WO2013058334A1 - Fluorine-containing composition - Google Patents

Abstract

Disclosed is a fluorine-containing composition containing a fluorine-containing polymer having a repeating unit derived from a first fluorine-containing monomer (a1) and a second fluorine-containing monomer (a2) represented by CH₂=C(-X)-C(=O)-Y-Z-Rf (formula (a)). (In the formula, X represents a hydrogen atom, a univalent organic group, or a halogen group; Y represents -O- or -NH-; Z represents a direct bond or bivalent organic group; and Rf represents a C_1-6 fluoroalkyl group in the first fluorine-containing monomer (a1) and a fluoroalkyl group having 12 or more carbon atoms in the second fluorine-containing monomer (a2).) The fluorine-containing composition exhibits the properties required of a surface treatment agent, examples of such properties include water- and oil-repellent, anti-fouling, and anti-corrosion properties, releasability, adhesiveness to a base, excellent texture, water resistance, oil resistance, and durability of said properties.

Description

Fluorine-containing composition

The present invention relates to a fluorine-containing composition. The fluorine-containing composition can be favorably used as a surface treatment agent, for example, a water / oil repellent, an antifouling agent and a release agent.

Conventionally, various fluorine-containing compounds have been proposed. The fluorine-containing compound has an advantage of excellent properties such as heat resistance, oxidation resistance, and weather resistance. The fluorine-containing compound is used as, for example, a water / oil repellent and an antifouling agent by utilizing the characteristic that the free energy of the fluorine-containing compound is low, that is, it is difficult to adhere. For example, US Pat. No. 5,247,008 discloses an aqueous copolymer of a perfluoroalkyl ester of (meth) acrylic acid, an alkyl ester of (meth) acrylic acid, and an aminoalkyl ester of (meth) acrylic acid. Finishing agents for textiles, leather, paper and mineral substrates, which are dispersions, are described.

For stable expression of the surface function as a water / oil repellent and antifouling agent, it is composed of a fluorine-containing monomer having a perfluoroalkyl group having 8 or more carbon atoms in which the perfluoroalkyl group is stably oriented on the surface. Polymers or copolymers have been considered effective.
However, in recent years, it has been pointed out by the EPA (United States Environmental Protection Agency) that the decomposition product of a fluorine-containing monomer having a perfluoroalkyl group having 8 or more carbon atoms is a compound having a high environmental load. Of a fluorine-containing monomer containing a perfluoroalkyl group having 8 or more carbon atoms constituting the fluorine-containing polymer or fluorine-containing copolymer in the water / oil repellent composition, antifouling agent composition or release agent composition Reduction of content is demanded.
On the other hand, in the conventional (per) fluoroalkyl ester of (meth) acrylic acid, the orientation of the perfluoroalkyl group on the surface is unstable with a perfluoroalkyl group having 6 or less carbon atoms. There is a disadvantage in that sufficient performance required as a soiling agent or mold release agent may not be provided.

US Pat. No. 5,247,008

One object of the present invention is to reduce the content of a fluorine-containing monomer containing a perfluoroalkyl group having 8 or more carbon atoms constituting the fluorine-containing polymer or fluorine-containing copolymer in the fluorine-containing composition, An object of the present invention is to provide a fluorine-containing polymer, a fluorine-containing copolymer and a fluorine-containing compound which give sufficient performance required as a water / oil repellent, an antifouling agent or a release agent. Other objects of the present invention include performance required as a surface treatment agent, such as water / oil repellency, antifouling properties, mold release properties, adhesion to substrates, corrosion resistance, texture, water resistance, oil resistance, and the like. A fluorine-containing composition having durability in performance is provided.

The present invention
(A1) Formula:
CH ₂ = C (-X ¹ ) -C (= O) -Y ¹ -Z ¹ -Rf ¹
[Wherein, X ¹ represents a hydrogen atom, a monovalent organic group or a halogen atom,
Y ¹ is —O— or —NH—,
Z ¹ is a direct bond or a divalent organic group,
Rf ¹ is a fluoroalkyl group having 1 to 6 carbon atoms. ]
A first fluorine-containing compound represented by formula (a2):
CH ₂ = C (-X ² ) -C (= O) -Y ² -Z ² -Rf ²
[Wherein X ² represents a hydrogen atom, a monovalent organic group or a halogen atom,
Y ² is —O— or —NH—,
Z ² is a direct bond or a divalent organic group,
Rf ² is the number of 12 or more fluoroalkyl group having a carbon. ]
A fluorine-containing compound mixed with a second fluorine-containing compound represented by the formula:
Furthermore, the present invention provides a mixed fluorine-containing compound (a mixture of fluorine-containing monomers) of a first fluorine-containing compound (first fluorine-containing monomer) and a second fluorine-containing compound (second fluorine-containing monomer). ) Containing a repeating unit derived from (i.e., a fluorine-containing copolymer).
In addition, the present invention provides a fluorine-containing composition comprising the fluorine-containing polymer.

According to the present invention, sufficient performance required as a water / oil repellent, antifouling agent or mold release agent can be obtained. The fluorine-containing composition has performance required as a surface treatment agent, for example, good water and oil repellency, antifouling properties, release properties, adhesion to substrates, corrosion resistance, texture, water resistance, oil resistance, these Durable performance.

In the present invention, the fluorine-containing composition can be used as a surface treatment agent (for example, a water / oil repellent, an antifouling agent and a release agent).
The fluorine-containing composition contains a fluorine-containing polymer. The fluorine-containing polymer has a repeating unit derived from a fluorine-containing monomer.

In the present invention, the fluorine-containing monomer (a) is used as a monomer constituting the fluorine-containing polymer. If necessary, a non-fluorine non-crosslinkable monomer (b) and / or a non-fluorine crosslinkable monomer (c) may be used.
The fluorine-containing polymer is a polymer comprising only the fluorine-containing monomer (a) (that is, a copolymer comprising the first fluorine-containing monomer (a1) and the second fluorine-containing monomer (a2)), Alternatively, it may be a copolymer comprising a non-fluorine non-crosslinkable monomer (b) and / or a non-fluorine crosslinkable monomer (c) in addition to the fluorine-containing monomer (a).

The (a) fluorine- containing monomer is a mixture of (a1) a first fluorine-containing monomer and (a2) a second fluorine-containing monomer. The first fluorine-containing monomer (a1) and the second fluorine-containing monomer (a2) are compounds having different Rf.
The first fluorine-containing monomer (a1) and the second fluorine-containing monomer (a2) have the formula:
CH ₂ = C (-X) -C (= O) -YZ-Rf
[Wherein X is a hydrogen atom, a monovalent organic group or a halogen atom,
Y is -O- or -NH-
Z is a direct bond or a divalent organic group,
Rf is a fluoroalkyl group having 1 to 6 carbon atoms in the first fluorine-containing monomer (a1), and is a fluoroalkyl group having 12 or more carbon atoms in the second fluorine-containing monomer (a2). ]
It is a fluorine-containing monomer shown by.

