JP6249048B2 - Surface treatment agent and method for producing the same - Google Patents

Description

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

  It is known that a polymer of a polymerizable compound having a perfluoroalkyl group or a perfluoroalkenyl group and an acrylic acid group or a methacrylic acid group is useful as a water / oil repellent agent for a textile fabric or the like. Aqueous dispersions dispersed in an aqueous medium with a surfactant are widely used industrially.

In addition, it is generally known that excellent durability can be imparted by copolymerizing the above-mentioned fluorine-containing polymerizable compound with a chlorine-containing polymerizable compound such as vinyl chloride or vinylidene chloride. Further, a water / oil repellent comprising a compound that traps hydrochloric acid generated from the copolymer has also been proposed.
The fluoroalkyl group in the side chain of these fluorine-containing (meth) acrylate polymers that are practically used usually has 8 or more carbon atoms, and is usually called “telomer”.

  There is a concern that "telomer" may generate PFOA (perfluorooctanoic acid), a fluorine-containing carboxylic acid having 8 carbon atoms, by decomposition or metabolism, and "telomer" is a foam extinguishing agent; care product and cleaning product It has also been published for use in many products, including water and oil repellent coatings and antifouling coatings on carpets, textiles, paper and leather (EPA OPPT FACT SHEEET April 14, 2003). (Http://www.epa.gov/optintr/pfoa/pfoafacts.pdf).

  In recent years, concerns about the environmental impact of PFOA have become apparent, and on April 14, 2003, the EPA (United States Environmental Protection Agency) announced that it would strengthen scientific research on PFOA.

  Under such circumstances, water and oil repellents having (meth) acrylate having a C6 perfluoroalkyl group as a monomer component have been developed, but (meth) acrylate having 8 or more carbon atoms is used as a monomer component. Not only the water and oil repellency is reduced compared to the water and oil repellent, but also the mechanical stability is insufficient, and the contamination of the processing cloth from the pretreatment process during the processing is mixed. In some cases, the dispersibility of the aqueous dispersion deteriorates and aggregation and sedimentation of the emulsion particles occur. For this reason, the performance of the treated product deteriorates, the polymer adheres to the mangle (gum up), and processing unevenness occurs in the processed cloth, but to date, this problem in water and oil repellent treatment (gum up) has been solved. It wasn't done.

  Conventionally, as a technique for simultaneously imparting water repellency and oil repellency to a surface, a polymer comprising a polymerized unit of a polymerizable monomer containing a perfluoroalkyl group (hereinafter, perfluoroalkyl group is referred to as Rf group) in the molecule Alternatively, an article is treated with a copolymer of this and another monomer or a low molecular compound having an Rf group in an organic solvent solution or an aqueous dispersion. This expression of water and oil repellency is attributed to the formation of a “low surface energy surface” having a low critical surface tension on the surface due to the surface orientation of the Rf group in the coating film. In order to achieve both water repellency and oil repellency, the orientation of Rf groups on the surface has been considered important. This Rf group-containing monomer achieves its purpose in terms of the expression of water and oil repellency, but other practical functions have been improved. For example, in order to improve durability against washing, dry cleaning, friction, etc., a monomer having a high hardness or a monomer having a cross-linking reactive group is used together with an Rf group-containing monomer, or the obtained copolymer is coated with film strength. Improvements have been made such as blending with high polymer and blending with blocked isocyanates. On the other hand, with regard to copolymers containing polymerized units of Rf group-containing monomers, studies have been made to soften the hard texture, and studies to lower the melting point of the Rf group in order to exhibit water repellency under low temperature curing conditions. . For example, an example in which an Rf group-containing monomer having a wide chain length range is copolymerized with an alkyl group-containing monomer is known. Similarly, a method using a silicone containing an Rf group having a wide chain length range and a method using a mercapto-containing silicone are known.

  For example, Japanese Patent No. 3624615 (quaternary copolymer having Rf group (meth) acrylate and stearyl (meth) acrylate and other two kinds of monomers as essential components), Japanese Patent No. 3343024 (fluorinated water and oil repellent) And Rf group-containing alcohol or perfluoropolyether group-containing alcohol having a specific chain length), JP-A-8-109580 (reaction product of amino group-containing silicone and Rf group-containing ester compound), WO2009 / 122919 (Rf Group (meth) acrylate monomer, copolymer containing hydrocarbon (meth) acrylate monomer and mercapto group-containing silicone), WO2009 / 113589 (without perfluoroalkyl group and having 20 to 30 carbon atoms) (Meth) acrylate having a group, halogen Olefin, and the fluorine-containing copolymer comprising a monomer having a fluoroalkyl group having 1 to 6 carbon atoms) and the like as a known example.

  WO2011 / 122442 discloses a treating agent composition comprising a fluoropolymer having a repeating unit derived from α-chloroacrylate and a (meth) acrylate monomer having a hydrocarbon group. In this publication, the emulsifier (surfactant) is not examined in detail.

Japanese Patent No. 3624615 Japanese Patent No. 3433024 JP-A-8-109580 WO2009 / 122919 WO2009 / 113589 WO2011-122442

  An object of the present invention is to provide a surface treating agent that imparts excellent water repellency to a substrate such as a textile product, and is excellent in dispersion stability of an aqueous dispersion due to contamination by impurities in the processing.

  In order to solve the above-mentioned problems, the present inventors have aimed to provide a surface treatment agent having excellent water repellency comprising a copolymer composition containing a fluorine monomer by adding an additive after completion of emulsion polymerization. We conducted an intensive study. As a result, it has been found that the above object can be achieved by adding a cationic emulsifier, and the present invention has been completed.

The present invention
(1) (a) a repeating unit derived from a fluorine-containing monomer that is an α-chloroacrylate having a fluoroalkyl group, and (b) a repeating unit derived from a non-fluorine monomer,
And (2) a surface treating agent comprising a cationic surfactant added after the polymerization of the fluoropolymer.

  According to the method for producing a surface treatment agent of the present invention, a surface treatment agent that imparts excellent water repellency to a substrate such as a textile product and is excellent in dispersion stability of an aqueous dispersion due to contamination by impurities in the processing treatment. Can be manufactured.

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

In the present invention, the fluorine-containing polymer is
(A) having a repeating unit derived from a fluorine-containing monomer (α-chloro-substituted acrylate) and (b) a repeating unit derived from a non-fluorine monomer.

(A) Fluorinated monomer (α-chloro-substituted fluorinated monomer)
The fluorine-containing monomer has the 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. ]
An α-chloro substituted fluorine-containing monomer represented by the formula:

