymerizable monomer
  • a polymerization unit (hereinafter, the term polymer is used in the meaning of homopolymer and copolymer) is treated as an organic solvent solution or an aqueous dispersion on textiles, paper, etc. A technique for imparting water repellency and oil repellency to these surfaces is known.
  • an aqueous medium dispersion in which a polymer having a monomer having the structure of formula (1) as a polymerization unit is dispersed in an aqueous medium is water repellent. It is widely used as an oil agent composition.
  • n is an integer of 6 to about 12
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents a hydrogen atom, a methyl group or an ethyl group.
  • n in the formula (1) that is, the number of carbon atoms of the perfluoroalkyl group is substantially 8 or more.
  • Such a carbon number of 8 or more Pafuruo port alkyl group (hereinafter, carbon atoms referred to 8 or more per full O b alkyl long chain R F group.)
  • the polymer having as a side chain, long chain R It is known that there is a microcrystalline melting point derived from the F group.
  • the strong crystallinity of the long-chain group effectively aligns the surface of the long-chain group.
  • a polymer having a polymer having a structure of formula (1) as a polymer unit is a major factor that has excellent water and oil repellency. It is said that there is.
  • monomers which contain long chain R F group as a side chain (hereinafter, referred to monomer containing a long chain R F group as a side chain crystalline R F group-containing monomer.) Is generally in the other Since the compatibility with the monomer is extremely poor, many organic solvents are required to obtain a homogeneous copolymer. In addition, it is known that when a textile product or the like is treated with a polymer containing them, the flexible texture of the object to be treated is likely to be impaired due to the strong side chain crystallinity of the long chain group.
  • the melting point derived from the crystallites of the R F group Among crystalline R F group-containing monomer High (usually 70 ° C or higher) crystalline R F group-containing monomer is indispensable.
  • the ozone layer such as a water-based and oil-repellent medium mainly composed of water, an alcohol-based solvent, a petroleum-based solvent called a weak solvent, or a hydrofluorocarbon.
  • a water-based and oil-repellent medium mainly composed of water, an alcohol-based solvent, a petroleum-based solvent called a weak solvent, or a hydrofluorocarbon.
  • the use of fluorinated solvents that are less affected by this is required.
  • water and oil repellents mainly composed of polymers composed of conventional crystalline group-containing monomers, from the viewpoint of solubility, dispersibility, etc., so-called strong compounds such as aromatics, ketones, esters, etc.
  • a fluorine-based solvent that has a large influence on the ozone layer, such as a solvent, a chlorine-based solvent, and black fluorocarbon.
  • polyatarylate poly having perfluoropolyether chains Ma W02_103103, W003_99904.
  • Polymers consisting of monomers containing R f groups with 6 or less carbon atoms include fluorine with side-chain crystallinity.
  • Copolymer with a monomer (WO02-83809), copolymer with a monomer without an Rf group having a crosslinkable functional group (WO04-35708), a sulfone containing an Rf group having a carbon number of less than
  • amide acrylate (Special Table 2003-513123)
  • copolymers with vinylidene chloride or butyl chloride (WO03-62521).
  • no water- and oil-repellent agents that give satisfactory practical performance have been found.
  • a technique using a mixture of a plurality of polymers and a technique using composite particles of a plurality of polymers are known. It is.
  • the durability is improved and the crosslinkable polymer containing a blocked isocyanate group is used as a blender or polymer extender (Japanese Patent Laid-Open Seki 54-128992, JP 10-501306), and polyamine polymers mixed with cationic polymers (JP 6-49319, JP 2002-220539).
  • a homopolymer has a non-fluorine-based mode having a specific glass transition temperature (T).
  • a technique for preparing a copolymer containing a noma is known. For example, if the homopolymer ⁇ is
  • Copolymers containing non-fluorinated monomers as polymerized units at a temperature below JP 60152585, JP 9 328677, such that the T of the homopolymer is above a specific temperature
  • Copolymers containing non-fluorinated monomers as polymerized units Japanese Patent Laid-Open Nos. 62-577 and 63-2 7585, as well as non-fluorinated monomers and monomers having a T above a specific temperature.
  • Copolymers contained therein Japanese Patent Laid-Open No. 53-50078
  • a water- and oil-repellent agent containing composite particles containing a monomer whose homopolymer T is not lower than a specific temperature as a polymerization unit may be used.
  • An object of the present invention is to provide a water / oil repellent composition that can be used as a substitute for a water / oil repellent containing a compound having the structure of the above formula (1) as a polymerized unit. That is, the polymer component despite being composed of only a polymer containing no crystalline R F group-containing monomer as polymerized units, water- and oil-repellent agent which can impart excellent water and oil repellency to a substrate pairs To provide a composition.
  • the present invention provides:
  • a polymer having as a unit, as well as polymer is (a 1) the amount of (a 1) and (a 2) a total of 50 mass 0/0 or more with respect to the
  • a Lima, quantity (a 1) and (a 2) Total fluorinated water repellent oil repellent composition comprising a polymer in excess of 50 mass 0/0 for in (a 2)
  • the present inventor has studied in detail the mechanism of the water and oil repellency and its strengthening method. As a result, the homopolymer has a T (glass transition temperature) of 50 ° C or higher.
  • a fluorine-containing monomer having a T of less than 50 ° C is referred to as “low T-containing F monomer”.
  • a copolymer with more than 50% by mass of the copolymer for example, 55% by mass or more, particularly 60% by mass or more, particularly 80% by mass or more and 100% by mass or less
  • the base material can be provided with performance that exceeds water repellency and the balance between water repellency and oil repellency, when used alone, and excellent repellent properties can be obtained without using a crystalline group-containing monomer.
  • the above-mentioned problem of imparting water / oil repellency to an object to be treated has been solved, and the invention has been completed.
  • the reason why water / oil repellency is improved by the above polymer blend is not necessarily clear, but the most reasonable explanation is as follows. It is.
  • the surface of the fibers constituting the cloth is (a) a region where the fibers are in contact with each other, and (b) a contact between the fibers.
