TWI625339B - Surface treatment agent and method of producing the same - Google Patents

Abstract

The present invention provides a surface treatment agent which imparts excellent water repellency to a substrate such as a fiber product, and which has excellent dispersion stability of an aqueous dispersion by mixing of inclusions during processing.

The surface treatment agent comprises: (1) a fluorine-containing polymer having (a) a repeating unit derived from a fluorine-containing monomer, the fluorine-containing monomer being an α-chloroacrylic acid having a fluoroalkyl group The ester, and (b) a repeating unit derived from a non-fluorinated monomer, and (2) a cationic surfactant added after the polymerization of the fluoropolymer.

Description

Surface treatment agent and method of producing the same

The present invention relates to a fluorine-containing composition (surface treatment agent) which has high water repellency and is excellent in stability when inclusions are contained in a treatment liquid, and the fluorine-containing composition contains α-chloroacrylate as a constituent monomer. Fluoropolymer.

A polymer having a perfluoroalkyl group or a perfluoroalkenyl group and an acrylic group or a methacrylic group-based polymerizable compound is known as a water-repellent oil-repellent agent for fiber fabrics and the like, and in particular, the polymer is borrowed. Aqueous dispersions dispersed in an aqueous medium by a surfactant are widely used in the industry.

Further, it is generally known that by copolymerizing the above-mentioned fluorine-containing polymerizable compound with a compound called a chlorine-containing polymerizable compound of vinyl chloride or vinyl chloride, excellent durability can be imparted. Further, there is also proposed a water-repellent oil-repellent agent containing a compound which captures hydrochloric acid produced by the copolymer.

The number of carbon atoms of the side chain fluoroalkyl group of the fluorine-containing (meth) acrylate-based polymer used in these applications is usually 8 or more, and is usually called "telomer".

"The telomer" has the possibility of generating PFOA (perfluorooctanoic acid) of a fluorine-containing carboxylic acid having a carbon number of 8 by decomposition or metabolism, and the "telomer" is also The public display is used in a variety of products including foam fire extinguishing agent; care products and cleaning products; water-repellent coating and anti-fouling processing on blankets, textiles, paper, leather (EPA OPPT FACT SHEET April 14, 2003) (http://www.epa.gov/opptintr/pfoa/pfoafacts.pdf).

In recent years, doubts about the environmental load of this PFOA have become apparent. On April 14, 2003, the EPA (US Environmental Protection Agency) published a scientific investigation to strengthen PFOA.

Under such circumstances, a water- and oil-repellent agent having a (meth) acrylate having a carbon number of 6 perfluoroalkyl groups as a monomer component has been developed, but a (meth)acrylic acid having a carbon number of 8 or more has been developed. Compared with the water-repellent and oil-repellent agent in which the ester is used as a monomer component, not only the water repellency and the oil-repellent property are lowered, but also the mechanical stability is insufficient, and in the processing, the pre-treatment step is adhered to the inclusion of the processing cloth or the like. When the substance is mixed, the dispersibility of the aqueous dispersion will be degraded and aggregation and sedimentation of the latex particles will occur. Therefore, the performance of the treated material is degraded, and the polymer may adhere to the mills (gum up), which may cause uneven processing in the processed cloth. Until now, the water-repellent treatment has not been solved. These problems (adhesive).

In the prior art, as a technique for imparting water repellency and oil repellency to the surface, a polymerization unit containing a polymerizable monomer having a perfluoroalkyl group (hereinafter, a perfluoroalkyl group is described as an Rf group) is contained. The polymer, or a copolymer thereof with other monomers, or a low molecular compound having an Rf group, is used as an organic solvent solution or an aqueous dispersion for article processing. This water repellency exhibits a "low surface energy surface" having a low critical surface tension on the surface due to the surface alignment of the Rf group in the coating film. In order to have both water repellency and oil repellency, it is considered that the focus is on the orientation of the Rf group in the surface. The monomer containing Rf group, although it is water-repellent In terms of oil repellency, the purpose is achieved, but improvements are needed in relation to other practical functions. For example, in order to improve the durability against washing, dry cleaning, rubbing, etc., it is possible to use a monomer having a high hardness or a monomer having a crosslinking reaction group while using an Rf-containing monomer, or The copolymer is mixed with a polymer having a high film strength, and is improved by mixing with a blocked isocyanate. On the other hand, regarding the copolymer of the polymer unit containing the Rf group-containing monomer, it was examined that the hard touch was soft, and the melting point of the Rf group was lowered in order to exhibit water repellency under low-temperature curing conditions. For example, an example in which an Rf-based monomer having a wide range of chain lengths is copolymerized with an alkyl group-containing monomer is known. Further, a method of using an anthrone having a wide range of Rf groups in a chain length range, and a method of using an anthranone containing a hydrogenthio group are similarly known.

For example, Japanese Patent No. 3624615 (a 4-membered copolymer in which Rf-based (meth) acrylate and (meth) styrene methacrylate and two other monomers are essential components), Japanese Patent No. 3343024 Bulletin (a fluorine-based water-repellent oil-repellent agent and a compound containing a specific chain length of Rf-based alcohol or a perfluoropolyether-containing alcohol), Japanese Patent Publication No. 8-109580 (Amino-containing anthrone) a reaction product with an ester compound containing an Rf group), WO 2009/122919 (a total of Rf-based (meth) acrylate monomers, hydrocarbon (meth) acrylate monomers, and thiol ketones containing thiol groups) Polymer), WO 2009/113589 (containing a (meth) acrylate having no perfluoroalkyl group and having an alkyl group having a carbon number of 20 to 30, a halogenated olefin, and a monomer having a fluoroalkyl group having 1 to 6 carbon atoms A well-known example such as a fluorine-containing copolymer).

WO 2011/122442 discloses a treating agent composition comprising a fluoropolymer having a repeating unit derived from an α-chloroacrylate and a (meth) acrylate monomer having a hydrocarbon group. In this publication, the emulsifier (surfactant) is not reviewed in detail.

[Previous Technical Literature] (Patent Literature)

Patent Document 1: Japanese Patent No. 3624615

Patent Document 2: Japanese Patent No.3433024

Patent Document 3: Japanese Patent Laid-Open No. Hei 8-109580

Patent Document 4: WO2009/122919

Patent Document 5: WO2009/113589

Patent Document 6: WO2011/122442

An object of the present invention is to provide a surface treatment agent which imparts excellent water repellency to a substrate such as a fiber product, and in which the dispersion stability of the aqueous dispersion is excellent by the incorporation of inclusions.

In order to solve the above problems, the inventors of the present invention have conducted intensive review for the purpose of providing a surface treatment agent having excellent water repellency, which is an additive which is added after the completion of emulsion polymerization, and which is a copolymer containing a fluorine monomer. Composition. As a result, it has been found that the above object can be attained by adding a cationic emulsifier, and the present invention has been completed.

The present invention provides a surface treatment agent comprising: (1) a fluorine-containing polymer having (a) a repeating unit derived from a fluorine-containing monomer, the fluorine-containing monomer having a fluorocarbon Alpha-chloroacrylate, and (b) a repeating unit derived from a non-fluorine monomer, and (2) a cationic surfactant added after polymerizing the fluoropolymer.

According to the method for producing a surface treatment agent of the present invention, it is possible to produce a surface treatment agent which imparts excellent water repellency to a substrate such as a fiber product, and which is excellent in dispersion stability of the aqueous dispersion by mixing the inclusions during the treatment. .

In the present invention, (a) a fluorine-containing monomer and (b) a non-fluorine monomer are used as a monomer.

In the present invention, the fluoropolymer has: (a) a repeating unit derived from a fluorine-containing monomer (?-chloro-substituted acrylate), and (b) a repeating unit derived from a non-fluorine monomer.

The fluoropolymer of the present invention may include only acrylates having a linear or branched hydrocarbon group having a carbon number of 12 to 30 from the monomer (a) and the monomer (b) ((b1)). Is a (b2) glass transition point (Tg) or a re-fraction unit derived from a (meth) acrylate monomer having a melting point (Tm) of 50 ° C or higher, or in addition to the monomer (a) and the monomer ( b) In addition to the recurring unit derived, there is a repeating unit derived from other monomers.

(a) Fluorine-containing monomer (α-chloro-substituted fluoromonomer)

The fluorine-containing monomer is an α-chloro-substituted fluorine-containing monomer represented by the following formula: CH ₂ =C(-Cl)-C(=O)-YZ-Rf

[wherein, Y is -O- or -NH-, Z is a direct bond or a divalent organic group, and Rf is a fluoroalkyl group having 1 to 20 carbon atoms].

The fluorine-containing monomer (a) is preferably an acrylate having a Y-group of -O-.

