JP5529121B2 - Aqueous polymer dispersion composition and surface treatment agent - Google Patents

Description

  An object of the present invention is to provide an aqueous water / oil repellent dispersion composition that can impart excellent water / oil repellency and durability even when the amount of the fluorine-containing monomer in the composition is reduced.

Various fluorocarbon polymers are widely used to impart oleophobic / oleophobic properties to fabrics and the like.
Attempts have been made to copolymerize a monomer having an adhesive group together with a fluoroalkyl-containing polymerizable monomer for the purpose of improving the durability of water and oil repellency against washing and dry cleaning.
In JP-B-38-22487 and JP-B-41-8579, an attempt was made to create an economically superior water / oil repellent composition by blending a polymer not containing fluoroalkyl with a polymer containing fluoroalkyl. ing.
In Japanese Patent Publication No. 49-42878 and USP3849521, it is proposed to use a polymerizable monomer having a specific structure as a polymer or copolymer that can be added without deteriorating the antifouling performance and durability. Yes.
In JP-A-06-228241, surface characteristics such as water / oil repellency and maintainability can be obtained by mixing two types of polymers having different fluoroalkyl group-containing polymers and a polymer not containing fluoroalkyl groups. It is disclosed that a resin composition having an improved surface can be obtained.

  Furthermore, in JP-A-61-264081, slip resistance is improved by mixing a polymer having at least one homopolymer or copolymer of a hydrocarbon-based polymerizable compound and having a glass transition point of 50 ° C. or higher. US Pat. No. 4,404,964 discloses a liquid repellent for carpets characterized in that a fluoroalkyl-containing polymer and a non-fluoroalkyl-containing polymer are mixed and both have a glass transition point or a melting point of 45 ° C. or higher. Is disclosed.

  On the other hand, for example, in JP-A-58-42682, JP-A-60-190408, JP-A-63-075082, JP-A-9-143877 and USP4070152, the water and oil repellency and flexibility are simultaneously applied to a substrate such as a fiber. Many blends of fluoroalkyl-containing resin emulsions and various silicone emulsions have been proposed for application.

  Further, in JP-A-2-14791, JP-A-3-76713, JP-A-11-269231, WO2004 / 041880, JP-A-3-231986, WO2004 / 108855, JP-A-8-109580 and JP-A-10-158402, reactive groups To achieve both flexibility and oil repellency for resin emulsions in which a fluoroalkyl group-containing monomer is bonded to silicone by polymerizing a polymerizable monomer containing a fluoroalkyl group with silicone having Many have been proposed.

  Further, in JP-A-2-47211, JP-A-6-507652 and JP-A-2000-186279, a composition obtained by mixing a copolymer of a fluoroalkyl group-containing monomer and an organosiloxane with a silicone emulsion for the same purpose. Proposals have been made, and in both cases, there was a problem that the water / oil repellency was lowered due to the lipophilicity of the silicone group.

  An object of the present invention is to provide a water and oil repellent containing a fluoropolymer that exhibits high water and oil repellency and is excellent in durability of water and oil repellency even when the amount of fluorine monomer is reduced. Is to provide.

  The inventors of the present invention have the object described above. (I) A fluoropolymer derived from a monomer comprising a fluoromonomer and polymerized in the presence of a functional organopolysiloxane, and ( II) It has been found that this can be achieved by a composition comprising a non-fluorinated polymer.

The present invention
(I) A fluorine-containing polymer having a repeating unit derived from a monomer containing a fluorine-containing monomer, which the functional organopolysiloxane has (or is derived from a functional organopolysiloxane) Provided is a water / oil repellent dispersion composition comprising a fluorine-containing polymer having a residue and (II) a non-fluorine polymer.

The present invention
(I) a fluorine-containing polymer,
(A) (a) 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,
Rf is a C1-C20 fluoroalkyl group. ]
And (B) mercapto functional organopolysiloxane, vinyl functional organopolysiloxane, (meth) acrylamide functional organopolysiloxane and (meth) acrylate functionality Provided is a fluorine-containing polymer comprising at least one functional organopolysiloxane selected from the group consisting of organopolysiloxanes, and (II) an aqueous water / oil repellent dispersion composition comprising a non-fluorine polymer. To do.

  The aqueous water / oil repellent dispersion composition of the present invention is useful for providing oil repellency to various surfaces. When textiles are treated, the fluorosilicone of the present invention can also provide a softer feel or texture than conventional fluorocarbon-based oil repellent treatments.

  According to the present invention, when a substrate is treated, the water / oil repellent composition can impart excellent water / oil repellency and durability thereof. When the substrate is a textile product, the treated textile product has a good texture.

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

In the present invention, the monomer (A) forming the fluoropolymer is
(A) a fluorine-containing monomer,
(B) A non-fluorine monomer different from the crosslinkable monomer present if necessary, and (c) a crosslinkable monomer present if necessary.

The fluorine-containing polymer may be a homopolymer formed from one type of monomer or a copolymer formed from two or more types of monomers.
The homopolymer has a repeating unit derived from the fluorine-containing monomer (a). The copolymer may have repeating units derived from two or more kinds of fluorine-containing monomers (a), or in addition to the repeating units derived from fluorine-containing monomers (a), It may have a repeating unit derived from the fluorine monomer (b) and, if necessary, the crosslinkable monomer (c).

  The fluorine-containing polymer can be produced by polymerizing the monomer (A) in the presence of the functional organopolysiloxane (B).

The fluorine-containing polymer constituting the surface treating agent of the present invention is
(A) a fluorine-containing monomer, and (b) a non-fluorine monomer different from the crosslinkable monomer, and (c) a crosslinkable monomer, if necessary.

(I) Fluoropolymer (first polymer)
(A) Monomer
(A) Fluorine-containing monomer Component (a) of the present invention has 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,
Rf is a C1-C20 fluoroalkyl group. ]
It is a fluorine-containing monomer shown by.
Z is, for example, a linear alkylene group having 1 to 20 carbon atoms or a branched alkylene group, for example, a group represented by the formula — (CH ₂ ) _x — (wherein x is 1 to 10), Alternatively, a group represented by the formula —SO ₂ N (R ¹ ) R ² — or a formula —CON (R ¹ ) R ² — (wherein R ¹ is an alkyl group having 1 to 10 carbon atoms, and R ² Is a linear alkylene group having 1 to 10 carbon atoms or a branched alkylene group.), Or a formula —CH ₂ CH (OR ³ ) CH ₂ — (wherein R ³ is a hydrogen atom, or , A group represented by an acyl group having 1 to 10 carbon atoms (for example, formyl or acetyl), a formula —Ar—CH ₂ — (wherein Ar is an arylene group optionally having a substituent). . group represented by) _{or,, - (CH 2) m} -SO 2 - (CH 2) - group, or _{- (CH 2) m -S- (} CH 2) n - group (where, m is 1 to 10, n is 0-10.) May be. X may be, for example, H, Me (methyl group), Cl, Br, I, F, CN, CF ₃ .

The fluorine-containing monomer (a) has the formula:
_{CH 2 = C (-X) -C} (= O) -Y-Z-Rf
[Wherein, X represents a hydrogen atom, a linear or branched alkyl group having 1 to 21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX ¹ X ² group (where X ¹ and X ² is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an 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 group having 6 to 18 carbon atoms or a cyclic aliphatic group, a —CH ₂ CH ₂ N (R ¹ ) SO ₂ — group (where R ¹ Is an alkyl group having 1 to 4 carbon atoms.), —CH ₂ CH (OZ ¹ ) CH ₂ — group (where Z ¹ is a hydrogen atom or an acetyl group), — (CH ₂ ) _m —SO ₂ - (CH _{2) n} - group, or _{- (CH 2) m -S- (} CH 2) n - group (where, m is 1 to 10, n is 0-10.), and
Rf is a linear or branched fluoroalkyl group having 1 to 20 carbon atoms. ]
It is preferable that it is an acrylate ester shown by these.

