JP6015003B2 - Method for producing fluorine-containing polymer and fluorine-containing composition - Google Patents

Description

  The present invention relates to a method for producing a fluorine-containing polymer and a fluorine-containing composition. According to the present invention, fluorine-containing heavy metals that impart excellent water repellency, oil repellency, and antifouling properties to textile products (for example, carpets), paper, nonwoven fabrics, stones, electrostatic filters, dust masks, and fuel cell components. Combines can be manufactured.

  Conventionally, various fluorine-containing compounds have been proposed. The fluorine-containing compound has an advantage of excellent properties such as heat resistance, oxidation resistance, and weather resistance. The fluorine-containing compound is used as, for example, a water / oil repellent and an antifouling agent by utilizing the characteristic that the free energy of the fluorine-containing compound is low, that is, it is difficult to adhere. For example, for example, US Pat. No. 5,247,008 discloses an aqueous copolymer of a perfluoroalkyl ester of acrylic acid or methacrylic acid, an alkyl ester of acrylic acid or methacrylic acid, and an aminoalkyl ester of acrylic acid or methacrylic acid. Finishing agents for textiles, leather, paper and mineral substrates, which are dispersions, are described.

  Examples of the fluorine-containing compound that can be used as a water / oil repellent include a fluorine-containing polymer having a (meth) acrylate ester having a fluoroalkyl group as a constituent monomer. In practical treatment of fibers with surface treatment agents, various research results so far indicate that dynamic contact angles, particularly receding contact angles, are important as surface characteristics, not static contact angles. That is, the advancing contact angle of water does not depend on the carbon number of the side chain of the fluoroalkyl group, but the receding contact angle of water is significantly smaller at 7 or less than the carbon number of the side chain of 8 or more. . Correspondingly, X-ray analysis shows that side chain crystallization occurs when the side chain has 7 or more carbon atoms. It is known that practical water repellency correlates with the side chain crystallinity, and the mobility of surface treatment agent molecules is an important factor in the development of practical performance (for example, Takashi Maekawa , Fine Chemicals, Vol23, No.6, P12 (1994)). For the above reason, the (meth) acrylate polymer having a short fluoroalkyl group with a side chain having 7 or less carbon atoms (especially 6 or less) has a problem of not satisfying the practical performance as it is because the side chain has low crystallinity. .

  From recent research results (EPA report "PRELIMINARY RISK ASSESSMENT OF THE DEVELOPMENTAL TOXICITY ASSOCIATED WITH EXPOSURE TO PERFLUOROOCTANOIC ACID AND ITS SALTS" (http://www.epa.gov/opptintr/pfoa/pfoara.pdf)) Concerns about the environmental impact of perfluorooctanoic acid) have become apparent, and on April 14, 2003, the EPA announced that it would strengthen scientific research on PFOA.

Meanwhile, Federal Register (FR Vol.68, No.73 / April 16,2003 [FRL-2303-8])
(Http://www.epa.gov/opptintr/pfoa/pfoafr.pdf) or
EPA Environmental News FOR RELEASE: MONDAY APRIL 14, 2003
EPA INTENSIFIES SCIENTIFIC INVESTIGATION OF A CHEMICAL PROCESSING AID (http://www.epa.gov/opptintr/pfoa/pfoaprs.pdf)
EPA OPPT FACT SHEET April 14, 2003
(Http://www.epa.gov/opptintr/pfoa/pfoafacts.pdf) has published that "telomers" may produce PFOA through degradation or metabolism. “Telomers” are also used in many products, including foams; care products and cleaning products; water and oil repellent coatings and antifouling coatings on carpets, textiles, paper and leather. We have also announced that.

  International Publication No. 2011/122442 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 conversion rate (polymerization rate) of α-chloroacrylate is not examined in detail.

International Publication No. 2011/122442

One object of the present invention is to provide a method for producing a fluorine-containing polymer having a high conversion rate (polymerization rate) of the fluorine-containing monomer.
Another object of the present invention is to provide a fluorine-containing composition with a reduced amount of residual monomer.
Another object of the present invention is to provide a fluorine-containing composition that imparts excellent water and oil repellency to a substrate such as a textile product and is excellent in preventing polymer adhesion to a roll in the processing.

