JP4984889B2 - Polymers and treatments for the treatment of leather and protein fibers - Google Patents

Description

  The present invention relates to a polymer, a treating agent, a treating method and a treated article for treating leather and protein fiber products.

  Leather and protein fibers are used in various applications. In recent years, there is a tendency that natural leather has no or only slight finishing treatment for tanned leather for clothing, furniture, shoe uppers, gloves, and the like. By omitting the finishing treatment, a tanned leather having properties such as the natural appearance, feel, texture, and flexibility of natural leather can be obtained.

However, the omission of the finishing treatment is accompanied by serious drawbacks such as an increase in water absorption, a decrease in waterproofness due to the formation of water droplets, and a decrease in antifouling property against oil stains. These drawbacks impede practical use of leather products such as complicated care.
Conventionally, in order to compensate for the drawbacks of tanned leather, by using a lot of oil agent (greasing agent) in a process called greasing, protection of leather fibers from water and chemicals (hydrophobization etc.), and Efforts are being made to achieve improvements in leather feel, bulge, gloss, flexibility and other appearance qualities.

  In order to improve the water and oil repellency of leather, it has been proposed to use a fluorine-containing compound. USP 3524760 discloses Rf group-containing fluoropolymer dispersions. Japanese Patent Application Laid-Open No. 2002-155300 discloses a treatment agent using a mixture of a fluorine-containing ionic polymer and a non-fluorine ionic polymer. Japanese Patent Application Laid-Open No. 2003-129380 discloses the use of a combination of a soil release agent (SR agent) made of a fluorine-containing hydrophilic polymer and a water / oil repellent. JP 2001-504874 A discloses a fluorinated monomer-containing amphiphilic polymer in order to impart waterproofness to leather.

However, any treatment used for leather treatment requires the requirement that excellent waterproofness be imparted without adversely affecting the appearance, feel, texture, flexibility, breathability or other desirable properties of tanned leather. It was not satisfying.
In addition to natural leather, artificial leather, synthetic leather, cashmere fiber, wool, silk, feathers, etc. are excellent without adversely affecting the appearance, feel, texture, flexibility, breathability or other desirable properties of the fiber. There has been no treatment agent and treatment method that satisfies the demand for waterproofness.
Next, I will explain the environmental problems of PFOA. From recent research results [EPA report "PRELIMINARY RISK ASSESSMENT OF THE DEVELOPMENTAL TOXICITY ASSOCIATED WITH EXPOSURE TO PERFLUOROOCTANOIC ACID AND ITS SALTS" (http://www.epa.gov/opptintr/pfoa/pfoara.pdf)] Concerns about the environmental impact of PFOA (perfluorooctanoic acid), a type of fluoroalkyl compound, have become apparent, and on April 14, 2003, EPA (US Environmental Protection Agency) will strengthen scientific research on PFOA Announced.
Meanwhile, Federal Register (FR Vol.68, No.73 / April 16, 2003 [FRL-2303-8], http://www.epa.gov/opptintr/pfoa/pfoafr.pdf) and EPA Environmental News FOR RELEASE : MONDAY APRIL 14, 2003 EPA INTENSIFIES SCIENTIFIC INVESTIGATION OF A CHEMICAL PROCESSING AID (http://www.epa.gov/opptintr/pfoa/pfoaprs.pdf) and EPA OPPT FACT SHEET April 14, 2003 (http: // www. epa.gov/opptintr/pfoa/pfoafacts.pdf) publishes that telomers can produce PFOA by degradation or metabolism (telomers mean long chain fluoroalkyl groups). We also announced that telomers are used in many products such as foam, water- and oil-repellent and antifouling foams, care products, cleaning products, carpets, textiles, paper and leather. Yes.
USP 3524760 JP 2002-155300 A JP 2003-129380 A JP-T-2001-504874

  It is an object of the present invention to provide a treating agent that imparts excellent waterproof properties to leather and protein fibers without adversely affecting the appearance, feel, texture, flexibility, breathability or other desirable properties.

［式中、Ｘは、フッ素原子、塩素原子、臭素原子、ヨウ素原子、ＣＦＸ¹Ｘ²基（但し、Ｘ¹およびＸ²は、水素原子、フッ素原子、塩素原子、臭素原子またはヨウ素原子である。）、シアノ基、炭素数１〜２１の直鎖状または分岐状のフルオロアルキル基、置換または非置換のベンジル基、置換または非置換のフェニル基、
Ｙは、直接結合、酸素原子を有していてもよい炭素数１〜１０の脂肪族基、酸素原子を有していてもよい炭素数６〜１０の芳香族基、環状脂肪族基または芳香脂肪族基、−ＣＨ₂ＣＨ₂Ｎ(Ｒ¹)ＳＯ₂−基（但し、Ｒ¹は炭素数１〜４のアルキル基である。）または−ＣＨ₂ＣＨ(ＯＹ¹)ＣＨ₂−基（但し、Ｙ¹は水素原子またはアセチル基である。）、
Ｒｆは炭素数１〜２１の直鎖状または分岐状のフルオロアルキル基、炭素数１〜２１のフルオロアルケニル基または、繰り返し単位：−Ｃ_３Ｆ_６Ｏ−、−Ｃ_２Ｆ_４Ｏ−および−ＣＦ_２Ｏ−からなる群から選択された少なくとも一種の繰り返し単位の合計数が１〜２００のフルオロエーテル基である。］
で示されるフッ素含有基を有するアクリレート単量体含フッ素単量体、
（Ｂ）カルボン酸基、リン酸基、ホスホン酸基、ホスフィン酸基、硫酸基、スルホン酸基およびスルフィン酸基からなる群から選択された少なくとも一種の酸基を含有する単量体、および
（Ｃ）疎水性基を含有する非フッ素単量体
からなる、含フッ素重合体を提供する。
別の態様において、本発明は、
（Ａ）３５〜９０重量％の、式：