The α-position of the fluorine-containing monomer may be substituted with a halogen atom or the like. Accordingly, in the formula (I), X represents a linear or branched alkyl group having 2 to 21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX ¹ X ² group (provided that X ¹ and X ² is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an 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 1-20, such as 8-10, in particular 8 or 10. The Rf group may have 1 to 6 carbon atoms. Examples of Rf groups 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 having 6 to 18 carbon atoms or a cyclic aliphatic group, a —CH ₂ CH ₂ N (R ¹ ) SO ₂ — group (provided that R ¹ Is an alkyl group having 1 to 4 carbon atoms.), —CH ₂ CH (OY ¹ ) CH ₂ — group (where Y ¹ is a hydrogen atom or an acetyl group), — (CH ₂ ) _m —SO ₂ - (CH _{2) n} - group _{or, - (CH 2) m -S-} (CH 2) n - group (where, m is 1 to 10, n is 0-10.) is. The aliphatic group is preferably an alkylene group (particularly having 1 to 4 carbon atoms, such as 1 or 2). The aromatic group and the cycloaliphatic group may be either substituted or unsubstituted. The S group or the SO ₂ group may be directly bonded to Rf.

Examples of the fluorine-containing monomer (a) are as follows, but are not limited thereto.
CH ₂ = C (-H) -C (= O) -O- (CH ₂ ) ₂ -Rf
CH ₂ = C (-H) -C (= O) -OC ₆ H ₄ -Rf
CH ₂ = C (-Cl) -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 N (-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 CH (-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 (-Cl) -C (= O) -O- (CH ₂ ) ₂ -S-Rf
CH ₂ = C (-Cl) -C (= O) -O- (CH ₂ ) ₂ -S- (CH ₂ ) ₂ -Rf
CH ₂ = C (-Cl) -C (= O) -O- (CH ₂ ) ₂ -SO ₂ -Rf
CH ₂ = C (-Cl) -C (= O) -O- (CH ₂ ) ₂ -SO _2- (CH ₂ ) ₂ -Rf
CH ₂ = C (-Cl) -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) -C (= 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 ) -C (= O) -O- (CH 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 (-Cl) -C (= O) -O- (CH ₂ ) ₃ -S-Rf
CH ₂ = C (-Cl) -C (= O) -O- (CH ₂ ) ₃ -S- (CH ₂ ) ₂ -Rf
CH ₂ = C (-Cl) -C (= O) -O- (CH ₂ ) ₃ -SO ₂ -Rf
CH ₂ = C (-Cl) -C (= O) -O- (CH ₂ ) ₃ -SO _2- (CH ₂ ) ₂ -Rf
CH ₂ = C (-CF ₃ ) -C (= O) -O- (CH ₂ ) ₃ -S-Rf
CH ₂ = C (-CF ₃ ) -C (= O) -O- (CH ₂ ) ₃ -S- (CH ₂ ) ₂ -Rf
CH ₂ = C (-CF ₃ ) -C (= O) -O- (CH ₂ ) ₃ -SO ₂ -Rf
CH ₂ = C (-CF ₃ ) -C (= O) -O- (CH ₂ ) ₃ -SO _2- (CH ₂ ) ₂ -Rf
CH ₂ = C (-CF ₂ H) -C (= O) -O- (CH ₂ ) ₃ -S-Rf
CH ₂ = C (-CF ₂ H) -C (= O) -O- (CH ₂ ) ₃ -S- (CH ₂ ) ₂ -Rf
CH ₂ = C (-CF ₂ H) -C (= O) -O- (CH ₂ ) ₃ -SO ₂ -Rf
CH ₂ = C (-CF ₂ H) -C (= O) -O- (CH ₂ ) ₃ -SO _2- (CH ₂ ) ₂ -Rf

CH ₂ = C (-CN) -C (= O) -O- (CH ₂ ) ₃ -S-Rf
CH ₂ = C (-CN) -C (= O) -O- (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) Non-fluorine monomer The fluoropolymer of the present invention may have a repeating unit derived from the non-fluorine monomer (b). The non-fluorine monomer (b) is different from the crosslinkable monomer (c). The monomer (b) is preferably a non-fluorine monomer having a carbon-carbon double bond. The monomer (b) is preferably a vinyl monomer containing no fluorine. The non-fluorine monomer (b) is generally a compound having one carbon-carbon double bond. Preferred examples of the non-fluorine monomer (b) include, for example, ethylene, vinyl acetate, vinyl halide (for example, vinyl chloride), vinylidene halide (for example, vinylidene chloride), acrylonitrile, styrene, polyethylene glycol ( Included are (meth) acrylates, polypropylene glycol (meth) acrylates, methoxypolyethylene glycol (meth) acrylates, methoxypolypropylene glycol (meth) acrylates, and vinyl alkyl ethers. The non-fluorine monomer (b) is not limited to these examples. The non-fluorine monomer (b) may contain vinyl halide and / or vinylidene halide.

The non-fluorine monomer (b) may be a (meth) acrylate ester having an alkyl group. The number of carbon atoms of the alkyl group may be 1 to 30, for example, 6 to 30 (for example, 10 to 30). For example, the non-fluorine monomer (b) has the general formula:
CH ₂ = CA ¹ COOA ²
[Wherein, A ¹ is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (for example, a chlorine atom, a bromine atom and an iodine atom),
A ² is an alkyl group represented by C _n H _{2n + 1} (n = 1 to 30). ]
An acrylate represented by

(C) Crosslinkable monomer The fluoropolymer of the present invention may have a repeating unit derived from the crosslinkable monomer (c). The crosslinkable monomer (c) may be a vinyl monomer having at least two reactive groups and / or carbon-carbon double bonds and not containing fluorine. 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 reactive groups are hydroxyl groups, epoxy groups, chloromethyl groups, blocked isocyanate groups, amino groups, carboxyl groups and the like.

  Examples of the crosslinkable monomer (c) include diacetone acrylamide, (meth) acrylamide, N-methylol acrylamide, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, 3-chloro-2-hydroxypropyl ( Examples include (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, butadiene, isoprene, chloroprene, glycerol (meth) acrylate, glycidyl (meth) acrylate and the like. However, it is not limited to these.

  By copolymerizing the monomer (b) and / or the monomer (c), water and oil repellency and antifouling properties, and these properties of cleaning resistance, washing resistance, solubility in solvents, In addition, various properties such as touch can be improved as necessary.

  In the fluorine-containing polymer, the amount of the non-fluorine monomer (b) is 0.1 to 100 parts by weight, for example 0.1 to 50 parts by weight with respect to 100 parts by weight of the fluorine-containing monomer (a). The amount of the crosslinkable monomer (c) may be 50 parts by weight or less, for example, 20 parts by weight or less, particularly 0.1 to 15 parts by weight.

  Monomer (A) can be polymerized in the presence of organopolysiloxane (B). Examples of the olefinically unsaturated comonomer contained in the monomer (A) include acrylic acid alkyl esters or methacrylic acid alkyl esters having an alkyl group having 1 to 30 carbon atoms (for example, butyl acrylate, ethyl acrylate, acrylic Acid methyl, methyl methacrylate or butyl methacrylate). Alkyl acrylates or alkyl methacrylates can be used to adjust the glass transition temperature (Tg) of the resulting polymer produced from the reaction of monomer (A) and organopolysiloxane (B); For example, an acrylic ester having a long-chain alkyl group having 4 to 20 carbon atoms (particularly 8 to 20 carbon atoms) (for example, stearyl acrylate or stearyl methacrylate, octyl acrylate, 2-ethylhexyl acrylate, or acrylic acid Dodecyl or dodecyl methacrylate) can be used to form softer polymers with lower Tg. Copolymers with alkyl acrylate monomers or alkyl methacrylate monomers can improve various properties, such as water and oil repellency and dirt release, such water and oil repellency. Further, the cleaning durability, stain detachment durability and abrasion resistance, solubility in solvents, hardness and feel (hand) can be improved.

