AQUEOUS POLYMER DISPERSION COMPOSITION AND

SURFACE TREATMENT AGENT

CROSS REFERENCE TO RELATED APPLICATIONS

This application has priority from US Application No. 61/096,924 filed September 15, 2008, disclosures of which are incorporated herein by reference.

TECHNICAL FIELD

This invention relates to an aqueous dispersion water- and oil-repellent composition wherein, even if an amount of a fluorine-containing monomer in the composition is decreased, the composition can give excellent water- and oil-repellency and excellent durability of water- and oil-repellency.

BACKGROUND ARTS

Fluorocarbon polymers are extensively used to impart oleophobicity/oil repellency to a fabric and the like.

For the purpose of improving durability of water- and oil-repellency against washing, dry cleaning and the like, the attempt of copolymerizing a an adhesive group-containing monomer with a fluoroalkyl-containing monomer has been done.

JP-B-38-22487 and JP-B-41-8579 attempt that a fluoroalkyl-containing polymer is blended with a fluoroalkyl-free polymer to create a water- and oil-repellent composition excellent cost economy.

JP-B-49-42878 and USP 3849521 propose to use a polymerizable monomer which had particular structure to give a polymer or copolymer which can be added without decreasing the soil resistance or durability.

JP-A-06-228241 discloses that a resin composition having surfaces having the improved surface properties such as the water- and oil-repellency and the maintenance of these properties can be obtained by mixing two different polymers having different contents of fluoroalkyl group with a fluoroalkyl group-free polymer.

In addition, JP- A-61-264081 discloses that at least one homopolymer or copolymer comprising a hydrocarbon-based polymerizable compound and having a glass transition temperature of 50 degrees C is mixed to improve slip resistance, and USP4043964 discloses a repellent agent for carpet comprising a fluoroalkyl group-containing polymer mixed with a fluoroalkyl group-free polymer, each of polymers having a glass transition point or melting points of at least 45 degrees C.

On the other hand, for example, JP- A-58-42682, JP-A-60- 190408, JP-A-63-075082, JP-A-9-143877 and USP 4070152 disclose a large number of blends of fluoroalkyl-containing resin emulsions with various silicone emulsions are proposed in order to simultaneously impart the water- and oil-repellency and softness to a substrate such as textile.

Also, JP-A-2-214791, JP-A-3-76713, JP-A-11-269231 ₃ WO2004 /041,880, JP-A-3-231986, WO2004 /108,855, JP-A-8-109580 and JP-A- 10- 158402 propose a large number of resin emulsions comprising a fluoroalkyl group-containing monomer bonded to a reactive group-containing silicone by polymerizing the fluoroalkyl group-containing polymerizable monomer to the silicone.

In addition, JP-A-2-247211, JP-T-6-507652 and JP-A-2000- 186279 propose also a composition comprising a mixture of a silicone emulsion with a copolymer of a fluoroalkyl group-containing monomer and an organosiloxane and silicone emulsion for the same purpose. But these have the problems, for example, that the water- and oil-repellency is decreased because of oleophilicity of the silicone group.

PROBLEMS TO BE SOLVED BY THE INVENTION

An object of the present invention is to provide a water-and oil-repellent agent comprising a fluorine-containing polymer which imparts excellent water- and oil-repellency and excellent durability of water- and oil-repellency, even if an amount of a fluorine-containing monomer is decreased.

SUMMARY OF THE INVENTION

The present inventors discovered that the above-mentioned object can be achieved by a composition comprising (I) a fluorine-containing polymer which is formed from a monomer comprising a fluorine-containing monomer and which is polymerized in the presence of a functional organopolysiloxane and (II) a fluorine-free polymer.

The present invention provides an aqueous dispersion water- and oil-repellent composition comprising:

(I) a fluorine-containing polymer comprising repeating units derived from a monomer comprising a fluorine-containing monomer, wherein the fluorine-containing polymer has a silicone moiety possessed by (or derived from) a functional organopolysiloxane, and

(II) a fluorine-free polymer.

This invention provides an aqueous dispersion water- and oil-repellent composition comprising: (I) a fluorine-containing polymer comprising:

(A) a monomer which comprises;

(a) a fluorine-containing monomer of the formula:

CH ₂ =C(-X)-C(=O)-Y-Z-Rf wherein X is a hydrogen atom, a monovalent organic group, or a halogen atom, Y is -O- or -NH-,

Z is a direct bond or a divalent organic group, and

Rf is a fluoroalkyl group having 1 to 20 carbon atoms, and

(B) at least one functional organopolysiloxane selected from the group consisting of a mercapto-functional organopolysiloxane, a vinyl-functional organopolysiloxane, a (meth)acrylamide-functional organopolysiloxane and a (meth)acrylate-functional organopolysiloxane, and (II) a fluorine-free polymer.

The aqueous dispersion water- and oil-repellent composition of the present invention is useful to provide oil repellent properties to a variety of surfaces. When treating textiles, the fluorosilicone of the present invention may also provide a softer hand or feel than conventional fluorocarbon based oil repellent treatments.

EFFECTS OF THE INVENTION According to the present invention, when a substrate is treated, the water- and oil-repellent composition can impart the excellent water- and oil-repellency, and durability thereof. When the substrate is a textile, the treated textile has good feeling.

MODE FOR CARRYING OUT THE INVENTION The water- and oil-repellent composition of the present invention comprises (I) the fluorine- and silicon-containing polymer and (II) the fluorine-fee polymer. The water- and oil-repellent composition may be an emulsion in a liquid such as water and/or an organic solvent. Generally, the polymer (I) and the polymer (II) are not present in the same particle.

In the present invention, the monomer (A) forming the fluorine-containing polymer comprises:

(a) a fluorine-containing monomer,

(b) optionally present, a fluorine-free monomer other than a crosslinkable monomer, and

(c) optionally present, a crosslinkable monomer.

The fluorine-containing polymer may be a homopolymer formed from one monomer or a copolymer formed from at least two monomers. The homopolymer has the repeating units derived from the fluorine-containing monomer (a). The copolymer may has the repeating units derived from at least two fluorine-containing monomers (a), or may have, in addition to the repeating units derived from the fluorine-containing monomer (a), the repeating units derived from the fluorine-free monomer (b) and optionally the crosslinkable monomer (c). The fluorine-containing polymer can be prepared by polymerizing the monomer (A) in the presence of the functional organopolysiloxane (B).

The fluorine-containing polymer constituting the surface treatment agent of the present invention comprises: (a) the fluorine-containing monomer, and optionally (b) the fluorine-free monomer other than the crosslinkable monomer, and optionally (c) the crosslinkable monomer.

(I) Fluorine-containing Polymer (First Polymer) (A) Monomer

(a) Fluorine-containing Monomer

Component (a) of the present invention is a fluorine-containing monomer of the formula:

CH ₂ =C(-X)-C(=O)- Y-Z-Rf wherein X is a hydrogen atom, a monovalent organic group, or a halogen atom,

Y is -O- or -NH-,

Z is a direct bond or a divalent organic group, and

Rf is a fluoroalkyl group having 1 to 20 carbon atoms. Z may be for example a linear or branched alkylene group having 1 to 20 carbon atoms, for example a group of the formula -(CH ₂ ) _X - where x is 1 to 10, a group of the formula -SO ₂ N (R^R ² - or of the formula -CON(R^R ² -, where R ¹ is an alkyl group having 1 to 10 carbon atoms and R ² is a linear or branched alkylene group having 1 to 10 carbon atoms, or a group of the formula -CH2CH(OR ³ )CH ₂ - where R ³ represents a hydrogen atom or an acyl group having 1 to 10 carbon atoms such as formyl or acetyl, or a group of the formula -Ar-CH ₂ - where Ar is an arylene group optionally having a substituent, or a

-(CH ₂ ) _m -SO ₂ -(CH ₂ ) _n - group, or a -(CH ₂ ) _m -S-(CH ₂ ) _n - group (wherein m is from 1 to 10 and n is from 0 to 10.). X may be for example H, Me (methyl group), Cl, Br, I, F, CN and/or CF ₃ .

The fluorine-containing monomer (a) is preferably an acrylate ester of the formula:

CH ₂ =C(-X)-C(=O)- Y-Z-Rf (I) wherein X is a hydrogen atom, a linear or branched alkyl group having 1 to 21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, a iodine atom, a CFX X group (wherein X and X is a hydrogen atom a fluorine atom, a chlorine atom, a bromine atom or a iodine atom), a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group; Y is -O- or -NH-; Z is a direct bond, an aliphatic group having 1 to 10 carbon atoms, an aromatic or cycloaliphatic group having 6 to 18 carbon atoms, a -CH ₂ CH2N(R ¹ )Sθ ₂ - group (wherein R ¹ is an alkyl group having 1 to 4 carbon atoms), a -CH ₂ CH(OZ ¹ ) CH ₂ - group (wherein Z ¹ is a hydrogen atom or an acetyl group.), a -(CH ₂ )I _n -SO ₂ -(CH ₂ )H- group, or a -(CH ₂ ) _m -S-(CH2)n- group (wherein m is from 1 to 10 and n is from 0 to 10.); and Rf is a linear or branched fluoroalkyl group having 1 to 20 carbon atoms. The alpha-position of the fluorine-containing monomer may be substituted with a halogen atom or the like. Accordingly, in the formula (I), X may be a linear or branched alkyl group having 2 to 21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, a iodine atom, a CFX ¹ X ² group (wherein X ¹ and X ² is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or a iodine atom.), a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group.

