CN103184690A - Surface treating agent and manufacturing method thereof - Google Patents

Abstract

The utility model provides a surface treating agent. By using the surface treating agent, fiber substrate can have good waterproof performance. The surface treating agent includes (1) fluorine-containing polymer provided with (a) a repetitive unit sourced from a fluorine-containing monomer acting as Alpha-chlorin acrylate of perfluoroalkyl and (b) a repetitive unit sourced from a non-fluorine-containing monomer; and (2) cationic surfactant added after the polymerization of fluorine-containing polymer.

Description

Surface treatment agent and its production method

technical field

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

Background technique

It is known that a polymer having a perfluoroalkyl group or a perfluoroalkenyl group and a polymerizable compound having an acrylic group or a methacrylic group can be used as a water and oil repellent agent for textiles and the like, especially by using a surfactant to make the polymer An aqueous dispersion obtained by dispersing a polymer in an aqueous medium is widely used industrially.

In addition, it is generally known that excellent durability can be imparted by copolymerizing a chlorine-containing polymerizable compound such as vinyl chloride or vinylidene chloride with the above-mentioned fluorine-containing polymerizable compound. Furthermore, a water and oil repellent containing a compound that captures hydrochloric acid generated from the copolymer has also been proposed.

These practically used fluorine-containing (meth)acrylate polymers usually have 8 or more carbon atoms in the fluoroalkyl group located in the side chain, and are generally called "telomers".

There is concern that "telomers" may be decomposed or metabolized into PFOA (perfluorooctanoic acid), which is a fluorine-containing carboxylic acid with 8 carbon atoms. In addition, "telomers" have also been published in foam fire extinguishers, care products, and cleaning products. Products, many products including water-repellent and oil-repellent coatings and anti-fouling coatings set in carpets, textiles, paper, and leather (EPAOPPT FACT SHEET April 14, 2003) (http://www.epa .gov/opptintr/pfoa/pfoafacts.pdf).

In recent years, concerns about the load of PFOA on the environment have become more and more apparent, and on April 14, 2003, EPA (US Environmental Protection Agency) published a scientific investigation on PFOA.

In this case, a water and oil repellent agent with a perfluoroalkyl (meth)acrylate having 6 carbon atoms was developed as a monomer component, but it is different from (meth)acrylate with a carbon number of 8 or more. Compared with the water-repellent and oil-repellent agent with acrylate as the monomer component, not only the water-repellent and oil-repellent properties are lowered, but also the mechanical stability is insufficient. When mixed, the dispersibility of the aqueous dispersion liquid may deteriorate, and aggregation and precipitation of emulsion particles may occur. Therefore, the performance of the treated material is lowered, and the polymer adheres (gum up) to the gin to cause treatment unevenness on the processed cloth. So far, this problem (gumup) in the water and oil repellent treatment has not been solved.

At present, as a technique for simultaneously imparting water repellency and oil repellency to the surface, a polymer that uses a polymerized unit of a polymerizable monomer containing a perfluoroalkyl group (hereinafter, the perfluoroalkyl group is referred to as an Rf group) in the molecule is used. Or the copolymer of the polymer and other monomers, or the low-molecular compound with Rf group is made into an organic solvent solution or an aqueous dispersion to treat articles. This expression of water and oil repellency is caused by the formation of a "low surface energy surface" on the surface with a low critical surface tension due to the surface orientation of the Rf groups in the coating film. In order to achieve both water repellency and oil repellency, the orientation of the Rf groups on the surface is considered to be important. The Rf group-containing monomer achieves the goal in terms of water and oil repellency, but still improves other practical functions. For example, in order to improve the durability of washing, dry cleaning, friction, etc., the following improvements have been made: a monomer that imparts high hardness or a monomer with a crosslinking reactive group is used together with an Rf-containing monomer; or the obtained Blending of copolymers with polymers with high cover film strength; blending with blocked isocyanates, etc. On the other hand, with regard to copolymers containing polymerized units of Rf group-containing monomers, researches have been conducted on softening the hard texture, research on lowering the melting point of Rf groups in order to express water repellency under low temperature curing conditions, and the like. For example, there is known an example in which a monomer having an Rf group having a wide range of chain lengths is copolymerized with an alkyl group-containing monomer. In addition, a method of using a silicone containing an Rf group having a similarly wide range of chain lengths, and a method of using a mercapto-containing silicone are known.

As a known example, for example, Japanese Patent No. 3624615 (a quaternary copolymer containing Rf-based (meth)acrylate, (meth)acrylic acid octadecyl ester and two other monomers as essential components), Japanese Patent No. 3433024 (complexes of fluorine-based water and oil repellent agents and Rf-based alcohols with specific chain lengths or perfluoropolyether-based alcohols), Japanese Patent Laid-Open No. 8-109580 (containing amino silicones and Reactants of Rf-based ester compounds), WO2009/122919 (copolymers composed of Rf-based (meth)acrylate monomers, hydrocarbon (meth)acrylate monomers and mercapto-containing silicones), WO2009/ 113589 (formed from monomers containing (meth)acrylates, halogenated olefins, and fluoroalkyl groups with 1 to 6 carbon atoms that do not have a perfluoroalkyl group but have an alkyl group with 20 to 30 carbon atoms fluorine-containing copolymers), etc.

WO2011/122442 discloses a treatment agent composition containing a fluoropolymer having repeating units derived from α-chloroacrylate and a (meth)acrylate monomer having a hydrocarbon group. In this gazette, there is no detailed study on emulsifiers (surfactants).

prior art literature

patent documents

Patent Document 1: Japanese Patent No. 3624615

Patent Document 2: Japanese Patent No. 3433024

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

Patent Document 4: WO2009/122919

Patent Document 5: WO2009/113589

Patent Document 6: WO2011/122442

Contents of the invention

The problem to be solved by the invention

An object of the present invention is to provide a surface treatment agent that imparts excellent water repellency to substrates such as fiber products, and has excellent dispersion stability of an aqueous dispersion due to inclusion of inclusions during processing.

method used to solve the problem

In order to solve the above-mentioned problems, the inventors of the present invention conducted intensive research for the purpose of providing a surface treatment agent having excellent water-repellent properties including a copolymer composition containing a fluorine monomer by adding additives after the emulsion polymerization is completed. As a result, they found that the above object can be achieved by adding a cationic emulsifier, and completed the present invention.

The invention provides a surface treatment agent, which contains:

(1) Fluoropolymers having:

(a) a repeating unit derived from a fluorine-containing monomer that is an alpha-chloroacrylate having a fluoroalkyl group, and

(b) repeating units derived from non-fluoromonomers; and

(2) Cationic surfactant added after polymerization of fluoropolymer.

The effect of the invention

According to the method for producing a surface treatment agent of the present invention, it is possible to produce a surface treatment agent that imparts excellent water repellency to substrates such as fiber products and that exhibits excellent dispersion stability of an aqueous dispersion due to inclusion of inclusions during processing.

Detailed ways

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

In the present invention, the fluoropolymer has:

(a) Repeat units derived from fluorine-containing monomers (α-chloro-substituted acrylates) and (b) repeat units derived from non-fluorine monomers.

The fluorine-containing polymer of the present invention may contain only acrylates and/or (b2) Repeating units of (meth)acrylate monomers having a glass transition temperature (Tg) or a melting point (Tm) of 50°C or higher), or may also be derived from monomers (a) and monomers (b) In addition to the repeating units of the monomer, there are repeating units derived from other monomers.

(a) Fluorine-containing monomers (α-chloro-substituted fluorine-containing monomers)

The fluorine-containing monomer is a fluorine-containing monomer substituted by α-chlorine 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,

Rf is a fluoroalkyl group having 1 to 20 carbon atoms. ].