  Other acrylate or methacrylate comonomers that may be used include polyethylene glycol acrylate or polyethylene glycol methacrylate, propylene glycol acrylate or propylene glycol methacrylate, methoxypolyethylene glycol acrylate or methoxypolyethylene glycol methacrylate, and methoxypropylene glycol acrylate or methoxy. Propylene glycol methacrylate is included. Other olefinically unsaturated comonomers that may be used include vinyl chloride, vinylidene chloride, styrene, acrylonitrile, methacrylonitrile, ethylene, vinyl alkyl ethers, isoprene, or vinyl esters such as vinyl acetate or vinyl propionate. ) Is included.

  Functional groups that are not reactive with amine groups but may be reactive with other functional groups to provide properties such as increased durability (durability) in textiles and other substrates Olefinically unsaturated comonomers may be used. Examples of such functional groups include hydroxyl, amino and amide, and examples of olefinically unsaturated comonomers containing such functional groups include acrylamide, methacrylamide, N-methylol acrylamide, hydroxyethyl methacrylate. Hydroxyethyl acrylate, 3-chloro-2-hydroxypropyl acrylate or 3-chloro-2-hydroxypropyl methacrylate, N, N-dimethylaminoethyl acrylate or N, N-dimethylaminoethyl methacrylate, and There are diethylaminoethyl acrylate or diethylaminoethyl methacrylate.

(B) Functional organopolysiloxane The functional organopolysiloxane may be a mercapto functional organopolysiloxane, a vinyl functional organopolysiloxane, a (meth) acrylamide functional organopolysiloxane, a (meth) acrylate functional organopolysiloxane or its It is a mixture. The functional organopolysiloxane (B) functions as a chain transfer agent. By the polymerization reaction, the functional organopolysiloxane (B) is bonded to the fluorine-containing polymer via the functional organic group.
Component (B) of the present invention may be a mercapto functional organopolysiloxane (ie, an organopolysiloxane having a mercapto functional organic group present in the molecule). As used herein, a “mercapto functional organic group” is, for example, any organic group containing a sulfur atom, such as — (CH ₂ ) _n —SH (where n is a number from 0 to 10). , In particular a number from 1 to 5. Mercapto group-containing silicone (B) (ie mercapto functional organopolysiloxane) has at least one (eg 1 to 500, especially 1 to 50, especially 2 to 40) mercapto groups and two or more siloxane bonds. A siloxane compound having a silicone moiety.

Component (B) of the present invention may be a vinyl functional organopolysiloxane (ie, an organopolysiloxane having a vinyl functional organic group present in the molecule). As used herein, a “vinyl functional organic group” is any organic group that contains a —CH═CH ₂ group, such as — (CH ₂ ) _n —CH═CH ₂ (where n is A number from 0 to 10, in particular from 1 to 5. The vinyl group-containing silicone (B) (i.e. vinyl functional organopolysiloxane (B)) has at least one (e.g. 1 to 500, in particular 1 to 50, especially 2 to 40) vinyl groups and two or more A siloxane compound having a silicone moiety having a siloxane bond.

Component (B) of the present invention may be a (meth) acrylamide functional organopolysiloxane (ie, 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 that includes a —NHC (═O) —CQ═CH ₂ group, such as — (CH ₂ ) _n —NHC (= O) —CQ═CH ₂ (where Q is a hydrogen atom or a methyl group, and n is a number from 0 to 10, in particular from 1 to 5). The (meth) acrylamide group-containing silicone (B) (i.e. (meth) acrylamide functional organopolysiloxane (B)) is at least one (e.g. 1-500, especially 1-50, especially 2-40) (meth). A siloxane compound having a silicone moiety having an acrylamide group and two or more siloxane bonds.

Component (B) of the present invention may be a (meth) acrylate functional organopolysiloxane (ie, an organopolysiloxane having a (meth) acrylate functional organic group present in the molecule). The term “(meth) acrylate” means acrylate or methacrylate. As used herein, “(meth) acrylate functional organic group” refers to —QOC (═O) CX═CH ₂ (where Q is a divalent organic group such as a C _1-20 hydrocarbon. Group, for example a C _1-10 alkylene group, X is methyl (Me) or hydrogen (H)). The (meth) acrylate group-containing silicone (B) (i.e. (meth) acrylate functional organopolysiloxane (B)) is at least one (e.g. 1-500, especially 1-50, especially 2-40) (meth). A siloxane compound having an acrylate group and a silicone moiety having two or more siloxane bonds.

Various organopolysiloxanes are widely known in the art and are often represented by the general formula R _n SiO _{(4-n) / 2} , in which case the organopolysiloxane can be any number of “M ”(Monofunctional) siloxy units (R ₃ SiO _0.5 ),“ D ”(bifunctional) siloxy units (R ₂ SiO),“ T ”(trifunctional) siloxy units (RSiO _1.5 ), Alternatively, it may contain “Q” siloxy units (SiO ₂ ) (wherein R is independently a monovalent organic group). These siloxy units can be combined in various ways to form cyclic, linear or branched structures. The chemical and physical properties of the resulting polymer structure can vary. For example, the organopolysiloxane can be a volatile or low viscosity liquid, a high viscosity liquid / gum, an elastomer or rubber, and a resin. R is independently a monovalent organic group, or R is a hydrocarbon group having 1 to 30 carbon atoms, or R is an alkyl group having 1 to 30 carbon atoms, or R Is methyl.

Organopolysiloxanes useful as component (B) in the present invention are those wherein at least one of the R groups in the formula R _n SiO _{(4-n) / 2} is a mercapto group, a vinyl group, a (meth) acrylamide group or a (meth) acrylate group. Or at least one of the R groups is a mercapto group, vinyl group, (meth) acrylamide group or (meth) acrylate group and one of the R groups is an organic functional group, or R One of the groups is characterized by being an organofunctional group that also contains a mercapto group, a vinyl group, a (meth) acrylamide group or a (meth) acrylate group. Organic functional groups and mercapto groups, vinyl groups, (meth) acrylamide groups or (meth) acrylate groups can be present in any siloxy unit having an R substituent. That is, the organic functional group and the mercapto group, vinyl group, (meth) acrylamide group or (meth) acrylate group can be present in any M unit, D unit or T unit. Typically, organofunctional groups and mercapto groups, vinyl groups, (meth) acrylamide groups or (meth) acrylate groups are present as R substituents in D siloxy units.

  As used herein, “organofunctional group” means an organic group containing any number of carbon atoms, but the group contains at least one atom that is different from carbon and hydrogen. . Representative examples of such organic functional groups include amines, amides, sulfonamides, quaternary groups, ethers, epoxies, phenols, esters, carboxyls, to name a few. , Ketone, halogen-substituted alkyl and aryl groups. Alternatively, the organic functional group is an amino functional organic group.

When the organofunctional group is an amino-functional organic group, the amino-functional organic group is herein shown in equation as ^{R N, wherein:} -R 1 NHR ^2, wherein: ^-R 1 NR ₂ ² or a formula: —R ¹ NHR ¹ NHR ² (wherein, each R ¹ is independently a divalent hydrocarbon group having 2 or more carbon atoms, and R ² is hydrogen or 1 to 10 carbon atoms) Which may be an alkyl group.). Each R ¹ is typically an alkylene group having 2 to 20 carbon atoms. R ¹ is, for example, —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 (CH ₃ ) 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 - it is exemplified by groups such as . The alkyl group R ² is as exemplified above for R. When R ² is an alkyl group, R ² is typically methyl.

Some examples of suitable amino-functional hydrocarbon groups include
_{-CH 2 CH 2 NH 2, -CH} 2 CH 2 CH 2 NH 2,
_{-CH 2 CHCH 3 NH 2, -CH} 2 CH 2 CH 2 CH 2 NH 2,
_{-CH 2 CH 2 CH 2 CH 2} CH 2 NH 2,
_{-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 3,
_{-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 3,
_{-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 3, and there is _{-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 .