In the first fluorinated monomer (a1) and the second fluorinated monomer (a2), X, Y and Z may be the same or different.
Therefore, the first fluorine-containing monomer (a1) has the formula:
CH ₂ = C (-X ¹ ) -C (= O) -Y ¹ -Z ¹ -Rf ¹
[Wherein, X ¹ represents a hydrogen atom, a monovalent organic group or a halogen atom,
Y ¹ is —O— or —NH—,
Z ¹ is a direct bond or a divalent organic group,
Rf ¹ is a fluoroalkyl group having 1 to 6 carbon atoms. ]
A compound represented by
The second fluorine-containing monomer (a2) has the formula:
CH ₂ = C (-X ² ) -C (= O) -Y ² -Z ² -Rf ²
[Wherein X ² represents a hydrogen atom, a monovalent organic group or a halogen atom,
Y ² is —O— or —NH—,
Z ² is a direct bond or a divalent organic group,
Rf ² is the number of 12 or more fluoroalkyl group having a carbon. ]
It is a compound shown by these.
X ¹ and X ² are synonymous with X, Y ¹ and Y ² are synonymous with Y, and Z ¹ and Z ² are synonymous with Z.

The fluorine-containing monomer (a) has the general formula:
CH ₂ = C (-X) -C (= O) -Y-Z-Rf
[Wherein, X is a hydrogen atom, a linear or branched alkyl group having 1 to 21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX ¹¹ X ¹² group (where X ¹¹ and X ¹² is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.), A cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, A substituted or unsubstituted phenyl group;
Y is —O— or —NH—;
Z is a direct bond, an aliphatic group having 1 to 10 carbon atoms, an aromatic group having 6 to 18 carbon atoms, an araliphatic group or a cyclic aliphatic group,
A group represented by the formula —R ² (R ¹ ) NSO ₂ — or a formula —R ² (R ¹ ) NCO— (wherein R ¹ is an alkyl group having 1 to 10 carbon atoms, and R ² represents carbon A straight-chain alkylene group or a branched alkylene group of 1 to 10),
A group represented by the formula —CH ₂ CH (OR ³ ) CH ₂ — (wherein R ³ represents a hydrogen atom or an acyl group having 1 to 10 carbon atoms), or
— (CH ₂ ) _m —SO ₂ — (CH ₂ ) _n — group or — (CH ₂ ) _m —S— (CH ₂ ) _n — group (where m is 1 to 10, n is 0 to 10, is there.),
Rf is a fluoroalkyl group having 1 to 6 carbon atoms in the first fluorine-containing monomer (a1), and is a fluoroalkyl group having 12 or more carbon atoms in the second fluorine-containing monomer (a2). ]
An acrylate ester or acrylamide represented by

In the fluorine-containing monomer (a), the α position (of acrylate or methacrylate) may be substituted with a halogen atom or the like. Accordingly, in the formula (1), X (that is, X ¹ and X ² ) is a linear or branched alkyl group having 2 to 21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, CFX ¹¹ X ¹² group (where X ¹¹ and X ¹² are hydrogen atom, fluorine atom, chlorine atom, bromine atom or iodine atom), cyano group, linear or branched fluoroalkyl having 1 to 21 carbon atoms It may be a group, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group.
Specific examples of X include H, Me (methyl group), Cl, Br, I, F, CN, and CF ₃ .

In Z (that is, Z ¹ and Z ² ), the aliphatic group is preferably an alkylene group (particularly having 1 to 4, for example, 1 or 2 carbon atoms). The aromatic group, araliphatic group or cycloaliphatic group may be substituted or unsubstituted.
Examples of Z (ie Z ¹ and Z ² ) are direct bonds,
A linear alkylene group having 1 to 20 carbon atoms or a branched alkylene group, for example, a group represented by the formula — (CH ₂ ) _x — (wherein x is 1 to 10, particularly 2 to 8); Or
A group represented by the formula —Ar—CH ₂ — (wherein Ar is an arylene group optionally having a substituent), or
-CH ₂ CH ₂ N (R ¹ ) SO ₂ -group (where R ¹ is an alkyl group having 1 to 4 carbon atoms), or
A group represented by the formula —CH ₂ CH (OR ³ ) CH ₂ — (wherein R ³ represents a hydrogen atom or an acyl group having 1 to 10 carbon atoms (eg, formyl or acetyl)); For example, a —CH ₂ CH (OZ ¹ ) CH ₂ — group (wherein Z ¹ is a hydrogen atom or an acetyl group), or a formula —Ar—CH ₂ — (wherein Ar represents a substituent if necessary) Or an arylene group having
— (CH ₂ ) _m —SO ₂ — (CH ₂ ) _n — group or — (CH ₂ ) _m —S— (CH ₂ ) _n — group (where m is 1 to 10, n is 0 to 10, Yes).

Z (that is, Z ¹ and Z ² ) is a direct bond, an aliphatic group having 1 to 10 carbon atoms, an aromatic group having 6 to 18 carbon atoms, an araliphatic group or a cyclic aliphatic group, —CH ₂ CH ₂ N (R ¹ ) SO ₂ — group (where R ¹ is an alkyl group having 1 to 4 carbon atoms) or —CH ₂ CH (OZ ¹ ) CH ₂ — group (where Z ¹ is a hydrogen atom or acetyl group) Or — (CH ₂ ) _m —SO ₂ — (CH ₂ ) _n — group or — (CH ₂ ) _m —S— (CH ₂ ) _n — group (where m is 1 to 10, n Is preferably 0 to 10.). The aliphatic group is preferably an alkylene group (particularly having 1 to 4, for example, 1 or 2 carbon atoms). The aromatic group, araliphatic group or cycloaliphatic group may be substituted or unsubstituted. The S group or SO ₂ group may be directly bonded to the Rf group.

In the first fluorinated monomer (a1) and the second fluorinated monomer (a2), the Rf group is preferably a perfluoroalkyl group.
In the first fluorine-containing monomer (a1), the Rf group (that is, Rf ¹ group) has 1 to 6 carbon atoms, for example 4 to 6 carbon atoms. In the first fluorine-containing monomer (a1), examples of the Rf group include —CF ₃ , —CF ₂ CF ₃ , —CF ₂ CF ₂ CF ₃ , —CF (CF ₃ ) ₂ , —CF ₂ CF _2. CF ₂ CF ₃ , —CF ₂ CF (CF ₃ ) ₂ , —C (CF ₃ ) ₃ , — (CF ₂ ) ₄ CF ₃ , — (CF ₂ ) ₂ CF (CF ₃ ) ₂ , —CF ₂ C ( _{CF 3) 3, -CF (CF} 3) CF 2 CF 2 CF 3, - (CF 2) 5 CF 3, - (CF 2) 3 CF (CF 3) 2 and the like.
In the second fluorine-containing monomer (a2), the Rf group (that is, Rf ² group) has 12 or more carbon atoms, for example, 12 to 30, particularly 14 to 20. In the second fluorine-containing monomer (a1), examples of the Rf group include C ₁₂ F ₂₅ , C ₁₃ F ₂₇ , C ₁₄ F ₂₉ , C ₁₅ F ₃₁ , C ₁₆ F ₃₃ , C ₁₇ F ₃₅ , C ₁₈ F ₃₇ , C ₁₉ F ₃₉ , C ₂₀ F ₄₁ , C ₂₅ F ₅₁ , C ₃₀ F ₆₁ may be mentioned.

