JP5397520B2 - Fluorine-containing composition and surface treatment agent - Google Patents

Description

  The present invention relates to a fluorine-containing composition and a surface treatment agent. 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. There is a demand for a water / oil repellent or antifouling agent in a polymer or copolymer composed of a fluorine-containing monomer not containing a perfluoroalkyl group having 8 or more carbon atoms. In conventional (per) fluoroalkyl esters of (meth) acrylic acid, perfluoroalkyl groups having 6 or less carbon atoms are unstable in the orientation of the perfluoroalkyl group on the surface, and are water and oil repellents and antifouling agents. Or, there is a disadvantage that sufficient performance required as a mold release agent may not be provided.

US Pat. No. 5,247,008

  One object of the present invention is to use it as a fluorine-containing monomer that gives sufficient performance required as a water / oil repellent, antifouling agent or mold release agent even for a perfluoroalkyl group having 6 or less carbon atoms. An object of the present invention is to provide a fluorine-containing compound. 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 has the formula:
CH ₂ = C (-X) -C (= O) -YZ-W-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 20 carbon atoms,
W is-(CL ¹ L ² -CL ³ L ⁴ ) _a- or-(CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a- .
(Here, at least one of L ^{1 to} L ⁴ is a chlorine atom,
At least one of the remaining L ^{1 to} L ⁴ is a hydrogen atom;
At least one of L ^{5 to} L ⁸ is a hydrocarbon group having 1 to 22 carbon atoms,
At least one remaining of L ⁵ ~L ⁸ is a fluorine atom,
a is an integer of 1 to 50. ]]
The fluorine-containing compound shown by these is provided.
Furthermore, the present invention provides a fluorine-containing polymer having a repeating unit derived from the fluorine-containing compound (fluorine-containing monomer).
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 even with a perfluoroalkyl group having 6 or less carbon atoms. 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 composed of only the fluorine-containing monomer (a) (that is, a homopolymer or a copolymer composed of two or more kinds of fluorine-containing monomers (a)), or a fluorine-containing monomer. 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 monomer (a).

(A) Fluorine- containing monomer Fluorine-containing monomer (a) has the formula:
CH ₂ = C (-X) -C (= O) -YZ-W-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 20 carbon atoms,
W is-(CL ¹ L ² -CL ³ L ⁴ ) _a- or-(CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a- .
(Here, at least one of L ^{1 to} L ⁴ is a chlorine atom,
At least one of the remaining L ^{1 to} L ⁴ is a hydrogen atom;
At least one of L ^{5 to} L ⁸ is a hydrocarbon group having 1 to 22 carbon atoms,
At least one remaining of L ⁵ ~L ⁸ is a fluorine atom,
a is an integer of 1 to 50. ]]
It is a fluorine-containing monomer shown by.

The fluorine-containing monomer (a) has the general formula:
CH ₂ = C (-X) -C (= O) -YZ-W-Rf
[Wherein, X represents a hydrogen atom, a linear or branched alkyl group having 1 to 21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX ¹ X ² group (where X ¹ and X ² is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.), A cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, 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 is 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 linear or branched fluoroalkyl group having 1 to 20 carbon atoms,
W is-(CL ¹ L ² -CL ³ L ⁴ ) _a- or-(CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a- .
(Here, at least one of L ^{1 to} L ⁴ is a chlorine atom,
At least one of the remaining L ^{1 to} L ⁴ is a hydrogen atom;
At least one of L ^{5 to} L ⁸ is a hydrocarbon group having 1 to 22 carbon atoms,
At least one remaining of L ⁵ ~L ⁸ is a fluorine atom,
a is an integer of 1 to 50. ]]
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 fluorine-containing monomer (a), X is a linear or branched alkyl group having 2 to 21 carbon atoms, fluorine atom, chlorine atom, bromine atom, iodine atom, CFX ¹ X ² group (provided that , X ¹ and X ² 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 It may be a substituted benzyl group or a substituted or unsubstituted phenyl group.
Specific examples of X include, for example, H, Me (methyl group), Cl, Br, I, F, CN, and CF ₃ .

In Z, 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 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).

The Rf group is preferably a perfluoroalkyl group. The carbon number of the Rf group is preferably 1 to 12, for example 1 to 6, particularly 4 to 6. Examples of Rf _{groups, -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 , — (CF ₂ ) ₄ CF (CF ₃ ) ₂ , —C ₈ F _{17 and the} like.

In the W group, at least one of L ^{1 to} L ⁴ (for example, 1 to 4) is a chlorine atom, and all the remaining L ^{1 to} L ⁴ (for example, 0 to 3, particularly 1 or 2). Is preferably a hydrogen atom. At least one of L ^{5 to} L ⁸ (for example, 1 to 3) is a hydrocarbon group having 1 to 22 carbon atoms, and all the remaining L ^{5 to} L ⁸ (for example, 1 to 3, especially 2). Or 3) is preferably a fluorine atom.
In the W group (L ^{5 to} L ⁸ group), the hydrocarbon group having 1 to 22 carbon atoms may be an aliphatic group, an aromatic group, an alicyclic group, or an araliphatic group. The aliphatic, aromatic, alicyclic or araliphatic hydrocarbon group is a linear or branched aliphatic group having 1 to 22 carbon atoms, an aromatic group having 6 to 22 carbon atoms, or 4 to 22 carbon atoms. Or an alicyclic group having 7 to 22 carbon atoms. Specific examples of the hydrocarbon group include an alkyl group (for example, having 1 to 6 carbon atoms) and a phenyl group.

The W group is derived from a compound having a double bond, CL ¹ L ² = CL ³ L ⁴ or CL ⁵ L ⁶ = CL ⁷ L ⁸ (L ^{1 to} L ⁸ are as defined above). It is preferable.
Specific examples of CL ¹ L ² = CL ³ L ⁴ or CL ⁵ L ⁶ = CL ⁷ L ⁸ include vinyl chloride, vinylidene chloride, CFL ⁵ = CF ₂ , CL ⁵ L ⁶ = CF ₂ (L ⁵ and L ⁶ Is a hydrocarbon group having 1 to 22 carbon atoms.
a may be an integer of 1 to 20, for example, an integer of 2 to 10.