  • the oil contact angle on the surface treated with the water / oil repellent agent is smaller than that of water, and it is considered that the oil is uniformly in contact with the surface of the cloth in the oil repellency test. Therefore, the presence or absence of minute defects in the water / oil repellent polymer film formed on the fiber greatly affects its oil repellency.
  • the mechanical load is easily exerted, so that defects in the polymer coating are likely to occur. Therefore, it is important to reduce the defects of the polymer film in this region in order to improve the oil repellency.
  • amorphous polymers are hard and brittle at temperatures below T, so fabrics are treated with high T polymers.
  • the polymer existing in the (a) region has a very high T and is somewhat softer than desirable.
  • Polymers that are essential constituents have low fluidity, so it is considered that most of them remain in the region (b). That is, a polymer mainly composed of a high T-containing F monomer and a low T-containing F
  • the conventional technology using a combination of different polymers in the water / oil repellent is based on the concept of role sharing at the interface between the outermost surface and the substrate in the water / oil repellent polymer film. While many cases can be explained, this is difficult to explain in the present invention, and can only be understood by assuming a completely new principle as described above.
  • T in the homopolymer of the F-containing monomer constituting the polymer is water- and oil-repellent in the polymer chain.
  • the temperature of 50 ° C, which separates the high Tg monomer from the low Tg monomer, is considered reasonable in that respect.
  • the water / oil repellent composition according to the present invention is conventionally required to obtain sufficient water / oil repellent performance, and does not have a long-chain RF group. There is no concern about a decrease in texture due to chain crystallinity, and excellent water and oil repellency can be imparted to the substrate. In particular, it is possible to achieve both water repellency and oil repellency for textile products.
  • the water / oil repellent composition of the present invention comprises a polymer (A) and a polymer (B) as essential components, and if necessary, an aqueous medium (C), a surfactant (D), an organic solvent (E ), A thermosetting agent (F), other poly 7 (G) (for example, non-fluorine polymer), an additive and the like.
  • the ratio of the polymer (A) and the polymer (B) in the water / oil repellent composition is such that the ratio of the polymer (A) to the total amount of the polymer (A) and the polymer (B) is 5 to 95% by mass, for example It may be 10-90% by weight, especially 20-80% by weight.
  • “parts” or “%” means “parts by mass” or “mass%” unless otherwise specified.
  • the polymer (A) and the polymer (B) need not be a single polymer, but may be a combination of two or more types of polymers.
  • the polymer (A) is a polymer containing a monomer (a) containing fluorine in the molecule, a polymer containing a fluorine atom in the molecule, and a monomer (b) as necessary.
  • the proportion of the monomer (b) is less than 40 mass 0/0, such as less than 20 wt%.
  • the proportion of monomer (b) in polymer (A) may be 0% by mass.
  • the lower limit of the proportion of the polymer monomers in (A) (b) is 0.1 mass 0/0, may in particular 1% by weight.
  • the polymer (B) is a polymer containing a monomer (a) containing fluorine in the molecule and a monomer (b) containing no fluorine atom in the molecule as necessary.
  • the proportion of the monomer (b) is 70%. Less than, for example, less than 50% by weight, especially less than 30% by weight.
  • the proportion of monomer (b) in polymer (B) may be 0% by mass.
  • the lower limit of the proportion of monomer (b) in polymer (A) may be 0.1% by weight, in particular 1% by weight.
  • the monomer (a) contained in the polymer (A) has a high T-containing F monomer (a 1 ) and, if necessary, a low T gg-containing F monomer (a 2 ) force.
  • the proportion of monomer (a 2 ) in the monomer (a) constituting the polymer (A) is less than 50% by mass, for example less than 35% by mass, in particular less than 20% by mass.
  • the proportion of the polymer (A) monomer to total monomers constituting (a) the (a 2) is 0 mass% or more, for example 5 wt% or more, it may be in particular 10 mass 0/0 above.
  • the monomer (a) contained in the polymer (B) comprises a low T-containing F g monomer (a 2 ) and, if necessary, a high T-containing F monomer (a 1 ). Construct polymer (B)
  • the proportion of monomer (a 1 ) in monomer (a) is less than 50% by weight, for example less than 35% by weight, in particular less than 20% by weight.
  • the proportion of the monomer (a 1 ) in the monomer (a) constituting the polymer (B) may be 0% by mass or more, for example, 5% by mass or more, particularly 10% by mass or more.
  • the monomer (a 1 ), monomer (a 2 ), and monomer (b) used in the polymer (A) or polymer (B) are each composed of two or more types of monomer forces even if they are a single monomer. Also good.
  • the monomer (a 1 ), monomer (a 2 ), and monomer (b) used for the polymer (B) may be the same as, or partially the same as, those used for the polymer (A). It doesn't matter.
  • the polymer (A) and the polymer (B) are copolymers, they are not limited to random copolymers, and may be blocks, graft copolymers, and the like.
  • the monomer composition is such that the average value of the polymer satisfies the above conditions.
  • the homopolymer T is the DSC g described in differential calorimetry tiIS _K_ 7121 _ 1987.
  • the molecular weight of the homopolymer here is about 10,000 or more. This is because if the molecular weight of the homopolymer is 10,000 or more, the T of the homopolymer hardly depends on the molecular weight.
  • the T-force of the homopolymer from the side chain amorphous fluorine-containing monomer (a a ) or the T-force of the homopolymer is 0 ° C or higher. Less than 0 ° C
  • One or more monomers can be selected and used Side chain amorphous fluorine-containing monomer (a a ) is a direct or bonded bond of monovalent or divalent polymerizable unsaturated group and one or more amorphous R f groups (R fa groups).
  • the compound is indirectly bonded through a group, and is preferably indirectly bonded.
  • the polymerizable unsaturated group an alkylene group, particularly an ethylene group is preferable.
  • the amorphous R f group (R fa group) as used herein is generally a perfluoroalkyl group having 6 or less carbon atoms, or 30 or less carbon atoms, such as 20 or less carbon atoms, particularly 10 carbon atoms.
