JP2016089087A - Water- and oil-repellent composition, method for producing the same and article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water- and oil-repellent composition that can produce an article good in all of water repellency, oil repellency and durability against heavy rain, to provide a method for producing the water- and oil-repellent composition and to provide an article good in all of water repellency, oil repellency and durability against heavy rain.SOLUTION: The water- and oil-repellent composition includes a copolymer having a constitutional unit based on a monomer (a), a constitutional unit based on a monomer (b) and a constitutional unit based on a monomer (c). A monomer (a): a compound represented by (Z-Y)X in which Z is a 1-6C perfluoroalkyl group or the like; Y is a divalent organic group or the like; n is 1 or 2; and X is a polymerizable unsaturated group; a monomer (b): a (meth)acrylate having no polyfluoroalkyl group and having a 12C or more alkyl group; and a monomer (c): a polyfluorovinyl ether or a polyfluoroallyl ether.SELECTED DRAWING: None

Description

  The present invention relates to a water / oil repellent composition, a method for producing the same, and an article treated with the water / oil repellent composition.

As a method for imparting water and oil repellency to the surface of an article (such as a textile product), it has a structural unit based on a monomer having a polyfluoroalkyl group (hereinafter, the polyfluoroalkyl group is referred to as ^Rf group) There is known a method of treating an article using a water / oil repellent composition in which a copolymer is dispersed in a medium. Articles treated with the water / oil repellent composition are required to have no significant decrease in water / oil repellency (heavy rain durability) even when exposed to heavy rain conditions.

As the water / oil repellent composition excellent in heavy rain durability, for example, the following water / oil repellent composition has been proposed.
A copolymer having a structural unit based on the following monomer (a) and a structural unit based on the following monomer (b), wherein the proportion of the structural unit based on the monomer (b) is monomer (a ) And 30 to 80 mol% of the total of the structural units based on the monomer (b) and the structural units based on the monomer (b) (100 mol%) (Patent Document 1).
Monomer (a): perfluoroalkyl group having a carbon number of 1-6 (. Hereinafter referred perfluoroalkyl group as R ^F group) having a (meth) acrylate.
Monomer (b): (meth) acrylate having an alkyl group having 20 to 30 carbon atoms.

International Publication No. 2008/136436

  However, articles treated with the water / oil repellent composition may have insufficient oil repellency.

  The present invention provides a water / oil repellent composition capable of obtaining an article having good water repellency, oil repellency and heavy rain durability, a method for producing the same, and water repellency, oil repellency and heavy rain durability. Provides an article that is good.

The present invention has the following aspects.
[1] Water and water repellency comprising a copolymer having a structural unit based on the following monomer (a), a structural unit based on the following monomer (b), and a structural unit based on the following monomer (c) Oil composition.
Monomer (a): A compound represented by the following formula (1).
(ZY) _n X (1).
However, Z is a C1-C6 perfluoroalkyl group, a group represented by the following formula (2-1) or a group represented by the following formula (2-2), and Y represents a fluorine atom. A divalent organic group or a single bond that is not present, n is 1 or 2, and X is a group represented by the following formulas (3-1) to (3-5) when n is 1 And when n is 2, it is one of the groups represented by the following formulas (4-1) to (4-4).
C _i F _{2i + 1} O (CFX ¹ CF ₂ O) _j CFX ² − (2-1),
_{C i F 2i + 1 (CH} 2 CF 2) p (CF 2 CF 2) q - ··· (2-2).
Where, i is an integer from 1 to 6, j is an integer of 0, ^{X 1} and ^{X 2} are each fluorine atom or a trifluoromethyl group, p is an integer of from 1 to 4 Yes, q is an integer from 1 to 3.
-CR = CH ₂ (3-1),
_{-C (O) OCR = CH 2} ··· (3-2),
_{-OC (O) CR = CH 2} ··· (3-3),
_{-OCH 2 -φ-CR = CH 2} ··· (3-4),
_{-OCH = CH 2 ··· (3-5)} .
However, R is a hydrogen atom, a methyl group, or a halogen atom, and φ is a phenylene group.
_{-CH [- (CH 2) m} CR = CH 2] - ··· (4-1),
_{-CH [- (CH 2) m} C (O) OCR = CH 2] - ··· (4-2),
_{-CH [- (CH 2) m} OC (O) CR = CH 2] - ··· (4-3),
-OC (O) CH = CHC (O) O- (4-4).
However, R is a hydrogen atom, a methyl group, or a halogen atom, and m is an integer of 0-4.
Monomer (b): (meth) acrylate having no polyfluoroalkyl group and having an alkyl group having 12 or more carbon atoms.
Monomer (c): One or both of polyfluorovinyl ether and polyfluoroallyl ether.
[2] The water / oil repellent composition according to [1], wherein the copolymer further includes a structural unit based on the following monomer (d).
Monomer (d): Halogenated olefin.
[3] The water / oil repellent composition according to [1] or [2], wherein the copolymer further has a structural unit based on the following monomer (e).
Monomer (e): A monomer having no fluorine atom and having a functional group capable of crosslinking.
[4] The proportion of the structural unit based on the monomer (a) in the copolymer is 5 to 40 of the structural units (100% by mass) based on all monomers constituting the copolymer. The proportion of the structural unit based on the monomer (b) in the copolymer is 40% of the structural units based on all the monomers constituting the copolymer (100 mass%). -94.9% by mass, and the proportion of the structural unit based on the monomer (c) in the copolymer is a structural unit based on all the monomers constituting the copolymer (100% by mass). Among them, the water / oil repellent composition according to any one of [1] to [3], which is 0.1 to 20% by mass.
[5] The water / oil repellent composition according to any one of [1] to [4], wherein the monomer (c) is the compound (5) or the compound (6).
CX ³ X ⁴ = CF (CF ₂ ) _a [OCFX ⁵ CFX ⁶ ] _b (O) _c (CFX ⁷ ) _d CH ₂ OH (5),
^{_{CX 3 X 4 = CF (CF}} 2) a [OCFX 5 CFX 6] b (O) c (CFX 7) d C (O) OR 3 ··· (6).
However, X ³ to X ⁷ are each independently a hydrogen atom, a fluorine atom or a trifluoromethyl group, R ³ is a hydrogen atom, an alkyl group or a substituted alkyl radical, a is 0 or 1 , B is an integer of 0 or more, c is 0 or 1 (however, when b is 0, c is 1), and d is an integer of 0 or more.
[6] Polymerization of monomer components including the following monomer (a), the following monomer (b), and the following monomer (c) in the medium in the presence of a surfactant and a polymerization initiator. And a method for producing a water / oil repellent composition, which is a copolymer.
Monomer (a): A compound represented by the following formula (1).
(ZY) _n X (1).
However, Z is a C1-C6 perfluoroalkyl group, a group represented by the following formula (2-1) or a group represented by the following formula (2-2), and Y represents a fluorine atom. A divalent organic group or a single bond that is not present, n is 1 or 2, and X is a group represented by the following formulas (3-1) to (3-5) when n is 1 And when n is 2, it is one of the groups represented by the following formulas (4-1) to (4-4).
C _i F _{2i + 1} O (CFX ¹ CF ₂ O) _j CFX ² − (2-1),
_{C i F 2i + 1 (CH} 2 CF 2) p (CF 2 CF 2) q - ··· (2-2).
Where, i is an integer from 1 to 6, j is an integer of 0, ^{X 1} and ^{X 2} are each fluorine atom or a trifluoromethyl group, p is an integer of from 1 to 4 Yes, q is an integer from 1 to 3.
-CR = CH ₂ (3-1),
_{-C (O) OCR = CH 2} ··· (3-2),
_{-OC (O) CR = CH 2} ··· (3-3),
_{-OCH 2 -φ-CR = CH 2} ··· (3-4),
_{-OCH = CH 2 ··· (3-5)} .
However, R is a hydrogen atom, a methyl group, or a halogen atom, and φ is a phenylene group.
_{-CH [- (CH 2) m} CR = CH 2] - ··· (4-1),
_{-CH [- (CH 2) m} C (O) OCR = CH 2] - ··· (4-2),
_{-CH [- (CH 2) m} OC (O) CR = CH 2] - ··· (4-3),
-OC (O) CH = CHC (O) O- (4-4).
However, R is a hydrogen atom, a methyl group, or a halogen atom, and m is an integer of 0-4.
Monomer (b): (meth) acrylate having no polyfluoroalkyl group and having an alkyl group having 12 or more carbon atoms.
Monomer (c): One or both of polyfluorovinyl ether and polyfluoroallyl ether.
[7] The method for producing a water / oil repellent composition according to [6], wherein the monomer component further comprises the following monomer (d).
Monomer (d): Halogenated olefin.
[8] The method for producing a water / oil repellent composition according to [6] or [7], wherein the monomer component further comprises the following monomer (e):
Monomer (e): A monomer having no fluorine atom and having a functional group capable of crosslinking.
[9] The ratio of the monomer (a) in the monomer component is 5 to 40% by mass in the monomer component (100% by mass), and the single amount in the monomer component The ratio of the body (b) is 40 to 94.9% by mass in the monomer component (100% by mass), and the ratio of the monomer (c) in the monomer component is The method for producing a water / oil repellent composition according to any one of [6] to [8], which is 0.1 to 20% by mass of the monomer component (100% by mass).
[10] The method for producing a water / oil repellent composition according to any one of [6] to [9], wherein the monomer (c) is the compound (5) or the compound (6).
CX ³ X ⁴ = CF (CF ₂ ) _a [OCFX ⁵ CFX ⁶ ] _b (O) _c (CFX ⁷ ) _d CH ₂ OH (5),
^{_{CX 3 X 4 = CF (CF}} 2) a [OCFX 5 CFX 6] b (O) c (CFX 7) d C (O) OR 3 ··· (6).
However, X ³ to X ⁷ are each independently a hydrogen atom, a fluorine atom or a trifluoromethyl group, R ³ is a hydrogen atom, an alkyl group or a substituted alkyl group, a is 0 or 1 , B is an integer of 0 or more, c is 0 or 1 (however, when b is 0, c is 1), and d is an integer of 0 or more.
[11] An article treated with the water / oil repellent composition of any one of [1] to [5].