The fluorine-containing monomer (a) has the general formula:
CH ₂ = C (−X) −C (= O) −O− (CH ₂ ) _b −W−Rf
[Wherein, X, W and Rf are as defined above,
b is an integer of 1 to 10. ]
It is preferable that it is a compound shown by these.
A preferred example of the fluorine-containing monomer (a) has the formula:
CH ₂ = C (-X) -C (= O) -O- (CH ₂ ) _b- (CHCl-CH ₂ ) _a -Rf,
CH ₂ = C (-X) -C (= O) -O- (CH ₂ ) _b- (CCl ₂ -CH ₂ ) _a -Rf,
CH ₂ = C (−X) −C (= O) −O− (CH ₂ ) _b − (CF ₂ -CFL ⁸ ) _a -Rf,
CH ₂ = C (−X) −C (= O) −O− (CH ₂ ) _b − (CFL ⁶ -CF ₂ ) _a -Rf
[Wherein, X, Rf, and a are as defined above,
L ⁶ and L ⁸ are each a hydrocarbon group having 1 to 22 carbon atoms (particularly, an alkyl group or a phenyl group),
b is an integer of 1 to 10. ]
It is a compound shown by these.

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- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf
_{CH 2 = C (-H) -C} (= O) -O-C 6 H 4 - (CL 1 L 2 -CL 3 L 4) a -Rf
CH ₂ = C (-Cl) -C (= O) -O- (CH ₂ ) _2- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf
CH ₂ = C (-H) -C (= O) -O- (CH ₂ ) ₂ N (-CH ₃ ) SO _2- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf
CH ₂ = C (-H) -C (= O) -O- (CH ₂ ) ₂ N (-C ₂ H ₅ ) SO _2- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf
CH ₂ = C (-H) -C (= O) -O-CH ₂ CH (-OH) CH _2- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf

CH ₂ = C (-H) -C (= O) -O-CH ₂ CH (-OCOCH ₃ ) CH _2- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf
CH ₂ = C (−H) −C (= O) −O− (CH ₂ ) ₂ −S- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf
CH ₂ = C (−H) −C (= O) −O− (CH ₂ ) ₂ −S− (CH ₂ ) _2- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf
CH ₂ = C (-H) -C (= O) -O- (CH ₂ ) ₃ -SO _2- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf
CH ₂ = C (−H) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ − (CH ₂ ) _2- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf
CH ₂ = C (-H) -C (= O) -NH- (CH ₂ ) _2- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf
CH ₂ = C (−CH ₃ ) −C (= O) −O− (CH ₂ ) ₂ −S- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf
CH ₂ = C (-CH ₃ ) -C (= O) -O- (CH ₂ ) ₂ -S- (CH ₂ ) _2- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf
CH ₂ = C (−CH ₃ ) −C (= O) −O− (CH ₂ ) ₃ −SO _2- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf
CH ₂ = C (-CH ₃ ) -C (= O) -O- (CH ₂ ) ₂ -SO _2- (CH ₂ ) _2- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf
CH ₂ = C (-CH ₃ ) -C (= O) -NH- (CH ₂ ) _2- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf

CH ₂ = C (−F) −C (= O) −O− (CH ₂ ) ₂ −S- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf
CH ₂ = C (−F) −C (= O) −O− (CH ₂ ) ₂ −S− (CH ₂ ) _2- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf
CH ₂ = C (−F) −C (= O) −O− (CH ₂ ) ₂ −SO _2- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf
CH ₂ = C (−F) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ − (CH ₂ ) _2- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf
CH ₂ = C (-F) -C (= O) -NH- (CH ₂ ) _2- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf
CH ₂ = C (-Cl) -C (= O) -O- (CH ₂ ) ₂ -S- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf
CH ₂ = C (-Cl) -C (= O) -O- (CH ₂ ) ₂ -S- (CH ₂ ) _2- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf
CH ₂ = C (-Cl) -C (= O) -O- (CH ₂ ) ₂ -SO _2- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf
CH ₂ = C (-Cl) -C (= O) -O- (CH ₂ ) ₂ -SO _2- (CH ₂ ) _2- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf
CH ₂ = C (-Cl) -C (= O) -NH- (CH ₂ ) _2- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf

CH ₂ = C (−CF ₃ ) −C (= O) −O− (CH ₂ ) ₂ −S- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf
CH ₂ = C (−CF ₃ ) −C (= O) −O− (CH ₂ ) ₂ −S− (CH ₂ ) _2- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf
CH ₂ = C (−CF ₃ ) −C (= O) −O− (CH ₂ ) ₂ −SO _2- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf
CH ₂ = C (−CF ₃ ) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ − (CH ₂ ) _2- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf
CH ₂ = C (-CF ₃ ) -C (= O) -NH- (CH ₂ ) _2- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf
CH ₂ = C (−CF ₂ H) −C (= O) −O− (CH ₂ ) ₂ −S- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf
CH ₂ = C (−CF ₂ H) −C (= O) −O− (CH ₂ ) ₂ −S− (CH ₂ ) _2- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf
CH ₂ = C (-CF ₂ H) -C (= O) -O- (CH ₂ ) ₂ -SO _2- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf
CH ₂ = C (-CF ₂ H) -C (= O) -O- (CH ₂ ) ₂ -SO _2- (CH ₂ ) _2- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf
CH ₂ = C (-CF ₂ H) -C (= O) -NH- (CH ₂ ) _2- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf
CH ₂ = C (−CN) −C (= O) −O− (CH ₂ ) ₂ −S- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf
CH ₂ = C (-CN) -C (= O) -O- (CH ₂ ) ₂ -S- (CH ₂ ) _2- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf
CH ₂ = C (-CN) -C (= O) -O- (CH ₂ ) ₂ -SO _2- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf
CH ₂ = C (-CN) -C (= O) -O- (CH ₂ ) ₂ -SO _2- (CH ₂ ) _2- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf
CH ₂ = C (-CN) -C (= O) -NH- (CH ₂ ) _2- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf

CH ₂ = C (−CF ₂ CF ₃ ) −C (= O) −O− (CH ₂ ) ₂ −S- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf
CH ₂ = C (−CF ₂ CF ₃ ) −C (= O) −O− (CH ₂ ) ₂ −S− (CH ₂ ) _2- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf
CH ₂ = C (−CF ₂ CF ₃ ) −C (= O) −O− (CH ₂ ) ₂ −SO _2- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf
CH ₂ = C (−CF ₂ CF ₃ ) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ − (CH ₂ ) _2- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf
CH ₂ = C (-CF ₂ CF ₃ ) -C (= O) -NH- (CH ₂ ) _2- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf
CH ₂ = C (−F) −C (= O) −O− (CH ₂ ) ₃ −S- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf
CH ₂ = C (−F) −C (= O) −O− (CH ₂ ) ₃ −S− (CH ₂ ) _2- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf
CH ₂ = C (−F) −C (= O) −O− (CH ₂ ) ₃ −SO _2- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf
CH ₂ = C (−F) −C (= O) −O− (CH ₂ ) ₃ −SO ₂ − (CH ₂ ) _2- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf
CH ₂ = C (-F) -C (= O) -NH- (CH ₂ ) _3- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf

CH ₂ = C (-Cl) -C (= O) -O- (CH ₂ ) ₃ -S- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf
CH ₂ = C (-Cl) -C (= O) -O- (CH ₂ ) ₃ -S- (CH ₂ ) _2- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf
CH ₂ = C (-Cl) -C (= O) -O- (CH ₂ ) ₃ -SO _2- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf
CH ₂ = C (-Cl) -C (= O) -O- (CH ₂ ) ₃ -SO _2- (CH ₂ ) _2- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf
CH ₂ = C (−CF ₃ ) −C (= O) −O− (CH ₂ ) ₃ −S- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf
CH ₂ = C (-CF ₃ ) -C (= O) -O- (CH ₂ ) ₃ -S- (CH ₂ ) _2- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf
CH ₂ = C (−CF ₃ ) −C (= O) −O− (CH ₂ ) ₃ −SO _2- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf
CH ₂ = C (−CF ₃ ) −C (= O) −O− (CH ₂ ) ₃ −SO ₂ − (CH ₂ ) _2- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf
CH ₂ = C (-CF ₂ H) -C (= O) -O- (CH ₂ ) ₃ -S- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf
CH ₂ = C (-CF ₂ H) -C (= O) -O- (CH ₂ ) ₃ -S- (CH ₂ ) _2- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf
CH ₂ = C (-CF ₂ H) -C (= O) -O- (CH ₂ ) ₃ -SO _2- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf
CH ₂ = C (-CF ₂ H) -C (= O) -O- (CH ₂ ) ₃ -SO _2- (CH ₂ ) _2- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf

CH ₂ = C (-CN) -C (= O) -O- (CH ₂ ) ₃ -S- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf
CH ₂ = C (-CN) -C (= O) -O- (CH ₂ ) ₃ -S- (CH ₂ ) _2- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf
CH ₂ = C (-CN) -C (= O) -O- (CH ₂ ) ₃ -SO _2- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf
CH ₂ = C (-CN) -C (= O) -O- (CH ₂ ) ₃ -SO _2- (CH ₂ ) _2- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf
CH ₂ = C (−CF ₂ CF ₃ ) −C (= O) −O− (CH ₂ ) ₃ −S- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf
CH ₂ = C (−CF ₂ CF ₃ ) −C (= O) −O− (CH ₂ ) ₃ −S− (CH ₂ ) _2- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf
CH ₂ = C (−CF ₂ CF ₃ ) −C (= O) −O− (CH ₂ ) ₃ −SO _2- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf
CH ₂ = C (−CF ₂ CF ₃ ) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ − (CH ₂ ) _2- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf

In the above specific examples, the following compounds in which (CL ¹ L ² -CL ³ L ⁴ ) is changed to (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) are also exemplified.
CH ₂ = C (−H) −C (= O) −O− (CH ₂ ) _2- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf
_{CH 2 = C (-H) -C} (= O) -O-C 6 H 4 - (CL 5 L 6 -CL 7 L 8) a -Rf
CH ₂ = C (-Cl) -C (= O) -O- (CH ₂ ) _2- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf
CH ₂ = C (-H) -C (= O) -O- (CH ₂ ) ₂ N (-CH ₃ ) SO _2- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf
CH ₂ = C (-H) -C (= O) -O- (CH ₂ ) ₂ N (-C ₂ H ₅ ) SO _2- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf
CH ₂ = C (-H) -C (= O) -O-CH ₂ CH (-OH) CH _2- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf
CH ₂ = C (-H) -C (= O) -O-CH ₂ CH (-OCOCH ₃ ) CH _2- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf
CH ₂ = C (−H) −C (= O) −O− (CH ₂ ) ₂ −S- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf
CH ₂ = C (−H) −C (= O) −O− (CH ₂ ) ₂ −S− (CH ₂ ) _2- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf
CH ₂ = C (-H) -C (= O) -O- (CH ₂ ) ₃ -SO _2- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf
CH ₂ = C (−H) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ − (CH ₂ ) _2- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf
CH ₂ = C (-H) -C (= O) -NH- (CH ₂ ) _2- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf
CH ₂ = C (−CH ₃ ) −C (= O) −O− (CH ₂ ) ₂ −S- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf
CH ₂ = C (-CH ₃ ) -C (= O) -O- (CH ₂ ) ₂ -S- (CH ₂ ) _2- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf
CH ₂ = C (-CH ₃ ) -C (= O) -O- (CH ₂ ) ₃ -SO _2- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf
CH ₂ = C (-CH ₃ ) -C (= O) -O- (CH ₂ ) ₂ -SO _2- (CH ₂ ) _2- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf
CH ₂ = C (-CH ₃ ) -C (= O) -NH- (CH ₂ ) _2- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf

CH ₂ = C (−F) −C (= O) −O− (CH ₂ ) ₂ −S- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf
CH ₂ = C (−F) −C (= O) −O− (CH ₂ ) ₂ −S− (CH ₂ ) _2- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf
CH ₂ = C (−F) −C (= O) −O− (CH ₂ ) ₂ −SO _2- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf
CH ₂ = C (−F) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ − (CH ₂ ) _2- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf
CH ₂ = C (-F) -C (= O) -NH- (CH ₂ ) _2- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf
CH ₂ = C (-Cl) -C (= O) -O- (CH ₂ ) ₂ -S- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf
CH ₂ = C (-Cl) -C (= O) -O- (CH ₂ ) ₂ -S- (CH ₂ ) _2- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf
CH ₂ = C (-Cl) -C (= O) -O- (CH ₂ ) ₂ -SO _2- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf
CH ₂ = C (-Cl) -C (= O) -O- (CH ₂ ) ₂ -SO _2- (CH ₂ ) _2- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf
CH ₂ = C (-Cl) -C (= O) -NH- (CH ₂ ) _2- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf

CH ₂ = C (−CF ₃ ) −C (= O) −O− (CH ₂ ) ₂ −S- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf
CH ₂ = C (−CF ₃ ) −C (= O) −O− (CH ₂ ) ₂ −S− (CH ₂ ) _2- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf
CH ₂ = C (−CF ₃ ) −C (= O) −O− (CH ₂ ) ₂ −SO _2- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf
CH ₂ = C (−CF ₃ ) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ − (CH ₂ ) _2- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf
CH ₂ = C (-CF ₃ ) -C (= O) -NH- (CH ₂ ) _2- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf
CH ₂ = C (−CF ₂ H) −C (= O) −O− (CH ₂ ) ₂ −S- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf
CH ₂ = C (-CF ₂ H) -C (= O) -O- (CH ₂ ) ₂ -S- (CH ₂ ) _2- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf
CH ₂ = C (−CF ₂ H) −C (= O) −O− (CH ₂ ) ₂ −SO _2- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf
CH ₂ = C (-CF ₂ H) -C (= O) -O- (CH ₂ ) ₂ -SO _2- (CH ₂ ) _2- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf
CH ₂ = C (-CF ₂ H) -C (= O) -NH- (CH ₂ ) _2- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf
CH ₂ = C (−CN) −C (= O) −O− (CH ₂ ) ₂ −S- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf
CH ₂ = C (-CN) -C (= O) -O- (CH ₂ ) ₂ -S- (CH ₂ ) _2- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf
CH ₂ = C (-CN) -C (= O) -O- (CH ₂ ) ₂ -SO _2- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf
CH ₂ = C (-CN) -C (= O) -O- (CH ₂ ) ₂ -SO _2- (CH ₂ ) _2- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf
CH ₂ = C (-CN) -C (= O) -NH- (CH ₂ ) _2- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf

CH ₂ = C (−CF ₂ CF ₃ ) −C (= O) −O− (CH ₂ ) ₂ −S- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf
CH ₂ = C (−CF ₂ CF ₃ ) −C (= O) −O− (CH ₂ ) ₂ −S− (CH ₂ ) _2- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf
CH ₂ = C (−CF ₂ CF ₃ ) −C (= O) −O− (CH ₂ ) ₂ −SO _2- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf
CH ₂ = C (−CF ₂ CF ₃ ) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ − (CH ₂ ) _2- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf
CH ₂ = C (-CF ₂ CF ₃ ) -C (= O) -NH- (CH ₂ ) _2- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf
CH ₂ = C (−F) −C (= O) −O− (CH ₂ ) ₃ −S- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf
CH ₂ = C (−F) −C (= O) −O− (CH ₂ ) ₃ −S− (CH ₂ ) _2- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf
CH ₂ = C (−F) −C (= O) −O− (CH ₂ ) ₃ −SO _2- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf
CH ₂ = C (−F) −C (= O) −O− (CH ₂ ) ₃ −SO ₂ − (CH ₂ ) _2- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf
CH ₂ = C (-F) -C (= O) -NH- (CH ₂ ) _3- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf

CH ₂ = C (-Cl) -C (= O) -O- (CH ₂ ) ₃ -S- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf
CH ₂ = C (-Cl) -C (= O) -O- (CH ₂ ) ₃ -S- (CH ₂ ) _2- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf
CH ₂ = C (-Cl) -C (= O) -O- (CH ₂ ) ₃ -SO _2- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf
CH ₂ = C (-Cl) -C (= O) -O- (CH ₂ ) ₃ -SO _2- (CH ₂ ) _2- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf
CH ₂ = C (−CF ₃ ) −C (= O) −O− (CH ₂ ) ₃ −S- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf
CH ₂ = C (−CF ₃ ) −C (= O) −O− (CH ₂ ) ₃ −S− (CH ₂ ) _2- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf
CH ₂ = C (−CF ₃ ) −C (= O) −O− (CH ₂ ) ₃ −SO _2- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf
CH ₂ = C (−CF ₃ ) −C (= O) −O− (CH ₂ ) ₃ −SO ₂ − (CH ₂ ) _2- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf
CH ₂ = C (−CF ₂ H) −C (= O) −O− (CH ₂ ) ₃ −S- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf
CH ₂ = C (-CF ₂ H) -C (= O) -O- (CH ₂ ) ₃ -S- (CH ₂ ) _2- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf
CH ₂ = C (−CF ₂ H) −C (= O) −O− (CH ₂ ) ₃ −SO _2- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf
CH ₂ = C (−CF ₂ H) −C (= O) −O− (CH ₂ ) ₃ −SO ₂ − (CH ₂ ) _2- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf

CH ₂ = C (−CN) −C (= O) −O− (CH ₂ ) ₃ −S- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf
CH ₂ = C (-CN) -C (= O) -O- (CH ₂ ) ₃ -S- (CH ₂ ) _2- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf
CH ₂ = C (-CN) -C (= O) -O- (CH ₂ ) ₃ -SO _2- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf
CH ₂ = C (−CN) −C (= O) −O− (CH ₂ ) ₃ −SO ₂ − (CH ₂ ) _2- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf
CH ₂ = C (−CF ₂ CF ₃ ) −C (= O) −O− (CH ₂ ) ₃ −S- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf
CH ₂ = C (−CF ₂ CF ₃ ) −C (= O) −O− (CH ₂ ) ₃ −S− (CH ₂ ) _2- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf
CH ₂ = C (−CF ₂ CF ₃ ) −C (= O) −O− (CH ₂ ) ₃ −SO _2- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf
CH ₂ = C (−CF ₂ CF ₃ ) −C (= O) −O− (CH ₂ ) ₂ −SO ₂ − (CH ₂ ) _2- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf
[In the above formula, Rf is a fluoroalkyl group having 1 to 20 carbon atoms,
At least one of L ^{1 to} L ⁴ is a chlorine atom;
At least one of the remaining L ^{1 to} L ⁴ is a hydrogen atom;
At least one of L ^{5 to} L ⁸ is a hydrocarbon group having 1 to 22 carbon atoms,
At least one remaining of L ⁵ ~L ⁸ is a fluorine atom,
a is an integer of 1 to 50. ]

The fluorine-containing monomer is obtained by adding ethylene for introducing a spacer group (Z group) to an iodine transfer reaction product of I-Rf and CL ¹ L ² = CL ³ L ⁴ , and further an acrylic acid compound (or It can be produced by reacting an acrylamide compound.
For example, CH ₂ = C (-H) -C (= O) -O- (CH ₂ ) _2- (CL ¹ L ² -CL ³ L ⁴ ) _a -Rf is I-Rf and CL ¹ L ² = It can be synthesized by adding ethylene to the iodine transfer reaction product of CL ³ L ⁴ followed by de-KI reaction with potassium acrylate. Similarly, CH ₂ = C (-H) -C (= O) -O- (CH ₂ ) _2- (CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a -Rf is the same for I-Rf and CL ⁵ L ⁶ = CL ⁷ L ^{8 It} can be synthesized by adding ethylene to an iodine transfer reactant and then de-KI reacting with potassium acrylate.

(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 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 linear or branched aliphatic hydrocarbon groups having 1 to 22 carbon atoms, cyclic aliphatic groups having 4 to 22 carbon atoms, and 6 to 6 carbon atoms. 22 aromatic hydrocarbon groups and C7-22 araliphatic hydrocarbon groups.

  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). A linear or branched aliphatic hydrocarbon group, a cyclic aliphatic group having 4 to 22 carbon atoms, an aromatic hydrocarbon group having 6 to 22 carbon atoms, and an 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 32 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 of the alkyl group may be 1 to 30, for example, 6 to 30 (for example, 10 to 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 cyclic hydrocarbon group preferably has 4 to 20 carbon atoms. Examples of the cyclic hydrocarbon group include C4-C20, particularly C5-C12 cyclic aliphatic groups, C6-C20 aromatic groups, and C7-C20 araliphatic groups. 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 a carbon-carbon double bond 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.