The fluorine-containing monomer (a) is preferably an acrylate ester in which the Y group is —O—.
The Z group is specifically a linear or branched aliphatic group (for example, an alkylene group) having 1 to 20 carbon atoms (for example, 1 to 10 carbon atoms, particularly 1 to 4, particularly 1 or 2). , For example, a group represented by the formula — (CH ₂ ) _x — (wherein x is 1 to 10), or
An aromatic group or cycloaliphatic group having 6 to 18 carbon atoms,
A group represented by the formula —R ² (R ¹ ) N—SO ₂ — or a formula —R ² (R ¹ ) N—CO— (wherein R ¹ is an alkyl group having 1 to 10 carbon atoms; ² is a linear alkylene group having 1 to 10 carbon atoms or a branched alkylene group.), For example, —CH ₂ CH ₂ N (R ¹ ) SO ₂ — group (where R ¹ is 1 to 4 carbon atoms) Or an alkyl group of
Formula —CH ₂ CH (OR ³ ) CH ₂ — [Ar— (O) _q ] _p — (wherein R ³ represents a hydrogen atom or an acyl group having 1 to 10 carbon atoms (for example, formyl or acetyl) ), Ar is an arylene group optionally having a substituent (for example, a phenylene group), p is 0 or 1, q is 0 or 1, or a group represented by
Formula — (CH ₂ ) _n —Ar— (O) _q — (wherein Ar is an arylene group optionally having a substituent (for example, phenylene group), n is 0 to 10, and q is 0 or 1) A group represented by
_{- (CH 2) m -SO 2} - (CH 2) n - group or a _{- (CH 2) m -S- (} CH 2) n - group (where, m is 1 to 10, n is 0-10 ).
The aromatic group or cycloaliphatic group may be substituted or unsubstituted. The S group or 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 preferably 1 to 12, for example 1 to 6, particularly 4 to 6. Examples of Rf _{groups, -CF 3, -CF 2 CF 3} , -CF 2 CF 2 CF 3, -CF (CF 3) 2, -CF 2 CF 2 CF 2 CF 3, -CF 2 CF (CF 3) ₂ , -C (CF ₃ ) ₃ ,-(CF ₂ ) ₄ CF ₃ ,-(CF ₂ ) ₂ CF (CF ₃ ) ₂ , -CF ₂ C (CF ₃ ) ₃ , -CF (CF ₃ ) CF ₂ CF ₂ CF ₃ , — (CF ₂ ) ₅ CF ₃ , — (CF ₂ ) ₃ CF (CF ₃ ) ₂ , — (CF ₂ ) ₄ CF (CF ₃ ) ₂ , —C ₈ F _{17 and the} like.

Specific examples of the fluorine-containing monomer (a) include, but are not limited to, for example, the following.
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-fluorine monomer The non-fluorine monomer (b) is a monomer containing no fluorine atom. The non-fluorine monomer (b) may be an acrylate ester compound having 4 to 32 carbon atoms. The non-fluorine monomer (b) has the formula:
CH = CR ¹ -C (= O) OR ²
[Wherein R ¹ is H, a C ₁ -C ₄ alkyl group, or halogen;
R ² is a C _{1 to} C ₃₀ hydrocarbon group (for example, an aliphatic group, an aromatic group, an araliphatic group). ]
The acrylate ester compound shown by these may be sufficient.

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 necessary.
The non-fluorine monomer (b) has (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) of 50. It may be at least one compound selected from the group consisting of (meth) acrylates that are at or above ° C.

(B1) Acrylate (b1) having a linear or branched hydrocarbon group having a linear or branched hydrocarbon group having 12 to 30 carbon atoms does not have a cyclic hydrocarbon group. The linear or branched hydrocarbon group may in particular be a linear hydrocarbon group. The linear or branched hydrocarbon group has 12 to 30 carbon atoms, and is generally a saturated aliphatic hydrocarbon group.

The acrylate (b1) having a linear or branched hydrocarbon group may be an alkyl acrylate ester. The number of carbon atoms in the alkyl group may be 12-30, for example 12-22, in particular 14-20. For example, the acrylate (b1) having a linear or branched hydrocarbon group has the formula:
CH ₂ = CHCOOA ¹
[Where:
A ¹ is an alkyl group represented by C _n H _{2n + 1} (n = 12 to 30, particularly 12 to 22). ]
An acrylate represented by

Specific examples of the acrylate (b1) having a linear or branched hydrocarbon group include, but are not limited to, the following.
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) The (meth) acrylate monomer (meth) acrylate monomer (b2) having a glass transition point (Tg) or melting point (Tm) of 50 ° C. or higher is a homopolymer glass transition point (Tg) or melting point. It is a (meth) acrylate monomer having (Tm) of 50 ° C. or higher. The (meth) acrylate monomer (b2) is a monomer other than the monomer (b1).
Glass transition point, melting point, respectively JIS K7121-1987 "Plastics transition temperature measuring method" in defined are extrapolated glass transition ending temperature _{(T eg),} melting peak temperature _{(T pm).}

The (meth) acrylate monomer (b2) has the formula:
CH = CR ¹¹ -C (= O) OR ¹²
[Wherein R ¹¹ is H, a C ₁ -C ₄ alkyl group, or halogen;
R ¹² is a C _{1 to} C ₃₀ linear, branched or cyclic aliphatic group, a C _{6 to} C ₂₀ aromatic group, or a C _{7 to} C ₂₅ araliphatic group. ]
It is preferable that it is an acrylate ester compound shown by these.

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 a methyl group.
Examples of R ¹² include alkyl groups (for example, having 1 to 6 carbon atoms) (for example, methyl group, ethyl group, propyl group, butyl group), cycloalkyl groups (for example, having 5 to 10 carbon atoms) (for example, A cyclohexyl group), a polycyclic aliphatic group (for example, a norbornyl group, a bornyl group, an isobornyl group, an adamantyl group), a phenyl group, a naphthyl group, and a benzyl group.
R ¹² preferably has a cyclic group, and is preferably a cycloalkyl group, a polycyclic aliphatic group, an aromatic group, or an araliphatic group. In particular, when R ¹¹ is a hydrogen atom, R ¹² preferably has a cyclic group, and is generally a cycloalkyl group, a polycyclic aliphatic group, an aromatic group, or an araliphatic group. .

As a specific example of the (meth) acrylate monomer (b2),
Cyclohexyl acrylate, isobornyl acrylate, bornyl acrylate, adamantyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, tricyclodecanyl acrylate, phenyl acrylate, naphthyl acrylate, benzyl acrylate, 2-t-butylphenyl acrylate, naphthyl Acrylate esters such as acrylates;
Methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, bornyl methacrylate, adamantyl methacrylate, dicyclopentanyl methacrylate, dicyclopentenyl methacrylate, tricyclodecanyl methacrylate, phenyl methacrylate, naphthyl Methacrylate esters such as methacrylate, benzyl methacrylate, (2-dimethylamino) ethyl methacrylate, aziridinyl methacrylate, aziridylinyl ethyl methacrylate, dicyclopentenyl methacrylate;
Although chloroacrylate ester, such as methyl chloroacrylate, can be illustrated, it is not limited to these.

(C) Other monomer other than non-fluorine monomer (b) (especially other than monomers (b1) and (b2)) (c), particularly non-fluorine monomers, such as Other non-fluorine non-crosslinkable monomers may be used.
Examples of other monomers (c) include, for example, ethylene, vinyl acetate, acrylonitrile, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, and methoxypolypropylene glycol (meth). Acrylates and vinyl alkyl ethers are included. 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 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 an olefin having 2 to 5 carbon atoms having 1 to 5 chlorine atoms. Preferred examples of halogenated olefins are vinyl halides such as vinyl chloride, vinyl bromide, vinyl iodide, vinylidene halides such as vinylidene chloride, vinylidene bromide, vinylidene iodide.

  The other monomer (c) may be a non-fluorine crosslinkable monomer. A non-fluorine crosslinkable monomer is a monomer which does not contain a fluorine atom. The non-fluorine crosslinkable monomer may be a compound having at least two reactive groups and / or carbon-carbon double bonds and not containing 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 reactive groups are hydroxyl groups, epoxy groups, chloromethyl groups, blocked isocyanate groups, amino groups, carboxyl groups, and the like.

  Non-fluorine crosslinkable monomers include, for example, diacetone acrylamide, (meth) acrylamide, N-methylol acrylamide, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) ) Acrylate, 2-acetoacetoxyethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, butadiene, isoprene, chloroprene, glycidyl (meth) acrylate, etc. However, it is not limited to these.