The Z group may specifically be a linear or branched aliphatic group having a carbon number of 1 to 20 (for example, a carbon number of 1 to 10, especially 1 to 4, particularly 1 or 2) (for example, An alkyl group, for example, a group represented by the formula -(CH ₂ ) _x - (wherein, x is 1 to 10), or an aromatic group having 6 to 18 carbon atoms or a cyclic aliphatic group, -R ² (R ¹ )N-SO ₂ - or a group represented by the formula -R ² (R ¹ )N-CO- (wherein R ¹ is an alkyl group having 1 to 10 carbon atoms, and R ² is carbon a linear alkyl group of 1 to 10 or a branched alkyl group, for example, a -CH ₂ CH ₂ N(R ¹ )SO ₂ - group (except, R ¹ is an alkyl group having 1 to 4 carbon atoms) Or a formula -CH ₂ CH(OR ³ )CH ₂ -[Ar-(O) _q ] _p - (wherein R ³ is a hydrogen atom or a fluorenyl group having a carbon number of 1 to 10 (for example, a fluorenyl group) Or an acetamyl group, etc., Ar is an extended aryl group having a substituent (for example, a phenyl group), p is 0 or 1, q is a group represented by 0 or 1), or is a formula -(CH ₂ ) _n -Ar-(O) _q - (wherein, Ar is an extended aryl group having a substituent as required (for example, a phenyl group), n is 0 to 10, and q is 0 or 1 ) the group shown, -(CH ₂ ) _m -SO ₂ -(CH ₂ ) _n -yl or -(CH ₂ ) _m -S-(CH ₂ ) _n -yl (only m is 1 to 1) 0, n is 0 to 10).

The aromatic 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.

The Rf group is preferably a perfluoroalkyl group. The carbon number of the Rf group is from 1 to 12, for example from 1 to 6, particularly preferably from 4 to 6. Examples of the Rf group are: -CF ₃ , -CF ₂ CF ₃ , -CF ₂ CF ₂ CF ₃ , -CF(CF ₃ ) ₂ , -CF ₂ CF ₂ CF ₂ CF ₃ , -CF ₂ CF (CF _{3 2} , -C(CF ₃ ) ₃ , -(CF ₂ ) ₄ CF ₃ , -(CF ₂ ) ₂ CF(CF ₃ ) ₂ , -CF ₂ C(CF ₃ ) ₃ , -CF(CF ₃ )CF ₂ CF ₂ CF ₃ , -(CF ₂ ) ₅ CF ₃ , -(CF ₂ ) ₃ CF(CF ₃ ) ₂ , -(CF ₂ ) ₄ CF(CF ₃ ) ₂ , -C ₈ F ₁₇ and the like.

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

CH ₂ =C(-Cl)-C(=O)-O-(CH ₂ ) ₂ -Rf

CH ₂ =C(-Cl)-C(=O)-O-(CH ₂ ) ₄ -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(-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(-Cl)-C(=O)-O-CH ₂ CH ₂ N(CH ₃ )SO ₂ -Rf

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

CH ₂ =C(-Cl)-C(=O)-O-CH ₂ -Ph-O-Rf (here, Ph is 1,4-phenylene)

CH ₂ =C(-Cl)-C(=O)-O-CH ₂ CH(OH)CH ₂ -Ph-O-Rf

CH ₂ =C(-Cl)-C(=O)-O-CH ₂ -Ph-Rf

CH ₂ =C(-Cl)-C(=O)-O-CH ₂ CH(OCOCH ₃ )CH ₂ -Ph-Rf

[In the above formula, Rf is a fluoroalkyl group having 1 to 20 carbon atoms].

(b) Non-fluorinated monomers

The non-fluorinated monomer (b) is a monomer having no fluorine atom. The non-fluorinated monomer (b) may be an acrylate compound having 4 to 32 carbon atoms. The non-fluorinated monomer (b) may be an acrylate compound represented by the formula: CH ₂ =CR ¹ -C(=O)OR ²

[wherein, R ¹ is H, a C ₁ to C ₄ alkyl group, or a halogen, and R ² is a C ₁ to C ₃₀ hydrocarbon group (for example, an aliphatic group, an aromatic group, an aromatic aliphatic group)].

The non-fluorine monomer (b) may be a non-fluorine non-crosslinkable monomer (for example, a (meth) acrylate, a halogenated olefin), or a non-fluorine crosslinkable monomer used as needed.

The non-fluorinated monomer (b) may be (b1) an acrylate having a linear or branched hydrocarbon group having 12 to 30 carbon atoms, and (b2) a glass transition point (Tg) or a melting point (Tm) At least one compound selected from the group consisting of (meth) acrylates at 50 ° C or higher.

(b1) an acrylate having a linear or branched hydrocarbon group having 12 to 30 carbon atoms

The acrylate (b1) having a linear or branched hydrocarbon group does not have a cyclic hydrocarbon group. A linear or branched hydrocarbon group may especially be a linear hydrocarbon group. A linear or branched hydrocarbon group having a carbon number of 12 to 30 is generally a saturated aliphatic hydrocarbon group.

The acrylate (b1) having a linear or branched hydrocarbon group may be an alkyl acrylate. The alkyl group may have a carbon number of 12 to 30, for example, 12 to 22, and particularly 14 to 20. For example, the acrylate (b1) having a linear or branched hydrocarbon group may be an acrylate represented by the following formula: CH ₂ =CHCOOA ¹

[wherein, A ¹ is an alkyl group represented by C _n H _2n+1 (n = 12 to 30, especially 12 to 22)].

Specific examples of the acrylate (b1) having a linear or branched hydrocarbon group include, for example, the following, but are not limited thereto.

CH ₂ =C(-H)-C(=O)-O-(CH ₂ ) ₁₁ -CH ₃

CH ₂ =C(-H)-C(=O)-O-(CH ₂ ) ₁₃ -CH ₃

CH ₂ =C(-H)-C(=O)-O-(CH ₂ ) ₁₅ -CH ₃

CH ₂ =C(-H)-C(=O)-O-(CH ₂ ) ₁₇ -CH ₃

CH ₂ =C(-H)-C(=O)-O-(CH ₂ ) ₂₁ -CH ₃

(ie, lauryl acrylate, myristyl acrylate, cetyl acrylate, stearyl acrylate, behenyl acrylate)

(b2) glass transition point (Tg) or (meth) acrylate monomer having a melting point (Tm) of 50 ° C or higher

The (meth) acrylate monomer (b2) is a glass transition point (Tg) of a homopolymer or a (meth) acrylate monomer having a melting point (Tm) of 50 ° C or higher. The (meth) acrylate monomer (b2) is a monomer other than the monomer (b1).

The glass transition point and melting point are the transition temperature (T _eg ) of the extrapolated glass and the melting peak temperature (T _pm ) according to JIS K7121-1987 "Method for measuring the transfer temperature of plastics".

The upper limit of the glass transition point (Tg) or the melting point (Tm) is 300 ° C, and may be, for example, 200 ° C.

The (meth) acrylate monomer (b2) is preferably an acrylate compound represented by the following formula: CH ₂ =CR ¹¹ -C(=O)OR ¹²

Wherein R ¹¹ is H, a C ₁ to C ₄ alkyl group, or a halogen, and R ¹² is a C ₁ to C ₃₀ linear, branched or cyclic aliphatic group, C ₆ to An aromatic group of C _{20 ,} an aromatic aliphatic group of C ₇ to C ₂₅ ].

R ^{11 is} , for example, a hydrogen atom, a methyl group, a chlorine atom, a bromine atom or an iodine atom. R ¹¹ is preferably a methyl group.

Examples of R ¹² are: (for example, a carbon number of 1 to 6) alkyl group (for example, methyl group, ethyl group, propyl group, butyl group), (for example, a carbon number of 5 to 10) cycloalkyl group (for example, Cyclohexyl), (for example, a carbon number of 7 to 20) polycyclic aliphatic groups (for example, norbornyl, borneol, isobornyl, adamantyl), phenyl, naphthyl, benzyl.

R ¹² is preferably a cyclic group, and a cycloalkyl group, a polycyclic aliphatic group, an aromatic group or an aromatic aliphatic group is preferred. In particular, when R ¹¹ is a hydrogen atom, R ¹² is preferably a cyclic group, and is usually a cycloalkyl group, a polycyclic aliphatic group, an aromatic group or an aromatic aliphatic group.