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, such as 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 1000 to 1000000, for example 5000 to 500000, in particular 3000 to 200000. 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 of dissolving a monomer in an organic solvent in the presence of a polymerization initiator, substituting with nitrogen as necessary, and heating and stirring in the range of 30 to 120 ° C. for 1 to 10 hours is employed. Examples of the polymerization initiator include azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, diisopropyl peroxydicarbonate, and the like. Can be mentioned. The polymerization initiator is used in the range of 0.01 to 20 parts by weight, for example, 0.01 to 10 parts by weight with respect to 100 parts by weight of the monomer.

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

  In emulsion polymerization, a method is adopted in which a monomer is emulsified in water in the presence of a polymerization initiator and an emulsifier, purged with nitrogen as 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, you may use in the range of 10-40 weight part. Examples of the low molecular weight monomer include methyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, etc., and 1 to 50 parts by weight with respect to 100 parts by weight of the total amount of monomers, For example, you may use in the range of 10-40 weight part.

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 textile 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 textile by a cleaning method, and may be applied to the textile by, 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 treated 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.

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

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 a water / oil repellency evaluation of a fluoropolymer, the dynamic contact angles of water droplets (surface tension 72 mN / m) and n-hexadecane droplets (surface tension 27 mN / m, hereinafter abbreviated as HD) were measured as follows. did. As an index of the dynamic contact angle, the falling angle (deg) and the hysteresis (deg) representing the difference between the advancing contact angle and the receding contact angle were measured and evaluated. That is, the fluoropolymer was made into a 1% solution in an organic solvent, applied to a glass substrate by a spin coating method (2000 rpm), and then dried to form a film. Next, using a contact angle meter (trade name “CA-VP”) manufactured by Kyowa Interface Science Co., Ltd., the dynamic contact angle of 20 μl of water drops or 5 μl of HD drops was measured. In accordance with JISR3257, the measurement is performed at a temperature of 15 to 20 ° C. and a relative humidity of 50 to 70%. The smaller the falling angle and the smaller the hysteresis, the better the water / oil repellency.

"Shower water repellency":
The water repellency of the shower is the water repellency No. JIS-L-1092 by the spray method. (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.

Synthesis example 1
40.0 g (0.090 mol) of I- (CF ₂ ) ₆ F was placed in a 300 ml autoclave, and oxygen in the system was removed by nitrogen substitution. Next, 39.4 g (0.630 mol) of vinyl chloride and 0.9 g of t-butyl peroxypivalate were added, and the temperature was gradually raised and maintained at 60 ° C. for 10 hours to conduct an iodine transfer reaction. The obtained iodine transfer reaction product was identified by gas chromatography, ¹ H-NMR, ¹⁹ F-NMR, and ¹³ C-NMR analysis.
Next, 36.9 g (0.045 mol) of the iodine transfer reaction product I- (CHCl-CH ₂ ) _6- (CF ₂ ) ₆ F (0.045 mol) obtained above was put into a 300 ml autoclave, and the oxygen in the system was replaced by nitrogen substitution. Was removed. Next, 1.9 g (0.068 mol) of ethylene and 0.7 g of t-butyl peroxypivalate were added, the temperature was gradually raised, and an iodine transfer reaction was carried out at 60 ° C. for 10 hours. The obtained iodine transfer reaction product was identified by gas chromatography, ¹ H-NMR, ¹⁹ F-NMR, and ¹³ C-NMR analysis.
Next, in a 300 ml autoclave, 50.0 g of t-butanol, 6.8 g (0.062 mol) of potassium acrylate, 0.05 g of hydroquinone, and the iodine transfer reaction product I-CH ₂ CH _2- (CHCl obtained above) -CH ₂ ) _6- (CF ₂ ) ₆ F 34.8 g (0.041 mol) was added, oxygen in the system was removed by nitrogen substitution, the temperature was gradually raised, and kept at 180 ° C. for 24 hours to remove KI. The esterification reaction with was carried out. The obtained esterification reaction product was identified by gas chromatography, ¹ H-NMR, ¹⁹ F-NMR, ¹³ C-NMR analysis, and fluorine-containing monomer CH ₂ = CH-COO-CH ₂ CH _2-. (CHCl—CH ₂ ) _6- (CF ₂ ) ₆ F was obtained.

Synthesis example 2
40.0 g (0.090 mol) of I- (CF ₂ ) ₆ F was placed in a 300 ml autoclave, and oxygen in the system was removed by nitrogen substitution. Next, 26.2 g (0.270 mol) of vinylidene chloride and 0.9 g of t-butyl peroxypivalate were added, and the temperature was gradually raised and maintained at 60 ° C. for 10 hours to conduct an iodine transfer reaction. The obtained iodine transfer reaction product was identified by gas chromatography, ¹ H-NMR, ¹⁹ F-NMR, and ¹³ C-NMR analysis.
Next, 28.8 g (0.045 mol) of the iodine transfer reaction product I- (CCl ₂ —CH ₂ ) ₂ — (CF ₂ ) ₆ F (0.045 mol) obtained above was placed in a 300 ml autoclave, and the system was replaced with nitrogen. Oxygen was removed. Next, 1.9 g (0.068 mol) of ethylene and 0.7 g of t-butyl peroxypivalate were added, the temperature was gradually raised, and an iodine transfer reaction was carried out at 60 ° C. for 10 hours. The obtained iodine transfer reaction product was identified by gas chromatography, ¹ H-NMR, ¹⁹ F-NMR, and ¹³ C-NMR analysis.
Next, in a 300 ml autoclave, 50.0 g of t-butanol, 7.7 g (0.062 mol) of potassium methacrylate, 0.05 g of hydroquinone, and the iodine transfer reaction product I-CH ₂ CH _2- (CCl obtained above) ₂ -CH ₂ ) _2- (CF ₂ ) ₆ F 27.4 g (0.041 mol) is added, oxygen in the system is removed by nitrogen substitution, the temperature is gradually raised, and the temperature is kept at 180 ° C. for 24 hours for removal. Esterification reaction with KI was performed. The obtained esterification reaction product was identified by gas chromatography, ¹ H-NMR, ¹⁹ F-NMR, ¹³ C-NMR analysis, and fluorine-containing monomer CH ₂ = C (CH ₃ ) -COO-CH. _{2 CH 2 - (CCl 2 -CH} 2) 2 - (CF 2) to give a ₆ F.

