TW201321442A - Fluorine-containing composition - Google Patents

Abstract

The present invention discloses a fluorine-containing composition which contains a fluorine-containing polymer containing (a) a repeat unit derived from a first fluorine-containing monomer (a1) and a second fluorine-containing monomer (a2) represented by the following formula. The fluorine-containing composition includes the required properties as a surface treating agent, such as water/oil-repellent ability, soil resistance, mold releasing ability, adhesive to substrate, corrosion resistance, touch feeling, water resistance, oil resistance, and durabilities of those abilities. Formula: CH2=C(-X)-C(=O)-Y-Z-Rf [In the formula, X represents a hydrogen atom, a monovalent organic group or a halogen atom, Y represents -O- or -NH-, Z represents a direct bond or a divalent organic group, Rf represents a fluoroalkyl group with a carbon number of 1 to 6 in the first fluorine-containing monomer (a1), and represents a fluoroalkyl group with a carbon number of 12 or more in the second fluorine-containing monomer (a2).]

Description

Fluorine-containing composition

This invention relates to a fluorine-containing composition. The fluorine-containing composition can be used as a good surface treatment agent such as a water-repellent oil-repellent agent, an anti-fouling agent, and a release agent.

In the past, various fluorine-containing compounds have been proposed. The fluorine-containing compound has the advantages of excellent heat resistance, oxidation resistance, weather resistance and the like. The fluorine-containing compound is used as a water-repellent oil-repellent agent and an antifouling agent because the free energy of the fluorine-containing compound is low, that is, it is difficult to adhere. A processing agent for fibrous articles, leather, paper, and mineral substrates, which is a perfluoroalkyl (meth) acrylate, and an alkyl (meth) acrylate, is disclosed, for example, in the specification of U.S. Patent No. 5,247,008. An aqueous dispersion of a copolymer of a base ester and an amine alkyl ester of (meth)acrylic acid.

The stability of the surface function of the water-repellent oil-repellent agent and the antifouling agent is a polymer composed of a fluorine-containing monomer having a perfluoroalkyl group having a carbon number of 8 or more and having a surface perfluoroalkyl stability. Or the copolymer is effective.

However, in recent years, the EPA (United States Environmental Protection Agency) pointed out that a decomposition product of a fluorine-containing monomer having a perfluoroalkyl group having a carbon number of 8 or more is a compound having a high environmental burden, and it is desired to reduce the composition of the water-repellent oil. Fluoride polymer or fluorine-containing copolymer in the composition of the agent, the antifouling composition or the release agent composition The content of the fluorine-containing monomer of the perfluoroalkyl group having a carbon number of 8 or more.

On the other hand, in the conventional (per)fluoroalkyl (meth)acrylic acid, the perfluoroalkyl group having 6 or less carbon atoms has a stable orientation of the perfluoroalkyl group on the surface, and cannot be used as a water repellent. Poor performance of the oil repellency, antifouling agent or release agent required.

[Previous Technical Literature] (Patent Literature)

Patent Document 1: US Patent No. 5247008

An object of the present invention is to provide a fluorine-containing polymer, a fluorine-containing copolymer, and a fluorine-containing compound which are capable of reducing the carbon content of a constituent fluoropolymer or a fluorine-containing copolymer in a fluorine-containing composition. The content of the fluoroalkyl group of the fluorine-containing monomer, and imparts sufficient properties as required for the water- and oil-repellent agent, the antifouling agent or the release agent. Another object of the present invention is to provide a fluorine-containing composition which has properties required as a surface treatment agent, such as water repellency, antifouling property, release property, adhesion to a substrate, corrosion resistance, Touch, water resistance, oil resistance, durability of these properties.

The present invention provides a fluorine-containing compound which is a fluorine-containing compound in which a first fluorine-containing compound (a1) and a second fluorine-containing compound (a2) are mixed, wherein the first fluorine-containing compound (a1) is represented by the following formula: CH ₂ =C(-X ¹ )-C(=O)-Y ¹ -Z ¹ -Rf ¹ wherein X ¹ is a hydrogen atom, a monovalent organic group or a halogen atom, and Y ¹ is -O- or Is -NH-, Z ¹ is a direct bond or a divalent organic group, and Rf ¹ is a fluoroalkyl group having 1 to 6 carbon atoms.

The second fluorine-containing compound (a2) is represented by the following formula: CH ₂ =C(-X ² )-C(=O)-Y ² -Z ² -Rf ² wherein X ² is a hydrogen atom, The valence organic group is a halogen atom, Y ² is -O- or -NH-, Z ² is a direct bond or a divalent organic group, and Rf ² is a fluoroalkyl group having a carbon number of 12 or more.

Further, the present invention provides a fluorine-containing polymer (i.e., a fluorine-containing copolymer) having a first fluorine-containing compound (first fluorine-containing monomer) and a second fluorine-containing compound (second fluorine-containing monomer) A repeating unit derived from the mixed fluorine-containing compound (mixture of fluorine-containing monomers).

Furthermore, the present invention provides a fluorine-containing composition comprising the fluorine-containing polymer.

According to the present invention, sufficient performance as required for the water- and oil-repellent agent, the antifouling agent or the release agent can be obtained. The fluorine-containing composition has properties required as a surface treatment agent, such as good water repellency, antifouling property, release property, adhesion to a substrate, corrosion resistance, touch, water resistance, oil resistance, Durability of these properties.

In the present invention, the fluorine-containing composition can be used as a surface treatment agent (for example, a water-repellent oil-repellent agent, an anti-fouling agent, and a release agent).

The fluorine-containing composition contains a fluorine-containing polymer. The fluoropolymer has a repeating unit derived from a fluoromonomer.

In the present invention, the fluorine-containing monomer (a) is used as a monomer constituting the fluoropolymer. It is also possible to use a non-fluorine non-crosslinkable monomer (b) and/or a non-fluorine crosslinkable monomer (c) as needed.

The fluoropolymer may be a polymer formed only of the fluorine-containing monomer (a) (that is, a copolymer of the first fluorine-containing monomer (a1) and the second fluorine-containing monomer (a2)). Or a copolymer of a fluorine-containing monomer (a) and a non-fluorine non-crosslinkable monomer (b) and/or a non-fluorine-crosslinkable monomer (c).

(a) fluoromonomer

The 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 different from Rf.