Specific examples of the (meth) acrylate monomer (b2) include cyclohexyl acrylate, isobornyl acrylate, borneol acrylate, adamantyl acrylate, dicyclopentanyl acrylate, and dicyclopentene acrylate. Acrylate, tricyclodecyl acrylate, phenyl acrylate, naphthyl acrylate, benzyl acrylate, 2-tert-butyl phenyl acrylate, naphthyl acrylate, etc.; methyl methacrylate, ethyl methacrylate , isopropyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, borneol methacrylate, adamantyl methacrylate, dicyclopentanyl methacrylate , dicyclopentenyl methacrylate, tricyclodecyl methacrylate, phenyl methacrylate, naphthyl methacrylate, benzyl methacrylate, methacrylic acid Methyl acrylate such as (2-dimethylamino)ethyl ester, aziridine methacrylate, aziridine ethyl methacrylate or dicyclopentenyl methacrylate; methyl chloroacrylate Isochloroacrylate, but is not limited thereto.

(c) other monomers

Other monomers (c) other than the non-fluorinated monomer (b) (especially, other than the monomers (b1) and (b2)), especially non-fluorinated monomers, such as other non-fluorine non-crosslinkable monomers, may be used. .

In other examples of the monomer (c), for example, ethylene, vinyl acetate, acrylonitrile, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxy polyethylene Alcohol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, and vinyl alkyl ether. Other monomers are not limited to these examples.

The other monomer (c) may be a halogenated olefin.

The halogenated olefin is preferably an olefin having 2 to 20 carbon atoms which is substituted with 1 to 10 chlorine atoms, a bromine atom or an iodine atom. The halogenated olefin is a chlorinated olefin having 2 to 20 carbon atoms, particularly preferably an olefin having 2 to 5 carbon atoms having 1 to 5 chlorine atoms. Desirable specific examples of the halogenated olefin are halogenated ethylene, for example, ethylene chloride, ethylene bromide, ethylene iodide, vinylidene halide, for example, vinylidene chloride, vinylene bromide, and vinyl iodide.

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

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

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

Examples of the non-fluorine-crosslinkable monomer include, for example, diacetone (meth) acrylamide, N-methylol (meth) acrylamide, hydroxymethyl (meth) acrylate, (methyl). Hydroxyethyl acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, 2-ethyl ethoxyethyl (meth) acrylate, butadiene, isoprene, chloroprene , monochlorovinyl acetate, vinyl methacrylate, glycidyl (meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate Etc., but not limited to this.

In the present specification, "(meth) acrylate" means acrylate or methacrylate, and "(meth) acrylamide" means acrylamide or methacrylamide.

In the fluoropolymer, the amount of the fluoromonomer (a) may be from 5 to 95% by weight, for example from 10 to 90% by weight, especially from 20 to 70% by weight, based on the fluoropolymer.

The molar ratio of the repeating unit of the fluoromonomer (a) to the non-fluorinated monomer (b) may be from 0.01/1 to 10/1, for example from 0.1/1 to 5/1.

The amount of the acrylate (b1) having a linear or branched hydrocarbon group may be from 1 to 1500 parts by weight, for example, from 4 to 800 parts by weight, based on 100 parts by weight of the fluorine-containing monomer (a), especially 10 to 400 parts by weight, the amount of the (meth) acrylate monomer (b2) may be 0 to 1500 by weight Parts, for example, 4 to 800 parts by weight, especially 10 to 400 parts by weight, and the other monomer (c) may be used in an amount of 0 to 100 parts by weight, for example, 1 to 70 parts by weight, particularly 3 to 50 parts by weight. .

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

In the present invention, a cationic surfactant (post-addition surfactant) can be generally added by copolymerizing monomers (a) and (b) in the presence of a surfactant (polymerization surfactant). The fluorine-containing composition (surface treatment agent) in which the fluoropolymer is dispersed in the medium is obtained.

The surfactant for polymerization is a nonionic surfactant, a cationic surfactant, an anionic surfactant, an amphoteric surfactant, or a combination thereof.

Nonionic surfactants (nonionic emulsifiers) are generally compounds having a polyethylene oxide (POE) group. From the viewpoint of environmental problems (biodegradability, environmental hormones, etc.), the nonionic surfactant is preferably a structure containing no aromatic group.

The nonionic surfactant may be: polyethylene oxide fatty acid ester, polyethylene oxide sorbitan fatty acid ester, polyethylene oxide sorbitol fatty acid ester, polyethylene oxide alkyl Ether, polyethylene oxide alkyl allyl ether, polyethylene oxide alkyl phenyl ether, polyethylene oxide alkyl amine, or polyethylene oxide alkyl amine fatty acid ester.

The nonionic surfactant is preferably a surfactant as shown in the following formula: R ⁶¹ O-(CH ₂ CH ₂ O) _r -(R ⁶² O) _s -R ⁶³

Wherein R ⁶¹ is an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms; R ⁶² is an alkylene group having 3 or more carbon atoms (for example, 3 to 10), and R ⁶³ is a hydrogen atom. An alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms, r is a number of 2 or more, and s is 0 or a number of 1 or more.

Examples of R ⁶² are: propyl, butyl. R ⁶³ is preferably a hydrogen atom. s can be 0.

A specific example of a nonionic surfactant is: C ₁₀ H ₂₁ O-(CH ₂ CH ₂ O) _r -(C ₃ H ₆ O) _s -H

C ₁₂ H ₂₅ O-(CH ₂ CH ₂ O) _r -(C ₃ H ₆ O) _s -H

C ₁₆ H ₃₁ O-(CH ₂ CH ₂ O) _r -(C ₃ H ₆ O) _s -H

C ₁₆ H ₃₃ O-(CH ₂ CH ₂ O) _r -(C ₃ H ₆ O) _s -H

C ₁₈ H ₃₅ O-(CH ₂ CH ₂ O) _r -(C ₃ H ₆ O) _s -H

C ₁₈ H ₃₇ O-(CH ₂ CH ₂ O) _r -(C ₃ H ₆ O) _s -H

C ₁₂ H ₂₅ O-(CH ₂ CH ₂ O) _r -(C ₃ H ₆ O) _s -C ₁₂ H ₂₅

C ₁₆ H ₃₁ O-(CH ₂ CH ₂ O) _r -(C ₃ H ₆ O) _s -C ₁₆ H ₃₁

C ₁₆ H ₃₃ O-(CH ₂ CH ₂ O) _r -(C ₃ H ₆ O) _s -C ₁₂ H ₂₅

iso-C ₁₃ H ₂₇ O-(CH ₂ CH ₂ O) _r -(C ₃ H ₆ O) _s -H

[wherein, r and s are the same meanings as described above] and the like.

The nonionic surfactant may be one type or a mixture of two or more types. The nonionic surfactant may be a nonionic surfactant having a ratio of r of 10 or more and s of 0, and a nonionic surfactant having a ratio of r of less than 10 and s of 0 (for example, molar ratio of 0.5). :1 to 20:1, for example 1:1 to 10:1, especially a mixture of 1.5:1 to 7:1).

A cationic surfactant (cationic emulsifier) is generally an ammonium salt. The cationic surfactant may be an ammonium salt represented by the formula: (R ⁵¹ ) _p N ⁺ (R ⁵² ) _4-p X ^-

Wherein R ⁵¹ is a linear or/or branched aliphatic (saturated and/or unsaturated) group of C12 or higher, and R ⁵² is H or a C1 to 4 alkyl group, benzyl group Polyethylene oxide group (the number of oxiranyl groups is, for example, 1 (especially 2, especially 3) to 50), X is an anion-forming group, and p is 1 or 2].

R ⁵¹ may be C ₁₂ to C ₅₀ , such as C ₁₈ to C ₄₀ , especially C ₂₀ to C ₃₅ , especially C ₂₂ to C ₃₀ . R ⁵² is preferably CH ₃ or C ₂ H ₅ . Specific examples of X are: a halogen atom such as F, Cl, Br, I, such as a C ₁ to ₄ carboxylate of CH ₃ COO ^- , a sulfate such as HSO ₄ ^- , such as a phosphate of H ₂ PO ₄ ^- .

Specific examples of the cationic surfactant include octyltrimethylammonium bromide, octyltrimethylammonium chloride, dodecyltrimethylammonium bromide, and dodecyltrimethyl. Ammonium chloride, myristyl trimethylammonium bromide, myristyl trimethylammonium chloride, cetyltrimethylammonium bromide, cetyltrimethylammonium chloride, stearyl Alkyltrimethylammonium halide such as methylammonium chloride; laurylpyridinium chloride; dioctyldimethylammonium bromide, dioctyldimethylammonium chloride, di(dodecyl)di Methylammonium bromide, di(dodecyl)dimethylammonium chloride, dimyristyldimethylammonium bromide, dimyristyldimethylammonium chloride, di(hexadecyl)di A dialkyldimethylammonium halide such as methylammonium bromide, di(hexadecyl)dimethylammonium chloride or distearyldimethylammonium chloride.

