KR20210093845A - Fluorine-containing polymer particles - Google Patents

Abstract

(식(1) (2) 중, R¹은 수소 또는 메틸기, R²는 불소를 포함하는 탄소수 1~10개의 탄화 수소기, R³은 벤질기 및 탄소수 5~10개의 환상 탄화 수소기로 이루어지는 군에서 선택되는 기, a, b는 중합도를 나타낸다)Provided is a fluorine-containing polymer particle capable of forming a coating film excellent in water repellency, antifouling property, chemical resistance, adhesiveness, and particle non-fusibility by mixing a small amount with other particles. Particles formed from a copolymer containing 30% by mass or more of the structural unit (X) derived from the fluorine-containing (meth)acrylic acid ester monomer (A) and 30% by mass or more of the structural unit (Y) of the (meth)acrylic acid ester monomer (B) As, the structural unit derived from the fluorine-containing (meth)acrylic acid ester monomer (A) is represented by the following general formula (1), and the structural unit derived from the (meth)acrylic acid ester monomer (B) is represented by the following general formula (2) characterized in that

(in formula (1) (2), R ¹ is hydrogen or a methyl group, R ² is a fluorine-containing hydrocarbon group having 1 to 10 carbon atoms, R ³ is a benzyl group and a group consisting of a cyclic hydrocarbon group having 5 to 10 carbon atoms. A group selected from, a, b represents a degree of polymerization)

Description

Fluorine-containing polymer particles

The present invention relates to fluorine-containing polymer particles, and to fluorine-containing polymer particles capable of forming a coating film excellent in water repellency, antifouling properties, chemical resistance, adhesion, and particle non-adhesion properties.

Fluorine-containing polymers have an advantage in that they are excellent in properties such as heat resistance, oxidation resistance, light resistance, and chemical resistance, and various fluorine-containing polymers have been proposed. By taking advantage of the low free energy of the fluorine-containing polymer, that is, it is difficult to adhere to other substances, the fluorine-containing polymer is used, for example, as a water and oil repellent agent and an antifouling agent (see, for example, Patent Documents 1 to 3) ). However, when a fluorine-containing polymer is added too much, it leads to the fall of chemical-resistance, and a cost increase, and it becomes a subject to reduce manufacturing cost.

In addition, the polymer particles are for the purpose of improving physical properties such as light diffusivity, blocking resistance, and sliding properties of the resin molded article or imparting other properties, and also as a base material of conductive fine particles responsible for spacers or electrical connections between microparts of electronic devices. used as particles. Therefore, various characteristics are calculated|required by the use for a polymer particle, and various proposals are made|formed in order to satisfy such a request|requirement (for example, refer patent documents 4-6).

However, fluorine-containing polymer particles that form a coating film having adhesiveness to another while suppressing thermal fusion between particles and having excellent water repellency, antifouling properties and chemical resistance have not yet been established.

Japanese Patent Laid-Open No. 2012-92316 Japanese Patent Laid-Open No. 2012-82414 Japanese Patent Publication No. 3002746 Japanese Patent Laid-Open No. 2000-204275 Japanese Patent Laid-Open No. 2001-163985 Japanese Patent Laid-Open No. 2005-298541

An object of the present invention is to provide a fluorine-containing polymer particle capable of forming a coating film excellent in water repellency, antifouling property, chemical resistance, adhesiveness, and particle non-fusibility by mixing a small amount into the coating film.

The fluorine-containing polymer particles of the present invention contain 30% by mass or more of the structural unit (X) derived from the fluorine-containing (meth)acrylic acid ester monomer (A), and 30% by mass or more of the structural unit (Y) derived from the (meth)acrylic acid ester monomer (B). As particles formed of a copolymer containing at least mass%, the structural unit derived from the fluorine-containing (meth)acrylic acid ester monomer (A) is a structural unit derived from the following general formula (1), the (meth)acrylic acid ester monomer (B) It is characterized in that it is represented by the following general formula (2).

(in formula (1) (2), R ¹ is hydrogen or a methyl group, R ² is a fluorine-containing hydrocarbon group having 1 to 10 carbon atoms, R ³ is a benzyl group and a group consisting of a cyclic hydrocarbon group having 5 to 10 carbon atoms. A group selected from, a, b represents a degree of polymerization.)

The fluorine-containing polymer particles of the present invention are added in a small amount to the coating film, and by maximizing the low surface free energy of fluorine itself, the characteristics of fluorine can be expressed on the surface of the coating film while maintaining the properties of other particles included in the coating film. there is. The fluorine-containing polymer particles have a structural unit (X) derived from a fluorine-containing (meth)acrylic acid ester monomer (A) having a low surface free energy and a structural unit derived from a (meth)acrylic acid ester monomer (B) having excellent chemical resistance, light resistance and adhesion. Since it contains, it can make it easy to express the characteristic of fluorine on the surface of a coating material.

Hereinafter, preferred embodiments according to the present invention will be described in detail. In addition, this invention is not limited only to embodiment described below, It should be understood as what includes various modified examples implemented in the range which does not change the summary of this invention. In addition, "- (meth)acrylate" in this specification is the concept which encompasses both "- acrylate" and "- methacrylate."

The fluorine-containing polymer particles of the present invention are formed of a copolymer comprising a structural unit (X) and a structural unit (Y).

The structural unit (X) is a repeating unit derived from a fluorine-containing (meth)acrylic acid ester monomer (A), and is represented by the following general formula (1).

(In formula (1), R ¹ is hydrogen or a methyl group, R ² is a fluorine-containing hydrocarbon group having 1 to 10 carbon atoms, and a indicates a degree of polymerization.)