When the second fluorinated monomer (a2) is mixed with the first fluorinated monomer (a1), the melting point of the monomer is lowered, the handleability is improved, and the non-fluorine copolymerized. It becomes easy to mix with a monomer (namely, monomer (b) and monomer (c)).

Specific examples of the fluorine-containing monomer (a) include, for example, the following, but are not limited thereto.
CH ₂ = C (-H) -C (= O) -O- (CH ₂ ) ₂ -Rf
CH ₂ = C (-H) -C (= O) -O-C ₆ H ₄ -Rf
CH ₂ = C (-Cl) -C (= O) -O- (CH ₂ ) ₂ -Rf
CH ₂ = C (-H) -C (= O) -O- (CH ₂ ) ₂ N (-CH ₃ ) SO ₂ -Rf
CH ₂ = C (-H) -C (= O) -O- (CH ₂ ) ₂ N (-C ₂ H ₅ ) SO ₂ -Rf
CH ₂ = C (-H) -C (= O) -O-CH ₂ CH (-OH) CH ₂ -Rf

CH ₂ = C (-H) -C (= O) -O-CH ₂ CH (-OCOCH ₃ ) CH ₂ -Rf
CH ₂ = C (-H) -C (= O) -O- (CH ₂ ) ₂ -S-Rf
CH ₂ = C (-H) -C (= O) -O- (CH ₂ ) ₂ -S- (CH ₂ ) ₂ -Rf
CH ₂ = C (-H) -C (= O) -O- (CH ₂ ) ₃ -SO ₂ -Rf
CH ₂ = C (-H) -C (= O) -O- (CH ₂ ) ₂ -SO _2- (CH ₂ ) ₂ -Rf
CH ₂ = C (-H) -C (= O) -NH- (CH ₂ ) ₂ -Rf
CH ₂ = C (-CH ₃ ) -C (= O) -O- (CH ₂ ) ₂ -S-Rf
CH ₂ = C (-CH ₃ ) -C (= O) -O- (CH ₂ ) ₂ -S- (CH ₂ ) ₂ -Rf
CH ₂ = C (-CH ₃ ) -C (= O) -O- (CH ₂ ) ₃ -SO ₂ -Rf
CH ₂ = C (-CH ₃ ) -C (= O) -O- (CH ₂ ) ₂ -SO _2- (CH ₂ ) ₂ -Rf
CH ₂ = C (-CH ₃ ) -C (= O) -NH- (CH ₂ ) ₂ -Rf

CH ₂ = C (-F) -C (= O) -O- (CH ₂ ) ₂ -S-Rf
CH ₂ = C (-F) -C (= O) -O- (CH ₂ ) ₂ -S- (CH ₂ ) ₂ -Rf
CH ₂ = C (-F) -C (= O) -O- (CH ₂ ) ₂ -SO ₂ -Rf
CH ₂ = C (-F) -C (= O) -O- (CH ₂ ) ₂ -SO _2- (CH ₂ ) ₂ -Rf
CH ₂ = C (-F) -C (= O) -NH- (CH ₂ ) ₂ -Rf
CH ₂ = C (-Cl) -C (= O) -O- (CH ₂ ) ₂ -S-Rf
CH ₂ = C (-Cl) -C (= O) -O- (CH ₂ ) ₂ -S- (CH ₂ ) ₂ -Rf
CH ₂ = C (-Cl) -C (= O) -O- (CH ₂ ) ₂ -SO ₂ -Rf
CH ₂ = C (-Cl) -C (= O) -O- (CH ₂ ) ₂ -SO _2- (CH ₂ ) ₂ -Rf
CH ₂ = C (-Cl) -C (= O) -NH- (CH ₂ ) ₂ -Rf

CH ₂ = C (-CF ₃ ) -C (= O) -O- (CH ₂ ) ₂ -S-Rf
CH ₂ = C (-CF ₃ ) -C (= O) -O- (CH ₂ ) ₂ -S- (CH ₂ ) ₂ -Rf
CH ₂ = C (-CF ₃ ) -C (= O) -O- (CH ₂ ) ₂ -SO ₂ -Rf
CH ₂ = C (-CF ₃ ) -C (= O) -O- (CH ₂ ) ₂ -SO _2- (CH ₂ ) ₂ -Rf
CH ₂ = C (-CF ₃ ) -C (= O) -NH- (CH ₂ ) ₂ -Rf
CH ₂ = C (-CF ₂ H) -C (= O) -O- (CH ₂ ) ₂ -S-Rf
CH ₂ = C (-CF ₂ H) -C (= O) -O- (CH ₂ ) ₂ -S- (CH ₂ ) ₂ -Rf
CH ₂ = C (-CF ₂ H) -C (= O) -O- (CH ₂ ) ₂ -SO ₂ -Rf
CH ₂ = C (-CF ₂ H) -C (= O) -O- (CH ₂ ) ₂ -SO _2- (CH ₂ ) ₂ -Rf
CH ₂ = C (-CF ₂ H) -C (= O) -NH- (CH ₂ ) ₂ -Rf
CH ₂ = C (-CN) -C (= O) -O- (CH ₂ ) ₂ -S-Rf
CH ₂ = C (-CN) -C (= O) -O- (CH ₂ ) ₂ -S- (CH ₂ ) ₂ -Rf
CH ₂ = C (-CN) -C (= O) -O- (CH ₂ ) ₂ -SO ₂ -Rf
CH ₂ = C (-CN) -C (= O) -O- (CH ₂ ) ₂ -SO _2- (CH ₂ ) ₂ -Rf
CH ₂ = C (-CN) -C (= O) -NH- (CH ₂ ) ₂ -Rf

CH ₂ = C (-CF ₂ CF ₃ ) -C (= O) -O- (CH ₂ ) ₂ -S-Rf
CH ₂ = C (-CF ₂ CF ₃ ) -C (= O) -O- (CH ₂ ) ₂ -S- (CH ₂ ) ₂ -Rf
CH ₂ = C (-CF ₂ CF ₃ ) -C (= O) -O- (CH ₂ ) ₂ -SO ₂ -Rf
CH ₂ = C (-CF ₂ CF ₃ ) -C (= O) -O- (CH ₂ ) ₂ -SO _2- (CH ₂ ) ₂ -Rf
CH ₂ = C (-CF ₂ CF ₃ ) -C (= O) -NH- (CH ₂ ) ₂ -Rf
CH ₂ = C (-F) -C (= O) -O- (CH ₂ ) ₃ -S-Rf
CH ₂ = C (-F) -C (= O) -O- (CH ₂ ) ₃ -S- (CH ₂ ) ₂ -Rf
CH ₂ = C (-F) -C (= O) -O- (CH ₂ ) ₃ -SO ₂ -Rf
CH ₂ = C (-F) -C (= O) -O- (CH ₂ ) ₃ -SO _2- (CH ₂ ) ₂ -Rf
CH ₂ = C (-F) -C (= O) -NH- (CH ₂ ) ₃ -Rf