The cationic surfactant may be one type or a mixture of two or more types. The cationic surfactant may be a cationic surfactant having a p of 1 [(R ⁵¹ )N ⁺ (R ⁵²⁾ ₃ X ^- ] and a cationic surfactant having a p of 2 [(R ⁵¹ ) ₂ N ⁺ (R ⁵² ) ₂ X ^- ] (for example, a molar ratio of 0.5:1 to 20:1, for example 1:1 to 10:1, especially 1.5:1 to 7:1).

Specific examples of the anionic surfactant include sodium lauryl sulfate, triethanolamine lauryl sulfate, sodium polysulfate lauryl ether sulfate, sodium polyoxyethylene nonylphenyl ether sulfate, and poly Ethylene oxide lauryl ether triethanolamine, sodium cocoyl sarcosine, N-cocoyl methyl taurate, polyethylene oxide sulfonate alkyl ether sulfate , sodium diether hexyl sulfosuccinate, sodium α-olefin sulfonate, sodium lauryl phosphate, sodium polyoxyethylene lauryl ether phosphate, perfluoroalkyl carboxylate (trade name UNIDYNE DS-101, 102 (Daikin Industrial Co., Ltd.)) and so on.

The amphoteric surfactant may be: alanine, imidazolium betaine, guanamine betain, or acetate betaine. Specific examples of the amphoteric surfactant include dodecylbetaine, stearylbetaine, dodecylcarboxymethylhydroxyethylimidazolium betaine, and dodecyldimethylamine. Beta acetate, fatty amidoxime dimethylaminoacetate betaine, and the like.

The surfactant for polymerization is preferably a mixture of a cationic surfactant and a nonionic surfactant. In the surfactant for polymerization, the weight ratio of the cationic surfactant to the nonionic surfactant may be from 10 to 99:90 to 1, for example, from 20 to 95:80 to 5, especially from 50 to 90:50 to 10, especially 55 to 80:45 to 20. The amount of the surfactant for polymerization may be from 0.5 to 30 parts by weight, for example, from 1 to 20 parts by weight, per 100 parts by weight of the monomer.

The post-addition surfactant is a cationic surfactant. Examples of the cationic surfactant include the same compounds as those for the polymerization surfactant. The amount of the post-addition surfactant may be 0.05 to 20 parts by weight, for example 0.1 to 10 parts by weight, especially 0.3 to 5 parts by weight, based on 100 parts by weight of the monomer (or fluoropolymer), especially In the range of 2 to 5 parts by weight.

The monomer may be polymerized in the presence of at least one compound selected from the group consisting of a blocked isocyanate compound and an organopolyoxyalkylene compound. The amount of the blocked isocyanate compound (or the organopolyoxyalkylene compound) may be from 0 to 100 parts by weight, for example, from 1 to 50 parts by weight, per 100 parts by weight of the monomer.

The fluoropolymer having a blocked isocyanate group can be obtained by polymerizing a monomer in the presence of a blocked isocyanate compound. The blocked isocyanate compound is an isocyanate blocked by at least one block agent. Examples of the blocking agent include anthraquinones, phenols, alcohols, mercaptans, decylamines, quinones, imidazoles, ureas, amines, imines, pyrazoles, and Active methylene compounds. Other examples of the terminal blocking agent include pyridinol, thiophenol, diketone, and ester. The blocked isocyanate compound can be modified by a compound having a hydrophilic group.

By polymerizing a monomer in the presence of an organopolyoxyalkylene compound (for example, a thiol-functional organopolysiloxane or a vinyl-functional organopolyoxane), a decyloxy group is obtained. Fluoropolymer. In one embodiment, the thiol-functional organopolyoxane has an oxirane unit having the following average formula: (R ₂ SiO) _a (RR ^N SiO) _b (RR ^S SiO) _c

[wherein, a is 0 to 4000, or 0 to 1000, or 0 to 400, b is 1 to 1000, or 1 to 100, or 1 to 50, c is 1 to 1000, or 1 to 100, or 1 to 50; R is independently a monovalent organic group, or R is a hydrocarbon group having 1 to 30 carbon atoms, or R is a monovalent alkyl group having 1 to 12 carbon atoms, or R is a methyl group; R ^N is a monovalent amine functional organic group, and R ^S is a monovalent hydrothio functional organic group].

The organofunctional group-based amino functional organic group R ^{N is} exemplified by the formula: -R ¹ NHR ² , the formula: -R ¹ NR ₂ ² or the formula: -R ¹ NHR ¹ NHR ² (wherein each R ^{1 is} independently a divalent hydrocarbon group having ² or more carbon atoms, and R ² is a group of hydrogen or an alkyl group having 1 to 20 carbon atoms. Each R ^{1 is} typically an alkylene group having 2 to 20 carbon atoms.

Several examples of suitable amine-functional hydrocarbyl groups are: -CH ₂ CH ₂ NH ₂ , -CH ₂ CH ₂ CH ₂ NH ₂ , -CH ₂ CHCH ₃ NH ₂ , -CH ₂ CH ₂ CH ₂ CH ₂ NH ₂ , -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ NH ₂ , -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ NH ₂ , -CH ₂ CH ₂ NHCH ₃ , -CH ₂ CH ₂ CH ₂ NHCH ₃ ,- CH ₂ (CH ₃ )CHCH ₂ NHCH ₃ , -CH ₂ CH ₂ CH ₂ CH ₂ NHCH ₃ , -CH ₂ CH ₂ NHCH ₂ CH ₂ NH ₂ , -CH ₂ CH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ NH ₂ , -CH ₂ CH ₂ CH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ CH ₂ NH ₂ , -CH ₂ CH ₂ NHCH ₂ CH ₂ NHCH ₃ , -CH ₂ CH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ NHCH ₃ ,- CH ₂ CH ₂ CH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ CH ₂ NHCH ₃ , and -CH ₂ CH ₂ NHCH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ CH ₃ . A typical amine functional group is -CH ₂ CH ₂ CH ₂ NH ₂ .

R ^S is exemplified by the formula: -R ¹ SR ² (wherein each R ^{1 is} independently a divalent hydrocarbon group having ² or more carbon atoms, and R ² is hydrogen or an alkyl group having 1 to 20 carbon atoms. ¹ and R ² are groups as shown in the above). Each R ^{1 is} typically an alkylene group having 2 to 20 carbon atoms. An example of a thiol-functional group is as follows: -CH ₂ CH ₂ CH ₂ SH, -CH ₂ CHCH ₃ SH, -CH ₂ CH ₂ CH ₂ CH ₂ SH, -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ SH , -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ SH, -CH ₂ CH ₂ SCH ₃ . A typical thiol-functional group is -CH ₂ CH ₂ CH ₂ SH.

The fluoropolymer in the present invention is generally produced by emulsion polymerization.

The emulsion polymerization is a method in which a monomer is emulsified in water in the presence of a polymerization initiator and an emulsifier, and after being substituted with nitrogen, it is stirred at 50 to 80 ° C for 1 to 10 hours and copolymerized. The polymerization initiator is: benzammonium peroxide, laurel peroxide, tert-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropenyl peroxide, ethidium peroxide, or Water-soluble ones such as nitrogen diisobutyl hydrazine-dihydrochloride, azobisisobutyronitrile, sodium peroxide, potassium persulfate, ammonium persulfate, or azobisisobutyronitrile, benzammonium peroxide, Oil-soluble ones such as di-tert-butyl oxide, lauryl peroxide, cumene hydroperoxide, tert-butyl peroxytrimethylacetate, and diisopropyl peroxydicarbonate. 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 a copolymer aqueous dispersion excellent in stability, it is preferred to use an emulsifying device capable of imparting strong breaking energy like a high pressure homogenizer or an ultrasonic homogenizer to granulate and polymerize the monomer in water. Further, as the emulsifier, various anionic, cationic or nonionic emulsifiers can be used. Relative to The amount of the emulsifier may be from 0.5 to 30 parts by weight, for example, from 1 to 20 parts by weight, per 100 parts by weight of the monomer. It is preferred to use an anionic and/or nonionic and/or cationic emulsifier. When the monomers are completely incompatible, it is preferred to add a solubilizing 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 may be enhanced by the addition of a solubilizing 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, examples of the low molecular weight monomer include methyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, and the like, and the total amount of the monomer is 100% by weight. The fraction may be used in the range of 1 to 50 parts by weight, for example, 10 to 40 parts by weight.

The fluorine-containing composition of the present invention is preferably in the form of a latex (particularly, an aqueous dispersion) or a gas gel. The fluorine-containing composition contains a fluorine-containing polymer (active component of a surface treatment agent) and a medium (particularly, a liquid medium such as an organic solvent and/or water). The amount of the medium, for example, may be 5 to 99.9% by weight, particularly 10 to 90% by weight, based on the fluorine-containing composition.