According to the water / oil repellent composition of the present invention, an article having good water repellency, oil repellency and heavy rain durability can be obtained.
According to the method for producing a water / oil repellent composition of the present invention, a water / oil repellent composition capable of obtaining an article having good water repellency, oil repellency and heavy rain durability can be produced.
The article of the present invention has good water repellency, oil repellency and heavy rain durability.

In the present specification, a compound represented by the formula (1) is referred to as a compound (1). The same applies to compounds represented by other formulas.
In this specification, a group represented by the formula (2-1) is referred to as a group (2-1). Groups represented by other formulas are also described in the same manner.
The following definitions of terms apply throughout this specification and the claims.
“(Meth) acrylate” is a general term for acrylate and methacrylate.
“Vinyl ether” means a compound having a vinyl group and an etheric oxygen atom bonded to the vinyl group, and “polyfluorovinyl ether” means a compound in which some or all of the hydrogen atoms of vinyl ether are substituted with fluorine atoms. means.
“Allyl ether” means a compound having an allyl group and an etheric oxygen atom bonded to the allyl group, and “polyfluoroallyl ether” is a compound in which some or all of the hydrogen atoms of allyl ether are substituted with fluorine atoms. Means a compound.
“Monomer” means a compound having a polymerizable unsaturated group.
“R ^f group” means a group in which part or all of the hydrogen atoms of an alkyl group are substituted with fluorine atoms.
“R ^F group” means a group in which all of the hydrogen atoms of an alkyl group are substituted with fluorine atoms.
The “number average molecular weight” and “mass average molecular weight” are values obtained in terms of polystyrene by gel permeation chromatography (GPC) method.

<Water / oil repellent composition>
The water / oil repellent composition of the present invention contains a specific copolymer as an essential component, and optionally contains a medium, a surfactant, and an additive.

(Copolymer)
The copolymer has a structural unit based on the monomer (a), a structural unit based on the monomer (b), and a structural unit based on the monomer (c).
The copolymer preferably further has a structural unit based on the monomer (d) and / or a structural unit based on the monomer (e).
The copolymer may have a structural unit based on the monomer (f) as necessary.

Monomer (a):
Monomer (a) is compound (1).
(ZY) _n X (1).

Z is an R ^F group having 1 to 6 carbon atoms, a group (2-1) or a group (2-2).
C _i F _{2i + 1} O (CFX ¹ CF ₂ O) _j CFX ² − (2-1),
_{C i F 2i + 1 (CH} 2 CF 2) p (CF 2 CF 2) q - ··· (2-2).
Where, i is an integer from 1 to 6, j is an integer of 0, ^{X 1} and ^{X 2} are each fluorine atom or a trifluoromethyl group, p is an integer of from 1 to 4 Yes, q is an integer from 1 to 3.
The number of carbon atoms of the R ^F group is 4-6 are preferable, 6 being most preferred. The ^RF group may be linear or branched, and is preferably linear.

Examples of Z include the following groups.
F (CF ₂ ) ₄ −,
F (CF ₂ ) _5- ,
F (CF ₂ ) _6- ,
(CF ₃ ) ₂ CF (CF ₂ ) _2- ,
_{C k F 2k + 1 O [} CF (CF 3) CF 2 O] h -CF (CF 3) -,
_{C k F 2k + 1 (CH} 2 CF 2) (CF 2 CF 2) r or the like.
However, k is an integer of 1-6, h is an integer of 0-10, r is 1 or 2.