CH ₂ = C (-Cl) -C (= O) -O- (CH ₂ ) ₃ -S-Rf
CH ₂ = C (-Cl) -C (= O) -O- (CH ₂ ) ₃ -S- (CH ₂ ) ₂ -Rf
CH ₂ = C (-Cl) -C (= O) -O- (CH ₂ ) ₃ -SO ₂ -Rf
CH ₂ = C (-Cl) -C (= O) -O- (CH ₂ ) ₃ -SO _2- (CH ₂ ) ₂ -Rf
CH ₂ = C (-CF ₃ ) -C (= O) -O- (CH ₂ ) ₃ -S-Rf
CH ₂ = C (-CF ₃ ) -C (= O) -O- (CH ₂ ) ₃ -S- (CH ₂ ) ₂ -Rf
CH ₂ = C (-CF ₃ ) -C (= O) -O- (CH ₂ ) ₃ -SO ₂ -Rf
CH ₂ = C (-CF ₃ ) -C (= O) -O- (CH ₂ ) ₃ -SO _2- (CH ₂ ) ₂ -Rf
CH ₂ = C (-CF ₂ H) -C (= O) -O- (CH ₂ ) ₃ -S-Rf
CH ₂ = C (-CF ₂ H) -C (= O) -O- (CH ₂ ) ₃ -S- (CH ₂ ) ₂ -Rf
CH ₂ = C (-CF ₂ H) -C (= O) -O- (CH ₂ ) ₃ -SO ₂ -Rf
CH ₂ = C (-CF ₂ H) -C (= O) -O- (CH ₂ ) ₃ -SO _2- (CH ₂ ) ₂ -Rf

CH ₂ = C (-CN) -C (= O) -O- (CH ₂ ) ₃ -S-Rf
CH ₂ = C (-CN) -C (= O) -O- (CH ₂ ) ₃ -S- (CH ₂ ) ₂ -Rf
CH ₂ = C (-CN) -C (= O) -O- (CH ₂ ) ₃ -SO ₂ -Rf
CH ₂ = C (-CN) -C (= O) -O- (CH ₂ ) ₃ -SO _2- (CH ₂ ) ₂ -Rf
CH ₂ = C (-CF ₂ CF ₃ ) -C (= O) -O- (CH ₂ ) ₃ -S-Rf
CH ₂ = C (-CF ₂ CF ₃ ) -C (= O) -O- (CH ₂ ) ₃ -S- (CH ₂ ) ₂ -Rf
CH ₂ = C (-CF ₂ CF ₃ ) -C (= O) -O- (CH ₂ ) ₃ -SO ₂ -Rf
CH ₂ = C (-CF ₂ CF ₃ ) -C (= O) -O- (CH ₂ ) ₂ -SO _2- (CH ₂ ) ₂ -Rf
[In the above formula, Rf is a fluoroalkyl group having 1 to 6 carbon atoms or 12 or more carbon atoms. ]

(B) Non-fluorine non-crosslinkable monomer The non-fluorine non-crosslinkable monomer (b) is a monomer containing no fluorine atom. The non-fluorine non-crosslinkable monomer (b) does not have a crosslinkable functional group. The non-fluorine non-crosslinkable monomer (b) is non-crosslinkable unlike the crosslinkable monomer (c). The non-fluorine non-crosslinkable monomer (b) is preferably a non-fluorine monomer having a carbon-carbon double bond. The non-fluorine non-crosslinkable monomer (b) is preferably a vinyl monomer containing no fluorine. The non-fluorine non-crosslinkable monomer (b) is generally a compound having one carbon-carbon double bond.

Preferred non-fluorine non-crosslinkable monomers (b) have the formula:
CH ₂ = CA ⁰ -T
[In the formula, A ⁰ is a hydrogen atom, a methyl group, or a halogen atom other than a fluorine atom (for example, a chlorine atom, a bromine atom and an iodine atom);
T is a hydrogen atom, a chlorine atom, a chain or cyclic hydrocarbon group having 1 to 22 carbon atoms, or a chain or cyclic organic group having 1 to 22 carbon atoms having an ester bond. ]
It may be a compound shown by these.

Examples of the linear or cyclic hydrocarbon group having 1 to 22 carbon atoms include a linear or branched aliphatic hydrocarbon group having 1 to 22 carbon atoms, a cyclic aliphatic group having 4 to 22 carbon atoms, and 6 to 6 carbon atoms. 22 aromatic hydrocarbon groups and aromatic aliphatic hydrocarbon groups having 7 to 22 carbon atoms.

Examples of the linear or cyclic organic group having 1 to 22 carbon atoms having an ester bond are -C (= O) -OQ and -OC (= O) -Q (where Q is 1 to 22 carbon atoms). Straight chain or branched aliphatic hydrocarbon group, cyclic aliphatic group having 4 to 22 carbon atoms, aromatic hydrocarbon group having 6 to 22 carbon atoms, and araliphatic hydrocarbon group having 7 to 22 carbon atoms). .

Preferred examples of the non-fluorine non-crosslinkable monomer (b) include, for example, vinyl halides such as ethylene and vinyl chloride, vinylidene halides such as vinylidene chloride, vinyl acetate, acrylonitrile, styrene, and polyethylene glycol (meth) acrylate. , Polypropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, carboxylic acid vinyl ester, and vinyl alkyl ether. Carboxylic acid vinyl ester is CH ₂ ═CH—O—C (═O) R ^{0 wherein} R ⁰ is an aliphatic, aromatic, alicyclic or araliphatic hydrocarbon group having 1 to 22 carbon atoms. It is. And specific examples of the carboxylic acid vinyl ester include vinyl cyclohexanecarboxylate, vinyl benzoate, vinyl propionate, vinyl butyrate, vinyl valerate, vinyl hexanoate, and vinyl 2-ethylhexanoate. , Vinyl caprylate, vinyl decanoate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, and vinyl behenate. The non-fluorine non-crosslinkable monomer (b) is not limited to these examples.