［式中、Ｘは、水素原子、メチル基、
Ｙは、直接結合、酸素原子を有していてもよい炭素数１〜１０の脂肪族基、酸素原子を有していてもよい炭素数６〜１０の芳香族基、環状脂肪族基または芳香脂肪族基、−ＣＨ₂ＣＨ₂Ｎ(Ｒ¹)ＳＯ₂−基（但し、Ｒ¹は炭素数１〜４のアルキル基である。）または−ＣＨ₂ＣＨ(ＯＹ¹)ＣＨ₂−基（但し、Ｙ¹は水素原子またはアセチル基である。）、
Ｒｆは炭素数１〜２１の直鎖状または分岐状のフルオロアルキル基、炭素数１〜２１のフルオロアルケニル基または、繰り返し単位：−Ｃ_３Ｆ_６Ｏ−、−Ｃ_２Ｆ_４Ｏ−および−ＣＦ_２Ｏ−からなる群から選択された少なくとも一種の繰り返し単位の合計数が１〜２００のフルオロエーテル基である。］
で示されるフッ素含有基を有するアクリレート単量体含フッ素単量体、
（Ｂ）５〜５０重量％の、カルボン酸基、リン酸基、ホスホン酸基、ホスフィン酸基、硫酸基、スルホン酸基およびスルフィン酸基からなる群から選択された少なくとも一種の酸基を含有する単量体、および
（Ｃ）２〜１８重量％の、疎水性基を含有する非フッ素単量体
からなる（重量％は、含フッ素重合体１００重量％に基づく。）、含フッ素重合体を提供する。The present invention
(A) a fluorine-containing monomer,
(B) a monomer containing at least one acid group selected from the group consisting of a carboxylic acid group, a phosphoric acid group, a phosphonic acid group, a phosphinic acid group, a sulfuric acid group, a sulfonic acid group, and a sulfinic acid group; C) The present invention relates to a fluorine-containing polymer for treating leather and protein fibers, comprising a non-fluorine monomer containing a hydrophobic group.
In one aspect, the present invention provides:

(A) Formula:

[Wherein X is a fluorine atom, chlorine atom, bromine atom, iodine atom, CFX ¹ X ² group (where X ¹ and X ² are a hydrogen atom, fluorine atom, chlorine atom, bromine atom or 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 a direct bond, an aliphatic group having 1 to 10 carbon atoms which may have an oxygen atom, an aromatic group having 6 to 10 carbon atoms which may have an oxygen atom, a cyclic aliphatic group or an aromatic group. An aliphatic group, a —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 —CH ₂ CH (OY ¹ ) CH ₂ — group ( Y ¹ is a hydrogen atom or an acetyl group.
Rf is a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, or fluoroalkenyl group of 1 to 21 carbon atoms, repeating _{units: -C 3 F 6 O -,} - C 2 F 4 O- and - The total number of at least one repeating unit selected from the group consisting of CF ₂ O— is a fluoroether group having 1 to 200. ]
An acrylate monomer having a fluorine-containing group represented by:
(B) a monomer containing at least one acid group selected from the group consisting of a carboxylic acid group, a phosphoric acid group, a phosphonic acid group, a phosphinic acid group, a sulfuric acid group, a sulfonic acid group, and a sulfinic acid group; C) Provided is a fluoropolymer comprising a non-fluorine monomer containing a hydrophobic group.
In another aspect, the invention provides:
(A) 35-90% by weight of the formula:

[Wherein X is a hydrogen atom, a methyl group,
Y is a direct bond, an aliphatic group having 1 to 10 carbon atoms which may have an oxygen atom, an aromatic group having 6 to 10 carbon atoms which may have an oxygen atom, a cyclic aliphatic group or an aromatic group. An aliphatic group, a —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 —CH ₂ CH (OY ¹ ) CH ₂ — group ( Y ¹ is a hydrogen atom or an acetyl group.
Rf is a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, or fluoroalkenyl group of 1 to 21 carbon atoms, repeating _{units: -C 3 F 6 O -,} - C 2 F 4 O- and - The total number of at least one repeating unit selected from the group consisting of CF ₂ O— is a fluoroether group having 1 to 200. ]
An acrylate monomer having a fluorine-containing group represented by:
(B) 5 to 50% by weight of at least one acid group selected from the group consisting of carboxylic acid group, phosphoric acid group, phosphonic acid group, phosphinic acid group, sulfuric acid group, sulfonic acid group and sulfinic acid group And (C) 2 to 18% by weight of a non-fluorine monomer containing a hydrophobic group (% by weight is based on 100% by weight of the fluoropolymer). I will provide a.

  According to the present invention, excellent waterproofness is imparted to leather and protein fibers without adversely affecting the appearance, feel, texture, flexibility, breathability or other desirable properties.

The fluoropolymer of the present invention has a repeating unit derived from each of the monomers (A), (B) and (C).
In the fluorine-containing polymer, examples of the fluorine-containing monomer (A) include at least one fluorine-containing group selected from the group consisting of a fluoroalkyl group, a fluoroalkenyl group and a fluoroether group (hereinafter referred to as “fluorine-containing group”). And the formula: —O—CO—CX═CH ₂ [wherein X is a hydrogen atom, a methyl group, 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. ] The monomer which has an unsaturated group represented by this. Since higher waterproofness is obtained, X is a fluorine atom, chlorine atom, bromine atom, iodine atom, CFX ¹ X ² group (where X ¹ and X ² are a hydrogen atom, fluorine atom, chlorine atom, 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, or a substituted or unsubstituted phenyl group.
Examples of the fluorine-containing monomer include an acrylate monomer having a fluorine-containing group, a maleate or fumarate monomer, or a urethane monomer.

［式中、Ｘは、水素原子、メチル基、フッ素原子、塩素原子、臭素原子、ヨウ素原子、ＣＦＸ¹Ｘ²基（但し、Ｘ¹およびＸ²は、水素原子、フッ素原子、塩素原子、臭素原子またはヨウ素原子である。）、シアノ基、炭素数１〜２１の直鎖状または分岐状のフルオロアルキル基、置換または非置換のベンジル基、置換または非置換のフェニル基、
Ｙは、直接結合、酸素原子を有していてもよい炭素数１〜１０の脂肪族基、酸素原子を有していてもよい炭素数６〜１０の芳香族基、環状脂肪族基または芳香脂肪族基、−ＣＨ₂ＣＨ₂Ｎ(Ｒ¹)ＳＯ₂−基（但し、Ｒ¹は炭素数１〜４のアルキル基である。）または−ＣＨ₂ＣＨ(ＯＹ¹)ＣＨ₂−基（但し、Ｙ¹は水素原子またはアセチル基である。）、
Ｒｆは炭素数１〜２１の直鎖状または分岐状のフルオロアルキル基、炭素数１〜２１のフルオロアルケニル基または、繰り返し単位：−Ｃ_３Ｆ_６Ｏ−、−Ｃ_２Ｆ_４Ｏ−および−ＣＦ_２Ｏ−からなる群から選択された少なくとも一種の繰り返し単位の合計数が１〜２００のフルオロエーテル基である。］
で示される。An acrylate monomer having a fluorine-containing group may be represented by the formula:

[Wherein, X represents a hydrogen atom, a methyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX ¹ X ² group (where X ¹ and X ² represent a hydrogen atom, a fluorine atom, a chlorine atom, bromine 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 a direct bond, an aliphatic group having 1 to 10 carbon atoms which may have an oxygen atom, an aromatic group having 6 to 10 carbon atoms which may have an oxygen atom, a cyclic aliphatic group or an aromatic group. An aliphatic group, a —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 —CH ₂ CH (OY ¹ ) CH ₂ — group ( Y ¹ is a hydrogen atom or an acetyl group.
Rf is a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, or fluoroalkenyl group of 1 to 21 carbon atoms, repeating _{units: -C 3 F 6 O -,} - C 2 F 4 O- and - The total number of at least one repeating unit selected from the group consisting of CF ₂ O— is a fluoroether group having 1 to 200. ]
Indicated by

In the formula (I), when the Rf group is a fluoroalkyl group, it is preferably a perfluoroalkyl group. The carbon number of the Rf group is 1 to 21, in particular 1 to 15, especially 2 to 15, for example 2 to 12. The upper limit of the carbon number of the Rf group may be 6 or 4. 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, - (CF 2) 7 CF 3, - (CF ₂ ) ₅ CF (CF ₃ ) ₂ ,-(CF ₂ ) ₆ CF (CF ₃ ) ₂ ,-(CF ₂ ) ₉ CF ₃ ,-(CF ₂ ) ₂ H, -CF ₂ CFHCF ₃ ,-( _{CF 2) 4 H, - (} CF 2) 6 H, - (CF 2) 8 H, - (CF 2) a ₁₀ H, and the like.
If Rf group is a fluoroalkenyl group, examples of the Rf _{group, -C (CF (CF 3)} 2) = C (CF 3) (CF 2 CF 2 CF 3), - C (CF (CF 3) 2) _{= C (CF 3) (CF} (CF 3) 2), - C (CF 3) = C (CF (CF 3) 2) is ₂ or the like.
When the Rf group is a fluoroether group, examples of the Rf group include F (CF ₂ CF ₂ CF ₂ O) _a CF ₂ CF ₂ —, F (CF (CF ₃ ) CF ₂ O) _a CF (CF ₃ ) — [Wherein, a is an average value of 2 to 100, particularly 5 to 50, such as 25].

Y is a direct bond, an aliphatic group having 1 to 10 carbon atoms which may have an oxygen atom, an aromatic group having 6 to 10 carbon atoms which may have an oxygen atom, a cyclic aliphatic group or an aromatic group. An aliphatic group, a —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 —CH ₂ CH (OY ¹ ) CH ₂ — group ( However, Y < ¹ > is a hydrogen atom or an acetyl group.). The aliphatic group is preferably an alkylene group (particularly having 1 to 4 carbon atoms, such as 1 or 2). The aromatic group and the cycloaliphatic group may be either substituted or unsubstituted.

Examples of the fluorine-containing monomer are as follows.
Rf- (CH ₂ ) ₁₀ OCOCH═CH _{2
Rf- (CH 2) 10 OCOC (} CH 3) = CH 2
Rf—CH ₂ OCOCH═CH _{2
Rf-CH 2 OCOC (CH 3} ) = CH 2
Rf- (CH ₂ ) ₂ OCOCH═CH ₂
Rf- (CH ₂ ) ₂ OCOC (CH ₃ ) ═CH _{2
Rf-SO 2 N (CH 3} ) (CH 2) 2 OCOCH = CH 2
_{Rf-SO 2 N (C 2} H 5) (CH 2) 2 OCOCH = CH 2
_{Rf-CH 2 CH (OCOCH 3} ) CH 2 OCOC (CH 3) = CH 2
_{Rf-CH 2 CH (OH)} CH 2 OCOCH = CH 2

[Wherein, Rf is a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a fluoroalkenyl group having 1 to 21 carbon atoms, or a repeating unit: -C ₃ F ₆ O-, -C ₂ F ₄ It is a fluoroether group in which the total number of at least one repeating unit selected from the group consisting of O— and —CF ₂ O— is 1 to 200. ]

A maleate or fumarate monomer having a fluorine-containing group for deriving a fluoropolymer is, for example,
formula:

［式中、ＲｆおよびＹは、式（Ｉ）の場合と同じ。］
で示される。formula:

[Wherein, Rf and Y are the same as those in the formula (I). ]
Indicated by

A urethane monomer having a fluorine-containing group for deriving a fluorine-containing polymer is
(A) a compound having at least two isocyanate groups,
(B) It is obtained by reacting a compound having one carbon-carbon double bond and at least one hydroxyl group or amino group, and (c) a fluorine-containing compound having one hydroxyl group or amino group.
Examples of the compound (a) are as follows.

Compound (a) is preferably diisocyanate. However, triisocyanates and polyisocyanates can also be used in the reaction.
For example, diisocyanate trimers, polymeric MDI (diphenyl metadiisocyanate), and adducts of diisocyanates with polyhydric alcohols such as trimethylolpropane, trimethylolethane, and glycerin can also be used in the reaction.
Examples of triisocyanates and polyisocyanates are as follows.

で示される化合物であってよい。Compound (b) is represented, for example, by the formula:

It may be a compound shown by these.

In the formula, X is the same as in the formula (I). p is 0-10 (for example, 1-5). An example of Z is as follows.

［式中、ｍおよびｎは、１〜３００の数である。］

[Wherein, m and n are numbers from 1 to 300. ]

Compound (c) has the formula:
Rf-Y-OH or Rf-Y-NH ₂
[Wherein, Rf and Y are the same as those in the formula (I). ]
It may be a compound shown by these.

であってよい。Examples of compound (c) are:

It may be.

  When the compound (a), (b) and (c) is a diisocyanate, the compound (a), (b) and (c) are each 1 mol of (b) and (c), and (a) is a triisocyanate, (A) 1 mol and (b) 1 mol and (c) 2 mol may be reacted.