The present invention
(A) a fluorine-containing monomer which is an α-chloroacrylate having a fluoroalkyl group,
(B) an acrylate monomer having a linear or branched hydrocarbon group having 12 to 30 carbon atoms, and (C) a third monomer that is a methacrylate monomer or aromatic olefin having a hydrocarbon group. Is provided in an amount of 0.8 mol or more of the third monomer (C) with respect to 1 mol of the fluorine-containing monomer (A). To do.
In addition, the present invention provides:
(A) a repeating unit derived from a fluorine-containing monomer which is an α-chloroacrylate having a fluoroalkyl group,
(B) a repeating unit derived from an acrylate monomer having a linear or branched hydrocarbon group having 12 to 30 carbon atoms, and (C) a methacrylate monomer or aromatic olefin having a hydrocarbon group. It has a repeating unit derived from a certain third monomer, and the amount of the repeating unit (C) of the third monomer is 0.8 mol with respect to 1 mol of the repeating unit of the fluorine-containing monomer (A). Provided is a fluoropolymer as described above.

Furthermore, the present invention provides (A) a repeating unit derived from a fluorine-containing monomer which is an α-chloroacrylate having a fluoroalkyl group,
(B) a repeating unit derived from an acrylate monomer having a linear or branched hydrocarbon group having 12 to 30 carbon atoms, and (C) a methacrylate monomer or aromatic olefin having a hydrocarbon group. It has a repeating unit derived from a certain third monomer, and the amount of the repeating unit (C) of the third monomer is 0. 1 mol per 1 mol of the repeating unit of the fluorine-containing monomer (A). A fluorine-containing composition comprising a fluorine-containing polymer that is 8 mol or more,
Provided is a fluorine-containing composition in which the residual amount of fluorine-containing monomer in the fluorine-containing composition is 10% or less.

According to the present invention, since the conversion rate (polymerization rate) of the fluorine-containing monomer is high, a fluorine-containing composition with a reduced amount of residual monomer can be obtained.
The fluorine-containing composition of the present invention imparts excellent water and oil repellency to a substrate such as a textile product, and is excellent in preventing polymer adhesion to a roll in the processing.

  In the present invention, (A) a fluorine-containing monomer (α-chloro-substituted fluorine-containing monomer), (B) a linear or branched hydrocarbon group-containing acrylate monomer, and (C) a monomer A third monomer other than (A) and (B) is used.

In the present invention, the fluorine-containing polymer is
(A) a repeating unit derived from a fluorine-containing monomer (α-chloro-substituted fluorine-containing monomer),
(B) having a repeating unit derived from a linear or branched hydrocarbon group-containing acrylate monomer, and (C) a repeating unit derived from a third 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. ]
It is a fluorine-containing monomer shown by.

The fluorine-containing monomer is preferably an acrylate ester whose 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 the following, but are not limited thereto.
CH ₂ = C (−Cl) −C (= O) −O− (CH ₂ ) ₂ −Rf
CH ₂ = C (-Cl) -C (= O) -O- (CH ₂ ) ₄ -Rf
CH ₂ = C (-Cl) -C (= O) -O- (CH ₂ ) ₂ -S-Rf
CH ₂ = C (−Cl) −C (= O) −O− (CH ₂ ) ₂ −S− (CH ₂ ) ₂ −Rf
CH ₂ = C (-Cl) -C (= O) -O- (CH ₂ ) ₂ -SO ₂ -Rf
CH ₂ = C (-Cl) -C (= O) -O- (CH ₂ ) ₂ -SO _2- (CH ₂ ) ₂ -Rf
CH ₂ = C (-Cl) -C (= O) -NH- (CH ₂ ) ₂ -Rf