The concentration of the fluoropolymer in the fluorine-containing composition 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 in an organic solvent or water and diluted, and adhered to the surface of the object to be treated by a known method such as dip coating, spray coating or bubble coating, and dried. Further, if necessary, it can be applied together with a suitable crosslinking agent for hardening. Further, in the present invention In the fluorine composition, an insecticide, a softener, an antibacterial agent, a flame retardant, an antistatic agent, a coating fixative, an anti-wrinkle agent, or the like may be added and used in combination. The concentration of the fluoropolymer in the treatment liquid in contact with the substrate may be from 0.01 to 10% by weight (especially, during 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 (eg, gas diffusion electrodes and gas diffusion supports), glass, paper, wood, leather, fur, asbestos, brick, cement, metals and oxides, kiln products, plastics, coated surfaces, and gypsum. As the fiber product, various examples can be cited. For example, animal and plant natural fibers such as cotton, hemp, wool, silk, synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, polypropylene, semi-synthetic such as hydrazine and acetate. Inorganic fibers such as fibers, glass fibers, carbon fibers, asbestos fibers, or such mixed fibers.

The fibrous product may be in any form such as a fiber or a cloth.

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

Fluoropolymers can be applied to fibrous substrates (e.g., fibrous articles, etc.) by any of the known methods for treating fibrous articles using liquids. 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 treated fibrous product 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 a washing method, for example, it may be applied to a fibrous product in a washing application or in a dry cleaning method or the like.

The fiber product to be treated, typically a cloth, which includes weaving Fabrics, needles and fabrics and felts in the form of non-woven fabrics, clothing, but also fibers or yarns or intermediate fiber products (for example, sliver or roving, etc.). The fiber material may be natural fiber (for example, cotton or wool), chemical fiber (for example, viscose rayon or lyocell), or synthetic fiber (for example, poly Ester, polyamide or acrylic fiber, or a mixture of fibers (for example, a mixture of natural fibers and synthetic fibers, etc.). The polymer produced by the present invention is particularly effective in making oleophobicity and oil repellency of cellulose-based fibers (for example, 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, the polymer can be applied as an aqueous solution or an aqueous emulsion in various stages of leather processing, for example, during wet processing of leather or during modification of leather. In leather.

Alternatively, the fibrous substrate can be paper. The manufactured polymer can be applied to pre-formed paper or can be applied during various stages of papermaking, for example, during drying of the paper.

The "treatment" means that the treatment agent is applied to the object to be treated 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 to the examples.

Hereinafter, the parts are either % or ratio, and unless otherwise specified, means parts by weight or % by weight or by weight.

The order of the tests is as follows.

Shower water test

The shower water repellency test was carried out in accordance with JIS-L-1092. The shower water repellency test (shown in Table 1 below) is indicated by the water repellency No.

A glass funnel having a volume of at least 250 ml and a spray nozzle capable of spraying 250 ml of water for 20 seconds to 30 seconds are used. The frame to which the test cloth was fixed was a metal product having a diameter of 15 cm. Three test pieces having a size of about 20 cm x 20 cm were prepared, and the test cloth was fixed on the frame so that the test cloth was not wrinkled. Place the center of the spray in the center of the test cloth. Room temperature water (250 ml) was placed in a glass funnel and the test cloth (spending from 25 seconds to 30 seconds) was sprayed. Remove the frame from the pedestal, grasp one end of the frame and lower the surface of the water spray, and gently slam the frame against the test bench or the like to allow excess water to fall. The frame was then rotated 180°, and after repeating the same procedure, the surface of the test cloth was observed and evaluated according to the water repellency No. of Table 1. The results were obtained from the average of 3 measurements.

Osmosis water test

The test cloth was fixed with a metallic frame having a diameter of 15 cm. Prepare three test cloths measuring approximately 20 cm x 20 cm, and fix the test cloth on the frame and The sheet does not wrinkle. 2 g of water was placed in the center of the test piece, and the penetration of the test piece after 5 minutes was evaluated.

○ no spots

△ see the spot

× see the spot that extends to the periphery

Inclusion stability test

The aqueous dispersion was diluted with a solid concentration of tap water to 0.6% by weight, and 0.03 wt% of a FIX agent for nylon was added thereto, and the mixture was appropriately stirred and mixed to observe the generation of aggregates.

○: no agglomerate produced at all

△: agglomerates are slightly produced

×: a large amount of aggregates are produced

Manufacturing example 1

In a 1 L autoclave, 37.25 g of CF ₃ CF ₂ -(CF ₂ CF ₂ ) _n -CH ₂ CH ₂ OCOC(Cl)=CH ₂ (n=2.0), 64.57 g of stearyl acrylate, and 220 g of pure water were placed. Dipropylene glycol monomethyl ether 37.24g, distearyl dimethyl ammonium chloride (cationic surfactant) 6.16g, stearyl trimethyl ammonium chloride (cationic surfactant) 1.74g, poly ring Ethylene oxide lauryl ether (EO: 20. EO represents the number of ethylene oxide units) (nonionic surfactant) 3.28 g, polyethylene oxide isotridecyl ether (EO: 3) (nonionic The surfactant was 1.30 g, 0.68 g of polyethylene oxide oleyl ether (EO: 50) (nonionic surfactant), and was ultrasonically dispersed and dispersed at 60 ° C for 15 minutes with stirring. 1.24 g of lauryl mercaptan was added, and after replacing the inside of the autoclave with nitrogen, 22.35 g of vinyl chloride (VCM) was pressed into the filling, and 2,2-azobis(2-amidinopropane) 2 hydrochloride was added to 0.62 g. (hereinafter, referred to as V-50) and a solution of 18 g of water were reacted at 60 ° C for 5 hours to obtain an aqueous dispersion of the polymer. The composition of the polymer is almost identical to the composition of the monomer placed. To the obtained aqueous dispersion, 1.0 g of stearyltrimethylammonium chloride (cationic surfactant) was added.

Manufacturing Example 2

In a 1 L autoclave, 37.25 g of CF ₃ CF ₂ -(CF ₂ CF ₂ ) _n -CH ₂ CH ₂ OCOC(Cl)=CH ₂ (n=2.0), 64.57 g of stearyl acrylate, and 220 g of pure water were placed. 37.24 g of dipropylene glycol monomethyl ether, 3.08 g of distearyl dimethyl ammonium chloride (cationic surfactant), 0.87 g of stearyl trimethylammonium chloride (cationic surfactant), poly ring Ethylene oxide lauryl ether (EO: 20. EO represents the number of ethylene oxide units) (nonionic surfactant) 5.74 g, polyethylene oxide isotridecyl ether (EO: 3) (nonionic 2.28 g of a surfactant, 2.28 g of polyethylene oxide oleyl ether (EO: 50) (nonionic surfactant), and ultrasonic dispersion at 60 ° C for 15 minutes under stirring. 1.24 g of lauryl mercaptan was added, and after replacing the inside of the autoclave with nitrogen, 22.35 g of vinyl chloride (VCM) was pressed into the filling, and 2,2-azobis(2-amidinopropane) 2 hydrochloride was added to 0.62 g. (hereinafter, referred to as V-50) and a solution of 18 g of water were reacted at 60 ° C for 5 hours to obtain an aqueous dispersion of the polymer. The composition of the polymer is almost identical to the composition of the monomer. To the obtained aqueous dispersion, 2.0 g of stearyltrimethylammonium chloride (cationic surfactant) was added.

Manufacturing Example 3

In a 500 ml reaction flask, placed CF ₃ CF ₂ -(CF ₂ CF ₂ ) _n -CH ₂ CH ₂ OCOC(Cl)=CH ₂ (n=2.0) 18.63 g, stearyl acrylate 12.42 g, methacrylic acid 31.04 g of isobornyl ester, 110 g of pure water, 18.62 g of dipropylene glycol monomethyl ether, 3.08 g of distearyl dimethyl ammonium chloride (cationic surfactant), stearyltrimethylammonium chloride (cation Surfactant) 0.87g, polyethylene oxide lauryl ether (EO: 20. EO represents the number of ethylene oxide units) (nonionic surfactant) 1.64g, polyethylene oxide isotridecane Ethyl ether (EO: 3) (nonionic surfactant) 0.65g, polyethylene oxide oleyl ether (EO: 50) (nonionic surfactant) 0.34g, super stirring at 60 ° C The sonic emulsion was dispersed for 15 minutes. After replacing the inside of the reaction flask with nitrogen, 0.62 g of lauryl mercaptan and 0.31 g of 2,2-azobis(2-amidinopropane) 2 hydrochloride (hereinafter referred to as V-50) and 9 g of water were added. The solution was reacted at 60 ° C for 5 hours to obtain an aqueous dispersion of the polymer. The composition of the polymer is almost identical to the composition of the monomer placed. To the obtained aqueous dispersion, 0.5 g of stearyltrimethylammonium chloride (cationic surfactant) was added.