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

The non-fluorine non-crosslinkable monomer (b) may be a (meth) acrylate monomer having a cyclic hydrocarbon group. The (meth) acrylate monomer having a cyclic hydrocarbon group is a compound having a (preferably monovalent) cyclic hydrocarbon group and a monovalent (meth) acrylate group. The monovalent cyclic hydrocarbon group and the monovalent (meth) acrylate group are directly bonded. Examples of the cyclic hydrocarbon group include saturated or unsaturated monocyclic groups, polycyclic groups, and bridged cyclic groups. The cyclic hydrocarbon group is preferably saturated. The carbon number of the cyclic hydrocarbon group is preferably 4-20. Examples of the cyclic hydrocarbon group include a cyclic aliphatic group having 4 to 20 carbon atoms, particularly 5 to 12 carbon atoms, an aromatic group having 6 to 20 carbon atoms, and an araliphatic group having 7 to 20 carbon atoms. The number of carbon atoms of the cyclic hydrocarbon group is particularly preferably 15 or less, for example 10 or less. It is preferred that the carbon atom in the ring of the cyclic hydrocarbon group is directly bonded to the ester group in the (meth) acrylate group. The cyclic hydrocarbon group is preferably a saturated cyclic aliphatic group. Specific examples of the cyclic hydrocarbon group are a cyclohexyl group, a t-butylcyclohexyl group, an isobornyl group, a dicyclopentanyl group, and a dicyclopentenyl group. The (meth) acrylate group is an acrylate group or a methacrylate group, but is preferably a methacrylate group. Specific examples of the monomer having a cyclic hydrocarbon group include cyclohexyl methacrylate, t-butylcyclohexyl methacrylate, benzyl methacrylate, isobornyl methacrylate, isobornyl acrylate, dicyclopentanyl methacrylate, dicyclopentanyl acrylate, And cyclopentenyl acrylate.

(C) Non-fluorine crosslinkable monomer The fluorine-containing polymer of the present invention may have a repeating unit derived from the non-fluorine crosslinkable monomer (c). The non-fluorine crosslinkable monomer (c) is a monomer containing no fluorine atom. The non-fluorine crosslinkable monomer (c) may be a compound having at least two reactive groups and / or carbon-carbon double bonds and not containing fluorine. The non-fluorine crosslinkable monomer (c) may be a compound having at least two carbon-carbon double bonds, or a compound having at least one carbon-carbon double bond and at least one reactive group. Examples of reactive groups are hydroxyl groups, epoxy groups, chloromethyl groups, blocked isocyanate groups, amino groups, carboxyl groups, and the like.
The non-fluorine crosslinkable monomer (c) may be mono (meth) acrylate, (meth) diacrylate or mono (meth) acrylamide having a reactive group. Alternatively, the non-fluorine crosslinkable monomer (c) may be di (meth) acrylate.
One example of the non-fluorine crosslinkable monomer (c) is a vinyl monomer having a hydroxyl group.

Examples of the non-fluorine crosslinkable monomer (c) include diacetone (meth) acrylamide, N-methylol (meth) acrylamide, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, and 3-chloro-2-hydroxy. Propyl (meth) acrylate, 2-acetoacetoxyethyl (meth) acrylate, butadiene, isoprene, chloroprene, vinyl monochloroacetate, vinyl methacrylate, glycidyl (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl Examples include glycol di (meth) acrylate, but are not limited thereto.
In the present specification, “(meth) acrylate” means acrylate or methacrylate, and “(meth) acrylamide” means acrylamide or methacrylamide.

By copolymerizing the non-fluorine non-crosslinkable monomer (b) and / or the non-fluorine crosslinkable monomer (c), water and oil repellency and antifouling properties, and cleaning resistance and washing resistance of these performances are obtained. Various properties such as solubility, solubility in solvents, hardness, and feel can be improved as necessary.

Weight of first fluorine-containing monomer (a1) and second fluorine-containing monomer (a2) in fluorine-containing monomer (a) (that is, a mixture of the first fluorine-containing compound and the second fluorine-containing compound) The ratio may be 10:90 to 90:10, for example 20:80 to 80:20, in particular 30:70 to 70:30.
In the fluorine-containing polymer, with respect to 100 parts by weight of the fluorine-containing monomer (a),
The amount of the non-fluorine non-crosslinkable monomer (b) is 1000 parts by weight or less, for example, 0.1 to 300 parts by weight, particularly 1 to 200 parts by weight,
The amount of the non-fluorine crosslinkable monomer (c) may be 50 parts by weight or less, for example, 30 parts by weight or less, particularly 0.1 to 20 parts by weight.

The number average molecular weight (Mn) of the fluoropolymer may generally be from 1,000 to 1,000,000, for example from 5,000 to 500,000, especially from 3,000 to 200,000. The number average molecular weight (Mn) of the fluoropolymer is generally measured by GPC (gel permeation chromatography).

The fluoropolymer in the present invention can be produced by any ordinary polymerization method, and the conditions for the polymerization reaction can be arbitrarily selected. Examples of such polymerization methods include solution polymerization, suspension polymerization, and emulsion polymerization.

In solution polymerization, a method is adopted in which a monomer is dissolved in an organic solvent in the presence of a polymerization initiator, and is purged with nitrogen as necessary, followed by heating and stirring in the range of 30 to 120 ° C. for 1 to 10 hours. Examples of the polymerization initiator include azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, and diisopropyl peroxydicarbonate. Can be mentioned. The polymerization initiator is used in the range of 0.01 to 20 parts by weight, for example, 0.01 to 10 parts by weight with respect to 100 parts by weight of the monomer.

Examples of the organic solvent are those which are inert to the monomer and dissolve them, such as acetone, chloroform, HCHC225, isopropyl alcohol, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, petroleum ether, Tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane, trichloro And trifluoroethane. The organic solvent is used in the range of 50 to 2000 parts by weight, for example, 50 to 1000 parts by weight with respect to 100 parts by weight of the total monomer.

In emulsion polymerization, a method is adopted in which a monomer is emulsified in water in the presence of a polymerization initiator and an emulsifier, and is purged with nitrogen if necessary, and stirred and copolymerized in the range of 50 to 80 ° C. for 1 to 10 hours. Is done. Polymerization initiators include benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidine dihydrochloride, azo Water-soluble materials such as bisisobutyronitrile, sodium peroxide, potassium persulfate, ammonium persulfate, azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide Oil-soluble ones such as t-butyl peroxypivalate and diisopropyl peroxydicarbonate are used. The polymerization initiator is used in the range of 0.01 to 10 parts by weight with respect to 100 parts by weight of the monomer.

In order to obtain an aqueous copolymer dispersion with excellent storage stability, the monomer is finely divided into water using an emulsifier that can impart strong crushing energy such as a high-pressure homogenizer or an ultrasonic homogenizer. It is desirable to polymerize using a soluble polymerization initiator. As the emulsifier, various anionic, cationic or nonionic emulsifiers can be used, and the emulsifier is used in the range of 0.5 to 20 parts by weight with respect to 100 parts by weight of the monomer. Preference is given to using anionic and / or nonionic and / or cationic emulsifiers. When the monomers are not completely compatible with each other, it is preferable to add a compatibilizing agent such as a water-soluble organic solvent or a low molecular weight monomer that is sufficiently compatible with these monomers. By adding a compatibilizing agent, it is possible to improve emulsifying properties and copolymerization properties.