The first fluorine-containing monomer (a1) and the second fluorine-containing monomer (a2) are fluorine-containing monomers represented by the following formula: CH ₂ =C(-X)-C(=O)-YZ-Rf [formula 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, and Rf is in the first fluorine-containing monomer (a1) In the middle, the fluoroalkyl group having 1 to 6 carbon atoms is a fluoroalkyl group having 12 or more carbon atoms in the second fluorine-containing monomer (a2).

In the first fluorine-containing monomer (a1) and the second fluorine-containing monomer (a2), X, Y And Z can be the same or different.

Therefore, the first fluorine-containing monomer (a1) is a compound represented by the following formula: CH ₂ =C(-X ¹ )-C(=O)-Y ¹ -Z ¹ -Rf ¹ wherein X ¹ is 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, and Rf ¹ is a fluoroalkyl group having 1 to 6 carbon atoms]

The second fluorine-containing monomer (a2) is a compound represented by the formula: CH ₂ =C(-X ² )-C(=O)-Y ² -Z ² -Rf ² wherein X ² is 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, and Rf ² is a fluoroalkyl group having a carbon number of 12 or more.

X ¹ and X ^{2 have the} same meaning as X, Y ¹ and Y ^{2 have the} same meaning as Y, and Z ¹ and Z ^{2 have the} same meaning as Z.

The fluorine-containing monomer (a) is preferably an acrylate or acrylamide represented by the following formula: CH ₂ =C(-X)-C(=O)-YZ-Rf [wherein, X is 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 (except that X ¹¹ and X ¹² are a hydrogen atom or a fluorine atom) , chlorine atom, bromine atom or iodine atom), cyano group, linear or branched fluoroalkyl group having 1 to 21 carbon atoms, substituted or unsubstituted benzyl group, substituted or unsubstituted benzene 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 aromatic aliphatic group or a cyclic aliphatic group. a radical of the formula -R ² (R ¹ )NSO ₂ - or a radical of the formula -R ² (R ¹ )NCO- (wherein R ¹ is an alkyl group having 1 to 10 carbon atoms, and R ² is a carbon number of 1 a straight-chain alkyl group of 10 or a branched alkyl group, and -CH ₂ CH(OR ³ )CH ₂ - (wherein R ³ represents a hydrogen atom or a fluorenyl group having 1 to 10 carbon atoms) ) the base shown, or -(CH ₂ ) _m -SO ₂ -(CH ₂ ) _n -yl or -(CH ₂ ) _m -S-(CH ₂ ) _n -yl (only m is 1 to 10, n is 0 to 10), and Rf is in the first fluorine-containing monomer (a1) Fluoroalkyl group having 1 to 6, the second fluorine-containing monomer (a2) is 12 or more carbon atoms of the fluoroalkyl group].

The fluorine-containing monomer (a) is an α-position of (acrylate or methacrylate) substituted with a halogen atom or the like. Thus, in the formula (1), X (i.e., X ¹ and X ² ) may be 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 (except 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 one having a carbon number of 1 to 21 or a branched fluorine Alkyl, substituted or unsubstituted benzyl, substituted or unsubstituted phenyl.

Specific examples of X include H, Me (methyl), Cl, Br, I, F, CN, and CF ₃ .

Among Z (i.e., Z ¹ and Z ² ), the aliphatic group is preferably an alkyl group (especially a carbon number of 1 to 4, for example, 1 or 2). The aromatic group, the aromatic aliphatic group or the cyclic aliphatic group may be substituted or unsubstituted.

Examples of Z (i.e., Z ¹ and Z ² ) may be: direct bonding, a linear alkyl group having 1 to 20 carbon atoms, or a branched alkyl group, for example, a formula -(CH ₂ ) _x - (wherein, x is a group represented by 1 to 10, especially 2 to 8), or a formula of -Ar-CH ₂ - (wherein, Ar is a aryl group having a substituent as required) Or a -CH ₂ CH ₂ N(R ¹ )SO ₂ - group (except that R ¹ is an alkyl group having 1 to 4 carbon atoms) or a formula -CH ₂ CH(OR ³ )CH ₂ - Wherein R ³ represents a hydrogen atom or a group represented by a fluorenyl group having 1 to 10 carbon atoms (for example, a fluorenyl group or an ethyl fluorenyl group), for example, a -CH ₂ CH(OZ ¹ )CH ₂ - group; (However, Z ¹ is a hydrogen atom or an ethyl fluorenyl group), or a group represented by the formula -Ar-CH ₂ - (wherein, Ar is a aryl group having a substituent as required), or - ( CH ₂ ) _m -SO ₂ -(CH ₂ ) _n -yl or -(CH ₂ ) _m -S-(CH ₂ ) _n -yl (except that m is 1 to 10 and n is 0 to 10).

Z (ie, 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 aromatic aliphatic group or a cyclic aliphatic group, -CH ₂ CH ₂ N(R ¹ )SO ₂ - group (except that R ¹ is an alkyl group having 1 to 4 carbon atoms) or -CH ₂ CH(OZ ¹ )CH ₂ - group (except that Z ¹ is a hydrogen atom or Is an ethane group) or -(CH ₂ ) _m -SO ₂ -(CH ₂ ) _n - group or -(CH ₂ ) _m -S-(CH ₂ ) _n - group (only, m is 1 to 10) , n is 0 to 10) is preferred. The aliphatic group is preferably an alkyl group (especially a carbon number of 1 to 4, such as 1 or 2). The aromatic group, the aromatic aliphatic group or the cyclic aliphatic group may be substituted or unsubstituted. The S group or the SO ₂ group may be directly bonded to the Rf group.

Among the first fluorine-containing monomer (a1) and the second fluorine-containing monomer (a2), the Rf group is preferably a perfluoroalkyl group.

Among the first fluorine-containing monomers (a1), the carbon number of the Rf group (i.e., Rf ¹ group) is from 1 to 6, for example, from 4 to 6. Among the first fluorine-containing monomers (a1), examples of the Rf group include -CF ₃ , -CF ₂ CF ₃ , -CF ₂ CF ₂ CF ₃ , -CF(CF ₃ ) ₂ , and 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 .

Among the second fluorine-containing monomers (a2), the carbon number of the Rf group (i.e., Rf ² group) is 12 or more, for example, 12 to 30, particularly 14 to 20. Among the second fluorine-containing monomers (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 , and C _{17 .} F ₃₅ , C ₁₈ F ₃₇ , C ₁₉ F ₃₉ , C ₂₀ F ₄₁ , C ₂₅ F ₅₁ , C ₃₀ F ₆₁ .

The second fluorinated monomer (a2) is mixed with the first fluorinated monomer (a1) to lower the melting point of the monomer, thereby improving the handleability and allowing the non-fluorinated monomer to be copolymerized (i.e., The mixing of the monomer (b) and the monomer (c) is easy.