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

Specifically, the Z group can be: a straight-chain or branched aliphatic group ( For example, an alkylene group), such as a group represented by the formula -(CH ₂ ) _x - (wherein, x is 1 to 10.),

An aromatic group or a cycloaliphatic group with 6 to 18 carbon atoms,

A group represented by the formula -R ² (R ¹ )N-SO ₂ - or the formula -R ² (R ¹ )N-CO- (wherein, R ¹ is an alkyl group with 1 to 10 carbon atoms, and R ² It is a linear or branched alkylene group with 1 to 10 carbon atoms.), such as -CH ₂ CH ₂ N(R ¹ )SO ₂ - group (where R ¹ is a group with 1 to 4 carbon atoms of the alkyl group.),

Formula -CH ₂ CH(OR ³ )CH ₂ -[Ar-(O) _q ] _p -(wherein, R ³ is a hydrogen atom or an acyl group with 1 to 10 carbon atoms (such as formyl or acetyl, etc.), Ar is an arylene group (for example, phenylene) having a substituent as necessary, p is 0 or 1, and q is 0 or 1.) The group represented by,

Formula -(CH ₂ ) _n -Ar-(O) _q -(wherein, Ar is an arylene group (for example, phenylene) having a substituent as necessary, n is 0-10, and q is 0 or 1. ), or

-(CH ₂ ) _m -SO ₂ -(CH ₂ ) _n -group or -(CH ₂ ) _m -S-(CH ₂ ) _n -group (where m is 1 to 10 and n is 0 to 10).

An aromatic group or a cycloaliphatic group may be substituted or unsubstituted. S group or _SO2 group can be directly combined with Rf group.

The Rf group is preferably a perfluoroalkyl group. The number of carbon atoms in the Rf group is preferably 1-12, for example 1-6, particularly preferably 4-6. Examples of Rf groups 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 , etc.

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

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 (where 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-fluorine monomer (b) is a monomer not containing a fluorine atom. The non-fluorine monomer (b) may be an acrylate compound having 4 to 32 carbon atoms. The non-fluorine monomer (b) may be an acrylate compound represented by the following formula,

CH=CR ¹ -C(=O)OR ²

[wherein, R ¹ is H, C ₁ ~ C ₄ alkyl or halogen,

R ² is a C ₁ -C ₃₀ hydrocarbon group (for example, an aliphatic group, an aromatic group, an araliphatic group). ].

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

The non-fluorine monomer (b) can be selected from (b1) acrylates having straight-chain or branched-chain hydrocarbon groups with 12 to 30 carbon atoms, and (b2) glass transition temperature (Tg) or melting point (Tm ) is at least one compound among (meth)acrylates at 50° C. or higher.

(b1) Acrylic esters having straight-chain or branched-chain hydrocarbon groups with 12 to 30 carbon atoms

The acrylate (b1) which has a linear or branched hydrocarbon group does not have a cyclic hydrocarbon group. The linear or branched hydrocarbon group may be, in particular, a linear hydrocarbon group. The linear or branched hydrocarbon group has 12 to 30 carbon atoms, and is generally preferably a saturated aliphatic hydrocarbon group.

The acrylate (b1) having a linear or branched hydrocarbon group may be an alkyl acrylate. The number of carbon atoms in the alkyl group may be 12-30, for example 12-22, especially 14-20. 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

[where,

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

Although the following compounds can be illustrated as a specific example of the acrylate (b1) which has a linear or branched hydrocarbon group, it is not limited to these compounds.

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) (methyl) having a glass transition temperature (Tg) or a melting point (Tm) of 50°C or higher Acrylate monomer

The (meth)acrylate monomer (b2) is a (meth)acrylate monomer whose glass transition temperature (Tg) or melting point (Tm) of a homopolymer is 50 degreeC or more. The (meth)acrylate monomer (b2) is a monomer other than the monomer (b1).

The glass transition temperature and melting point are the extrapolated glass transition end temperature (T _eg ) and melting peak temperature (T _pm ) specified in JIS K7121-1987 "Methods for Determination of Transition Temperature of Plastics", respectively.

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

The (meth)acrylate monomer (b2) is preferably an acrylate compound represented by the following formula,

CH=CR ¹¹ -C(=O)OR ¹²

[wherein, R ¹¹ is H, C ₁ to C ₄ alkyl or halogen,

R ¹² is a C ₁ -C ₃₀ linear, branched or cyclic aliphatic group, a C ₆ -C ₂₀ aromatic group, or a C ₇ -C ₂₅ araliphatic group. ].

Examples of R ¹¹ are a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, and an iodine atom. R ¹¹ is preferably methyl.

Examples of R ¹² are (for example, carbon number 1-6) alkyl group (for example, methyl, ethyl, propyl, butyl), (for example, carbon number 5-10) cycloalkyl group (for example, cyclohexyl group) , (for example, those having 7 to 20 carbon atoms) polycyclic aliphatic groups (for example, norbornyl, bornyl, isobornyl, adamantyl), phenyl, naphthyl, benzyl.

R ¹² preferably has a cyclic group, preferably a cycloalkyl group, a polycyclic aliphatic group, an aromatic group or an araliphatic group. Especially when R ¹¹ is a hydrogen atom, R ¹² preferably has a cyclic group, generally a cycloalkyl group, a polycyclic aliphatic group, an aromatic group or an araliphatic group.

Specific examples of the (meth)acrylate monomer (b2) include:

Cyclohexyl acrylate, isobornyl acrylate, bornyl acrylate, adamantyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, tricyclodecanyl acrylate, phenyl acrylate, naphthyl acrylate, benzyl acrylate , 2-tert-butylphenyl acrylate, naphthyl acrylate and other acrylates;

Methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, bornyl methacrylate, adamantine methacrylate Alkyl esters, dicyclopentyl methacrylate, dicyclopentenyl methacrylate, tricyclodecanyl methacrylate, phenyl methacrylate, naphthyl methacrylate, benzyl methacrylate, methacrylic acid (2-Dimethylamino) ethyl ester, aziridine methacrylate, aziridinyl ethyl methacrylate, dicyclopentenyl methacrylate and other methacrylates;

Chloroacrylates, such as methchloroacrylate, are not limited to these compounds.

(c) Other monomers

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

Examples of other monomers (c) include, for example: ethylene, vinyl acetate, acrylonitrile, polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylates, methoxypolypropylene glycol (meth)acrylates and vinyl alkyl ethers. Other monomers are not limited to these examples.

Other monomers (c) may be halogenated olefins.

The halogenated olefin is preferably an olefin having 2 to 20 carbon atoms substituted with 1 to 10 chlorine atoms, bromine atoms or iodine atoms. The halogenated olefin is preferably a chlorinated olefin having 2 to 20 carbon atoms, particularly preferably a olefin having 2 to 5 carbon atoms having 1 to 5 chlorine atoms. Preferable specific examples of halogenated olefins are vinyl halides such as vinyl chloride, vinyl bromide, and vinyl iodide, and vinylidene halides such as vinylidene chloride, vinylidene bromide, and vinylidene iodide.

Other monomers (c) may be non-fluorinated cross-linkable monomers. The fluorine-free cross-linking monomer is a monomer not containing a fluorine atom. The fluorine-free cross-linking monomer may be a fluorine-free compound having at least 2 reactive groups and/or a carbon-carbon double bond. The non-fluorinated cross-linking monomer may be a compound having at least 2 carbon-carbon double bonds or a compound having at least 1 carbon-carbon double bond and at least 1 reactive group. Examples of reactive groups are hydroxyl, epoxy, chloromethyl, blocked isocyanate, amino, carboxyl and the like.

The non-fluorinated cross-linking monomer may be mono(meth)acrylate, di(meth)acrylate or mono(meth)acrylamide having a reactive group. Alternatively, the non-fluorinated cross-linkable monomer may be di(meth)acrylate.

One example of a non-fluorinated cross-linkable monomer is a vinyl monomer having a hydroxyl group.

Examples of non-fluorinated cross-linking monomers include diacetone (meth)acrylamide, N-methylol (meth)acrylamide, methylol (meth)acrylate, and hydroxyethyl (meth)acrylate. Esters, 3-chloro-2-hydroxypropyl (meth)acrylate, 2-acetoacetoxyethyl (meth)acrylate, butadiene, isoprene, chloroprene, monochloroacetic acid Vinyl ester, vinyl methacrylate, glycidyl (meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, etc., but not limited on these substances.

