JP2015129249A - Method for producing water-repellent, oil-repellent agent composition, water-repellent, oil-repellent agent composition and method for treating article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water-repellent, oil-repellent agent composition capable of exhibiting excellent water repellency, oil repellency and dynamic water repellency and to provide a method for producing the same and a method for treating an article.SOLUTION: There is provided a method for producing a water-repellent, oil-repellent agent composition comprising a copolymer composition (E) through the following steps (1) and (2): a step (1) of obtaining a copolymer composition (C) by polymerization of a monomer component (I) containing the following monomer (B) in the presence of a polymer (A) having unsaturated double bonds on either one or both of a main chain and a side chain; a step (2) of obtaining a copolymer composition by polymerization of a monomer component (II) composed of the following monomer (d) in the presence of the copolymer composition (C). Monomer (b): a monomer containing no fluorine atom of which homopolymer has a glass transition point or a melting point of 40 to 120°C. Monomer (d): a monomer having a polyfluoroalkyl group having 1 to 6 carbon atoms.

Description

  The present invention relates to a method for producing a water / oil repellent composition, a water / oil repellent composition, and a method for treating an article.

As a method for imparting water and oil repellency to the surface of an article such as a fabric, a copolymer having a polyfluoroalkyl group having 8 or more carbon atoms (hereinafter, polyfluoroalkyl group is also referred to as ^Rf group) is used as an aqueous medium There has been known a method of treating an article using a water / oil repellent composition comprising an emulsion dispersed in the composition.
However, recently, according to the US Environmental Protection Agency (EPA), a compound having an R ^f group having 8 or more carbon atoms is decomposed in the environment and in the living body, and the decomposition products accumulate, that is, the environmental load is large. It has been pointed out. Therefore, a water / oil repellent composition that does not have an ^Rf group having 8 or more carbon atoms is required.

The water / oil repellent composition having no R ^f group having 8 or more carbon atoms is composed of an emulsion containing a copolymer having a constitutional unit based on a monomer having an R ^f group having 6 or less carbon atoms. An oil agent composition has been proposed (Patent Document 1).
However, the water / oil repellent composition described above may not sufficiently exhibit water repellency, oil repellency, and water repellency (hereinafter referred to as dynamic water repellency) against water falling from a high place (rainfall). is there.

International Publication No. 2008/136435

  An object of the present invention is to provide a water / oil repellent composition that has a low environmental load and can exhibit excellent water repellency, oil repellency and dynamic water repellency on the surface of the article, a method for producing the same, and a method for treating the article. It is.

The present invention provides a method for producing a water / oil repellent composition, a water / oil repellent composition, and a method for treating an article having the following configurations [1] to [13].
[1] A method for producing a water / oil repellent composition comprising producing a water / oil repellent composition containing the copolymer composition (E) through the following steps (1) and (2).
Step (1): Monomer component containing the following monomer (b) in the presence of the polymer (A) containing an unsaturated double bond in one or both of the main chain and the side chain ( A step of polymerizing I) to obtain a copolymer composition (C).
Step (2): In the presence of the copolymer composition (C), a monomer component (II) comprising the following monomer (d) is polymerized to obtain a copolymer composition (E). Process.
Monomer (b): A monomer which does not contain a fluorine atom and whose homopolymer has a glass transition point or melting point of 40 to 120 ° C.
Monomer (d): A monomer having a C 1-6 R ^f group.
[2] The method for producing a water / oil repellent composition according to [1], wherein the polymer (A) has a structural unit based on the monomer (a) having a conjugated diene structure.
[3] The monomer (b) is selected from the group consisting of (meth) acrylic acid esters, (meth) acrylamides, (meth) acrylonitriles, vinyl chloride, and monomers having a crosslinkable functional group. The method for producing a water / oil repellent composition according to [1] or [2], wherein the water / oil repellent composition is at least one kind.
[4] The method for producing a water / oil repellent composition according to any one of [1] to [3], wherein the monomer (d) is a compound represented by the following general formula (d1): .
Z-Y-X (d1)
However, Z is a C 1-6 R ^f group (however, among the carbon atoms in the R ^f group, at least one fluorine atom is bonded to the carbon atom bonded to Y), or carbon. A perfluorooxaalkyl group having 2 to 50 carbon atoms (however, when the carbon number is 8 or more, the terminal group is a perfluoroalkyl group having 6 or less carbon atoms);
Y is a divalent organic group having no fluorine atom, or a single bond,
X is a polymerizable unsaturated _{^{group, -CR 1 = CH 2, -COOCR}} 1 = CH 2, -OCOCR 1 = CH 2, - (R 2) N (O =) CR 1 = CH 2, - SCOCR ¹ ═CH ₂ or —OCH═CH ₂ (wherein R ¹ is a hydrogen atom, a methyl group, a halogen atom or a trifluoromethyl group, and R ² is a hydrogen atom or an alkyl group).
[5] In the general formula (d1),
Z is a perfluoroalkyl group having 1 to 6 carbon atoms or a perfluorooxaalkyl group having 2 to 20 carbon atoms (however, when the carbon number is 8 or more, the terminal group is a perfluoroalkyl group having 6 or less carbon atoms). Yes,
Y is ^{_{- (CH 2) m -,}} - Q 1 -Ar-Q 2 -, or ^{-Q 1 -Ar-Q 2 -Ar-} Q 3 - ( provided that, m is 1 to 4, Ar is an arylene group Q ^{1 to} Q ³ are each independently a divalent organic group having no fluorine atom, or a single bond.
The method for producing a water / oil repellent composition according to [4], wherein X is —OCOCR ¹ ═CH ₂ (wherein R ¹ is a hydrogen atom, a methyl group, a halogen atom or a trifluoromethyl group).
[6] The mass ratio ((A) / (I)) between the polymer (A) and the monomer component (I) in the step (1) is 5/95 to 95/5. The method for producing a water / oil repellent composition according to any one of [1] to [5].
[7] The mass ratio ((C) / (II)) between the copolymer composition (C) and the monomer component (II) in the step (2) is 5/1 to 1/5. The method for producing a water / oil repellent composition according to any one of [1] to [6].
[8] The method according to any one of [1] to [7], wherein the step (1) and the step (2) are each performed in the presence of an aqueous medium, a surfactant, and a radical polymerization initiator. A method for producing a water / oil repellent composition.
[9] The polymer (A) has a structural unit based on the monomer (a) having a conjugated diene structure,
The method for producing a water / oil repellent composition according to any one of [1] to [8], wherein the monomer (a) is at least one selected from the group consisting of isoprene, butadiene, and chloroprene. .
[10] The method for producing a water / oil repellent composition according to any one of [1] to [9], wherein the polymer (A) has a mass average molecular weight of 1,000 to 50,000.
[11] The monomer component (I) includes a monomer having a crosslinkable functional group, and the crosslinkable functional group is a hydroxy group, a carboxy group, an isocyanate group, a glycidyl group, a methylol group, or a hydrolysis. The method for producing a water / oil repellent composition according to any one of [1] to [10], which is at least one selected from the group consisting of a hydrophilic silanol group.
[12] A water / oil repellent composition obtained by the method for producing a water / oil repellent composition according to any one of [1] to [11].
[13] A method for treating an article, comprising a step of treating the article with the water / oil repellent composition according to [12].

According to the method for producing a water / oil repellent composition of the present invention, it is possible to produce a water / oil repellent composition that has a small environmental load and can exhibit excellent water repellency, oil repellency and dynamic water repellency on the surface of an article. .
The water / oil repellent composition of the present invention has a small environmental load and can exhibit excellent water repellency, oil repellency and dynamic water repellency on the surface of the article.
According to the article processing method of the present invention, the surface of the article can exhibit excellent water repellency, oil repellency and dynamic water repellency with a small environmental load.

In this specification, a compound represented by the formula (d1) is referred to as a compound (d1). The same applies to compounds represented by other formulas.
The monomer in the present specification means a compound having a polymerizable unsaturated group.
R ^f group represents a polyfluoroalkyl group. The polyfluoroalkyl group is a group in which part or all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms. Further, some or all of the remaining hydrogen atoms may be substituted with chlorine atoms.
However, of the carbon atoms in the R ^f group, and in which at least one fluorine atom to carbon atom (carbon atom bonds tail) that bound to groups other than ^the R ^f group is attached. For example, in the case of a compound represented by F (CF ₂ ) ₆ (CH ₂ ) ₂ OC (O) C (CH ₃ ) ═CH _2, it is F (CF ₂ ) ₆ (CH ₂ ) ₂ that corresponds to the R ^f group. Rather than F (CF ₂ ) ₆ .
The perfluorooxaalkyl group refers to a perfluoroalkyl group having one or more etheric oxygen atoms between carbon atoms.
The perfluoroalkyl group is a group in which all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms.
(Meth) acrylic acid ester ((meth) acrylate) indicates acrylic acid ester (acrylate) or methacrylic acid ester (methacrylate). (Meth) acrylamide represents acrylamide or methacrylamide. (Meth) acrylonitrile refers to acrylonitrile or methacrylonitrile.

<Method for producing water / oil repellent composition>
The method for producing a water / oil repellent composition of the present invention is characterized by producing a water / oil repellent composition comprising a copolymer composition (E) through the following steps (1) and (2). To do.
Step (1): Monomer component containing the following monomer (b) in the presence of the polymer (A) containing an unsaturated double bond in one or both of the main chain and the side chain ( A step of polymerizing I) to obtain a copolymer composition (C).
Step (2): In the presence of the copolymer composition (C), a monomer component (II) comprising the following monomer (d) is polymerized to obtain a copolymer composition (E). Process.
Monomer (b): A monomer which does not contain a fluorine atom and whose homopolymer has a glass transition point or melting point of 40 to 120 ° C.
Monomer (d): A monomer having a C 1-6 R ^f group.

In the step (1), hydrogen on carbon adjacent to the unsaturated double bond of the polymer (A) is withdrawn, and the monomer constituting the monomer component (I) is considered to be graft polymerized. Therefore, in the copolymer composition (C), a graft copolymer in which a graft chain having a structural unit based on the monomer component (I) is bonded to the polymer (A) (hereinafter referred to as polymer (B)). Is also included).
The copolymer composition (C) includes a polymer other than the polymer (B), for example, a polymer obtained by polymerizing only the monomer constituting the monomer component (I) (hereinafter referred to as polymer (B ′)). Or unreacted polymer (A) or the like.

In the step (2), when the hydrogen on the carbon adjacent to the position of the unsaturated double bond derived from the polymer (A) of the polymer (B) is withdrawn, and the monomer component (II) is graft-polymerized Conceivable. Therefore, the copolymer composition (E) has a graft chain having a structural unit based on the monomer component (I) and a structural unit based on the monomer component (II) in the polymer (A). A graft copolymer bonded to a graft chain (hereinafter also referred to as polymer (D)) is included.
The copolymer composition (E) includes a polymer other than the polymer (D), for example, a polymer obtained by polymerizing only the monomer (d) (hereinafter, also referred to as polymer (D ′)), copolymer. The polymer etc. which were contained in the unification composition (C) may be contained.