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, particularly 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) is 0.01 / 1 to 10/1, for example, 0.1 / 1 to 5/1 Good.

For 100 parts by weight of the fluorine-containing monomer (a),
The amount of the acrylate (b1) having a linear or branched hydrocarbon group is 1-1500 parts by weight, for example, 4-800 parts by weight, particularly 10-400 parts by weight,
The amount of the (meth) acrylate monomer (b2) is 0 to 1500 parts by weight, such as 4 to 800 parts by weight, particularly 10 to 400 parts by weight,
The amount of the other monomer (c) may be 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 1000 to 1000000, for example 5000 to 500000, in particular 3000 to 200000. The number average molecular weight (Mn) of the fluoropolymer is generally measured by GPC (gel permeation chromatography).

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

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

  A nonionic surfactant (nonionic emulsifier) is generally a compound having a polyoxyethylene (POE) group. The nonionic surfactant preferably has a structure that does not contain an aromatic group because of environmental problems (biodegradability, environmental hormones, etc.).

  Nonionic surfactants include polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene It may be an alkylamine or a polyoxyethylene alkylamine fatty acid ester.

Nonionic surfactants have the formula:
R ⁶¹ O— (CH ₂ CH ₂ O) _r — (R ⁶² O) _s —R ⁶³
[Wherein, R ⁶¹ represents an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms, R ⁶² represents an alkylene group having 3 or more carbon atoms (for example, 3 to 10), and R ⁶³ represents 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. ]
It is preferable that it is surfactant shown by these.
Examples of R ⁶² are a propylene group and a butylene group. R ⁶³ is preferably a hydrogen atom. s may be 0.

Specific examples of the nonionic surfactant (b2) represented by the formula (23) are as follows:
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 as defined above. ]
Etc.
The nonionic surfactant may be only one kind or a mixture of two or more kinds. The nonionic surfactant is a nonionic surfactant in which r is 10 or more and s is 0 and a nonionic surfactant in which r is less than 10 and s is 0 (for example, a molar ratio of 0.5: 1-20: 1, for example 1: 1 to 10: 1, in particular 1.5: 1 to 7: 1).

Cationic surfactants (cationic emulsifiers) are generally ammonium salts. The cationic surfactant has the formula:
(R ⁵¹ ) _p N ⁺ (R ⁵² ) _4-p X ⁻
[Wherein R ⁵¹ represents a C12 or higher linear and / or branched aliphatic (saturated and / or unsaturated) group,
R ⁵² is H or an alkyl group of C1-4, benzyl group, polyoxyethylene group (number of oxyethylene groups, for example, 1 (particularly 2, especially 3) to 50)
X is a group that forms an anion,
p is 1 or 2. ]
It may be an ammonium salt represented by

R ⁵¹ may be C12 to C50, for example C12 to C30. R ⁵² is preferably CH ₃ or C ₂ H ₅ . Specific examples of X include halogens such as F, Cl, Br, and I, C _1-4 carboxylates such as CH ₃ COO ⁻ , sulfates such as HSO ₄ ^— , and phosphates such as H ₂ PO ₄ ^—. is there.

Specific examples of the cationic surfactant include octyltrimethylammonium bromide, octyltrimethylammonium chloride, dodecyltrimethylammonium bromide, dodecyltrimethylammonium chloride, myristyltrimethylammonium bromide, myristyltrimethylammonium chloride, cetyltrimethylammonium bromide, cetyltrimethylammonium chloride Alkyltrimethylanium halides such as stearyltrimethylammonium chloride;
Lauryl pyridinium chloride;
Dioctyldimethylammonium bromide, Dioctyldimethylammonium chloride, Didodecyldimethylammonium bromide, Didodecyldimethylammonium chloride, Dimyristyldimethylammonium bromide, Dimyristyldimethylammonium chloride, Dicetyldimethylammonium bromide, Dicetyldimethylammonium chloride, Distearyldimethylammonium Examples thereof include dialkyl dimethyl ammonium halides such as chloride.

The cationic surfactant may be only one kind or a mixture of two or more kinds. Cationic surfactants include cationic surfactants [(R ⁵¹ ) N ⁺ (R ⁵² ) ₃ X ⁻ ] with p = 1 and cationic surfactants [(R ⁵¹ ) ₂ N with p = ₂ ⁺ (R ⁵² ) ₂ X ⁻ ] (eg in a molar ratio of 0.5: 1 to 20: 1, such as 1: 1 to 10: 1, in particular 1.5: 1 to 7: 1). It's okay.

  Specific examples of anionic surfactants include sodium lauryl sulfate, lauryl sulfate triethanolamine, polyoxyethylene lauryl ether sodium sulfate, polyoxyethylene nonylphenyl ether sodium sulfate, polyoxyethylene lauryl ether sulfate triethanolamine, cocoyl sarcosine. Sodium, sodium N-cocoyl methyl taurine, sodium polyoxyethylene coconut alkyl ether sulfate, sodium diether hexyl sulfosuccinate, sodium α-olefin sulfonate, sodium lauryl phosphate, sodium polyoxyethylene lauryl ether, perfluoroalkyl carboxyl Acid salts (trade names: Unidyne DS-101, 102 (manufactured by Daikin Industries, Ltd.)) and the like.

  Amphoteric surfactants may be alanines, imidazolinium betaines, amide betaines, betaine acetate, and the like. Specific examples of the amphoteric surfactant include dodecylbetaine, octadecylbetaine, dodecylcarboxymethylhydroxyethylimidazolinium betaine, dodecyldimethylaminoacetic acid betaine, fatty acid amidopropyldimethylaminoacetic acid betaine and the like.

  The polymerization surfactant 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 is 10 to 99:90 to 1, for example, 20 to 95:80 to 5, particularly 50 to 90:50 to 10, Specially, it may be 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 1 to 20 parts by weight with respect to 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 described above for the polymerization surfactant. The amount of the surfactant for post-addition is 0.05 to 20 parts by weight, for example 0.1 to 10 parts by weight, particularly 0.3 to 5 parts by weight, based on 100 parts by weight of the monomer (or fluoropolymer). It may be in the range of parts by weight.

  The monomer may be polymerized in the presence of at least one compound selected from the group consisting of 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 with respect to 100 parts by weight of the monomer.

  By polymerizing the monomer in the presence of a blocked isocyanate compound, a fluoropolymer having a blocked isocyanate group is obtained. A blocked isocyanate compound is an isocyanate that is blocked by at least one blocking agent. Examples of blocking agents include oximes, phenols, alcohols, mercaptans, amides, imides, imidazoles, ureas, amines, imines, pyrazoles, and active methylene compounds. Other examples of blocking agents include pyridinols, thiophenols, diketones and esters. The blocked isocyanate compound may be modified with a compound having a hydrophilic group.

By polymerizing the monomer in the presence of an organopolysiloxane compound (for example, mercapto functional organopolysiloxane, vinyl functional organopolysiloxane), a fluorinated polymer having a siloxane group is obtained. In one embodiment, the mercaptofunctional organopolysiloxane has siloxy units having the following average formula:
(R ₂ SiO) _a (RR ^N SiO) _b (RR ^S SiO) _c
[Wherein a is 0 to 4000, alternatively 0 to 1000, alternatively 0 to 400,
b is 1-1000, alternatively 1-100, alternatively 1-50,
c is 1-1000, alternatively 1-100, alternatively 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 having 1 to 12 carbon atoms,
Alternatively, R is a methyl group;
^RN is a monovalent amino functional organic group as defined above;
R ^S is a monovalent mercapto functional organic group as defined above. ]

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

  In emulsion polymerization, a method is employed in which a monomer is emulsified in water in the presence of a polymerization initiator and an emulsifier, and after nitrogen substitution, is stirred and copolymerized in the range of 50 to 80 ° C. for 1 to 10 hours. . Polymerization initiators include benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidine dihydrochloride, azo Water-soluble materials such as bisisobutyronitrile, sodium peroxide, potassium persulfate, ammonium persulfate, azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide Oil-soluble ones such as t-butyl peroxypivalate and diisopropyl peroxydicarbonate are used. The polymerization initiator is used in the range of 0.01 to 10 parts by weight with respect to 100 parts by weight of the monomer.