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

CH ₂ = C (-Cl) -C (= O) -O-CH ₂ CH ₂ N (CH ₃ ) SO ₂ -Rf
CH ₂ = C (-Cl) -C (= O) -O-CH ₂ CH (OCOCH ₃ ) CH ₂ -Rf
CH ₂ = C (-Cl) -C (= O) -O-CH ₂ -Ph-O-Rf (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) Second monomer (an acrylate monomer having a linear or branched hydrocarbon group having 12 to 30 carbon atoms)
The second monomer (B) is a monomer having no fluoroalkyl group. The monomer (B) does not have a cyclic hydrocarbon group. The second monomer (B) is generally a monomer that does not contain a fluorine atom. 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 second monomer (B) 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 second monomer (B) 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 second monomer (B) include, but are not limited to, for example, 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)

(C) Third monomer The third monomer (C) is a methacrylate monomer having a hydrocarbon group and / or an aromatic olefin. The third monomer (C) is a monomer other than the monomers (A) and (B). The third monomer (C) does not have a fluoroalkyl group.
Generally, in a methacrylate monomer having a hydrocarbon group, the hydrocarbon group is directly bonded to an ester bond as an alcohol residue. The hydrocarbon group is a linear or branched hydrocarbon group or a cyclic hydrocarbon group.

The straight-chain or branched hydrocarbon group is generally a straight-chain or branched hydrocarbon group, particularly a straight-chain hydrocarbon group. The linear or branched hydrocarbon group has 1 to 30 carbon atoms, and is generally a saturated aliphatic hydrocarbon group.
Examples of the cyclic hydrocarbon group include saturated or unsaturated monocyclic groups, polycyclic groups, and bridged cyclic groups. The cyclic hydrocarbon group is preferably saturated. The cyclic hydrocarbon group preferably has 4 to 20 carbon atoms. Examples of the cyclic hydrocarbon group include a cyclic aliphatic group having 4 to 20 carbon atoms, particularly 5 to 12 carbon atoms, an aromatic group having 6 to 20 carbon atoms, and an araliphatic group having 7 to 20 carbon atoms. The number of carbon atoms of the cyclic hydrocarbon group is particularly preferably 15 or less, for example 10 or less. The cyclic hydrocarbon group is preferably a saturated cyclic aliphatic group. Specific examples of the cyclic hydrocarbon group are a cyclohexyl group, a t-butylcyclohexyl group, an isobornyl group, a dicyclopentanyl group, and a dicyclopentenyl group.

A methacrylate monomer having a hydrocarbon group has the formula:
CH ₂ = C (CH ₃ ) COOA ²
[Where:
A ² is a linear or branched hydrocarbon group or a cyclic hydrocarbon group, for example, an alkyl group represented by C _n H _{2n + 1} (n = 1 to 30). ]
It may be a methacrylate represented by

The aromatic olefin includes a vinyl group and an optionally substituted aromatic group (aromatic ring) (for example, a benzene ring, or a group having two or more benzene rings (for example, naphthalene group, anthracene group), or azulene). It is a compound that has. In the aromatic olefin, the vinyl group and the aromatic ring are preferably bonded directly.
Aromatic olefins have the formula:
^{_{CH 2 = C (G 1)}} -Ar (G 2) r
[Wherein Ar is an aromatic ring (eg, benzene, naphthalene),
G ¹ and G ² are each independently an alkyl group having 1 to 10 carbon atoms (for example, 1 to 4), or a halogen atom (especially chlorine, bromine, iodine),
r is a number from 0 to 5 (for example, 0 to 2). ]
It may be a compound shown by these.
G ² is a substituent on the aromatic ring (Ar).

  Specific examples of the third monomer include methyl methacrylate, ethyl methacrylate, butyl methacrylate, lauryl methacrylate, stearyl methacrylate, 2-ethylhexyl methacrylate, cycloalkyl methacrylate, isobornyl methacrylate, adamantyl methacrylate, benzyl methacrylate, and polyoxyalkylene methacrylate. , Polyoxyalkylene dimethacrylate, (2-dimethylamino) ethyl methacrylate, methacrylate having polysiloxane, aziridinyl methacrylate, aziridyliniethyl methacrylate, styrene, α-methylstyrene, α-methyl-p-methylstyrene, o-methylstyrene, m-methylstyrene, p -Methyl styrene, 2,4 dimethyl styrene, ethyl styrene, Examples include, but are not limited to, tert-butyl styrene, o-chloro styrene, m-chloro styrene, p-chloro styrene, p-bromo styrene, 2-methyl-1, 4-chloro styrene, 2, 4 dibromo styrene, vinyl naphthalene and the like. It is not something.