In the formula (I), the Rf group is preferably a perfluoroalkyl group. The carbon number of the Rf group is from 1 to 20, for example, from 8 to 10, particularly 8 or 10. The carbon number of the Rf group may be from 1 to 6. Examples of the Rf group include -CF ₃ , -CF ₂ CF ₃ , -CF ₂ CF ₂ CF ₃ , -CF(CF ₃ ) ₂ , -CF ₂ CF ₂ CF ₂ CF ₃ , -CF ₂ CF(CF ₃ ) ₂ , -C(CF ₃ ) ₃ , -(CF ₂ ) ₄ CF ₃ , -(CF ₂ ) ₂ CF(CF ₃ ) ₂ , -CF ₂ C(CF ₃ ) ₃ , -CF(CF ₃ )CF ₂ CF ₂ CF ₃ , -(CF ₂ ) ₅ CF ₃ , -(CF ₂ ) ₃ CF(CF ₃ ) ₂ , and C ₈ F ₁₇ .

Z is preferably an aliphatic group having 1 to 10 carbon atoms, an aromatic group or cycloaliphatic group having 6 to 18 carbon atoms, a -CH ₂ CH ₂ N(R ¹ )SO ₂ - group (R ¹ is an alkyl group having 1 to 4 carbon atoms.), a -CH ₂ CH(OY ¹ )CH ₂ - group (Y ¹ is a hydrogen atom or an acetyl group.), a -(CH ₂ ) _m -SO ₂ -(CH ₂ ) _n - group, or a

-(CH ₂ ) _m -S-(CH ₂ ) _n - group (wherein m is from 1 to 10 and n is from 0 to 10.). The aliphatic group is preferably an alkylene group (particularly the carbon number is from 1 to 4, for example, 1 or 2.). The aromatic group and cycloaliphatic group may be substituted or unsubstituted. The S or SO ₂ - group may be directly bonded to the Rf group. The non-limiting examples of the fluorine-containing monomer (a) are as follows:

CH ₂ =C(-H)-C(=O)-O-(CH ₂ ) ₂ -Rf CH ₂ =C(-H)-C(=O)-O-C ₆ H ₄ -Rf

CH ₂ =C(-C1)-C(=O)-O-(CH ₂ ) ₂ -Rf

CH ₂ =C(-H)-C(=O)-O-(CH ₂ ) ₂ N(-CH ₃ ) SO ₂ -Rf

CH ₂ =C(-H)-C(=O)-O-(CH ₂ ) ₂ NC-C ₂ H ₅ ) SO ₂ -Rf

CH ₂ =C(-H)-C(=O)-O-CH ₂ CH(-OH) CH ₂ -Rf

CH ₂ =C(-H)-C(=O)-O-CH ₂ CHC-OCOCH ₃ ) CH ₂ -Rf

CH ₂ =C(-H)-C(=O)-O-(CH ₂ ) ₂ -S-Rf

CH ₂ =C(-H)-C(=O)-O-(CH ₂ ) ₂ -S-(CH ₂ ) ₂ -Rf

CH ₂ =C(-H)-C(=O)-O-(CH ₂ ) ₃ -SO ₂ -Rf CH ₂ =C(-H)-C(=O)-O-(CH ₂ ) ₂ -SO ₂ -(CH ₂ ) ₂ -Rf

CH ₂ =C(-H)-C(=O)-NH-(CH ₂ ) ₂ -Rf

CH ₂ =C(-CH ₃ )-C(=O)-O-(CH ₂ ) ₂ -S-Rf

CH ₂ =C(-CH ₃ )-C(=O)-O-(CH ₂ ) ₂ -S-(CH ₂ ) ₂ -Rf

CH ₂ =C(-CH ₃ )-C(=O)-O-(CH ₂ ) ₃ -SO ₂ -Rf CH ₂ =C(-CH ₃ )-C(=O)-O-(CH ₂ ) ₂ -SO ₂ -(CH ₂ ) ₂ -Rf

CH ₂ =C(-CH ₃ )-C(=O)-NH-(CH ₂ ) ₂ -Rf

CH ₂ =C(-F)-C(=O)-O-(CH ₂ ) ₂ -S-Rf CH ₂ =C(-F)-C(=O)-O-(CH ₂ ) ₂ -S-(CH ₂ ) ₂ -Rf CH ₂ =C(-F)-C(=O)-O-(CH ₂ ) ₂ -SO ₂ -Rf CH ₂ =C(-F)-C(=O)-O-(CH ₂ ) ₂ -SO ₂ -(CH ₂ ) ₂ -Rf CH ₂ =C(-F)-C(=O)-NH-(CH ₂ ) ₂ -Rf CH ₂ =C(-C1)-C(=O)-O-(CH ₂ ) ₂ -S-Rf CH ₂ =C(-C1)-C(=O)-O-(CH ₂ ) ₂ -S-(CH ₂ ) ₂ -Rf CH ₂ =C(-C1)-C(=O)-O-(CH ₂ ) ₂ -SO ₂ -Rf