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

In the fluorine-containing polymer, the amount of the fluorine-containing monomer (a) may be 5 to 95% by weight of the fluorine-containing polymer, for example, 10 to 90% by weight, especially 20 to 70% by weight.

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

With respect to 100 parts by weight of the fluorine-containing monomer (a),

The amount of acrylate (b1) having a linear or branched hydrocarbon group is 1 to 1500 parts by weight, for example 4 to 800 parts by weight, especially 10 to 400 parts by weight,

The amount of (meth)acrylate monomer (b2) is 0 to 1500 parts by weight, for example 4 to 800 parts by weight, especially 10 to 400 parts by weight,

The amount of other monomers (c) may be 0 to 100 parts by weight, for example, 1 to 70 parts by weight, especially 3 to 50 parts by weight.

The number average molecular weight (Mn) of the fluoropolymer may generally be 1,000 to 1,000,000, for example, 5,000 to 500,000, particularly 3,000 to 200,000. The number average molecular weight (Mn) of a fluoropolymer is generally measured by GPC (Gel Permeation Chromatography).

In the present invention, generally, after copolymerizing the monomers (a) and (b) in the presence of a surfactant (surfactant for polymerization), a cationic surfactant (surfactant for post-addition) is added to obtain A fluorine-containing composition (surface treatment agent) in which a fluorine-containing polymer is dispersed in a medium.

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 polyoxyethylene (POE) group. In view of environmental problems (biodegradability, environmental hormones, etc.), the nonionic surfactant preferably has a structure that does not contain an aromatic group.

The nonionic surfactant can be polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkylene Propyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene alkylamine or polyoxyethylene alkylamine fatty acid ester.

The nonionic surfactant is preferably a surfactant represented by the following formula,

R ⁶¹ O-(CH ₂ CH ₂ O) _r -(R ⁶² O) _s -R ⁶³

[In the formula, R ⁶¹ is an alkyl group with 1 to 22 carbon atoms or an alkenyl group with 2 to 22 carbon atoms, R ⁶² is an alkylene group with 3 or more carbon atoms (for example, 3 to 10), and R ⁶³ is 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 a number of 0 or 1 or more. ].

Examples of R ⁶² are propylene, butylene. R ⁶³ is preferably a hydrogen atom. s can be 0.

Specific examples of nonionic surfactants are:

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

[In the formula, r and s have the same meaning as above. ]wait.

The nonionic surfactant may be only 1 type, or may be a mixture of 2 or more types. The nonionic surfactant can be a nonionic surfactant with r being more than 10 and s being 0 and a nonionic surfactant with r lower than 10 and s being 0 (for example, the molar ratio is 0.5:1 to 20 :1, such as 1:1 to 10:1, especially 1.5:1 to 7:1) mixture.

Cationic surfactants (cationic emulsifiers) are generally ammonium salts. The cationic surfactant may be an ammonium salt represented by the following formula,

(R ⁵¹ ) _p N ^＋ (R ⁵² ) _4-p X ^-

[wherein, R ⁵¹ is a straight-chain and/or branched aliphatic (saturated and/or unsaturated) group above C12,

R ⁵² is H or C1-4 alkyl group, benzyl group, polyoxyethylene group (the number of oxyethylene groups is, for example, 1-50, especially 2-50, especially 3-50),

X is an anion-forming group,

p is 1 or 2. ].

R ⁵¹ may be C ₁₂ -C ₅₀ , for example, C ₁₈ -C ₄₀ , especially C ₂₀ -C ₃₅ , especially C ₂₂ -C ₃₀ . R ⁵² is preferably CH ₃ or C ₂ H ₅ . Specific examples of X are halogens such as F, Cl, Br, and I, C _1-4 carboxylic acid esters such as CH ₃ COO ^- , sulfuric acid esters such as HSO ₄ ^- , phosphoric acid such as H ₂ PO ₄ ^- ester.

Specific examples of cationic surfactants include: octyltrimethylammonium bromide, octyltrimethylammonium chloride, dodecyltrimethylammonium bromide, dodecyltrimethylammonium chloride Ammonium Chloride, Myristyltrimethylammonium Bromide, Myristyltrimethylammonium Chloride, Cetyltrimethylammonium Bromide, Cetyltrimethylammonium Chloride, Octadecyl Alkyltrimethylammonium halides such as alkyltrimethylammonium chloride;

Laurylpyridinium chloride;

Dioctyldimethylammonium bromide, Dioctyldimethylammonium chloride, Didodecyldimethylammonium bromide, Didodecyldimethylammonium chloride, Ditetradecyldi Methyl ammonium bromide, ditetradecyl dimethyl ammonium chloride, dihexadecyl dimethyl ammonium bromide, dihexadecyl dimethyl ammonium chloride, dioctadecyl dimethyl ammonium Dialkyldimethylammonium halides such as ammonium chloride, etc.

A cationic surfactant may be only 1 type, or may be a mixture of 2 or more types. The cationic surfactant can be a cationic surfactant with p being 1 [(R ⁵¹ )N ⁺ (R ⁵² ) ₃ X ^- ] and a cationic surfactant with p being 2 [(R ⁵¹ ) ₂ N ⁺ ( R ⁵² ) ₂ X ⁻ ] (eg molar ratio 0.5:1-20:1, eg 1:1-10:1, especially 1.5:1-7:1) mixture.

Specific examples of anionic surfactants include sodium lauryl sulfate, triethanolamine lauryl sulfate, sodium polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene nonylphenyl ether sulfate, polyoxyethylene lauryl ether Triethanolamine Sulfate, Sodium Cocoyl Sarcosinate, Sodium N Cocoyl Methyl Taurate, Sodium Polyoxyethylene Cocoalkyl Ether Sulfate, Sodium Diether Hexyl Sulfosuccinate, Sodium Alpha Olefin Sulfonate, Sodium lauryl phosphate, sodium polyoxyethylene lauryl ether phosphate, perfluoroalkyl carboxylate (trade name Unidyne DS-101, 102 (manufactured by Daikin Industries, Ltd.)) and the like.

The amphoteric surfactants may be alanines, imidazolium betaines, amide betaines, or acetic acid betaines. Specific examples of amphoteric surfactants include: dodecyl betaine, octadecyl betaine, dodecylcarboxymethylhydroxyethylimidazolium betaine, dodecyldimethylglycine Betaine, fatty amidopropyl dimethyl glycine betaine, etc.

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

The surfactant for post-addition is a cationic surfactant. Examples of the cationic surfactant include the same compounds as those described above for the polymerization surfactant. With respect to 100 parts by weight of the monomer (or fluoropolymer), the amount of the surfactant for post-addition can 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, especially 2 ~5 parts by weight.

The monomer can be polymerized in the presence of at least one compound selected from blocked isocyanate compounds and organopolysiloxane compounds. The amount of the blocked isocyanate compound (or organopolysiloxane compound) may be 0 to 100 parts by weight, for example, 1 to 50 parts by weight, relative to 100 parts by weight of the monomer.

A fluorine-containing polymer having a blocked isocyanate group can be obtained by polymerizing a monomer in the presence of a blocked isocyanate compound. Blocked isocyanate compounds are isocyanates blocked with at least one blocking agent. Examples of blocking agents include oximes, phenols, alcohols, thiols, amides, imides, imidazoles, ureas, amines, imines, pyrazoles, and activated methylenes. base compounds. Other examples of blocking agents include hydroxypyridines, thiophenols, diketones, and esters. The blocked isocyanate compound can be modified with a compound having a hydrophilic group.