Mercapto-functional organic groups are represented by R ^S in the formulas herein, and by groups represented by the formula: —R ¹ SR ² , wherein each R ¹ and R ² are as described above. Illustrated. Examples of mercapto functional groups are:
-CH ₂ CH ₂ CH ₂ SH, -CH ₂ CHCH ₃ SH, -CH ₂ CH ₂ CH ₂ CH ₂ SH,
-CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ SH, -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ SH,
-CH ₂ CH ₂ SCH ₃ . Typically, the mercapto functional group is —CH ₂ CH ₂ CH ₂ SH.

The vinyl functional organic group is indicated by R ^V in the formulas herein. Examples of vinyl functional organic groups are:
-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 ₂ , -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, vinyl-functional group is -CH = CH _2.

(Meth) acrylamide-functional organic group, in the formulas herein depicted with R ^AM, wherein: -R1-NH-C (= O) -CQ = CH 2 ( wherein, R1 is at least 2 carbon A divalent hydrocarbon group having an atom, Q is a hydrogen atom or a methyl group.). Examples of (meth) acrylamide functional groups are as follows:
-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 ₂ , -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 (CH 3) = 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 .

(Meth) acrylate-functional organic groups, in the formulas herein depicted with R ^MA, the formula: -R1-OC (= O) -CQ = CH 2 ( wherein, R1 is at least two carbon atoms And a divalent hydrocarbon group, Q is a hydrogen atom or a methyl group.) Examples of (meth) acrylate functional groups are as follows:
-CH2CH2CH2-OC (= O) -CH = CH 2, -CH2CH2CH2-OC (= O) -C (CH3) = CH 2,
-CH2CHCH3-OC (= O) -CH = CH 2, -CH2CHCH3-OC (= O) -C (CH3) = CH 2,
-CH2CH2CH2CH2-OC (= O) -C (CH3) = CH 2, -CH2CH2CH2CH2-OC (= O) -C (CH3) = CH 2. Typically, the (meth) acrylate functional group is —CH ₂ CH ₂ CH ₂ —OC (═O) —C (CH 3) ═CH ₂ .

In a preferred embodiment, the functional organopolysiloxane (denoted as B ′) has siloxy units having the following average formula:
(R ₂ SiO) _a (RR ^N SiO) _b (RR ^FO SiO) _c
[Wherein, a is 0 to 4000, alternatively 1 to 1000, alternatively 2 to 400,
b is 0 to 1000, alternatively 1 to 100, alternatively 2 to 50;
c is 1-1000, alternatively 2-100, alternatively 3-50;
Each R is independently a monovalent organic group;
Or each R is a C1-C30 hydrocarbon,
Alternatively, each R is a monovalent alkyl group having 1 to 12 carbon atoms,
Alternatively, each R is a methyl group;
Each R ^N is amino-functional monovalent organic group as defined above,
Each ^RFO is a monovalent mercapto functional organic group (R ^S ), a monovalent vinyl functional organic group (R ^V ), a monovalent (meth) acrylamide functionality as defined above. Organic groups (R ^AM ) or monovalent (meth) acrylate functional organic groups (R ^MA ). ]

R ^N group is R ^F (where R ^F is a monovalent organic functional organic group as described above, for example, hydroxyl group, amine group, amide group, sulfonamide group, quaternary group, ether group, epoxy group) Group, phenol group, ester group, carboxyl group, ketone group, halogen-substituted alkyl group and aryl group. For example, the functional organopolysiloxane has siloxy units having the following average formula:
(R ₂ SiO) _a (RR ^F SiO) _b (RR ^FO SiO) _c
[Wherein the groups and subscripts (ie, a, b and c) are as defined above. ]
R ^FO 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 ^AM ) or It is a divalent (meth) acrylate functional organic group (R ^MA ).

  The organopolysiloxane (B ′) may be terminated with a hydrogen atom (this is a silanol group in the terminal siloxy unit of the terpolymer), or an alkyl group having 1 to 30 carbon atoms. Good (this would be an alkoxy group in the terminal siloxy unit of the terpolymer). When an alkyl group is used, the alkyl group may be a linear or branched alkyl having 1 to 30 carbon atoms, or the alkyl group may have 4 to 20 carbon atoms (or 8 to 20 carbon atoms). Long chain alkyl group (for example, stearyl etc.). Alternatively, the organopolysiloxane may have a trimethylsilyl group at the end.

［式中、ａは、０〜４０００、あるいは、１〜１０００、あるいは、２〜４００であり、
ｂは、０〜１０００、あるいは、１〜１００、あるいは、２〜５０であり、
ｃは、１〜１０００、あるいは、２〜１００、あるいは、３〜５０であり；
それぞれのＲ’は、独立して、Ｈ、炭素数１〜４０のアルキル基またはMe₃Siである。］。 The organopolysiloxane (B ′) of this preferred embodiment is represented, for example, by the following average formula:

[Wherein, a is 0 to 4000, alternatively 1 to 1000, alternatively 2 to 400,
b is 0 to 1000, alternatively 1 to 100, alternatively 2 to 50;
c is 1-1000, alternatively 2-100, alternatively 3-50;
Each R ′ is independently H, an alkyl group having 1 to 40 carbon atoms, or Me ₃ Si. ].

  The amino-mercapto functional organopolysiloxane terpolymer (B ′) of this preferred embodiment is known in the art for producing organopolysiloxane terpolymers containing amino functional groups and / or mercapto functional groups. Can be manufactured by any technique. Typically, the organopolysiloxane (B ′) has an amino functional alkoxy silane, a mercapto functional silane monomer, an alkoxy terminus or a silanol terminus, as illustrated by the general reaction scheme below. It is produced by a condensation polymerization reaction with an organopolysiloxane.

  The condensation of organopolysiloxanes is widely known in the art and is typically catalyzed by the addition of strong bases (such as alkali metal hydroxides) or tin compounds. Alternatively, copolymerization of functionalized cyclosiloxanes can be used.

For example, the vinyl group-containing silicone (B) has the formula:

[Wherein R ¹ represents 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, Me ₃ Si or H,
B is a C1-C10 divalent saturated hydrocarbon group in which one or two ether bonds may be interposed,
C is a hydroxyl group, amine group, amide group, sulfonamide group, quaternary group, ether group, epoxy group, phenol group, ester group, carboxyl group, ketone group, halogen-substituted alkyl group or aryl group,
a, b and c are integers indicating the number of repeating units, a is 1 to 4000, for example 2 to 2000, b is 0 to 1000, preferably 1 to 800, c is 0 to 1000, preferably 1 to 800. ]
Indicated by

［式中、R¹基などの基および下付の符号は上記と同意義である。］ Examples of the vinyl group-containing silicone (B) are as follows.

[Wherein, the group such as the R ¹ group and the subscript are as defined above. ]

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

［式中、ａは、０〜４０００、あるいは、１〜１０００、あるいは、２〜４００であり、
ｂは、０〜１０００、あるいは、１〜１００、あるいは、２〜５０であり、
ｃは、１〜１０００、あるいは、２〜１００、あるいは、３〜５０であり；
それぞれのＲ’は、Ｈ、炭素数１〜４０のアルキル基またはＭｅ_３Ｓｉである。］
で示されるものであってよい。 The organopolysiloxane (B ′) of this preferred embodiment has, for example, an average formula:

[Wherein, a is 0 to 4000, alternatively 1 to 1000, alternatively 2 to 400,
b is 0 to 1000, alternatively 1 to 100, alternatively 2 to 50;
c is 1-1000, alternatively 2-100, alternatively 3-50;
Each R ′ is H, an alkyl group having 1 to 40 carbon atoms, or Me ₃ Si. ]
It may be shown by.

  The vinyl-amino functional organopolysiloxane terpolymer (B ′) of this preferred embodiment is known in the art for producing organopolysiloxane terpolymers containing amino functional groups and / or vinyl functional groups. Can be manufactured by any technique. Typically, the organopolysiloxane terpolymer (B ′) is amino-functionalized in the presence of an end-blocking agent such as hexamethyldisiloxane, as illustrated by the general reaction scheme below. It is produced by an equilibrium polymerization reaction of alkoxysilane, 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane and octamethylcyclotetrasiloxane.