CH ₂ =C(-C1)-C(=O)-O-(CH ₂ ) ₂ -SO ₂ -(CH ₂ ) ₂ -Rf CH ₂ =C(-C1)-C(=O)-NH-(CH ₂ ) ₂ -Rf

CH ₂ =C(-CF ₃ )-C(=O)-O-(CH ₂ ) ₂ -S-Rf CH ₂ =C(-CF ₃ )-C(=O)-O-(CH ₂ ) ₂ -S-(CH ₂ ) ₂ -Rf

CH ₂ =C(-CF ₃ )-C(=O)-O-(CH ₂ ) ₂ -SO ₂ -Rf

CH ₂ =C(-CF ₃ )-C(=O)-O-(CH ₂ ) ₂ -SO ₂ -(CH ₂ ) ₂ -Rf

CH ₂ =C(-CF ₃ )-C(=O)-NH-(CH ₂ ) ₂ -Rf

CH ₂ =C(-CF ₂ H)-C(=O)-O-(CH ₂ ) ₂ -S-Rf CH ₂ =C(-CF ₂ H)-Q=O)-O-(CH ₂ ) ₂ -S-(CH ₂ ) ₂ -Rf

CH ₂ =C(-CF ₂ H )-C(=O)-O-(CH ₂ ) ₂ -SO ₂ -Rf

CH ₂ =C(-CF ₂ H )-C(=O)-O-(CH ₂ ) ₂ -SO ₂ -(CH ₂ ) ₂ -Rf

CH ₂ =C(-CF ₂ H )-C(=O)-NH-(CH ₂ ) ₂ -Rf

CH ₂ =C(-CN)-C(=O)-O-(CH ₂ ) ₂ -S-Rf CH ₂ =C(-CN)-C(=O)-O-(CH ₂ ) ₂ -S-(CH ₂ ) ₂ -Rf

CH ₂ =C(-CN )-C(=O)-O-(CH ₂ ) ₂ -SO ₂ -Rf

CH ₂ =C(-CN )-C(=O)-O-(CH ₂ ) ₂ -SO ₂ -(CH ₂ ) ₂ -Rf

CH ₂ =C(-CN )-C(-O)-NH-(CH ₂ ) ₂ -Rf

CH ₂ =C(-CF ₂ CF ₃ )-C(=O)-O-(CH ₂ ) ₂ -S-Rf CH ₂ =C(-CF ₂ CF ₃ )-C(=O)-O-(CH ₂ ) ₂ -S-(CH ₂ ) ₂ -Rf

CH ₂ =C(-CF ₂ CF ₃ MX=OMHCH ₂ ) ₂ -SO ₂ -Rf

CH ₂ =C(-CF ₂ CF ₃ )-C(=O)-O-(CH ₂ ) ₂ -SO ₂ -(CH ₂ ) ₂ -Rf

CH ₂ =C(-CF ₂ CF ₃ )-C(=O)-NH-(CH ₂ ) ₂ -Rf CH ₂ =C(-F)-C(=O)-O-(CH ₂ ) ₃ -S-Rf

CH ₂ =C(-F)-C(=O)-O-(CH ₂ ) ₃ -S-(CH ₂ ) ₂ -Rf

CH ₂ =C(-F)-C(=O)-O-(CH ₂ ) ₃ -SO ₂ -Rf

CH ₂ =C(-F)-C(=O)-O-(CH ₂ ) ₃ -SO ₂ -(CH ₂ ) ₂ -Rf

CH ₂ =C(-F)-C(=O)-NH-(CH ₂ ) ₃ -Rf

CH ₂ =C(-C1)-C(=O)-O-(CH ₂ ) ₃ -S-Rf

CH ₂ =C(-C1)-C(=O)-O-(CH ₂ ) ₃ -S-(CH ₂ ) ₂ -Rf

CH ₂ =C(-C1)-C(=O)-O-(CH ₂ ) ₃ -SO ₂ -Rf

CH ₂ =C(-C1)-C(=O)-O-(CH ₂ ) ₃ -SO ₂ -(CH ₂ ) ₂ -Rf CH ₂ =C(-CF ₃ )-C(=O)-O-(CH ₂ J ₃ -S-Rf

CH ₂ =C(-CF ₃ )-C(=O)-O-(CH ₂ ) ₃ -S-(CH ₂ ) ₂ -Rf CH ₂ =C(-CF ₃ MX=O)-O-(CH ₂ ) ₃ -SO ₂ -Rf

CH ₂ =C(-CF ₃ )-C(=0)-0-(CH ₂ ) ₃ -SO ₂ -(CH ₂ ) ₂ -Rf

CH ₂ =C(-CF ₂ H)-C(=0)-0-(CH ₂ ) ₃ -S-Rf CH ₂ =C(-CF ₂ H)-C(=0)-0-(CH ₂ ) ₃ -S-(CH ₂ ) ₂ -Rf

CH ₂ =C(-CF ₂ H )-C(=0)-0-(CH ₂ ) ₃ -SO ₂ -Rf

CH ₂ =C(-CF ₂ H MX=O)-O-(CH ₂ ) ₃ -SO ₂ -(CH ₂ ) ₂ -Rf

CH ₂ =C(-CN)-C(=0)-0-(CH ₂ ) ₃ -S-Rf CH ₂ =C(-CN)-C(=0)-0-(CH ₂ ) ₃ -S-(CH ₂ ) ₂ -Rf CH ₂ =C(-CN )-C(=O)-O-(CH ₂ ) ₃ -SO ₂ -Rf CH ₂ =C(-CN )-C(=O)-O-(CH ₂ ) ₃ -SO ₂ -(CH ₂ ) ₂ -Rf CH ₂ =C(-CF ₂ CF ₃ )-C(=O)-O-(CH ₂ ) ₃ -S-Rf CH ₂ =C(-CF ₂ CF ₃ )-C(=O)-O-(CH ₂ ) ₃ -S-(CH ₂ ) ₂ -Rf CH ₂ =C(-CF ₂ CF ₃ )-C(=O)-O-(CH ₂ ) ₃ -SO ₂ -Rf

CH ₂ =C(-CF ₂ CF ₃ )-C(=O)-O-(CH ₂ ) ₂ -SO ₂ -(CH ₂ ) ₂ -Rf wherein Rf is a linear or branched fluoroalkyl group having 1 to 20 carbon atoms.

(b) Fluorine-free monomer The fluorine-containing polymer may have the repeating units derived from the fluorine-free monomer (b). The fluorine-free monomer (b) is other than the crosslinkable monomer (c). The monomer (b) is preferably a fluorine-free monomer having a carbon-carbon double bond. The monomer (b) is preferably a vinyl monomer which is free from fluorine. The fluorine-free monomer (b) is generally a compound having one carbon-carbon double bond. Preferable examples of the fluorine-free monomer (b) include, for example, ethylene, vinyl acetate, vinyl halide such as vinyl chloride, vinylidene halide such as vinylidene chloride, acrylonitrile, styrene, polyethyleneglycol (meth)acrylate, polypropyleneglycol (meth)acrylate, methoxypolyethyleneglycol (meth)acrylate, methoxypolypropyleneglycol (meth)acrylate, and vinyl alkyl ether. The fluorine-free monomer (b) is not limited to these examples. The fluorine-free monomer (b) may contain vinyl halide and/or vinylidene halide.

The fluorine-free monomer (b) may be a (meth)acrylate ester having an alkyl group. The number of carbon atoms of the alkyl group may be from 1 to 30, for example, from 6 to 30, e.g., from 10 to 30. For example, the fluorine-free monomer

(b) may be acrylates of the general formula: CH ₂ =CA ¹ COOA ² wherein A ¹ is a hydrogen atom, a methyl group, or a halogen atom (for example, a chlorine atom, a bromine atom and a iodine atom) other than a fluorine atom, and

A ² is an alkyl group represented by C _n H _2n+ ! (n = 1 to 30).

(c) Crosslinkάble monomer

The fluorine-containing polymer may contain the repeating units derived from the crosslinkable monomer (c). The crosslinkable monomer (c) may be a fluorine-free vinyl monomer having at least two reactive groups and/or carbon-carbon double bonds. The crosslinkable monomer (c) may be a compound having at least two carbon-carbon double bonds, or a compound having at least one carbon-carbon double bond and at least one reactive group. Examples of the reactive group include a hydroxyl group, an epoxy group, a chloromethyl group, a blocked isocyanate group, an amino group and a carboxyl group.

Examples of the crosslinkable monomer (c) include diacetoneacrylamide, (meth)acrylamide, N-methylolacrylamide, hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, N,N-dimethylaminoethyl

(meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, butadiene, isoprene, chloroprene, glycerol (meth)acrylate and glycidyl (meth)acrylate, to which the crosslinkable monomer is not limited.

The copolymerization with the monomer (b) and/or the monomer (c) can optionally improve various properties such as water repellency and soil resistance; cleaning durability and washing durability of said repellency and resistance; solubility in solvent; hardness; and feeling.

In the fluorine-containing polymer, the amount of the fluorine-free monomer (b) may be from 0.1 to 100 parts by weight, for example, from 0.1 to 50 parts by weight, and the amount of the crosslinkable monomer (c) may be at most 50 parts by weight, for example, at most 20 parts by weight, particularly, from 0.1 to 15 parts by weight, based on 100 parts by weight of the fluorine-containing monomer (a).

The monomer (A) can be polymerized in the presence of the organopolysiloxane (B). Examples of an olefinically unsaturated co-monomer included in the monomer (A) include alkyl acrylate or methacrylate esters having 1 to 30 carbon atoms in the alkyl group such as butyl acrylate, ethyl acrylate, methyl acrylate, methyl methacrylate or butyl methacrylate. The alkyl acrylate or methacrylate can be used to adjust the glass transition temperature (Tg) of the resulting polymeric product resulting from the reaction of the monomer (A) and the organopolysiloxane (B); for example an acrylate having a long chain alkyl group of 4-20, particularly 8-20 carbon atoms such as stearyl acrylate or methacrylate, octyl acrylate, 2-ethylhexyl acrylate or dodecyl acrylate or methacrylate can be used to form a softer polymer of lower Tg. Copolymers with an alkyl acrylate or methacrylate monomer may improve various properties such as water- and oil- repellency and soil releasability, cleaning durability, washing durability and abrasion resistance of such repellency and releasability, solubility in solvent, hardness and feel (handle). Other acrylate or methacrylate comonomers which can be used include polyethylene glycol acrylate or methacrylate, polypropylene glycol acrylate or methacrylate, methoxypolyethylene glycol acrylate or methacrylate and methoxypolypropylene glycol acrylate or methacrylate. Other olefinically unsaturated comonomers which can be used include vinyl chloride, vinylidene chloride, styrene, acrylonitrile, methacrylonitrile, ethylene, a vinyl alkyl ether, isoprene or a vinyl ester such as vinyl acetate or vinyl propionate. The olefinically unsaturated comonomer can be used which contains a functional group that, although not reactive with amine groups, may be reactive with other functional groups to give properties such as increased substantivity on textiles and other substrates. Examples of such functional groups are hydroxyl, amino and amide, and examples of olefinically unsaturated comonomers containing them are acrylamide, methacrylamide, N-niethylolacrylamide, hydroxyethyl methacrylate, hydroxyethyl acrylate, 3-chloro-2-hydroxypropyl acrylate or methacrylate, N, N-dimethylaminoethyl acrylate or methacrylate and diethylaminoethyl acrylate or methacrylate.

(B) Functional Oreanopolysiloxane

The functional organopolysiloxane is a mercapto-functional organopolysiloxane, a vinyl-functional organopolysiloxane, a (meth)acrylamide-functional organopolysiloxane, a (meth)acrylate-functional siloxane or a mixture thereof. The functional organopolysiloxane (B) functions as a chain transfer agent. By a polymerization reaction, the functional organopolysiloxane (B) bonds to the fluorine-containing polymer though the functional oragnic group.

Component (B) of the present invention may be a mercapto-functional organopolysiloxane, that is, an organopolysiloxane having a mercapto-functional organic group present in the molecule. As used herein, a "mercapto-functional organic group" is any organic group containing a sulfur atom, such as -(CH ₂ ) _n -SH (n is the number of 0 to 10, particularly 1 to 5). The mercapto group-containing silicone (B) (that is, the mercapto-functional organopolysiloxane (B)) is a siloxane compound which has at least one (for example, 1 to 500, particularly 1 to 50, especially 2 to 40) mercapto group and a silicone moiety having two or more siloxane linkages.

Component (B) of the present invention may be a vinyl-functional organopolysiloxane, that is, an organopolysiloxane having a vinyl-functional organic group present in the molecule. As used herein, a "vinyl-functional organic group" is a group containing a -CH=CH ₂ group, such as -(CHi) _n -CH=CH ₂ (n is the number of 0 to 10, particularly 1 to 5). The vinyl group-containing silicone (B) (that is, the vinyl-functional organopolysiloxane (B)) is a siloxane compound which has at least one (for example, 1 to 500, particularly 1 to 50, especially 2 to 40) vinyl group and a silicone moiety having two or more siloxane linkages.