Fluoropolymers with siloxane groups are obtained by polymerizing monomers in the presence of organopolysiloxane compounds (e.g. mercapto-functional organopolysiloxanes, vinyl-functional organopolysiloxanes) . In one embodiment, the mercapto-functional organopolysiloxane contains siloxyl units having the following average formula:

(R ₂ SiO) _a (RR ^N SiO) _b (RR ^S SiO) _c

[wherein, a is 0-4000, or 0-1000, or 0-400,

b is 1-1000, or 1-100, or 1-50,

c is 1-1000, or 1-100, or 1-50;

R is independently a monovalent organic group,

Alternatively, R is a hydrocarbon having 1 to 30 carbon atoms,

Alternatively, R is a monovalent alkyl group with 1 to 12 carbon atoms,

Alternatively, R is methyl;

R ^N is a monovalent amino-functional organic group,

R ^S is a monovalent mercapto-functional organic group. ]

The amino-functional organic group R ^N as an organic functional group consists of the formula: -R ¹ NHR ² , the formula: -R ¹ NR ₂ ² or the formula: -R ¹ NHR ¹ NHR ² (where 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.) Group examples. Typically, each R ¹ is an alkylene group having 2 to 20 carbon atoms.

A few examples of preferred amino 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

_{-CH2CH2NHCH2CH2NHCH2CH2CH2CH3 . _ _ _ _ _ _} Typically, _{the amino} functional group is _{-CH2CH2CH2NH2 .}

R ^S has the formula: -R ¹ SR ² (wherein, each R ¹ is independently a divalent hydrocarbon group with 2 or more carbon atoms, and R ² is hydrogen or an alkyl group with 1 to 20 carbon atoms. In the formula, each R ¹ and R ² are as above.) Examples of groups shown. Typically, each R ¹ is an alkylene group having 2 to 20 carbon atoms. An example of a thiol functional group is described by the following formula:

-CH ₂ CH ₂ CH ₂ SH, -CH ₂ CHCH ₃ SH, -CH ₂ CH ₂ CH ₂ CH ₂ SH,

_{-CH2CH2CH2CH2CH2SH , -CH2CH2CH2CH2CH2CH2SH , _ _ _ _ _ _ _}

_{-CH2CH2SCH3 . _} Typically, _the mercapto _functional group is _-CH2CH2CH2SH .

Fluoropolymers in the present invention are generally produced by emulsion polymerization.

In the emulsion polymerization, the monomer is emulsified in water in the presence of a polymerization initiator and an emulsifier, nitrogen substitution is carried out, and the method of stirring and copolymerizing in the range of 50-80 degreeC for 1-10 hours is employ|adopted. As polymerization initiators, benzoyl peroxide, lauroyl peroxide, tert-butyl peroxybenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azo Water-soluble polymerization initiators such as bisisobutylamidine-dihydrochloride, azobisisobutyronitrile, sodium peroxide, potassium persulfate, ammonium persulfate, or azobisisobutyronitrile, benzoyl peroxide, Oil-soluble polymerization initiators such as di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, and diisopropyl peroxydicarbonate. A polymerization initiator is used in the range of 0.01-10 weight part with respect to 100 weight part of monomers.

In order to obtain an aqueous copolymer dispersion excellent in standing stability, it is preferable to micronize and polymerize monomers in water using an emulsification device capable of imparting strong crushing energy such as a high-pressure homogenizer or an ultrasonic homogenizer. Moreover, various emulsifiers of anionic type, cationic type, or nonionic type can be used as an emulsifier. The quantity of an emulsifier can be the range of 0.5-30 weight part with respect to 100 weight part of monomers, for example, the range of 1-20 weight part. When the monomers are not completely compatible, it is preferable to add a compatibilizing agent that makes these monomers fully compatible, for example, add a water-soluble organic solvent or a low molecular weight monomer. Emulsibility and copolymerizability can be improved by adding a compatibilizer.

Examples of water-soluble organic solvents include: acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, ethanol, etc., with respect to 100 parts by weight of water, the range of 1 to 50 parts by weight can be , For example, it is used in the range of 10-40 weight part. In addition, examples of low-molecular-weight monomers include methyl methacrylate, glycidyl methacrylate, and 2,2,2-trifluoroethyl methacrylate, etc., based on 100 wt. Parts can be used in a range of 1 to 50 parts by weight, for example, in a range of 10 to 40 parts by weight.

The fluorine-containing composition of the present invention is preferably in the form of an emulsion (especially an aqueous dispersion) or an aerosol. Fluorocompositions contain a fluoropolymer (active ingredient of a surface treatment agent) and a medium (especially a liquid medium such as an organic solvent and/or water). For example, the amount of the medium may be 5 to 99.9% by weight, particularly 10 to 90% by weight, relative to the fluorine-containing composition.

In the fluorine-containing composition, the concentration of the fluorine-containing polymer may be 0.01-95% by weight, for example, 5-50% by weight.

The fluorine-containing composition of the present invention can be applied to an object to be treated by a conventionally known method. Usually, the fluorine-containing composition is dispersed in an organic solvent or water, diluted, attached to the surface of the object to be treated by known methods such as dip coating, spray coating, and foam coating, and dried. Alternatively, it can be applied and cured with an appropriate crosslinker if desired. Furthermore, an insect repellant, a softener, an antibacterial agent, a flame retardant, an antistatic agent, a paint fixing agent, an anti-wrinkle agent, and the like may be added to the fluorine-containing composition of the present invention and used together. The concentration of the fluoropolymer in the treatment liquid in contact with the substrate may be 0.01 to 10% by weight (especially in the case of dip coating), for example, 0.05 to 10% by weight.

As the object to be treated with the fluorine-containing composition of the present invention (such as water and oil repellent), can enumerate: fiber products, stone materials, filters (such as electrostatic filters), dust covers, parts of fuel cells ( Such as gas diffusion electrode and gas diffusion support), glass, paper, wood, leather, fur, asbestos, brick, cement, metal and oxide, ceramic industrial products, plastic, painted surface and wall powder, etc. Various examples can be mentioned as a fiber product. Examples include natural animal and vegetable fibers such as cotton, hemp, wool, and silk, synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene, and semi-synthetic fibers such as rayon and acetate fibers. Fiber, glass fiber, carbon fiber, asbestos fiber and other inorganic fibers, or their mixed fibers.

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

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

The fluorine-containing polymer can be applied to a fibrous substrate (for example, a fibrous product) by any of known methods for treating a fibrous product in a liquid. When the fiber product is cloth, the cloth may be soaked in the solution, or the solution may be attached or sprayed on the cloth. In order to express the oil repellency of the treated fiber product, it is preferably dried, for example, heated at 100°C to 200°C.

Alternatively, the fluoropolymer may be applied to the fibrous product using a laundering process, for example, laundering may be applied or applied to the fibrous product in a dry cleaning process or the like.

Typically, the fiber product to be treated is cloth, including textiles, wovens, non-wovens, cloth in the form of clothing and carpets, but can also be fibers, yarns or intermediate fiber products (such as slivers or rovings, etc.) . Fiber product materials can be natural fibers (such as cotton or wool, etc.), chemical fibers (such as viscose or Lyocell (レオセル), etc.), synthetic fibers (such as polyester, polyamide or acrylic fibers, etc.), or can be fiber Mixtures (such as mixtures of natural and synthetic fibers, etc.). The polymers of manufacture of the present invention are particularly effective in rendering cellulosic fibers such as cotton or rayon, etc., oleophobic and repellent. Additionally, the methods of the present invention generally render the fibrous article hydrophobic and water repellent.

Alternatively, the fibrous substrate may be leather. In order to make the leather hydrophobic and oleophobic, the manufacturing polymer can be applied from an aqueous solution or an aqueous emulsion to the leather at various stages of leather processing, such as during the wet processing of leather or during the finishing of leather. leather.

Alternatively, the fibrous substrate may be paper. Manufacturing polymers can be applied to preformed paper, or can be applied in various stages of papermaking, such as during drying of the paper.

"Treatment" refers to applying a treatment agent to an object to be treated by dipping, spraying, coating, or the like. Through the treatment, the fluorine-containing polymer as an active ingredient of the treatment agent penetrates into the inside of the object to be treated and/or adheres to the surface of the object to be treated.

[Example]

Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these Examples.

Hereinafter, unless otherwise specified, parts, %, or ratios represent parts by weight, % by weight, or ratio by weight.

The test procedure is described below.