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

The fluoropolymer can be used for surface treatment of various substrates such as fibers.
The fluoropolymer can be applied to a fibrous substrate (eg, a fiber product, etc.) by any of the known methods for treating a fiber product with a liquid. The concentration of the fluorosilicone reaction product in the solution applied to the textile product may be, for example, 0.5 wt% to 20 wt%, alternatively 1 wt% to 5 wt%. When the textile product is a fabric, the fabric may be immersed in the solution, or the solution may be attached or sprayed onto the fabric. The treated fiber product is dried and preferably heated at, for example, 100 ° C. to 200 ° C. in order to develop oil repellency.

Alternatively, the fluoropolymer may be applied to the fiber product by a cleaning method, and may be applied to the fiber product in, for example, a laundry application or a dry cleaning method.

The textile products to be treated are typically fabrics, which include woven, knitted and non-woven fabrics, fabrics and carpets in clothing form, but fibers or yarns or intermediate fiber products (eg sliver or It may be a roving yarn). The textile product material may be natural fibers (such as cotton or wool), chemical fibers (such as viscose rayon or rheocell), or synthetic fibers (such as polyester, polyamide or acrylic fibers), or May be a mixture of fibers, such as a mixture of natural and synthetic fibers. The production polymer of the present invention is particularly effective in making cellulosic fibers (such as cotton or rayon) oleophobic and oleophobic. The method of the present invention also generally makes the textile product hydrophobic and water repellent.

Alternatively, the fibrous base material may be leather. In order to make the production polymer hydrophobic and oleophobic, aqueous solutions or aqueous emulsifications at various stages of leather processing, for example during the wet processing of leather or during the finishing of leather You may apply it to leather from things.
Alternatively, the fibrous substrate may be paper. The production polymer may be applied to preformed paper or may be applied at various stages of papermaking, for example during the drying period of the paper.

The fluorine-containing composition of the present invention is preferably in the form of a solution, an emulsion (particularly an aqueous emulsion) or an aerosol. The fluorine-containing composition comprises a fluorine-containing polymer (active component of the surface treatment agent) and a medium (in particular, a liquid medium such as an organic solvent and / or water). The amount of the medium may be, for example, 5 to 99.9% by weight, particularly 10 to 80% by weight, based on the fluorine-containing composition.
In the fluorine-containing composition, the concentration of the fluorine-containing polymer may be 0.01 to 95% by weight, for example, 5 to 50% by weight.

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

Examples of objects to be treated with the fluorine-containing composition (for example, water and oil repellent) of the present invention include textile products, stone materials, filters (for example, electrostatic filters), dust masks, and fuel cell components (for example, gas). Diffusion electrodes and gas diffusion supports), glass, paper, wood, leather, fur, asbestos, bricks, cement, metals and oxides, ceramic products, plastics, painted surfaces, plasters and the like. Various examples can be given as textile products. For example, natural animal and vegetable fibers such as cotton, hemp, wool, and silk, synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene, semi-synthetic fibers such as rayon and acetate, glass fibers, and carbon fibers , Inorganic fibers such as asbestos fibers, or mixed fibers thereof.

The fiber product may be in the form of a fiber, cloth or the like. When the carpet is treated with the fluorine-containing composition of the present invention, the carpet may be formed after the fibers or yarns are treated with the fluorine-containing composition, or the formed carpet is treated with the fluorine-containing composition. Also good.
The fluorine-containing composition of the present invention can also be used as an internal release agent or an external release agent.

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

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these Examples.
In the following, “%” represents “% by weight” unless otherwise specified.
The test (analysis of fluoropolymer and measurement of water / oil repellency) was performed as follows.

"Water and oil repellency":
As an evaluation of water / oil repellency of the fluoropolymer, contact angle measurement was performed. That is, the fluoropolymer was made into a 1 wt% solution in HCFC-225 solvent, applied to a glass substrate by a spin coating method (2000 rpm), and then heat-treated at 75 ° C. for 3 minutes to form a film. Next, using a contact angle meter (trade name “CA-VP”) manufactured by Kyowa Interface Science Co., Ltd., the contact angle was measured at a temperature of 15 to 20 ° C. and a relative humidity of 50 to 70% according to JIS R3257.
[Static contact angle]:
Water repellency measures the static contact angle of water droplets (surface tension 72 mN / m, 2 μl), and oil repellency measures the static contact angle of n-hexadecane droplets (surface tension 27 mN / m, 2 μl, hereinafter abbreviated as HD). And evaluated. The larger the angle of static contact angle, the higher the water and oil repellency.
[Dynamic contact angle]:
Water repellency measures the dynamic contact angle of a water drop (20 μl), and oil repellency measures the dynamic contact angle of an HD drop (5 μl). As an indicator of the dynamic contact angle, a drop angle (deg), a forward contact angle, The hysteresis (deg) represented by the difference in receding contact angle was evaluated. The smaller the falling angle and hysteresis, the higher the water and oil repellency.

"Shower water repellency":
Shower water repellency was measured according to JIS-L-1092 water repellency No. (See Table 1 below).

"Water repellency test":
Store the treated test cloth in a constant temperature and humidity machine at a temperature of 21 ° C. and a humidity of 65% for 4 hours or more. A test solution (isopropyl alcohol (hereinafter abbreviated as IPA), water, and a mixture thereof, as shown in Table 2) also stored at a temperature of 21 ° C. is used. The test is performed in a constant temperature and humidity chamber at a temperature of 21 ° C. and a humidity of 65%. When 0.05 ml of the test liquid is gently dropped on the test cloth and left for 30 seconds, if the liquid remains on the test cloth, the test liquid is passed. For water repellency, the maximum IPA content (% by volume) of the passed test solution was scored, and from a poor water repellency to a good level, Fail, 0, 1, 2, 3, 4, 5, 6 , 7, 8, 9 and 10.

"Oil repellency test":
Store the treated test cloth in a constant temperature and humidity machine at a temperature of 21 ° C. and a humidity of 65% for 4 hours or more. A test solution (shown in Table 3) also stored at a temperature of 21 ° C. is used. The test is performed in a constant temperature and humidity chamber at a temperature of 21 ° C. and a humidity of 65%. When 0.05 ml is gently dropped on the test cloth and left to stand for 30 seconds, if the liquid remains on the test cloth, the test liquid is passed. The oil repellency is the highest score of the passed test solution, and evaluated from 9 grades of Fail, 1, 2, 3, 4, 5, 6, 7, and 8 from a poor oil repellency to a good level.

Example 1
To a 300 ml autoclave, CH ₂ = CH-COO- (CH ₂ ) _2- (CF ₂ ) ₁₄ F (hereinafter abbreviated as 29-FA) 7.4 g (9 mmol), CH ₂ = CH-COO- (CH ₂ ) _2- (CF ₂ ) ₁₆ F (hereinafter abbreviated as 33-FA) 0.9 g (1 mmol), 2- (perfluorohexyl) ethyl acrylate (CH ₂ = CH-COO- (CH ₂ ) _2- (CF ₂ ) ₆ F (hereinafter abbreviated as 13-FA) 4.2 g (10 mmol), HCFC225 50 g, and t-butyl peroxypivalate 0.1 g were added, and oxygen in the system was removed by nitrogen substitution. Next, the temperature was gradually raised and the polymerization reaction was carried out at 60 ° C. for 12 hours. The reaction solution cooled to room temperature was poured into a large amount of acetone to precipitate a polymer, collected by filtration, washed, and then vacuum dried to obtain a fluorinated copolymer.