In the monomer (B) having an acid group, the acid group includes a carboxylic acid group (—C (═O) OH), a phosphoric acid group (—OP (═O) (OH) ₂ ), a phosphonic acid group (— P (= O) (OH) ₂ ), phosphinic acid group (-P (= O) H (OH)), sulfate group (-OS (= O) ₂ OH), sulfonic acid group (-S (= O) ₂ OH) and a sulfinic acid group (—S (═O) OH).
An acid group becomes a site | part which can form a salt.
By forming a salt, solubility or dispersibility in water is improved. Further, the acid group contributes to the binding property when the leather or protein fiber contains a metal.

  Specific examples of the monomer having a carboxylic acid group include methacrylic acid, acrylic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl phthalic acid, 2-acryloyloxyethyl phthalate. Acid, 2-methacryloyloxyethylhexahydrophthalic acid, 2-acryloyloxyethylhexahydrophthalic acid, 2-acryloyloxypropylphthalic acid, 2-acryloyloxypropylhexahydrophthalic acid, 2-acryloyloxypropyltetrahydrophthalic acid, itacone Examples include acid, carboxyethyl acrylate, methacryloxyethyl trimellitic acid, crotonic acid, N-acryloylalanine, maleic anhydride, citraconic anhydride, and 4-vinylbenzoic acid.

Specific examples of the monomer having a phosphoric acid group include 2-methacryloyloxyethyl acid phosphate, 2-acryloyloxyethyl acid phosphate, acid phosphoxypropyl methacrylate, 3-chloro-2-acid phosphoxypropyl methacrylate, Examples include 2-methacryloyloxyethyl acid phosphate monoethanolamine half salt.
Specific examples of the monomer having a phosphonic acid group include vinylphosphonic acid.
Specific examples of the monomer having a sulfonic acid group include acrylamide-tert.butylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl acrylate, 2-sulfoethyl methacrylate, 2-sulfopropyl acrylate. , 4-sulfophenyl acrylate, 2-hydroxy-3-sulfopropyl acrylate, 2-acrylamidopropane sulfonic acid, 4-methacrylamidobenzene sulfonic acid, p-styrene sulfonic acid, vinyl sulfonic acid and the like.
Specific examples of the monomer having a sulfinic acid group include p-vinylbenzenesulfinic acid.

［式中、Ｒ^１は水素原子または有機基、ｘはこの化合物の数平均分子量が３００〜２００００、特に１０００になるような数である。］
などが好ましい。In the non-fluorine monomer (C) containing a hydrophobic group, examples of the hydrophobic group are a hydrocarbon group or a silicon-containing group. Examples of the hydrocarbon group are an aliphatic hydrocarbon group (for example, an alkyl group and an alkenyl group), a cyclic aliphatic hydrocarbon group, and an aromatic hydrocarbon group. Carbon number of a hydrocarbon group may be 1-30, for example, 4-30. An example of a silicon-containing group is a polysiloxane group.
The non-fluorine monomer (C) may be a (meth) acrylic acid ester containing an alkyl group. Carbon number of an alkyl group may be 1-30. For example, the non-fluorine monomer (C) has the general formula:
CH ₂ = CA ¹ COOA ²
[Wherein, A ¹ is a hydrogen atom or a methyl group, and A ² is an alkyl group represented by C _n H _{2n + 1} (n = 1 to 30). ]
It may be an acrylate represented by
The non-fluorine monomer (C) may be a (meth) acrylic acid ester containing a polysiloxane group.
From the viewpoint of waterproofness and texture, for example, a (meth) acrylic acid ester containing an alkyl group having 4 to 30 carbon atoms or a (meth) acrylic acid ester of the following formula containing a polysiloxane group

[Wherein, R ¹ is a hydrogen atom or an organic group, and x is a number such that the number average molecular weight of this compound is 300 to 20000, particularly 1000. ]
Etc. are preferable.

The monomer constituting the fluorinated polymer may contain another monomer (D) in addition to the monomers (A) to (C). Examples of other monomers (D) include ethylene, vinyl acetate, vinyl halide (eg, vinyl chloride), vinylidene halide (eg, vinylidene chloride), acrylonitrile, styrene, benzyl (meth) acrylate, 2- Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycerol mono (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meta ) Acrylate, tetrahydrofurfuryl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, vinyl alkyl ketone, vinyl alkyl ether, isoprene, chloroprene, While diene is illustrative and not limited thereto.
The weight average molecular weight of the fluorine-containing polymer may be, for example, 2000 to 5000000, particularly 3000 to 5000000, particularly 10,000 to 1000000. The weight average molecular weight of the fluoropolymer is determined by GPC (gel permeation chromatography) (polystyrene conversion).

In the fluoropolymer, with respect to 100 parts by weight of the monomer (A),
The amount of monomer (B) is 5 to 100 parts by weight, for example 10 to 90 parts by weight, in particular 15 to 80 parts by weight, especially 15 to 60 parts by weight,
The amount of monomer (C) is 1 to 100 parts by weight, for example 1 to 90 parts by weight, in particular 2 to 60 parts by weight, especially 3 to 40 parts by weight,
The amount of monomer (D) may be 0 to 100 parts by weight, for example 0 to 70 parts by weight, in particular 0.1 to 50 parts by weight, in particular 1 to 30 parts by weight.
In the formula (I), when X is hydrogen or a methyl group,
The amount of monomer (A) is 35 to 90% by weight, for example 40 to 80% by weight,
The amount of the monomer (B) is 5 to 50% by weight, such as 10 to 40% by weight,
The amount of the monomer (C) is preferably 2 to 18% by weight, for example 3 to 16% by weight (based on 100% by weight of the fluoropolymer). When the amount of the monomer (C) is 2% by weight or more, the waterproof property is high, and when the amount of the monomer (C) is 18% by weight or less, a treatment containing a fluoropolymer is performed. The stability of the agent is high. In this case, the fluoropolymer is preferably composed of the components (A) to (C), but the monomer (D) is contained in an amount of 0 to 40% by weight, for example 0.1 to 20% by weight. But you can.
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 a polymerization method include solution polymerization and emulsion polymerization.

  In solution polymerization, a method in which a monomer is dissolved in an organic solvent in the presence of a polymerization initiator, and after nitrogen substitution, is heated and stirred, for example, in the range of 50 to 120 ° C. for 1 to 10 hours. Examples of the polymerization initiator include azobisisobutyronitrile, azobisisovaleronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, Examples include diisopropyl peroxydicarbonate. The polymerization initiator may be used in the range of 0.01 to 5 parts by weight with respect to 100 parts by weight of the monomer.