Spray water repellency test

A spray water repellency test was performed in accordance with JIS-L-1092. The spray water repellency test is represented by water repellency No. (number) (as shown in Table 1 described below).

Use a glass funnel with a volume of at least 250ml and a nozzle capable of spraying 250ml of water in 20-30 seconds. The frame for fixing the test cloth is made of metal with a diameter of 15 cm. Three test cloths having a size of approximately 20 cm×20 cm were prepared, and the test cloths were fixed to the frame so that the test cloths were not wrinkled. Place the center of the spray on the center of the test cloth. Water (250 mL) at room temperature was put into the glass funnel, and the test cloth was sprayed (over a period of 25 seconds to 30 seconds). Remove the frame from the table, hold one end of the frame so that the water-sprayed surface is on the lower side, and lightly bump the frame on a test bench or the like to drop excess water. Next, the frame was rotated by 180°, and the same procedure was repeated. Thereafter, the surface of the test cloth was observed and evaluated according to the water repellency No. in Table 1. Results were obtained from the average of 3 determinations.

[Table 1]

Water repellency number state 5 No adhesion and wetting of the surface 4 Surface slightly exhibits adherent wetting 3 Surface showing partial wetting 2 Surface showing wetting 1 The entire surface shows wetting

Osmotic water repellency test

The test cloth is fixed with a metal frame with a diameter of 15 cm. Three test cloths having a size of about 20 cm×20 cm were prepared, and the test cloths were fixed to the frame so that there were no wrinkles on the sheet. Put 2 g of water in the center of the test piece, and evaluate the penetration into the test piece after 5 minutes.

○: No penetration

△: Penetration is seen

×: Penetration spreading to the surrounding was observed.

Inclusion Stability Test

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

○: There is no generation of aggregates at all

△: Agglomerates are slightly generated

×: A large amount of aggregates are generated

Manufacturing example 1

Add CF ₃ CF ₂ -(CF ₂ CF ₂ ) _n -CH ₂ CH ₂ OCOC(Cl)=CH ₂ (n=2.0) 37.25g, octadecyl acrylate 64.57g, pure water 220g into a 1L autoclave , Dipropylene glycol monomethyl ether 37.24g, Dioctadecyldimethylammonium chloride (cationic surfactant) 6.16g, Octadecyltrimethylammonium chloride (cationic surfactant) 1.74g, Polyoxyethylene lauryl ether (EO: 20. EO represents the number of ethylene oxide units) (nonionic surfactant) 3.28g, polyoxyethylene isotridecyl ether (EO: 3) (nonionic surfactant ) 1.30 g, polyoxyethylene oleyl ether (EO: 50) (nonionic surfactant) 0.68 g, emulsified and dispersed by ultrasonic waves at 60° C. for 15 minutes under stirring. Add 1.24 g of lauryl mercaptan, replace nitrogen in the autoclave, press fill with 22.35 g of vinyl chloride (VCM), add 0.62 g of 2,2-azobis(2-amidinopropane) 2 hydrochloride ( 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 a polymer. The composition of the polymer is substantially identical to that of the feed monomer. 1.0 g of octadecyltrimethylammonium chloride (cationic surfactant) was added to the obtained aqueous dispersion.

Manufacturing example 2

Add CF ₃ CF ₂ -(CF ₂ CF ₂ ) _n -CH ₂ CH ₂ OCOC(Cl)=CH ₂ (n=2.0) 37.25g, octadecyl acrylate 64.57g, pure water 220g into a 1L autoclave , Dipropylene glycol monomethyl ether 37.24g, Dioctadecyldimethylammonium chloride (cationic surfactant) 3.08g, Octadecyltrimethylammonium chloride (cationic surfactant) 0.87g, Polyoxyethylene lauryl ether (EO: 20. EO represents the number of ethylene oxide units) (nonionic surfactant) 5.74g, polyoxyethylene isotridecyl ether (EO: 3) (nonionic surfactant ) 2.28 g, polyoxyethylene oleyl ether (EO: 50) (nonionic surfactant) 1.19 g, emulsified and dispersed by ultrasonic waves at 60° C. for 15 minutes while stirring. Add 1.24 g of lauryl mercaptan, replace nitrogen in the autoclave, press fill with 22.35 g of vinyl chloride (VCM), add 0.62 g of 2,2-azobis(2-amidinopropane) 2 hydrochloride ( 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 a polymer. The composition of the polymer is substantially identical to that of the feed monomer. 2.0 g of octadecyltrimethylammonium chloride (cationic surfactant) was added to the obtained aqueous dispersion.

Manufacturing example 3

Add CF ₃ CF ₂ -(CF ₂ CF ₂ ) _n -CH ₂ CH ₂ OCOC(Cl)=CH ₂ (n=2.0) 18.63g, octadecyl acrylate 12.42g, methacrylic acid to a 500ml reaction flask 31.04g of isobornyl ester, 110g of pure water, 18.62g of dipropylene glycol monomethyl ether, 3.08g of dioctadecyldimethylammonium chloride (cationic surfactant), 3.08g of octadecyltrimethylammonium chloride ( Cationic surfactant) 0.87g, polyoxyethylene lauryl ether (EO: 20. EO represents the number of ethylene oxide units) (nonionic surfactant) 1.64g, polyoxyethylene isotridecyl ether (EO: 3) (nonionic surfactant) 0.65 g, polyoxyethylene oleyl ether (EO: 50) (nonionic surfactant) 0.34 g, emulsified and dispersed by ultrasonic waves at 60° C. for 15 minutes while stirring. After nitrogen substitution in the reaction flask, 0.62 g of lauryl mercaptan, 0.31 g of 2,2-azobis(2-amidinopropane) 2 hydrochloride (hereinafter referred to as V-50) and 9 g of water were added. solution, reacted at 60°C for 5 hours to obtain an aqueous dispersion of the polymer. The composition of the polymer is substantially identical to that of the feed monomer. 0.5 g of octadecyltrimethylammonium chloride (cationic surfactant) was added to the obtained aqueous dispersion.

Manufacturing Example 4

Add CF ₃ CF ₂ -(CF ₂ CF ₂ ) _n -CH ₂ CH ₂ OCOC(Cl)=CH ₂ (n=2.0) 18.63g, octadecyl acrylate 12.42g, methacrylic acid to a 500ml reaction flask 31.04g of isobornyl ester, 110g of pure water, 18.62g of dipropylene glycol monomethyl ether, 1.54g of dioctadecyldimethylammonium chloride (cationic surfactant), 1.54g of octadecyltrimethylammonium chloride ( Cationic surfactant) 0.44g, polyoxyethylene lauryl ether (EO: 20. EO represents the number of ethylene oxide units) (nonionic surfactant) 2.87g, polyoxyethylene isotridecyl ether (EO: 20. 3) (Nonionic surfactant) 1.14g, polyoxyethylene oleyl ether (EO: 50) (nonionic surfactant) 0.60g, emulsify and disperse with ultrasonic waves at 60°C for 15 minutes under stirring. Add 0.62 g of lauryl mercaptan, replace nitrogen in the autoclave, press fill with 22.35 g of vinyl chloride (VCM), add 0.31 g of 2,2-azobis(2-amidinopropane) 2 hydrochloride ( Hereinafter, a solution of V-50) and 9 g of water was reacted at 60° C. for 5 hours to obtain an aqueous dispersion of a polymer. The composition of the polymer is substantially identical to that of the feed monomer. 1.0 g of octadecyltrimethylammonium chloride (cationic surfactant) was added to the obtained aqueous dispersion.