Component (B) of the present invention may be a (meth)acrylamide-functional organopolysiloxane, that is, an organopolysiloxane having a (meth)acrylamide-functional organic group present in the molecule. The term "(meth)acrylamide" means acrylamide or methacrylamide. As used herein, a

"(meth)acrylamide-functional organic group" is a group containing a -NH-C(=O)-CQ=CH ₂ group, such as -(CH ₂ ) _n -NH-C(=O)-CQ=CH ₂ (wherein Q is a hydrogen atom or a methyl group, and n is the number of 0 to 10, particularly 1 to 5). The (meth)acrylamide group-containing silicone (B) (that is, the (meth)acrylamide-functional organopolysiloxane (B)) is a siloxane compound which has at least one (for example, 1 to 500, particularly 1 to 50, especially 2 to 40) (meth)acrylamide group and a silicone moiety having two or more siloxane linkages.

Component (B) of the present invention may be a (meth)acrylate-functional organopolysiloxane, that is, an organopolysiloxane having a (meth)acrylate-functional organic group present in the molecule. The term "(meth)acrylate" means acrylate or methacrylate. As used herein, a "(meth)acrylate-functional organic group" is a group containing a -Q-O-C(=O)CX=CH ₂ where Q is a divalent organic group, for example, a C _1-20 hydrocarbon group such as a C _1-10 alkylene group, and X is Me or H. The (meth)acrylate group-containing silicone (B) (that is, the (meth)acrylate-functional organopolysiloxane (B)) is a siloxane compound which has at least one (for example, 1 to 500, particularly 1 to 50, especially 2 to 40) (meth)acrylate group and a silicone moiety having two or more siloxane linkages.

Organopolysiloxanes are well known in the art and are often designated by the general formula R _n Si0 _(4-n)/2) where the organopolysiloxanes may comprise any number of "M" (mono functional) siloxy units (R ₃ SiO ₀₅ ), "D" (difunctional) siloxy units (R ₂ SiO), "T" (trifunctional) siloxy units (RSiOu), or "Q" siloxy units (SiO ₂ ) where R is independently a monovalent organic group. These siloxy units can be combined in various manners to form cyclic, linear, or branched structures. The chemical and physical properties of the resulting polymeric structures can vary. For example organopolysiloxanes can be volatile or low viscosity fluids, high viscosity fluids/gums, elastomers or rubbers, and resins. R is independently a monovalent organic group, alternatively R is a hydrocarbon group containing 1 to 30 carbons, alternatively R is an alkyl group containing 1 to 30 carbon atoms, or alternatively R is methyl. The organopolysiloxanes useful as component (B) in the present invention are characterized by having at least one of the R groups in the formula R _n Si0( _4-n ) _/ 2 be a mercapto, vinyl or (meth)acrylamide group, or alternatively at least one of the R groups be a mercapto, vinyl or (meth)acrylamide group and one of the R groups be an organofunctional group, or alternatively one of the R groups be an organofunctional group also containing a mercapto, vinyl, (meth)acrylamide or (meth)acrylate group. The organofunctional group and mercapto, vinyl, (meth)acrylamide or (meth)acrylate functional group may be present on any siloxy unit having an R substituent, that is, they may be present on any M, D, or T unit. Typically, the organofunctional groups and mercapto, vinyl, (meth)acrylamide or (meth)acrylate groups are present as a R substituent on a D siloxy unit.

As used herein, "organofunctional group" means an organic group containing any number of carbon atoms, but the group contains at least one atom other than carbon and hydrogen. Representative examples of such organofunctional groups include, amines, amides, sulfonamides, quaternaries, ethers, epoxy, phenols, esters, carboxyls, ketones, halogen substituted alkyls and aryls group, to name a few. Alternatively, the organofunctional group is an amino-functional organic group.

When the organofunctional group is an amino-functional organic group, the amino-functional organic group is designated in the formulae herein as R and is illustrated by groups having the formula: -R ¹ NHR ² , -RlNR ₂ ² , or -R ¹ NHR ¹ NHR ² , wherein each R ¹ is independently a divalent hydrocarbon group having at least 2 carbon atoms, and R ² is hydrogen or an alkyl group which may have 1 to 10 carbon atoms. Each RI is typically an alkylene group having from 2 to 20 carbon atoms. Rl is illustrated by groups such as; -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -, -CH ₂ CHCH ₃ -, -CH ₂ CH ₂ CH ₂ CH ₂ -, -CH ₂ CH(CH3)CH ₂ -, -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -, -CH ₂ CH ₂ CH(CH ₂ CH ₃ )CH ₂ CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -, and

-CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -. The alkyl groups R ² are as illustrated above for R. When R ² is an alkyl group, it is typically methyl.

Some examples of suitable amino-functional hydrocarbon groups are; -CH ₂ CH ₂ NH ₂ ,

-CH ₂ CH ₂ CH ₂ NH ₂ , -CH ₂ CHCH ₃ NH, -CH ₂ CH ₂ CH ₂ CH ₂ NH ₂ ,

-CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ NH ₂₅ -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ NH ₂ ,

-CH ₂ CH ₂ NHCH ₃ , -CH ₂ CH ₂ CH ₂ NHCH ₃ , -CH ₂ (CH ₃ )CHCH ₂ NHCH ₃ ,

-CH ₂ CH ₂ CH ₂ CH ₂ NHCH ₃₅ -CH ₂ CH ₂ NHCH ₂ CH ₂ NH ₂ , -CH ₂ CH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ NH ₂ , -CH ₂ CH ₂ CH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ CH ₂ NH ₂ ,

-CH ₂ CH ₂ NHCH ₂ CH ₂ NHCH ₃₅ -CH ₂ CH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ NHCH ₃ ,

-CH ₂ CH ₂ CH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ CH ₂ NHCH ₃₅ and

-CH ₂ CH ₂ NHCH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ CH ₃ . Typically, the amino-functional group is -CH ₂ CH ₂ CH ₂ NH ₂ .

The mercapto-functional organic group is designated in the formulae herein as

R ^s and is illustrated by groups having the formula: -RISR ² , wherein each Rl and R ² is as defined above. The mercapto-functional group is illustrated by the following formulae; -CH ₂ CH ₂ CH ₂ SH ₅ -CH ₂ CHCH ₃ SH ₅ -CH ₂ CH ₂ CH ₂ CH ₂ SH, -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ SH ₅ -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ SH, -CH2CH2SCH3. Typically, the mercapto-fϊinctional group is -CH ₂ CH ₂ CH ₂ SH.

The vinyl-functional organic group is designated in the formulae herein as R ^v . The vinyl-functional organic group is illustrated by the following formulae; -CH=CH ₂ , -CH ₂ CH ₂ CH ₂ -CH=CH ₂ , -CH ₂ CHCH ₃ -CH=CH ₂ ,

-CH ₂ CH ₂ CH ₂ CH ₂ -CH=CH ₂₅ -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -CH=CH ₂ , -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -CH=CH ₂ . Typically, the vinyl-functional group is -CH=CH ₂ .

The (meth)acrylamide-functional organic group is designated in the formulae herein as R^ and is illustrated by groups having the formula: -R ¹ -NH-C(=O)-CQ=CH ₂ group (wherein R^ is a divalent hydrocarbon group having at least 2 carbon atoms, and Q is a hydrogen atom or a methyl group). The (meth)acrylamide-functional group is illustrated by the following formulae; -CH ₂ CH ₂ CH ₂ -NH-C(=O)-CH=CH ₂ , -CH ₂ CH ₂ CH ₂ -NH-C(=O)-C(CH ₃ )=CH ₂₃ -CH ₂ CHCH ₃ -NH-C(=O)-CH=CH ₂ ,

-CH ₂ CHCH ₃ -NH-C(=O)-C(CH ₃ )=CH ₂ , -CH ₂ CH ₂ CH ₂ CH ₂ -NH-C(=O)-C(CH3)=CH ₂ , -CH ₂ CH ₂ CH ₂ CH ₂ -NH-C(=O)-C(CH ₃ )=CH ₂ . Typically, the (meth)acrylamide-functional group is -CH ₂ CH ₂ CH ₂ -NH-C(=O)-C(CH ₃ )=CH ₂ .

The (meth)acrylate-functional organic group is designated in the formulae herein as R^ and is illustrated by groups having the formula: -Rl-O-C(=O)-CQ=CH ₂ group (wherein R^ is a divalent hydrocarbon group having at least 2 carbon atoms, and Q is a hydrogen atom or a methyl group). The (meth)acrylate-functional group is illustrated by the following formulae; -CH ₂ CH ₂ CH ₂ -O-C(=O)-CH=CH ₂ , -CH ₂ CH ₂ CH2-O-C(=O)-C(CH ₃ )=CH ₂ , -CH ₂ CHCH ₃ -O-C(=O)-CH=CH ₂ , -CH2CHCH3-O-C(=O)-C(CH3)=CH ₂ , -CH2CH2CH2CH2-O-C(=O)-C(CH3)=CH ₂ , -CH2CH ₂ CH2CH ₂ -O-C(=O)-C(CH3)=CH ₂ . Typically, the (meth)acrylate-functional group is -CH2CH ₂ CH2-O-C(=O)-C(CH3)=CH ₂ .