  The organic solvent is inert to the monomer and dissolves them. For example, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4-dioxane, acetone , Methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, isopropyl alcohol, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane, trichlorotrifluoroethane, etc. Is mentioned. The organic solvent may be used in the range of 50 to 1000 parts by weight with respect to 100 parts by weight of the total amount of monomers.

  Emulsion polymerization employs a method in which a monomer is emulsified in water in the presence of a polymerization initiator and an emulsifier, and after nitrogen substitution, for example, is stirred and copolymerized in the range of 50 to 80 ° C. for 1 to 10 hours. The Polymerization initiators include water-soluble compounds such as azobisisobutylamidine dihydrochloride, sodium peroxide, potassium persulfate, ammonium persulfate, azobisisobutyronitrile, azobisisovaleronitrile, benzoyl peroxide, Oil-soluble ones such as -t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, diisopropyl peroxydicarbonate are used. The polymerization initiator may be used in the range of 0.01 to 5 parts by weight with respect to 100 parts by weight of the monomer.

  In order to obtain an aqueous copolymer dispersion having 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 polymerizable polymerization initiator. As the emulsifier, various anionic, cationic or nonionic emulsifiers can be used. Examples of emulsifiers are hydrocarbon emulsifiers, fluorine emulsifiers and silicone emulsifiers. You may use the quantity of an emulsifier in 0.5-50 weight part with respect to 100 weight part of monomers, for example, 0.5-10 weight part. 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, N-methyl-2-pyrrolidone, and the like. On the other hand, you may use in 1-50 weight part, for example, 10-40 weight part.

  In the present invention, the treating agent comprises (1) a fluoropolymer and (2) a liquid medium such as water and / or an organic solvent. The treatment agent generally also contains a neutralizing agent. The treatment agent may be in the form of a fluoropolymer solution (aqueous solution or organic solvent solution) or a fluoropolymer dispersion (in water or an organic solvent). Since the fluoropolymer of the present invention has an acid group, it can form a salt with a base (that is, a neutralizing agent). The fluorine-containing polymer in which the salt is formed can be dissolved in water to form an aqueous solution of the fluorine-containing polymer. After polymerization, particularly solution polymerization (particularly solution polymerization in an organic solvent), a neutralizing agent and water, generally an aqueous solution of a neutralizing agent, may be added to form a treating agent. After polymerization, the organic solvent may be removed before or after adding the neutralizing agent and water.

Examples of bases added to the fluoropolymer include ammonia, amines (eg, triethylamine, diethylamine, triethanolamine, diethanolamine, etc.), basic metal salts (eg, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate). , Sodium acetate, etc.). The amount of the base to be added may be 0.1 to 3 equivalents, for example 0.5 to 1.5 equivalents, per equivalent of the acid groups of the fluoropolymer.
In the treatment agent, the amount of the fluoropolymer is not particularly limited and may be appropriately selected from a range in which it can be uniformly dissolved or dispersed. For example, it may be 0.1 to 80% by weight, for example 0.2 to 20% by weight, based on the treatment agent.

  Substrates, ie leather and protein fiber products, are treated with the treatment agent of the present invention. Examples of leather are natural leather (eg cowhide, pig leather, sheep leather, goat leather, horse leather, deer leather, kangaroo leather), synthetic leather and artificial leather (eg suede artificial leather, nubuck artificial leather, silver With artificial leather). The protein fiber product includes a fiber itself, a thread-like product formed from the fiber, or a fabric-like product. Examples of protein fibers other than natural leather include cashmere fibers, wool, silk, and feathers.

When natural leather is treated, the leather is generally tanned with a metal salt, vegetable tannin, aldehyde or the like, and then the substrate is treated with the treatment agent of the present invention (ie, treatment solution). The treatment with the treatment agent of the present invention is performed before, during or after the greasing step. The treatment with non-fluorine chemicals such as hydrocarbon-based greasing agents, synthetic tannins and dyes can be performed before, after or simultaneously with the treatment with the treatment agent of the present invention. It is preferable to treat the substrate with the treating agent of the present invention after treating with the non-fluorine agent.
“Treatment” means that the treating agent is applied to the substrate by dipping, spraying, coating, or the like. By the treatment, the fluoropolymer which is an active ingredient of the treatment agent penetrates into the base material and / or adheres to the surface of the base material.

The treatment of the substrate with the non-fluorine agent and the treatment agent of the present invention can be performed, for example, by treating the substrate with these agents at a temperature of 0 to 80 ° C., particularly 20 to 50 ° C., for 0.5 to 24 hours, particularly 20 to 120 minutes. This can be done by dipping. The treatment can also be performed by spraying or applying a treatment liquid. The method of the present invention can be carried out at a high temperature of 80 to 120 ° C., for example. It is preferable to adjust the pH of the treatment liquid to 4 or less.
After applying the treatment agent, the liquid medium (water and / or organic solvent) present in the treatment agent is removed from the leather or protein fiber.

  Leather and protein fiber products treated in accordance with the present invention, such as tanned leather, can be used to tan tanned leather products such as clothes, furniture, shoes, bags, gloves, etc., regardless of the material of the tanned leather, or Can be used for manufacturing.

  When treating cashmere and wool fiber products, the treatment with the treatment agent of the present invention is generally performed after or before the final finishing step (texture adjusting step). Cashmere and wool fiber products can be immersed in a water bath containing the treatment agent of the present invention at a temperature of 0 to 80 ° C., particularly 20 to 50 ° C., for 0.5 to 24 hours, particularly 5 to 50 minutes. It is preferable to adjust the pH of the treatment liquid to the acidic side (pH 2.5 or lower).

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.

Example 1
In a 200 cc four-necked flask equipped with a stirrer, inert gas inlet, reflux condenser and thermometer, CF ₃ CF ₂ (CF ₂ CF ₂ ) ₃ CH ₂ CH ₂ OCOCH = CH ₂ 12.0 g, stearyl acrylate 1.0 g, 7.0 g of acrylic acid and 30.0 g of tetrahydrofuran were added, the temperature was raised to 60 ° C., 0.2 g of azobisisovaleronitrile was added, and a polymerization reaction was performed at 60 ° C. with stirring for 12 hours or more. Gas chromatography showed that the conversion of the polymerization reaction was 97% or more. An aqueous solution containing 1.7 g of ammonia was added to the obtained polymer solution, tetrahydrofuran was distilled off under reduced pressure, and then diluted with water to prepare a treatment liquid having a solid content concentration of 25%.
The chrome-tanned cowhide with the back cut was processed according to the following steps.