Manufacturing Example 5

Add CF ₃ CF ₂ -(CF ₂ CF ₂ ) _n -CH ₂ CH ₂ OCOC(Cl)=CH ₂ (n=2.0) 14.9 g, octadecyl acrylate 13.47 g, methacrylic acid to a 500 ml reaction flask 33.71g of isobornyl ester, 110g of pure water, 18.62g of dipropylene glycol monomethyl ether, 3.08g of dioctadecyldimethylammonium chloride (cationic surfactant), 3.08g of octadecyltrimethylammonium chloride ( Cationic surfactant) 0.87g, polyoxyethylene lauryl ether (EO: 20. EO represents the number of ethylene oxide units) (nonionic surfactant) 1.64g, polyoxyethylene isotridecyl ether (EO: 3) (nonionic surfactant) 0.65 g, polyoxyethylene oleyl ether (EO: 50) (nonionic surfactant) 0.34 g, emulsified and dispersed by ultrasonic waves at 60° C. for 15 minutes while stirring. After nitrogen substitution in the reaction flask, 0.62 g of lauryl mercaptan, 0.31 g of 2,2-azobis(2-amidinopropane) 2 hydrochloride (hereinafter referred to as V-50) and 9 g of water were added. solution, reacted at 60°C for 5 hours to obtain an aqueous dispersion of the polymer. The composition of the polymer is substantially identical to that of the feed monomer. 0.5 g of octadecyltrimethylammonium chloride (cationic surfactant) was added to the obtained aqueous dispersion.

Manufacturing example 6

Add CF ₃ CF ₂ -(CF ₂ CF ₂ ) _n -CH ₂ CH ₂ OCOC(Cl)=CH ₂ (n=2.0) 14.9 g, octadecyl acrylate 13.47 g, methacrylic acid to a 500 ml reaction flask 33.71g of isobornyl ester, 110g of pure water, 18.62g of dipropylene glycol monomethyl ether, 1.54g of dioctadecyldimethylammonium chloride (cationic surfactant), 1.54g of octadecyltrimethylammonium chloride ( Cationic surfactant) 0.44g, polyoxyethylene lauryl ether (EO: 20. EO represents the number of ethylene oxide units) (nonionic surfactant) 2.87g, polyoxyethylene isotridecyl ether (EO: 20. 3) (Nonionic surfactant) 1.14g, polyoxyethylene oleyl ether (EO: 50) (nonionic surfactant) 0.60g, emulsify and disperse with ultrasonic waves at 60°C for 15 minutes under stirring. Add 0.62 g of lauryl mercaptan, replace nitrogen in the autoclave, press fill with 22.35 g of vinyl chloride (VCM), add 0.31 g of 2,2-azobis(2-amidinopropane) 2 hydrochloride ( Hereinafter, a solution of V-50) and 9 g of water was reacted at 60° C. for 5 hours to obtain an aqueous dispersion of a polymer. The composition of the polymer is substantially identical to that of the feed monomer. 1.0 g of octadecyltrimethylammonium chloride (cationic surfactant) was added to the obtained aqueous dispersion.

Manufacturing example 7

Add CF ₃ CF ₂ -(CF ₂ CF ₂ ) _n -CH ₂ CH ₂ OCOC(Cl)=CH ₂ (n=2.0) 14.9 g, octadecyl acrylate 13.47 g, methacrylic acid to a 500 ml reaction flask 33.71g of isobornyl ester, 110g of pure water, 18.62g of dipropylene glycol monomethyl ether, 3.08g of dioctadecyldimethylammonium chloride (cationic surfactant), 3.08g of octadecyltrimethylammonium chloride ( Cationic surfactant) 0.87g, polyoxyethylene lauryl ether (EO: 20. EO represents the number of ethylene oxide units) (nonionic surfactant) 1.64g, polyoxyethylene isotridecyl ether (EO: 3) (nonionic surfactant) 0.65 g, polyoxyethylene oleyl ether (EO: 50) (nonionic surfactant) 0.34 g, emulsified and dispersed by ultrasonic waves at 60° C. for 15 minutes while stirring. After nitrogen substitution in the reaction flask, 0.62 g of lauryl mercaptan, 0.31 g of 2,2-azobis(2-amidinopropane) 2 hydrochloride (hereinafter referred to as V-50) and 9 g of water were added. solution, reacted at 60°C for 5 hours to obtain an aqueous dispersion of the polymer. The composition of the polymer is substantially identical to that of the feed monomer. 1.0 g of dicocoyl dimethyl ammonium chloride was added to the obtained aqueous dispersion liquid.

Manufacturing example 8

Add CF ₃ CF ₂ -(CF ₂ CF ₂ ) _n -CH ₂ CH ₂ OCOC(Cl)=CH ₂ (n=2.0) 14.9 g, octadecyl acrylate 13.47 g, methacrylic acid to a 500 ml reaction flask 33.71g of isobornyl ester, 110g of pure water, 18.62g of dipropylene glycol monomethyl ether, 3.08g of dioctadecyldimethylammonium chloride (cationic surfactant), 3.08g of octadecyltrimethylammonium chloride ( Cationic surfactant) 0.87g, polyoxyethylene lauryl ether (EO: 20. EO represents the number of ethylene oxide units) (nonionic surfactant) 1.64g, polyoxyethylene isotridecyl ether (EO: 3) (nonionic surfactant) 0.65 g, polyoxyethylene oleyl ether (EO: 50) (nonionic surfactant) 0.34 g, emulsified and dispersed by ultrasonic waves at 60° C. for 15 minutes while stirring. After nitrogen substitution in the reaction flask, 0.62 g of lauryl mercaptan, 0.31 g of 2,2-azobis(2-amidinopropane) 2 hydrochloride (hereinafter referred to as V-50) and 9 g of water were added. solution, reacted at 60°C for 5 hours to obtain an aqueous dispersion of the polymer. The composition of the polymer is substantially identical to that of the feed monomer. 1.0 g of didecyldimethylammonium chloride (cationic surfactant) was added to the obtained aqueous dispersion.

Manufacturing Example 9

Add CF ₃ CF ₂ -(CF ₂ CF ₂ ) _n -CH ₂ CH ₂ OCOC(Cl)=CH ₂ (n=2.0) 18.63g, octadecyl acrylate 12.42g, methacrylic acid to a 500ml reaction flask Cyclohexyl ester 31.04g, pure water 110g, dipropylene glycol monomethyl ether 18.62g, dioctadecyldimethylammonium chloride (cationic surfactant) 3.08g, octadecyltrimethylammonium chloride ( Cationic surfactant) 0.87g, polyoxyethylene lauryl ether (EO: 20. EO represents the number of ethylene oxide units) (nonionic surfactant) 1.64g, polyoxyethylene isotridecyl ether (EO: 3) (nonionic surfactant) 0.65 g, polyoxyethylene oleyl ether (EO: 50) (nonionic surfactant) 0.34 g, emulsified and dispersed by ultrasonic waves at 60° C. for 15 minutes while stirring. After nitrogen substitution in the reaction flask, 0.62 g of lauryl mercaptan, 0.31 g of 2,2-azobis(2-amidinopropane) 2 hydrochloride (hereinafter referred to as V-50) and 9 g of water were added. solution, reacted at 60°C for 5 hours to obtain an aqueous dispersion of the polymer. The composition of the polymer is substantially identical to that of the feed monomer. 0.5 g of octadecyltrimethylammonium chloride (cationic surfactant) was added to the obtained aqueous dispersion.

Manufacturing example 10

Add CF ₃ CF ₂ -(CF ₂ CF ₂ ) _n -CH ₂ CH ₂ OCOC(Cl)=CH ₂ (n=2.0) 16.77g, octadecyl acrylate 12.98g, methacrylic acid to a 500ml reaction flask Cyclohexyl ester 32.34g, pure water 110g, dipropylene glycol monomethyl ether 18.62g, dioctadecyldimethylammonium chloride (cationic surfactant) 3.08g, octadecyltrimethylammonium chloride ( Cationic surfactant) 0.87g, polyoxyethylene lauryl ether (EO: 20. EO represents the number of ethylene oxide units) (nonionic surfactant) 1.64g, polyoxyethylene isotridecyl ether (EO: 3) (nonionic surfactant) 0.65 g, polyoxyethylene oleyl ether (EO: 50) (nonionic surfactant) 0.34 g, emulsified and dispersed by ultrasonic waves at 60° C. for 15 minutes while stirring. After nitrogen substitution in the reaction flask, 0.62 g of lauryl mercaptan, 0.31 g of 2,2-azobis(2-amidinopropane) 2 hydrochloride (hereinafter referred to as V-50) and 9 g of water were added. solution, reacted at 60°C for 5 hours to obtain an aqueous dispersion of the polymer. The composition of the polymer is substantially identical to that of the feed monomer. 0.5 g of octadecyltrimethylammonium chloride (cationic surfactant) was added to the obtained aqueous dispersion.