  Equilibrium prepared organopolysiloxanes are widely known in the art and are typically catalyzed by the addition of strong acids or bases (such as alkali metal hydroxides) or sulfonic acids. Alternatively, copolymerization of functionalized alkoxysilanes and silanol terminated polydimethylsiloxanes can be used.

Typically, (meth) acrylamide functional organopolysiloxanes can be made by reaction of amino functional organopolysiloxanes with (meth) acrylic anhydride. In the reaction, the amino group (—NH ₂ ) is converted to a (meth) acrylamide group (—NH—C (═O) —CQ═CH ₂ (wherein Q is a hydrogen atom or a methyl group)). . For example, a (meth) acrylamide functional organopolysiloxane is a ≡Si— (CH ₂ ) _n —NH—C (═O) —CQ═CH ₂ group, where Q is a hydrogen atom or a methyl group, n May be 0 to 10, in particular 1 to 5.).

Typically, (meth) acrylate functional organopolysiloxanes can be made by reaction of carbinol functional organopolysiloxanes with (meth) acrylic anhydride. In the reaction, the carbinol group (—OH) is converted to a (meth) acrylate group (—OC (═O) —CQ═CH ₂ (wherein Q is a hydrogen atom or a methyl group)). For example, a (meth) acrylate functional organopolysiloxane has a ≡Si— (CH ₂ ) _n —OC (═O) —CQ═CH ₂ group, where Q is a hydrogen atom or a methyl group, and n is 0 -10, in particular 1-5).

  The fluorine-containing polymer may have a weight average molecular weight of 2,000 to 5,000,000, in particular, a weight average molecular weight of 3,000 to 5,000,000, especially 10,000 to 1,000. It may have a weight average molecular weight of 1,000. The weight average molecular weight (polystyrene conversion) of the fluoropolymer can be measured by GPC (gel permeation chromatography).

  In the fluorine-containing polymer, the repeating unit may not be located as shown in the chemical formula, and the fluorine-containing polymer may be a random polymer or a block copolymer.

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

  In bulk polymerization, the monomer and functional organopolysiloxane mixture is purged with nitrogen, a polymerization initiator is added, and the mixture is stirred at 30 to 80 ° C. for several hours (2 to 15 hours) for polymerization. Is adopted. Examples of the polymerization initiator include azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, diisopropyl peroxydicarbonate, and the like. Can be mentioned. The polymerization initiator is used in the range of 0.01 to 20 parts by weight, for example, 0.01 to 10 parts by weight with respect to 100 parts by weight of the monomer.

  In the case of solution polymerization, a mixture of a monomer and a functional organopolysiloxane is dissolved in a suitable organic solvent that is soluble and inert, and polymerized in the same manner as described above. Examples of the organic solvent include hydrocarbon solvents, ester solvents, ketone solvents, alcohol solvents, silicone solvents, and fluorine-containing solvents. Examples of the organic solvent are those which are inert to the monomer and dissolve them, such as 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, trichloro And trifluoroethane. The organic solvent is used in the range of 50 to 2000 parts by weight, for example, 50 to 1000 parts by weight with respect to 100 parts by weight of the total amount of monomers.

  In solution polymerization, a method in which a monomer is dissolved in an organic solvent in the presence of a polymerization initiator, and after nitrogen substitution, is heated and stirred in the range of 30 to 120 ° C. for 1 to 10 hours.

  In the case of emulsion polymerization, a mixture of a monomer and a functional organopolysiloxane is emulsified in water using an appropriate emulsifier, and then polymerized in the same manner as described above. In some combinations of monomers (a)-(c) and functional organopolysiloxane, the weak compatibility of monomer and functional organopolysiloxane in water leads to poor copolymerization. In such cases, a method may be employed in which a suitable co-solvent, such as glycol and alcohol and / or low molecular weight monomer, is added to increase the compatibility of the mixture. The hydrophobic group in the emulsifier used in emulsion polymerization may be any of hydrocarbon type, silicon-containing type and fluorine-containing type. Regarding the ionicity of the hydrophilic group, any one of a nonionic group, an anionic group, a cationic group and an amphoteric group is used. Polymerization initiators for emulsion polymerization are benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidine-2 Water-soluble ones such as hydrochloride, azobisisobutyronitrile, sodium peroxide, potassium persulfate, ammonium persulfate, azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, Oil-soluble ones such as cumene hydroperoxide, t-butyl peroxypivalate and diisopropyl peroxydicarbonate are used. The polymerization initiator is used in the range of 0.01 to 10 parts by weight with respect to 100 parts by weight of the monomer.

  In emulsion polymerization, a monomer is emulsified in water in the presence of a polymerization initiator and an emulsifier, and after nitrogen substitution, for example, in the range of 30 to 120 ° C., particularly 50 to 80 ° C., stirring for 1 to 10 hours, A polymerization method is employed.

  When the monomers are not completely compatible with each other, it is preferable to add a compatibilizing agent such as a water-soluble organic solvent or a low molecular weight monomer that is sufficiently compatible with these monomers. By adding a compatibilizing agent, it is possible to improve emulsifying properties and copolymerization properties.

  Examples of the water-soluble organic solvent include acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, ethanol and the like, and 1 to 50 parts by weight with respect to 100 parts by weight of water. For example, you may use in the range of 10-40 weight part. Examples of the low molecular weight monomer include methyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, etc., and 1 to 50 parts by weight with respect to 100 parts by weight of the total amount of monomers, For example, you may use in the range of 10-40 weight part.

Various emulsifiers such as an anionic emulsifier, a cationic emulsifier or a nonionic emulsifier can be used as the emulsifier, and the emulsifier is used in an amount of 0.5 to 20 parts by weight with respect to 100 parts by weight of the monomer. The emulsifier used in the emulsion polymerization can have a hydrophobic group which can be a hydrocarbon, silicone or fluorine-containing compound and a hydrophilic group which can be nonionic, anionic, cationic or amphoteric. A combination of anionic and nonionic emulsifiers is preferred to obtain both emulsion stability and skin safety. The amount of the anionic emulsifier may be 5 to 80% by weight, preferably 10 to 60% by weight, based on the sum of the anionic emulsifier and the nonionic emulsifier. Preferably, the anionic emulsifier is polyoxyethylene alkyl (preferably C ₁ -C ₃₀ alkyl) ether sulfate, nonionic emulsifiers are fatty acid sorbitan esters, polyoxyethylene fatty acid sorbitan esters, polyoxyethylene hardened castor oil and / Or polyoxyethylene fatty acid sorbite ester.

  In order to obtain a copolymer aqueous dispersion having a high polymer content and very fine and stable particles, an emulsifier that can impart powerful crushing energy such as a high-pressure homogenizer or an ultrasonic homogenizer is used. It is desirable to prepare a fine particle of the mixture by dispersing a mixture of the monomer and the functional organopolysiloxane in water, and then polymerize.

  The fluoropolymer (I) is preferably present as fine particles in a medium such as an aqueous medium. The average particle size of the fine particles of the fluoropolymer (I) is preferably 0.0001 to 1 μm, for example 0.01 to 0.5 μm. When the average particle size is within this range, the amount of the emulsifier may be small in order to obtain a stable dispersion, the water and oil repellency is high, and the polymer fine particles exist stably. The average particle diameter can be measured by a dynamic light scattering spectrum and an electron microscope. When polymerization is carried out in the presence of an emulsifier by an ordinary emulsion polymerization method, an average particle size of 0.0001 to 1 μm is obtained.

The fluorosilicone reaction product of monomer (A) and organopolysiloxane (B) can be prepared by any reaction method known in the art for polymerizing such monomers. . Preferably, the fluorosilicone is
I) Formula (A):
_{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,
Rf is a C1-C20 fluoroalkyl group. ]
A monomer comprising a fluorine-containing monomer represented by
(B) It can be produced by the method of the present invention comprising reacting by a polymerization reaction in the presence of a functional organopolysiloxane, preferably by a radical polymerization reaction.