  • the carbon number of the perfluoroalkyl group may be 1 or more, for example, 2 or more.
  • the carbon number of the perfluoro (poly) ether group may be 3 or more, for example, 5 or more.
  • the perfluoro (poly) ether group is preferably represented by the structure of the following formula (2). FR fPFPE- [CF (CF)]-(CF)-(2)
  • R fPFPE represents the perfluoropolyether chain structure, [CF (CF) CF ⁇ ] [CF CFCF ⁇ ] [CF CF O] [CF O].
  • a preferred side chain amorphous fluorine-containing monomer (a a ) can be represented by the following general formula (3).
  • n 1 or 2
  • X is a polymerizable unsaturated group
  • ⁇ represents a substituted or unsubstituted phenylene group. Is a hydrogen atom, halogen atom, cyano group, alkyl group having 1 to 6 carbon atoms, halogen-substituted alkyl group having carbon atoms:! To 6 or phenyl group. or represents a base Njinore group
  • R b is a hydrogen atom, the number of carbon atoms:.! represents an alkyl group or phenylene Le group 1-6).
  • R fa is the above-mentioned amorphous R f group
  • Y is a divalent organic group or a single bond.
  • a preferred structure of Y which is a divalent organic group can be represented by the following formula (4). -(CH) T (CH) (CHR a )-(4)
  • R a is the same as described above.
  • T is a single bond
  • _CH CH-, -CONR b-, -OCONR b -,-SO NR b -,-SO one, one NHCONH-, -CH (OH)-
  • side chain amorphous fluorine-containing monomers (a a )
  • a compound in which the side chain mobility is limited due to short side chains or branching, particularly its metatalylate and ⁇ Rogen-substituted attalylates have a homopolymer wrinkle of 50 ° C or higher.
  • side chain amorphous g (a a )
  • the glass transition temperature T is lower than T.
  • T can be considered to be 50 ° C or less even when no clear transition point is found by the above DSC measurement method.
  • T force 5 of monomer (a 1 ). C or more, for example 60 to: 160. Be C.
  • T of the monomer (a 2 ) is gg
  • a monomer (a 2 ) homopolymer may be in a molten state at room temperature.
  • the T of the monomer (a 2 ) is, for example, _100. C ⁇ +45. C, especially _80. C ⁇ + 40. G in C
  • F (CF) (CH) OCOCCl CH (T: 45 ° C)
  • F (CF) (CH) OCOCH CH (T: 42 ° C)
  • the polymer (A) and the polymer (B) may be a copolymer containing a monomer containing a fluorine atom other than the monomer (a) or a copolymerizable monomer (b) singly or in combination.
  • a polymer can also be used.
  • Examples of the copolymerizable monomer (b) include the following (hereinafter, acrylate, methacrylate and ⁇ -halogen (for example, black mouth) substituted acrylate are generically named. This is also referred to as attalylate analog, and the same applies to acrylamide analog, acrylic acid analog, etc.) That is, an acrylate analog; an acrylamide analog (b 1 ); an acrylonitrile analog; a 2-alkyl ether (halogenated alkyl) vinyl ether; an ethylene, propylene, isoprene, butene, dodecylethylene, heter Olefins and gens such as xene and butadiene; halogen-substituted ethylenes such as vinyl chloride, vinyl bromide, vinylidene chloride and black-opened plane; 2-chloro-1,3-butane, 2,3-dichloro-opened 1,3 _Halogen-substituted butadienes such
  • attalylate analog examples include an acrylate arylate having a benzene ring such as phenyl acrylate, benzyl acrylate, and the like.
  • acrylate arylate having a benzene ring such as phenyl acrylate, benzyl acrylate, and the like.
  • Cyclohexenorea tallylate analogues Cyclododecyl attalate analogues, Dicyclopentyl acrylate derivatives such as dicyclopentyl acrylate analogues; Methyl acrylate derivatives , Ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, t-butyl acrylate, 3,3-dimethyl_2-butyl acrylate C1-C12 saturated alkyl such as analog, hexyl acrylate, octyl acrylate, 2_ethyl hexyl acrylate, decyl acrylate, lauryl acrylate Alkyl acrylate derivatives having a group; Silatalylate analog, cetyl (meth) acrylate, hexadecyl acrylate, stearyl acrylate
  • acrylamide analogs (b 1 ) include acrylamide analogs, N_methyl atrylamide analogs, N-stearyl acrylamide, N-cetyl acrylamide, N, N-dimethyl acrylamide analogs, N, N-J Tylacrylamide analog, N, N-diisopropylacrylamide analog, N-methoxymethylacrylamide analog, N-ethoxymethylacrylamide analog, N-butoxymethylacrylamide analog, N-methylolacrylamide analog, N-butoxymethylol Acrylamide analogs, N-butyrolol athlamide analogs, diacetone acrylamide analogs, methylol-diacetone acrylamide Preferred examples thereof include:
  • the monomer (b) may be a monomer having a reactive group other than the polymerizable unsaturated bond, including the above acrylamide analog.
  • reactive groups include an epoxy group, a hydroxyxenore group, Carboxyl group, acid anhydride group, amide group, amino group, alkoxysilyl group
  • Monomers having a reactive group other than the polymerizable unsaturated bond include blocked isocyanate group-containing acrylate (b 2 ); 3-chloro-2-hydroxypropyl acrylate, 2-hydroxyethyl Atalylate analogs, 2-hydroxypropyl atallylate analogs, 4-hydroxybutyl atarylate analogs, glycerin monotalylate analogs, trimethylolpropane monoatarylate analogs, glycerin monoatarylate analogs, 2-hydride Atoxylates with hydroxyl groups such as xyloxy-3-phenoxypropyl attalylate analogues; Ataliates with epoxy groups such as glycidyl acrylate, aziridinyl acrylate derivatives, aziridinyl ethyl acrylate derivatives Rate analogs; N, N, N-stearyldimethylammo Nittalylate analogues, N, N, N-cetyldimethylammonium attalylate analogue
  • the blocked isocyanate group-containing acrylate ester (b 2 ) includes 2_isocyanate acetylate analogue, or an acrylate derivative having a functional group capable of binding to the isocyanate group and a polyisocyanate.