Manufacturing Example 4

In a 500 ml reaction flask, placed CF ₃ CF ₂ -(CF ₂ CF ₂ ) _n -CH ₂ CH ₂ OCOC(Cl)=CH ₂ (n=2.0) 18.63 g, stearyl acrylate 12.42 g, methacrylic acid 31.04 g of isobornyl ester, 110 g of pure water, 18.62 g of dipropylene glycol monomethyl ether, 1.54 g of distearyl dimethyl ammonium chloride (cationic surfactant), stearyl trimethyl ammonium chloride (cation Surfactant) 0.44g, polyethylene oxide lauryl ether (EO: 20. EO represents the number of ethylene oxide units) (nonionic surfactant) 2.87g, polyethylene oxide isotridecane Ethyl ether (EO: 3) (nonionic surfactant) 1.14g, polyethylene oxide oleyl ether (EO: 50) (nonionic surfactant) 0.60g, super stirring at 60 ° C The sonic emulsion was dispersed for 15 minutes. 0.62 g of lauryl mercaptan was added, and after replacing the inside of the autoclave with nitrogen, 22.35 g of vinyl chloride (VCM) was pressed into the filling, and 2,2-azobis(2-amidinopropane) 2 hydrochloride was added in an amount of 0.31 g. (hereinafter, referred to as V-50) and a solution of 9 g of water were reacted at 60 ° C for 5 hours to obtain an aqueous dispersion of the polymer. The composition of the polymer is almost identical to the composition of the monomer placed. To the obtained aqueous dispersion, 1.0 g of stearyltrimethylammonium chloride (cationic surfactant) was added.

Manufacturing Example 5

In a 500 ml reaction flask, 14.3 g of CF ₃ CF ₂ -(CF ₂ CF ₂ ) _n -CH ₂ CH ₂ OCOC(Cl)=CH ₂ (n=2.0), 13.47 g of stearyl acrylate, methacrylic acid were placed. 33.71 g of isobornyl ester, 110 g of pure water, 18.62 g of dipropylene glycol monomethyl ether, 3.08 g of distearyl dimethyl ammonium chloride (cationic surfactant), stearyltrimethylammonium chloride (cation Surfactant) 0.87g, polyethylene oxide lauryl ether (EO: 20. EO represents the number of ethylene oxide units) (nonionic surfactant) 1.64g, polyethylene oxide isotridecane Ethyl ether (EO: 3) (nonionic surfactant) 0.65g, polyethylene oxide oleyl ether (EO: 50) (nonionic surfactant) 0.34g, super stirring at 60 ° C The sonic emulsion was dispersed for 15 minutes. After replacing the inside of the reaction flask with nitrogen, 0.62 g of lauryl mercaptan and 0.31 g of 2,2-azobis(2-amidinopropane) 2 hydrochloride (hereinafter referred to as V-50) and 9 g of water were added. The solution was reacted at 60 ° C for 5 hours to obtain an aqueous dispersion of the polymer. The composition of the polymer is almost identical to the composition of the monomer placed. To the obtained aqueous dispersion, 0.5 g of stearyltrimethylammonium chloride (cationic surfactant) was added.

Manufacturing Example 6

In a 500 ml reaction flask, 14.3 g of CF ₃ CF ₂ -(CF ₂ CF ₂ ) _n -CH ₂ CH ₂ OCOC(Cl)=CH ₂ (n=2.0), 13.47 g of stearyl acrylate, methacrylic acid were placed. 33.71 g of isobornyl ester, 110 g of pure water, 18.62 g of dipropylene glycol monomethyl ether, 1.54 g of distearyl dimethyl ammonium chloride (cationic surfactant), stearyltrimethylammonium chloride (cation Surfactant) 0.44g, polyethylene oxide lauryl ether (EO: 20. EO represents the number of ethylene oxide units) (nonionic surfactant) 2.87g, polyethylene oxide isotridecane Ethyl ether (EO: 3) (nonionic surfactant) 1.14g, polyethylene oxide oleyl ether (EO: 50) (nonionic surfactant) 0.60g, super stirring at 60 ° C The sonic emulsion was dispersed for 15 minutes. 0.62 g of lauryl mercaptan was added, and after replacing the inside of the autoclave with nitrogen, 22.35 g of vinyl chloride (VCM) was pressed into the filling, and 2,2-azobis(2-amidinopropane) 2 hydrochloride was added in an amount of 0.31 g. (hereinafter, referred to as V-50) and a solution of 9 g of water were reacted at 60 ° C for 5 hours to obtain an aqueous dispersion of the polymer. The composition of the polymer is almost identical to the composition of the monomer placed. To the obtained aqueous dispersion, 1.0 g of stearyltrimethylammonium chloride (cationic surfactant) was added.

Manufacturing Example 7

In a 500 ml reaction flask, 14.3 g of CF ₃ CF ₂ -(CF ₂ CF ₂ ) _n -CH ₂ CH ₂ OCOC(Cl)=CH ₂ (n=2.0), 13.47 g of stearyl acrylate, methacrylic acid were placed. 33.71 g of isobornyl ester, 110 g of pure water, 18.62 g of dipropylene glycol monomethyl ether, 3.08 g of distearyl dimethyl ammonium chloride (cationic surfactant), stearyltrimethylammonium chloride (cation Surfactant) 0.87g, polyethylene oxide lauryl ether (EO: 20. EO represents the number of ethylene oxide units) (nonionic surfactant) 1.64g, polyethylene oxide isotridecane Ethyl ether (EO: 3) (nonionic surfactant) 0.65g, polyethylene oxide oleyl ether (EO: 50) (nonionic surfactant) 0.34g, super stirring at 60 ° C The sonic emulsion was dispersed for 15 minutes. After replacing the inside of the reaction flask with nitrogen, 0.62 g of lauryl mercaptan and 0.31 g of 2,2-azobis(2-amidinopropane) 2 hydrochloride (hereinafter referred to as V-50) and 9 g of water were added. The solution was reacted at 60 ° C for 5 hours to obtain an aqueous dispersion of the polymer. The composition of the polymer is almost identical to the composition of the monomer placed. To the obtained aqueous dispersion was added 1.0 g of dicocoyldimethylammonium chloride.

Manufacturing Example 8

In a 500 ml reaction flask, 14.3 g of CF ₃ CF ₂ -(CF ₂ CF ₂ ) _n -CH ₂ CH ₂ OCOC(Cl)=CH ₂ (n=2.0), 13.47 g of stearyl acrylate, and methacrylic acid were placed. 33.71 g of borneol ester, 110 g of pure water, 18.62 g of dipropylene glycol monomethyl ether, 3.08 g of distearyl dimethyl ammonium chloride (cationic surfactant), stearyltrimethylammonium chloride (cationic) Surfactant) 0.87g, polyethylene oxide lauryl ether (EO: 20. EO represents the number of ethylene oxide units) (nonionic surfactant) 1.64g, polyethylene oxide isotridecyl Ether (EO: 3) (nonionic surfactant) 0.65 g, polyethylene oxide oleyl ether (EO: 50) (nonionic surfactant) 0.34 g, supersonic at 60 ° C with stirring Emulsified and dispersed for 15 minutes. After replacing the inside of the reaction flask with nitrogen, 0.62 g of lauryl mercaptan and 0.31 g of 2,2-azobis(2-amidinopropane) 2 hydrochloride (hereinafter referred to as V-50) and 9 g of water were added. The solution was reacted at 60 ° C for 5 hours to obtain an aqueous dispersion of the polymer. The composition of the polymer is almost identical to the composition of the monomer placed. 1.0 g of dimethyl dimethyl ammonium chloride (cationic surfactant) was added to the obtained aqueous dispersion.

Manufacturing Example 9

In a 500 ml reaction flask, placed CF ₃ CF ₂ -(CF ₂ CF ₂ ) _n -CH ₂ CH ₂ OCOC(Cl)=CH ₂ (n=2.0) 18.63 g, stearyl acrylate 12.42 g, methacrylic acid ring 31.04 g of hexyl ester, 110 g of pure water, 18.62 g of dipropylene glycol monomethyl ether, 3.08 g of distearyl dimethyl ammonium chloride (cationic surfactant), stearyltrimethylammonium chloride (cationic) Surfactant) 0.87g, polyethylene oxide lauryl ether (EO: 20. EO represents the number of ethylene oxide units) (nonionic surfactant) 1.64g, polyethylene oxide isotridecyl Ether (EO: 3) (nonionic surfactant) 0.65 g, polyethylene oxide oleyl ether (EO: 50) (nonionic surfactant) 0.34 g, supersonic at 60 ° C with stirring Emulsified and dispersed for 15 minutes. After replacing the inside of the reaction flask with nitrogen, 0.62 g of lauryl mercaptan and 0.31 g of 2,2-azobis(2-amidinopropane) 2 hydrochloride (hereinafter referred to as V-50) and 9 g of water were added. The solution was reacted at 60 ° C for 5 hours to obtain an aqueous dispersion of the polymer. The composition of the polymer is almost identical to the composition of the monomer placed. To the obtained aqueous dispersion, 0.5 g of stearyltrimethylammonium chloride (cationic surfactant) was added.