Y is a divalent organic group having no fluorine atom or a single bond.
As the divalent organic group, an alkylene group is preferable. The alkylene group may be linear or branched. The alkylene group is —O—, —NH—, —CO—, —SO ₂ —, —S—, —CD ¹ ═CD ² — (wherein D ¹ and D ² are a hydrogen atom or a methyl group, respectively. Etc.).

Examples of Y include the following groups.
-CH ₂ -,
—CH ₂ CH ₂ —
- _{(CH 2)} 3 -,
_{-CH 2 CH 2 CH (CH 3} ) -,
-CH = _CH-CH 2 -,
_-S-CH 2 CH 2 -,
-SO ₂ -CH ₂ CH ₂ -,
_{-CH 2 CH 2 CH 2 -S-} CH 2 CH 2 -,
_{-CH 2 CH 2 CH 2 -SO 2} -CH 2 CH 2 - and the like.

n is 1 or 2.
X is any one of groups (3-1) to (3-5) when n is 1, and when n is 2, X is any of groups (4-1) to (4-4). Either.

-CR = CH ₂ (3-1),
_{-C (O) OCR = CH 2} ··· (3-2),
_{-OC (O) CR = CH 2} ··· (3-3),
_{-OCH 2 -φ-CR = CH 2} ··· (3-4),
_{-OCH = CH 2 ··· (3-5)} .
However, R is a hydrogen atom, a methyl group, or a halogen atom, and φ is a phenylene group. R is preferably a hydrogen atom, a methyl group or a chlorine atom.

_{-CH [- (CH 2) m} CR = CH 2] - ··· (4-1),
_{-CH [- (CH 2) m} C (O) OCR = CH 2] - ··· (4-2),
_{-CH [- (CH 2) m} OC (O) CR = CH 2] - ··· (4-3),
-OC (O) CH = CHC (O) O- (4-4).
However, R is a hydrogen atom, a methyl group, or a halogen atom, and m is an integer of 0-4. R is preferably a hydrogen atom, a methyl group or a chlorine atom.

Examples of the compound (1) include polymerizability with other monomers, copolymer film flexibility, adhesion of the copolymer to the article, dispersibility or solubility in the medium, and ease of emulsion polymerization. from the point, acrylate having an R ^F group having a carbon number of 1-6, methacrylates, acrylates are preferred, which are substituted with alpha-position a halogen atom, acrylate having an R ^F group having a carbon number of 4-6, methacrylate, alpha-position Is more preferably an acrylate substituted with a halogen atom.
As the compound (1), Z is an ^{R F} group having 4 to 6 carbon atoms, Y is an alkylene group having 1 to 4 carbon atoms, n is 1, X is a group (3-3) , R is particularly preferably a hydrogen atom, a methyl group or a chlorine atom.

Preferable specific examples of the compound (1) include the following.
_{C 6 F 13 C 2 H 4} OCOC (CH 3) = CH 2,
C ₆ F ₁₃ C ₂ H ₄ OCOCH═CH ₂ ,
C ₆ F ₁₃ C ₂ H ₄ OCOCCl═CH ₂ ,
_{C 4 F 9 C 2 H 4} OCOC (CH 3) = CH 2,
_{C 4 F 9 C 2 H 4} OCOCH = CH 2,
_{C 4 F 9 C 2 H 4} OCOCCl = CH 2.

Monomer (b):
The monomer (b) is a (meth) acrylate having no R ^f group and having an alkyl group having 12 or more carbon atoms. 18-30 are preferable and, as for carbon number of an alkyl group, 20-24 are more preferable.
If the carbon number of the alkyl group is at least the lower limit, the heavy rain durability of the article treated with the water / oil repellent composition will be good. When the number of carbon atoms of the alkyl group is not more than the above upper limit, handling in the polymerization operation is easy, and a copolymer can be obtained with good yield.
As the monomer (b), stearyl (meth) acrylate or behenyl (meth) acrylate is preferable, behenyl (meth) acrylate is more preferable, and behenyl acrylate is further preferable.

Monomer (c):
The monomer (c) is either or both of polyfluorovinyl ether (excluding the monomer (a)) and polyfluoroallyl ether.
Since the copolymer has a structural unit based on the monomer (c), oil repellency derived from the structural unit based on the monomer (a) and heavy rain durability derived from the structural unit based on the monomer (b) Both sexes can be fully demonstrated.

As the monomer (c), the compound (5) or the compound (6) is preferable.
CX ³ X ⁴ = CF (CF ₂ ) _a [OCFX ⁵ CFX ⁶ ] _b (O) _c (CFX ⁷ ) _d CH ₂ OH (5),
_{^{CX 3 X 4 = CF (CF}} 2) a [OCFX 5 CFX 6] b (O) c (CFX 7) d C (O) OR 3 ··· (6).

X ^{3 to} X ⁷ are each independently a hydrogen atom, a fluorine atom or a trifluoromethyl group.
R ³ is a hydrogen atom, an alkyl group or a substituted alkyl group, preferably an alkyl group. 1-12 are preferable and, as for carbon number of an alkyl group, 1-6 are especially preferable. The alkyl group may be linear or branched.
a is 0 or 1;
b is an integer greater than or equal to 0, 1-20 are preferable and 1-5 are more preferable.
c is 0 or 1. However, when b is 0, c is 1.
d is an integer greater than or equal to 0, 1-20 are preferable and 1-5 are more preferable.

Examples of the compound (5) include the following compounds.
CF ₂ = CFOCF ₂ CF ₂ CF ₂ CH ₂ OH,
CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ CH ₂ OH,
_{CH 2 = CFCF 2 OCF (CF} 3) CF 2 OCF (CF 3) CH 2 OH,
_{CH 2 = CFCF 2 OCF (CF} 3) CF 2 OCF (CF 3) CF 2 OCF (CF 3) CH 2 OH.