Specific examples of the fluorine-containing monomer (a) include the following, but are not limited thereto.

CH ₂ =C(-H)-C(=O)-O-(CH ₂ ) ₂ -Rf

CH ₂ =C(-H)-C(=O)-OC ₆ H ₄ -Rf

CH ₂ =C(-Cl)-C(=O)-O-(CH ₂ ) ₂ -Rf

CH ₂ =C(-H)-C(=O)-O-(CH ₂ ) ₂ N(-CH ₃ )SO ₂ -Rf

CH ₂ =C(-H)-C(=O)-O-(CH ₂ ) ₂ N(-C ₂ H ₅ )SO ₂ -Rf

CH ₂ =C(-H)-C(=O)-O-CH ₂ CH(-OH)CH ₂ -Rf

CH ₂ =C(-H)-C(=O)-O-CH ₂ CH(-OCOCH ₃ )CH ₂ -Rf

CH ₂ =C(-H)-C(=O)-O-(CH ₂ ) ₂ -S-Rf

CH ₂ =C(-H)-C(=O)-O-(CH ₂ ) ₂ -S-(CH ₂ ) ₂ -Rf

CH ₂ =C(-H)-C(=O)-O-(CH ₂ ) ₃ -SO ₂ -Rf

CH ₂ =C(-H)-C(=O)-O-(CH ₂ ) ₂ -SO ₂ -(CH ₂ ) ₂ -Rf

CH ₂ =C(-H)-C(=O)-NH-(CH ₂ ) ₂ -Rf

CH ₂ =C(-CH ₃ )-C(=O)-O-(CH ₂ ) ₂ -S-Rf

CH ₂ =C(-CH ₃ )-C(=O)-O-(CH ₂ ) ₂ -S-(CH ₂ ) ₂ -Rf

CH ₂ =C(-CH ₃ )-C(=O)-O-(CH ₂ ) ₃ -SO ₂ -Rf

CH ₂ =C(-CH ₃ )-C(=O)-O-(CH ₂ ) ₂ -SO ₂ -(CH ₂ ) ₂ -Rf

CH ₂ =C(-CH ₃ )-C(=O)-NH-(CH ₂ ) ₂ -Rf

CH ₂ =C(-F)-C(=O)-O-(CH ₂ ) ₂ -S-Rf

CH ₂ =C(-F)-C(=O)-O-(CH ₂ ) ₂ -S-(CH ₂ ) ₂ -Rf

CH ₂ =C(-F)-C(=O)-O-(CH ₂ ) ₂ -SO ₂ -Rf

CH ₂ =C(-F)-C(=O)-O-(CH ₂ ) ₂ -SO ₂ -(CH ₂ ) ₂ -Rf

CH ₂ =C(-F)-C(=O)-NH-(CH ₂ ) ₂ -Rf

CH ₂ =C(-Cl)-C(=O)-O-(CH ₂ ) ₂ -S-Rf

CH ₂ =C(-Cl)-C(=O)-O-(CH ₂ ) ₂ -S-(CH ₂ ) ₂ -Rf

CH ₂ =C(-Cl)-C(=O)-O-(CH ₂ ) ₂ -SO ₂ -Rf

CH ₂ =C(-Cl)-C(=O)-O-(CH ₂ ) ₂ -SO ₂ -(CH ₂ ) ₂ -Rf

CH ₂ =C(-Cl)-C(=O)-NH-(CH ₂ ) ₂ -Rf

CH ₂ =C(-CF ₃ )-C(=O)-O-(CH ₂ ) ₂ -S-Rf

CH ₂ =C(-CF ₃ )-C(=O)-O-(CH ₂ ) ₂ -S-(CH ₂ ) ₂ -Rf

CH ₂ =C(-CF ₃ )-C(=O)-O-(CH ₂ ) ₂ -SO ₂ -Rf

CH ₂ =C(-CF ₃ )-C(=O)-O-(CH ₂ ) ₂ -SO ₂ -(CH ₂ ) ₂ -Rf

CH ₂ =C(-CF ₃ )-C(=O)-NH-(CH ₂ ) ₂ -Rf

CH ₂ =C(-CF ₂ H)-C(=O)-O-(CH ₂ ) ₂ -S-Rf

CH ₂ =C(-CF ₂ H)-C(=O)-O-(CH ₂ ) ₂ -S-(CH ₂ ) ₂ -Rf

CH ₂ =C(-CF ₂ H)-C(=O)-O-(CH ₂ ) ₂ -SO ₂ -Rf

CH ₂ =C(-CF ₂ H)-C(=O)-O-(CH ₂ ) ₂ -SO ₂ -(CH ₂ ) ₂ -Rf

CH ₂ =C(-CF ₂ H)-C(=O)-NH-(CH ₂ ) ₂ -Rf

CH ₂ =C(-CN)-C(=O)-O-(CH ₂ ) ₂ -S-Rf

CH ₂ =C(-CN)-C(=O)-O-(CH ₂ ) ₂ -S-(CH ₂ ) ₂ -Rf

CH ₂ =C(-CN)-C(=O)-O-(CH ₂ ) ₂ -SO ₂ -Rf

CH ₂ ==C(-CN)-C(=O)-O-(CH ₂ ) ₂ -SO ₂ -(CH ₂ ) ₂ -Rf

CH ₂ =C(-CN)-C(=O)-NH-(CH ₂ ) ₂ -Rf

CH ₂ =C(-CF ₂ CF ₃ )-C(=O)-O-(CH ₂ ) ₂ -S-Rf

CH ₂ =C(-CF ₂ CF ₃ )-C(=O)-O-(CH ₂ ) ₂ -S-(CH ₂ ) ₂ -Rf

CH ₂ =C(-CF ₂ CF ₃ )-C(=O)-O-(CH ₂ ) ₂ -SO ₂ -Rf

CH ₂ =C(-CF ₂ CF ₃ )-C(=O)-O-(CH ₂ ) ₂ -SO ₂ -(CH ₂ ) ₂ -Rf

CH ₂ =C(-CF ₂ CF ₃ )-C(=O)-NH-(CH ₂ ) ₂ -Rf

CH ₂ =C(-F)-C(=O)-O-(CH ₂ ) ₃ -S-Rf

CH ₂ =C(-F)-C(=O)-O-(CH ₂ ) ₃ -S-(CH ₂ ) ₂ -Rf

CH ₂ =C(-F)-C(=O)-O-(CH ₂ ) ₃ -SO ₂ -Rf

CH ₂ =C(-F)-C(=O)-O-(CH ₂ ) ₃ -SO ₂ -(CH ₂ ) ₂ -Rf

CH ₂ =C(-F)-C(=O)-NH-(CH ₂ ) ₃ -Rf

CH ₂ =C(-Cl)-C(=O)-O-(CH ₂ ) ₃ -S-Rf

CH ₂ =C(-Cl)-C(=O)-O-(CH ₂ ) ₃ -S-(CH ₂ ) ₂ -Rf

CH ₂ =C(-Cl)-C(=O)-O-(CH ₂ ) ₃ -SO ₂ -Rf

CH ₂ =C(-Cl)-C(=O)-O-(CH ₂ ) ₃ -SO ₂ -(CH ₂ ) ₂ -Rf

CH ₂ =C(-CF ₃ )-C(=O)-O-(CH ₂ ) ₃ -S-Rf

CH ₂ =C(-CF ₃ )-C(=O)-O-(CH ₂ ) ₃ -S-(CH ₂ ) ₂ -Rf

CH ₂ =C(-CF ₃ )-C(=O)-O-(CH ₂ ) ₃ -SO ₂ -Rf

CH ₂ =C(-CF ₃ )-C(=O)-O-(CH ₂ ) ₃ -SO ₂ -(CH ₂ ) ₂ -Rf

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

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

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

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

CH ₂ =C(-CN)-C(=O)-O-(CH ₂ ) ₃ -S-Rf

CH ₂ =C(-CN)-C(=O)-O-(CH ₂ ) ₃ -S-(CH ₂ ) ₂ -Rf

CH ₂ =C(-CN)-C(=O)-O-(CH ₂ ) ₃ -SO ₂ -Rf

CH ₂ =C(-CN)-C(=O)-O-(CH ₂ ) ₃ -SO ₂ -(CH ₂ ) ₂ -Rf

CH ₂ =C(-CF ₂ CF ₃ )-C(=O)-O-(CH ₂ ) ₃ -S-Rf

CH ₂ =C(-CF ₂ CF ₃ )-C(=O)-O-(CH ₂ ) ₃ -S-(CH ₂ ) ₂ -Rf

CH ₂ =C(-CF ₂ CF ₃ )-C(=O)-O-(CH ₂ ) ₃ -SO ₂ -Rf

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

(b) Non-fluorine non-crosslinkable monomer

The non-fluorine non-crosslinkable monomer (b) is a monomer having no fluorine atom. The non-fluorine non-crosslinkable monomer (b) has no crosslinkable functional group. The non-fluorine non-crosslinkable monomer (b) is different from the crosslinkable monomer (c) and is non-crosslinkable. The non-fluorine non-crosslinkable monomer (b) is desirably a non-fluorine monomer having a carbon-carbon double bond. The non-fluorine non-crosslinkable monomer (b) is desirably a fluorine-free ethylene monomer. The non-fluorine non-crosslinkable monomer (b) is generally a compound having one carbon-carbon double bond.