(D) Other monomer monomers (A), (B) and other monomers (D) other than (C), for example, other non-fluorine non-crosslinkable monomers may be used. .
Examples of other monomers include, for example, ethylene, vinyl acetate, acrylonitrile, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, and Vinyl alkyl ethers are included. Other monomers are not limited to these examples.

The other monomer 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 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, with respect to 1 mol of the fluorine-containing monomer (A),
The amount of the acrylate monomer (B) is 0.1 mol or more, for example 0.2 to 20 mol, particularly 0.5 to 10 mol,
The amount of the third monomer (C) may be 0.8 mol or more, for example, 0.9 to 20 mol, particularly 1 to 10 mol.
The amount of the other monomer (D) may be 0 to 10 mol, for example, 0.01 to 5 mol with respect to 1 mol of the fluorine-containing monomer (A).

  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, a fluorine-containing composition in which the monomers (A) to (C) (and other monomers (D) if necessary) are copolymerized and the fluorine-containing polymer is dispersed or dissolved in a medium is obtained. obtain.

  The conversion rate (polymerization rate) of the fluorinated monomer (A) is a high value and is 90% or more, for example 92% or more, particularly 95% or more. In the fluorine-containing composition, the amount of residual monomer (the amount of unreacted fluorine-containing monomer (A)) is 10% or less with respect to the amount of charged monomer (the amount of charged fluorine-containing monomer (A)), for example, 8%, especially 5% or less.

  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 can be produced by any ordinary polymerization method, and the conditions for the polymerization reaction can be arbitrarily selected. Examples of such polymerization methods include solution polymerization, suspension polymerization, and emulsion polymerization.

  In solution polymerization, a method in which a monomer is dissolved in an organic solvent in the presence of a polymerization initiator, and after nitrogen substitution, is heated and stirred in the range of 30 to 120 ° C. for 1 to 10 hours. Examples of the polymerization initiator include azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, and diisopropyl peroxydicarbonate. Can be mentioned. The polymerization initiator is used in the range of 0.01 to 20 parts by weight, for example, 0.01 to 10 parts by weight with respect to 100 parts by weight of the monomer.

  Examples of the organic solvent are those which are inert to the monomer and dissolve them, such as acetone, chloroform, HCHC225, isopropyl alcohol, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, petroleum ether, Tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane, trichloro And trifluoroethane. The organic solvent is used in the range of 50 to 2000 parts by weight, for example, 50 to 1000 parts by weight with respect to 100 parts by weight of the total amount of monomers.

  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 having excellent storage stability, the monomer is polymerized in water using an emulsifier that can impart powerful crushing energy such as a high-pressure homogenizer or ultrasonic homogenizer. It is desirable to do. As the emulsifier, various anionic, cationic or nonionic emulsifiers can be used, and the emulsifier is used in the range of 0.5 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 a solution, 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 80% 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 specimen frame is a metal frame having a diameter of 15 cm. Three test piece sheets having a size of about 20 cm × 20 cm are prepared, and the sheet is fixed to the test piece holder frame so that the sheet is not wrinkled. Center the spray on the center of the sheet. Room temperature water (250 mL) is placed in a glass funnel and sprayed onto the specimen sheet (over a time period of 25-30 seconds). Remove the holding frame from the base, grab one end of the holding frame, tap the front surface down and dab the opposite end with a hard substance. Rotate the holding frame 180 ° further and repeat the same procedure to drop excess water drops. Wet specimens are compared to wet reference standards to score 0, 50, 70, 80, 90 and 100 in order of poor water repellency. Results are obtained from the average of three measurements.

Monomer conversion The monomer conversion (polymerization rate) was determined by gas chromatography (Shimadzu GC-14B).