  In order to obtain a copolymer aqueous dispersion with excellent storage stability, the monomer is made into fine particles in water using an emulsifier that can impart strong crushing energy such as a high-pressure homogenizer or an ultrasonic homogenizer. It is desirable to do. As the emulsifier, various anionic, cationic or nonionic emulsifiers can be used. The amount of the emulsifier may be in the range of 0.5 to 30 parts by weight, for example 1 to 20 parts by weight with respect to 100 parts by weight of the monomer. Preference is given to using anionic and / or nonionic and / or cationic emulsifiers. When the monomers are not completely compatible with each other, it is preferable to add a compatibilizing agent such as a water-soluble organic solvent or a low molecular weight monomer that is sufficiently compatible with these monomers. By adding a compatibilizing agent, it is possible to improve emulsifying properties and copolymerization properties.

  Examples of the water-soluble organic solvent include acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, ethanol and the like, and 1 to 50 parts by weight with respect to 100 parts by weight of water. For example, you may use in the range of 10-40 weight part. Examples of the low molecular weight monomer include methyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, etc., and 1 to 50 parts by weight with respect to 100 parts by weight of the total amount of monomers, For example, you may use in the range of 10-40 weight part.

The fluorine-containing composition of the present invention is preferably in the form of an emulsion or an aerosol. The fluorine-containing composition comprises a fluorine-containing polymer (active component of the surface treatment agent) and a medium (in particular, a liquid medium such as an organic solvent and / or water). The amount of the medium may be, for example, 5 to 99.9% by weight, particularly 10 to 90% by weight, based on the fluorine-containing composition.
In the fluorine-containing composition, the concentration of the fluorine-containing polymer may be 0.01 to 95% by weight, for example 5 to 50% by weight.

  The fluorine-containing composition of the present invention can be applied to an object to be treated by a conventionally known method. Usually, the fluorine-containing composition is dispersed in an organic solvent or water, diluted, and attached to the surface of an object to be treated by a known method such as dip coating, spray coating, foam coating, etc., and then dried. Taken. Further, if necessary, it may be applied together with an appropriate crosslinking agent and cured. Furthermore, insecticides, softeners, antibacterial agents, flame retardants, antistatic agents, paint fixing agents, anti-wrinkle agents, and the like can be added to the fluorine-containing composition of the present invention. The concentration of the fluoropolymer in the treatment liquid brought into contact with the substrate may be 0.01 to 10% by weight (particularly in the case of dip coating), for example 0.05 to 10% by weight.

  Examples of objects to be treated with the fluorine-containing composition (for example, water and oil repellent) of the present invention include textile products, stone materials, filters (for example, electrostatic filters), dust masks, and fuel cell components (for example, gas). Diffusion electrodes and gas diffusion supports), glass, paper, wood, leather, fur, asbestos, bricks, cement, metals and oxides, ceramic products, plastics, painted surfaces, plasters and the like. Various examples can be given as textile products. For example, natural animal and vegetable fibers such as cotton, hemp, wool, and silk, synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene, semi-synthetic fibers such as rayon and acetate, glass fibers, and carbon fibers , Inorganic fibers such as asbestos fibers, or mixed fibers thereof.

The fiber product may be in the form of a fiber, cloth or the like.
The fluorine-containing composition of the present invention can also be used as an internal release agent or an external release agent.

  The fluoropolymer can be applied to a fibrous substrate (eg, a fiber product, etc.) by any of the known methods for treating a fiber product with a liquid. When the textile product is a fabric, the fabric may be immersed in the solution, or the solution may be attached or sprayed onto the fabric. The treated textile product is dried and preferably heated at, for example, 100 ° C. to 200 ° C. in order to develop oil repellency.

  Alternatively, the fluoropolymer may be applied to the textile by a cleaning method, and may be applied to the textile by, for example, a laundry application or a dry cleaning method.

  The textile products to be treated are typically fabrics, which include woven, knitted and non-woven fabrics, fabrics and carpets in clothing form, but fibers or yarns or intermediate fiber products (eg sliver or It may be a roving yarn). The textile product material may be natural fibers (such as cotton or wool), chemical fibers (such as viscose rayon or rheocell), or synthetic fibers (such as polyester, polyamide or acrylic fibers), or May be a mixture of fibers, such as a mixture of natural and synthetic fibers. The production polymer of the present invention is particularly effective in making cellulosic fibers (such as cotton or rayon) oleophobic and oleophobic. The method of the present invention also generally makes the textile product hydrophobic and water repellent.

Alternatively, the fibrous base material may be leather. In order to make the production polymer hydrophobic and oleophobic, aqueous solutions or aqueous emulsifications at various stages of leather processing, for example during the wet processing of leather or during the finishing of leather You may apply it to leather from things.
Alternatively, the fibrous substrate may be paper. The production polymer may be applied to preformed paper or may be applied at various stages of papermaking, for example during the drying period of the paper.

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

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these Examples.
In the following, parts or% or ratio represents parts by weight or weight% or weight ratio unless otherwise specified.
The test procedure is as follows.

Shower water repellency test A shower water repellency test was conducted according to JIS-L-1092. The shower water repellency test was performed (as shown in Table 1 below). Represented by
Use a glass funnel with a volume of at least 250 ml and a spray nozzle that can spray 250 ml of water for 20-30 seconds. The frame for fixing the test cloth is made of metal having a diameter of 15 cm. Three test cloths having a size of about 20 cm × 20 cm are prepared, and the test cloth is fixed to the frame so that the test cloth is not wrinkled. Center spray on center of test cloth. Room temperature water (250 mL) is placed in a glass funnel and sprayed onto the test cloth (over a time period of 25-30 seconds). Remove the frame from the table, grab one end of the frame and place the surface sprayed with water down, and lightly hit the frame against a laboratory table to drop excess water droplets. Subsequently, the frame was rotated 180 °, and the same procedure was repeated. Evaluate according to Results are obtained from the average of three measurements.

The dyed water repellency test cloth is fixed with a metal frame having a diameter of 15 cm. Three test cloths having a size of about 20 cm × 20 cm are prepared, and the test cloth is fixed to the frame so that the sheet is not wrinkled. 2 g of water is placed in the center of the test piece and the penetration of the test piece after 5 minutes is evaluated.
○ No stain △ Stain is seen × Stain spreading around is seen.

Contaminant 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 a FIX agent for nylon was added thereto, and the mixture was stirred well to observe the occurrence of aggregates.
○: There is no generation of agglomerates. △: Agglomerates are slightly generated.