Example 2
13-FA was changed to 4.3 g of 2- (perfluorohexyl) ethyl methacrylate (CH ₂ ═C (CH ₃ ) —COO— (CH ₂ ) ₂ — (CF ₂ ) ₆ F, hereinafter abbreviated as 13-FMA). Except for changing to 10 mmol), the same procedure as in Example 1 was repeated to obtain a fluorinated copolymer.
Example 3
The same as Example 1 except that 13-FA is changed to 4.5 g (10 mmol) of CH ₂ = CCl—COO— (CH ₂ ) ₂ — (CF ₂ ) ₆ F (hereinafter abbreviated as 13-FCLA). The procedure was repeated to obtain a fluorinated copolymer.

Comparative Example 1
In a 300 ml autoclave, 2- (perfluorooctyl) ethyl acrylate (CH ₂ = CH—COO— (CH ₂ ) ₂ — (CF ₂ ) ₈ F, hereinafter abbreviated as 17-FA) 10.8 g (20 mmol), HCFC225 50 g and 0.1 g of t-butyl peroxypivalate were added, and oxygen in the system was removed by nitrogen substitution. Next, the temperature was gradually raised and the polymerization reaction was carried out at 60 ° C. for 12 hours. The reaction solution cooled to room temperature was poured into a large amount of acetone to precipitate a polymer, collected by filtration, washed, and then vacuum dried to obtain a fluoropolymer.

Comparative Example 2
A fluoropolymer was obtained by repeating the same procedure as in Comparative Example 1 except that 17-FA was changed to 8.6 g (20 mmol) of 13-FMA.

Example 4
The fluorine-containing copolymer obtained in Example 1 was made into a 1% solution in HCFC225 solvent, applied to a glass substrate by a spin coating method (2000 rpm), and then heat-treated at 75 ° C. for 3 minutes to form a film. About the obtained coating film, the static contact angle and the dynamic contact angle were measured.

Example 5
Except for using the fluorine-containing copolymer obtained in Example 2, the same procedure as in Example 4 was repeated to form a film. About the obtained coating film, the static contact angle and the dynamic contact angle were measured.

Example 6
Except for using the fluorine-containing copolymer obtained in Example 3, the same procedure as in Example 4 was repeated to form a film. About the obtained coating film, the static contact angle and the dynamic contact angle were measured.

Comparative Example 3
A film was formed by repeating the same procedure as in Example 4 except that the fluoropolymer obtained in Comparative Example 1 was used. About the obtained coating film, the static contact angle and the dynamic contact angle were measured.

Comparative Example 4
A film was formed by repeating the same procedure as in Example 4 except that the fluoropolymer obtained in Comparative Example 2 was used. About the obtained coating film, the static contact angle and the dynamic contact angle were measured.
Regarding the measurement results of Examples 4 to 6 and Comparative Examples 3 to 4, the results of static contact angles are shown in Table 4, the results of dynamic contact angles of water drops are shown in Table 5, and the results of dynamic contact angles of HD drops are shown. Table 6 shows.

Example 7
In a 1 L autoclave, 29-FA 88.1 g (0.108 mol), 33-FA 10.7 g (0.012 mol), 13-FMA 51.2 g (0.118 mol), stearyl acrylate 75.0 g (0.231 mol) , 3.0 g (0.017 mol) of 3-chloro-2-hydroxypropyl methacrylate, 300 g of pure water, 80 g of tripropylene glycol, 0.45 g of acetic acid, 6 g of octadecyltrimethylammonium chloride, 9 g of polyethylene glycol lauryl ether The mixture was emulsified and dispersed with ultrasonic waves at 60 ° C. for 15 minutes. After emulsification, 1.5 g of n-dodecyl mercaptan was added, and 45 g (0.720 mol) of vinyl chloride was further injected and filled. Further, 1.12 g of 2,2′-azobis (2-amidinopropane) dihydrochloride was added and reacted for 5 hours to obtain an aqueous dispersion of a fluorinated copolymer. Finally, it was diluted with water so as to be a 20% aqueous dispersion of the fluorinated copolymer.

Example 8
The same procedure as in Example 7 was repeated except that stearyl acrylate was changed to 87.9 g (0.231 mol) of behenyl acrylate to obtain a 20% aqueous dispersion of a fluorinated copolymer.

Comparative Example 5
In a 1 L autoclave, 17-FA 150 g (0.279 mol), stearyl acrylate 75.0 g (0.231 mol), 3-chloro-2-hydroxypropyl methacrylate 3.0 g (0.017 mol), pure water 300 g, tripropylene glycol 80 g, 0.45 g of acetic acid, 6 g of octadecyltrimethylammonium chloride, and 9 g of polyethylene glycol lauryl ether were added and emulsified and dispersed with ultrasonic waves at 60 ° C. for 15 minutes with stirring. After emulsification, 1.5 g of n-dodecyl mercaptan was added, and 45 g (0.720 mol) of vinyl chloride was further injected and filled. Further, 1.12 g of 2,2′-azobis (2-amidinopropane) dihydrochloride was added and reacted for 5 hours to obtain an aqueous dispersion of a fluorinated copolymer. Finally, it was diluted with water so as to be a 20% aqueous dispersion of the fluorinated copolymer.

Comparative Example 6
The same procedure as in Comparative Example 5 was repeated except that 17-FA was changed to 150 g (0.347 mol) of 13-FMA to obtain a 20% aqueous dispersion of a fluorinated copolymer.

Example 9
1.0 g of the aqueous dispersion of the fluorine-containing copolymer obtained in Example 7 and 0.3 g of NICCA Assist V2 (MDI-based blocked isocyanate, Nikka Chemical Co., Ltd.) were diluted with 98.7 g of water, A treatment solution was obtained. A Polyester cloth (taffeta, 25 cm × 25 cm) and a T / C blended cloth (Polyester 65 / Cotton 35, Broad, 25 cm × 25 cm) are immersed in the obtained treatment liquid and squeezed with a roll to obtain a wet pickup of 40% and 60%, respectively. It was made to become. Next, the fabric was completely dried by drying at 120 ° C. for 3 minutes and further heat treating at 160 ° C. for 2 minutes. Table 7 shows the results of shower water repellency test, water repellency test, and oil repellency test on the obtained fabric. For the purpose of evaluating washing durability, the treated fabric is washed according to the AATCC method at a bath temperature of 40 ° C. in a normal condition with a washing time of 12 minutes (not including the time for rinsing), and tumbler-dried. This was set as one cycle, and the treated water repellency test, water repellency test, and oil repellency test were also performed on the treated cloths that were subjected to this cycle repeatedly. The results are shown in Table 7.