Component (A) and component (B) in this method are as described above.
This method can also be carried out in the presence of a polar organic solvent. The polar organic solvent is one or more alcohol solvents selected from butanol, t-butanol, isopropanol, butoxyethanol, methyl isobutyl ketone, methyl ethyl ketone, butyl acetate or ethyl acetate, ketone solvents or ester solvents, and / or Alternatively, it may be an aromatic hydrocarbon (such as xylene, toluene or trimethylbenzene), a mixture of one or more thereof.

  The initiator for the radical polymerization reaction may be any compound known in the art for initiating the radical reaction, such as an organic peroxide or an azo compound. Representative non-limiting examples include azo compounds such as azobisisobutyronitrile or azobisisovaleronitrile (AIVN), peroxides such as benzoyl peroxide, and the like. The polymerization temperature is typically in the range of 50 ° C to 120 ° C.

Alternatively, the polymerization reaction product can be obtained using emulsion polymerization techniques in which all components are polymerized in the presence of water, a surfactant and a polymerization initiator.
The fluorosilicone reaction product may contain various ratios of monomer (A) and organopolysiloxane (B) as controlled by the amount of each component (A) and component (B). The fluorosilicone comprises 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% by weight). (90% by weight) of the organopolysiloxane (B) (where the sum of (A) and (B) (% by weight) is equal to 100%). Fluorosilicone products having a large proportion of organopolysiloxane can provide greater persistence to the fibrous substrate or softness of the treated material. Production polymers having a large proportion of fluorine-containing monomers can provide maximum hydrophobicity and oleophobicity.

  The fluorosilicone reaction product is generally obtained as a solution. The fluorosilicone reaction product can be isolated by evaporating the solvent. In order to be applied as an oil repellent, the fluorosilicone reaction product generally needs to be in liquid form, and the solution obtained by the reaction is often diluted to a solution suitable for application to textiles. be able to. Alternatively, the fluorosilicone reaction product can be dissolved in a different solvent, such as a high boiling polar organic solvent, for application to textiles. Alternatively, the fluorosilicone reaction product can be emulsified by mixing with water and an emulsifier, such as a cationic surfactant and / or a nonionic surfactant or an anionic surfactant. The fluorosilicone reaction product can be isolated prior to emulsification, or the solution of the polymerization product can be emulsified, if necessary, by removal of the solvent. If the resulting polymer is obtained by emulsion polymerization, the emulsion is generally used and diluted as necessary without isolating the resulting polymer.

(II) Non-fluorine polymer (second polymer)
Non-fluorine polymer (II) contains a vinyl monomer. The vinyl monomer is a monomer that does not contain a fluorine atom, and preferably does not contain 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 ⁴ ₂
(9) CH ₂ = CR ¹ CONHCH ₂ OH

[Where:
R ¹ is a hydrogen atom, a methyl group or a halogen atom (for example, a chlorine atom, a bromine atom and an iodine atom),
R ² is an alkyl group having 1 to 18 carbon atoms,
R ³ represents a hydrocarbon group having 1 to 30 carbon atoms (for example, an aliphatic group, an aromatic group, and an araliphatic group), such as a phenyl group, an alkyl group, and a substituted phenyl group,
R ⁴ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms,
D is a chlorine atom, a bromine atom or an iodine atom. ]

The non-fluoropolymer (II) has a combination of at least one monomer of formula (1) and / or (2) and at least one monomer of formula (3) and / or (4) It is preferable. The non-fluorine polymer (II) contains the monomer (1) and / or (2) in an amount of at least 20% by weight, more preferably at least 40% by weight, such as 50% by weight, based on the polymer (II). It is preferably included in an amount of 90% by weight. The non-fluorine polymer (II) contains the monomer (3) and / or (4) in an amount of at least 10% by weight, more preferably at least 20% by weight, based on the polymer (II). preferable. Monomers (3) and / or (4) may not be contained in the non-fluorine polymer (II) . The remaining components other than the monomers (1) to (4) may be the monomers (5) to (9).

  The polymer (II) may contain the crosslinkable monomer (c) described for the polymer (I). In the polymer (II), the amount of the monomer (c) may be 50% by weight or less, for example, 0.1 to 30% by weight with respect to the polymer (II).

  The non-fluorinated polymer (II) may have a weight average molecular weight of 2,000 to 5,000,000, in particular 3,000 to 5,000,000, especially 10,000 to 1,000,000. The weight average molecular weight (polystyrene conversion) can be determined by GPC (gel permeation chromatography).

The non- fluorine polymer of the present invention is preferably produced by solution polymerization and emulsion polymerization. Emulsion polymerization is particularly preferred. By emulsion polymerization, a dispersion in which the particles of the polymer (II) are dispersed in a liquid medium is obtained.

  Emulsion polymerization is carried out in an aqueous medium, preferably in the presence of a polymerization initiator. The polymerization initiator may be a peroxide compound and an azo compound. Examples of the polymerizable initiator include water-soluble initiators (for example, 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 (eg azobisisobutyronitrile, benzoyl peroxide, di-tert- Butyl peroxide, lauryl peroxide, cumene peroxide, t-butyl peroxypivalate and diisopropyl peroxycarbonate).

  A chain transfer agent may be added to adjust the molecular weight of the resulting polymer (II).

  The emulsifier is preferably present in the emulsion of polymer (II). Various emulsifiers such as anionic emulsifiers, cationic emulsifiers, nonionic emulsifiers and amphoteric emulsifiers may be used in amounts ranging from 0.5 to 30 parts by weight per 100 parts by weight of monomer. For example, for the stability of the emulsion, a combination of an anionic emulsifier and a cationic emulsifier and a combination of a nonionic emulsifier and an amphoteric emulsifier are preferred. The amount of the emulsifier is preferably 1 to 20 parts by weight with respect to 100 parts by weight of the polymer (II).

  The average particle size of the polymer (II) is preferably 0.03 to 0.5 micrometers. At such particle sizes, the required amount of emulsifier and / or self-emulsifying monomer is small and no sedimentation of the particles occurs.

  In the water / oil repellent composition of the present invention, the polymer (I) and the polymer (II) are not present in the same particle, but are present in different particles. Preferably, polymer (I) and polymer (II) are separately polymerized to obtain polymer (I) particles and polymer (II) particles, respectively, and then polymer (I) particles. (Ie, dispersion of polymer (I)) is mixed with particles of polymer (II) (ie, dispersion of polymer (II)). The water / oil repellent composition of the present invention comprises a dispersion of polymer (I), a dispersion of polymer (II), and, if necessary, an aqueous agent.

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

The surface treating agent water and oil repellent composition can be applied to fibrous substrates (eg, textile products, etc.) by any of the known methods for treating textile products with liquids. The concentration of the polymers (I) and (II) in the liquid applied to the textile product may be, for example, 0.5 wt% to 20 wt%, alternatively 1 wt% to 5 wt%. When the textile product is a cloth, the cloth may be immersed in the liquid, or the liquid may be attached to or sprayed on the cloth. The treated textile product is dried and preferably heated at, for example, 100 ° C. to 200 ° C. in order to develop oil repellency.

  Alternatively, the fluorosilicone reaction product may be applied to the textile by a cleaning method, such as a laundry application or a dry cleaning method.

  The textile products to be treated are typically fabrics, which include woven, knitted and non-woven fabrics, fabrics and carpets in clothing form, but fibers or yarns or intermediate fiber products (eg sliver or It may be a roving yarn). The textile product material may be natural fibers (such as cotton or wool), chemical fibers (such as viscose rayon or rheocell), or synthetic fibers (such as polyester, polyamide or acrylic fibers), or May be a mixture of fibers, such as a mixture of natural and synthetic fibers. The production polymer of the present invention is particularly effective in making cellulosic fibers (such as cotton or rayon) oleophobic and oleophobic. The method of the present invention also generally makes the textile product hydrophobic and water repellent. The fiber treatment with the polymer of the present invention imparts oil repellency to the fabric, while at the same time imparting an improvement in texture compared to the untreated fabric and also known fluoropolymer fiber treatment. It also provides an improvement in texture compared to the fabric treated with the agent.