In a preferable embodiment, the functional organopolysiloxane (designated B') comprises siloxy units having the average formula:

(R ₂ SiO) _a (RR ^N SiO) _b (RR ^FO SiO) _c where; a is 0-4000, alternatively 1 to 1000, alternatively 2 to 400, b is 0-1000, alternatively 1 to 100, alternatively 2 to 50, c is 1 - 1000, alternatively 2 to 100, alternatively 3 to 50;

R is independently a monovalent organic group, alternatively R is a hydrocarbon containing 1- 30 carbon atoms, alternatively R is a monovalent alkyl group containing 1 - 12 carbons, or alternatively R is a methyl group; R ^N is a monovalent ammo-functional organic group as defined above,

R ^F0 each is a monovalent mercapto-functional organic group (R ^s ), a monovalent vinyl-functional organic group (R ^v ), a monovalent (meth)acrylamide-functional organic group (R^) or a monovalent (meth)acrylate-functional organic group (R ¹ ^) ₅ as defined above.

The R ^N group may be R ^F wherein R ^F may be a monovalent organofunctional organic group as defined above, such as hydroxyls, amines, amides, sulfonamides, quaternaries, ethers, epoxy, phenols, esters, carboxyls, ketones, halogen-substituted alkyls and aryls group. For example, the functional organopolysiloxane may comprise siloxy units having the average formula: (R ₂ SiO) _a (RR ^F SiO) _b (RR ^FO SiO) _c wherein the groups and subscripts (that is, a, b and c) are the same define above. The R ^FO group is a monovalent mercapto-functional organic group (R ^s ), a monovalent vinyl-functional organic group (R ^v ), a monovalent (meth)acrylamide-functional organic group (R ^M ) or a monovalent (meth)acrylate-functional organic group (R ¹ ^).

Organopolysiloxane (B') may be terminated with a hydrogen atom (resulting in a silanol group on the terminal siloxy unit of the terpolymer), or with an alkyl group containing 1 - 30 carbon atoms (resulting in an alkoxy group on the terminal siloxy unit of the terpolymer). When an alkyl group is used, the alkyl group can be a linear or branched alkyl, containing 1 - 30 carbons, alternatively the alkyl group can be a long chain alkyl group of 4-20, alternatively 8-20 carbon atoms such as stearyl. Alternatively the organopolysiloxane can be terminated with a trimethylsilyl group.

The organopolysiloxane (B ') of this preferable embodiment can be represented by the following average formula for example;

(CH ₂ J ₃ SH

I

R ¹ O(SiMe ₂ O) ₃ (SiMeO) ₁₃ (SiMeO) ₀ R ¹

I

(CH ₂ ) ₃ NH ₂

where; a is 0-4000, alternatively 1 to 1000, alternatively 2 to 400, b is 0-1000, alternatively 1 to 100, alternatively 2 to 50, c is 1- 1000, alternatively 2 to 100, alternatively 3 to 50; and R' is H, an alkyl group having 1 to 40 carbon atoms, or Me ₃ Si. The amino-mercapto-functional organopolysiloxane teφolymers of this preferable embodiment (B') can be prepared by any technique known in the art for preparation of organopolysiloxane terpolymers containing amino and/or mercapto-functional groups. Typically, the organopolysiloxanes (B') are prepared via a condensation polymerization reaction of an amino-functional alkoxy silane, a mercapto-functional silane monomer, and organopolysiloxane having alkoxy or silanol termination as illustrated by the following general reaction scheme.

HO(SiMe ₂ O) _n H (CH ₂ ) ₃ SH

+

ROH (MeO) ₂ SiMe(CH ₂ ) ₃ NH ₂ RO(SiMe ₂ O) _a (SiMeO) _b (SiMeO) _c R

+ Catalyst (EtO) ₂ Si(CH ₂ ) ₃ SH (CH ₂ ) ₃ NH ₂

Condensation organopolysiloxanes are well known in the art and are typically catalyzed by the addition of a strong base, such as an alkaline metal hydroxide or a tin compound. Alternatively co-polymerization of the functionalized cyclosiloxanes could be used.

The vinyl group-containing silicone (B) is of, for example, the formula:

R ¹ R ² R ³

R ¹ — O+SiO-) — (-SiO:) — ("SiO-) — R ¹

CH2=CH B R ³ wherein R ¹ is a methyl group, a methoxy group, a phenyl group, or a hydroxyl group, R ² is a methyl group, a methoxy group, a phenyl group, or a hydroxyl group, R ³ is a methyl group, a methoxy group, a phenyl group, or a hydroxyl group, R' is a hydrogen atom, an alkyl group having 1 to 40 carbon atoms, or Me ₃ Si ₅ B is a divalent saturated hydrocarbon group having 1-10 carbon atoms which may be interrupted with one or two ether linkages,

C is hydroxyls, amines, amides, sulfonamides, quaternaries, ethers, epoxy, phenols, esters, carboxyls, ketones, halogen-substituted alkyls or aryls group, a, b, and c are integers showing the number of repeat units, a is from 1 to 4000, for example, 2 to 2000, b is from 0 to 1000, preferably from 1 to 800 ,and c is from 0 to

1000, preferably from 1 to 800.

The example of vinyl group-containing silicone (B) is as follows.

R ¹ R ² R ³

R ³ ₃ Si— O+SiO-) — (-SiO-)- (-SiO-) — SiR ² 3

I

CH2=CH B D

R ³

I

C

wherein the groups such as the R ¹ group and the subscripts are defined as the same as above-mentioned.

The functional group C is particularly preferably an amino group (that is, the vinyl group-containing silicone (B) is a vinylamino silicone). The amino group has the effect of remarkably improving the affinity with other materials constituting the cosmetic and with a human body skin.

The organopolysiloxane (B') of the above-mentioned preferable embodiment can be represented by the following average formula for example;

CH=CH,

RO(SiMe ₂ O) _a (SiMeO) _b (SiMeO) _o R'

I (CH ₂ J ₃ NH ₂

where; a is 0-4000, alternatively 1 to 1000, alternatively 2 to 400, b is 0-1000, alternatively 1 to 100, alternatively 2 to 50, c is 1- 1000, alternatively 2 to 100, alternatively 3 to 50; and R' is H, an alkyl group having 1 to 40 carbon atoms, or Me ₃ Si.

The vinylamino functional organopolysiloxane terpolymers of this preferable embodiment (B') can be prepared by any technique known in the art for preparation of organopolysiloxane terpolymers containing amino and/or vinyl functional groups. Typically, the organopolysiloxanes (B ') are prepared via an equilibration polymerization reaction of an amino functional alkoxy silane,

2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane, octamethylcyclotetrasiloxane in the presence of an end-blocking agent such as hexamethydisiloxane for example, as illustrated by the following general reaction scheme. (MeO) ₂ SiMe(CH ₂ ) ₃ NH

+ CH=CH ₂

(Me ROH

= ₂ 2 ^u Si ^lu O)i ₄ 4 I Me ₃ SiO(SiMe ₂ O) ₃ (SiMeO) ₁₁ (SiMeO) ₀ SiMe ₃ +

Catalyst

(MeViSiO) ₄

(CH ₂ J ₃ NH ₂

+ Me ₃ SiOSiMe ₃

Equilibration prepared organopolysiloxanes are well known in the art and are typically catalyzed by the addition of a strong acid or base, such as an alkaline metal hydroxide or a sulphonic acid. Alternatively co-polymerization of the functionalized alkoxysilanes and silanol terminated polydimethylsiloxanes could be used.

Typically, the (meth)acrylamide-functional organopolysiloxane can be prepared by reacting the amino-functional organopolysiloxane with (meth)acrylic anhydride. In the reaction, amino group (-NH ₂ ) is converted into (meth)acrylamide group ((-NH-C(=O)-CQ=CH ₂ (wherein Q is a hydrogen atom or a methyl group)). For example, the (meth)acrylamide-functional organopolysiloxane may have a ≡Si-(CH ₂ ) _n -NH-C(=O)-CQ=CH2 group (wherein Q is a hydrogen atom or a methyl group, and n is the number of O to 10, particularly 1 to 5).

Typically, the (meth)acrylate-functional organopolysiloxane can be prepared by reacting a carbinol-functional organopolysiloxane with (meth)acrylic anhydride. In the reaction, with a carbinol functional siloxane, the carbinol group (-OH) is converted into a (meth)acrylate group ((-O-C(=O)-CQ=CH ₂ (wherein Q is a hydrogen atom or a methyl group)). For example, the methacrylate-functional organopolysiloxane may have a ≡Si-(CH ₂ ) _n -O-C(=O)-CQ=CH ₂ group (wherein Q is a hydrogen atom or a methyl group, and n is the number of 0 to 10, particularly 1 to 5). The fluorine-containing polymer may have a weight-average molecular weight of 2,000 to 5,000,000, particularly 3,000 to 5,000,000, especially 10,000 to 1,000,000. The weight-average molecular weight (in terms of polystyrene) of the fluorine-containing polymer can be determined by GPC (Gel Permeation

Chromatography).

In the fluorine-containing polymer, the repeating units may not be positioned as shown in the chemical formulae, and the fluorine-containing polymer may be a random polymer or block copolymer.

The fluorine-containing polymer of the present invention can be produced by bulk polymerization, solution polymerization and emulsion polymerization.