Production Example 1
1L autoclave _{CF 3 CF 2 - (CF 2} CF 2) n -CH 2 CH 2 OCOC (Cl) = CH 2 (n = 2.0) 37.25g, stearyl acrylate 64.57G, pure water 220 g, dipropylene 37.24 g of glycol monomethyl ether, 6.16 g of distearyldimethylammonium chloride (cationic surfactant), 1.74 g of stearyltrimethylammonium chloride (cationic surfactant), polyoxyethylene lauryl ether (EO: 20. EO is (Represents the number of ethylene oxide units) (nonionic surfactant) 3.28 g, polyoxyethylene isotridecyl ether (EO: 3) (nonionic surfactant) 1.30 g, polyoxyethylene oleyl ether (EO: 50) (Nonionic surfactant) 0 Put 68 g, 15 minutes at 60 ° C. under stirring, they were charged and emulsified by ultrasonic wave. 1.24 g of lauryl mercaptan was added, the inside of the autoclave was replaced with nitrogen, and then 22.35 g of vinyl chloride (VCM) was press-fitted and 0.62 g of 2,2-azobis (2-amidinopropane) dihydrochloride (hereinafter referred to as V) −50) and 18 g of water were added and reacted at 60 ° C. for 5 hours to obtain an aqueous dispersion of polymer. The composition of the polymer almost coincided with the composition of the charged monomer. 1.0 g of stearyltrimethylammonium chloride (cationic surfactant) was added to the obtained aqueous dispersion.

Production Example 2
1L autoclave _{CF 3 CF 2 - (CF 2} CF 2) n -CH 2 CH 2 OCOC (Cl) = CH 2 (n = 2.0) 37.25g, stearyl acrylate 64.57G, pure water 220 g, dipropylene 37.24 g of glycol monomethyl ether, 3.08 g of distearyldimethylammonium chloride (cationic surfactant), 0.87 g of stearyltrimethylammonium chloride (cationic surfactant), polyoxyethylene lauryl ether (EO: 20, EO is Represents the number of ethylene oxide units) (nonionic surfactant) 5.74 g, polyoxyethylene isotridecyl ether (EO: 3) (nonionic surfactant) 2.28 g, polyoxyethylene oleyl ether (EO: 50) (Nonionic surfactant) 1 Put 19 g, 15 minutes at 60 ° C. under stirring, they were charged and emulsified by ultrasonic wave. 1.24 g of lauryl mercaptan was added, the inside of the autoclave was replaced with nitrogen, and then 22.35 g of vinyl chloride (VCM) was press-fitted and 0.62 g of 2,2-azobis (2-amidinopropane) dihydrochloride (hereinafter referred to as V) −50) and 18 g of water were added and reacted at 60 ° C. for 5 hours to obtain an aqueous dispersion of polymer. The composition of the polymer almost coincided with the composition of the charged monomer. To the obtained aqueous dispersion, 2.0 g of stearyltrimethylammonium chloride (cationic surfactant) was added.

Production Example 3
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) 18.63 g, stearyl acrylate 12.42 g, isobornyl methacrylate 31 0.04 g, pure water 110 g, dipropylene glycol monomethyl ether 18.62 g, distearyldimethylammonium chloride (cationic surfactant) 3.08 g, stearyltrimethylammonium chloride (cationic surfactant) 0.87 g, polyoxyethylene Lauryl ether (EO: 20, EO represents the number of ethylene oxide units) (nonionic surfactant) 1.64 g, polyoxyethylene isotridecyl ether (EO: 3) (nonionic surfactant) 0.65 g, poly Oxyethylene oleyl ether (EO: 50) (nonionic surfactant) was added in an amount of 0.34 g, and the mixture was emulsified and dispersed with ultrasonic waves at 60 ° C. for 15 minutes with stirring. After replacing the inside of the reaction flask with nitrogen, a solution of 0.62 g of lauryl mercaptan, 0.31 g of 2,2-azobis (2-amidinopropane) dihydrochloride (hereinafter referred to as V-50) and 9 g of water was added. The mixture was reacted at 0 ° C. for 5 hours to obtain an aqueous polymer dispersion. The composition of the polymer almost coincided with the composition of the charged monomer. 0.5 g of stearyltrimethylammonium chloride (cationic surfactant) was added to the obtained aqueous dispersion.

Production Example 4
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) 18.63 g, stearyl acrylate 12.42 g, isobornyl methacrylate 31 0.04 g, 110 g pure water, 18.62 g dipropylene glycol monomethyl ether, 1.54 g distearyldimethylammonium chloride (cationic surfactant), 0.44 g stearyltrimethylammonium chloride (cationic surfactant), polyoxyethylene Lauryl ether (EO: 20, EO represents the number of ethylene oxide units) (nonionic surfactant) 2.87 g, polyoxyethylene isotridecyl ether (EO: 3) (nonionic surfactant) 1.14 g, poly Oxyethylene oleyl ether (EO: 50) (nonionic surfactant) 0.60 g was added and emulsified and dispersed with ultrasonic waves at 60 ° C. for 15 minutes with stirring. 0.62 g of lauryl mercaptan was added, the inside of the autoclave was replaced with nitrogen, and then 22.35 g of vinyl chloride (VCM) was press-fitted and 0.31 g (hereinafter referred to as V) of 2,2-azobis (2-amidinopropane) dihydrochloride. −50) and 9 g of water were added and reacted at 60 ° C. for 5 hours to obtain an aqueous dispersion of the polymer. The composition of the polymer almost coincided with the composition of the charged monomer. 1.0 g of stearyltrimethylammonium chloride (cationic surfactant) was added to the obtained aqueous dispersion.

Production Example 5
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) 14.9 g, stearyl acrylate 13.47 g, isobornyl methacrylate 33 .71 g, pure water 110 g, dipropylene glycol monomethyl ether 18.62 g, distearyldimethylammonium chloride (cationic surfactant) 3.08 g, stearyltrimethylammonium chloride (cationic surfactant) 0.87 g, polyoxyethylene Lauryl ether (EO: 20, EO represents the number of ethylene oxide units) (nonionic surfactant) 1.64 g, polyoxyethylene isotridecyl ether (EO: 3) (nonionic surfactant) 0.65 g, poly Oxyethylene oleyl ether (EO: 50) (nonionic surfactant) 0.34 g was added and emulsified and dispersed with ultrasonic waves at 60 ° C. for 15 minutes with stirring. After replacing the inside of the reaction flask with nitrogen, a solution of 0.62 g of lauryl mercaptan, 0.31 g of 2,2-azobis (2-amidinopropane) dihydrochloride (hereinafter referred to as V-50) and 9 g of water was added. The mixture was reacted at 0 ° C. for 5 hours to obtain an aqueous polymer dispersion. The composition of the polymer almost coincided with the composition of the charged monomer. 0.5 g of stearyltrimethylammonium chloride (cationic surfactant) was added to the obtained aqueous dispersion.

Production Example 6
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) 14.9 g, stearyl acrylate 13.47 g, isobornyl methacrylate 33 .71 g, pure water 110 g, dipropylene glycol monomethyl ether 18.62 g, distearyldimethylammonium chloride (cationic surfactant) 1.54 g, stearyltrimethylammonium chloride (cationic surfactant) 0.44 g, polyoxyethylene Lauryl ether (EO: 20, EO represents the number of ethylene oxide units) (nonionic surfactant) 2.87 g, polyoxyethylene isotridecyl ether (EO: 3) (nonionic surfactant) 1.14 g, poly Oxyethylene oleyl ether (EO: 50) (nonionic surfactant) 0.60 g was added and emulsified and dispersed with ultrasonic waves at 60 ° C. for 15 minutes with stirring. 0.62 g of lauryl mercaptan was added, the inside of the autoclave was replaced with nitrogen, and then 22.35 g of vinyl chloride (VCM) was press-fitted and 0.31 g (hereinafter referred to as V) of 2,2-azobis (2-amidinopropane) dihydrochloride. −50) and 9 g of water were added and reacted at 60 ° C. for 5 hours to obtain an aqueous dispersion of the polymer. The composition of the polymer almost coincided with the composition of the charged monomer. 1.0 g of stearyltrimethylammonium chloride (cationic surfactant) was added to the obtained aqueous dispersion.