(Polymer (A))
The polymer (A) contains an unsaturated double bond in one or both of the main chain and the side chain.
Examples of the unsaturated double bond include —CH═CH—, —CH═C (CH ₃ ) —, —CH═CCl—, —CH═CH ₂ , —CH═CH (CH ₃ ) and the like.
In the polymer (A), the hydrocarbon group adjacent to the site having the unsaturated bond, that is, the hydrogen at the allylic position, is easily extracted by the radical initiator and becomes the starting point of graft polymerization.

As the polymer (A), a polymer having a structural unit based on the monomer (a) having a conjugated diene structure is preferable. An unsaturated double bond is introduced into the main chain or the side chain by the polymerization of the monomer (a). As the monomer (a), isoprene, butadiene, chloroprene and the like are preferable from the viewpoint of availability. The structural unit based on the monomer (a) contained in the polymer (A) may be one type or two or more types.
The structural unit based on the monomer (a) may be either a 1-2 bond or a 1-4 bond. The structural unit based on the monomer (a) has 1-4 bonds in that it imparts appropriate elongation to a film (water / oil repellent film) formed by processing the water / oil repellent composition on the surface of the article. The content is preferably 50% by mass or more, and particularly preferably composed of only 1-4 bonds. As a result, the durability of the water / oil repellent film is improved. For example, a processed cloth treated with a water / oil repellent composition has water repellency, oil repellency and dynamic water repellency excellent in durability against repeated washing.
The polymer (A) may contain a structural unit based on a monomer other than the monomer (a) in addition to the structural unit based on the monomer (a). As the monomer other than the monomer (a), styrene, ethylene, propylene, vinyl chloride and the like are preferable.
The content of the structural unit based on the monomer (a) in the polymer (A) is the sum of the monomers constituting the polymer (A) from the point that the monomer component (I) is easily graft polymerized. Of (100% by mass), 50% by mass or more is preferable.
As the polymer (A), polybutadiene, polyisoprene, polychloroprene and the like are preferable from the viewpoint of availability.

1000-50000 are preferable and, as for the mass average molecular weight of a polymer (A), 5000-30000 are more preferable. Within this range, the polymer (A) is easily dispersed in water, and the water / oil repellent film formed by processing the water / oil repellent composition on the surface of the article is excellent in strength.
The mass average molecular weight of the polymer (A) is a value in terms of polystyrene measured by gel permeation chromatography (GPC).

(Monomer component (I))
The monomer component (I) contains at least the monomer (b). A monomer (b) is a monomer which does not contain a fluorine atom and whose glass transition point or melting point of a homopolymer is 40 to 120 ° C.
When the monomer (b) does not contain a fluorine atom and the homopolymer of the monomer (b) has a glass transition point or a melting point of 40 to 120 ° C., the water / oil repellent composition is removed from the surface of the article. The water- and oil-repellent film formed by processing is excellent in dynamic water repellency and excellent in processability of the water / oil repellent composition on the article surface.
45-120 degreeC is preferable and, as for the glass transition point or melting | fusing point of the homopolymer of a monomer (b), 60-120 degreeC is especially preferable.
In the present invention, the glass transition point and melting point of the homopolymer of monomer (b) are respectively the glass transition point and melting point as measured by differential scanning calorimetry (heat flux DSC) (JIS K7121).

The monomer (b) is preferably a monomer having high radical polymerizability in order to facilitate grafting to the polymer (A) by radical reaction to form a graft chain.
Examples of the monomer (b) having high radical polymerizability include (meth) acrylic acid esters, (meth) acrylamides, (meth) acrylonitriles, vinyl chloride, monomers having a crosslinkable functional group, and the like. It is done. Any of these monomers may be used alone or in combination of two or more.

The monomer (b) preferably includes at least one selected from the group consisting of (meth) acrylic acid esters, (meth) acrylamides, and (meth) acrylonitriles, and (meth) acrylic acid esters It is particularly preferable that These monomers have high radical stability and are suitable for the graft reaction.
Specific examples of the preferred monomer (b) include methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, isobornyl methacrylate, stearyl methacrylate, behenyl methacrylate, t-butyl methacrylate, isopropyl methacrylate, And phenyl methacrylate.
The monomer (b) contained in the monomer component (I) may be one type or two or more types.
The monomer component (I) may be composed of the monomer (b), or may be a mixture of the monomer (b) and another monomer other than the monomer (b).
Examples of other monomers include monomers (d), vinylidene chloride, vinyl esters, styrenes, α-olefins, vinyl ethers, and monomers having a crosslinkable functional group not corresponding to monomer (b). Examples thereof include monomers (monomers having a crosslinkable functional group and a homopolymer having a glass transition point or a melting point of less than 40 ° C. or more than 120 ° C.), (meth) acrylic acid esters other than those described above, and the like.

The proportion of the monomer (b) in the monomer component (I) is preferably 30% by mass or more with respect to the total (100% by mass) of all monomers constituting the monomer component (I). 50 mass% or more is more preferable, 60 mass% or more is further more preferable, and 80 mass% or more is the most preferable. When the proportion of the monomer (b) is 50% by mass or more, the dynamic water repellency is excellent.
The monomer component (I) is particularly preferably composed of the monomer (b).

The monomer component (I) preferably contains a monomer having a crosslinkable functional group. Thereby, it is excellent in the adhesiveness of a water / oil repellent film and the article surface.
The crosslinkable functional group is preferably at least one selected from a hydroxy group, a carboxy group, an isocyanate group, a glycidyl group, a methylol group, and a hydrolyzable silanol group from the viewpoint of adhesion to an article.
The monomer having a crosslinkable functional group may be included as a part of the monomer (b) or may be included as a monomer other than the monomer (b). That is, the monomer having a crosslinkable functional group may have a homopolymer having a glass transition point or melting point of 40 to 120 ° C, and the homopolymer has a glass transition point or melting point of less than 40 ° C or more than 120 ° C. It may be what is. These may be used in combination.
Specific examples of the monomer having a crosslinkable functional group include the following compounds.

  2-isocyanatoethyl (meth) acrylate, 3-isocyanatopropyl (meth) acrylate, 4-isocyanatobutyl (meth) acrylate, 2-butanone oxime adduct of 2-isocyanatoethyl (meth) acrylate, 2-isocyanate Pyrazole adduct of natoethyl (meth) acrylate, 3,5-dimethylpyrazole adduct of 2-isocyanatoethyl (meth) acrylate, 3-methylpyrazole adduct of 2-isocyanatoethyl (meth) acrylate, 2-isocyanate Ε-Caprolactam adduct of natoethyl (meth) acrylate, 2-butanone oxime adduct of 3-isocyanatopropyl (meth) acrylate, pyrazole adduct of 3-isocyanatopropyl (meth) acrylate.

  3,5-dimethylpyrazole adduct of 3-isocyanatopropyl (meth) acrylate, 3-methylpyrazole adduct of 3-isocyanatopropyl (meth) acrylate, ε-caprolactam addition of 3-isocyanatopropyl (meth) acrylate 4-isocyanatobutyl (meth) acrylate 2-butanone oxime adduct, 4-isocyanatobutyl (meth) acrylate pyrazole adduct, 4-isocyanatobutyl (meth) acrylate 3,5-dimethylpyrazole addition 4-isocyanatobutyl (meth) acrylate 3-methylpyrazole adduct, 4-isocyanatobutyl (meth) acrylate ε-caprolactam adduct.

  Methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, butoxymethyl (meth) acrylamide, diacetone acrylamide, γ-methacryloyloxypropyltrimethoxysilane, vinyltrimethoxysilane, dimethylaminoethyl (meth) acrylate, diethylaminoethyl ( (Meth) acrylate, dimethylaminopropyl (meth) acrylate, (meth) acryloylmorpholine, (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxypropyltrimethylammonium chloride, (meth) acrylamidoethyltrimethylammonium chloride, (meth) Acrylamidepropyltrimethylammonium chloride.

  t-butyl (meth) acrylamide sulfonic acid, (meth) acrylamide, N-methyl (meth) acrylamide, N-methylol (meth) acrylamide, N-butoxymethyl (meth) acrylamide, diacetone (meth) acrylamide, glycidyl (meth) Acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-chloro-2-hydroxypropyl methacrylate, polyoxyalkylene glycol mono (meth) acrylate, ( (Meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyhexahydrophthalic acid, 2- (meth) acryloyloxyethyl acid phosphate, allyl Meth) acrylate, 2-vinyl-2-oxazoline, 2-vinyl-4-methyl - (2-vinyl oxazoline) polycaprolactone ester of hydroxyethyl (meth) acrylate.

  Tri (meth) allyl isocyanurate (T (M) AIC, manufactured by Nippon Kasei Co., Ltd.), triallyl cyanurate (TAC, manufactured by Nippon Kasei Co., Ltd.), phenylglycidyl ethyl acrylate tolylene diisocyanate (AT-600, manufactured by Kyoeisha Chemical Co., Ltd.) ), 3- (methylethylketoxime) isocyanatomethyl-3,5,5-trimethylcyclohexyl (2-hydroxyethyl methacrylate) cyanate (Tech Coat HE-6P, manufactured by Kyo Silk Chemical Co., Ltd.). Polycaprolactone ester of hydroxyethyl (meth) acrylate (Placcel FA, FM series, manufactured by Daicel Chemical Industries).

  Monochloro vinyl acetate, 2-chloroethyl vinyl ether, 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxyisopropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxycyclohexyl vinyl ether, 1,6- Hexanediol monovinyl ether, 1,4-cyclohexanedimethanol monovinyl ether, diethylene glycol monovinyl ether, triethylene glycol monovinyl ether, dipropylene glycol monovinyl ether, vinyl glycidyl ether, 2-aminoethyl vinyl ether, 3-aminopropyl vinyl ether, 2-amino Butyl vinyl ether, allyl vinyl ether, 1,4-butyl Emissions divinyl ether, nonanediol divinyl ether, white hexanediol divinyl ether, cyclohexanedimethanol divinyl ether, triethylene glycol divinyl ether, trimethylolpropane trivinyl ether, pentaerythritol tetravinyl ether.

  Among the monomers having the crosslinkable functional group, N-methylol (meth) acrylamide, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, 3-chloro-2-hydroxypropyl methacrylate, hydroxyethyl Preference is given to polycaprolactone esters of (meth) acrylate (Placcel FA, FM series, manufactured by Daicel Chemical Industries).

5-50 mass% is preferable with respect to the sum total (100 mass%) of all the monomers which comprise monomer component (I), and, as for content of the monomer which has a crosslinkable functional group, 10-30 mass % Is more preferable.
The content of the monomer having a crosslinkable functional group is preferably 1 to 30% by mass, and 5 to 20% by mass with respect to the total (100% by mass) of all the structural units constituting the polymer (A). More preferred.

(Monomer component (II))
Monomer component (II) consists of monomer (d). The monomer (d) is a monomer having a C 1-6 R ^f group.
The R ^f group is preferably a group in which at least 20% of hydrogen atoms in the alkyl group are substituted with fluorine atoms, and more preferably a group in which at least 80% is substituted with fluorine atoms. Further, some or all of the remaining hydrogen atoms may be substituted with chlorine atoms.
The R ^f group may be linear or branched. In the case of a branched shape, those having a short branch at the end far from the bond or in the vicinity thereof are preferable.