In the bulk polymerization, a method is adopted in which a mixture of the monomers and the functional organopolysiloxane is purged by nitrogen, a polymerization initiator is then added, and the mixture is stirred in the range of from 30 to 80°C for several (2 to 15) hours to be polymerized. Examples of the polymerization initiator include azobisisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate and diisopropyl peroxydicarbonate. The polymerization initiator may be used in the amount within the range from 0.01 to 20 parts by weight, for example, from 0.01 to 10 parts by weight, based on 100 parts by weight of the monomers.

In the case of the solution polymerization, the mixture of the monomers and the functional organopolysiloxane is dissolved in a suitable organic solvent in which these can dissolve and to which these are inert, and then polymerized in the same manner as described earlier. Examples of the organic solvent include a hydrocarbon-based solvent, an ester-based solvent, a ketone-based solvent, an alcohol-based solvent, a silicone-based solvent, and a fluorine-containing solvent. The organic solvent is inert to the monomer and dissolves the monomer, and examples thereof include acetone, chloroform, HCHC225, isopropyl alcohol, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, 1,1 ,2,2-tetrachloroethane, 1,1,1 -trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane and trichlorotrifluoroethane. The organic solvent may be used in the amount within the range from 50 to 2,000 parts by weight, for example, from 50 to 1,000 parts by weight, based on 100 parts by weight of total of the monomers.

In the solution polymerization, there can be used a method of dissolving the monomer(s) into an organic solvent in the presence of a polymerization initiator, replacing the atmosphere by nitrogen, and stirring the mixture with heating, for example, at the temperature within the range from 30 degrees C to 120 degrees C for 1 hour to 10 hours.

In the case of the emulsion polymerization, the polymerization is carried out in the same manner as described above after emulsifying a mixture of the monomers and the functional organopolysiloxane in water using a proper emulsifier. In some combinations of the monomers (a) to (c) and the functional organopolysiloxane, a poor compatibility of the monomers and the functional organopolysiloxane in water results in a poor copolymerizability. In such a case, a method in which a proper auxiliary solvent such as glycols and alcohols and/or a low molecular weight monomer is added to improve the compatibility of the mixture is adopted. A hydrophobic group in the emulsifier to be used in the emulsion polymerization may be any of hydrocarbon type, silicon-containing type and fluorine-containing type. As for the ionicity of a hydrophilic group, any of nonionic one, anionic one, cationic one and amphoteric one may be used. As the polymerization initiator for emulsion polymerization, for example, water-soluble initiators (e.g., benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidine dihydrochloride, azobisisobutyronitrile, sodium peroxide, potassium persulfate and ammonium persulfate) and oil-soluble initiators (e.g., azobisisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate and diisopropyl peroxydicarbonate) are used. The polymerization initiator may be used in the amount within the range from 0.01 to

10 parts by weight based on 100 parts by weight of the monomers.

In the emulsion polymerization, there can be used a method of emulsifying monomers in water in the presence of a polymerization initiator and an emulsifying agent, replacing the atmosphere by nitrogen, and polymerizing with stirring, for example, at the temperature within the range from 30 degrees C to 120 degrees C, for example, from 50 degrees C to 80 degrees C, for 1 hour to 10 hours.

When the monomers are not completely compatibilized, a compatibilizing agent capable of sufficiently compatibilizing them (e.g., a water-soluble organic solvent and a low-molecular weight monomer) is preferably added to these monomers. By the addition of the compatibilizing agent, the emulsifiability and polymerizability can be improved.

Examples of the water-soluble organic solvent include acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol and ethanol. The water-soluble organic solvent may be used in the amount within the range from 1 to 50 parts by weight, e.g., from 10 to 40 parts by weight, based on 100 parts by weight of water. Examples of the low-molecular weight monomer are methyl methacrylate, glycidyl methacrylate,

2,2,2-trifluoroethyl methacrylate. The low-molecular weight monomer may be used in the amount within the range from 1 to 50 parts by weight, e.g., from 10 to 40 parts by weight, based on 100 parts by weight of total of monomers.

As the emulsifying agent, various emulsifying agents such as an anionic emulsifying agent, a cationic emulsifying agent and a nonionic emulsifying agent can be used in the amount within the range from 0.5 to 20 parts by weight based on 100 parts by weight of the monomers. The emulsifying agent used in the emulsion polymerization may have a hydrophobic group which may be a hydrocarbon, a silicone or a fluorine-containing compound, and hydrophilic group which may be nonionic, anionic, cationic or amphoteric. A combination of the anionic emulsifying agent and the nonionic emulsifying agent is preferable in order to obtain both the stability of the emulsion and safety to skin. The amount of the anionic emulsifying agent is from 5 to 80 % by weight, preferably from 10 to 60 % by weight, based on the total of the anionic emulsifying agent and the nonionic emulsifying agent. Preferably, the anionic emulsifying agent is polyoxyethylene alkyl (preferably C ₁ to C ₃₀ alkyl) ether sulfate salt, and the nonionic emulsifying agent is fatty acid sorbitan ester, polyoxyethylene fatty acid sorbitan ester, polyoxyethylene hardened castor oil and/or polyoxyethylene fatty acid sorbit ester.

In order to obtain a polymer dispersion in water, which has a high polymer solid content and which has very fine and stable particles, it is desirable that the mixture of the monomers and the functional organopolysiloxane is dispersed in water by using an emulsifying device capable of applying a strong shearing energy (e.g., a high-pressure homogenizer and an ultrasonic homogenizer) to prepare the fine particles of the mixture, and then the polymerization is conducted.

The fluorine-containing polymer (I) is preferably in the form of fine particles in a medium such as an aqueous medium. An average particle diameter of the fluorine-containing polymer (I) is preferably 0.0001 to 1 micrometer, for example, 0.01 to 0.5 micrometers. In this range of the average particle diameter, an amount of the emulsifying agent is low for the purpose of obtaining a stable dispersion, the excellent water- and oil repellency can be obtained and polymer particles can be present stably. The average particle diameter can be measured by a dynamic light scattering spectrophotometer and an electron microscope. A usual emulsion polymerization can give the average particle diameter of 0.0001 to 1 micrometer by conducting the polymerization in the presence of an emulsifying agent.

The fluorosilicone reaction product of the monomer (A) and the organopolysiloxane (B) may be prepared by any reaction process known in the art to effect polymerisation of such monomers. Preferably, the fluorosilicone may be prepared according to the process of the present invention comprising; I) reacting,

(A) a monomer comprising a fluorine-containing monomer of the formula: CH ₂ =C(-X)-C(=O)- Y-Z-Rf wherein X is a hydrogen atom, a monovalent organic group, or a halogen atom, Y is -O- or -NH-,

Z is a direct bond or a divalent organic group, and Rf is a fluoroalkyl group having 1 to 20 carbon atoms, in the presence of

(B) a functional organopolysiloxane, via a polymerization reaction, preferably a free radical polymerisation reaction.

Components (A) and (B) in the process are the same as described above.

The process may also be conducted in the presence of a polar organic solvent. The polar organic solvent can be one or more alcohol, ketone or ester solvents selected from butanol, t-butanol, isopropanol, butoxyethanol, methyl isobutyl ketone, methyl ethyl ketone, butyl acetate or ethyl acetate and/or an aromatic hydrocarbon such as xylene, toluene or trimethylbenzene a blend of one or more of these.

The initiator for the free radical polymerisation reaction can be any compound known in the art for initiating free radical reactions, such as organic peroxides or azo compounds. Representative, non-limiting examples are; azo compounds such as azobisisobutyronitrile or azobisisovaleronitrile (AIVN), peroxides such as benzoyl peroxide. The polymerisation temperature typically ranges 50-120°C.

Alternatively the polymeric reaction product can be obtained using the technique of emulsion polymerisation, where all the components are polymerised in the presence of water, surfactants and polymerisation initiator.

The fluorosilicone reaction product can contain various ratios of the monomer (A) and the organopolysiloxane (B), as controlled by the amount of each of components

(A) and (B). The fluorosilicone may contain 5 to 99.9% by weight, preferably 10 to 95% by weight of the monomer (A), and 0.1 to 95% by weight, preferably 5 to 90% by weight of the organopolysiloxane (B) with the proviso that sum of the wt % of (A) and

(B) equals 100%. A fluorosilicone product having a high proportion of organopolysiloxane may provide greater substantivity to fibrous substrates or softness of handle of the treated material. A polymeric product having a high proportion of fluorine-containing monomer may provide maximum hydrophobicity and oleophobicity.

The fluorosilicone reaction product is generally obtained as a solution. It can be isolated by evaporation of the solvent. For application as an oil repellent, the fluorosilicone reaction product is generally required in liquid form and the solution obtained by reaction can often be diluted to a solution suitable for application to textiles. Alternatively the fluorosilicone reaction product can be dissolved in a different solvent for application to textiles, for example in a polar organic solvent of higher boiling point. The fluorosilicone reaction product can alternatively be emulsified by mixing with water and an emulsifying agent, such as a cationic surfactant and/or a nonionic or anionic surfactant. The fluorosilicone reaction product can be isolated before emulsifϊcation or the polymerisation product solution can be emulsified, optionally with removal of solvent. If the polymeric product is obtained by emulsion polymerisation, the emulsion is generally used, diluted as required, without isolating the polymeric product.