Production Example 7
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) 14.9 g, stearyl acrylate 13.47 g, isobornyl methacrylate 33 .71 g, pure water 110 g, dipropylene glycol monomethyl ether 18.62 g, distearyldimethylammonium chloride (cationic surfactant) 3.08 g, stearyltrimethylammonium chloride (cationic surfactant) 0.87 g, polyoxyethylene Lauryl ether (EO: 20, EO represents the number of ethylene oxide units) (nonionic surfactant) 1.64 g, polyoxyethylene isotridecyl ether (EO: 3) (nonionic surfactant) 0.65 g, poly Oxyethylene oleyl ether (EO: 50) (nonionic surfactant) 0.34 g was added and emulsified and dispersed with ultrasonic waves at 60 ° C. for 15 minutes with stirring. After replacing the inside of the reaction flask with nitrogen, a solution of 0.62 g of lauryl mercaptan, 0.31 g of 2,2-azobis (2-amidinopropane) dihydrochloride (hereinafter referred to as V-50) and 9 g of water was added. The mixture was reacted at 0 ° C. for 5 hours to obtain an aqueous polymer dispersion. The composition of the polymer almost coincided with the composition of the charged monomer. 1.0 g of dicocoyldimethylammonium chloride was added to the obtained aqueous dispersion.

Production Example 8
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) 14.9 g, stearyl acrylate 13.47 g, isobornyl methacrylate 33 .71 g, pure water 110 g, dipropylene glycol monomethyl ether 18.62 g, distearyldimethylammonium chloride (cationic surfactant) 3.08 g, stearyltrimethylammonium chloride (cationic surfactant) 0.87 g, polyoxyethylene Lauryl ether (EO: 20, EO represents the number of ethylene oxide units) (nonionic surfactant) 1.64 g, polyoxyethylene isotridecyl ether (EO: 3) (nonionic surfactant) 0.65 g, poly Oxyethylene oleyl ether (EO: 50) (nonionic surfactant) 0.34 g was added and emulsified and dispersed with ultrasonic waves at 60 ° C. for 15 minutes with stirring. After replacing the inside of the reaction flask with nitrogen, a solution of 0.62 g of lauryl mercaptan, 0.31 g of 2,2-azobis (2-amidinopropane) dihydrochloride (hereinafter referred to as V-50) and 9 g of water was added. The mixture was reacted at 0 ° C. for 5 hours to obtain an aqueous polymer dispersion. The composition of the polymer almost coincided with the composition of the charged monomer. 1.0 g of didecyldimethylammonium chloride (cationic surfactant) was added to the obtained aqueous dispersion.

Production Example 9
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) 18.63 g, stearyl acrylate 12.42 g, cyclohexyl methacrylate 31.04 g , 110 g of pure water, 18.62 g of dipropylene glycol monomethyl ether, 3.08 g of distearyldimethylammonium chloride (cationic surfactant), 0.87 g of stearyltrimethylammonium chloride (cationic surfactant), polyoxyethylene lauryl ether (EO: 20. EO represents the number of ethylene oxide units) (nonionic surfactant) 1.64 g, polyoxyethylene isotridecyl ether (EO: 3) (nonionic surfactant) 0.65 g, polyoxyethylene Ole Ale Ter (EO: 50) (nonionic surfactant) 0.34 g was added, and the mixture was emulsified and dispersed with ultrasonic waves at 60 ° C. for 15 minutes with stirring. After replacing the inside of the reaction flask with nitrogen, a solution of 0.62 g of lauryl mercaptan, 0.31 g of 2,2-azobis (2-amidinopropane) dihydrochloride (hereinafter referred to as V-50) and 9 g of water was added. The mixture was reacted at 0 ° C. for 5 hours to obtain an aqueous polymer dispersion. The composition of the polymer almost coincided with the composition of the charged monomer. 0.5 g of stearyltrimethylammonium chloride (cationic surfactant) was added to the obtained aqueous dispersion.

Production 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, cyclohexyl methacrylate 32.34 g , 110 g of pure water, 18.62 g of dipropylene glycol monomethyl ether, 3.08 g of distearyldimethylammonium chloride (cationic surfactant), 0.87 g of stearyltrimethylammonium chloride (cationic surfactant), polyoxyethylene lauryl ether (EO: 20. EO represents the number of ethylene oxide units) (nonionic surfactant) 1.64 g, polyoxyethylene isotridecyl ether (EO: 3) (nonionic surfactant) 0.65 g, polyoxyethylene Ole Ale Ter (EO: 50) (nonionic surfactant) 0.34 g was added, and the mixture was emulsified and dispersed with ultrasonic waves at 60 ° C. for 15 minutes with stirring. After replacing the inside of the reaction flask with nitrogen, a solution of 0.62 g of lauryl mercaptan, 0.31 g of 2,2-azobis (2-amidinopropane) dihydrochloride (hereinafter referred to as V-50) and 9 g of water was added. The mixture was reacted at 0 ° C. for 5 hours to obtain an aqueous polymer dispersion. The composition of the polymer almost coincided with the composition of the charged monomer. 0.5 g of stearyltrimethylammonium chloride (cationic surfactant) was added to the obtained aqueous dispersion.

Comparative production example 1
_CF 3 _CF 2 in 1L autoclave _{- (CF 2 CF 2) n} -CH 2 CH 2 OCOC (CH 3) = CH 2 (n = 2.0) 37.25g, stearyl acrylate 64.57G, pure water 220 g, di 37.24 g of propylene glycol monomethyl ether, 3.08 g of distearyldimethylammonium chloride (cationic surfactant), 0.87 g of stearyltrimethylammonium chloride (cationic surfactant), polyoxyethylene lauryl ether (EO: 20. EO) Represents the number of ethylene oxide units) (nonionic surfactant) 5.74 g, polyoxyethylene isotridecyl ether (EO: 3) (nonionic surfactant) 2.28 g, polyoxyethylene oleyl ether (EO: 50) ) (Nonionic surfactant) 1.19 g was added and emulsified and dispersed with ultrasonic waves at 60 ° C. for 15 minutes with stirring. 1.24 g of lauryl mercaptan was added, the inside of the autoclave was replaced with nitrogen, and then 22.35 g of vinyl chloride (VCM) was press-fitted and 0.62 g of 2,2-azobis (2-amidinopropane) dihydrochloride (hereinafter referred to as V) −50) and 18 g of water were added and reacted at 60 ° C. for 5 hours to obtain an aqueous dispersion of polymer. The composition of the polymer almost coincided with the composition of the charged monomer. To the obtained aqueous dispersion, 2.0 g of stearyltrimethylammonium chloride (cationic surfactant) was added.