Examples of the R ^f group include F (CF ₂ ) ₄ —, F (CF ₂ ) ₅ —, F (CF ₂ ) ₆ —, (CF ₃ ) ₂ CF (CF ₂ ) ₂ —, and H (CF ₂ ). _{6 -, HCF 2 CF 2 -} , Cl (CF 2) 4 -, and the like.
As the R ^f group, a group represented by F (CF ₂ ) _h — (where h is an integer of 1 to 6), or C ₂ F ₅ (CM ¹ M ² CM ³ M ⁴ ) ₂ — (However, M ^{1 to} M ⁴ are each independently a hydrogen atom, a fluorine atom, or a chlorine atom, and at least one of M ^{1 to} M ⁴ is a fluorine atom).
The ^the R ^f group, from the viewpoint of water and oil repellency, a perfluoroalkyl group in which all are substituted by fluorine atoms of the hydrogen atoms of the alkyl group are _{preferred, F (CF 2) 4 -} , F (CF 2) 5 - , F (CF ₂ ) ₆ -is particularly preferable.

As a monomer (d), if it has a C1-C6 ^Rf group, it will not specifically limit, A well-known monomer can be used.
As the monomer (d), the compound (d1) is preferable from the viewpoint of oil repellency and dynamic contact angle.
Z-Y-X (d1)
However, Z is a C 1-6 R ^f group (however, among the carbon atoms in the R ^f group, at least one fluorine atom is bonded to the carbon atom bonded to Y), or carbon. A perfluorooxaalkyl group having 2 to 50 carbon atoms (however, when the carbon number is 8 or more, the terminal group is a perfluoroalkyl group having 6 or less carbon atoms);
Y is a divalent organic group having no fluorine atom, or a single bond,
X is a polymerizable unsaturated _{^{group, -CR 1 = CH 2, -COOCR}} 1 = CH 2, -OCOCR 1 = CH 2, - (R 2) N (O =) CR 1 = CH 2, - SCOCR ¹ ═CH ₂ or —OCH═CH ₂ (wherein R ¹ is a hydrogen atom, a methyl group, a halogen atom or a trifluoromethyl group, and R ² is a hydrogen atom or an alkyl group).

The ^the R ^f group having 1 to 6 carbon atoms are the same as those described above.
The perfluoroalkyl oxaalkyl group, for _{example, C k F 2k + 1 O} [CF (CF 3) CF 2 O] e CF (CF 3) -, C 3 F 7 O [CF (CF 3) CF 2 O] e (CF ₂ ) _j- and the like. k is an integer of 1 to 6, and an integer of 3 to 6 is particularly preferable. e is preferably an integer of 0 to 5, and particularly preferably an integer of 0 to 3. j is preferably an integer of 1 to 6, particularly preferably an integer of 3 to 6.
Z is a perfluoroalkyl group having 1 to 6 carbon atoms or a perfluorooxaalkyl group having 2 to 20 carbon atoms (however, when the carbon number is 8 or more, the terminal group is a perfluoroalkyl group having 6 or less carbon atoms). ) Is preferred.

The divalent organic group having no fluorine atom for Y is preferably a divalent group containing a hydrocarbon group. The hydrocarbon group may be saturated or unsaturated. Examples of the hydrocarbon group include an alkylene group, a linear or branched unsaturated hydrocarbon group, and an arylene group.
The group containing a hydrocarbon group may be a group composed of a hydrocarbon group, or may further contain a group other than a hydrocarbon group. Examples of the group other than the hydrocarbon group include —O—, —NH—, —CO—, —SO ₂ — and the like.
Examples of the divalent group containing a hydrocarbon ^{group, -R M -Q-R N -} 2 divalent organic group (represented ^by, R M, ^{R N} are each independently a single bond, one or more A saturated or unsaturated hydrocarbon group having 1 to 22 carbon atoms which may contain an oxygen atom, and at least one of R ^M and R ^N is the hydrocarbon group, Q is a single bond, —OCONH— _{, -CONH -, -. SO 2} NH- or a -NHCONH-) is preferred.

Y is preferably a divalent group containing an alkylene group. The alkylene group may be linear or branched. The alkylene group may be linear or branched.
The divalent group containing an alkylene group may be a group composed of an alkylene group or may further contain a group other than an alkylene group. As a group other than an alkylene group, —O—, —NH—, —CO—, —SO ₂ —, —CD ₁ = CD ₂ — (wherein D ₁ and D ₂ are each independently a hydrogen atom or a methyl group. And the like.
The divalent group containing an alkylene _{group, -CH 2 -, - CH 2} CH 2 -, - CH 2 CH 2 CH 2 -, - (CH 2) 11 -, - CH 2 CH 2 CH (CH 3) _{-, - CH = CHCH 2 -} , - (CH 2 CHR 3 O) p CH 2 CH 2 - ( Here, p is an integer of from 1 to 10, ^{R 3} is hydrogen atom or a methyl group.), - _{C 2} H ₄ OCONHC ₂ H ₄ —, —C ₂ H ₄ OC (═O) OC ₂ H ₄ —, —COOC ₂ H ₄ — and the like are preferable. Among _{them, - (CH 2) m -} ( provided that, m is an integer from 1 to 4.) Are preferred, _{-CH 2} CH 2 - is particularly preferred.

Y is also preferably a divalent group containing an arylene group.
Examples of the divalent group containing an arylene group include -Q ¹ -Ar-Q ^2- , -Q ¹ -Ar-Q ² -Ar-Q ^3- (wherein Ar is an arylene group, Q ¹ to Q ³ is independently a divalent organic group having no fluorine atom or a single bond.
Examples of the arylene group include a phenylene group.
The divalent organic group having no fluorine atom in Q ^{1 to} Q ³ is preferably a divalent group containing an alkylene group. Examples of the divalent group containing an alkylene group include those described above.

X is a polymerizable unsaturated ^{_{group, -CR 1 = CH 2, -COOCR}} 1 = CH 2, -OCOCR 1 = CH 2, - (R 2) N (O =) CR 1 = CH 2, - SCOCR ¹ ═CH ₂ or —OCH═CH ₂ (wherein R ¹ is a hydrogen atom, a methyl group, a halogen atom or a trifluoromethyl group, and R ² is a hydrogen atom or an alkyl group).
Examples of the halogen atom for R ¹ include a fluorine atom and a chlorine atom.
The alkyl group for R ² is preferably a methyl group.
X is —OCOCR ¹ ═CH from the viewpoint of polymerizability with other monomers, flexibility of the formed water / oil repellent film, adhesion to articles, solubility in solvents, or ease of emulsion polymerization. ₂ is preferred, and —OCOCCH ₃ ═CH ₂ is particularly preferred.

From the above, as the compound (d1), Z is a perfluoroalkyl group having 1 to 6 carbon atoms or a perfluorooxaalkyl group having 2 to 20 carbon atoms. . 6 are the following perfluoroalkyl group), Y is ^{_{- (CH 2) m -,}} - Q 1 -Ar-Q 2 -, or ^{-Q 1 -Ar-Q 2 -Ar-} Q 3 - ( However, m is 1 to 4, Ar is an arylene ^group, the Q 1 to Q ³ are each independently a divalent organic group having no fluorine atom, or a single bond.), X is It is preferable that —OCOCR ¹ ═CH ₂ (wherein R ¹ is a hydrogen atom, a methyl group, a halogen atom or a trifluoromethyl group). Among them, it is preferable that Z is a C 1-6 perfluoroalkyl group, Y is — (CH ₂ ) _m —, and X is —OCOC (CH ₃ ) ═CH ₂ .

The monomer (d) contained in the monomer component (II) may be one type or two or more types.
As the monomer (d), from the viewpoint of polymerizability with other monomers, flexibility of the formed water / oil repellent film, adhesion to articles, solubility in solvents, ease of emulsion polymerization, etc. A (meth) acrylate having an R ^f group is preferred, and a methacrylate having an R ^f group is particularly preferred.
As the monomer (d), CH ₂ ═C (CH ₃ ) COO (CH ₂ ) _m (CF ₂ ) _h F (where m is 1 to 4) from the viewpoint of water repellency / oil repellency and polymerization reactivity. And h is an integer of 1 to _6. ), and CH ₂ ═C (CH ₃ ) COO (CH ₂ ) ₂ (CF ₂ ) ₆ F is particularly preferable.

(Process (1))
In the step (1), the monomer component (I) containing the monomer (b) is polymerized in the presence of the polymer (A) to obtain a copolymer composition (C).
The mass ratio ((A) / (I)) between the polymer (A) and the monomer component (I) to be reacted in the step (1) is preferably 5/95 to 95/5. When (A) / (I) is within the above range, the water / oil repellent film formed from the water / oil repellent composition is excellent in flexibility and dynamic water repellency. (A) / (I) is more preferably 5/95 to 20/80 from the viewpoint of dynamic water repellency.

  As the polymerization method of the monomer component (I), solution polymerization or emulsion polymerization is preferable, and emulsion polymerization is more preferable from the viewpoint of easy water dispersion. In the case of solution polymerization, step (1) is typically performed in the presence of a solvent and a radical polymerization initiator. In the case of emulsion polymerization, step (1) is typically carried out in the presence of an aqueous medium, a surfactant and a radical polymerization initiator.

  The medium (solvent) used for the solution polymerization is preferably one having a low chain transfer property. Specific examples include alcohol, glycol, glycol ether, halogen compound, hydrocarbon, ketone, ester, ether, nitrogen compound, sulfur compound and the like.

  Examples of alcohol include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methylpropanol, 1,1-dimethylethanol, 1-pentanol, 2-pentanol, and 3-pentanol. 2-methyl-1-butanol, 3-methyl-1-butanol, 1,1-dimethylpropanol, 3-methyl-2-butanol, 1,2-dimethylpropanol, 1-hexanol, 2-methyl-1-pen Examples include butanol, 4-methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, 3-heptanol, and 1,4-butanediol.

  As glycol and glycol ether, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol , Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol dimethyl ether, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monoethyl ether, and the like.

Examples of the halogen compound include halogenated hydrocarbons and halogenated ethers.
Examples of the halogenated hydrocarbon include hydrochlorofluorocarbon, hydrofluorocarbon, hydrobromocarbon and the like.
Examples of the halogenated ether include hydrofluoroether.
Examples of hydrofluoroethers include separated hydrofluoroethers and non-separable hydrofluoroethers. The separated hydrofluoroether is a compound in which an R ^f group or a perfluoroalkylene group and an alkyl group or an alkylene group are bonded via an etheric oxygen atom. The non-separable hydrofluoroether is a hydrofluoroether containing a partially fluorinated alkyl group or alkylene group.

Examples of the hydrocarbon include aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons.
As aliphatic hydrocarbons, pentane, 2-methylbutane, 3-methylpentane, hexane, 2,2-dimethylbutane, 2,3-dimethylbutane, heptane, octane, 2,2,4-trimethylpentane, 2,2 , 3-trimethylhexane, decane, undecane, dodecane, 2,2,4,6,6-pentamethylheptane, tridecane, tetradecane, hexadecane and the like.
Examples of the alicyclic hydrocarbon include cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, and ethylcyclohexane.
Examples of the aromatic hydrocarbon include benzene, toluene, xylene, metaxylene hexafluoride, paraxylene hexafluoride and the like.
Examples of the ketone include acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, and methyl isobutyl ketone.