Synthesis example 3
40.0 g (0.090 mol) of I- (CF ₂ ) ₆ F was placed in a 300 ml autoclave, and oxygen in the system was removed by nitrogen substitution. Next, 99.6 g (0.630 mol) of CF ₂ = CF (C ₆ H ₅ ) (trifluorostyrene) and 0.9 g of t-butyl peroxypivalate were added, and the temperature was gradually raised. Iodine transfer reaction was carried out with keeping time. The obtained iodine transfer reaction product was identified by gas chromatography, ¹ H-NMR, ¹⁹ F-NMR, and ¹³ C-NMR analysis.
Next, 62.8 g (0.045 mol) of the iodine transfer reaction product I- (CF ₂ -CF (C ₆ H ₅ )) _6- (CF ₂ ) ₆ F obtained above was placed in a 300 ml autoclave, and nitrogen was added. The oxygen in the system was removed by substitution. Next, 1.9 g (0.068 mol) of ethylene and 0.7 g of t-butyl peroxypivalate were added, the temperature was gradually raised, and an iodine transfer reaction was carried out at 60 ° C. for 10 hours. The obtained iodine transfer reaction product was identified by gas chromatography, ¹ H-NMR, ¹⁹ F-NMR, and ¹³ C-NMR analysis.
Next, in a 300 ml autoclave, 50.0 g of t-butanol, 6.8 g (0.062 mol) of potassium acrylate, 0.05 g of hydroquinone, and the iodine transfer reaction product I—CH ₂ CH ₂ — (CF ₂ -CF (C ₆ H ₅ )) _6- (CF ₂ ) ₆ F 58.3 g (0.041 mol) was added, the oxygen in the system was removed by nitrogen substitution, the temperature was gradually raised, and the temperature was increased to 180 ° C. The esterification reaction by de-KI was carried out for 24 hours. The obtained esterification reaction product was identified by gas chromatography, ¹ H-NMR, ¹⁹ F-NMR, ¹³ C-NMR analysis, and fluorine-containing monomer CH ₂ = CH-COO-CH ₂ CH _2-. (CF ₂ -CF (C ₆ H ₅ )) _6- (CF ₂ ) ₆ F was obtained.

Example 1
To 300ml autoclave, fluorinated monomer _{CH 2 = CH-COO-CH} 2 CH 2 - (CHCl-CH 2) 6 - (CF 2) 6 F 10.0g, HCFC225 50g, t- butyl peroxypivalate 0 0.1 g was 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.

Example 2
The same procedure as in Example 1 was performed except that the fluorine-containing monomer was changed to CH ₂ = C (CH ₃ ) -COO-CH ₂ CH _2- (CHCl-CH ₂ ) _2- (CF ₂ ) ₆ F. Repeatedly, a fluoropolymer was obtained.

Example 3
The same procedure as in Example 1 was repeated except that the fluorinated monomer was changed to CH ₂ = CCl—COO—CH ₂ CH ₂ — (CHCl—CH ₂ ) ₂ — (CF ₂ ) ₆ F, and fluorinated A polymer was obtained.

Example 4
The same procedure as in Example 1 was repeated except that the fluorine-containing monomer was changed to CH ₂ = CH-COO-CH ₂ CH _2- (CHCl-CH ₂ ) _6- (CF ₂ ) ₂ F, and the fluorine-containing monomer was repeated. A polymer was obtained.

Example 5
The same procedure as in Example 1 except that the fluorine-containing monomer is changed to CH ₂ = C (CH ₃ ) -COO-CH ₂ CH _2- (CCl ₂ -CH ₂ ) _2- (CF ₂ ) ₆ F Was repeated to obtain a fluoropolymer.

Example 6
The same procedure as in Example 1 was repeated except that the fluorine-containing monomer was changed to CH ₂ = CCl—COO—CH ₂ CH ₂ — (CCl ₂ —CH ₂ ) ₂ — (CF ₂ ) ₆ F. A fluoropolymer was obtained.

Example 7
Same as Example 1 except that the fluorine-containing monomer is changed to CH ₂ = CH-COO-CH ₂ CH _2- (CF ₂ -CF (C ₆ H ₅ )) _6- (CF ₂ ) ₆ F The procedure was repeated to obtain a fluoropolymer.

Example 8
Except for changing the fluorine-containing monomer to CH ₂ = C (CH ₃ ) -COO-CH ₂ CH _2- (CF ₂ -CF (C ₆ H ₅ )) _2- (CF ₂ ) ₆ F The same procedure as in Example 1 was repeated to obtain a fluoropolymer.

Example 9
Same as Example 1 except that the fluorine-containing monomer is changed to CH ₂ = CCl—COO—CH ₂ CH ₂ — (CF ₂ —CF (C ₆ H ₅ )) ₂ — (CF ₂ ) ₆ F The procedure was repeated to obtain a fluoropolymer.

Example 10
Same as Example 1 except that the fluorine-containing monomer is changed to CH ₂ = CH-COO-CH ₂ CH _2- (CF ₂ -CF (C ₆ H ₅ )) _6- (CF ₂ ) ₂ F The procedure was repeated to obtain a fluoropolymer.

Example 11
Except for changing the fluorine-containing monomer to CH ₂ = C (CH ₃ ) -COO-CH ₂ CH _2- (CF (C ₆ H ₅ ) -CF ₂ ) _2- (CF ₂ ) ₆ F The same procedure as in Example 1 was repeated to obtain a fluoropolymer.

Example 12
Same as Example 1 except that the fluorine-containing monomer is changed to CH ₂ = CCl-COO-CH ₂ CH _2- (CF (C ₆ H ₅ ) -CF ₂ ) _2- (CF ₂ ) ₆ F The procedure was repeated to obtain a fluoropolymer.

Comparative Example 1
The fluorine-containing monomer _{CH 2 = CH-COO-CH} 2 -CH 2 - except for changing (CF ₂₎ to ₆ F, repeat the same procedure as in Example 1 to obtain a fluorine-containing polymer.

Comparative Example 2
Except for changing the fluorine-containing monomer to CH ₂ = C (CH ₃ ) —COO—CH ₂ —CH ₂ — (CF ₂ ) ₆ F, the same procedure as in Example 1 was repeated to obtain a fluorine-containing polymer. Obtained.

Example 13
The fluoropolymer obtained in Example 1 was made into a 1% solution in HCFC225 solvent, applied to a glass substrate by spin coating (2000 rpm), and then vacuum-dried at room temperature for 48 hours to form a film. Table 4 shows the results of measuring the falling angle and hysteresis of water drops, and Table 5 shows the results of measuring the falling angle and hysteresis of HD drops.

Example 14
A film was formed by repeating the same procedure as in Example 13 except that the fluoropolymer obtained in Example 2 was used. Table 4 shows the results of measuring the falling angle and hysteresis of water drops, and Table 5 shows the results of measuring the falling angle and hysteresis of HD drops.