Comparative Manufacturing Example 1

Add CF ₃ CF ₂ -(CF ₂ CF ₂ ) _n -CH ₂ CH ₂ OCOC(CH ₃ )=CH ₂ (n=2.0) 37.25g, octadecyl acrylate 64.57g, pure water into a 1L autoclave 220g, dipropylene glycol monomethyl ether 37.24g, dioctadecyldimethyl ammonium chloride (cationic surfactant) 3.08g, octadecyltrimethylammonium chloride (cationic surfactant) 0.87g , Polyoxyethylene lauryl ether (EO: 20. EO represents the number of ethylene oxide units) (nonionic surfactant) 5.74g, polyoxyethylene isotridecyl ether (EO: 3) (nonionic surfactant agent) 2.28g, polyoxyethylene oleyl ether (EO: 50) (nonionic surfactant) 1.19g, emulsified and dispersed by ultrasonic waves at 60°C for 15 minutes under stirring. Add 1.24 g of lauryl mercaptan, replace nitrogen in the autoclave, press fill with 22.35 g of vinyl chloride (VCM), add 0.62 g of 2,2-azobis(2-amidinopropane) 2 hydrochloride ( 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 a polymer. The composition of the polymer is substantially identical to that of the feed monomer. 2.0 g of octadecyltrimethylammonium chloride (cationic surfactant) was added to the obtained aqueous dispersion.

Comparative Manufacturing Example 2

Add CF ₃ CF ₂ -(CF ₂ CF ₂ ) _n -CH ₂ CH ₂ OCOCH=CH ₂ (n=3.0) 37.25g, octadecyl acrylate 64.57g, pure water 220g, dipropylene glycol into a 1L autoclave Monomethyl ether 37.24g, dioctadecyldimethylammonium chloride (cationic surfactant) 3.08g, octadecyltrimethylammonium chloride (cationic surfactant) 0.87g, polyoxyethylene Lauryl ether (EO: 20. EO represents the number of ethylene oxide units) (nonionic surfactant) 5.74g, polyoxyethylene isotridecyl ether (EO: 3) (nonionic surfactant) 2.28g 1.19 g of polyoxyethylene oleyl ether (EO: 50) (nonionic surfactant) was emulsified and dispersed by ultrasonic waves at 60° C. for 15 minutes while stirring. Add 1.24 g of lauryl mercaptan, replace nitrogen in the autoclave, press fill with 22.35 g of vinyl chloride (VCM), add 0.62 g of 2,2-azobis(2-amidinopropane) 2 hydrochloride ( 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 a polymer. The composition of the polymer is substantially identical to that of the feed monomer. 2.0 g of octadecyltrimethylammonium chloride (cationic surfactant) was added to the obtained aqueous dispersion.

Comparative Manufacturing Example 3

Add CF ₃ CF ₂ -(CF ₂ CF ₂ ) _n -CH ₂ CH ₂ OCOC(Cl)=CH ₂ (n=2.0) 37.25g, octadecyl acrylate 64.57g, pure water 220g into a 1L autoclave , Dipropylene glycol monomethyl ether 37.24g, Dioctadecyldimethylammonium chloride (cationic surfactant) 3.08g, Octadecyltrimethylammonium chloride (cationic surfactant) 0.87g, Polyoxyethylene lauryl ether (EO: 20. EO represents the number of ethylene oxide units) (nonionic surfactant) 5.74g, polyoxyethylene isotridecyl ether (EO: 3) (nonionic surfactant ) 2.28 g, polyoxyethylene oleyl ether (EO: 50) (nonionic surfactant) 1.19 g, emulsified and dispersed by ultrasonic waves at 60° C. for 15 minutes while stirring. Add 1.24 g of lauryl mercaptan, replace nitrogen in the autoclave, press fill with 22.35 g of vinyl chloride (VCM), add 0.62 g of 2,2-azobis(2-amidinopropane) 2 hydrochloride ( 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 a polymer. The composition of the polymer is substantially identical to that of the feed monomer. No cationic emulsifier was added to the obtained aqueous dispersion.

Comparative Manufacturing Example 4

Add CF ₃ CF ₂ -(CF ₂ CF ₂ ) _n -CH ₂ CH ₂ OCOC(Cl)=CH ₂ (n=2.0) 18.63g, octadecyl acrylate 12.42g, methacrylic acid to a 500ml reaction flask 31.04g of isobornyl ester, 110g of pure water, 18.62g of dipropylene glycol monomethyl ether, 1.54g of dioctadecyldimethylammonium chloride (cationic surfactant), 1.54g of octadecyltrimethylammonium chloride ( Cationic surfactant) 0.44g, polyoxyethylene lauryl ether (EO: 20. EO represents the number of ethylene oxide units) (nonionic surfactant) 2.87g, polyoxyethylene isotridecyl ether (EO: 20. 3) (Nonionic surfactant) 1.14g, polyoxyethylene oleyl ether (EO: 50) (nonionic surfactant) 0.60g, emulsify and disperse with ultrasonic waves at 60°C for 15 minutes under stirring. Add 0.62 g of lauryl mercaptan, replace nitrogen in the autoclave, press fill with 22.35 g of vinyl chloride (VCM), add 0.31 g of 2,2-azobis(2-amidinopropane) 2 hydrochloride ( Hereinafter, a solution of V-50) and 9 g of water was reacted at 60° C. for 5 hours to obtain an aqueous dispersion of a polymer. The composition of the polymer is substantially identical to that of the feed monomer. 1.0 g of polyoxyethylene cocoamide (nonionic surfactant) was added to the obtained aqueous dispersion liquid.

Comparative Manufacturing Example 5

Add CF ₃ CF ₂ -(CF ₂ CF ₂ ) _n -CH ₂ CH ₂ OCOC(Cl)=CH ₂ (n=2.0) 18.63g, octadecyl acrylate 12.42g, methacrylic acid to a 500ml reaction flask 31.04g of isobornyl ester, 110g of pure water, 18.62g of dipropylene glycol monomethyl ether, 1.54g of dioctadecyldimethylammonium chloride (cationic surfactant), 1.54g of octadecyltrimethylammonium chloride ( Cationic surfactant) 0.44g, polyoxyethylene lauryl ether (EO: 20. EO represents the number of ethylene oxide units) (nonionic surfactant) 2.87g, polyoxyethylene isotridecyl ether (EO: 20. 3) (Nonionic surfactant) 1.14g, polyoxyethylene oleyl ether (EO: 50) (nonionic surfactant) 0.60g, emulsify and disperse with ultrasonic waves at 60°C for 15 minutes under stirring. Add 0.62 g of lauryl mercaptan, replace nitrogen in the autoclave, press fill with 22.35 g of vinyl chloride (VCM), add 0.31 g of 2,2-azobis(2-amidinopropane) 2 hydrochloride ( Hereinafter, a solution of V-50) and 9 g of water was reacted at 60° C. for 5 hours to obtain an aqueous dispersion of a polymer. The composition of the polymer is substantially identical to that of the feed monomer. 1.0 g of lauryl dimethylamine oxide (ampholytic surfactant) was added to the obtained aqueous dispersion liquid.

Regarding the production of aqueous dispersions, Table A shows the feed composition.

Examples 1-10 and Comparative Examples 1-5

Using the aqueous dispersions obtained in Manufacturing Examples 1 to 10 (Manufacturing Examples 1 to 10) and Comparative Manufacturing Examples 1 to 5 (Comparative Examples 1 to 5), test cloths were produced, 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 dipped in the treatment liquid, squeezed with a cloth mangle, set to a liquid squeeze rate of 65%, dried at 100°C for 2 minutes, and dried at 160°C for 1 minute to prepare a test cloth. The spray water repellency test and the osmotic water repellency test were carried out using the test cloth. Table B shows the test results.