Example 10
The fabric was treated by repeating the same procedure as in Example 9 except that the aqueous dispersion of the fluorinated copolymer obtained in Example 8 was used. Table 7 shows the results of a shower water repellency test, a water repellency test, and an oil repellency test including the washing durability of the obtained fabric.

Comparative Example 7
The fabric was treated by repeating the same procedure as in Example 9 except that the aqueous dispersion of the fluorinated copolymer obtained in Comparative Example 5 was used. Table 7 shows the results of a shower water repellency test, a water repellency test, and an oil repellency test including the washing durability of the obtained fabric.

Comparative Example 8
The fabric was treated by repeating the same procedure as in Example 9 except that the aqueous dispersion of the fluorinated copolymer obtained in Comparative Example 6 was used. Table 7 shows the results of a shower water repellency test, a water repellency test, and an oil repellency test including the washing durability of the obtained fabric.

From Tables 4 to 6, it can be seen that the fluorine-containing copolymer of the present invention has high measured values of static contact angle and low measured values of falling angle and hysteresis. In particular, the small drop angle and hysteresis indicate that the environmental responsiveness to water droplets and HD droplets is small, and it can be seen that the fluorinated copolymer of the present invention is excellent in water and oil repellency. Further, from Table 7, it can be seen that the water- and oil-repellency of the fluorine-containing copolymer of the present invention is excellent also in the use of water and oil-repellent agents for fibers.

Claims (12)

1. (A)
   (A1) Formula:
   CH ₂ = C (-X ¹ ) -C (= O) -Y ¹ -Z ¹ -Rf ¹
   [Wherein, X ¹ represents a hydrogen atom, a monovalent organic group or a halogen atom,
   Y ¹ is —O— or —NH—,
   Z ¹ is a direct bond or a divalent organic group,
   Rf ¹ is a fluoroalkyl group having 1 to 6 carbon atoms. ]
   A first fluorine-containing monomer represented by formula (a2):
   CH ₂ = C (-X ² ) -C (= O) -Y ² -Z ² -Rf ²
   [Wherein X ² represents a hydrogen atom, a monovalent organic group or a halogen atom,
   Y ² is —O— or —NH—,
   Z ² is a direct bond or a divalent organic group,
   Rf ² is the number of 12 or more fluoroalkyl group having a carbon. ]
   A fluorine-containing composition comprising a fluorine-containing polymer having a repeating unit derived from a fluorine-containing monomer comprising the second fluorine-containing monomer represented by
2. In the first fluorine-containing monomer (a1) and the second fluorine-containing monomer (a2),
   X ¹ and X ² are the same or different and each represents a hydrogen atom, a linear or branched alkyl group having 1 to 21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a CFX ¹¹ X ¹² group (provided that , X ¹¹ and X ¹² are a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, substituted or non-substituted A substituted benzyl group, a substituted or unsubstituted phenyl group;
   Z ¹ and Z ² are the same or different and are a direct bond, an aliphatic group having 1 to 10 carbon atoms, an aromatic group having 6 to 18 carbon atoms, an araliphatic group or a cyclic aliphatic group,
   A group represented by the formula —R ² (R ¹ ) NSO ₂ — or a formula —R ² (R ¹ ) NCO— (wherein R ¹ is an alkyl group having 1 to 10 carbon atoms, and R ² represents carbon A straight-chain alkylene group or a branched alkylene group of 1 to 10),
   A group represented by the formula —CH ₂ CH (OR ³ ) CH ₂ — (wherein R ³ represents a hydrogen atom or an acyl group having 1 to 10 carbon atoms), or
   — (CH ₂ ) _m —SO ₂ — (CH ₂ ) _n — group or — (CH ₂ ) _m —S— (CH ₂ ) _n — group (where m is 1 to 10, n is 0 to 10, The fluorine-containing composition according to claim 1.
3. 3. The fluorine-containing composition according to claim ¹ , wherein Y ¹ and Y ² are —O— in the first fluorine-containing monomer (a1) and the second fluorine-containing monomer (a2).
4. Rf is a perfluoroalkyl group having 1 to 6 carbon atoms in the first fluorine-containing monomer (a1), and a perfluoroalkyl group having 12 or more carbon atoms in the second fluorine-containing monomer (a2). Item 4. The fluorine-containing composition according to any one of Items 1 to 3.
5. The fluorine-containing composition according to any one of claims 1 to 4, wherein the fluorine-containing polymer further comprises (b) a repeating unit derived from a non-fluorine non-crosslinkable monomer.
6. The fluorine-containing composition according to any one of claims 1 to 5, wherein the fluorine-containing polymer further has (c) a repeating unit derived from a non-fluorine crosslinkable monomer.
7. The fluorine-containing composition according to any one of claims 1 to 6, further comprising a liquid medium.
8. The fluorine-containing composition according to any one of claims 1 to 7, which is a water / oil repellent, an antifouling agent or a release agent.
9. (A1) Formula:
   CH ₂ = C (-X ¹ ) -C (= O) -Y ¹ -Z ¹ -Rf ¹
   [Wherein, X ¹ represents a hydrogen atom, a monovalent organic group or a halogen atom,
   Y ¹ is —O— or —NH—,
   Z ¹ is a direct bond or a divalent organic group,
   Rf ¹ is a fluoroalkyl group having 1 to 6 carbon atoms. ]
   A first fluorine-containing monomer represented by formula (a2):
   CH ₂ = C (-X ² ) -C (= O) -Y ² -Z ² -Rf ²
   [Wherein X ² represents a hydrogen atom, a monovalent organic group or a halogen atom,
   Y ² is —O— or —NH—,
   Z ² is a direct bond or a divalent organic group,
   Rf ² is the number of 12 or more fluoroalkyl group having a carbon. ]
   A fluorine-containing polymer comprising a repeating unit derived from a fluorine-containing monomer comprising the second fluorine-containing monomer represented by
10. (A1) Formula:
    CH ₂ = C (-X ¹ ) -C (= O) -Y ¹ -Z ¹ -Rf ¹
    [Wherein, X ¹ represents a hydrogen atom, a monovalent organic group or a halogen atom,
    Y ¹ is —O— or —NH—,
    Z ¹ is a direct bond or a divalent organic group,
    Rf ¹ is a fluoroalkyl group having 1 to 6 carbon atoms. ]
    A first fluorine-containing compound represented by:
    (A2) Formula:
    CH ₂ = C (-X ² ) -C (= O) -Y ² -Z ² -Rf ²
    [Wherein X ² represents a hydrogen atom, a monovalent organic group or a halogen atom,
    Y ² is —O— or —NH—,
    Z ² is a direct bond or a divalent organic group,
    Rf ² is the number of 12 or more fluoroalkyl group having a carbon. ]
    A mixed fluorine-containing compound with a second fluorine-containing compound represented by
11. A method for treating a substrate, comprising treating with the fluorine-containing composition according to any one of claims 1 to 8.
12. A textile product treated with the fluorine-containing composition according to any one of claims 1 to 8.