The preferred non-fluorine non-crosslinkable monomer (b) may be a compound of the formula: CH ₂ =CA ⁰ -T [wherein A ⁰ is a hydrogen atom, a methyl group, or a halogen other than a fluorine atom. An 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 ring having an ester bond. An organic group having 1 to 22 carbon atoms].

Examples of the chain-like or cyclic hydrocarbon group having 1 to 22 carbon atoms are, for example, a linear or branched aliphatic hydrocarbon group having 1 to 22 carbon atoms, a cyclic aliphatic group having 4 to 22 carbon atoms, and carbon. An aromatic hydrocarbon group of 6 to 22 and an aromatic aliphatic hydrocarbon group of 7 to 22 carbon atoms.

Examples of the organic group having a chain-bonded or cyclic carbon number of 1 to 22, for example, -C(=O)-OQ and -OC(=O)-Q (here, Q is carbon) A linear or branched aliphatic hydrocarbon group of 1 to 22, a cyclic aliphatic group having 4 to 22 carbon atoms, an aromatic hydrocarbon group having 6 to 22 carbon atoms, and an aromatic aliphatic hydrocarbon group having 7 to 22 carbon atoms).

Preferred examples of the non-fluorine non-crosslinkable monomer (b) include, for example, vinyl halide such as ethylene or vinyl chloride, vinylidene halide such as vinylidene chloride, vinyl acetate, acrylonitrile, styrene, and polyethylene glycol. (Meth) acrylate, polypropylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, vinyl carboxylate, and vinyl Alkyl ether. The vinyl carboxylate is CH ₂ =CH-OC(=O)R ⁰ [wherein R ⁰ is an aliphatic, aromatic, alicyclic or aromatic aliphatic hydrocarbon group having 1 to 22 carbon atoms] The compound shown is preferred. Specific examples of the vinyl carboxylate include vinyl cyclohexanecarboxylate, vinyl benzylate, vinyl propionate, vinyl butyrate, vinyl valerate, and vinyl hexanoate. , 2-ethylhexanoic acid vinyl ester, vinyl octanoate, vinyl decanoate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl laurate. 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 having an alkyl group. The alkyl group may have a carbon number of from 1 to 30, for example, may be from 6 to 30 (for example, from 10 to 30). For example, the non-fluorine non-crosslinkable monomer (b) is an acrylate represented by the following formula: CH ₂ = CA ¹ COOA ² [wherein, A ¹ is a hydrogen atom, a methyl group, or a fluorine atom. A halogen atom (for example, a chlorine atom, a bromine atom, and an iodine atom), and A ² is an alkyl group represented by C _n H _2n+1 (n=1 to 30). For example, it may be stearyl (meth) acrylate or phenyl (meth) acrylate.

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 cyclic hydrocarbon group (ideally a monovalent cyclic hydrocarbon group) and a monovalent (meth) acrylate group. The monovalent cyclic hydrocarbon group is directly bonded to the monovalent (meth) acrylate group. Examples of the cyclic hydrocarbon group include a saturated or unsaturated monocyclic group, a polycyclic group, a bridged ring group, and the like. The cyclic hydrocarbon group is preferably saturated. The carbon number of the cyclic hydrocarbon group is preferably from 4 to 20. Examples of the cyclic hydrocarbon group include a cyclic aliphatic group having 4 to 20 carbon atoms (especially 5 to 12), an aromatic group having 6 to 20 carbon atoms, and an aromatic aliphatic group having 7 to 20 carbon atoms. The carbon number of the cyclic hydrocarbon group is preferably 15 or less, for example, 10 or less. ring The carbon atom in the ring of the hydrocarbon group is preferably bonded directly 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 tert-butylcyclohexyl group, an isobornyl group, a dicyclopentyl group, and a dicyclopentenyl group. The (meth) acrylate group is an acrylate group or a methacrylate group, and a methacrylate group is preferred. Specific examples of the monomer having a cyclic hydrocarbon group include cyclohexyl methacrylate, t-butylcyclohexyl methacrylate, benzyl methacrylate, isobornyl methacrylate, and isobornyl acrylate. Ester, dicyclopentanyl methacrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, and the like.