Alternatively, the fibrous base material may be leather. In order to make the production polymer hydrophobic and oleophobic, aqueous solutions or aqueous emulsifications at various stages of leather processing, for example during the wet processing of leather or during the finishing of leather You may apply it to leather from things.
Alternatively, the fibrous substrate may be paper. The production polymer may be applied to preformed paper or may be applied at various stages of papermaking, for example during the drying period 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 comprises a fluoropolymer and a medium (for example, a liquid medium, in particular, 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. The amount of the organic solvent may be 40% by weight or less, for example 0.1 to 20% by weight, based on the medium. In the surface treatment agent, the concentration of the fluoropolymer may be, for example, 0.1 to 50% by weight.

  The surface treatment agent of the present invention can be applied to an object to be treated by a conventionally known method. The surface treatment agent can be applied by dipping, spraying or coating. Usually, the surface treatment agent is dispersed in an organic solvent or water, diluted, and attached to the surface of the object to be treated by a known method such as dip coating, spray coating, foam coating, etc., and then dried. It is done. Further, if necessary, it may be applied together with an appropriate crosslinking agent and cured. Furthermore, an insect repellent, a softening agent, an antibacterial agent, a flame retardant, an antistatic agent, a paint fixing agent, an anti-wrinkle agent, and the like can be added to the surface treatment agent of the present invention. The concentration of the fluorine-containing compound in the treatment liquid brought into contact with the substrate may be 0.01 to 10% by weight (particularly in the case of dip coating), for example 0.05 to 10% by weight (particularly in the case of spray coating). .

  The article to be treated with the surface treating agent (for example, water / oil repellent) of the present invention is preferably a textile product. Various examples can be given as textile products. For example, natural animal and vegetable fibers such as cotton, hemp, wool, and silk, synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene, semi-synthetic fibers such as rayon and acetate, glass fibers, and carbon fibers , Inorganic fibers such as asbestos fibers, or mixed fibers thereof.

  The fiber product may be in the form of fiber, yarn, cloth or the like.

  “Treatment” means that a treatment agent is applied to an object to be treated by dipping, spraying, coating, or the like. By the treatment, the fluoropolymer which is an active ingredient of the treatment agent penetrates into the treatment object and / or adheres to the surface of the treatment object.

  The following preparation examples and examples further illustrate the invention in detail but should not be construed as limiting the scope of the invention. Unless otherwise indicated, all parts and percentages in these examples are based on weight and all measurements were obtained at about 23 ° C.

Shower water repellency test (JIS-L-1092)
The shower water repellency test was conducted according to JIS-L-1092. The shower water repellency test was performed (as shown in Table 1 below). Represented by
Use a glass funnel with a volume of at least 250 ml and a spray nozzle that can spray 250 ml of water for 20-30 seconds. The specimen frame is a metal frame having a diameter of 15 cm. Three test piece sheets having a size of about 20 cm × 20 cm are prepared, and the sheet is fixed to the test piece holder frame so that the sheet is not wrinkled. Center the spray on the center of the sheet. Room temperature water (250 mL) is placed in a glass funnel and sprayed onto the specimen sheet (over a time period of 25-30 seconds). Remove the holding frame from the base, grab one end of the holding frame, tap the front surface down and dab the opposite end with a hard substance. Rotate the holding frame 180 ° further and repeat the same procedure to drop excess water drops. Wet specimens are compared to wet reference standards to score 0, 50, 70, 80, 90 and 100 in order of poor water repellency. Results are obtained from the average of three measurements. The indication “+” after the number indicates that the property is higher than the number, and the indication “−” indicates that the property is lower than the number.

Oil repellency test (according to AATCC test method 118-1992)
Store the treated test cloth in a constant temperature and humidity chamber with a temperature of 21 ° C and a humidity of 65% for at least 4 hours. The test solution (shown in Table 2 ) is also stored at a temperature of 21 ° C. The test is performed in a constant temperature and humidity chamber at a temperature of 21 ° C and a humidity of 65%. Gently drop 50 μL of the test solution onto the test cloth in 5 drops, leave it for 30 seconds, and if 4 or 5 drops remain on the test cloth, pass the test solution. And The oil repellency is evaluated based on 9 levels of Fail, 1, 2, 3, 4, 5, 6, 7 and 8 from the poor oil repellency to a good level, with the highest number of test solutions passed. The indication “+” after the number indicates that the property is higher than the number, and the indication “−” indicates that the property is lower than the number.

Water and oil repellent washing durability
Washing by JIS L-0217-103 method is repeated 5 times, and the subsequent water and oil repellency is evaluated (HL5). HL0 means that the evaluation was performed without washing.

The average particle size of the average particle size dispersion is measured using a laser light scattering method (manufactured by Otsuka Electronics Co., Ltd., optical fiber particle analyzer FPAR-1000).

The meanings of the abbreviations are as follows.
Monomer n-BA: n-butyl acrylate N-MAM: N-methylol acrylamide TM: 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: 2,2,3,3,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluorononyl acrylate

Chain transfer agent Si-SH: Amino mercaptosiloxane L-SH described below: Lauryl mercaptan

Emulsifier C2ABT: Di-cured tallow alkyl dimethyl ammonium chloride PP-40R: Sorbitan monopalmitate K220: Polyethylene glycol lauryl ether BO50: Polyoxyethylene oleyl ether EAD-8: Polyoxyethylene (3) tridecyl ether

Other TPG: Tripropylene glycol NC-32W: 2,2′-azobis (2-amidinopropane) dihydrochloride

Synthesis of amino mercapto functional siloxane:
Siloxane A (Si-SH)
A three-necked round bottom flask equipped with a condenser, top stirrer, and thermocouple was charged with a first silanol-terminated polydimethylsiloxane (323 g, Mn about 900), a second silanol-terminated polydimethylsiloxane (380 g, Mn about 300), mercapto Propylmethyldimethoxysilane (230 g), aminopropylmethyldiethoxysilane (27 g), trimethylethoxysilane (42 g), barium hydroxide (0.62 g) and sodium orthophosphate (0.25 g) were charged. The reaction mixture was heated to 75 ° C. and kept at this temperature for 3 hours. The volatiles were then removed at 75 ° C. for 4 hours under reduced pressure (200 mbar) to give aminomercaptosiloxane.

  The physical and structural properties of aminomercaptosiloxane (siloxane A, Si-SH) are listed in the following table:

Synthesis example 1
In a 500 mL container, n-BA (84.31 g), N-MAM (1.69 g), TM (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 (138.13 g), TPG (24.88 g) were added and pre-dispersed with a homomixer. The resulting mixture was processed for 5 minutes while cooling to obtain an emulsion of the monomer mixture.
This emulsion is put into a 500 mL separable flask equipped with a cooling tube, a nitrogen introduction tube, and a thermometer, and after nitrogen substitution, the initiator NC-32W (1.02 g) is dissolved in water (5 g) and added. Thereafter, the temperature was raised to 60 ° C., followed by polymerization for 3 hours to obtain a dispersion of non-fluorinated polymer particles having a solid content of 36.9% and an average particle size of 0.182 μm (256.4 g).

Synthesis Examples 2 to 25
In the same manner as in Synthesis Example 1, the monomer mixtures shown in Tables 3 to 8 were emulsified. When VCl was used as the monomer, a 500 mL stainless steel autoclave was used, and in other cases, a cooling tube, a nitrogen introduction tube, and a thermometer were provided. Polymerization was carried out in a 500 mL separable flask to obtain various non-fluorine polymer particles or various fluoropolymers.