  • a reaction product obtained by reacting cyanate (b 3 ) in a ratio in which at least one isocyanate group remains is preferred.
  • a mono- or diester of an acrylic acid analog and a polyhydric alcohol which is preferable to an acrylate arylate analog, is particularly preferable.
  • the polyhydric alcohol include ethylene glycol, polyoxyethylene glycol, propylene glycol, polyoxypropylene glycol, glycerol, trimethylolpropane monoalkylene oxide adduct, pentaerythritol and the like.
  • polyisocyanates (b 3 ) examples include aromatic polyisocyanates such as 4,4'-diphenylmethane diisocyanate and tolylene diisocyanate, hexamethylene diisocyanate. , Aliphatic polyisocyanates such as lysine diisocyanate, isophorone diisocyanate
  • alicyclic polyisocyanates such as bis (isocyanatemethyl) cyclohexane and norbornene diisocyanate, and modified products such as nurate modified products, prepolymer modified products and burette modified products.
  • modified products such as nurate modified products, prepolymer modified products and burette modified products.
  • Particularly preferred are aliphatic isocyanates, alicyclic isocyanates, and their nurate modified products, prepolymer modified products, and burette modified products.
  • Preferred blocking agents for the isocyanate group (b 4 ) include oximes, alkyl ketoximes, phenols, alkanols, ⁇ -diketones, malonic esters, ratatas and the like. Specific examples include pyrazole, 3-methylbiazole, 3,5-dimethylbiazole, indazole, methyl ethyl ketoxime, cyclohexanone oxime, ⁇ -force prolatatam, acetoacetate ethyl, acetylacetone, phenol, cresol, and methanol.
  • 2 butanone oxime, 3-methyl virazole, 3, 5 dimethylpyrazole, cyclohexane oxime, methyl ketyl ketoxime, ethyl acetoacetate, ⁇ -force prolatatam, jetyl Malonate and pyrazole are preferred.
  • Specific examples of the blocked isocyanate group-containing attalylate analogs include the following. 2_ Compound that isocyanate group of isocyanate acetyl acrylate is blocked with methyl ketyl oxime, 2_ Isocyanate group of isocyanate acetyl acrylate is blocked with ⁇ -force prolatatam, A compound in which the isocyanate group of the 1: 1 reaction (molar ratio) of isophorone dicyanoate and 2-hydroxyethyl acrylate is blocked with methyl ethyl ketoxime, isophorone diisocyanate and 2-hydroxypropyl alicyclic 1: 1 (molar ratio) to the rate analog 1: 1 Molar ratio of norbornene diisocyanate and 2-hydroxyethyl atylate analog, the isocyanate group of the reactant blocked with methyl ethyl ketoxime 1 (Molar ratio) A compound blocked with luketoxime.
  • the method for preparing the polymer (A) and the polymer (B) as the active ingredients is not particularly limited, and for example, a solution polymerization method using an organic solvent, a non-aqueous method, or the like.
  • Conventional polymerization techniques such as dispersion polymerization, dispersion polymerization using water as a dispersion medium, emulsion polymerization, suspension polymerization, and bulk polymerization can be employed.
  • an emulsion polymerization method When the polymerization is performed in an aqueous medium, it is preferable to apply an emulsion polymerization method or a dispersion polymerization method, and an emulsion polymerization method is particularly preferable.
  • the emulsion polymerization method it is preferable to start polymerization after sufficiently emulsifying the monomer using a high-pressure emulsifier or the like.
  • a mixture of a monomer, a surfactant, and an aqueous medium is mixed and dispersed in advance with a homomixer or a high-pressure emulsion machine before the polymerization is started, thereby improving the yield of the finally obtained polymer. It is possible.
  • a liquid (also referred to as a dispersion) in which the polymer (A) is dispersed as particles in an aqueous medium and a dispersion of the polymer (B), or a mixture thereof are obtained.
  • the obtained copolymer solution, dispersion, and emulsion can be used as a composition as it is or after dilution.
  • a copolymer obtained by solution polymerization, emulsion polymerization, or other polymerization method may be separated and dissolved, dispersed, or emulsified in a solvent, dispersion medium, or emulsification medium as necessary to obtain a composition.
  • an aqueous medium (C) is used as a polymerization medium.
  • the aqueous medium (C) is a medium containing water, and may be water alone or an organic solvent as a polymerization auxiliary solvent if desired.
  • one or more water-soluble organic solvents (c) selected from the group consisting of ketones, ethers, alcohols (particularly monohydric alcohols and saturated polyhydric alcohols) and nitrogen compounds are preferable.
  • ketones methyl ether ketone, methyl isobutyl ketone, acetone, etc. are preferred.
  • Monoethers of saturated polyhydric alcohols, dialkyl ethers, monoalkyl ether monoacyl esters, dioxanes, etc. are preferred, and nitrogen compounds are preferred.
  • N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide and the like are preferable.
  • ether-based organic solvents are most preferable from the viewpoint of low flammability.
  • the water-soluble organic solvent (c) can be used alone or in combination.
  • Water in aqueous media The amount of the soluble organic solvent (c) is preferably 10 to 50 parts by mass, more preferably 5 to 100 parts by mass with respect to 100 parts by mass of the total amount of the polymer (A) and the polymer (B). If there is too much water-soluble organic solvent (c), the durability of water and oil repellency against washing may be reduced. Further, the amount of the aqueous medium may be 10 to 5000 parts by mass, for example 100 to 1000 parts by mass, with respect to 100 parts by mass of the polymer to be polymerized.
  • Specific examples of the monohydric alcohol used in the aqueous medium include ethyl alcohol and isopropyl alcohol.
  • saturated polyhydric alcohol compounds having 2 to 4 hydroxyl groups are preferable.
  • saturated polyhydric alcohol compounds having 2 to 4 hydroxyl groups are preferable. Examples include tripropylene glycol, tetrapropylene glycol, hexylene glycol, glycerin, trimethylolethane, and trimethylolpropane.