Examples of the ester include methyl acetate, ethyl acetate, butyl acetate, methyl propionate, methyl lactate, ethyl lactate, and pentyl lactate.
Examples of the ether include diisopropyl ether, dioxane, tetrahydrofuran (hereinafter referred to as THF) and the like.
Examples of the nitrogen compound include pyridine, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like.
Examples of the sulfur compound include dimethyl sulfoxide and sulfolane.
Of these, one or more media selected from the group consisting of toluene, metaxylene hexafluoride, paraxylene hexafluoride, and hydrofluoroether are preferred because of their low solubility and low chain transfer.
These media may be used individually by 1 type, and 2 or more types may be mixed and used for them.

In emulsion polymerization, it is necessary to disperse the polymer (A) in an aqueous medium, and in the emulsion of the polymer (A) prepared by emulsion polymerization of the monomer (a) using a surfactant. Preferred is a method in which the monomer component (I) is polymerized, or the polymer (A) and the monomer component (I) are forcibly emulsified in an aqueous medium before polymerization using a surfactant. . Among these, a method using forced emulsification is preferable from the viewpoint of the stability of the copolymer composition (C) obtained by polymerization. Forced emulsification can be performed using an emulsifier. As the emulsifier, a pressure type emulsifier such as a gorin homogenizer is preferable.
As a medium (aqueous medium) used for emulsion polymerization, at least water is used. In order to improve the dispersion stability and freezing stability, it is preferable to add a water-soluble organic solvent. As the water-soluble organic solvent, it is preferable to use one kind of alcohol, glycol, glycol ether, glycol ester, or a mixture of two or more kinds of media.
Alcohols, glycols, and glycol ethers as water-soluble organic solvents used for emulsion polymerization are the same as those used for solution polymerization. Examples of glycol esters include dipropylene glycol.
5-50 mass% is preferable with respect to water, and, as for the usage-amount of a water-soluble organic solvent, 10-30 mass% is more preferable.

As the surfactant, any one or a combination of two or more selected from an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant can be used. As the surfactant in the step (1), a nonionic surfactant alone or a combination of a nonionic surfactant and a cationic surfactant is preferable from the viewpoint of affinity for an article. Preferable examples of these surfactants are the same as those mentioned in the step (2) described later.
It is preferable that the usage-amount of surfactant is 1-10 mass parts with respect to a total of 100 mass parts of a polymer (A) and monomer component (I), and 3-6 mass parts is more preferable. When the content is 1 part by mass or more, the dispersion stability of the copolymer composition (C) is excellent, and when the content is 10 parts by mass or less, the water-repellent and water-repellent property formed by treating the article surface with the water / oil repellent composition. Excellent oil film performance.

Examples of the polymerization initiator include a thermal polymerization initiator, a photopolymerization initiator, a radiation polymerization initiator, a radical polymerization initiator, an ionic polymerization initiator, and the like, and a radical polymerization initiator is preferably used.
As the radical polymerization initiator, a general-purpose initiator such as an azo polymerization initiator, a peroxide polymerization initiator, or a redox initiator is used depending on the polymerization temperature.
The radical polymerization initiator used in the solution polymerization is preferably a peroxide polymerization initiator. Examples include di-t-butyl peroxide, dibenzoyl peroxide, dilauroyl peroxide, diisobutyryl peroxide, dipropyl peroxydicarbonate, diisopropyl peroxydicarbonate, di-2ethylhexyl-peroxydicarbonate, t -Butylperoxyneodecanoate, t-hexylperoxypivalate, t-hexylperoxyneodecanoate, cumylperoxyneodecanoate, t-butylperoxyheptanoate, t-butylperoxypi Examples thereof include barate and disuccinic acid peroxide.
As a radical polymerization initiator used in emulsion polymerization, a water-soluble initiator is preferable, and an azo compound is particularly preferable. Examples of the azo compound include 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2′-azobis (2 -Methylpropionate), 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (2-methylpropionamide) dihydrochloride, 2,2'-azobis [2- (2 -Imidazolin-2-yl) propane] disulfate, 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (2-imidazoline) -2-yl) propane] acetate, 2,2′-azobis [N- (2-carboxyethyl) 2-methylpropionamidine] hydrate, 2,2′-azobis (1-imino-1-pyrrolidino-2 -Methylpropane) Dihydrochloride is mentioned.
As for the usage-amount of a radical polymerization initiator, 0.5-5 mass parts is preferable with respect to 100 mass parts of monomer components (I).

  The polymerization conditions in step (1) are preferably low temperature conditions in order to improve the grafting efficiency, and polymerization in a short time is desirable in order to improve the stability of the emulsion. The temperature is preferably 40 to 80 ° C, more preferably 50 to 70 ° C. The polymerization time is preferably 4 to 72 hours, more preferably 6 to 48 hours.

(Process (2))
In step (2), a monomer component (II) comprising monomer (d) is polymerized in the presence of the copolymer composition (C) obtained in step (1) to obtain a copolymer. A composition (E) is obtained.
The mass ratio ((C) / (II)) of the copolymer composition (C) and the monomer component (II) to be reacted in the step (2) is 5 / It is preferably 1 to 1/5, and 2.5 / 1 to 1/2 is particularly preferable from the viewpoint of emulsion stability.

As a polymerization method of the monomer component (II), solution polymerization or emulsion polymerization is preferable, and emulsion polymerization is more preferable from the viewpoint of easy water dispersion.
In the case of emulsion polymerization, the step (2) includes the step of containing the polymer (B) in that the monomer component (II) is easily graft polymerized to the polymer (B) and a dense phase separation structure is easily developed. Particularly preferred is a step of polymerizing the polymer composition (C) in a form swollen by the monomer component (II).
Examples of the method of swelling the copolymer composition (C) with the monomer component (II) include, for example, the copolymer emulsion obtained in the step (1) (the particles of the copolymer composition (C) are a medium). For example, a method in which the monomer component (II) is added to and stirred.
Whether the copolymer composition (C) is swollen by the monomer component (II) depends on the average particle diameter of the particles contained in the copolymer emulsion obtained in the step (1) and the monomer component ( It can be confirmed by comparing the average particle size of the particles contained in the copolymer emulsion after adding II). If the average particle size of the particles contained in the copolymer emulsion after addition of the monomer component (II) is larger, it is determined that the copolymer composition (C) is swollen by the monomer (d). it can.
In the case of solution polymerization, step (2) is typically carried out in the presence of a solvent and a radical polymerization initiator. In the case of emulsion polymerization, step (2) is typically carried out in the presence of an aqueous medium, a surfactant and a radical polymerization initiator. Examples of the medium (solvent, aqueous medium) and radical polymerization initiator are the same as those in step (1).

The surfactant acts as a dispersion stabilizer during the polymerization in the step (2).
Examples of the surfactant include a hydrocarbon-based surfactant or a fluorine-based surfactant, and an anionic surfactant, a nonionic surfactant, a cationic surfactant, or an amphoteric surfactant, respectively. Can be mentioned.
The surfactant in the step (2) is preferably a combination of a nonionic surfactant and a cationic surfactant or an amphoteric surfactant, or an anionic surfactant alone, from the viewpoint of dispersion stability. A combination of a nonionic surfactant and a cationic surfactant is more preferred.
The ratio of the nonionic surfactant to the cationic surfactant (nonionic surfactant / cationic surfactant) is preferably 97/3 to 40/60 (mass ratio).
In a specific combination of a nonionic surfactant and a cationic surfactant, the total amount with respect to the copolymer composition (E) (100% by mass) can be reduced to 5% by mass or less. Adverse effects on water repellency can be reduced.
The nonionic surface active agents, one or more is preferably selected from the group consisting of a surfactant s ¹ ~s ^6.
Examples of the cationic surfactant, the following surfactant s ⁷ is preferred.
Examples of the amphoteric surfactant, the following surfactants s ⁸ is preferred.
As the surfactant, a polymer surfactant may be used. The polymeric surface active agents, for example, the following surfactant s ^9.

Surfactant s ¹ :
Surfactant s ¹ is polyoxyalkylene monoalkyl ether, polyoxyalkylene monoalkenyl ether, polyoxyalkylene monoalkapolyenyl ether, or polyoxyalkylene monopolyfluoroalkyl ether.
The surfactant s ¹ is preferably polyoxyalkylene monoalkyl ether, polyoxyalkylene monoalkenyl ether, or polyoxyalkylene monopolyfluoroalkyl ether. Surfactant s ¹ may be used alone or in combination of two or more thereof.
The number of carbon atoms as the alkyl group, alkenyl group, alkapolyenyl group or polyfluoroalkyl group (hereinafter, the alkyl group, alkenyl group, alkapolyenyl group and polyfluoroalkyl group are collectively referred to as R ^s group) is 4 to 4 26 is preferred.
The R ^s group may be linear or branched. The branched R ^s group is preferably a secondary alkyl group, a secondary alkenyl group, or a secondary alkapolyenyl group. In the R ^s group, part or all of the hydrogen atoms may be substituted with fluorine atoms. Specific examples of R ^s group include octyl group, dodecyl group, tetradecyl group, hexadecyl group, stearyl group (octadecyl group), behenyl group (docosyl group), oleyl group (9-octadecenyl group), heptadecylfluorooctyl group, Examples include tridecylfluorohexyl group, 1H, 1H, 2H, 2H-tridecylfluorooctyl group, 1H, 1H, 2H, 2H-nonafluorohexyl group and the like.
The polyoxyalkylene (hereinafter referred to as POA) chain includes a chain in which two or more polyoxyethylene (hereinafter referred to as POE) chains and / or polyoxypropylene (hereinafter referred to as POP) chains are connected. preferable. The POA chain may be a chain composed of one kind of POA chain or a chain composed of two or more kinds of POA chains. When composed of two or more POA chains, each POA chain is preferably linked in a block form.

The surfactant ^{s 1,} compound ^{(s 11)} more preferred.
_{^{R 10 O [CH 2 CH (}} CH 3) O] s - (CH 2 CH 2 O) r H ··· (s 11).
However, R ¹⁰ is an alkyl group having 8 or more carbon atoms or an alkenyl group having 8 or more carbon atoms, r is an integer of 5 to 50, and s is an integer of 0 to 20. In R ¹⁰ , a part of hydrogen atoms may be substituted with fluorine atoms.
If r is 5 or more, it becomes soluble in water and is uniformly dissolved in an aqueous medium, so that the permeability of the water / oil repellent composition to articles is good. When r is 50 or less, hydrophilicity is suppressed and water repellency is improved.
If s is 20 or less, it becomes soluble in water and is uniformly dissolved in an aqueous medium, so that the permeability of the water / oil repellent composition to the article is good.
When r and s are 2 or more, the POE chain and the POP chain are linked in a block shape.