Comparative production example 2
1L autoclave _{CF 3 CF 2 - (CF 2} CF 2) n -CH 2 CH 2 OCOCH = CH 2 (n = 3.0) 37.25g, stearyl acrylate 64.57G, pure water 220 g, dipropylene glycol monomethyl ether 37.24 g, distearyldimethylammonium chloride (cationic surfactant) 3.08 g, stearyltrimethylammonium chloride (cationic surfactant) 0.87 g, polyoxyethylene lauryl ether (EO: 20, EO is the number of ethylene oxide units) (Nonionic surfactant) 5.74 g, polyoxyethylene isotridecyl ether (EO: 3) (nonionic surfactant) 2.28 g, polyoxyethylene oleyl ether (EO: 50) (nonionic) Surfactant) 1.19 Was placed for 15 minutes at 60 ° C. under stirring, they were charged and emulsified by ultrasonic wave. 1.24 g of lauryl mercaptan was added, the inside of the autoclave was replaced with nitrogen, and then 22.35 g of vinyl chloride (VCM) was press-fitted and 0.62 g of 2,2-azobis (2-amidinopropane) dihydrochloride (hereinafter referred to as V) −50) and 18 g of water were added and reacted at 60 ° C. for 5 hours to obtain an aqueous dispersion of polymer. The composition of the polymer almost coincided with the composition of the charged monomer. To the obtained aqueous dispersion, 2.0 g of stearyltrimethylammonium chloride (cationic surfactant) was added.

Comparative production example 3
1L autoclave _{CF 3 CF 2 - (CF 2} CF 2) n -CH 2 CH 2 OCOC (Cl) = CH 2 (n = 2.0) 37.25g, stearyl acrylate 64.57G, pure water 220 g, dipropylene 37.24 g of glycol monomethyl ether, 3.08 g of distearyldimethylammonium chloride (cationic surfactant), 0.87 g of stearyltrimethylammonium chloride (cationic surfactant), polyoxyethylene lauryl ether (EO: 20, EO is Represents the number of ethylene oxide units) (nonionic surfactant) 5.74 g, polyoxyethylene isotridecyl ether (EO: 3) (nonionic surfactant) 2.28 g, polyoxyethylene oleyl ether (EO: 50) (Nonionic surfactant) 1 Put 19 g, 15 minutes at 60 ° C. under stirring, they were charged and emulsified by ultrasonic wave. 1.24 g of lauryl mercaptan was added, the inside of the autoclave was replaced with nitrogen, and then 22.35 g of vinyl chloride (VCM) was press-fitted and 0.62 g of 2,2-azobis (2-amidinopropane) dihydrochloride (hereinafter referred to as V) −50) and 18 g of water were added and reacted at 60 ° C. for 5 hours to obtain an aqueous dispersion of polymer. The composition of the polymer almost coincided with the composition of the charged monomer. No cationic emulsifier was added to the obtained aqueous dispersion.

Comparative production example 4
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) 18.63 g, stearyl acrylate 12.42 g, isobornyl methacrylate 31 0.04 g, 110 g pure water, 18.62 g dipropylene glycol monomethyl ether, 1.54 g distearyldimethylammonium chloride (cationic surfactant), 0.44 g stearyltrimethylammonium chloride (cationic surfactant), polyoxyethylene Lauryl ether (EO: 20, EO represents the number of ethylene oxide units) (nonionic surfactant) 2.87 g, polyoxyethylene isotridecyl ether (EO: 3) (nonionic surfactant) 1.14 g, poly Oxyethylene oleyl ether (EO: 50) (nonionic surfactant) 0.60 g was added and emulsified and dispersed with ultrasonic waves at 60 ° C. for 15 minutes with stirring. 0.62 g of lauryl mercaptan was added, the inside of the autoclave was replaced with nitrogen, and then 22.35 g of vinyl chloride (VCM) was press-fitted and 0.31 g (hereinafter referred to as V) of 2,2-azobis (2-amidinopropane) dihydrochloride. −50) and 9 g of water were added and reacted at 60 ° C. for 5 hours to obtain an aqueous dispersion of the polymer. The composition of the polymer almost coincided with the composition of the charged monomer. 1.0 g of polyoxyethylene cocoylamine was added to the obtained aqueous dispersion.

Comparative Production Example 5
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) 18.63 g, stearyl acrylate 12.42 g, isobornyl methacrylate 31 0.04 g, 110 g pure water, 18.62 g dipropylene glycol monomethyl ether, 1.54 g distearyldimethylammonium chloride (cationic surfactant), 0.44 g stearyltrimethylammonium chloride (cationic surfactant), polyoxyethylene Lauryl ether (EO: 20, EO represents the number of ethylene oxide units) (nonionic surfactant) 2.87 g, polyoxyethylene isotridecyl ether (EO: 3) (nonionic surfactant) 1.14 g, poly Oxyethylene oleyl ether (EO: 50) (nonionic surfactant) 0.60 g was added and emulsified and dispersed with ultrasonic waves at 60 ° C. for 15 minutes with stirring. 0.62 g of lauryl mercaptan was added, the inside of the autoclave was replaced with nitrogen, and then 22.35 g of vinyl chloride (VCM) was press-fitted and 0.31 g (hereinafter referred to as V) of 2,2-azobis (2-amidinopropane) dihydrochloride. −50) and 9 g of water were added and reacted at 60 ° C. for 5 hours to obtain an aqueous dispersion of the polymer. The composition of the polymer almost coincided with the composition of the charged monomer. 1.0 g of lauryl dimethylamine oxide was added to the obtained aqueous dispersion.

  The preparation composition for the production of the aqueous dispersion is shown in Table A.

Examples 1-10 and Comparative Examples 1-5
Test cloths were prepared 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), and water repellency was evaluated.
A treatment liquid is prepared by diluting the aqueous dispersion with water so that the solid content concentration is 0.5% by weight. A polyester cloth was dipped in the treatment liquid and squeezed with a mangle to obtain a wet pickup of 65%, dried at 100 ° C. for 2 minutes, and dried at 160 ° C. for 1 minute to prepare a test cloth. The test cloth was subjected to a shower water repellency test and a soaking water repellency test. The test results are shown in Table B.

In the table, the meanings of the abbreviations are as follows.

The fluorine-containing composition of the present invention can be used for imparting excellent water repellency, oil repellency, and antifouling properties to textile products, paper, nonwoven fabrics, stone materials, electrostatic filters, dust masks, and fuel cell components.