Examples of the compound (6) include the following compounds.
CF ₂ = CFOCF ₂ CF ₂ CF ₂ C (O) OCH ₃ ,
CF ₂ = CFOCF ₂ CF ₂ CF ₂ C (O) OC ₂ H ₅ ,
CF ₂ = CFOCF ₂ CF ₂ CF ₂ C (O) OC ₃ H ₇ ,
CF ₂ = CFOCF ₂ CF ₂ CF ₂ C (O) OC ₄ H ₉ ,
CF ₂ = CFOCF ₂ CF ₂ CF ₂ C (O) OC ₅ H ₁₁ ,
CF ₂ = CFOCF ₂ CF ₂ CF ₂ C (O) OC ₆ H ₁₃ ,
CF ₂ = CFOCF ₂ CF ₂ CF ₂ C (O) OC ₈ H ₁₇ ,
_{CF 2 = CFOCF 2 CF (CF} 3) OCF 2 CF 2 C (O) OCH 3,
_{CF 2 = CFOCF 2 CF (CF} 3) OCF 2 CF 2 C (O) OC 2 H 5,
CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ C (O) OC ₃ H ₇ ,
CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ C (O) OC ₄ H ₉ ,
CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ C (O) OC ₅ H ₁₁ ,
CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ C (O) OC ₆ H ₁₃ ,
_{CF 2 = CFOCF 2 CF (CF} 3) OCF 2 CF 2 C (O) OC 8 H 17.
_{CH 2 = CFCF 2 OCF (CF} 3) CF 2 OCF (CF 3) COOCH 3,
_{CH 2 = CFCF 2 OCF (CF} 3) CF 2 OCF (CF 3) CF 2 OCF (CF 3) C (O) OCH 3,
CF ₂ = CFOCF ₂ CF ₂ CF ₂ C (O) OH,
_{CH 2 = CFCF 2 OCF (CF} 3) CF 2 OCF (CF 3) C (O) OH,
_{CH 2 = CFCF 2 OCF (CF} 3) CF 2 OCF (CF 3) CF 2 OCF (CF 3) C (O) OH.

  Compound (5) and compound (6) can be produced by known methods described in Japanese Patent No. 1454966, Japanese Patent No. 3012324, Japanese Patent Application Laid-Open No. 2008-138219, and the like.

As the monomer (c), polyfluorovinyl ether having a crosslinkable functional group or polyfluoroallyl ether having a crosslinkable functional group may be used.
The functional group capable of crosslinking is preferably a functional group having at least one bond among a covalent bond, an ionic bond and a hydrogen bond, or a functional group capable of forming a crosslinked structure by the interaction of the bonds.

  Examples of the functional group include a hydroxyl group, an isocyanate group, a blocked isocyanate group, an alkoxysilyl group, an amino group, an alkoxymethylamide group, a silanol group, an ammonium group, an amide group, an epoxy group, a hydroxyl group, an oxazoline group, a carboxyl group, and an alkenyl group. A sulfonic acid group, and the like, and an epoxy group, a blocked isocyanate group, an alkoxysilyl group, an amino group, or a carboxyl group are preferable, and a hydroxyl group or a carboxyl group is particularly preferable from the viewpoint of reactivity with various functional groups.

As the monomer (c), the following compounds are particularly preferable.
CF ₂ = CFOCF ₂ CF ₂ CF ₂ CH ₂ OH,
CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ CH ₂ OH,
_{CH 2 = CFCF 2 OCF (CF} 3) CF 2 OCF (CF 3) CH 2 OH,
CF ₂ = CFOCF ₂ CF ₂ CF ₂ C (O) OCH ₃ ,
CF ₂ = CFOCF ₂ CF ₂ CF ₂ C (O) OC ₂ H ₅ ,
CF ₂ = CFOCF ₂ CF ₂ CF ₂ C (O) OH,
_{CH 2 = CFCF 2 OCF (CF} 3) CF 2 OCF (CF 3) COOCH 3,
CF ₂ = CFOCF ₂ CF ₂ CF ₂ C (O) OH,
_{CH 2 = CFCF 2 OCF (CF} 3) CF 2 OCF (CF 3) C (O) OH.

Monomer (d):
The monomer (d) is a halogenated olefin.
An article treated with a water / oil repellent composition, because the adhesiveness to the article is improved by combining the constituent unit based on the monomer (b) and the constituent unit based on the monomer (d). The durability of heavy rain is further improved.

  The halogenated olefin is preferably a chlorinated olefin or a fluorinated olefin, and specific examples include vinyl chloride, vinylidene chloride, tetrafluoroethylene, and vinylidene fluoride. From the viewpoint of adhesion to the article, vinyl chloride or vinylidene chloride is more preferable, and vinyl chloride is particularly preferable.

Monomer (e):
The monomer (e) is a monomer that does not have a fluorine atom and has a functional group capable of crosslinking.
When the copolymer has a structural unit based on the monomer (e), the durability (washing durability and heavy rain durability) of the article treated with the water / oil repellent composition is further improved.

The functional group capable of crosslinking is preferably a functional group having at least one bond among a covalent bond, an ionic bond and a hydrogen bond, or a functional group capable of forming a crosslinked structure by the interaction of the bonds.
The functional group includes isocyanate group, blocked isocyanate group, alkoxysilyl group, amino group, alkoxymethylamide group, silanol group, ammonium group, amide group, epoxy group, hydroxyl group, oxazoline group, carboxyl group, alkenyl group, sulfone. Acid groups and the like are preferable. In particular, an epoxy group, a hydroxyl group, a blocked isocyanate group, an alkoxysilyl group, an amino group, or a carboxyl group is preferable.

As the monomer (e), (meth) acrylates, acrylamides, vinyl ethers, or vinyl esters are preferable.
As the monomer (e), the following compounds may be mentioned.

  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, trimethoxyvinylsilane, vinyltrimethoxysilane, dimethylaminoethyl (meth) acrylate , Diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, (meth) acryloylmorpholine, (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxypropyltrimethylammonium chloride, (meth) acrylamidoethyltrimethylammonium chloride , (Meth) acrylamidopropyltrimethylammonium 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, Nippon Kasei Co., Ltd.), triallyl cyanurate (TAC, 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.).

  As the monomer (d), N-methylol (meth) acrylamide, N-butoxymethyl (meth) acrylamide, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-isocyanatoethyl ( 3,5-dimethylpyrazole adduct of (meth) acrylate, 3,5-dimethylpyrazole adduct of 3-isocyanatopropyl (meth) acrylate, diacetone acrylamide, glycidyl methacrylate, polycaprolactone ester of hydroxyethyl (meth) acrylate, Polycaprolactone ester of hydroxyethyl (meth) acrylate, AT-600 or Techcoat HE-6P is preferred. As monomer (d), N-methylol (meth) acrylamide, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3,5-dimethyl of 2-isocyanatoethyl (meth) acrylate A pyrazole adduct or a 3,5-dimethylpyrazole adduct of 3-isocyanatopropyl (meth) acrylate is particularly preferable.

Monomer (f):
The monomer (f) is a monomer excluding the monomer (a), the monomer (b), the monomer (c), the monomer (d), and the monomer (e).
As the monomer (f), the following compounds may be mentioned.
Methyl acrylate, ethyl acrylate, propyl acrylate, butyl methacrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, butyl methacrylate, n-hexyl (meth) acrylate, vinyl acetate, vinyl propionate, butene, isoprene, butadiene, Ethylene, propylene, vinylethylene, pentene, ethyl-2-propylene, butylethylene, cyclohexylpropylethylene, decylethylene, dodecylethylene, hexene, isohexylethylene, neopentylethylene, (1,2-diethoxycarbonyl) ethylene, ( 1,2-dipropoxycarbonyl) ethylene, methoxyethylene, ethoxyethylene, butoxyethylene, 2-methoxypropylene, pentyloxy Styrene, cyclo pentanoyloxy ethylene, cyclopentyl acetoxystyrene ethylene, styrene, alpha-methyl styrene, p- methyl styrene, hexyl styrene, octyl styrene, nonyl styrene, chloroprene.