(C) non-fluorine crosslinkable monomer

The fluoropolymer 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 having no fluorine atom. The non-fluorine-crosslinkable monomer (c) is a compound having at least two reactive groups and/or a carbon-carbon double bond and having no 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 the reactive group are, for example, a hydroxyl group, an epoxy group, a chloromethyl group, a blocked isocyanate group, an amine group, a carboxyl group or the like.

The non-fluorine-crosslinkable monomer (c) may be a mono(meth)acrylate having a reactive group, (meth)diacrylate or mono(meth)acrylamide. Alternatively, the non-fluorine crosslinkable monomer (c) may be a di(meth)acrylate.

One example of the non-fluorine crosslinkable monomer (c) is an ethylene monomer having a hydroxyl group.

As the non-fluorine crosslinkable monomer (c), for example, diacetone (A) can be exemplified Base) acrylamide, N-methylol (meth) acrylamide, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, 3-chloro-2-hydroxypropionate (meth) acrylate Ester, 2-ethylindenyl ethyl methacrylate, butadiene, isoprene, chloroprene, vinyl monochloroacetate, vinyl methacrylate, (meth)acrylic acid Glycidyl ester, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, etc., but 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), it is possible to improve the water repellency and the antifouling property and the cleaning resistance of such properties as needed. Various properties such as netness, washing resistance, solubility in solvents, hardness, and touch.

The weight ratio of the first fluorine-containing monomer (a1) to the second fluorine-containing monomer (a2) in the fluorine-containing monomer (a) (that is, a mixture of the first fluorine-containing compound and the second fluorine-containing compound) It can be from 10:90 to 90:10, for example from 20:80 to 80:20, especially from 30:70 to 70:30.

Among the fluoropolymers, 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, based on 100 parts by weight of the fluorine-containing monomer (a), especially The amount of the non-fluorine-crosslinkable monomer (c) is 50 parts by weight or less, for example, 30 parts by weight or less, particularly preferably 0.1 to 20 parts by weight, per 1 to 200 parts by weight.

The number average molecular weight (Mn) of the fluoropolymer is generally 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 determined by GPC (gel permeation chromatography).

The fluoropolymer in the present invention can be produced by any of the usual polymerization methods, and the conditions of the polymerization reaction can also be arbitrarily selected. As such a polymerization method, solution polymerization, suspension polymerization, and emulsion polymerization can be mentioned.

The solution polymerization is carried out by dissolving a monomer in an organic solvent in the presence of a polymerization initiator, subjecting it to nitrogen substitution as needed, and heating and stirring in the range of 30 to 120 ° C for 1 to 10 hours. Examples of the polymerization initiator include azobisisobutyronitrile, benzammonium peroxide, di-tert-butyl peroxide, lauryl peroxide, cumene hydroperoxide, and peroxypivalic acid. Third butyl ester, diisopropyl peroxydicarboxylate, and the like. The polymerization initiator is used in an amount of 0.01 to 20 parts by weight, for example, 0.01 to 10 parts by weight, per 100 parts by weight of the monomer.

As the organic solvent, those which are inert to the monomer and which dissolve the monomers include, for example, acetone, chloroform, HCHC225, isopropanol, pentane, hexane, heptane, octane, cyclohexane. , benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4-two Alkane, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene , perchloroethylene, tetrachlorodifluoroethane, trichlorotrifluoroethane, and the like. The organic solvent is used in the range of 50 to 2000 parts by weight, for example, 50 to 1000 parts by weight, based on 100 parts by weight of the total of the monomers.

The emulsion polymerization is carried out by emulsifying the monomer in water in the presence of a polymerization initiator and an emulsifier, and performing nitrogen substitution as needed, at 50 to The method of copolymerizing by stirring in the range of 80 ° C for 1 to 10 hours. The polymerization initiator can be used: benzammonium peroxide, lauroyl peroxide, tert-butyl peroxybenzylate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropenyl peroxide, ethidium peroxide Water-soluble, azobisisobutylphosphonium-dihydrochloride, azobisisobutyronitrile, sodium peroxide, potassium persulfate, ammonium persulfate, or azobisisobutyronitrile, benzammonium peroxide Oil-soluble, such as di-tert-butyl peroxide, lauryl peroxide, cumene hydroperoxide, tert-butyl peroxypivalate, diisopropyl peroxydicarboxylate. 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 dispersion of the copolymer which is excellent in stability, it is preferred to use an emulsifying device which can impart strong breaking energy, such as a high-pressure homogenizer or an ultrasonic homogenizer, to start the micro-particles in water and use oil-soluble polymerization. Polymerization. Further, as the emulsifier, various anionic, cationic or nonionic emulsifiers can be used, and the emulsifier is used in an amount of from 0.5 to 20 parts by weight based on 100 parts by weight of the monomer. It is preferred to use an anionic and/or nonionic and/or cationic emulsifier. In the case where the monomers are completely incompatible, it is preferred to add a compatibilizing agent which is sufficiently compatible with the monomers, for example, a water-soluble organic solvent or a low molecular weight monomer. Emulsifying properties and copolymerization properties can be improved by adding a compatibilizing agent.

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, etc., and 1 part by weight of water can be used. It is in the range of 50 parts by weight, for example, 10 to 40 parts by weight. Further, as a monomer having a low molecular weight, methyl methacrylate or methacrylic acid is exemplified. The water glyceride, 2,2,2-trifluoroethyl methacrylate, etc. are used in the range of 1 to 50 parts by weight, for example, 10 to 40 parts by weight, based on 100 parts by weight of the total amount of the monomers.

The fluoropolymer may be a fluoropolymer in order to surface-treat various substrates such as fibers.