Example 15
A film was formed by repeating the same procedure as in Example 13 except that the fluoropolymer obtained in Example 3 was used. Table 4 shows the results of measuring the falling angle and hysteresis of water drops, and Table 5 shows the results of measuring the falling angle and hysteresis of HD drops.

Example 16
A film was formed by repeating the same procedure as in Example 13 except that the fluoropolymer obtained in Example 4 was used. Table 4 shows the results of measuring the falling angle and hysteresis of water drops, and Table 5 shows the results of measuring the falling angle and hysteresis of HD drops.

Example 17
A film was formed by repeating the same procedure as in Example 13 except that the fluoropolymer obtained in Example 5 was used. Table 4 shows the results of measuring the falling angle and hysteresis of water drops, and Table 5 shows the results of measuring the falling angle and hysteresis of HD drops.

Example 18
A film was formed by repeating the same procedure as in Example 13 except that the fluoropolymer obtained in Example 6 was used. Table 4 shows the results of measuring the falling angle and hysteresis of water drops, and Table 5 shows the results of measuring the falling angle and hysteresis of HD drops.

Example 19
A film was formed by repeating the same procedure as in Example 13 except that the fluoropolymer obtained in Example 7 was used. Table 4 shows the results of measuring the falling angle and hysteresis of water drops, and Table 5 shows the results of measuring the falling angle and hysteresis of HD drops.

Example 20
A film was formed by repeating the same procedure as in Example 13 except that the fluoropolymer obtained in Example 8 was used. Table 4 shows the results of measuring the falling angle and hysteresis of water drops, and Table 5 shows the results of measuring the falling angle and hysteresis of HD drops.

Example 21
A film was formed by repeating the same procedure as in Example 13 except that the fluoropolymer obtained in Example 9 was used. Table 4 shows the results of measuring the falling angle and hysteresis of water drops, and Table 5 shows the results of measuring the falling angle and hysteresis of HD drops.

Example 22
A film was formed by repeating the same procedure as in Example 13 except that the fluoropolymer obtained in Example 10 was used. Table 4 shows the results of measuring the falling angle and hysteresis of water drops, and Table 5 shows the results of measuring the falling angle and hysteresis of HD drops.

Example 23
A film was formed by repeating the same procedure as in Example 13 except that the fluoropolymer obtained in Example 11 was used. Table 4 shows the results of measuring the falling angle and hysteresis of water drops, and Table 5 shows the results of measuring the falling angle and hysteresis of HD drops.

Example 24
A film was formed by repeating the same procedure as in Example 13 except that the fluoropolymer obtained in Example 12 was used. Table 4 shows the results of measuring the falling angle and hysteresis of water drops, and Table 5 shows the results of measuring the falling angle and hysteresis of HD drops.

Comparative Example 3
A film was formed by repeating the same procedure as in Example 13 except that the fluoropolymer obtained in Comparative Example 1 was used. Table 4 shows the results of measuring the falling angle and hysteresis of water drops, and Table 5 shows the results of measuring the falling angle and hysteresis of HD drops.

Comparative Example 4
A film was formed by repeating the same procedure as in Example 13 except that the fluoropolymer obtained in Comparative Example 2 was used. Table 4 shows the results of measuring the falling angle and hysteresis of water drops, and Table 5 shows the results of measuring the falling angle and hysteresis of HD drops.

Example 25
In 1 L autoclave, fluorine-containing monomer CH ₂ = C (CH ₃ ) —COO—CH ₂ CH ₂ — (CHCl—CH ₂ ) ₂ — (CF ₂ ) ₆ F 150 g (0.269 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, acetic acid 0.45 g, octadecyltrimethylammonium chloride 6 g, polyethylene glycol lauryl ether 9 g 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 the fluorine-containing copolymer of the present invention. Finally, it was diluted with water so as to be a 20% aqueous dispersion of the fluorinated copolymer.

Example 26
Change the fluorine-containing monomer to CH ₂ = CCl—COO—CH ₂ CH ₂ — (CCl ₂ —CH ₂ ) ₂ — (CF ₂ ) ₆ F 150 g (0.232 mol), and stearyl acrylate to behenyl acrylate Except for changing to 87.9 g (0.231 mol), the same procedure as in Example 25 was repeated to obtain a 20% aqueous dispersion of the fluorinated copolymer of the present invention.

Example 27
Change the fluorine-containing monomer to CH ₂ = C (CH ₃ ) -COO-CH ₂ CH _2- (CF ₂ -CF (C ₆ H ₅ )) _2- (CF ₂ ) ₆ F 150 g (0.200 mol) Except that, the same procedure as in Example 25 was repeated to obtain a 20% aqueous dispersion of the fluorine-containing copolymer of the present invention.

Example 28
Other than changing the fluorine-containing monomer to CH ₂ = CCl—COO—CH ₂ CH ₂ — (CF (C ₆ H ₅ ) —CF ₂ ) ₂ — (CF ₂ ) ₆ F 150 g (0.195 mol) The same procedure as in Example 25 was repeated to obtain a 20% aqueous dispersion of the fluorine-containing copolymer of the present invention.

Comparative Example 5
The fluorine-containing monomer _{CH 2 = CH-COO-CH} 2 -CH 2 - (CF 2) except for changing the ₈ F 150g _(0.279mol), repeat the same procedure as in Example 13, the fluorocopolymer A 20% aqueous dispersion of polymer was obtained.

Comparative Example 6
The same procedure as in Example 13 was repeated except that the fluorine-containing monomer was changed to 150 g (0.347 mol) of CH ₂ ═C (CH ₃ ) —COO—CH ₂ —CH ₂ — (CF ₂ ) ₆ F. A 20% aqueous dispersion of the fluorinated copolymer was obtained.

Example 29
1.0 g of the aqueous dispersion of the fluorine-containing copolymer obtained in Example 25 and 0.3 g of NICCA Assist V2 (MDI 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 6 shows the results of the shower water repellency test, the water repellency test, and the 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 6.

Example 30
The fabric was treated by repeating the same procedure as in Example 29 except that the aqueous dispersion of the fluorine-containing copolymer obtained in Example 26 was used. Table 6 shows the results of the shower water repellency test, the water repellency test, and the oil repellency test including the washing durability of the obtained fabric.

Example 31
The cloth was treated by repeating the same procedure as in Example 29 except that the aqueous dispersion of the fluorine-containing copolymer obtained in Example 27 was used. Table 6 shows the results of the shower water repellency test, the water repellency test, and the oil repellency test including the washing durability of the obtained fabric.