Production Example 1
In a 300 mL autoclave, CF ₃ CF _2- (CF ₂ CF ₂ ) _n -CH ₂ CH ₂ OCOC (Cl) = CH ₂ (n = 2.0) (C6SFClA) 18.63 g, stearyl acrylate (StA) 21.73 g, 2- 1. Ethylhexyl methacrylate (2EHMA) 21.73 g, pure water 110 g, dipropylene glycol monomethyl ether 18.62 g, stearyltrimethylammonium chloride 2.57 g, polyoxyethylene lauryl ether (EO: 20. EO represents the number of ethylene oxide units) 65 g and 1.21 g of polyoxyethylene isotridecyl ether (EO: 3) were 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. After polymerization, the conversion rate of C6SFClA (fluorinated monomer) was calculated by gas chromatography.

Production Examples 2 to 14 and Comparative Production Examples 1 to 6
An aqueous dispersion was prepared in the same procedure as in Production Example 1. The amount of monomer charged and the conversion rate of the fluorine-containing monomer are shown in Table 2.

Example 1
The aqueous liquid produced in Production Example 3 (each of 5 g and 7.5 g) was diluted with pure water to prepare a test solution (1000 g). One polyester taffeta cloth (510 mm × 205 mm) and one nylon taffeta cloth (510 mm × 205 mm) were immersed in this test solution, passed through a mangle, and treated with a pin tenter at 160 ° C. for 2 minutes. The test cloth was subjected to a shower water repellency test. The results are shown in Table 3.

Example 2 and Comparative Examples 1-2
The polymer produced in Comparative Production Example 2 (Comparative Example 1), Production Example 6 (Example 2) and Comparative Production Example 4 (Comparative Example 2) was treated in the same manner as in Example 1, and a shower water repellency test was conducted. The results are shown in Table 3.

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

注） Ｆ：含フッ素単量体
Ｘ：第３単量体（StAとBeA以外の単量体）

Note) F: Fluorine-containing monomer X: Third monomer (monomer other than StA and BeA)

The fluorine-containing composition of the present invention imparts excellent water repellency, oil repellency and antifouling properties to textile products (for example, carpets), paper, non-woven fabrics, stones, electrostatic filters, dust masks, and fuel cell components. Can be used for.

Claims (8)