Examples 1-26, Comparative Examples 1-3
Dispersion liquid mixtures obtained by blending the polymer particle dispersion liquids obtained in Synthesis Examples 1 to 25 with water so that the solid content concentration is 30% by weight are blended at the mixing ratios shown in Tables 9 to 15. It was.

Test Examples 1-20
The polymer particle dispersions obtained in the above Examples 1 to 20 were evaluated for water and oil repellency. The evaluation results are shown in Table 16.

Comparative Test Examples 1-6
The polymer particle dispersions obtained in the above Synthesis Examples 16, 17, and 19 to 22 were evaluated for water and oil repellency. The evaluation results are shown in Table 17.

Comparative Test Examples 7-9
The polymer particle dispersions obtained in the above Comparative Examples 1 to 3 were evaluated for water and oil repellency. The evaluation results are shown in Table 18.

Test Examples 21 to 26
The polymer particle dispersions obtained in Examples 21 to 26 were evaluated for water / oil repellency. The evaluation results are shown in Table 19.

Comparative Test Examples 10-13
The polymer particle dispersions obtained in Synthesis Examples 18 and 23 to 25 were evaluated for water and oil repellency. The evaluation results are shown in Table 20.

Test Examples 27 to 46
The polymer particle dispersions obtained in Examples 1 to 20 were evaluated for water / oil repellency at a low concentration. The evaluation results are shown in Table 21 below.

Comparative Test Examples 14-19
The polymer particle dispersions obtained in the above Synthesis Examples 16, 17, and 19 to 22 were evaluated for water / oil repellency at a low concentration. The evaluation results are shown in Table 22.

Comparative Test Examples 20-22
The polymer particle dispersions obtained in the above Comparative Examples 1 to 3 were evaluated for water / oil repellency at a low concentration. The evaluation results are shown in Table 23.

Test Examples 47-52
The polymer particle dispersions obtained in Examples 21 to 26 were evaluated for water / oil repellency at a low concentration. The evaluation results are shown in Table 24.

Comparative Test Examples 23 to 26
The polymer particle dispersions obtained in Synthesis Examples 18 and 23 to 25 were evaluated for water and oil repellency at a low concentration. The evaluation results are shown in Table 25.

Test Examples 53 and 54 and Comparative Test Examples 27-30
Various fabrics obtained by treating the polymer particle dispersions shown in Tables 26 to 29 with a test method for water and oil repellency were evaluated for water and oil repellency washing durability.
The evaluation results are shown in Tables 26 to 29.

Claims (20)

A fluoropolymer having repeating units formed from monomers comprising (I) a fluorine-containing monomer, a fluorine-containing polymer having a silicone residue formed from functional organopolysiloxane, and ( II) An aqueous water / oil repellent dispersion composition comprising a non-fluorinated polymer having a repeating unit formed from a vinyl monomer,
Monomer (A) has the formula (a):
_{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,
Rf is a C1-C20 fluoroalkyl group. ]
Comprising a fluorine-containing monomer represented by
The functional organopolysiloxane (B) was selected from the group consisting of mercapto functional organopolysiloxane, vinyl functional organopolysiloxane, (meth) acrylamide functional organopolysiloxane and (meth) acrylate functional organopolysiloxane. An aqueous water / oil repellent dispersion composition which is at least one kind . The fluorine-containing monomer (a) has the formula:
_{CH 2 = C (-X) -C} (= O) -Y-Z-Rf
[Wherein, X represents a hydrogen atom, a linear or branched alkyl group having 1 to 21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX ¹ X ² group (where X ¹ and X ² is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an 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 group having 6 to 18 carbon atoms or a cyclic aliphatic group, a —CH ₂ CH ₂ N (R ¹ ) SO ₂ — group (where R ¹ Is an alkyl group having 1 to 4 carbon atoms) or —CH ₂ CH (OZ ¹ ) CH ₂ — group (where Z ¹ is a hydrogen atom or an acetyl group), — (CH ₂ ) _m —SO ₂ - (CH _{2) n} - group, or _{- (CH 2) m -S- (} CH 2) n - group (where, m is 1 to 10, n is 0-10.), and
Rf is a linear or branched fluoroalkyl group having 1 to 20 carbon atoms. ]
The composition of Claim 1 which is an acrylate ester shown by these.   The functional organopolysiloxane (B) is an amino-mercapto functional organopolysiloxane, amino-vinyl functional organopolysiloxane, amino- (meth) acrylamide functional organopolysiloxane and amino- (meth) acrylate functional organopoly. The composition of claim 1, wherein the composition is at least one selected from the group consisting of siloxanes. The functional organopolysiloxane (B) has the average formula:
(R ₂ SiO) _a (RR ^N SiO) _b (RR ^FO SiO) _c
[Wherein, a is 0 to 4000,
b is 0 to 1000;
c is 1-1000;
Each R is independently a monovalent organic group;
Each R ^N is amino-functional monovalent organic group,
Each R ^FO is a monovalent mercapto functional organic group (R ^S ), a monovalent vinyl functional organic group (R ^V ), or a monovalent (meth) acrylamide functional organic group (R ^AM ). Or it is a monovalent (meth) acrylate functional organic group (R ^MA ). ]
The composition according to claim 1, which is an amino-functional organopolysiloxane having a siloxy unit represented by: The amino-mercapto functional organopolysiloxane has the average formula:

[Wherein, a is 0 to 4000,
b is 0 to 1000;
c is 1-1000;
Each R ′ is H, an alkyl group having 1 to 40 carbon atoms, or Me ₃ Si. ].
The composition of Claim 4 shown by these. The vinyl-amino functional organopolysiloxane has the average formula:

[Wherein, a is 0 to 4000,
b is 0 to 1000;
c is 1-1000;
Each R ′ is independently H, an alkyl group having 1 to 40 carbon atoms, or Me ₃ Si. ].
The composition of Claim 4 shown by these. In addition to the fluorine-containing monomer (a), the monomer (A)
(B) monomer containing no fluorine atom
The composition of claim 1 comprising a. The monomer (A) is further
(C) Crosslinkable monomer
The composition of claim 7 comprising: The non-fluorine monomer (b) has the general formula:
CH ₂ = CA ¹ COOA ²
[Wherein A ¹ is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom,
A ² is an alkyl group represented by C _n H _{2n + 1} (n = 1 to 30). ]
The composition according to claim 7, which is an acrylate represented by: The composition according to claim 8 , wherein the crosslinkable monomer (c) is a non-fluorine monomer having at least two selected from the group consisting of a reactive group and a carbon-carbon double bond. In the crosslinkable monomer (c), the reactive group is a hydroxyl group, an epoxy group, a chloromethyl group, at least Tanedea Ru claims selected from the group consisting of blocked isocyanate group, an amino group and a carboxyl group 8 A composition according to 1. A composition according to claim 1 , wherein X is chlorine. The composition according to claim 1, wherein the non-fluorine polymer (II) has a repeating unit formed from a vinyl monomer containing no fluorine atom.   The composition according to claim 1, wherein the non-fluoropolymer (II) does not contain a silicon atom. The vinyl monomer in the non-fluorine polymer (II) is
(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 ⁴ ₂ ,
(9) CH ₂ = CR ¹ CONHCH ₂ OH
[Where:
R ¹ is a hydrogen atom, a methyl group or a halogen atom,
R ² is an alkyl group having 1 to 18 carbon atoms,
R ³ is a hydrocarbon group having 1 to 30 carbon atoms,
R ⁴ is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms,
D is a chlorine atom, a bromine atom or an iodine atom. ]
The composition according to claim 1, wherein the composition is at least one selected from the group consisting of: At least one monomer selected from the group consisting of formula (1) and formula (2) and at least one selected from the group consisting of formula (3) and formula (4) the composition of claim 1 5 comprising the monomers.   A surface treatment agent comprising the composition according to claim 1. A method for treating a substrate with the surface treating agent according to claim 17 . A substrate treated with the surface treatment agent according to claim 17 . The substrate according to claim 19 , which is a textile product.