Process I Water washing / water draining process II Neutralization process III Water washing / water draining process IV Dyeing / greasing / treatment liquid addition / pH reduction / water draining process V Water washing / water draining

The processing of the tanned leather can be carried out without major changes, except that the processing liquid is added to the wet processing drum in the normal wet processing operation of post-tanning.
In the water washing of Steps I and V, about 3 times the weight of the leather was added to the drum, and then the drum was rotated at 30 ° C. for about 10 minutes and then drained.
The water washing in Step III was performed in the same manner except that the temperature was 50 ° C.

  In Step II neutralization, an aqueous solution of one or more neutralizing agents is added to the drum at about 1.5 times the weight of the tanned leather, and then the drum is rotated at 30 ° C. for about 60 minutes. The pH of the bath was 6.0-6.5. The neutralizing agents used were sodium formate and sodium bicarbonate. After neutralization, the used neutralization bath was discarded and subjected to a water washing treatment.

In Step IV, water at 50 ° C, about twice the weight of tanned leather, acid dye of 2% of tanned leather weight (Sella Fast Black FN manufactured by TFL), and greasing agent of 12% of tanned leather weight (Nippon Seika Co., Ltd.) Sulfonated oil: Cincoline L) was added to a drum containing tanned leather, rotated at 50 ° C. and pH 5.5 to 6.5 for 40 minutes, and then treated solution (25% concentration) of 8% of tanned leather weight. ) Was added and rotated for an additional 20 minutes.
Thereafter, formic acid of 1 to 2% of the weight of the tanned leather was added and rotated for another 20 minutes to adjust the pH of the bath to 3.3 to 3.7 and then drained.
After the final step V (water washing step), it was further thoroughly washed with a flowing water system and air-dried indoors. The following evaluation was performed after leaving for 24 hours.
The evaluation results are shown in Table 1.
(1) Texture The texture such as surface texture and flexibility was determined by the texture.

(2) Water absorption The water absorption (% by weight) was measured according to JIS K6550-1994 (water absorption test mass method). If the water absorption exceeds 40%, it can be determined that the waterproof property is weak.

(3) Water repellency The water repellency (point) was measured according to JIS L1092-1977. If the water repellency is less than 70, it can be determined that the waterproof property is weak.

(4) Dynamic waterproofing degree It evaluated based on measuring IUP-10 and measuring the frequency | count of bending until water penetrate | invades leather and penetrate | invades inside.

Example 2
Using the same apparatus as in Example 1, 12.0 g CF ₃ CF ₂ (CF ₂ CF ₂ ) ₃ CH ₂ CH ₂ OCOCH = CH ₂ , 4.0 g stearyl acrylate, 4.0 g acrylic acid, 30.0 g isopropyl alcohol, 60 After raising the temperature to 0 ° C., 0.2 g of azobisisovaleronitrile was added, and the polymerization reaction was carried out with stirring at 60 ° C. for 12 hours or more. Gas chromatography showed that the conversion of the polymerization reaction was 97% or more.
An aqueous solution containing 1.0 g of ammonia was added to the obtained polymer solution, isopropyl alcohol was distilled off under reduced pressure, and then diluted with water to prepare a treatment solution having a solid content concentration of 25%.
The treatment and evaluation were carried out in the same manner as in Example 1.
The evaluation results are shown in Table 1.

Example 3
Using the same apparatus as in Example 1, CF ₃ CF ₂ (CF ₂ CF ₂ ) ₃ CH ₂ CH ₂ OCOCH = CH ₂ 10.0 g, CF ₃ CF ₂ (CF ₂ CF ₂ ) ₄ CH ₂ CH ₂ OCOCH = CH ₂ Add 2.0 g, 3.0 g of stearyl acrylate, 5.0 g of acrylic acid, and 30.0 g of acetone, heat up to 60 ° C, add 0.2 g of azobisisovaleronitrile, and stir the polymerization reaction at 60 ° C for 12 hours or more. went. Gas chromatography showed that the conversion of the polymerization reaction was 97% or more.
An aqueous solution containing 1.2 g of ammonia was added to the obtained polymer solution, acetone was distilled off under reduced pressure, and then diluted with water to prepare a treatment liquid having a solid content concentration of 25%.
The treatment and evaluation were carried out in the same manner as in Example 1.
The evaluation results are shown in Table 1.

Example 4
Using the same apparatus as in Example 1, CF ₃ CF ₂ (CF ₂ CF ₂ ) ₃ CH ₂ CH ₂ OCOCH = CH ₂ 12.0 g, CF ₃ CF ₂ (CF ₂ CF ₂ ) ₄ CH ₂ CH ₂ OCOCH = CH ₂ Add 2.0 g, 1.0 g of lauryl acrylate, 5.0 g of acrylic acid and 30.0 g of acetone, heat up to 60 ° C, add 0.2 g of azobisisovaleronitrile, and stir the polymerization reaction at 60 ° C for 12 hours or more. went. Gas chromatography showed that the conversion of the polymerization reaction was 97% or more.
An aqueous solution containing 1.2 g of ammonia was added to the obtained polymer solution, acetone was distilled off under reduced pressure, and then diluted with water to prepare a treatment liquid having a solid content concentration of 25%.
The treatment and evaluation were carried out in the same manner as in Example 1.
The evaluation results are shown in Table 1.

Example 5
A polymerization reaction was performed in the same manner as in Example 3 except that acrylic acid was changed to 2-methacryloyloxyethyl acid phosphate, and a treatment liquid was prepared and treated and evaluated in the same manner as in Example 1.
The evaluation results are shown in Table 1.

Example 6
Using the same apparatus as in Example 1, 14.0 g of CF ₃ CF ₂ CF ₂ CF ₂ CH ₂ CH ₂ OCOCCl = CH ₂ , 1.0 g of stearyl acrylate, 5.0 g of acrylic acid and 30.0 g of tetrahydrofuran were added, and the temperature was raised to 60 ° C. Thereafter, 0.2 g of azobisisovaleronitrile was added, and a polymerization reaction was performed while stirring at 60 ° C. for 12 hours or more. Gas chromatography showed that the conversion of the polymerization reaction was 97% or more.
An aqueous solution containing 1.2 g of ammonia was added to the obtained polymer solution, tetrahydrofuran was distilled off under reduced pressure, and then diluted with water to prepare a treatment liquid having a solid content concentration of 25%.
The treatment and evaluation were carried out in the same manner as in Example 1.
The evaluation results are shown in Table 1.