Manufacturing Example 10

In a 500 ml reaction flask, CF ₃ CF ₂ -(CF ₂ CF ₂ ) _n -CH ₂ CH ₂ OCOC(Cl)=CH ₂ (n=2.0) 16.77 g, stearyl acrylate 12.98 g, methacrylic acid were placed. 32.34 g of cyclohexyl ester, 110 g of pure water, 18.62 g of dipropylene glycol monomethyl ether, 3.08 g of distearyl dimethyl ammonium chloride (cationic surfactant), stearyltrimethylammonium chloride (cation Surfactant) 0.87g, polyethylene oxide lauryl ether (EO: 20. EO represents the number of ethylene oxide units) (nonionic surfactant) 1.64g, polyethylene oxide isotridecane Ethyl ether (EO: 3) (nonionic surfactant) 0.65g, polyethylene oxide oleyl ether (EO: 50) (nonionic surfactant) 0.34g, super stirring at 60 ° C The sonic emulsion was dispersed for 15 minutes. After replacing the inside of the reaction flask with nitrogen, 0.62 g of lauryl mercaptan and 0.31 g of 2,2-azobis(2-amidinopropane) 2 hydrochloride (hereinafter referred to as V-50) and 9 g of water were added. The solution was reacted at 60 ° C for 5 hours to obtain an aqueous dispersion of the polymer. The composition of the polymer is almost identical to the composition of the monomer placed. To the obtained aqueous dispersion, 0.5 g of stearyltrimethylammonium chloride (cationic surfactant) was added.

Comparative manufacturing example 1

In a 1 L autoclave, 37.25 g of CF ₃ CF ₂ -(CF ₂ CF ₂ ) _n -CH ₂ CH ₂ OCOC(CH ₃ )=CH ₂ (n=2.0), 64.57 g of stearyl acrylate, and 220 g of pure water were placed. , dipropylene glycol monomethyl ether 37.24g, distearyl dimethyl ammonium chloride (cationic surfactant) 3.08g, stearyl trimethyl ammonium chloride (cationic surfactant) 0.87g, poly Ethylene oxide lauryl ether (EO: 20. EO represents the number of ethylene oxide units) (nonionic surfactant) 5.74 g, polyethylene oxide isotridecyl ether (EO: 3) (non 1.28 g of ionic surfactant), 1.19 g of polyethylene oxide oleyl ether (EO: 50) (nonionic surfactant), and ultrasonic dispersion at 60 ° C for 15 minutes while stirring. 1.24 g of lauryl mercaptan was added, and after replacing the inside of the autoclave with nitrogen, 22.35 g of vinyl chloride (VCM) was pressed into the filling, and 2,2-azobis(2-amidinopropane) 2 hydrochloride was added to 0.62 g. (hereinafter, referred to as V-50) and a solution of 18 g of water were reacted at 60 ° C for 5 hours to obtain an aqueous dispersion of the polymer. The composition of the polymer is almost identical to the composition of the monomer placed. To the obtained aqueous dispersion, 2.0 g of stearyltrimethylammonium chloride (cationic surfactant) was added.

Comparative manufacturing example 2

In a 1 L autoclave, 37.25 g of CF ₃ CF ₂ -(CF ₂ CF ₂ ) _n -CH ₂ CH ₂ OCOCH=CH ₂ (n=3.0), 64.57 g of stearyl acrylate, 220 g of pure water, and dipropylene glycol were placed. Methyl ether 37.24g, distearyl dimethyl ammonium chloride (cationic surfactant) 3.08g, stearyl trimethyl ammonium chloride (cationic surfactant) 0.87g, polyethylene oxide Lauryl ether (EO: 20. EO represents the number of ethylene oxide units) (nonionic surfactant) 5.74 g, polyethylene oxide isotridecyl ether (EO: 3) (nonionic interfacial activity) 2.28 g of a polyethylene oxide oleyl ether (EO: 50) (nonionic surfactant) 1.19 g, which was ultrasonically dispersed by ultrasonic wave at 60 ° C for 15 minutes while stirring. 1.24 g of lauryl mercaptan was added, and after replacing the inside of the autoclave with nitrogen, 22.35 g of vinyl chloride (VCM) was pressed into the packed, and 2,2-azobis(2-amidinopropane) 2 hydrochloride was 0.62 g ( Hereinafter, a solution of V-50) and 18 g of water was reacted at 60 ° C for 5 hours to obtain an aqueous dispersion of the polymer. The composition of the polymer is almost identical to the composition of the monomer placed. To the obtained aqueous dispersion, 2.0 g of stearyltrimethylammonium chloride (cationic surfactant) was added.

Comparative Manufacturing Example 3

In a 1 L autoclave, 37.25 g of CF ₃ CF ₂ -(CF ₂ CF ₂ ) _n -CH ₂ CH ₂ OCOC(Cl)=CH ₂ (n=2.0), 64.57 g of stearyl acrylate, and 220 g of pure water were placed. 37.24 g of dipropylene glycol monomethyl ether, 3.08 g of distearyl dimethyl ammonium chloride (cationic surfactant), 0.87 g of stearyl trimethylammonium chloride (cationic surfactant), poly ring Ethylene oxide lauryl ether (EO: 20. EO represents the number of ethylene oxide units) (nonionic surfactant) 5.74 g, polyethylene oxide isotridecyl ether (EO: 3) (nonionic 2.28 g of a surfactant, 2.28 g of polyethylene oxide oleyl ether (EO: 50) (nonionic surfactant), and ultrasonic dispersion at 60 ° C for 15 minutes with stirring. 1.24 g of lauryl mercaptan was added, and after replacing the inside of the autoclave with nitrogen, 22.35 g of vinyl chloride (VCM) was pressed into the filling, and 2,2-azobis(2-amidinopropane) 2 hydrochloride was added to 0.62 g. (hereinafter, referred to as V-50) and a solution of 18 g of water were reacted at 60 ° C for 5 hours to obtain an aqueous dispersion of the polymer. The composition of the polymer is almost identical to the composition of the monomer placed. No cationic emulsifier was added to the obtained aqueous dispersion.

Comparative Manufacturing Example 4

In a 500 ml reaction flask, placed CF ₃ CF ₂ -(CF ₂ CF ₂ ) _n -CH ₂ CH ₂ OCOC(Cl)=CH ₂ (n=2.0) 18.63 g, stearyl acrylate 12.42 g, methacrylic acid 31.04 g of isobornyl ester, 110 g of pure water, 18.62 g of dipropylene glycol monomethyl ether, 1.54 g of distearyl dimethyl ammonium chloride (cationic surfactant), stearyl trimethyl ammonium chloride (cation Surfactant) 0.44g, polyethylene oxide lauryl ether (EO: 20. EO represents the number of ethylene oxide units) (nonionic surfactant) 2.87g, polyethylene oxide isotridecane Ethyl ether (EO: 3) (nonionic surfactant) 1.14g, polyethylene oxide oleyl ether (EO: 50) (nonionic surfactant) 0.60g, super stirring at 60 ° C The sonic emulsion was dispersed for 15 minutes. 0.62 g of lauryl mercaptan was added, and after replacing the inside of the autoclave with nitrogen, 22.35 g of vinyl chloride (VCM) was pressed into the filling, and 2,2-azobis(2-amidinopropane) 2 hydrochloride was added in an amount of 0.31 g. (hereinafter, referred to as V-50) and a solution of 9 g of water were reacted at 60 ° C for 5 hours to obtain an aqueous dispersion of the polymer. The composition of the polymer is almost identical to the composition of the monomer placed. 1.0 g of polyethylene oxide cocoylamine (nonionic surfactant) was added to the obtained aqueous dispersion.