  N, N-dimethyl (meth) acrylamide, vinyl alkyl ether, vinyl alkyl ketone, butyl acrylate, propyl methacrylate, benzyl (meth) acrylate, octyl (meth) acrylate, decyl methacrylate, cyclododecyl acrylate, 3-ethoxypropyl acrylate, methoxy -Butyl acrylate, 2-ethylbutyl acrylate, 1,3-dimethylbutyl acrylate, 2-methylpentyl acrylate, aziridinylethyl (meth) acrylate, 2-ethylhexyl polyoxyalkylene (meth) acrylate, polyoxyalkylene di (meth) ) Acrylate.

  Crotonic acid alkyl ester, maleic acid alkyl ester, fumaric acid alkyl ester, citraconic acid alkyl ester, mesaconic acid alkyl ester, triallyl cyanurate, allyl acetate, N-vinylcarbazole, maleimide, N-methylmaleimide, silicone on side chain (Meth) acrylate having a urethane bond, (meth) acrylate having a polyoxyalkylene chain whose terminal is an alkyl group having 1 to 4 carbon atoms, alkylene di (meth) acrylate, and the like.

The proportion of the structural unit based on the monomer (a) is determined from the viewpoint of the water / oil repellency and durability of the article treated with the water / oil repellent composition, and all monomers constituting the copolymer. Among the structural units based on (100% by mass), 5 to 40% by mass is preferable, 10 to 30% by mass is more preferable, and 12 to 25% by mass is more preferable.
The proportion of the structural unit based on the monomer (b) is determined from the viewpoint of the water / oil repellency and durability of the article treated with the water / oil repellent composition. 40 to 94.9% by mass is preferable, 40 to 84.9% by mass is more preferable, and 40 to 82.9% by mass is more preferable.
The proportion of the structural unit based on the monomer (c) is that all monomers constituting the copolymer from the viewpoint of the water / oil repellency and durability of the article treated with the water / oil repellent composition. Is preferably 0.1 to 20% by mass, more preferably 0.1 to 15% by mass, and still more preferably 0.1 to 13% by mass.
The proportion of the structural unit based on the monomer (d) is determined from the viewpoint of water / oil repellency and durability of the article treated with the water / oil repellent composition, and all monomers constituting the copolymer. Is preferably 0 to 30% by mass, more preferably 5 to 25% by mass, and still more preferably 5 to 22% by mass.
The proportion of the structural unit based on the monomer (e) is determined from the viewpoint of water / oil repellency and durability of the article treated with the water / oil repellent composition, and all monomers constituting the copolymer. Is preferably 0 to 10% by mass, more preferably 0 to 8% by mass.
The proportion of the structural unit based on the monomer (f) is determined from the viewpoint of water / oil repellency and durability of the article treated with the water / oil repellent composition, and all monomers constituting the copolymer. Is preferably 0 to 35% by mass, more preferably 0 to 15% by mass.
The ratio of the structural unit based on the monomer in the present invention is calculated based on the amount of monomer charged at the time of producing the copolymer.

The weight average molecular weight (Mw) of the copolymer is preferably 8,000 to 500,000, and more preferably 10,000 to 400,000. When the weight average molecular weight (Mw) of the copolymer is within the above range, both water repellency and oil repellency can be expressed.
The number average molecular weight (Mn) of the copolymer is preferably 3000 to 200000, and more preferably 5000 to 18000. When the number average molecular weight (Mn) of the copolymer is within the above range, both water repellency and oil repellency can be expressed.

(Medium)
Examples of the medium include water, alcohol, glycol, glycol ether, glycol ester, halogen compound, hydrocarbon, ketone, ester, ether, nitrogen compound, sulfur compound, inorganic solvent, organic acid, etc., solubility, easy handling From this point, one or more media selected from the group consisting of water, alcohol, glycol, glycol ether and glycol ester are preferred.

  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, and 3-heptanol.

  As glycol and glycol ether, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl 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 Ether, dipropylene glycol dimethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol, tripropylene glycol monomethyl ether, polypropylene glycol, hexylene glycol, 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 aromatic hydrocarbons include benzene, toluene, xylene 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 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.
Examples of the inorganic solvent include liquid carbon dioxide.
Examples of the organic acid include acetic acid, propionic acid, malic acid, lactic acid, itaconic acid and the like.

A medium may be used individually by 1 type, and 2 or more types may be mixed and used for it. When two or more media are used in combination, it is preferable to use a mixture with water. By using a mixed medium, it is easy to control the solubility and dispersibility of the copolymer, and it is easy to control the permeability, wettability, solvent drying rate and the like of the article during processing.
When the water / oil repellent composition of the present invention is a composition containing 20% by mass of a copolymer, it preferably contains 0-40% by mass of the medium other than water, more preferably 1-20% by mass. .

(Surfactant)
Examples of the surfactant include a hydrocarbon-based surfactant and a fluorine-based surfactant, and an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant, respectively. .
As the surfactant, a combination of a nonionic surfactant and an amphoteric surfactant is preferable from the viewpoint of compatibility with the additive, and from the viewpoint of the stability of the copolymer emulsion, the nonionic surfactant is used. These are preferably used alone or in combination with a nonionic surfactant and a cationic surfactant.
The ratio of the nonionic surfactant to the cationic surfactant (nonionic surfactant / cationic surfactant) is preferably 97/3 to 40/60 (mass ratio).

Examples of the nonionic surfactant include surfactants s ^{1 to} s ⁶ described in International Publication No. 2010/047258 and International Publication No. 2010/123042, and an amidoamine interface described in Japanese Patent No. 5569614. One or more selected from activators are preferred.
When the surfactant contains a cationic surfactant, the surfactant s ⁷ described in International Publication No. 2010/047258 and International Publication No. 2010/123042 is preferable as the cationic surfactant.
When the surfactant contains an amphoteric surfactant, the amphoteric surfactant, WO 2010/047258, surfactant ^{s 8} as described in WO 2010/123042 preferred.
Further, as the surfactant, WO 2010/047258, it may be used WO 2010/123042 surfactants described in JP ^{s 9} (polymeric surfactant).
The preferable aspect of surfactant is the same as the preferable aspect described in international publication 2010/047258 and international publication 2010/123042.