R ¹⁰ is preferably linear or branched. The number of carbon atoms of R ¹⁰ is from 8 to 22 is preferred.
r is preferably an integer of 10 to 30.
s is preferably an integer of 0 to 10.
Examples of the compound (s ¹¹ ) include the following compounds. However, the POE chain and the POP chain are linked in a block shape.
_{C 18 H 37 O [CH 2} CH (CH 3) O] 2 - (CH 2 CH 2 O) 30 H,
_{C 18 H 35 O- (CH 2} CH 2 O) 30 H,
_{C 16 H 33 O [CH 2} CH (CH 3) O] 5 - (CH 2 CH 2 O) 20 H,
_{C 12 H 25 O [CH 2} CH (CH 3) O] 2 - (CH 2 CH 2 O) 15 H,
_{(C 8 H 17) (C} 6 H 13) CHO- (CH 2 CH 2 O) 15 H,
_{C 10 H 21 O [CH 2} CH (CH 3) O] 2 - (CH 2 CH 2 O) 15 H,
_{C 6 F 13 CH 2 CH 2} O- (CH 2 CH 2 O) 15 H,
_{C 6 F 13 CH 2 CH 2} O [CH 2 CH (CH 3) O] 2 - (CH 2 CH 2 O) 15 H,
_{C 4 F 9 CH 2 CH 2} O [CH 2 CH (CH 3) O] 2 - (CH 2 CH 2 O) 15 H.

Surfactant s ² :
Surfactant s ^2, one or more carbons in the molecule - is a nonionic surfactant made of a compound having a carbon triple bond and one or more hydroxyl groups.
The surfactant s ² is preferably a nonionic surfactant made of a compound having one carbon-carbon triple bond and one or two hydroxyl groups in the molecule.
Surfactant s ² may have a POA chain in the molecule. Examples of the POA chain include a POE chain, a POP chain, a chain in which a POE chain and a POP chain are connected randomly, or a chain in which a POE chain and a POP chain are connected in a block form.

Surfactant ^{s 2,} compound ^{(s 21) ~ (s 24} ) is preferably.
HO—C (R ¹¹ ) (R ¹² ) —C≡C— (CR ¹³ ) (R ¹⁴ ) —OH (s ²¹ ),
_{^{HO- (A 1 O) u -}} (CR 11) (R 12) -C≡C-C (R 13) (R 14) - (OA 2) v -OH ··· (s 22),
HO—C (R ¹⁵ ) (R ¹⁶ ) —C≡C—H (s ²³ ),
_{^{HO- (A 3 O) w -C}} (R 15) (R 16) -C≡C-H ··· (s 24).

A ^{1 to} A ³ are each an alkylene group.
u and v are each an integer of 0 or more, and (u + v) is an integer of 1 or more.
w is an integer of 1 or more.
When u, v, and w are each 2 or more, A ^{1 to} A ³ may be the same or different.
The POA chain ((A ¹ O) _u , (OA ² ) _v , (A ³ O) _w ) is preferably a POE chain, a POP chain, or a chain containing a POE chain and a POP chain. The number of repeating units (u, v, w) of the POA chain is preferably 1-50.
R ^{11 to} R ¹⁶ are each a hydrogen atom or an alkyl group. As an alkyl group, a C1-C12 alkyl group is preferable and a C1-C4 alkyl group is more preferable. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and an isobutyl group.

As the compound (s ²² ), the compound (s ²⁵ ) is preferable.

However, x and y are integers of 0-100, respectively.
Compound (s ²⁵⁾ may be used alone or in combination of two or more thereof.
As the compound (s ²⁵ ), a compound in which x and y are 0, a compound in which the sum of x and y is 1 to 4 on average, or a compound in which the sum of x and y is on average 10 to 30 is preferable.

Surfactant s ³ :
Surfactant s ³ is a nonionic surfactant comprising a compound in which a POE chain is linked to a POA chain in which two or more oxyalkylenes having 3 or more carbon atoms are continuously linked, and both ends are hydroxyl groups. It is.
The POA chain is preferably polyoxytetramethylene (hereinafter referred to as POT) and / or POP chain.
Surfactant ^{s 3,} compound ^{(s 31)} or compound ^{(s 32)} is preferably.
_{HO (CH 2 CH 2 O)} g1 (C 3 H 6 O) t (CH 2 CH 2 O) g2 H ··· (s 31),
_{HO (CH 2 CH 2 O)} g1 (CH 2 CH 2 CH 2 CH 2 O) t (CH 2 CH 2 O) g2 H ··· (s 32).

g1 is an integer of 0-200.
t is an integer of 2 to 100.
g2 is an integer of 0-200.
When g1 is 0, g2 is an integer of 2 or more. When g2 is 0, g1 is an integer of 2 or more.
-C ₃ H ₆ O- _{may, -CH (CH 3) CH 2} - is a even _{better, -CH 2 CH (CH 3)} - is a even _{better, -CH (CH 3) CH 2} - and - A mixture of CH ₂ CH (CH ₃ ) — may be used.
The POA chain is block-shaped.

Examples of the surfactant s ³ include the following compounds.
_{HO- (CH 2 CH 2 O)} 15 - (C 3 H 6 O) 35 - (CH 2 CH 2 O) 15 H,
_{HO- (CH 2 CH 2 O)} 8 - (C 3 H 6 O) 35 - (CH 2 CH 2 O) 8 H,
HO— (CH ₂ CH ₂ O) ₄₅ — (C ₃ H ₆ O) ₁₇ — (CH ₂ CH ₂ O) ₄₅ H,
_{HO- (CH 2 CH 2 O)} 34 - (CH 2 CH 2 CH 2 CH 2 O) 28 - (CH 2 CH 2 O) 34 H.

Surfactant s ⁴ :
Surfactant s ⁴ is a nonionic surfactant having an amine oxide moiety in the molecule.
Surfactant ^{s 4,} compound ^{(s 41)} is preferably.
(R ¹⁷ ) (R ¹⁸ ) (R ¹⁹ ) N (→ O) (s ⁴¹ ).
R ^{17 to} R ¹⁹ are each a monovalent hydrocarbon group.
In the present invention, a surfactant having amine oxide (N → O) is treated as a nonionic surfactant.
Compound (s ⁴¹⁾ may be used alone or in combination of two or more thereof.

As the compound (s ⁴¹ ), the compound (s ⁴² ) is preferable from the viewpoint of dispersion stability of the copolymer.
(R ²⁰ ) (CH ₃ ) ₂ N (→ O) (s ⁴² ).
R ²⁰ is an alkyl group having 6 to 22 carbon atoms, an alkenyl group having 6 to 22 carbon atoms, a phenyl group to which an alkyl group having 6 to 22 carbon atoms is bonded, or an alkenyl group having 6 to 22 carbon atoms bonded thereto. Or a fluoroalkyl group having 6 to 13 carbon atoms. R ²⁰ is preferably an alkyl group having 8 to 22 carbon atoms, an alkenyl group having 8 to 22 carbon atoms, or a polyfluoroalkyl group having 4 to 9 carbon atoms.

Examples of the compound (s ⁴² ) include the following compounds.
[H (CH ₂ ) ₁₂ ] (CH ₃ ) ₂ N (→ O),
[H (CH ₂ ) ₁₄ ] (CH ₃ ) ₂ N (→ O),
[H (CH ₂ ) ₁₆ ] (CH ₃ ) ₂ N (→ O),
[H (CH ₂ ) ₁₈ ] (CH ₃ ) ₂ N (→ O),
[F (CF ₂ ) ₆ (CH ₂ ) ₂ ] (CH ₃ ) ₂ N (→ O),
[F (CF ₂ ) ₄ (CH ₂ ) ₂ ] (CH ₃ ) ₂ N (→ O).

Surfactant s ⁵ :
Surfactant s ⁵ is a nonionic surfactant made of a polyoxyethylene mono (substituted phenyl) ether condensate or polyoxyethylene mono (substituted phenyl) ether.
The substituted phenyl group is preferably a phenyl group substituted with a monovalent hydrocarbon group, and more preferably a phenyl group substituted with an alkyl group, an alkenyl group or a styryl group.
Surfactant s ⁵ includes polyoxyethylene mono (alkylphenyl) ether condensate, polyoxyethylene mono (alkenylphenyl) ether condensate, polyoxyethylene mono (alkylphenyl) ether, polyoxyethylene mono (alkenyl). Phenyl) ether or polyoxyethylene mono [(alkyl) (styryl) phenyl] ether is preferred.
As the polyoxyethylene mono (substituted phenyl) ether condensate or polyoxyethylene mono (substituted phenyl) ether, formaldehyde condensate of polyoxyethylene mono (nonylphenyl) ether, polyoxyethylene mono (nonylphenyl) ether, poly Oxyethylene mono (octylphenyl) ether, polyoxyethylenemono (oleylphenyl) ether, polyoxyethylenemono [(nonyl) (styryl) phenyl] ether, polyoxyethylenemono [(oleyl) (styryl) phenyl] ether, etc. Can be mentioned.

Surfactant s ⁶ :
Surfactant s ⁶ is a nonionic surfactant made of a fatty acid ester of a polyol.
The polyol represents glycerin, sorbitan, sorbit, polyglycerin, polyethylene glycol, polyoxyethylene glyceryl ether, polyoxyethylene sorbitan ether, polyoxyethylene sorbit ether.
Surfactant s ⁶ includes a 1: 1 (molar ratio) ester of stearic acid and polyethylene glycol, a 1: 4 (molar ratio) ester of ether of sorbite and polyethylene glycol and oleic acid, and polyoxyethylene glycol. 1: 1 (molar ratio) ester of ether of sorbitan and stearic acid, 1: 1 (molar ratio) ester of ether of polyethylene glycol and sorbitan and oleic acid, 1: 1 (molar ratio) of dodecanoic acid and sorbitan Ratio) ester, 1: 1 or 2: 1 (molar ratio) ester of oleic acid and decaglycerin, and 1: 1 or 2: 1 (molar ratio) ester of stearic acid and decaglycerin.

Surfactant s ⁷ :
Surfactant s ⁷ is a cationic surfactant in the form of a substituted ammonium salt.
The surfactant s ⁷ is preferably an ammonium salt in which one or more hydrogen atoms bonded to a nitrogen atom are substituted with an alkyl group, an alkenyl group, or a POA chain having a terminal hydroxyl group, and the compound (s ⁷¹ ) is more preferable. preferable.
[(R ²¹ ) ₄ N ⁺ ] · X ⁻ (s ⁷¹ ).
R ²¹ is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, a fluoroalkyl group having 1 to 9 carbon atoms, or a POA chain having a hydroxyl group at the end. The four R ²¹ may be the same or different, but the four R ²¹ are not hydrogen atoms at the same time.
R ²¹ is preferably a long-chain alkyl group having 6 to 22 carbon atoms, a long-chain alkenyl group having 6 to 22 carbon atoms, or a fluoroalkyl group having 1 to 9 carbon atoms.
When R ²¹ is an alkyl group other than a long-chain alkyl group, R ²¹ is preferably a methyl group or an ethyl group.
When R ²¹ is a POA chain having a hydroxyl group at the end, the POA chain is preferably a POE chain.
X ⁻ is a counter ion. X ⁻ is preferably a chlorine ion, an ethylsulfate ion, or an acetate ion.
Examples of the compound (s ⁷¹ ) include monostearyl trimethylammonium chloride, monostearyldimethylmonoethylammonium ethyl sulfate, mono (stearyl) monomethyldi (polyethylene glycol) ammonium chloride, monofluorohexyltrimethylammonium chloride, di (tallow alkyl) dimethylammonium. Examples include chloride and dimethyl monococonut amine acetate.