Example 32
The fabric was treated by repeating the same procedure as in Example 29 except that the aqueous dispersion of the fluorine-containing copolymer obtained in Example 28 was used. Table 6 shows the results of the shower water repellency test, the water repellency test, and the 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 29 except that the aqueous dispersion of the fluorinated copolymer obtained in Comparative Example 5 was used. Table 6 shows the results of the shower water repellency test, the water repellency test, and the 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 29 except that the aqueous dispersion of the fluorine-containing copolymer obtained in Comparative Example 6 was used. Table 6 shows the results of the shower water repellency test, the water repellency test, and the oil repellency test including the washing durability of the obtained fabric.

  As can be seen from Tables 4 and 5, the fluoropolymer of the present invention has low measured values for the falling angle and hysteresis. The small falling angle and hysteresis indicate that the environmental responsiveness to water droplets and HD droplets is small, indicating that the fluoropolymer of the present invention is excellent in water and oil repellency. Table 6 also shows that the water- and oil-repellency of the fluorine-containing copolymer of the present invention is excellent even in the use of water- and oil-repellent agents for fibers.

Claims (12)

(A) Formula:
CH ₂ = C (-X) -C (= O) -YZ-W-Rf
[ Wherein , X represents a hydrogen atom , a linear or branched alkyl group having 1 to 21 carbon atoms , a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX ¹ X ² group (where X ¹ and X ² is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.), A cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, A substituted or unsubstituted phenyl group ;
Y is —O— or —NH—;
Z is 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 is 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)
Rf is a perfluoroalkyl group having 1 to 20 carbon atoms,
W is-(CL ¹ L ² -CL ³ L ⁴ ) _a- or-(CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a- .
(Here, at least one of L ^{1 to} L ⁴ is a chlorine atom,
All the remaining L ^{1 to} L ⁴ are hydrogen atoms,
At least one of L ^{5 to} L ⁸ is a hydrocarbon group having 1 to 22 carbon atoms,
All the remaining L ^{5 to} L ⁸ are fluorine atoms,
a is an integer of 1 to 50. ]]
A fluorine-containing composition comprising a fluorine-containing polymer having a repeating unit derived from a fluorine-containing monomer represented by the formula: The fluorine-containing monomer (a) has the general formula:
CH ₂ = C (−X) −C (= O) −O− (CH ₂ ) _b −W−Rf
[Wherein, X represents a hydrogen atom, a linear or branched alkyl group having 1 to 21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX ¹ X ² group (where X ¹ and X ² is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.), A cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, A substituted or unsubstituted phenyl group,
Rf is a linear or branched perfluoroalkyl group having 1 to 20 carbon atoms,
W is-(CL ¹ L ² -CL ³ L ⁴ ) _a- or-(CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a- (wherein at least one of L ^{1 to} L ⁴ is A chlorine atom,
All the remaining L ^{1 to} L ⁴ are hydrogen atoms,
At least one of L ^{5 to} L ⁸ is a hydrocarbon group having 1 to 22 carbon atoms,
All the remaining L ^{5 to} L ⁸ are fluorine atoms,
a is an integer of 1 to 50. ),
b is an integer of 1 to 10. ]
The fluorine-containing composition of Claim 1 shown by these. The fluorine-containing monomer (a) has the formula:
CH ₂ = C (-X) -C (= O) -O- (CH ₂ ) _b- (CHCl-CH ₂ ) _a -Rf,
CH ₂ = C (-X) -C (= O) -O- (CH ₂ ) _b- (CCl ₂ -CH ₂ ) _a -Rf,
CH ₂ = C (−X) −C (= O) −O− (CH ₂ ) _b − (CF ₂ -CFL ⁸ ) _a -Rf,
CH ₂ = C (−X) −C (= O) −O− (CH ₂ ) _b − (CFL ⁶ -CF ₂ ) _a -Rf
[Wherein, X, Rf, and a are as defined above,
L ⁶ and L ⁸ are hydrocarbon groups having 1 to 22 carbon atoms,
b is an integer of 1 to 10. ]
The fluorine-containing composition of Claim 1 or 2 shown by these. Rf is a C1-C6 perfluoroalkyl group, The fluorine-containing composition in any one of Claims 1-3 . The fluorine-containing composition according to any one of claims 1 to 4 , wherein the fluorine-containing polymer further has (b) a repeating unit derived from a non-fluorine non-crosslinkable monomer. 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. The fluorine-containing composition according to any one of claims 1 to 6 , further comprising a liquid medium. The water and oil repellent, fluorine-containing composition according to any one of claims 1 to 7 which is an antifouling agent or a release agent. (A) Formula:
CH ₂ = C (-X) -C (= O) -YZ-W-Rf
[ Wherein , X represents a hydrogen atom , a linear or branched alkyl group having 1 to 21 carbon atoms , a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX ¹ X ² group (where X ¹ and X ² is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.), A cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, A substituted or unsubstituted phenyl group ;
Y is —O— or —NH—;
Z is 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 is 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)
Rf is a perfluoroalkyl group having 1 to 20 carbon atoms,
W is-(CL ¹ L ² -CL ³ L ⁴ ) _a- or-(CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a- .
(Here, at least one of L ^{1 to} L ⁴ is a chlorine atom,
All the remaining L ^{1 to} L ⁴ are hydrogen atoms,
At least one of L ^{5 to} L ⁸ is a hydrocarbon group having 1 to 22 carbon atoms,
All the remaining L ^{5 to} L ⁸ are fluorine atoms,
a is an integer of 1 to 50. ]]
A fluorine-containing polymer having a repeating unit derived from a fluorine-containing monomer represented by formula:
(A) Formula:
CH ₂ = C (-X) -C (= O) -YZ-W-Rf
[ Wherein , X represents a hydrogen atom , a linear or branched alkyl group having 1 to 21 carbon atoms , a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX ¹ X ² group (where X ¹ and X ² is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.), A cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, A substituted or unsubstituted phenyl group ;
Y is —O— or —NH—;
Z is 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 is 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)
Rf is a perfluoroalkyl group having 1 to 20 carbon atoms,
W is-(CL ¹ L ² -CL ³ L ⁴ ) _a- or-(CL ⁵ L ⁶ -CL ⁷ L ⁸ ) _a- .
(Here, at least one of L ^{1 to} L ⁴ is a chlorine atom,
All the remaining L ^{1 to} L ⁴ are hydrogen atoms,
At least one of L ^{5 to} L ⁸ is a hydrocarbon group having 1 to 22 carbon atoms,
All the remaining L ^{5 to} L ⁸ are fluorine atoms,
a is an integer of 1 to 50. ]]
A fluorine-containing compound represented by The method to process a base material consisting of processing with the fluorine-containing composition in any one of Claims 1-8 . A textile product treated with the fluorine-containing composition according to any one of claims 1 to 8 .