Preferable specific examples of the nonionic surfactant include the following compounds.
_{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) 26 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.
_{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)} 9 - (C 3 H 6 O) 20 - (CH 2 CH 2 O) 9 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.

Preferable specific examples of the cationic surfactant include the following compounds.
Stearyltrimethylammonium chloride,
Stearyl dimethyl monoethylammonium ethyl sulfate,
Stearyl monomethyldi (polyethylene glycol) ammonium chloride,
Fluorohexyltrimethylammonium chloride,
Di (tallow alkyl) dimethylammonium chloride,
Dimethyl monococonut amine acetate,
Amidoamine quaternary ammonium salts described in Japanese Patent No. 5569614.

Preferable specific examples of the amphoteric surfactant include the following compounds.
Dodecyl betaine,
Stearyl betaine,
Dodecylcarboxymethylhydroxyethyl imidazolinium betaine,
Betaine dodecyldimethylaminoacetate,
Fatty acid amidopropyldimethylaminoacetic acid betaine.

  1-10 mass parts is preferable with respect to a copolymer (100 mass parts), and, as for the total amount of surfactant, 2-8 mass parts is more preferable.

(Additive)
Additives include penetrants, antifoaming agents, water absorbing agents, antistatic agents, antifungal agents, texture modifiers, film-forming aids, water-soluble polymers (polyacrylamide, polyvinyl alcohol, etc.), thermosetting agents (melamine) Resin, urethane resin, 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 resin, fiber stabilizer and the like.

(Method for producing water / oil repellent composition)
The water / oil repellent composition of the present invention can be produced, for example, by the following method (i) or (ii).
(I) A monomer component containing monomers (a) to (c) and, if necessary, monomers (d) to (f) in the medium in the presence of a surfactant and a polymerization initiator. A method of polymerizing to obtain a copolymer solution, dispersion or emulsion, and then adding another medium, other surfactant or additive as necessary.
(Ii) In the presence of a surfactant and a polymerization initiator, a monomer component containing the monomers (a) to (c) and, if necessary, the monomers (d) to (f) in the medium A method of polymerizing to obtain a solution, dispersion or emulsion of the copolymer, then separating the copolymer, and adding a medium, a surfactant and, if necessary, an additive to the copolymer.
Examples of the polymerization method include a dispersion polymerization method, an emulsion polymerization method, and a suspension polymerization method.

As a method for producing a water / oil repellent composition, monomers (a) to (c), and optionally monomers (d) to (c) in an aqueous medium in the presence of a surfactant and a polymerization initiator. A method of obtaining a copolymer emulsion by emulsion polymerization of the monomer component containing f) is preferred.
From the viewpoint of improving the yield of the copolymer, it is preferable to pre-emulsify a mixture comprising a monomer, a surfactant and an aqueous medium before emulsion polymerization. For example, a mixture comprising a monomer, a surfactant and an aqueous medium is mixed and dispersed with a homomixer or a high-pressure emulsifier.

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 water-soluble or oil-soluble radical polymerization initiator is preferable.
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. As the radical polymerization initiator, an azo compound is particularly preferable, and when polymerization is performed in an aqueous medium, a salt of the azo compound is more preferable. The polymerization temperature is preferably 20 to 150 ° C.

In the polymerization of the monomer, a molecular weight modifier may be used. As the molecular weight regulator, aromatic compounds, mercapto alcohols or mercaptans are preferable, and alkyl mercaptans are particularly preferable. As a molecular weight modifier, mercaptoethanol, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, stearyl mercaptan, α-methylstyrene dimer (CH ₂ ═C (Ph) CH ₂ C (CH ₃ ) ₂ Ph. However, Ph is a phenyl group.) Etc. are mentioned.

  The proportions of the monomers (a) to (f) are the same as the proportions of the structural units based on the monomers (a) to (f) described above because the monomers remaining after the polymerization are hardly detected. There are also preferred embodiments.

  In the water / oil repellent composition of the present invention, the copolymer is preferably dispersed as particles in the medium. The average particle size of the copolymer is preferably 10 to 1000 nm, more preferably 10 to 300 nm, and particularly preferably 10 to 200 nm. If the average particle size is within this range, it is not necessary to use a large amount of a surfactant or the like, the water and oil repellency is good, no discoloration occurs when dyed fabrics are treated, Thus, the dispersed particles can exist stably and do not settle. The average particle size of the copolymer can be measured by a dynamic light scattering device, an electron microscope or the like.

The solid content concentration of the water / oil repellent composition of the present invention is preferably 25 to 40% by mass in the water / oil repellent composition (100% by mass) immediately after the production of the water / oil repellent composition.
The solid content concentration of the water / oil repellent composition of the present invention is preferably 0.2 to 5% by mass in the water / oil repellent composition (100% by mass) when the article is processed.
The solid content concentration of the water / oil repellent composition is calculated from the mass of the water / oil repellent composition before heating and the mass after drying in a convection dryer at 120 ° C. for 4 hours.

(Mechanism of action)
In the water / oil repellent composition of the present invention described above, in addition to the structural unit based on the monomer (a) and the structural unit based on the monomer (b), the structure based on the monomer (c) Since the copolymer further includes a unit, an article having good water repellency, oil repellency, and heavy rain durability can be obtained by treating the article with the water / oil repellent composition. .
Further, in the water / oil repellent composition of the present invention, since the copolymer does not have a structural unit based on a monomer having an R 7 ^F group having 7 or more carbon atoms, the influence on the environment has been pointed out. Perfluorooctanoic acid (PFOA), perfluorooctane sulfonic acid (PFOS), and precursors and analogs thereof (content when the solid content concentration is 20%) described in International Publication No. 2009/081822 The LC-MS / MS analysis value can be made below the detection limit.

<Article>
The article of the present invention is an article treated with the water / oil repellent composition of the present invention.
Articles treated with the water / oil repellent composition of the present invention include fibers (natural fibers, synthetic fibers, blended fibers, etc.), various fiber products, nonwoven fabrics, resins, paper, leather, wood, metals, stones, concrete, Examples thereof include gypsum and glass.
Examples of the treatment method include a method of applying or impregnating the water / oil repellent composition to the article by a known coating method and then drying.

  When the article is treated with the water / oil repellent composition of the present invention, since the film is flexible, the texture of the fiber product becomes flexible and high quality water / oil repellency can be imparted to the article. In addition, it has excellent surface adhesion and can impart water and oil repellency even at low temperature curing. In addition, there is little deterioration in performance due to friction or washing, and the performance at the initial stage of processing can be stably maintained. Moreover, when processed to paper, excellent size, water repellency and oil resistance can be imparted to paper even under low temperature drying conditions. When treated on a resin, glass or metal surface, it is possible to form a water / oil repellent film having good adhesion to the article and excellent film forming properties.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these.
Examples 1 to 7, 8, 10, and 11 are examples, and 9 and 12 are comparative examples.