Example 7
Using the same apparatus as in Example 1, CF ₃ CF ₂ (CF ₂ CF ₂ ) ₃ CH ₂ CH ₂ OCOCH = CH ₂ 12.0 g, stearyl acrylate 2.0 g, styrene 1.0 g, citraconic anhydride 5.0 g, tetrahydrofuran 30.0 g The temperature was raised to 60 ° C., 0.2 g of azobisisovaleronitrile was added, and the polymerization reaction was carried out with stirring at 60 ° C. for 12 hours or more. An aqueous solution containing 1.5 g of ammonia was added to the obtained polymer solution, tetrahydrofuran was distilled off under reduced pressure, and then diluted with water to prepare a treatment liquid having a solid content concentration of 25%.
The treatment and evaluation were carried out in the same manner as in Example 1.
The evaluation results are shown in Table 1.

［式中、Ｒ１は水素原子または有機基、ｘはこの化合物の数平均分子量が１０００になるような数である。］（チッソ社製サイラプレーンFM-0711）0.5g、アクリル酸4.0ｇ及びテトラヒドロフラン30.0ｇを入れ、60℃に昇温後、アゾビスイソヴァレロニトリル 0.2ｇを入れ、60℃で12時間以上攪拌しながら重合反応を行った。ガスクロマトグラフィーにより重合反応の転化率が97％以上であることが示された。
得た重合体溶液に、アンモニア1.2gを含む水溶液を加えて減圧下でテトラヒドロフランを留去し、その後水で希釈して固形分濃度25％の処理液を調製した。
実施例１と同様に処理し評価を行った。
評価結果を表１に示す。Example 8
Use the same apparatus as in Example _{1, CF 3 CF 2 CF 2} CF 2 CH 2 CH 2 OCOCF = CH 2 14.0g, stearyl acrylate 1.5g, polysiloxane group-containing methacrylic acid ester:

[Wherein R1 is a hydrogen atom or an organic group, and x is a number such that the number average molecular weight of this compound is 1000. ] (Sissoplane FM-0711 manufactured by Chisso Corporation) 0.5g, acrylic acid 4.0g and tetrahydrofuran 30.0g were added. After heating to 60 ° C, azobisisovaleronitrile 0.2g was added and stirred at 60 ° C for 12 hours or more. The polymerization reaction was carried out. Gas chromatography showed that the conversion of the polymerization reaction was 97% or more.
An aqueous solution containing 1.2 g of ammonia was added to the obtained polymer solution, tetrahydrofuran was distilled off under reduced pressure, and then diluted with water to prepare a treatment liquid having a solid content concentration of 25%.
The treatment and evaluation were carried out in the same manner as in Example 1.
The evaluation results are shown in Table 1.

Comparative Example 1
In Step IV of Example 1, leather was prepared and evaluated according to the same steps as in Example 1 without adding the treating agent of the present invention.
The evaluation results are shown in Table 1.

Comparative Example 2
In Example 2, a polymerization reaction was carried out in the same manner except that acrylic acid was changed to methoxypolyethylene glycol methacrylate, water was added to the resulting polymer solution, isopropyl alcohol was distilled off under reduced pressure, and then diluted with water. Thus, a treatment liquid having a solid concentration of 25% was prepared.
The treatment and evaluation were carried out in the same manner as in Example 1.
The evaluation results are shown in Table 1.

Comparative Example 3
Using the same apparatus as in Example 1, 12.0 g of CF ₃ CF ₂ (CF ₂ CF ₂ ) ₃ CH ₂ CH ₂ OCOCH = CH ₂ , 8.0 g of acrylic acid and 30.0 g of tetrahydrofuran were added, and the temperature was raised to 60 ° C. 0.2 g of azobisisovaleronitrile was added, and the polymerization reaction was carried out at 60 ° C. with stirring for 12 hours or more. Gas chromatography showed that the conversion of the polymerization reaction was 97% or more.
An aqueous solution containing 1.9 g of ammonia was added to the obtained polymer solution, tetrahydrofuran was distilled off under reduced pressure, and then diluted with water to prepare a treatment solution having a solid content concentration of 25%.
The treatment and evaluation were carried out in the same manner as in Example 1.
The evaluation results are shown in Table 1.

Comparative Example 4
A polymerization reaction was performed in the same manner as in Example 3 except that stearyl acrylate was changed to methoxypolyethylene glycol methacrylate, and a treatment liquid was prepared and treated and evaluated in the same manner as in Example 1.
The evaluation results are shown in Table 1.
Comparative Example 5
Using the same apparatus as in Example 1, 12.0 g of CF ₃ CF ₂ (CF ₂ CF ₂ ) ₃ CH ₂ CH ₂ OCOCH = CH ₂ , 8.0 g of stearyl acrylate and 30.0 g of tetrahydrofuran were added, and the temperature was raised to 60 ° C. 0.2 g of azobisisovaleronitrile was added, and the polymerization reaction was carried out at 60 ° C. with stirring for 12 hours or more. Gas chromatography showed that the conversion of the polymerization reaction was 97% or more.
As a result of adding water to the obtained polymer solution, a precipitate was formed, and a uniform treatment liquid could not be obtained.

Example 9
Using the treatment liquid prepared in Example 2, the aldehyde-tanned cowhide that had been back-cured was treated according to the following steps.
Process I Water washing / water draining process II Neutralization process III Water washing / water draining process IV Dyeing / greasing / treatment liquid addition / pH reduction / water draining process V Capping / water draining process VI Water washing / water draining

Steps I, II, III and IV were carried out in the same manner as in Example 1.
In Step V, about 20% of water of the tanned leather and about 0.5% of formic acid of the tanned leather are added to the drum containing the tanned leather and rotated at 20 ° C for 5 minutes. 4% by weight of metal tanning agent (zirconium tanning agent manufactured by Bayer: Blancorol ZB33) was added and rotated for another 45 minutes.
Thereafter, water at 50 ° C., which is about 1.5 times the weight of the tanned leather, was added and rotated at 50 ° C. for 30 minutes, and then an aqueous sodium bicarbonate solution was added and rotated for another 30 minutes to adjust the pH of the bath to 3. After adjusting to 3 to 3.7, drained.
Step VI was performed in the same manner as Step V of Example 1.
Evaluation was conducted in the same manner as in Example 1 after being left for 24 hours.
The evaluation results are shown in Table 2.