Fluoropolymers can be applied to fibrous substrates (e.g., fibrous articles, etc.) by any method known for treating fibrous articles with liquids. The concentration of the fluoroquinone reaction product to be applied to the solution of the fibrous product is, for example, 0.5% by weight to 20% by weight, or 1% by weight to 5% by weight. When the fibrous product is a cloth, the cloth may be immersed in the solution, or the solution may be attached or sprayed onto the cloth. The fiber product to be treated is dried in order to exhibit oil repellency, and is preferably heated, for example, at 100 ° C to 200 ° C.

Alternatively, the fluoropolymer may be applied to the fibrous product by cleaning, for example, by a washing application or a dry cleaning method.

The fibrous product to be treated is typically a cloth, which is a cloth and a felt comprising a woven fabric, a knitted fabric, and a non-woven fabric, a garment material, but may also be a fiber, or a yarn, or an intermediate fiber product (for example, Sliver or thick yarn, etc.). The fiber material may be natural fiber (for example, cotton or wool), chemical fiber (for example, mucus or lyocell, or synthetic fiber (for example, polyester, polyfluorene). Amine or acrylic fiber, or a mixture of fibers (for example, a mixture of natural fibers and synthetic fibers, etc.). The production of the polymer of the present invention is particularly effective in making oleophobicity and oil repellency of cellulose-based fibers (e.g., cotton or enamel). Further, in the method of the present invention, the fibrous product is generally made hydrophobic and water repellency.

Alternatively, the fibrous substrate may be leather. In order to make the leather hydrophobic and oleophobic, an aqueous solution or an aqueous emulsion of the polymer can be applied to the leather at various stages of leather processing, for example, during wet processing of the leather, or during modification of the leather.

Alternatively, the fibrous substrate may also be paper. The manufactured polymer can be applied to pre-formed paper or applied at various stages of papermaking, such as during drying of the paper.

The fluorine-containing composition of the present invention is preferably in the form of a solution, a latex (especially an aqueous latex) or an aerosol. The fluorine-containing composition is a fluoropolymer (active ingredient of a surface treatment agent) and a medium (especially a liquid medium such as an organic solvent and/or water). The amount of the medium is, for example, from 5 to 99.9% by weight, particularly preferably from 10 to 80% by weight, based on the fluorine-containing composition.

Among the fluorine-containing compositions, the concentration of the fluoropolymer may be from 0.01 to 95% by weight, for example from 5 to 50% by weight.

The fluorine-containing composition of the present invention can be applied to a workpiece by a conventionally known method. Usually, the fluorine-containing composition is dispersed and diluted in an organic solvent or water, and adhered to the surface of the object to be treated and dried by a known method such as dip coating, spray coating, or foam coating. Further, if necessary, it can be applied together with a suitable crosslinking agent and hardened. Further, in the fluorine-containing composition of the present invention, an insecticide, a softener, an antibacterial agent, a flame retardant, an antistatic agent, a paint fixing agent, an anti-wrinkle agent or the like may be used in combination. Fluoropolymer in the treatment liquid in contact with the substrate The concentration may be from 0.01 to 10% by weight (especially in the case of dip coating), for example from 0.05 to 10% by weight.

Examples of the object to be treated which is treated with the fluorine-containing composition (for example, water-repellent oil-repellent agent) of the present invention include fiber products, stone materials, filters (for example, electrostatic filters), dust covers, and fuel cells. Components (for example, gas diffusion electrodes and gas diffusion supports), glass, paper, wood, leather, fur, asbestos, brick, cement, metal and oxide, kiln products, plastics, coated surfaces, and plaster. As the fiber product, various examples can be cited. For example, it may be exemplified by: animal or plant natural fibers such as cotton, hemp, wool, silk; synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, polypropylene; Semi-synthetic fibers; inorganic fibers such as glass fibers, carbon fibers, and asbestos fibers, or such mixed fibers.

The fibrous product may be in any form such as fiber or cloth. When the felt is treated using the fluorine-containing composition of the present invention, the fiber or the yarn may be treated with a fluorine-containing composition to form a felt, or the formed felt may be treated with a fluorine-containing composition.

The fluorine-containing composition of the present invention can be used as an internal release agent or an external release agent.

The "treatment" means that the treatment agent is applied to the workpiece by dipping, spraying, coating, or the like. By treatment, the fluoropolymer of the active ingredient of the treatment agent penetrates into the interior of the object to be treated and/or adheres to the surface of the object to be treated.

[Examples]

Hereinafter, the present invention will be described in detail by way of examples, but the invention is not limited by the examples.

In the following, unless otherwise specified, % means weight%.

The test (analysis of the fluoropolymer and measurement of the water repellency) was carried out by the following method.

"Water and oil":

As an evaluation of the water repellency of the fluoropolymer, the contact angle measurement was carried out. Namely, the fluoropolymer was formed into a 1 wt% solution in a solvent of HCFC-225, and coated on 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, a contact angle meter (trade name "CA-VP") manufactured by Kyowa Interface Science Co., Ltd. was used, and a contact angle of 15 to 20 ° C and a relative humidity of 50 to 70% was measured in accordance with JIS R 3257.

[Static contact angle]:

The water repellency is a static contact angle for measuring water droplets (surface tension: 72 mN/m, 2 μl), and the oil repellency is a static contact angle for measuring n-hexadecane droplets (surface tension: 27 mN/m, 2 μl, hereinafter, referred to as HD). Evaluation. The static contact angle is high in the angle of the water.

[Dynamic contact angle]:

The water repellency is the dynamic contact angle of the water droplets (20 μl). The oil repellency is the dynamic contact angle of the HD droplets (5 μl). As the index of the dynamic contact angle, the gliding angle (deg), and the advancing contact angle and the receding contact angle are evaluated. The hysteresis (deg) shown by the difference. The slip angle and the small lag are high in water repellency.

"spray water":

The spray water repellency is by the spray method of JIS-L-1092, and the water repellency No. Indicates (refer to Table 1 below).

"Water repellency test":

The treated test cloth was stored in a constant temperature and humidity machine at a temperature of 21 ° C and a humidity of 65% for 4 hours or more. The test solution (isopropyl alcohol (hereinafter abbreviated as IPA), water, and a mixture thereof, as shown in Table 2) was used at a temperature of 21 ° C. The test was carried out in a constant temperature and humidity chamber at a temperature of 21 ° C and a humidity of 65%. The test solution was gently dropped on the test cloth by 0.05 ml, and after standing for 30 seconds, if the liquid droplet remained on the test cloth, the test liquid was regarded as "qualified". The water repellency is the maximum of the IPA content (% by volume) of the qualified test liquid as the number of points, from the poor water repellency to the good level, to fail (Fail), 0, 1, 2, 3, 4, The 12 stages of 5, 6, 7, 8, 9 and 10 were evaluated.