(Water repellency)
The test fabric was evaluated for water repellency according to the spray test of JIS L 1092. The water repellency was expressed in 5 grades of 1-5. The larger the score, the better 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.

(Water repellent friction durability)
Using a Martindale friction tester, 2 mL of water was dropped on the friction surface of the test cloth, the friction surface of the test cloth was rubbed 500 times, and air-dried overnight in a room at a temperature of 25 ° C. and a humidity of 55%. The water repellency of the friction surface of the cloth was evaluated.

(Water-repellent washing durability)
For the test cloth, washing was repeated 20 times according to the water washing method of Schedule 103 of JIS L 0217. After washing, it was air-dried overnight in a room with a room temperature of 25 ° C. and a humidity of 55%, and then the water repellency of the test cloth was evaluated.

(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. A grade marked with + (−) indicates that each property is slightly better (bad).

(Durable torrential rain)
For the test cloth, according to the method described in JIS L 1092 (C) (Bundesmann test), the rainfall is 100 cc / min, the rain water temperature is 20 ° C., and the rain time is 10 minutes. evaluated. The water repellency was expressed in 5 grades of 1-5. The larger the score, the better 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).

(Durable rain wash durability)
For the test cloth, washing was repeated 5 times according to the water washing method of Appendix 103 of JIS L 0217. After washing, it was air-dried overnight in a room at room temperature of 25 ° C. and humidity of 55%, and then the heavy rain durability of the test cloth was evaluated.

(Abbreviation)
Monomer (a):
_{C6FMA: C 6 F 13 C 2} H 4 OC (O) C (CH 3) = CH 2.

Monomer (b):
BeA: behenyl acrylate,
STA: Stearyl acrylate.

Monomer (c):
_{PFVBE-OH: CF 2 = CFOCF} 2 CF 2 CF 2 CH 2 OH,
_{PFVBEME: CF 2 = CFOCF 2 CF} 2 CF 2 C (O) OCH 3.

Monomer (d):
VCl: Vinyl chloride.

Monomer (e):
HEMA: 2-hydroxyethyl methacrylate,
N-MAM: N-methylol acrylamide.

Surfactant s ¹ :
PEO-20: 10% by mass aqueous solution of polyoxyethylene oleyl ether (manufactured by Kao Corporation, Emulgen (registered trademark) E430, approximately 26 mol of ethylene oxide adduct).

Surfactant s ³ :
P204: 10 mass% aqueous solution of ethylene oxide propylene oxide polymer (manufactured by NOF Corporation, Pronon (registered trademark) 204, the proportion of ethylene oxide is 40 mass%).

Surfactant s ⁷ :
TMAC: 10% by mass aqueous solution of stearyltrimethylammonium chloride.

Medium:
DPM: Dipropylene glycol monomethyl ether,
Water: Ion exchange water.

Molecular weight regulator:
DoSH: n-dodecyl mercaptan.

Polymerization initiator:
VA061A: 10% by mass aqueous solution of acetate of 2,2′-azobis [2- (2-imidazolin-2-yl) propane] (manufactured by Wako Pure Chemical Industries, Ltd., VA061).

[Example 1]
In a glass beaker, 4.5 g of C6FMA, 15.0 g of BeA, 0.05 g of PFVBE-OH, 6.23 g of PEO-20, 0.25 g of TMAC, 1.25 g of P204, 15.0 g of DPM 29.7 g of water and 0.25 g of DoSH 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 60 ° C. to obtain an emulsion. The obtained emulsion was put into a stainless steel reaction vessel and cooled to 40 ° C. or lower. After adding 2.49 g of VA061A and replacing the gas phase with nitrogen, 5.4 g of VCl was added. While stirring, the polymerization reaction was carried out at 60 ° C. for 15 hours to obtain a copolymer emulsion. Table 3 shows the proportion of structural units based on each monomer.

  After the copolymer emulsion is diluted with distilled water and the solid content concentration is adjusted to 1% by mass, a melamine resin crosslinking agent (DIC, Becamine (registered trademark) M3) and an acid catalyst (DIC, accelerator) ACX) was added so that each concentration would be 0.3% by mass to obtain a water / oil repellent composition.

  Dyeed polyester taffeta or dyed nylon taffeta was immersed in the water / oil repellent composition and squeezed so that the wet pickups were 35% by mass and 86% by mass, respectively. This was dried at 110 ° C. for 60 seconds and then dried at 170 ° C. for 60 seconds to obtain a test cloth. The test cloth was evaluated for oil repellency, water repellency, water repellency friction durability, water repellency washing durability, heavy rain durability and heavy rain durability. The results are shown in Tables 4 and 5.

[Examples 2 to 12]
A copolymer emulsion was obtained in the same manner as in Example 1 except that the type of monomer and / or the charged amount was changed to the amount shown in Table 2. Table 3 shows the proportion of structural units based on each monomer.
A water / oil repellent composition was obtained in the same manner as in Example 1 except that the emulsion was used.
A test cloth was obtained in the same manner as in Example 1 except that the water / oil repellent composition was used. The test cloth was evaluated for oil repellency, water repellency, water repellency friction durability, water repellency washing durability, heavy rain durability and heavy rain durability. The results are shown in Tables 4 and 5.

  The water / oil repellent composition of the present invention comprises fiber products (clothing articles (sportswear, coats, blousons, work clothes, uniforms, etc.), bags, industrial materials, etc.), non-woven fabrics, leather products, wood, stones, concretes. It is useful as a water / oil repellent for imparting water / oil repellency to building materials. Moreover, it is useful as a coating agent for filtration materials, a surface protective agent, a coating agent for electronics, and an antifouling coating agent used in the presence of an organic solvent liquid or its vapor. Furthermore, it is also useful for applications where water and oil repellency is imparted by mixing and molding with fiber such as polypropylene and nylon.