Comparative Example 6
A leather was produced and evaluated according to the same steps as in Example 9 without adding the treating agent of the present invention in Step IV of Example 9.
The evaluation results are shown in Table 2.

Example 10
Using the treatment solution prepared in Example 2, nylon suede-like artificial leather was treated according to the following steps.
Process I Soaking in water, adding treatment liquid, reducing pH, draining process II Washing with water, draining In process I, water of about 4 times the weight of nylon suede artificial leather (object to be treated) is added to the drum. Was rotated at 50 ° C. for about 5 minutes, and then a processing solution (25% concentration) of 16% of the weight of the object to be processed was added and further rotated for 20 minutes.
Thereafter, formic acid of 1 to 2% of the weight of the object to be treated was added, and the mixture was further rotated for 20 minutes to adjust the pH of the bath to 3.3 to 3.7, and then drained.
Step II (water washing step) was performed in the same manner as Step V of Example 1.
Evaluation was conducted in the same manner as in Example 1 after being left for 24 hours.
The evaluation results are shown in Table 3.

Comparative Example 7
The artificial leather was treated and evaluated according to the same steps as in Example 10 without adding the treating agent of the present invention in Step I of Example 10.
The evaluation results are shown in Table 3.

Claims (13)

(A) a fluorine-containing monomer,
(B) a monomer containing at least one acid group selected from the group consisting of a carboxylic acid group, a phosphoric acid group, a phosphonic acid group, a phosphinic acid group, a sulfuric acid group, a sulfonic acid group, and a sulfinic acid group; C) A fluorine-containing polymer for treating leather and protein fibers, comprising a non-fluorine monomer containing a hydrophobic group ,
The fluorine-containing monomer (A) is at least one fluorine-containing group selected from the group consisting of a fluoroalkyl group, a fluoroalkenyl group or a fluoroether group, and a formula: —O—CO—CX═CH ₂ [wherein , X is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a CFX ¹ X ² group (where 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, a substituted or unsubstituted benzyl group, and a substituted or unsubstituted phenyl group. ] The fluorine-containing polymer which is a compound containing the unsaturated group represented by these .   The fluorine-containing polymer according to claim 1, wherein the hydrophobic group of the monomer (C) is a hydrocarbon group and / or a silicon-containing group. The fluorine-containing polymer according to claim 2 , wherein the monomer (C) is a non-fluorinated alkyl group-containing monomer and / or a polysiloxane group-containing monomer.   The fluorine-containing polymer according to claim 1, wherein the acid group in the fluorine-containing polymer is in the form of a salt by adding a base as a neutralizing agent. (A) Formula:

[Wherein X is a fluorine atom, chlorine atom, bromine atom, iodine atom, CFX ¹ X ² group (where X ¹ and X ² are a hydrogen atom, fluorine atom, chlorine atom, bromine atom or 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 a direct bond, an aliphatic group having 1 to 10 carbon atoms which may have an oxygen atom, an aromatic group having 6 to 10 carbon atoms which may have an oxygen atom, a cyclic aliphatic group or an aromatic group. An aliphatic group, a —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 —CH ₂ CH (OY ¹ ) CH ₂ — group ( Y ¹ is a hydrogen atom or an acetyl group.
Rf is a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, or fluoroalkenyl group of 1 to 21 carbon atoms, repeating _{units: -C 3 F 6 O -,} - C 2 F 4 O- and - The total number of at least one repeating unit selected from the group consisting of CF ₂ O— is a fluoroether group having 1 to 200. ]
An acrylate monomer having a fluorine-containing group represented by:
(B) a monomer containing at least one acid group selected from the group consisting of a carboxylic acid group, a phosphoric acid group, a phosphonic acid group, a phosphinic acid group, a sulfuric acid group, a sulfonic acid group, and a sulfinic acid group; The fluorine-containing polymer according to claim 1, comprising a non-fluorine monomer containing a hydrophobic group. (A) 35-90% by weight of the formula:

[Wherein X is a hydrogen atom, a methyl group,
Y is a direct bond, an aliphatic group having 1 to 10 carbon atoms which may have an oxygen atom, an aromatic group having 6 to 10 carbon atoms which may have an oxygen atom, a cyclic aliphatic group or an aromatic group. An aliphatic group, a —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 —CH ₂ CH (OY ¹ ) CH ₂ — group ( Y ¹ is a hydrogen atom or an acetyl group.
Rf is a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, or fluoroalkenyl group of 1 to 21 carbon atoms, repeating _{units: -C 3 F 6 O -,} - C 2 F 4 O- and - The total number of at least one repeating unit selected from the group consisting of CF ₂ O— is a fluoroether group having 1 to 200. ]
An acrylate monomer having a fluorine-containing group represented by:
(B) 5 to 50% by weight of at least one acid group selected from the group consisting of carboxylic acid group, phosphoric acid group, phosphonic acid group, phosphinic acid group, sulfuric acid group, sulfonic acid group and sulfinic acid group And (C) 2 to 18% by weight of a non-fluorine monomer containing a hydrophobic group (% by weight is based on 100% by weight of the fluoropolymer). The fluorine-containing polymer as described.   (1) A treatment agent for leather and protein fibers comprising the fluoropolymer according to claim 1 and (2) a liquid medium. The treatment agent according to claim 7 , wherein the liquid medium (2) is water and / or an organic solvent.   A method for producing a leather and a protein fiber treatment agent, wherein the fluorine-containing polymer according to claim 1 is prepared by solution polymerization, and then neutralized and water is added to form a salt.   A treatment for leather and protein fibers comprising preparing the fluorine-containing polymer according to claim 1 by solution polymerization, and removing an organic solvent before or after adding a neutralizer and water to form a salt. Production method. A method for treating leather and protein fibers, comprising treating leather or protein fibers with the treatment agent according to claim 7 . The method according to claim 11 , comprising removing the liquid medium after applying the treatment agent containing the liquid medium to leather or protein fiber. Leather and protein fiber treated by the method of claim 11 .