(II) Fluorine-free Polymer (Second Polymer)

The fluorine-free polymer (II) contains a vinyl monomer. The vinyl monomer is free from a fluorine atom and is preferably free from a silicon atom.

The vinyl monomer may be as follows:

(1) CH ₂ =CR ¹ CO ₂ R ² ,

(2) CH ₂ =CHO ₂ CR ² ,

(3) CH ₂ =CHR ³ , (4) CH ₂ =CHD,

(5) CH ₂ =CD ₂ ,

(6) CH ₂ =CHCH ₂ O ₂ CR ² ,

(7) CH ₂ =CHCOR ² ,

(8) CH ₂ =CR ¹ CO ₂ CH ₂ CH ₂ NR^, (9) CH ₂ =CR ¹ CONHCH ₂ OH wherein

R ¹ : a hydrogen atom, a methyl group, or a halogen atom (such as a chlorine atom, a bromine atom and a iodine atom), R ² : an alkyl group having 1 to 18 carbon atoms, R ³ : a hydrocarbon group (such as an aliphatic group, an aromatic group and an araliphatic group) having 1 to 30 carbon atoms such as phenyl, alkyl and substituted phenyl,

R ⁴ : a hydrogen atom, or an alkyl group having 1 to 18 carbon atoms, D: a chlorine atom, a bromine atom or a iodine atom.

The fluorine-free polymer (II) preferably comprises the combination of at least one monomer of formulae (1) and/or (2) with at least one monomer of the formulae (3) and/or (4). Preferably, the fluorine-free polymer (II) contains the monomer (1) and/or (2) in the amount of preferably at least 20% by weight, more preferably at least 40% by weight, for example, from 50% to 90 % by weight based on the polymer (II).

Preferably, the fluorine-free polymer (I) contains the monomer (3) and/or (4) in the amount of preferably at least 10% by weight, more preferably at least 20% by weight, based on the polymer (II). The monomer (3) and/or (4) may not be contained in the fluorine-free polymer (I). The remaining components other than monomers (1) to (4) may be the monomers (5) to (9).

The polymer (II) may contain the crosslinkable monomer (c) explained in the polymer (I). In the polymer (II), the amount of the monomer (c) is, at most 50 % by weight, for example, from 0.1 to 30% by weight, based on the polymer (II).

The fluorine-free polymer (II) may have a weight-average molecular weight of 2,000 to 5,000,000, particularly 3,000 to 5,000,000, especially 10,000 to 1,000,000. The weight-average molecular weight (in terms of polystyrene) of the fluorine-containing polymer (II) can be determined by GPC (Gel Permeation Chromatography). The fluorine-containing polymer of the present invention is preferably be produced by solution polymerization and emulsion polymerization. The emulsion polymerization is particularly preferable. The emulsion polymerization gives a dispersion wherein particles of the polymer (II) are dispersed in an aqueous medium.

The emulsion polymerization is conducted in an aqueous medium, preferably in the presence of a polymerization initiator. The polymerization initiator may be a peroxide compound and an azo compound. The polymerization initiator includes, for example, water-soluble initiators (e.g., benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidine dihydrochloride, azobisisobutyronitrile, sodium peroxide, potassium persulfate and ammonium persulfate) and oil-soluble initiators (e.g., azobisisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate and diisopropyl peroxydicarbonate).

For controlling the molecular weight of the resultant polymer (II), a chain transfer agent may be added.

An emulsifying agent is preferably present in the emulsion of the polymer (II).

Various emulsifying agents such as an anionic emulsifying agent, a cationic emulsifying agent and a nonionic emulsifying agent and an amphoteric emulsifying agent can be used in the amount within the range from 0.5 to 30 parts by weight based on 100 parts by weight of the monomers. A combination of the nonionic emulsifying agent and the cationic emulsifying agent and a combination of the nonionic emulsifying agent and the amphoteric emulsifying agent are preferable, for example, in order to obtain the stability of the emulsion. The amount of the emulsifying agent is preferably from 1 to 20 parts by weight, based on 100 parts by weight of the polymer (II).

The average particle diameter of the polymer (II) is preferably from 0.03 to 0.5 micrometers. In such a particle diameter, the required amount of emulsifying agent and/or self-emulsifying monomer is low and the sedimentation of particles is not caused.

In the water- and oil-repellent composition of the present invention, the polymer (I) and the polymer (II) are not present in the same particle and are present in different particles. Preferably, the polymer (I) and the polymer (II) are separately polymerized to give each of the particles of polymer (I) and the particles of polymer (II), and then the particles of polymer (I) (that is, the dispersion of polymer (I)) is mixed with the particles of polymer (II) (that is, the dispersion of polymer (II)). The water- and oil-repellent composition of the present invention comprises the dispersion of polymer (I) and the dispersion of polymer (II), and, if necessary, an aqueous agent and the like.

In the water- and oil-repellent composition of the present invention, the weight ratio of the polymer (I) and the polymer (II) is preferably from 40:60 to 90:10, particularly from 50:50 to 80:20. Such weight ratio gives excellent water- and oil-repellency and excellent durability of water- and oil-repellency. The solid content of the water- and oil-repellent composition of the present invention is preferably from 0.1 to 70 % by weight, particularly from 1 to 50 % by weight. An amount of the fluorine-containing monomer may be from 10 to 80% weight, preferably 20 to 70 % by weight, based on the total of the polymers (I) and (H).

Surface treatment agent The water- and oil-repellent composition can be applied to fibrous substrates such as textiles by any of the methods known for treatment of textiles with liquids. The concentration of the polymers (I) and (II) in the solution applied to the textile can for example be 0.5 to 20% by weight, alternatively 1 to 5%. When the textile is a fabric, the fabric can be immersed in the liquid or can be padded or sprayed with the liquid. The treated textile is dried and is preferably heated, for example at 100-200 ⁰ C, to develop the oil repellency.

Alternatively, the fluorosilicone reaction product can be applied to a textile via a cleaning process, such as in a laundry application or dry cleaning process.

The textile which is treated is typically a fabric, including woven, knitted and nonwoven fabrics, fabrics in garment form and carpet, but may also be a fibre or yarn or intermediate textile product such as a sliver or roving. The textile material can be a natural fibre such as cotton or wool, a manmade fibre such as viscose rayon or lyocell or a synthetic fibre such as polyester, polyamide or acrylic fibre, or can be a mixture of fibres such as a mixture of natural and synthetic fibres. The polymeric product of the invention is particularly effective in rendering cellulosic fibres such as cotton or rayon oleophobic and oil repellent. The process of the invention generally also renders the textile hydrophobic and water repellent. Fabric treatment with the polymeric product of the invention imparts oil repellency to fabrics whilst at the same time imparting an improvement in feel compared to untreated fabric and also imparting an improvement in feel compared to fabric treated with known fluoropolymer textile treatment agents.

The fibrous substrate can alternatively be leather. The polymeric product can be applied to leather from aqueous solution or emulsion at various stages of leather processing, for example during leather wet end processing or during leather finishing, to render the leather hydrophobic and oleophobic.

The fibrous substrate can alternatively be paper. The polymeric product can be applied to preformed paper or at various stages of papermaking, for example during drying of the paper.

The surface treatment agent of the present invention is preferably in the form of a solution, an emulsion or an aerosol. The surface treatment agent generally comprises the fluorine-containing polymer and a medium (such as a liquid medium, particularly an aqueous medium, for example, water or a mixture of water and an organic solvent). The organic solvent in the aqueous medium is generally a water-soluble organic solvent. An amount of the organic solvent may be at most 40 % by weight, for example, 0.1 to 20 % by weight, based on the medium. The concentration of the fluorine-containing polymer in the surface treatment agent may be, for example, from 0.1 to 50 % by weight.

The surface treatment agent can be applied to a substrate to be treated by a know procedure. The application of the surface treatment agent can be conducted by immersion, spraying and coating. Usually, the surface treatment agent is diluted with an organic solvent or water, is adhered to surfaces of the substrate by a well-known procedure such as an immersion coating, a spray coating and a foam coating, and is dried. If necessary, the treatment liquid is applied together with a suitable crosslinking agent, followed by curing. It is also possible to add mothproofing agents, softeners, antimicrobial agents, flame retardants, antistatic agents, paint fixing agents, crease-proofing agents, etc. to the surface treatment agent. The concentration of the fluorine-containing compound in the treatment liquid contacted with the substrate may be from 0.01 to 10% by weight (particularly for immersion coating), for example, from 0.05 to 10% by weight (particularly for spray coating), based on the treatment liquid.

The substrate to be treated with the surface treatment agent (for example, a water- and oil-repellent agent) of the present invention is preferably a textile. The textile includes various examples. Examples of the textile include animal- or vegetable-origin natural fibers such as cotton, hemp, wool and silk; synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride and polypropylene; semisynthetic fibers such as rayon and acetate; inorganic fibers such as glass fiber, carbon fiber and asbestos fiber; and a mixture of these fibers.

The textile may be in any form such as a fiber, a yarn and a fabric.

The term "treatment" means that the treatment agent is applied to the substrate by immersion, spray, coating or the like. The fluorine-containing polymer which is an active component of the treatment agent can penetrate the internal of the substrate or can adhere on the surface of the substrate by the treatment. EXAMPLES

The following Preparative Examples and Examples further illustrate the present invention in detail but are not to be construed to limit the scope thereof. All parts and percentages in the examples are on a weight basis and all measurements were obtained at about 23 °C, unless indicated to the contrary.