Surfactant s ⁸ :
Surfactant s ⁸ is alanine compounds, imidazolinium betaines, amide betaines or betaine acetate.
As the hydrophobic group, a long-chain alkyl group having 6 to 22 carbon atoms, a long-chain alkenyl group having 6 to 22 carbon atoms, or a fluoroalkyl group having 1 to 9 carbon atoms is preferable.
Surfactant s ^8, dodecyl betaine, stearyl betaine, dodecyl carboxymethyl hydroxyethyl imidazolinium betaine, dodecyl dimethylamino betaine, such as fatty acid amidopropyl dimethylamino acetic acid betaine.

Surfactant s ⁹ :
Surfactant s ⁹ may, of a hydrophilic monomer and a hydrocarbon based hydrophobic monomer and / or fluorine-based hydrophobic monomer, block copolymer, random copolymer, or a hydrophilic copolymer It is a polymer surfactant comprising a hydrophobic modified product.
Surfactant s ^9, block or random copolymer derived from polyethylene glycol (meth) acrylate with a long chain alkyl acrylate, a block or random copolymer derived from polyethylene glycol (meth) acrylate and fluoro (meth) acrylate, acetate Block or random copolymer of vinyl and long chain alkyl vinyl ether, block or random copolymer of vinyl acetate and long chain alkyl vinyl ester, polymer of styrene and maleic anhydride, condensation of polyvinyl alcohol and stearic acid Products, condensation products of polyvinyl alcohol and stearyl mercaptan, condensation products of polyallylamine and stearic acid, condensation products of polyethyleneimine and stearyl alcohol, methylcellulose, hydroxypropylmethylcellulose, hydride Examples include roxyethyl methylcellulose.
Commercially available surfactant s ⁹ includes Kuraray's MP polymer (product numbers: MP-103, MP-203), Elf Atchem's SMA resin, Shin-Etsu Chemical's Metros, Nippon Shokubai's Epomin RP, and AGC Seimi. Examples include Surflon (product numbers: S-381, S-393) manufactured by Chemical Corporation.
Surfactant s ^9, when the medium is often a mixing ratio in the case or organic solvent in the organic solvent, is preferably surfactant s ^91.
Surfactant s ⁹¹ : a polymer surfactant comprising a block copolymer or a random copolymer (modified polyfluoroalkyl thereof) of a lipophilic monomer and a fluorine monomer.
Surfactant s ⁹¹ includes a copolymer of alkyl acrylate and fluoro (meth) acrylate, a copolymer of alkyl vinyl ether and fluoroalkyl vinyl ether, and the like.
Examples of a commercial product of surfactant ^{s 91,} AGC Seimi Chemical Co., Surflon (product number: S-383, SC-100 series) and the like.

As the combination of surfactants, surfactant s ¹ and surfactant s ² and surfactant are used from the viewpoint of excellent water repellency and durability of the water / oil repellent composition and stability of the obtained emulsion. A combination with the agent s ⁷ , or a combination of the surfactant s ¹ , the surfactant s ³ and the surfactant s ⁷ , or a surfactant s ¹ , the surfactant s ² , the surfactant s ³ and the surfactant. A combination with the agent s ⁷ is preferable, and the above combination in which the surfactant s ⁷ is the compound (s ⁷¹ ) is more preferable.
1-10 mass parts is preferable with respect to copolymer composition (E) (100 mass parts), and, as for the total amount of surfactant, 1-7 mass parts is more preferable.

In the polymerization in the step (2), a film forming aid may be added.
Specific examples of the film forming aid include the following.
Methyl glycol, 2-ethoxyethanol, isopropyl glycol, butyl glycol, butyl cellosolve, allyl glycol, dimethyl glycol, isobutyl glycol, methyl diglycol, butyl diglycol, isobutyl diglycol, benzyl glycol, dimethyl diglycol, ethyl carbitol acetate, methyl Triglycol, methyltriglycol, butyltriglycol, dimethyltriglycol, methylpolyglycol, methylpropyleneglycol, methylpropylenetriglycol, propylpropyleneglycol, methylpropylenediglycol, ethyleneglycolmonomethylether, ethyleneglycolmonoethylether, ethyleneglycol Monoisopropyl ether, ethylene glycol buty Ether, ethylene glycol monoisobutyl ether, ethylene glycol monoallyl ether, ethylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, diethylene glycol monobenzyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monoethyl ether acetate, triethylene glycol Ethylene glycol monomethyl ether, triethylene glycol monobutyl ether, triethylene glycol dimethyl ether, polyethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monopropyl ether Dipropylene glycol, dipropylene glycol monomethyl ether, tripropylene glycol, tripropylene glycol monomethyl ether.
The amount of the film-forming aid added is preferably 10 to 200% by mass with respect to the solid content concentration of the emulsion of the copolymer composition (E). In addition, when the aqueous medium used for superposition | polymerization acts as a film-forming aid, it is preferable to make the addition amount at the time of counting the said aqueous medium as a film-forming aid into the said range.

  The polymerization conditions in the step (2) are preferably low-temperature conditions in order to improve the grafting efficiency, and polymerization in a short time is desirable in order to improve the stability of the emulsion. The temperature is preferably 40 to 80 ° C, more preferably 50 to 70 ° C. The polymerization time is preferably 4 to 48 hours, more preferably 6 to 24 hours.

The reaction liquid after polymerization in the step (2) includes the copolymer composition (E).
As described above, the copolymer composition (E) includes the polymer (D), that is, the polymer (A), a graft chain having a structural unit based on the monomer component (I), and the monomer component. A graft copolymer in which a graft chain having a structural unit based on (II) is bonded is included.
The copolymer composition (E) may contain, in addition to the polymer (D), the raw material polymer (A) and various polymers by-produced in the steps (1) and (2). Examples of the by-product polymer include a polymer (B) which is a graft copolymer in which a graft chain having a structural unit based on the monomer (b) is bonded to the polymer (A), and a monomer component. Examples thereof include a polymer (B ′) in which only the monomer constituting (I) is polymerized, and a polymer (D ′) in which only the monomer component (II) is polymerized.

  The reaction solution may be used as it is for the preparation of the water / oil repellent composition, and if necessary, it may be subjected to treatment such as recovery of the copolymer composition (E) from the reaction solution and dissolution in a solvent. Also good.

(Preparation of water / oil repellent composition)
A water / oil repellent composition can be prepared using the copolymer composition (E) obtained through the steps (1) and (2).
The preparation here may be any preparation as long as the copolymer composition (E) is used as a raw material of the water / oil repellent composition. The case where the copolymer composition (E) is directly used as the water repellent composition is also included in the preparation. Further, another copolymer composition or a water / oil repellent composition may be added to the copolymer composition (E), or various additives may be added.
The preparation preferably includes a step of diluting the copolymer composition (E) to a predetermined concentration with a medium such as water or an organic solvent.

  Additives include penetrants, antifoaming agents, water absorbing agents, antistatic agents, antistatic polymers, antifungal agents, texture modifiers, film-forming aids, water-soluble polymers (polyacrylamide, polyvinyl alcohol, etc.) , Thermosetting agent (melamine resin, urethane resin, triazine ring-containing compound, isocyanate compound, etc.), epoxy curing agent (isophthalic acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, dodecanedioic acid dihydrazide, 1,6-hexamethylenebis (N, N-dimethylsemicarbazide), 1,1,1 ′, 1′-tetramethyl-4,4 ′-(methylene-di-para-phenylene) disemicarbazide, spiroglycol, etc.), thermosetting catalyst, crosslinking catalyst , Synthetic resins, fiber stabilizers, inorganic fine particles and the like.

  As the water / oil repellent composition other than the copolymer composition (E), a water / oil repellent composition containing a copolymer capable of expressing water repellency and / or oil repellency, for example, a commercially available water repellent, commercially available Oil repellents, commercially available water / oil repellents, commercially available SR agents, and the like, which may contain a water repellent compound having no fluorine atom. Examples of the water repellent compound having no fluorine atom include paraffinic compounds, aliphatic amide compounds, alkylethyleneurea compounds, silicone compounds, and the like.

The solid content concentration of the copolymer composition (E) in the water / oil repellent composition is preferably 0.5 to 3% by mass with respect to the total amount of the water / oil repellent composition.
The water / oil repellent composition may contain 0.1 to 1% by mass of a crosslinking agent and 0.1 to 5% by mass of an auxiliary solvent or a penetrant with respect to the total amount of the water and oil repellent composition. preferable.

<Article processing method>
The method for treating an article of the present invention includes a step of treating the article with the water / oil repellent composition of the present invention.
Examples of articles to be treated include fibers (natural fibers, synthetic fibers, blended fibers, etc.), various fiber products, nonwoven fabrics, resins, paper, leather, metals, stones, concrete, gypsum, glass and the like.
As a treatment method, for example, a treatment liquid containing a water / oil repellent composition is applied to an article by a known coating method and then dried, or the article is immersed in a treatment liquid containing a water / oil repellent composition. Thereafter, a method of drying is mentioned.
By treating in this way, a film (water / oil repellent film) containing the copolymer composition (E) is formed on the surface of the article.

After the step of treating the article with the water / oil repellent composition of the present invention, antistatic processing, softening processing, antibacterial processing, deodorizing processing, waterproofing processing, and the like may be further performed.
Examples of waterproofing include processing for providing a waterproof film. Examples of the waterproof membrane include a porous membrane obtained from a urethane resin or an acrylic resin, a nonporous membrane obtained from a urethane resin or an acrylic resin, a polytetrafluoroethylene membrane, or a moisture-permeable waterproof membrane combining these.