Comparative Manufacturing Example 5

In a 500 ml reaction flask, placed CF ₃ CF ₂ -(CF ₂ CF ₂ ) _n -CH ₂ CH ₂ OCOC(Cl)=CH ₂ (n=2.0) 18.63 g, stearyl acrylate 12.42 g, methacrylic acid 31.04 g of isobornyl ester, 110 g of pure water, 18.62 g of dipropylene glycol monomethyl ether, 1.54 g of distearyl dimethyl ammonium chloride (cationic surfactant), stearyl trimethyl ammonium chloride (cation Surfactant) 0.44g, polyethylene oxide lauryl ether (EO: 20. EO represents the number of ethylene oxide units) (nonionic surfactant) 2.87g, polyethylene oxide isotridecane Ethyl ether (EO: 3) (nonionic surfactant) 1.14g, polyethylene oxide oleyl ether (EO: 50) (nonionic surfactant) 0.60g, super stirring at 60 ° C The sonic emulsion was dispersed for 15 minutes. 0.62 g of lauryl mercaptan was added, and after replacing the inside of the autoclave with nitrogen, 22.35 g of vinyl chloride (VCM) was pressed into the filling, and 2,2-azobis(2-amidinopropane) 2 hydrochloride was added in an amount of 0.31 g. (hereinafter, referred to as V-50) and a solution of 9 g of water were reacted at 60 ° C for 5 hours to obtain an aqueous dispersion of the polymer. The composition of the polymer is almost identical to the composition of the monomer placed. To the obtained aqueous dispersion, 1.0 g of lauryl dimethylamine oxide (amphoteric surfactant) was added.

Regarding the manufacture of the aqueous dispersion, the feed composition is shown in Table A.

Examples 1 to 10 and Comparative Examples 1 to 5

Using the aqueous dispersions obtained in Production Examples 1 to 10 (Production Examples 1 to 10) and Comparative Production Examples 1 to 5 (Comparative Examples 1 to 5), test cloths were prepared, and water repellency was evaluated.

The aqueous dispersion was diluted with water so that the solid content concentration became 0.5% by weight to prepare a treatment liquid. The polyester cloth was immersed in the treatment liquid, twisted by a rolling mill, and the wet picking rate was 65%, dried at 100 ° C for 2 minutes, and dried at 160 ° C for 1 minute to prepare a test cloth. This test cloth was used for the shower water repellency test and the osmosis water repellency test. The test results are shown in Table B.

In the table, the meaning of the abbreviated symbols is as follows.

C6SFClA C ₆ F ₁₃ CH ₂ CH ₂ OCOC(Cl)=CH ₂

C6SFMA C ₆ F ₁₃ CH ₂ CH ₂ OCOC(CH ₃ )=CH ₂

C8SFA C ₈ F ₁₇ CH ₂ CH ₂ OCOCH=CH ₂

VCM chlorinated ethylene

StA stearyl acrylate

IBMA isobornyl methacrylate (Tg > 50 ° C)

CHMA cyclohexyl methacrylate (Tg>50°C)

[Industrial availability]

The fluorine-containing composition of the present invention can be used in components such as fiber products, paper, non-woven fabrics, stone materials, electrostatic filters, dust covers, and fuel cells to impart excellent water repellency, oil repellency, and antifouling properties.

Claims (17)

A surface treatment agent comprising: (1) a fluorine-containing polymer having (a) a repeating unit derived from a fluorine-containing monomer, wherein the fluorine-containing monomer is a fluoroalkyl group a chloroacrylate, and (b) a repeating unit derived from a non-fluorine monomer, and (2) a cationic surfactant added after polymerization of the fluoropolymer, wherein the fluoromonomer (a) is A fluorine-containing monomer represented by the following formula: CH ₂ =C(-Cl)-C(=O)-YZ-Rf [wherein, Y is -O-, and Z is a direct bond or a divalent organic group. Rf is a fluoroalkyl group having 1 to 20 carbon atoms], and the above non-fluorinated monomer (b) is: (b1) an acrylate having a linear or branched hydrocarbon group having 12 to 30 carbon atoms, which has The linear or branched hydrocarbon group acrylate (b1) having 12 to 30 carbon atoms is an acrylate represented by the following formula: CH ₂ =CHCOOA ¹ [wherein A ¹ is C _n H _2n+1 (n=12 to 30), the above-mentioned cationic surfactant is an ammonium salt represented by the following formula: (R ⁵¹ ) _p N ⁺ (R ⁵² ) _4-p X ^- [wherein R ⁵¹ C12 is more linear and / or branched aliphatic group, R ⁵² is H or C1 to 4 alkyl, benzyl, polyethylene oxide , X is an anion forming group, p is 1 or 2]. The surface treatment agent according to claim 1, wherein in the fluorine-containing copolymer, the repeating unit (a) of the fluorine-containing monomer/the mooring unit (b) of the non-fluorine monomer The ratio is from 0.01/1 to 10/1. The surface treatment agent according to claim 1 or 2, wherein in the repeating unit (a) of the fluorine-containing monomer, the Z group is a linear or branched aliphatic having 1 to 20 carbon atoms. a group having 6 to 18 carbon atoms or a cyclic aliphatic group, a formula -R ² (R ¹ )N-SO ₂ - or a group represented by the formula -R ² (R ¹ )N-CO- (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- [Ar-(O) _q ] _p - (wherein R ³ is a hydrogen atom or a fluorenyl group having 1 to 10 carbon atoms, Ar is an extended aryl group having a substituent as needed, and p is 0 or 1, q is a group represented by 0 or 1), a formula -(CH ₂ ) _n -Ar-(O) _q - (wherein, Ar is an extended aryl group having a substituent as needed, and n is 0 to 10, q is a group represented by 0 or 1), or is -(CH ₂ ) _m -SO ₂ -(CH ₂ ) _n - group or -(CH ₂ ) _m -S-(CH ₂ ) _n - Base (only, m is 1 to 10, and n is 0 to 10). The surface treatment agent according to claim 1 or 2, wherein the hydrocarbon group in the acrylate (b1) having a linear or branched hydrocarbon group is 12 to 22. The surface treatment agent according to claim 1 or 2, wherein the hydrocarbon group in the acrylate (b1) having a linear or branched hydrocarbon group is an alkyl group. The surface treatment agent according to claim 1 or 2, wherein the non-fluorinated monomer (b) is at least one selected from the group consisting of: Lauryl acrylate, myristyl acrylate, cetyl acrylate, stearyl acrylate and behenyl acrylate. The surface treatment agent according to claim 1 or 2, wherein the amount of the fluorine-containing monomer (a) is from 5 to 95% by weight based on the fluoropolymer. The surface treatment agent according to claim 1 or 2, wherein the fluoropolymer further comprises a repeating unit containing a monomer having a reactive group in the molecule as a copolymerizable monomer. The surface treatment agent according to claim 8, wherein the reactive group in the monomer having a reactive group in the molecule is a hydroxyl group. The surface treatment agent according to claim 1 or 2, which comprises a blocked polyisocyanate. The surface treatment agent according to claim 1 or 2, which further comprises a surfactant for polymerization. The surface treatment agent according to claim 1 or 2, which further comprises an aqueous medium. The surface treatment agent according to claim 1 or 2, wherein the surface treatment agent is an aqueous dispersion, and the concentration of the fluoropolymer in the aqueous dispersion is 0.01 to 95% by weight, and relative to the fluoropolymer The amount of the cationic surfactant is from 0.05 to 20 parts by weight per 100 parts by weight. A method for producing a surface treatment agent, the surface treatment agent comprising: (1) a fluorine-containing polymer having (a) a repeating unit derived from a fluorine-containing monomer, wherein the fluorine-containing monomer has a fluoroalkyl group of α-chloroacrylate, and (b) a re-fraction unit derived from a non-fluorine monomer, and (2) a cationic surfactant added after polymerization of the fluoropolymer, the surface treatment agent The method for producing is to obtain a surface treatment of the fluoropolymer dispersed in the medium by copolymerizing the monomers (a) and (b) in the presence of a polymerization surfactant, and then adding a cationic surfactant. The fluorine-containing monomer (a) is a fluorine-containing monomer represented by the following formula: CH ₂ =C(-Cl)-C(=O)-YZ-Rf [wherein Y is -O-, Z Is a direct bond or a divalent organic group, Rf is a fluoroalkyl group having 1 to 20 carbon atoms, and the above non-fluorinated monomer (b) is: (b1) having a linear number of 12 to 30 carbon atoms or a branched hydrocarbon-based acrylate having a linear or branched hydrocarbon group having a carbon number of 12 to 30 (b1) as an acrylate represented by the following formula: CH ₂ =CHCOOA ¹ , A ¹ is _{C n H 2n + 1 (n} = 12 30) shown in the hydrocarbon group], the cationic surfactant is an ammonium salt of the formula ^{_{shown: (R 51) p N +}} (R 52) 4-p X - [ wherein, R ⁵¹ is a linear C12 or more a chain and/or a branched aliphatic group, R ⁵² is H or a C1 to 4 alkyl group, a benzyl group, a polyethylene oxide group, X is an anion-forming group, and p is 1 or 2]. A water-repellent oil-repellent composition which is a surface treatment agent according to any one of claims 1 to 13. A method of treating a substrate comprising treating with a surface treatment agent according to any one of claims 1 to 13. A method of producing a treated fibrous product, which comprises applying the surface treating agent according to any one of claims 1 to 13 to a fibrous product.