  • (mono or poly) alkyl ethers of saturated polyhydric alcohols include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and acetates thereof; diethylene glycol mono Methyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, and their acetates; triethylene glycol monomethyl ethere, triethyleneglycol monoethylenoleateol, triethyleneglycol monomonopropylene ether, and their acetates; Propylene glycol monomethyl ether, propylene glycol monomethino ethenore, propylene glycol mono mono propylenoate, And their acetates; dipropylene glycol monomethyl ether, dipropylene glycol monoethyl enoate ethere, dipropylene glycol monomono propinoate ethere, and their acetates thereof; diethylene glyco
  • diethylene glycol monomethyl ether dipropylene glycol monomethyl ether, and dipropylene glycol dimethyl ether are particularly preferred.
  • dipropylene glycol tripropylene glycol, tetrapropylene glycol, and polypropylene glycol in which five or more oxypropylene groups are connected are preferable.
  • the polymerization reaction for obtaining the polymer (A) and the polymer (B) can be initiated by heat, light, radiation, a radical polymerization initiator, an ionic polymerization initiator, etc., but it is water-soluble or oil-soluble.
  • General purpose initiators such as azo-type, peroxide-type, persulfate, redox-type, etc. that are preferably used with radical polymerization initiators can be used depending on the polymerization temperature, especially azo-type compounds and their Salts are preferred.
  • oil-soluble polymerization initiator examples include 2, 2'-azobis (2-methylpropionitryl), 2, 2, 1azobis (2-methylbutyronitrile), 2, 2'-azobis ( 2, 4-dimethyl valeronitrile), 2, 2, 1-azobis (2, 4-dimethyl 4-methoxyvaleronitryl), 1, 1 '_ azobis (cyclohexane 1-carbonitryl), dimethinole 2, 2 , Monoazobis (2-methyl propionate), 2, 2, monoazobis (2-isobutyronitrile), benzoyl peroxide, di-tertiary monobutyl peroxide, lauryl peroxide, tamenhydro Preferred examples include peroxide, t_butyl peroxybivalate, diisopropyl peroxydicarbonate, t_butyl perpivalate, and the like.
  • water-soluble polymerization initiator examples include 2, 2'-azobisisobutylamidine dihydrochloride, 2, 2'-azobis (2_methylpropionamidine) hydrochloride, 2, 2 '—Azobis [2 _ (2—imidazoline _ 2_yl) propane] hydrochloride, 2, 2'—Azobis [2— (2—imidazoline _ 2_yl) propane] sulfate hydrate, 2, 2'—azobis [2— (5-methyl_2_imidazoline-2-yl) propane] hydrochloride, 1-hydroxycyclohexyl hydroperoxide, 3_Carboxypropionyl peroxide, acetyl peroxide, sodium peroxide, potassium persulfate, barium persulfate, ammonium persulfate, hydrogen peroxide, etc. are preferred.
  • the polymerization temperature in emulsion polymerization is not particularly limited, but 20 to: 150 ° C is preferred, and 30 to 80 ° C is particularly preferred.
  • the molecular weight of the polymer can be determined by a polystyrene conversion value by gel permeation chromatography.
  • the mass average molecular weights of the polymer (A) and the polymer (B) are preferably in the range of 5,000 to 500,000, and particularly preferably 10,000 to 250,000. When the average molecular weight of the polymer is in the range of 5,000 to 500,000, the polymer can sufficiently cover the substrate, so that high water / oil repellency can be imparted and high durability can be obtained.
  • the molecular weight can be adjusted by using a chain transfer agent, and it is generally desirable to use a chain transfer agent.
  • the chain transfer agent is particularly preferably an alkylthiol which is preferably a mercaptan such as alkylthiol, alkylenedithiol or thiocyanouric acid or an aromatic compound.
  • the emulsion polymerization is preferably carried out using a surfactant (D).
  • a surfactant D
  • Nonionic surfactants (d n ), cationic surfactants (d c ), anionic surfactants (d a ), and amphoteric surfactants (d b ) are not particularly limited in the surfactant used.
  • One or more of the known or well-known surfactants may be employed, but nonionic surfactants (d n ), cationic surfactants (cf) or amphoteric surfactants are particularly preferred.
  • Agent (d n ) is preferred.
  • nonionic surfactant (d n ) and cationic surfactant (d c ), or nonionic surfactant (d n ) and amphoteric surfactant ( A combination of d b ) is preferred. It is also possible to use a polymer surfactant.
  • the amount of the surfactant (D) is preferably from 0.0:! To 30 parts by mass, particularly from 0.5 to 15 parts per 100 parts by mass of the total amount of the polymer (A) and the polymer (B). About mass parts are preferred. If the amount of the surfactant is too small, the stability of the dispersion may be lowered.
  • the amount of the surfactant may be reduced.
  • nonionic surfactant (d n ) a polyoxyalkylene monoalkyl ether, a mono-alkenyl ether, a polyoxyalkylene monoalkyl polyenyl ether, a polyoxyethylene mono (substituted phenyl) ether condensate , Polyoxyethylene mono (substituted phenyl) ether, polyoxyethylene polyoxyalkylene, alkylamine polyoxyethylene, alkylamido polyoxyethylene, alkylamine oxide, alkane (C — C) thiol, ethylene oxide and alkyl (C — C) with Amin
  • Examples thereof include a combined product, a condensation product of ethylene oxide and oleic acid, and a condensation product of ethylene oxide and sorbitan monofatty acid (C C).
  • nonionic surfactant (d n ) examples include polyoxyethylene lauryl ether, polyoxyethylene tridecyl ether, polyoxyethylene octyl ether, polyoxyethylene hexadecyl ether, polyoxyethylene octyl ether.
  • a cationic surfactant comprising a substituted ammonium salt.
  • a cationic surfactant comprising a substituted ammonium salt one or more hydrogen atoms bonded to the nitrogen atom of the ammonium salt are substituted with an alkyl group, an alkenyl group, or a polyoxyalkylene group having a terminal hydroxyl group.