"oil oil test":

The treated test cloth was stored in a constant temperature and humidity machine at a temperature of 21 ° C and a humidity of 65% for 4 hours or more. The test solution (shown in Table 3) was used at a temperature of 21 ° C. The test was carried out in a constant temperature and humidity chamber at a temperature of 21 ° C and a humidity of 65%. Gently dropping 0.05 ml on the test cloth and leaving it on the test cloth after leaving for 30 seconds, the test liquid was regarded as "qualified". The oil repellency is set to the highest point of the qualified test liquid, and the oil repellency is poor. To the good level, the nine stages of Fail, 1, 2, 3, 4, 5, 6, 7, and 8 are evaluated.

Example 1

In 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) was placed. 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 tert-butyl peroxypivalate 0.1 g, and the oxygen in the system was removed by nitrogen replacement. Next, the temperature was gradually raised, and polymerization was carried out at 60 ° C for 12 hours. The reaction liquid cooled to room temperature was poured into a large amount of acetone to precipitate a polymer, which was filtered, washed, and dried under vacuum to obtain a fluorinated copolymer.

Example 2

In addition to changing 13-FA to 2-(perfluorohexyl)ethyl methacrylate (CH ₂ =C(CH ₃ )-COO-(CH ₂ ) ₂ -(CF ₂ ) ₆ F, hereinafter, abbreviated as 13-FMA The same operation as in Example 1 was repeated except for 4.3 g (10 mmol) to obtain a fluorine-containing copolymer.

Example 3

The same procedure as in Example 1 was repeated except that 13-FA was changed to CH ₂ =CCl-COO-(CH ₂ ) ₂ -(CF ₂ ) ₆ F (hereinafter, abbreviated as 13-FCLA) 4.5 g (10 mmol). Operation gives a fluorine-containing copolymer.

Comparative example 1

In a 300 ml autoclave, 2-0.8% (perfluorooctyl)ethyl acrylate (CH ₂ =CH-COO-(CH ₂ ) ₂ -(CF ₂ ) ₈ F, hereinafter referred to as 17-FA) was placed in an amount of 10.8 g ( 20 mmol), HCFC225 50 g, and tert-butyl peroxypivalate 0.1 g, the oxygen in the system was removed by nitrogen replacement. Next, the temperature was slowly raised, and polymerization was carried out at 60 ° C for 12 hours. The reaction liquid cooled to room temperature was poured into a large amount of acetone to precipitate a polymer, which was filtered, washed, and dried under vacuum to obtain a fluoropolymer.

Comparative example 2

The same procedure as in Comparative Example 1 was repeated except that 17-FA was changed to 13-FMA 8.6 g (20 mmol) to obtain a fluoropolymer.

Example 4

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

Example 5

The same operation as in Example 4 was repeated except that the fluorinated copolymer obtained in Example 2 was used, and a film was formed. Regarding the obtained coating film, the static contact angle and the dynamic contact angle were measured.

Example 6

The same operation as in Example 4 was repeated except that the fluorinated copolymer obtained in Example 3 was used, and a film was formed. Regarding the obtained coating film, the static contact angle and the dynamic contact angle were measured.

Comparative example 3

The same operation as in Example 4 was repeated except that the fluoropolymer obtained in Comparative Example 1 was used, and a film was formed. Regarding the obtained coating film, the static contact angle and the dynamic contact angle were measured.

Comparative example 4

The same operation as in Example 4 was repeated except that the fluoropolymer obtained in Comparative Example 2 was used, and a film was formed. Regarding the obtained coating film, the static contact angle and the dynamic contact angle were measured.

With respect to the measurement results of Examples 4 to 6 and Comparative Examples 3 to 4, the results of the static contact angle are shown in Table 4, and the results of the dynamic contact angle of the water drop are shown in Table 5, and the dynamic contact angle of the HD drop is The results are shown in Table 6.

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), and stearyl acrylate 75.0 g (0.231 mol) were placed. 3-Chloro-2-hydroxypropyl methacrylate 3.0 g (0.017 mol), 300 g of pure water, 80 g of tripropylene glycol, 0.45 g of acetic acid, 6 g of octadecyltrimethylammonium chloride, polyethylene glycol lauryl ether 9 g was dispersed by ultrasonic wave emulsification at 60 ° C for 15 minutes with stirring. After the emulsification, 1.5 g of n-dodecyl mercaptan was added, and further, 45 g (0.720 mol) of vinyl chloride was charged. Further, 1.12 g of 2,2'-azobis(2-methylamidinopropane) 2 hydrochloride was added, and the mixture was reacted for 5 hours to obtain an aqueous dispersion of a fluorinated copolymer. Finally, it was diluted with water to become a 20% aqueous dispersion of the fluorocopolymer.

Example 8

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

Comparative Example 5

In a 1 L autoclave, 17-FA 150 g (0.279 mol), styrene acrylate 75.0 g (0.231 mol), 3-chloro-2-hydroxypropyl methacrylate 3.0 g (0.017 mol), and pure water were placed. 300 g, 80 g of tripropylene glycol, 0.45 g of acetic acid, 6 g of octadecyltrimethylammonium chloride, and 9 g of polyethylene glycol lauryl ether were emulsified and dispersed by ultrasonic wave at 60 ° C for 15 minutes. After the emulsification, 1.5 g of n-dodecyl mercaptan was added, and further, 45 g (0.720 mol) of vinyl chloride was charged. Further, 1.12 g of 2,2'-azobis(2-methylamidinopropane) 2 hydrochloride was added, and the mixture was reacted for 5 hours to obtain an aqueous dispersion of a fluorinated copolymer. Finally, it was diluted with water to become a 20% aqueous dispersion of the fluorocopolymer.

Comparative Example 6

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

Example 9

1.0 g of an aqueous dispersion of the fluorinated copolymer obtained in Example 7 and 0.3 g of NICCA Assist V2 (MDI-based blocked isocyanate, Nisshin Chemical Co., Ltd.) were diluted with 98.7 g of water to obtain a treatment liquid. Dipping a polyester cloth (taffeta, 25 cm × 25 cm) and a T/C blended cloth (polyester 65 / cotton 35, Broad, 25 cm × 25 cm) in the obtained treatment liquid, and twisting with a drum The wet pickup ratio was 40% and 60%, respectively. Next, the treatment of the cloth was completed by drying at 120 ° C for 3 minutes and further heat treatment at 160 ° C for 2 minutes. Regarding the obtained cloth, the results of the spray water test, the water repellency test, and the oil repellency test are shown in Table 7. Still, to assess the durability of washing The treated cloth is washed under the normal conditions of a bath temperature of 40 ° C and a washing time of 12 minutes (excluding the time of washing, etc.) under the normal conditions of the AATCC method, and the drum is dried, and this is regarded as one cycle. For the treatment cloth that repeats this cycle, the spray water test, the water repellency test, and the oil repellency test are also performed. The results are shown in Table 7.