<Effect>
According to the water / oil repellent composition of the present invention produced by the method for producing the water / oil repellent composition of the present invention, the surface of the article is excellent even if it does not contain an ^Rf group having 8 or more carbon atoms. Water, oil repellency and dynamic water repellency can be developed. In particular, it exhibits an excellent effect on dynamic water repellency.
The water / oil repellent composition that has been conventionally proposed as a water / oil repellent composition having no R ^f group having 8 or more carbon atoms (Patent Document 1) may not sufficiently exhibit water repellency, oil repellency, and dynamic water repellency. . This is because, when the water / oil repellent composition has an R ^f group having 8 or more carbon atoms, the water repellent film formed has a microcrystalline structure, whereas in the case of an R ^f group having 6 or less carbon atoms, This is probably because the water-repellent film does not have a microcrystalline structure.
The reason why the water / oil repellent composition of the present invention exhibits the above-mentioned effects can be considered as follows.
In the copolymer composition (E), the polymer (D), that is, the polymer (A), has a graft chain having a structural unit based on the monomer component (I) (hereinafter referred to as graft chain B). And a graft copolymer in which a graft chain having a structural unit based on the monomer component (II) (hereinafter referred to as graft chain D) is bonded.
The graft chain D has an R ^f group derived from the monomer (d). By distributing R ^f groups on the surface of the water-repellent film, the water- and oil-repellent film can exhibit water repellency, oil repellency and dynamic water repellency. However, the polymer (graft chain D) composed of the monomer (d) tends to have a glass transition point lower than room temperature. Conventionally, water repellency, oil repellency and dynamic water repellency, particularly dynamic water repellency, were not sufficiently developed because the glass transition point of the polymer composed of the monomer (d) is low, under room temperature conditions. structure is liable to change in the water-repellent film, when water is in contact, low affinity ^the R ^f group with water is moved to the article side from water-repellent film surface side, is ^the R ^f group in the water-repellent film surface This is thought to be less.
Since the graft chain B includes a structural unit based on the monomer (b) that does not contain a fluorine atom, the graft chain B has low compatibility with the graft chain D and expresses a dense phase separation structure in the water-repellent film. Further, since the monomer (b) has a glass transition point or melting point of the homopolymer of 40 to 120 ° C., the glass transition point or melting point of the graft chain B tends to be higher than the graft chain D and higher than room temperature. There is. Therefore, the structure of the graft chain B in the water-repellent film hardly changes in structure at room temperature. Since the structure is reinforced by such a phase that does not easily change, the structure of the phase of the graft chain D in the water-repellent film is also difficult to change. Therefore, when water contacts the surface of the water-repellent film, the R ^f group is suppressed from moving from the surface of the water-repellent film to the article side, and the surface of the water-repellent film is sufficient even after contact with water. An amount of R ^f group is present, and it is considered that water repellency, oil repellency and dynamic water repellency are sufficiently developed.

Accordingly, by treating the article with the water / oil repellent composition of the present invention, excellent water repellency, oil repellency and dynamic water repellency can be imparted to the surface of the article.
In the present invention, the content of perfluorooctanoic acid (PFOA), perfluorooctanesulfonic acid (PFOS), precursors thereof, and analogs (solid content concentration of 20), which has been pointed out to affect the environment. % Content) can be made below the detection limit as an analysis value of LC-MS / MS (liquid chromatograph-tandem mass spectrometer) by the method described in International Publication No. 2009/081822.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by the following description.
The measurement / evaluation methods and materials used in each example are shown below.

<Physical properties of copolymer>
The copolymer collected by the following separation method was measured for contact angle and dynamic contact angle.

<Separation method from copolymer emulsion>
6 g of the copolymer emulsion was dropped into 60 g of 2-propanol (hereinafter referred to as IPA) and stirred to precipitate a solid. After centrifugation at 3000 rpm for 5 minutes, the resulting solid was decanted. Again, 12 g of IPA was added and stirred well. After centrifuging at 3000 rpm for 5 minutes, the obtained solid was separated from the supernatant and vacuum dried at 40 ° C. overnight to obtain a copolymer.

<Method for separating copolymer solution>
The solvent was removed from 20 g of the copolymer solution with an evaporator, and the resulting residue was vacuum dried at 40 ° C. overnight to obtain a copolymer.

<Contact angle measurement>
(Static contact angle)
The separated copolymer was dissolved in a mixed solvent of a fluorinated solvent (manufactured by Asahi Glass Co., Ltd., AK-225) / THF = 1/1 (volume ratio) to obtain a 2% by mass solution, and spin-coated on a glass substrate. . The substrate was then heated in an oven at 150 ° C. for 10 minutes. After cooling the substrate, the contact angle between water and n-hexadecane was measured using DM300 manufactured by Kyowa Interface Chemical Co., Ltd.
(Dynamic contact angle)
The separated copolymer was dissolved in a mixed solvent of a fluorinated solvent (manufactured by Asahi Glass Co., Ltd., AK-225) / THF = 1/1 (volume ratio) to obtain a 2% by mass solution, and spin-coated on a glass substrate. . The substrate was then heated in an oven at 150 ° C. for 10 minutes. After cooling the substrate, the advancing contact angle and receding contact angle of water were measured using DCAT11 manufactured by Dataphysics.

≪Evaluation of test cloth≫
The test fabric prepared using the prepared water / oil repellent composition was evaluated for oil repellency, oil repellency and dynamic water repellency.

(Oil repellency)
The test cloth was evaluated for oil repellency according to the test method of AATCC-TM118-1966. The oil repellency was represented by the grade shown in Table 1. It shows that oil repellency is so high that a score is large. A grade marked with + (−) indicates that each property is slightly better (bad).

(Water repellency)
The test fabric was evaluated for water repellency according to the spray test of JIS L1092-1992. The water repellency was expressed in five grades 1 to 5 shown in Table 2. The larger the score, the higher the water repellency. Those with grade 3 or higher are considered to exhibit water repellency. A grade marked with + (−) indicates that each property is slightly better (bad) than the standard grade.

(Dynamic water repellency)
For the test cloth, according to the method described in JIS L1092 (C) method (Bundesmann test), the rainfall is 100 cc / min, the rain water temperature is 20 ° C., the rain time is 30 minutes, and the water repellency is evaluated. did. The water repellency was expressed in 5 grades of 1-5. The larger the score, the higher the dynamic water repellency. A grade of 3 or higher is considered to exhibit dynamic water repellency. A grade marked with + (−) indicates that each property is slightly better (bad).

<Materials used (abbreviations)>
(Monomer)
_{C6FMA: F (CF 2) 6} (CH 2) 2 OC (O) C (CH 3) = CH 2 ( glass transition point of the homopolymer = 35 ° C.).
αCl—C6FA: F (CF ₂ ) ₆ (CH ₂ ) ₂ OC (O) C (Cl) ═CH ₂ (glass transition point of homopolymer = 85 ° C.).

MMA: Methyl methacrylate (glass transition point of homopolymer = 105 ° C.).
IBMA: Isobutyl methacrylate (glass transition point of homopolymer = 65 ° C.).
VMA: Behenyl methacrylate (melting point of homopolymer = 55 ° C.).
HEMA: 2-hydroxyethyl methacrylate (glass transition point of homopolymer = 55 ° C.).
MOI-BP: Reaction product obtained by blocking 2-isocyanatoethyl methacrylate with 3-5 dimethylpyrazole (glass transition point of homopolymer = 35 ° C.).
AN: Acrylonitrile (glass transition point of homopolymer = 104 ° C.).
VdCl: Vinylidene chloride (glass transition point of homopolymer = −17 ° C.).

Among the above monomers, C6FMA and αCl-C6FA are monomer (d).
MMA, IBMA, VMA, HEMA and AN are monomers (b).
HEMA and MOI-BP are monomers having a crosslinkable functional group.
VdCl is a monomer that does not correspond to any of the monomer (d), the monomer (b), and the monomer having a crosslinkable functional group.

(Polymer (A))
Rubber:
LIR-30: Kuraray polyisoprene, Mw = 28000.
LIR-15: Kuraray polyisoprene, Mw = 19500.
UC-102: Kuraray polyisoprene, Mw = 17000, with an average of 2 to 3 molecules of methacryloyl group added per molecule.
SBR-307: Kuraray polybutadiene, Mw = 8000.

(Surfactant s ¹ )
PEO-20: 10% by mass aqueous solution of polyoxyethylene oleyl ether (manufactured by Kao Corporation, Emulgen E430, approximately 26 mol of ethylene oxide adduct).
(Surfactant s ⁷ )
TMAC: 10% by mass aqueous solution of trimethylammonium chloride (manufactured by Lion Corporation, ARCARD 18-63).
(Surfactant s ³ )
P-204: 10 mass% aqueous solution of ethylene oxide propylene oxide polymer (Nippon Yushi Co., Ltd., Pronon 204, the ratio of ethylene oxide is 40 mass%).

(Molecular weight regulator)
nDOSH: n-dodecyl mercaptan.

(Polymerization initiator)
VA-061A: 10% by mass aqueous solution of acetate of 2,2′-azobis [2- (2-imidazolin-2-yl) propane] (manufactured by Wako Pure Chemical Industries, Ltd., VA-061).
BPO: Benzoyl peroxide.
PBPV: 50% by mass xylene solution of t-butyl peroxypivalate.

(Medium)
DPGMME: Dipropylene glycol monomethyl ether.
Water: Ion exchange water.

<Example 1 (emulsion polymerization)>
(First stage polymerization)
In a glass beaker, 17.3 g of UC-102, 41.5 g of IBMA, 10.38 g of HEMA, 2.9 g of nDOSH, 20.8 g of PEO-20, 3.5 g of TMAC, 3 of P-204 .5 g, 20.8 g of DPGMME, and 113.5 g of water were added and heated at 60 ° C. for 30 minutes, and then mixed using a homomixer (manufactured by Nippon Seiki Seisakusho, Biomixer) to obtain a mixed solution. .
The obtained liquid mixture was processed at 40 MPa using a high-pressure emulsifier (manufactured by APV Lanier Co., Ltd., Minilab) while maintaining the temperature at 50 ° C. to obtain an emulsion. The obtained emulsion was put into a glass reactor and cooled to 30 ° C. or lower. After adding 1.4 g of VA-061A and substituting the gas phase with nitrogen, a polymerization reaction was carried out at 65 ° C. for 15 hours with stirring to obtain an emulsion of the copolymer composition (C-1).

(Second stage polymerization)
To a glass reactor, 50.8 g of the obtained copolymer composition (C-1) emulsion, 42.6 g of water, and 6.0 g of C6FMA were added, followed by heating and stirring at 50 ° C. for 30 minutes. , 0.8 g of PBPV was added. 8 hours and 16 hours after the addition of PBPV, 6.0 g of C6FMA and 0.8 g of PBPV were added, respectively. Stirring was continued for 8 hours after addition after 16 hours to obtain an emulsion of the copolymer composition (E-1).

Of the raw materials used in the first-stage polymerization and the second-stage polymerization, Table 3 shows the parts by mass of each raw material when the total amount of the rubber and each monomer used in the first-stage polymerization is 100 parts by mass. The total amount of rubber and each monomer used in the first stage polymerization can be regarded as the amount of the copolymer composition (C-1).
The copolymer composition (E-1) was recovered from the emulsion of the copolymer composition (E-1), and the static contact angle and the dynamic contact angle were measured. Table 3 shows the measurement results.

(Preparation of water / oil repellent composition from emulsion of copolymer composition (E-1) and preparation of test cloth)
After diluting the emulsion of the obtained copolymer composition (E-1) with distilled water and adjusting the solid content concentration to 1.0 mass%, a trimethylol melamine resin (manufactured by DIC Corporation, which is a thermosetting agent). Beckamine M-3) and an organic amine salt catalyst (catalyst ACX, manufactured by DIC) as a thermosetting catalyst were added so that each concentration was 0.3% by mass, and a block that was a combination aid Deisocyanate (manufactured by Meisei Chemical Industry Co., Ltd., Makernate CX) was added so that the concentration was 0.3% by mass to obtain a water / oil repellent composition.
A dyed nylon cloth was dipped in the obtained water / oil repellent composition and squeezed so that the wet pickup was 42% by mass. This was dried at 110 ° C. for 90 seconds and then dried at 170 ° C. for 60 seconds to obtain a test cloth.
The obtained test cloth was evaluated for water repellency (water repellency after air drying), oil repellency, and dynamic water repellency. Each evaluation result is shown in Table 3.