  • mono (long-chain alkyl) amine hydrochloride mono (long-chain alkyl) dimethylamine hydrochloride, mono (long-chain alkyl) dimethylamine acetate, mono (long Amine salts such as alkenyl) dimethylamine hydrochloride, di (long chain alkyl) monomethylamine hydrochloride, mono (long chain alkyl) trimethylammonium chloride, di (long chain alkyl) dimethylammonium chloride, mono (long chain) Alkyl) monomethyldi (polyoxyethylene) ammonium chloride, di (long chain alkyl) monomethyl Quaternary ammonium salts such as tilmono (polyoxyethylene) ammonium chloride, mono (long-chain alkyl) dibenzyldodecyldi (hydropolyoxyethylene) ammonium chloride, methylamine'ethyl sulfate and the like.
  • mono (long Amine salts such as alkenyl) dimethylamine hydroch
  • the counter ion is preferably a chlorine ion, an ethyl sulfate ion, or an acetate ion.
  • Long chain alkyls and long chain alkenyls may have 8 to 50 carbon atoms, for example 12 to 22 carbon atoms.
  • cationic surfactant (d c ) examples include dimethylmonococonutamine acetate, tetradecylamine acetate, octadecylamine acetate, beef tallow alkylpropylene diamine acetate, N -[2- (Jetylamino) ethyl] oleamide hydrochloride, octadecyltrimethylammonium chloride, dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium chloride, trimethylo Kutadecyl ammonium chloride, behenyl trimethyl ammonium chloride, (Dodeci Nium chloride, benzyl tetradecyl dimethyl ammonium chloride, benzyl otadecyl dimethyl ammonium chloride, biphenyl trimethyl ammonium chloride, oct
  • amphoteric surface active agent (d b) is Aranin acids, imidazo linear ⁇ beam betaines, Ryo Midobetain acids, or amphoteric surface active agent comprising acetic betaine, etc.
  • amphoteric surfactant (d b ) include dodecyl betaine, octadecyl betaine, dodecyl carboxymethyl hydroxyethyl imidazolinium betaine, dodecyl dimethylaminoacetic acid betaine, fatty acid amidopropyldimethylamino. Examples include betaine acetate.
  • anionic surfactant (d a ) examples include sodium lauryl sulfate, triethanolamine lauryl sulfate, sodium polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene nouryl phenyl ether sulfate, polyoxyethylene lauryl ether.
  • the water / oil repellent composition of the present invention may contain an organic solvent or an aqueous medium (C) as a medium in addition to the polymer (A) and the polymer (B).
  • the aqueous medium (C) the same emulsion polymerization medium as described above can be used.
  • the medium used for the polymerization can be used as it is, but after polymerization, water or a water-soluble organic solvent (c) One or both may be added.
  • the water-soluble organic solvent (c) used in this case may be the same or different or partially different from that used during polymerization. ,.
  • the polymer (A) and the polymer (B) or a solution thereof may be dispersed and emulsified in the aqueous medium (C) together with the surfactant (D) to form a water / oil repellent composition.
  • the same surfactant (D) as in the aforementioned emulsion polymerization can be used.
  • the content of the aqueous medium (C) is preferably 40 to 98% by mass and more preferably 70 to 90% by mass with respect to the water / oil repellent composition.
  • a monomer having a short-chain R f group used in the present invention is generally more compatible with other monomers not containing fluorine than a monomer containing a crystalline R F group. Even if the amount of the soluble organic solvent (c) is small, a homogeneous polymer can be obtained immediately, and since it does not contain the water-soluble organic solvent (c) at all, a water- and oil-repellent composition having a low environmental impact due to volatile organic substances is obtained. It is also possible.
  • the polymer (A) and the polymer (B) are preferably present as dispersed in the medium as fine particles.
  • the average particle size of the fine particles is 10 to: OOOnm force 10 to 300 nm force S, and particularly preferable particle size range is 10 to 200 nm. If the particle size is too small, a large amount of emulsifier or self-emulsifying monomer is required to obtain a stable dispersion, resulting in decreased water and oil repellency or when processed into dyed fabrics. There is a risk of discoloration. Also, if the particle size is too large, it will be difficult for the dispersed particles to stably exist in the medium and may settle out. Therefore, it is not preferable.
  • the average particle diameter can be measured with a dynamic light scattering device, an electron microscope or the like.
  • the polymer (A) and the polymer (B) are not present in the same particle even if they are present in the same particle, and separate particles are used. It may be formed or may be an intermediate one.
  • a water / oil repellent composition in which the polymer (A) and the polymer (B) are not present in the same particle and form separate particles, for example, the polymer (A) and the polymer (B)
  • a method of mixing and preparing each dispersion is preferably used.
  • the polymer (B) is polymerized into the emulsion dispersion of the polymer (A).
  • a method in which monomers are added all at once or divided into several stages, followed by polymerization by adding a polymerization initiator, so-called seed polymerization, or a method of polymer (B) emulsified dispersion with polymer (B) This can be achieved by a method in which a monomer and an initiator for polymerizing A) are prepared and a multi-stage polymerization such as seed polymerization is performed.
  • the polymer (A) and the polymer (B) are present in the same particle, they may have a homogeneous structure with no restrictions on the phase structure, or the so-called core-shell type layer separation structure, Phase separation structures such as island type phase separation structure and spinodal type phase separation structure can be freely adopted.
  • the repellent and oil repellent composition of the present invention may contain a thermosetting agent (F).
  • thermosetting agent (F) include a blocked isocyanate compound (f 1 ), an amino resin compound (f 2 ), a polymer (f 3 ) not containing a fluorine-containing monomer having a crosslinkable monomer as an essential polymerization unit, Examples include urethane resin compounds. Blocked isocyanate compounds (f and amino resin compounds (f 2 ) are preferred.
  • the blocked isocyanate compound (f 1 ) is a compound having no polymerizable unsaturated group, and the isocyanate group of the polyisocyanate (b 3 ) is converted into the blocking agent described above.
  • a compound having a structure completely blocked by (b 4 ) is preferred.