Another aspect of the present invention is as follows.
<1>
(1) (a) a repeating unit derived from a fluorine-containing monomer that is an α-chloroacrylate having a fluoroalkyl group, and (b) a repeating unit derived from a non-fluorine monomer,
And (2) a surface treatment agent comprising a cationic surfactant added after the polymerization of the fluoropolymer.
<2>
<1> wherein the molar ratio of the repeating unit (a) of the fluorine-containing monomer / the repeating unit (b) of the non-fluorine monomer in the fluorine-containing copolymer is 0.01 / 1 to 10/1. Surface treatment agent.
<3>
The fluorine-containing monomer (a) has the 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 surface treating agent according to <1> or <2>, which is a fluorine-containing monomer represented by
<4>
The non-fluorine monomer (b) has the formula:
CH = CR ¹ -C (= O) OR ²
[Wherein R ¹ is H, a C ₁ -C ₄ alkyl group, or halogen;
R ² is a C _{1 to} C ₃₀ hydrocarbon group (for example, an aliphatic group, an aromatic group, an araliphatic group). ]
The surface treating agent in any one of <1>-<3> which is an acrylate ester compound shown by these.
<5>
The non-fluorine monomer (b) is (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) of 50. The surface treating agent according to any one of <1> to <4>, wherein the surface treating agent is at least one compound selected from the group consisting of (meth) acrylates having a temperature of at least ° C.
<6>
The acrylate (b1) having a linear or branched hydrocarbon group has the formula:
CH ₂ = CHCOOA ¹
[Where:
A ¹ is an alkyl group represented by C _n H _{2n + 1} (n = 12 to 30). ]
The surface treating agent according to <5>, which is an acrylate represented by
<7>
The surface treating agent according to <6>, wherein the alkyl group in the acrylate (b1) having a linear or branched hydrocarbon group has 12 to 22 carbon atoms.
<8>
(Meth) acrylate (b2) has the formula:
CH = CR ¹¹ -C (= O) OR ¹²
[Wherein R ¹¹ is H, a C ₁ -C ₄ alkyl group, or halogen;
R ¹² is a C _{1 to} C ₃₀ linear, branched or cyclic aliphatic group, a C _{6 to} C ₂₀ aromatic group, or a C _{7 to} C ₂₅ araliphatic group. ]
The surface treating agent according to <5>, which is an acrylate compound represented by the formula:
<9>
The non-fluorine monomer (b) is lauryl acrylate, myristyl acrylate, cetyl acrylate, stearyl acrylate, behenyl acrylate;
Cyclohexyl acrylate, isobornyl acrylate, bornyl acrylate, adamantyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, tricyclodecanyl acrylate, phenyl acrylate, naphthyl acrylate, benzyl acrylate, 2-t-butylphenyl acrylate, naphthyl Acrylate;
Methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, bornyl methacrylate, adamantyl methacrylate, dicyclopentanyl methacrylate, dicyclopentenyl methacrylate, tricyclodecanyl methacrylate, phenyl methacrylate, naphthyl <1> to at least one selected from the group consisting of methacrylate, benzyl methacrylate, (2-dimethylamino) ethyl methacrylate, aziridinyl methacrylate, aziridyliniethyl methacrylate, dicyclopentenyl methacrylate; and methyl chloroacrylate <8> The surface treating agent according to any one of the above.
<10>
The surface treatment agent according to any one of <1> to <9>, wherein the fluorinated polymer further contains a repeating unit of a monomer containing a reactive group in the molecule as a copolymerizable monomer.
<11>
<10> The surface treating agent according to <10>, wherein the reactive group in the monomer containing a reactive group in the molecule is a hydroxyl group.
<12>
The surface treating agent according to any one of <1> to <11>, containing a blocked polyisocyanate.
<13>
By copolymerizing monomers (a) and (b) in the presence of a surfactant (polymerization surfactant), and then adding a cationic surfactant (post-addition surfactant) The surface treatment agent according to any one of <1> to <12>, wherein a surface treatment agent in which a fluoropolymer is dispersed in a medium is obtained.
<14>
Cationic surfactant (surfactant for post-addition) has the formula:
(R ⁵¹ ) _p N ⁺ (R ⁵² ) _4-p X ⁻
[Wherein R ⁵¹ represents a C12 or higher linear and / or branched aliphatic (saturated and / or unsaturated) group,
R ⁵² is H or an alkyl group of C1-4, benzyl group, polyoxyethylene group (number of oxyethylene groups, for example, 1 (particularly 2, especially 3) to 50)
X is a group that forms an anion,
p is 1 or 2. ]
The surface treating agent in any one of <1>-<13> which is an ammonium salt shown by these.
<15>
The surface treating agent according to any one of <1> to <14>, which also contains an aqueous medium.
<16>
The surface treating agent according to any one of <1> to <15>, which is an aqueous dispersion.
<17>
(1) (a) a repeating unit derived from a fluorine-containing monomer that is an α-chloroacrylate having a fluoroalkyl group, and (b) a repeating unit derived from a non-fluorine monomer,
And (2) a method for producing a surface treatment agent comprising a cationic surfactant added after the polymerization of the fluoropolymer,
By copolymerizing monomers (a) and (b) in the presence of a surfactant (polymerization surfactant), and then adding a cationic surfactant (post-addition surfactant) The manufacturing method of the surface treating agent which obtains the surface treating agent which the fluoropolymer disperse | distributed to the medium.
<18>
<1>-<16> A water / oil repellent composition which is the surface treating agent according to any one of the above.
<19>
<1> -The method of processing a base material which consists of processing with the surface treating agent in any one of <16>.
<20>
<1>-<16> The textiles processed by the surface treating agent in any one.

Claims (14)

(1) (a) a repeating unit derived from a fluorine-containing monomer that is an α-chloroacrylate having a fluoroalkyl group, and (b) a repeating unit derived from a non-fluorine monomer,
And (2) a surface treatment agent comprising a post-polymerization cationic surfactant.
The fluorine-containing monomer (a) has the 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. ]
A fluorine-containing monomer represented by
The non-fluorine monomer (b) is (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 has the formula:
CH ₂ = CHCOOA ¹
Wherein, A ¹ _is a hydrocarbon group represented by C _{n H 2n + 1} (where, n = 12 to 30). ]
An acrylate represented by
The cationic surfactant for addition after polymerization has the formula:
(R ⁵¹ ) _p N ⁺ (R ⁵² ) _4-p X ⁻
[Wherein R ⁵¹ represents a linear and / or branched aliphatic group of C12 or more,
R ⁵² represents H or a C1-4 alkyl group, a benzyl group, a polyoxyethylene group,
X is a group that forms an anion,
p is 1 or 2. ]
A surface treatment agent which is an ammonium salt represented by The molar ratio of the repeating unit (a) of the fluorine-containing monomer / the repeating unit (b) of the non-fluorine monomer in the fluorine-containing copolymer is 0.01 / 1 to 10/1. Surface treatment agent. The surface treatment agent according to claim 1, wherein the alkyl group in the acrylate (b1) having a linear or branched hydrocarbon group has 12 to 22 carbon atoms. The surface treating agent according to any one of claims 1 to 3, wherein the non-fluorine 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 any one of claims 1 to 4, wherein the fluorinated polymer further contains a repeating unit of a monomer containing a reactive group in the molecule as a copolymerizable monomer. The surface treating agent according to claim 5, wherein the reactive group in the monomer containing a reactive group in the molecule is a hydroxyl group. The surface treating agent according to any one of claims 1 to 6, comprising a blocked polyisocyanate. Furthermore, the surface treating agent in any one of Claims 1-7 containing surfactant for superposition | polymerization. The surface treating agent according to any one of claims 1 to 8, which also contains an aqueous medium. It is an aqueous dispersion, The surface treating agent in any one of Claims 1-9. (1) (a) a repeating unit derived from a fluorine-containing monomer that is an α-chloroacrylate having a fluoroalkyl group, and (b) a repeating unit derived from a non-fluorine monomer,
And (2) a method for producing a surface treatment agent comprising a cationic surfactant for post-polymerization addition,
The fluorine-containing monomer (a) has the 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. ]
A fluorine-containing monomer represented by
The non-fluorine monomer (b) is (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 has the formula:
CH ₂ = CHCOOA ¹
Wherein, A ¹ _is a hydrocarbon group represented by C _{n H 2n + 1} (where, n = 12 to 30). ]
An acrylate represented by
The cationic surfactant for addition after polymerization has the formula:
(R ⁵¹ ) _p N ⁺ (R ⁵² ) _4-p X ⁻
[Wherein R ⁵¹ represents a linear and / or branched aliphatic group of C12 or more,
R ⁵² represents H or a C1-4 alkyl group, a benzyl group, a polyoxyethylene group,
X is a group that forms an anion,
p is 1 or 2. ]
An ammonium salt represented by
After the monomers (a) and (b) are copolymerized in the presence of the polymerization surfactant, the post-polymerization addition cationic surfactant is added to disperse the fluoropolymer in the medium. A method for producing a surface treatment agent to obtain a surface treatment agent. The water / oil repellent composition which is a surface treating agent in any one of Claims 1-10. The method to process a base material consisting of processing with the surface treating agent in any one of Claims 1-10. The manufacturing method of the processed textiles including applying the surface treating agent in any one of Claims 1-10 to a textiles.