<Examples 2 to 5>
Copolymer compositions (C-2) to (C-5) by performing the first stage polymerization in the same manner as in Example 1 except that the amount (parts by mass) of each raw material was changed to the ratio shown in Table 3. And then the second stage polymerization was carried out to obtain emulsions of copolymer compositions (E-2) to (E-5).
The copolymer was recovered from the obtained copolymer emulsion, and the static contact angle and the dynamic contact angle were measured. Table 3 shows the measurement results.
Further, from the obtained copolymer emulsion, a water / oil repellent composition was prepared in the same manner as in Example 1, a test cloth was prepared, and water repellency (water repellency after air drying), oil repellency, dynamic water repellency was prepared. Evaluated. Each evaluation result is shown in Table 3.

<Comparative Example 1>
In a glass beaker, 230.9 g of C6FMA, 2.9 g of HEMA, 2.9 g of nDOSH, 7.2 g of PEO-20, 1.4 g of STMC, 1.4 g of TMAC, 86.6 g of DPG, water Of 447.4 g was added and heated at 55 ° C. for 30 minutes, and then mixed using a homomixer (manufactured by Nippon Seiki Seisakusho, Biomixer) to obtain a mixed solution.
The obtained liquid mixture was processed at 40 MPa using a high-pressure emulsifier (manufactured by APV Lanier Co., Ltd., Minilab) while maintaining the temperature at 50 ° C. to obtain an emulsion. The obtained emulsion was put into a glass reactor and cooled to 30 ° C. or lower. After adding 54.8 g of VdCl and 1.4 g of VA-061A and replacing the gas phase with nitrogen, polymerization reaction was carried out at 65 ° C. for 15 hours with stirring to obtain an emulsion of copolymer (CE-1). It was.
The copolymer (CE-1) was recovered from the obtained emulsion of the copolymer (CE-1), and the static contact angle and the dynamic contact angle were measured. Table 3 shows the measurement results.
In addition, a water / oil repellent composition was prepared from the obtained copolymer (CE-1) emulsion in the same manner as in Example 1, a test cloth was prepared, and water repellency (water repellency after air drying), water repellency was obtained. Oiliness and dynamic water repellency were evaluated. Each evaluation result is shown in Table 3.

<Example 6 (solution polymerization)>
(First stage polymerization)
Into a glass flask equipped with a condenser tube was charged 5.0 g of LIR-30, 9.3 g of VMA, 3.2 g of AN, 2.0 g of HEMA, 62.1 g of toluene, and 0.33 g of BPO. After replacing the phase with nitrogen, the polymerization reaction was carried out at 50 ° C. for 48 hours with stirring to obtain a solution of a copolymer composition (C-6).

(Second stage polymerization)
After adding 12.6 g of the solution obtained by the first stage polymerization, 21.1 g of toluene, 9.7 g of C6FMA, and 0.2 g of BPO to a glass flask equipped with a condenser tube, and replacing the gas phase with nitrogen While stirring, the polymerization reaction was carried out at 50 ° C. for 48 hours to obtain a copolymer composition (E-6) solution.

Of the raw materials used in the first-stage polymerization and second-stage polymerization, Table 4 shows the parts by mass of each raw material when the total amount of the rubber and each monomer used in the first-stage polymerization is 100 parts by mass. The total amount of rubber and each monomer used in the first stage polymerization can be regarded as the amount of the copolymer composition (C-6).
The copolymer composition (E-6) was recovered from the copolymer composition (E-6) solution obtained by the second stage polymerization, and the static contact angle and the dynamic contact angle were measured. Table 4 shows the measurement results.

(Preparation of water / oil repellent composition from copolymer composition (E-6) solution and preparation of test cloth)
The copolymer recovered from the copolymer solution is dissolved in a mixed solvent of fluorinated solvent (AK-225, manufactured by Asahi Glass Co., Ltd.) / THF = 1/1 (volume ratio) to obtain a 1% by mass solution, and a crosslinking agent. Isocyanate (MF-B60B, manufactured by Asahi Kasei Chemicals Co., Ltd.) was added so that the concentration was 0.3% by mass to obtain a water / oil repellent composition.
A dyed nylon cloth was dipped in the water / oil repellent composition and squeezed so that the wet pickup was 42% by mass. After drying this at 25 degreeC overnight, what was dried at 170 degreeC for 60 second was used as the test cloth.
The obtained test cloth was evaluated for water repellency (water repellency after air drying), oil repellency, and dynamic water repellency. Each evaluation result is shown in Table 4.

<Examples 7 to 9>
Copolymer compositions (C-7) to (C-9) are obtained by conducting the first stage polymerization in the same manner as in Example 6 except that the amount (parts by mass) of each raw material is changed to the ratio shown in Table 5. A solution was obtained, and then second-stage polymerization was performed to obtain copolymer composition (E-7) to (E-9) solutions.
The copolymer compositions (E-7) to (E-9) are recovered from the obtained copolymer composition (E-7) to (E-9) solution, and the static contact angle and dynamic contact are recovered. The corner was measured. Table 4 shows the measurement results.
Also, a water / oil repellent composition was prepared from the recovered copolymer in the same manner as in Example 6, a test cloth was prepared, and water repellency (water repellency after air drying), oil repellency, and dynamic water repellency were evaluated. did. Each evaluation result is shown in Table 4.

<Comparative Example 2>
Into a glass flask equipped with a condenser tube was charged 5.0 g of LIR-30, 10.0 g of MMA, 30.0 g of C6FMA, 5.0 g of HEMA, 57.0 g of toluene, and 0.33 g of BPO. After the phase was replaced with nitrogen, the polymerization reaction was carried out at 50 ° C. for 48 hours with stirring to obtain a copolymer (CE-2) solution.
The copolymer (CE-2) was recovered from the obtained copolymer (CE-2) solution, and the static contact angle and the dynamic contact angle were measured. Table 4 shows the measurement results.
Further, a water / oil repellent composition was prepared from the recovered copolymer (CE-2) in the same manner as in Example 6, a test cloth was prepared, and water repellency (water repellency after air drying), oil repellency, The water repellency was evaluated. Each evaluation result is shown in Table 4.

  The nylon cloth before the treatment with the water / oil repellent composition used for evaluation of the test cloth had an oil repellency score of 0, a water repellency score of 1, and a dynamic water repellency score of 1.

  As shown in the results of Tables 3 to 4, it was confirmed that oil repellency, water repellency and dynamic water repellency were imparted by treating with the water / oil repellent composition of Examples 1-9. The dynamic water repellency of the test cloth treated with the water / oil repellent composition of Examples 1-9 is superior to the dynamic water repellency of the test cloth treated with the water / oil repellent composition of Comparative Examples 1-2. It was.

Claims (13)

A method for producing a water and oil repellent composition comprising producing a water and oil repellent composition comprising a copolymer composition (E) through the following steps (1) and (2).
Step (1): Monomer component containing the following monomer (b) in the presence of the polymer (A) containing an unsaturated double bond in one or both of the main chain and the side chain ( A step of polymerizing I) to obtain a copolymer composition (C).
Step (2): In the presence of the copolymer composition (C), a monomer component (II) comprising the following monomer (d) is polymerized to obtain a copolymer composition (E). Process.
Monomer (b): A monomer which does not contain a fluorine atom and whose homopolymer has a glass transition point or melting point of 40 to 120 ° C.
Monomer (d): A monomer having a polyfluoroalkyl group having 1 to 6 carbon atoms.   The method for producing a water / oil repellent composition according to claim 1, wherein the polymer (A) has a structural unit based on the monomer (a) having a conjugated diene structure.   The monomer (b) is at least one selected from the group consisting of (meth) acrylic acid esters, (meth) acrylamides, (meth) acrylonitriles, vinyl chloride, and monomers having a crosslinkable functional group. The method for producing a water / oil repellent composition according to claim 1 or 2, which is a seed. The method for producing a water / oil repellent composition according to any one of claims 1 to 3, wherein the monomer (d) is a compound represented by the following general formula (d1).
Z-Y-X (d1)
However, Z is a C1-C6 polyfluoroalkyl group (however, among the carbon atoms in the ^Rf group, at least one fluorine atom is bonded to the carbon atom bonded to Y), or A perfluorooxaalkyl group having 2 to 50 carbon atoms (however, when the carbon number is 8 or more, the terminal group is a perfluoroalkyl group having 6 or less carbon atoms);
Y is a divalent organic group having no fluorine atom, or a single bond,
X is a polymerizable unsaturated _{^{group, -CR 1 = CH 2, -COOCR}} 1 = CH 2, -OCOCR 1 = CH 2, - (R 2) N (O =) CR 1 = CH 2, - SCOCR ¹ ═CH ₂ or —OCH═CH ₂ (wherein R ¹ is a hydrogen atom, a methyl group, a halogen atom or a trifluoromethyl group, and R ² is a hydrogen atom or an alkyl group). In the general formula (d1),
Z is a perfluoroalkyl group having 1 to 6 carbon atoms or a perfluorooxaalkyl group having 2 to 20 carbon atoms (however, when the carbon number is 8 or more, the terminal group is a perfluoroalkyl group having 6 or less carbon atoms). Yes,
Y is ^{_{- (CH 2) m -,}} - Q 1 -Ar-Q 2 -, or ^{-Q 1 -Ar-Q 2 -Ar-} Q 3 - ( provided that, m is 1 to 4, Ar is an arylene group Q ^{1 to} Q ³ are each independently a divalent organic group having no fluorine atom, or a single bond.
The method for producing a water / oil repellent composition according to claim 4, wherein X is —OCOCR ¹ ═CH ₂ (wherein R ¹ is a hydrogen atom, a methyl group, a halogen atom or a trifluoromethyl group).   The mass ratio ((A) / (I)) between the polymer (A) and the monomer component (I) in the step (1) is 5/95 to 95/5. The manufacturing method of the water / oil repellent composition as described in any one of -5.   In the step (2), the mass ratio ((C) / (II)) between the copolymer composition (C) and the monomer component (II) is 5/1 to 1/5. The manufacturing method of the water / oil repellent composition as described in any one of Claims 1-6.   The water / oil repellent composition according to any one of claims 1 to 7, wherein the step (1) and the step (2) are each carried out in the presence of an aqueous medium, a surfactant and a radical polymerization initiator. Manufacturing method. The polymer (A) has a structural unit based on the monomer (a) having a conjugated diene structure,
The method for producing a water / oil repellent composition according to any one of claims 1 to 8, wherein the monomer (a) is at least one selected from the group consisting of isoprene, butadiene, and chloroprene.   The method for producing a water / oil repellent composition according to any one of claims 1 to 9, wherein the polymer (A) has a mass average molecular weight of 1,000 to 50,000.   The monomer component (I) includes a monomer having a crosslinkable functional group, and the crosslinkable functional group is a hydroxy group, a carboxy group, an isocyanate group, a glycidyl group, a methylol group, or a hydrolyzable silanol group. The method for producing a water / oil repellent composition according to any one of claims 1 to 10, which is at least one selected from the group consisting of:   The water / oil repellent composition obtained by the manufacturing method of the water / oil repellent composition according to any one of claims 1 to 11.   A method for treating an article, comprising the step of treating the article with the water / oil repellent composition according to claim 12.