Example 10

The cloth was treated in the same manner as in Example 9 except that the aqueous dispersion of the fluorinated copolymer obtained in Example 8 was used. Regarding the obtained cloth, the results of the shower water repellency test, the water repellency test, and the oil repellency test including the washing durability are shown in Table 7.

Comparative Example 7

The cloth was treated in the same manner as in Example 9 except that the aqueous dispersion of the fluorinated copolymer obtained in Comparative Example 5 was used. Regarding the obtained cloth, the results of the shower water repellency test, the water repellency test, and the oil repellency test including the washing durability are shown in Table 7.

Comparative Example 8

The cloth was treated in the same manner as in Example 9 except that the aqueous dispersion of the fluorinated copolymer obtained in Comparative Example 6 was used. Regarding the obtained cloth, the results of the shower water repellency test, the water repellency test, and the oil repellency test including the washing durability are shown in Table 7.

As is apparent from Tables 4 to 6, the fluorine-containing copolymer of the present invention has a high measured value of the static contact angle and a low measured value of the slip angle and hysteresis. In particular, the sliding angle and the hysteresis were small, indicating that the environmental correspondence between the water droplets and the HD droplets was small, and it was found that the fluorine-containing copolymer of the present invention is excellent in water repellency and oil repellency. Further, as is clear from Table 7, the use of the water-repellent and oil-repellent agent of the fiber is also excellent in the water-repellent property of the fluorine-containing copolymer of the present invention.

Claims (12)

A fluorine-containing composition comprising a fluorine-containing polymer having a repeating unit derived from a fluorine-containing monomer (a), the fluorine-containing monomer (a) comprising: (a1) The first fluorine-containing monomer is shown: CH ₂ =C(-X ¹ )-C(=O)-Y ¹ -Z ¹ -Rf ¹ wherein X ¹ is a hydrogen atom, a monovalent organic group or a halogen An 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, and (a2) is represented by the following formula The second fluorine-containing monomer: CH ₂ =C(-X ² )-C(=O)-Y ² -Z ² -Rf ² wherein X ² is 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, and Rf ² is a fluoroalkyl group having a carbon number of 12 or more. The fluorine-containing composition according to claim 1, wherein X ¹ and X ² are the same or different in the first fluorine-containing monomer (a1) and the second fluorine-containing monomer (a2). , which means: 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, and a CFX ¹¹ X ¹² group (only, 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, a substituted or unsubstituted benzyl group, a substituted or not Substituted phenyl; Z ¹ and Z ² are the same or different, meaning: direct bonding, aliphatic group having 1 to 10 carbon atoms, aromatic group having 6 to 18 carbon atoms, aromatic aliphatic group or ring An aliphatic group, a formula -R ² (R ¹ )NSO ₂ - or a group represented by the formula -R ² (R ¹ )NCO- (wherein R ¹ is an alkyl group having 1 to 10 carbon atoms, R ² Is a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group, and -CH ₂ CH(OR ³ )CH ₂ - (wherein R ³ represents a hydrogen atom or a carbon number of 1 to 10) a group represented by a fluorenyl group, or a -(CH ₂ ) _m -SO ₂ -(CH ₂ ) _n - group or a -(CH ₂ ) _m -S-(CH ₂ ) _n - group (only, m Is 1 to 10 n is 0 to 10). The fluorine-containing composition according to claim 1 or 2, wherein among the first fluorine-containing monomer (a1) and the second fluorine-containing monomer (a2), Y ¹ and Y ² are -O -. The fluorine-containing composition according to any one of claims 1 to 3, wherein, in the first fluorine-containing monomer (a1), Rf is a perfluoroalkyl group having 1 to 6 carbon atoms. Among the 2 fluorine-containing monomers (a2), a perfluoroalkyl group having 12 or more carbon atoms. The fluorine-containing composition according to any one of claims 1 to 4, wherein the fluoropolymer further comprises a repeating unit derived from (b) a non-fluorine non-crosslinkable monomer. The fluorine-containing composition according to any one of claims 1 to 5, wherein the fluoropolymer further comprises a repeating unit derived from (c) a non-fluorine crosslinkable monomer. The fluorine-containing composition as described in any one of claims 1 to 6 a substance that contains a liquid medium. The fluorine-containing composition according to any one of claims 1 to 7, which is a water-repellent oil-repellent agent, an antifouling agent or a release agent. A fluoropolymer having a repeating unit derived from a fluorine-containing monomer, the fluorine-containing monomer comprising: (a1) a first fluorine-containing monomer represented by the following formula: CH ₂ =C(-X ¹ )-C(=O)-Y ¹ -Z ¹ -Rf ¹ wherein X ¹ is a hydrogen atom, a monovalent organic group or a halogen atom, Y ¹ is -O- or -NH-, and Z ¹ is a direct bond or a divalent organic group, Rf ¹ is a fluoroalkyl group having 1 to 6 carbon atoms, and (a2) a second fluorine-containing monomer represented by the following formula: CH ₂ =C(-X ² )- C(=O)-Y ² -Z ² -Rf ² wherein X ² is a hydrogen atom, a monovalent organic group or a halogen atom, Y ² is -O- or -NH-, and Z ² is a direct bond. The junction or a divalent organic group, Rf ² is a fluoroalkyl group having a carbon number of 12 or more]. A mixed fluorine-containing compound mixed: (a1) a first fluorine-containing compound represented by the following formula: CH ₂ =C(-X ¹ )-C(=O)-Y ¹ -Z ¹ -Rf ¹ X ¹ is 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, and Rf ¹ is a carbon number of 1 to 6. a fluoroalkyl group, and (a2) a second fluorine-containing compound represented by the following formula: CH ₂ =C(-X ² )-C(=O)-Y ² -Z ² -Rf ² [wherein, X ² Is 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, and Rf ² is a fluoroalkyl group having a carbon number of 12 or more] . A method of treating a substrate obtained by treating the fluorine-containing composition according to any one of claims 1 to 8. A fiber product which is a fluorine-containing composition treated according to any one of claims 1 to 8.