Shower water repeϋency test (7IS-L-1092)

Shower water repellency test was conducted according to JIS-L-1092. The shower water repellency was expressed by water repellency No. (as shown in the below-described Table 1 ) .

A glass funnel which has a volume of at least 250 ml and a spray nozzle which can spray 250 ml of water for 20-30 seconds are used. A test piece frame is a metal frame having a diameter of 15 cm. Three sheets of a test piece having a size of about 20cm x 20cm are prepared and the sheet is mounted on a test piece holding frame so that the sheet has no wrinkle. The center of the spray was located on the center of the sheet.

Room temperature water (250 mL) is charged into the glass funnel and sprayed on the test piece sheet (for time of 25-30 seconds). The holding flame is removed from a stand, one edge of the holding flame is grasped so that a front surface is downside and the other edge is lightly hit with a stiff substance. The holding flame is further rotated 180° and the same procedure is repeated to drop excess water droplets. The wet test piece is compared with a wet comparison standard to grade 0, 50, 70, 80, 90 and 100 points in order of poor water-repellency to excellent water repellency. The results are obtained from an average of three measurements. The indication "+" after a numeral value means that the property is higher than said numeral value and the indication "-" after a numeral value means that the property is lower than said numeral value. Table 1

Water repellency State

No.

100 No wet or water droplets adhesion on surface

90 No wet but small water droplets adhesion on surface

80 Separate small water droplets-like wet on surface

70 Wet on half of surface and separate small wet which penetrates fabric

50 Wet on whole surface

0 Wet on front and back whole surfaces

Oil-repellencv test (According to AATCC Test Method 118-1992)

A treated fabric is stored in a thermo-hygrostat having a temperature of 21 ⁰ C and a humidity of 65% for at least 4 hours. A test liquid (shown in Table 3) which has been also stored at 21 ⁰ C is used. The test is conducted in an air-conditioned room having a temperature of 21 ⁰ C and a humidity of 65%. Five droplets of the test liquid wherein one droplet has an amount of 50 μL are softly dropped by a micropipette on the fabric. If 4 or 5 droplets remain on the fabric after standing for 30 seconds, the test liquid passes the test. The oil-repellency is expressed by a maximum point of the test liquid which passes the test. The oil-repellency is evaluated as nine levels which are Fail, 1, 2, 3, 4, 5, 6, 7 and 8 in order of a bad level to an excellent level. The indication "+" after a numeral value means that the property is higher than said numeral value and the indication "-" after a numeral value means that the property is lower than said numeral value.

Washing durability of water- and oil-repellency

Washing is conducted repeatedly five times according to JIS L-0217-103 method, and then water- and oil-repellency is evaluated (HL-5). HLO means that the evaluation is made after no washing.

Average particle size

The average particle size of an emulsion is measured by using LASER type light method (Fiber-Optics Particle Analyzer FPAR manufactured by Otsuka Denshi K.K. Co., Ltd.).

The meanings of abbreviations are as follows: Monomers n-BA: n-Butyl acrylate

N-MAM : N-Methylol acrylamide,

T-M : 3-Chloro-2-hydroxypropyl methacrylate n-BMA : n-Butyl methacrylate t-BMA : t-Butyl methacrylate

StA : Stearyl acrylate

VCl : Vinyl chloride

13FMA 3,3,4,4,5,5,6,6,7,7,8,8,8-Tridecafluorooctyl methacrylate,

17FA : 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-Heptadecafluorodecyl acrylate

Chain transfer agents

Si-SH: Below-explained aminomercaptosiloxane L-SH: Lauryl mercaptan

Emulsifiers

C2ABT : Di-harden tallow alkyl dimethyl ammonium chloride,

PP-40R: Sorbitan monopalmitate,

K220: Polyethyleneglycol lauryl ether,

BO50: Polyoxyethylene oleyl ether,

EAD-8: Polyoxyethylene(3)tridecyl ether

Others TPG: Tripropylene glycol

NC-32W : 2,2'-Azobis(2-amidinopropane) dihydrochloride

Synthesis of aminomercapto-functional siloxane: Siloxane A TSi-SH)

Into a three necked round bottomed flask fitted with a condenser, overhead stirrer and thermocouple were charged first silanol-terminated polydimethylsiloxane (323 g, Mn: about 900), second silanol-terminated polydimethylsiloxane (380 g, Mn: about 300), mercaptopropylmethyldimethoxysilane (230 g), aminopropylmethyldiethoxysilane (27 g), trimethylethoxysilane (42 g), barium hydroxide (0.62 g) and sodium orthophosphate (0.25 g). The reaction mixture was heated to 75 ⁰ C and held at this temperature for three hours. Then the volatiles were removed under reduced pressure (200mbar) at 75 ⁰ C for four hours to yield an aminomercaptosiloxane.

The physical and structural properties of the aminomercaptosiloxane (Silane A ₃ Si-SH) are described in the table below:

Synthetic Example 1

In a 500 niL reactor, charged were n-BA (84.31 g), N-MAM (1.69 g), T-M (0.84 g), L-SH (0.62 g), C2ABT (1.01 g), PP-40R (1.35 g), K220 (5.85 g), BO50 (1.45 g), water (138.13g), and TPG (24.88 g). The mixture is previously by a homomixer, and then treated for 5 minutes in an ultrasonic wave emulsifier to give an emulsion of a monomer mixture.

The monomer emulsion was charged into a 500 mL separable flask equipped with a condenser, a nitrogen introducing tube and a thermometer. The atmosphere of the flask was replaced with nitrogen, a solution of an initiator (NC-32W, 1.02g) in water (5g) was added. The mixture was warmed to 6O ⁰ C and the polymerization was conducted for 3 hours to give a dispersion (256.4g) of fluorine-free polymer particles having a solid content of 36.9% by weight and an average particle diameter of 0.182μm.

Synthetic Examples 2 to 25 In the same manner as in Synthetic Example 1, monomer mixtures shown in

Tables 3 to 8 were emulsified. The polymerization was conducted in a 500 mL stainless autoclave when VCl is used as a monomer or the polymerization was conducted in a 500 mL separable flask equipped with a condenser, a nitrogen introducing tube and a thermometer when VCl is not used as a monomer, to give various fluorine-free polymer particles or various fluorine-containing polymer.

Table 3

Table 4

Table 5

Table 6

Table 7

Table 8

Examples 1 to 26 and Comparative Examples 1 to 3

Polymer particle dispersions obtained in Synthetic Examples 1 to 25 were diluted with water to give a solid concentration of 30% by weight. The diluted dispersions were blended as in mixing ratios shown in Tables 9 to 15 to a dispersion mixture.

Table 9

(,O

Table 10

Table 11

Table 13

Table 14

Table 15

Test Examples 1 to 20

As to the polymer particle dispersions in the above-mentioned Examples 1 to 20, water repellency and oil repellency were evaluated. The results are shown in Table 16.

Table 16

Comparative Test Examples 1 to 6

As to the polymer particle dispersions in the above-mentioned Synthetic Examples 16, 17, and 19 to 22, water repellency and oil repellency were evaluated. The results are shown in Table 17.

Comparative Test Examples 7 to 9

As to the polymer particle dispersions in the above-mentioned Comparative Examples 1 to 3, water repellency and oil repellency were evaluated. The results are shown in Table 18. Table 18

Test Examples 21 to 26

As to the polymer particle dispersions in the above-mentioned Examples 21 to 26, water repellency and oil repellency were evaluated. The results are shown in Table 19.

Comparative Test Examples 10 to 13

As to the polymer particle dispersions in the above-mentioned Synthetic Examples 18, and 23 to 25, water repellency and oil repellency were evaluated. The results are shown in Table 20.

Table 20

Test Examples 27 to 46

As to the polymer particle dispersions in the above-mentioned Examples 1 to 20, water repellency and oil repellency at low concentrations were evaluated. The results are shown in Table 21.

Table 21

Comparative Test Examples 14 to 19

As to the polymer particle dispersions in the above-mentioned Synthetic Examples 16, 17, and 19 to 22, water repellency and oil repellency at low concentrations were evaluated. The results are shown in Table 22. Table 22

Comparative Test Examples 20 to 22

As to the polymer particle dispersions in the above-mentioned Comparative Examples 1 to 3, water repellency and oil repellency at low concentrations were evaluated. The results are shown in Table 23.

Table 23

Test Examples 47 to 52

As to the polymer particle dispersions in the above-mentioned Examples 21 to 26, water repellency and oil repellency at low concentrations were evaluated. The results are shown in Table 24.

Table 24

Comparative Test Examples 23 to 26

As to the polymer particle dispersions in the above-mentioned Synthetic Examples 18, and 23 to 25, water repellency and oil repellency at low concentrations were evaluated. The results are shown in Table 25.

Table 25

Test Examples 53 and 54 and Comparative Test Examples 27 to 30

As to the polymer particle dispersions shown in Tables 26 to 29, wash durability of water repellency and oil repellency were evaluated. The results are shown in Tables 26 to 29.

Table 26

Table 27

Table 28

CTl

Table 29