  • an acrylate amide analog (b 1 ) or a blocked isocyanate group-containing acrylate copolymer. (B 2 ) is preferred, especially N-methylol acrylamide and 2-isocyanate ethyl methacrylate block. Preferred are isomers.
  • the amino resin compound (f 2 ) is a compound obtained by addition condensation of an amino group-containing compound and a compound having a reactive group with an amino group, and includes alcohols such as melamine, guanamine, or urea. Furthermore, addition condensates of amines and formaldehyde, and addition condensates of melamine, guanamine, urea and the like with formaldehyde further include alcohols, compounds obtained by addition condensation of amines, and derivatives thereof.
  • amino resin compound (f 2 ) examples include urea resins; alkylated urea resins such as butylated urea resins; melamine resins such as trimethylol melamine and hexamethylol melamine; methylated melamine resins and n-butylated Alkyl melamine resin such as melamine resin, methylated n-butylated melamine resin, i-butylated melamine resin; benzoguanamine resin; n-butylated benzoguanamine resin, i Examples include alkyl benzoamine amine resins, alkyl benzoamine amine resins, petit laur urea melamine resins, and aceto guanamine resins.
  • alkylated urea resins such as butylated urea resins
  • melamine resins such as trimethylol melamine and hexamethylol melamine
  • the amino resin compound (f 2 ) in the present invention is preferably substantially soluble in water at room temperature.
  • amino succinic compounds (f 2 ) such as those manufactured by Sumitomo Chemical Co., Ltd. (for example, trade name Sumtex Resin), manufactured by Dainippon Ink Co., Ltd., Mitsui Chemicals, etc. Things are available.
  • the amount of the thermosetting agent (F) is preferably 5 to 100 parts by mass, and more preferably 5 to 70 parts by mass with respect to 100 parts by mass of the polymer (A) + the polymer (B).
  • the polymer (A), the polymer (B), and the above-mentioned polymer heat are used as a filler extender or to develop various physical properties in the article to be treated.
  • Polymers (G) other than the curing agents (f 2 , f 3 ) can be blended.
  • the other polymer (G) may be a non-fluorine polymer.
  • the other polymer (G) is a polymer containing no R f group, such as a water-soluble polymer and organopolysiloxanes. Examples of the water-soluble polymer include polyacrylamide, polybutyl alcohol, and derivatives thereof.
  • organopolysiloxanes examples include methylnoid diene polysiloxanes typified by silicone water repellents, terminal OH group-blocked dimethylpolysiloxanes, bur group-containing polysiloxanes, and silicone softeners. Amino group, epoxy group, polyether in side chain And various modified silicone oils modified by introducing a group, a carboxyl group, a hydroxyl group, a trifluoroalkyl group, an alcohol ester group, an alkyl group, and the like.
  • Silicone desperation is a solution in which a silicone resin or silicone rubber in an initial polymerization state is dissolved in a solvent, and when heated, it condenses to form a film having a three-dimensional network structure.
  • onoreganopolysiloxanes there are many types of commercial products of these onoreganopolysiloxanes. Examples of the line of products sold include SH200, PRX413, SH8011, SD8000 (product names of Toray Industries, Inc., Silicone Co.), KP-801M, KPN-3504 (product names of Shin-Etsu Chemical Co., Ltd.), and the like.
  • the amount of the polymer (G), for example, the amount of the organopolysiloxane is preferably about 0.05 to about 10% by mass, preferably about 0.5 to 5% by mass with respect to the water / oil repellent composition of the present invention. .
  • the water / oil repellent composition in the present invention contains an antifoaming agent as necessary.
  • an antifoaming agent various water-based ones can be used, for example, lower alcohols such as methanol, ethanol, butanol, etc .; higher alcohols such as amyl alcohol, polypropylene alcohol and derivatives thereof; oleic acid, tall Fats and oils such as oil, mineral oil, stone wall, etc .; surfactants such as sorbitan fatty acid ester, polyethylene glycol fatty acid ester, and plenoronic type nonionic surfactant; silicone surfactants such as siloxane and silicone resin Can be used alone or in combination.
  • Typical commercial antifoam products include Ade forcenate B, Adecanate B1068, etc. B-series (Asahi Denka Kogyo Co., Ltd.); Formaster DL, Nopco NXZ, SN deformers 113, 325, 308, 368 SN Deformer series; Dehydran 129 3, Dehydran 1513 (manufactured by Sannopco); Furonon SB_110N, SB_210, 510, 551, Aqualen 800, 805, Aqualen 1488 (Kyoeisha Chemical Co., Ltd.); Surfynol 104E (Acetylene-based antifoaming agent manufactured by Air Products & Chemical Co., Ltd.); KS-607A (manufactured by Shin-Etsu Chemical Co., Ltd.); FS Antifoam (manufactured by Dowco Jung); BYK_020, 031, 073, W (manufactured by Big Chemi Co., Ltd.) Dehydr
  • a so-called film forming aid may be used.
  • a film-forming aid one or more compounds selected from generally used alcohols, glycol ethers, linear or cyclic silicones, esters, diesters, ketones and ethers are used. Can be used without limitation. These compounds may contain a fluorine atom in the molecule.
  • film forming aids include methyl acetate, ethyl acetate, butyl acetate, dipropylene glycol monomethyl ether, 1-methoxy-2-propanol, acetic acid diethylene glycol monoethyl ether, di-ethylene adipate ⁇ -butyl, butyl carbide
  • examples include tall acetate, otamethyl trisiloxane, decamethylcyclopentane siloxane, dimethyl phthalate, and jetyl succinate.
  • the amount of the film-forming aid used is in the range of 0.:! To 70 parts by mass per 100 parts by mass of the polymer, and particularly preferably 5 to 60 parts by mass. Further, by using these compounds together with the aqueous medium (C) at the time of emulsion polymerization, a homogeneous copolymer having a small composition distribution can be obtained.
  • additive components can be blended as necessary.