In the tables, the meanings of the abbreviated symbols are 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 vinyl chloride

StA octadecyl acrylate

IBMA Isobornyl Methacrylate (Tg>50℃)

CHMA cyclohexyl methacrylate (Tg>50°C)

[Table 2]

[table 3]

[table 5]

Form B

example Spray water repellency test Osmotic water repellency test Inclusion Stability Example 1 5 ○ ○ Example 2 5 ○ ○ Example 3 5 ○ ○ Example 4 5 ○ ○ Example 5 5 ○ ○ Example 6 5 ○ ○ Example 7 5 ○ ○ Example 8 5 ○ ○ Example 9 5 ○ ○ Example 10 5 ○ ○ Comparative example 1 3 △ ○ Comparative example 2 4 △ ○ Comparative example 3 3 x x Comparative example 4 3 △ x Comparative Example 5 3 x x

Industrial availability

The fluorine-containing composition of the present invention can be used to impart excellent water repellency, oil repellency, and stain resistance to fiber products, paper, nonwoven fabrics, stone materials, electrostatic filters, dust covers, and fuel cell components.

Claims (20)

1. surface conditioning agent, it is characterized in that: it contains:

(1) fluoropolymer, this fluoropolymer has:

(a) be derived from as have fluoroalkyl the α-Lv Bingxisuan ester fluorochemical monomer repetitive and

(b) be derived from the repetitive of non-fluorine monomer; And

(2) cationic surface active agent that after the polymerization of fluoropolymer, adds.

2. surface conditioning agent as claimed in claim 1 is characterized in that:

The mol ratio of the repetitive (b) of the repetitive of the fluorochemical monomer in the fluorinated copolymer (a)/non-fluorine monomer is 0.01/1～10/1.

3. surface conditioning agent as claimed in claim 1 or 2 is characterized in that:

Fluorochemical monomer (a) is by the fluorochemical monomer shown in the following formula,

CH ₂=C(-Cl)-C(=O)-Y-Z-Rf

In the formula, Y is-O-or-NH-,

Z is the organic group of directly combination or divalence,

Rf is the fluoroalkyl of carbon number 1～20.

4. as each described surface conditioning agent in the claim 1～3, it is characterized in that:

Non-fluorine monomer (b) is by the acrylate compounds shown in the following formula,

CH=CR ¹-C(=O)O-R ²

In the formula, R ¹Be H, C ₁～C ₄Alkyl or halogen,

R ²Be C ₁～C ₃₀Alkyl (for example being aliphatic group, aromatic group, aromatic-aliphatic group).

5. as each described surface conditioning agent in the claim 1～4, it is characterized in that:

Non-fluorine monomer (b) is for being selected from (b1) and having the acrylate of the straight chain shape of carbon number 12～30 or chain alkyl and (b2) glass transition temperature (Tg) or fusing point (Tm) being at least a kind of compound in (methyl) acrylate more than 50 ℃.

6. surface conditioning agent as claimed in claim 5 is characterized in that:

Acrylate (b1) with straight chain shape or chain alkyl is by the acrylate shown in the following formula,

CH ₂＝CHCOOA ¹

In the formula, A ¹For by C _nH _2n+1Alkyl shown in (n=12～30).

7. surface conditioning agent as claimed in claim 6 is characterized in that:

Carbon number with the alkyl in the acrylate (b1) of straight chain shape or chain alkyl is 12～22.

8. surface conditioning agent as claimed in claim 5 is characterized in that:

(methyl) acrylate (b2) is by the acrylate compounds shown in the following formula,

CH=CR ¹¹-C(=O)O-R ¹²

In the formula, R ¹¹Be H, C ₁～C ₄Alkyl or halogen,

R ¹²Be C ₁～C ₃₀The aliphatic group of straight chain shape, chain or ring-type, C ₆～C ₂₀Aromatic group, C ₇～C ₂₅The aromatic-aliphatic group.

9. as each described surface conditioning agent in the claim 1～8, it is characterized in that:

Non-fluorine monomer (b) is for being selected from lauryl acrylate, acrylic acid myristyl ester, acrylic acid cetyl ester, acrylic acid stearyl, acrylic acid docosyl ester;

Cyclohexyl acrylate, isobornyl acrylate, acrylic acid norbornene ester, acrylic acid adamantane esters, acrylic acid two ring pentyl esters, acrylic acid two cyclopentene esters, acrylic acid three ring esters in the last of the ten Heavenly stems, phenyl acrylate, acrylic acid naphthalene ester, benzyl acrylate, acrylic acid 2-tert-butyl group phenyl ester, acrylic acid naphthalene ester;

Methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, the metering system tert-butyl acrylate, cyclohexyl methacrylate, isobornyl methacrylate, the methacrylic acid norbornene ester, the methacrylic acid adamantane esters, methacrylic acid two ring pentyl esters, methacrylic acid two cyclopentene esters, methacrylic acid three ring esters in the last of the ten Heavenly stems, phenyl methacrylate, methacrylic acid naphthalene ester, benzyl methacrylate, methacrylic acid (2-dimethylamino) ethyl ester, methacrylic acid aziridine ester, methacrylic acid '-aziridino ethyl ester, methacrylic acid two cyclopentene esters; With

In the methylallyl chloride acid esters at least a kind.

10. as each described surface conditioning agent in the claim 1～9, it is characterized in that:

Fluoropolymer also comprises and contains the repetitive of the monomer of reactive group as co-polymerized monomer at molecule.

11. surface conditioning agent as claimed in claim 10 is characterized in that:

The above-mentioned reactive group that contains in the monomer of reactive group at molecule is hydroxyl.

12. as each described surface conditioning agent in the claim 1～11, it is characterized in that:

Contain the enclosed type polyisocyanate.

13. as each described surface conditioning agent in the claim 1～12, it is characterized in that:

By in the presence of surfactant (polymerization surfactant), make monomer (a) and (b) after the copolymerization, add cationic surface active agent (back interpolation surfactant), can access the surface conditioning agent that in medium, is dispersed with fluoropolymer.

14. as each described surface conditioning agent in the claim 1～13, it is characterized in that:

Cationic surface active agent (back interpolation surfactant) is by the ammonium salt shown in the following formula,

(R ⁵¹) _pN ^＋(R ⁵²) _4-pX ^-

In the formula, R ⁵¹Be aliphatic (the saturated and/or unsaturated) group of the straight chain shape more than the C12 and/or a chain,

R ⁵²Be alkyl, benzyl, the polyoxyethylene groups (quantity of oxyethylene group is 1～50 for example, is in particular 2～50, is in particular 3～50) of H or C1～4,

X is the group of formation anion,

P is 1 or 2.

15. as each described surface conditioning agent in the claim 1～14, it is characterized in that:

Also contain aqueous medium.

16. as each described surface conditioning agent in the claim 1～15, it is characterized in that:

It is aqueous liquid dispersion.

17. the manufacture method of a surface conditioning agent is characterized in that:

It is for the manufacture of following surface conditioning agent, and this surface conditioning agent contains:

(1) fluoropolymer, this fluoropolymer has:

(a) be derived from as have fluoroalkyl the α-Lv Bingxisuan ester fluorochemical monomer repetitive and

(b) be derived from the repetitive of non-fluorine monomer; And

(2) cationic surface active agent that after the polymerization of fluoropolymer, adds,

In described manufacture method, by in the presence of surfactant (polymerization surfactant), make monomer (a) and (b) add cationic surface active agent (back add use surfactant) after the copolymerization, can access the surface conditioning agent that in medium, is dispersed with fluoropolymer.

18. a water extraction oil extracticn agent composition is characterized in that:

It is each described surface conditioning agent in the claim 1～16.

19. a method of handling base material is characterized in that:

Comprise and utilize the step that each described surface conditioning agent is handled in the claim 1～16.

20. a fibre is characterized in that:

It is handled by each described surface conditioning agent in the claim 1～16 and obtains.