(A) a fluorine-containing monomer which is an α-chloroacrylate having a fluoroalkyl group,
(B) straight or acrylate monomers having a branched hydrocarbon group having 12 to 30 carbon atoms, and a third copolymerized monomers is a (C) Kaori aromatic olefins, fluorine-containing monomeric A method for producing a fluoropolymer, characterized in that it is carried out in an amount of 0.8 mol or more of the third monomer (C) with respect to 1 mol of the body (A),
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,
A linear or branched aliphatic group having 1 to 20 carbon atoms,
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).
Formula —CH ₂ CH (OR ³ ) CH ₂ — [Ar— (O) _q ] _p — (wherein R ³ is a hydrogen atom or an acyl group having 1 to 10 carbon atoms, Ar is a substituent. An optionally substituted arylene group, p is 0 or 1, and q is 0 or 1.)
Shown by the formula — (CH ₂ ) _n —Ar— (O) _q — (wherein Ar is an arylene group optionally having a substituent, n is 0 to 10, and q is 0 or 1). Group, or
_{- (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 ) And
Rf is a fluoroalkyl group having 1 to 20 carbon atoms. ]
A fluorine-containing monomer represented by
The monomer (B) having a linear or branched hydrocarbon group has the formula:
CH ₂ = CHCOOA ¹
[Wherein, A ¹ is an alkyl group represented by C _n H _{2n + 1} (n = 12 to 30). ]
An acrylate represented by
The third monomer (C) has the formula is Kaoru aromatic olefins:
^{_{CH 2 = C (G 1)}} -Ar (G 2) r
[Wherein Ar is an aromatic ring,
G ¹ and G ² are each independently an alkyl group having 1 to 10 carbon atoms or a halogen atom,
r is a number from 0 to 5. ]
The manufacturing method of the fluorine-containing polymer which is a compound shown by these. The production method according to claim 1, wherein the alkyl group in the monomer (B) has 12 to 22 carbon atoms. (A) a repeating unit derived from a fluorine-containing monomer which is an α-chloroacrylate having a fluoroalkyl group,
(B) it is derived from a linear or branched repeating units derived from acrylate monomer having a hydrocarbon group, and (C) Kaori third monomer is aromatic olefins having 12 to 30 carbon atoms And the amount of the repeating unit (C) of the third monomer is 0.8 mol or more with respect to 1 mol of the repeating unit of the fluorine-containing monomer (A). And
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,
A linear or branched aliphatic group having 1 to 20 carbon atoms,
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).
Formula —CH ₂ CH (OR ³ ) CH ₂ — [Ar— (O) _q ] _p — (wherein R ³ is a hydrogen atom or an acyl group having 1 to 10 carbon atoms, Ar is a substituent. An optionally substituted arylene group, p is 0 or 1, and q is 0 or 1.)
Shown by the formula — (CH ₂ ) _n —Ar— (O) _q — (wherein Ar is an arylene group optionally having a substituent, n is 0 to 10, and q is 0 or 1). Group, or
_{- (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 ) And
Rf is a fluoroalkyl group having 1 to 20 carbon atoms. ]
A fluorine-containing monomer represented by
The monomer (B) having a linear or branched hydrocarbon group has the formula:
CH ₂ = CHCOOA ¹
[Wherein, A ¹ is an alkyl group represented by C _n H _{2n + 1} (n = 12 to 30). ]
An acrylate represented by
The third monomer (C) has the formula is Kaoru aromatic olefins:
^{_{CH 2 = C (G 1)}} -Ar (G 2) r
[Wherein Ar is an aromatic ring,
G ¹ and G ² are each independently an alkyl group having 1 to 10 carbon atoms or a halogen atom,
r is a number from 0 to 5. ]
A fluorine-containing polymer, which is a compound represented by (A) a repeating unit derived from a fluorine-containing monomer which is an α-chloroacrylate having a fluoroalkyl group,
(B) it is derived from a linear or branched repeating units derived from acrylate monomer having a hydrocarbon group, and (C) Kaori third monomer is aromatic olefins having 12 to 30 carbon atoms And the amount of the repeating unit (C) of the third monomer is 0.8 mol or more with respect to 1 mol of the repeating unit of the fluorine-containing monomer (A). And a fluorine-containing composition comprising an aqueous medium,
The residual amount of the fluorine-containing monomer in the fluorine-containing composition is 10% or less,
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,
A linear or branched aliphatic group having 1 to 20 carbon atoms,
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).
Formula —CH ₂ CH (OR ³ ) CH ₂ — [Ar— (O) _q ] _p — (wherein R ³ is a hydrogen atom or an acyl group having 1 to 10 carbon atoms, Ar is a substituent. An optionally substituted arylene group, p is 0 or 1, and q is 0 or 1.)
Shown by the formula — (CH ₂ ) _n —Ar— (O) _q — (wherein Ar is an arylene group optionally having a substituent, n is 0 to 10, and q is 0 or 1). Group, or
_{- (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 ) And
Rf is a fluoroalkyl group having 1 to 20 carbon atoms. ]
A fluorine-containing monomer represented by
The monomer (B) having a linear or branched hydrocarbon group has the formula:
CH ₂ = CHCOOA ¹
[Wherein, A ¹ is an alkyl group represented by C _n H _{2n + 1} (n = 12 to 30). ]
An acrylate represented by
The third monomer (C) has the formula is Kaoru aromatic olefins:
^{_{CH 2 = C (G 1)}} -Ar (G 2) r
[Wherein Ar is an aromatic ring,
G ¹ and G ² are each independently an alkyl group having 1 to 10 carbon atoms or a halogen atom,
r is a number from 0 to 5. ]
The fluorine-containing composition which is a compound shown by these. The fluorine-containing composition according to claim 4, which is an aqueous dispersion. The fluorine-containing composition according to claim 4 or 5, which is a water / oil repellent composition. The method to process a base material consisting of processing with the fluorine-containing composition of any one of Claims 4-6. The manufacturing method of the processed textiles including applying the fluorine-containing composition of any one of Claims 4-6 to textiles.