Claims (11)

A water / oil repellent composition comprising a copolymer having a structural unit based on the following monomer (a), a structural unit based on the following monomer (b), and a structural unit based on the following monomer (c) .
Monomer (a): A compound represented by the following formula (1).
(ZY) _n X (1).
However, Z is a C1-C6 perfluoroalkyl group, a group represented by the following formula (2-1) or a group represented by the following formula (2-2), and Y represents a fluorine atom. A divalent organic group or a single bond that is not present, n is 1 or 2, and X is a group represented by the following formulas (3-1) to (3-5) when n is 1 And when n is 2, it is one of the groups represented by the following formulas (4-1) to (4-4).
C _i F _{2i + 1} O (CFX ¹ CF ₂ O) _j CFX ² − (2-1),
_{C i F 2i + 1 (CH} 2 CF 2) p (CF 2 CF 2) q - ··· (2-2).
Where, i is an integer from 1 to 6, j is an integer of 0, ^{X 1} and ^{X 2} are each fluorine atom or a trifluoromethyl group, p is an integer of from 1 to 4 Yes, q is an integer from 1 to 3.
-CR = CH ₂ (3-1),
_{-C (O) OCR = CH 2} ··· (3-2),
_{-OC (O) CR = CH 2} ··· (3-3),
_{-OCH 2 -φ-CR = CH 2} ··· (3-4),
_{-OCH = CH 2 ··· (3-5)} .
However, R is a hydrogen atom, a methyl group, or a halogen atom, and φ is a phenylene group.
_{-CH [- (CH 2) m} CR = CH 2] - ··· (4-1),
_{-CH [- (CH 2) m} C (O) OCR = CH 2] - ··· (4-2),
_{-CH [- (CH 2) m} OC (O) CR = CH 2] - ··· (4-3),
-OC (O) CH = CHC (O) O- (4-4).
However, R is a hydrogen atom, a methyl group, or a halogen atom, and m is an integer of 0-4.
Monomer (b): (meth) acrylate having no polyfluoroalkyl group and having an alkyl group having 12 or more carbon atoms.
Monomer (c): One or both of polyfluorovinyl ether and polyfluoroallyl ether. The water / oil repellent composition according to claim 1, wherein the copolymer further comprises a structural unit based on the following monomer (d).
Monomer (d): Halogenated olefin. The water / oil repellent composition according to claim 1 or 2, wherein the copolymer further comprises a structural unit based on the following monomer (e).
Monomer (e): A monomer having no fluorine atom and having a functional group capable of crosslinking. The proportion of the structural unit based on the monomer (a) in the copolymer is 5 to 40% by mass in the structural unit (100% by mass) based on all monomers constituting the copolymer. Yes,
The proportion of the structural unit based on the monomer (b) in the copolymer is 40 to 94.9 mass out of the structural units (100 mass%) based on all monomers constituting the copolymer. %
The proportion of the structural unit based on the monomer (c) in the copolymer is 0.1 to 20 mass out of the structural units (100 mass%) based on all the monomers constituting the copolymer. The water / oil repellent composition according to any one of claims 1 to 3, wherein the composition is%. The water / oil repellent composition according to any one of claims 1 to 4, wherein the monomer (c) is the compound (5) or the compound (6).
CX ³ X ⁴ = CF (CF ₂ ) _a [OCFX ⁵ CFX ⁶ ] _b (O) _c (CFX ⁷ ) _d CH ₂ OH (5),
^{_{CX 3 X 4 = CF (CF}} 2) a [OCFX 5 CFX 6] b (O) c (CFX 7) d C (O) OR 3 ··· (6).
However, X ³ to X ⁷ are each independently a hydrogen atom, a fluorine atom or a trifluoromethyl group, R ³ is a hydrogen atom, an alkyl group or a substituted alkyl group, a is 0 or 1 , B is an integer of 0 or more, c is 0 or 1 (however, when b is 0, c is 1), and d is an integer of 0 or more. In the presence of a surfactant and a polymerization initiator, a monomer component containing the following monomer (a), the following monomer (b), and the following monomer (c) is polymerized in the medium, A method for producing a water / oil repellent composition, which is a polymer.
Monomer (a): A compound represented by the following formula (1).
(ZY) _n X (1).
However, Z is a C1-C6 perfluoroalkyl group, a group represented by the following formula (2-1) or a group represented by the following formula (2-2), and Y represents a fluorine atom. A divalent organic group or a single bond that is not present, n is 1 or 2, and X is a group represented by the following formulas (3-1) to (3-5) when n is 1 And when n is 2, it is one of the groups represented by the following formulas (4-1) to (4-4).
C _i F _{2i + 1} O (CFX ¹ CF ₂ O) _j CFX ² − (2-1),
_{C i F 2i + 1 (CH} 2 CF 2) p (CF 2 CF 2) q - ··· (2-2).
Where, i is an integer from 1 to 6, j is an integer of 0, ^{X 1} and ^{X 2} are each fluorine atom or a trifluoromethyl group, p is an integer of from 1 to 4 Yes, q is an integer from 1 to 3.
-CR = CH ₂ (3-1),
_{-C (O) OCR = CH 2} ··· (3-2),
_{-OC (O) CR = CH 2} ··· (3-3),
_{-OCH 2 -φ-CR = CH 2} ··· (3-4),
_{-OCH = CH 2 ··· (3-5)} .
However, R is a hydrogen atom, a methyl group, or a halogen atom, and φ is a phenylene group.
_{-CH [- (CH 2) m} CR = CH 2] - ··· (4-1),
_{-CH [- (CH 2) m} C (O) OCR = CH 2] - ··· (4-2),
_{-CH [- (CH 2) m} OC (O) CR = CH 2] - ··· (4-3),
-OC (O) CH = CHC (O) O- (4-4).
However, R is a hydrogen atom, a methyl group, or a halogen atom, and m is an integer of 0-4.
Monomer (b): (meth) acrylate having no polyfluoroalkyl group and having an alkyl group having 12 or more carbon atoms.
Monomer (c): One or both of polyfluorovinyl ether and polyfluoroallyl ether. The method for producing a water / oil repellent composition according to claim 6, wherein the monomer component further comprises the following monomer (d).
Monomer (d): Halogenated olefin. The method for producing a water / oil repellent composition according to claim 6 or 7, wherein the monomer component further comprises the following monomer (e).
Monomer (e): A monomer having no fluorine atom and having a functional group capable of crosslinking. The ratio of the monomer (a) in the monomer component is 5 to 40% by mass in the monomer component (100% by mass),
The ratio of the monomer (b) in the monomer component is 40 to 94.9% by mass in the monomer component (100% by mass),
The ratio of the said monomer (c) in the said monomer component is 0.1-20 mass% among the said monomer components (100 mass%), Any one of Claims 6-8. A method for producing the water / oil repellent composition described in 1. The method for producing a water / oil repellent composition according to any one of claims 6 to 9, wherein the monomer (c) is the compound (5) or the compound (6).
CX ³ X ⁴ = CF (CF ₂ ) _a [OCFX ⁵ CFX ⁶ ] _b (O) _c (CFX ⁷ ) _d CH ₂ OH (5),
^{_{CX 3 X 4 = CF (CF}} 2) a [OCFX 5 CFX 6] b (O) c (CFX 7) d C (O) OR 3 ··· (6).
However, X ³ to X ⁷ are each independently a hydrogen atom, a fluorine atom or a trifluoromethyl group, R ³ is a hydrogen atom, an alkyl group or a substituted alkyl group, a is 0 or 1 , B is an integer of 0 or more, c is 0 or 1 (however, when b is 0, c is 1), and d is an integer of 0 or more.   An article treated with the water / oil repellent composition according to any one of claims 1 to 5.