  • other water and oil repellents stin blockers, softeners, cross-linking promoting catalysts, texture modifiers, penetrants, insect repellents, antibacterial agents, flame retardants, antistatic agents, polishes, antifungal agents
  • a water absorbing agent, an anti-shrinking agent, a dye, a pigment, a dye stabilizer, an antioxidant, a deoxidizing agent, a wrinkle adjusting agent and the like can be appropriately used in combination.
  • the total amount of polymer ( ⁇ ) and polymer ( ⁇ ) is 50% by mass or more, preferably 75% by mass or more of the total solid content.
  • the water / oil repellent composition of the present invention is diluted to an arbitrary concentration according to the purpose and application, and is treated by an arbitrary method according to the type of article to be treated, the preparation form of the composition, and the like.
  • Applicable to goods For example, dipping, coating, spraying, padding, roll coating, spin coating A method of adhering to the surface of the article to be treated and drying by using a combination of these methods is employed.
  • a method for processing the article a method in which the article is immersed in a water / oil repellent treatment liquid containing the polymer (A) and the polymer (B) is preferable, but the article containing the polymer (B) and not containing the polymer (A) is preferable.
  • the polymer (A) containing polymer (B) After immersing the article in the composition, the polymer (A) containing polymer (B), the method of immersing in the water / oil repellent treatment liquid, and the polymer (A) containing polymer (B) It is also preferable to immerse the article in the water / oil repellent treatment solution and then immerse it in the water / oil repellent treatment solution containing the polymer (B) and not containing the polymer (A).
  • An effective method is to remove the excess treatment liquid with a roll or the like and then dry it.
  • Articles to be treated with the water / oil repellent composition of the present invention are not particularly limited, fiber products such as fibers, fiber woven fabrics, fiber knitted fabrics, and nonwoven fabrics, and ceramics such as glass, gypsum, asbestos, bricks, cement, and concrete. Products, leather products such as fur, wood, paper, pulp products, metals and their oxides, stones, resins, painted surfaces and plasters.
  • An article treated with the water / oil repellent composition of the present invention has both excellent water repellency and oil repellency, and is excellent in durability.
  • Uses of these items include sportswear, coats, blousons, surgical clothes, work clothes, uniforms and other clothing items, dust masks, shoes, bags, umbrellas, Rikiichi, curtains, wallpaper, tents, architecture Materials, filtration materials, electronics or optical system parts and elements, etc.
  • the water / oil repellent composition of the present invention is suitable for treating textile products.
  • textile products include animal and vegetable natural fibers such as cotton, hemp, wool, and silk, polyamides, polyesters, polybulal alcohol, polyacrylonitrile, polysalts, and polypropylene, synthetic fibers such as rayon and acetate.
  • Semi-synthetic fiber, glass fiber, carbon fiber, tuss Preferable examples include inorganic fibers such as the best fiber, and blended fibers thereof, and any form such as fiber, yarn, fabric, and nonwoven fabric may be used.
  • the water repellency is shown by the water repellency (see Table 1 below) by the spray method of JIS-L-1092.
  • Oil repellency is according to AATCC _TM118-1966. Drop the test solution shown in Table 2 below into two places on the test cloth, observe the penetration state after 30 seconds, and give a test solution that does not show immersion. The highest point of oil repellency was shown as an oil repellency pick-up.
  • Polymerization Examples 2 to 7 polymerization was performed in the same manner as in Polymerization Example 1 with the monomer compositions shown in Table 3 below, to obtain polymers P2 to P7, respectively.
  • Example 5F A (a1 HFIP-MA (a1 9FMA (a2 6FOMA1 (a2 t A (a1 HFIP-MA (a1 9FMA (a2 6FOMA1 (a2 t A (a1 HFIP-MA (a1 9FMA (a2 6FOMA1 (a2 t A (a1 HFIP-MA (a1 9FMA (a2 6FOMA1 (a2 t A)
  • StA Stearyl Atarylate
  • Polymers P1 to P7 obtained by the above method were mixed at a ratio (mass%) shown in Table 4 to prepare a treatment liquid as a 1 mass% solution of the fluorinated solvent HCFC-225.
  • Nylon taffeta cloth (force Nebo Naturine, nylon 6, amber-dyed cloth) is immersed in the treatment solution, treated at 500 rpm for 18 seconds in a centrifuge, air-dried at room temperature for 1 second, and then heat treated at 150 ° C for 5 minutes. Then, the water and oil repellency of the treated cloth was evaluated. The results are shown in Table 5.
  • the + mark in the table indicates slightly better than the performance shown in each.

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Abstract

L’invention concerne une composition hydrofuge et oléorésistante contenant du fluor comprenant (A) un polymère contenant des unités dérivées d’un monomère contenant du fluor (a1) ce qui produit un homopolymère ayant une température de transition vitreuse (Tg) supérieure ou égale à 50°C et des unités optionnelles dérivées d’un monomère contenant du fluor (a2) ce qui produit un homopolymère ayant une Tg inférieure à 50°C sous réserve que les unités dérivées du monomère (a1) représentent au moins 50% en masse de la quantité totale d’unités dérivées des monomères (a1) et (a2) et (B) un polymère comprenant des unités optionnelles dérivées d’un monomère contenant du fluor (a1) ce qui produit un homopolymère ayant une Tg supérieure ou égale à 50°C et des unités dérivées d’un monomère contenant du fluor (a2) ce qui produit un homopolymère ayant une Tg inférieure à 50°C sous réserve que les unités dérivées du monomère (a2) représentent plus de 50% en masse de la quantité totale d’unités dérivées des monomères (a1) et (a2).
PCT/JP2005/017739 2004-10-06 2005-09-27 Composition hydrofuge et oléorésistante contenant du fluor WO2006038493A1 (fr)

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US8176981B2 (en) 2007-01-19 2012-05-15 3M Innovative Properties Company Fluorinated surfactants and methods of using the same
WO2013058156A1 (fr) * 2011-10-18 2013-04-25 ユニマテック株式会社 Copolymère contenant du fluor et agent de modification de surface le contenant comme ingrédient actif
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JP7103017B2 (ja) 2017-08-07 2022-07-20 Ａｇｃ株式会社 撥水剤組成物、および物品
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