In Formula (1), R<^1> is mutually independently hydrogen or a methyl group. The monomer of R ¹ is hydrogen represents acrylate, and the monomer of R ¹ is a methyl group represents methacrylate.

R ² is a hydrocarbon group having 1 to 10 carbon atoms containing fluorine, preferably a hydrocarbon group having 2 to 10 carbon atoms containing fluorine. The hydrocarbon group may have an unsaturated bond, and any of a linear hydrocarbon group and a branched hydrocarbon group may be sufficient as it. In R ² , at least one part of hydrogen in the hydrocarbon group is substituted with fluorine. As for R ² , all hydrogens in the hydrocarbon group may be substituted with fluorine.

As R ² , for example, —CH ₂ CF ₃ , —CH ₂ CF ₂ CF ₂ H, —CH ₂ CF ₂ CF ₃ , —CH ₂ CF ₂ CFHCF ₃ , —CH ₂ (CF ₂ ) ₃ CF ₂ H , -CH ₂ CH ₂ (CF ₂ ) ₃ CF ₃ , -CH ₂ (CF ₂ ) ₅ CF ₂ H, -CH ₂ CH ₂ (CF ₂ ) ₅ CF ₃ , -CH ₂ CH ₂ (CF ₂ ) ₇ CF ₃ , —CH(CF ₃ ) ₂ , —CH ₂ CCH ₃ (CF ₃ ) _{2 ,} and the like.

The fluorine-containing (meth)acrylic acid ester monomer (A) is a hydrocarbon group (R ² ) having 1 to 10 carbon atoms in which the ester portion contains fluorine.

As a fluorine-containing (meth)acrylic acid ester monomer (A),

CH ₂ =CHCOOCH ₂ CF ₃ (3FA),

CH ₂ =CHCOOCH ₂ CF ₂ CF ₂ H(4FA),

CH ₂ =CHCOOCH ₂ CF ₂ CF ₃ (5FA),

CH ₂ =CHCOOCH ₂ CF ₂ CFHCF ₃ (6FA),

CH ₂ =CHCOOCH ₂ (CF ₂ ) ₃ CF ₂ H(8FA),

CH ₂ =CHCOOCH ₂ CH ₂ (CF ₂ ) ₃ CF ₃ (9FA),

CH ₂ =CHCOOCH ₂ (CF ₂ ) ₅ CF ₂ H(12FA),

CH ₂ =CHCOOCH ₂ CH ₂ (CF ₂ ) ₅ CF ₃ (13FA),

CH ₂ =CHCOOCH ₂ CH ₂ (CF ₂ ) ₇ CF ₃ (17FA),

CH ₂ =CHCOOCH(CF ₃ ) ₂ (HFIP-A),

CH ₂ =CHCOOCH ₂ CCH ₃ (CF ₃ ) ₂ (6FNP-A),

CH ₂ =C(CH ₃ )COOCH ₂ CF ₃ (3FMA),

CH ₂ =C(CH ₃ )COOCH ₂ CF ₂ CF ₂ H(4FMA),

CH ₂ =C(CH ₃ )COOCH ₂ CF ₂ CF ₃ (5FMA),

CH ₂ =C(CH ₃ )COOCH ₂ CF ₂ CFHCF ₃ (6FMA),

CH ₂ =C(CH ₃ )COOCH ₂ (CF ₂ ) ₃ CF ₂ H(8FMA),

CH ₂ =C(CH ₃ )COOCH ₂ CH ₂ (CF ₂ ) ₃ CF ₃ (9FMA),

CH ₂ =C(CH ₃ )COOCH ₂ (CF ₂ ) ₅ CF ₂ H(12FMA),

CH ₂ =C(CH ₃ )COOCH ₂ CH ₂ (CF ₂ ) ₅ CF ₃ (13FMA),

CH ₂ =C(CH ₃ )COOCH ₂ CH ₂ (CF ₂ ) ₇ CF ₃ (17FMA),

CH ₂ =C(CH ₃ )COOCH(CF ₃ ) ₂ (HFIP-MA),

CH ₂ =C(CH ₃ )COOCH ₂ CCH ₃ (CF ₃ ) ₂ (6FNP-MA)

and the like are exemplified.

The structural unit (Y) is a repeating unit derived from the (meth)acrylic acid ester monomer (B), and is represented by the following general formula (2).

(In formula (2), R ¹ is hydrogen or a methyl group, R ³ is a group selected from the group consisting of a benzyl group and a cyclic hydrocarbon group having 5 to 10 carbon atoms, and b represents a degree of polymerization)

In Formula (2), R<^1> represents hydrogen or a methyl group.

R ³ is a group selected from the group consisting of a benzyl group and a cyclic hydrocarbon group having 5 to 10 carbon atoms. The ^{structural unit having R 3} may be constituted by a single number or a plurality, and preferably, 1-3 types of structural units different from each other may be included. In addition, with another structural unit, R<^3> shall differ from each other, and/or shall differ by acrylate and methacrylate.

Examples of the cyclic hydrocarbon group having 5 to 10 carbon atoms include a monocyclic group, a polycyclic group and a crosslinked cyclic group. In addition, either saturated or unsaturated may be sufficient as a cyclic hydrocarbon group. Examples of the cyclic hydrocarbon group having 5 to 10 carbon atoms include a cyclohexyl group, a t-butylcyclohexyl group, a dicyclopentanyl group, a dicyclopentenyl group, and an isobornyl group.

The (meth)acrylic acid ester monomer (B) is a (meth)acrylate having ^{a group (R 3} ) selected from the group consisting of a benzyl group and a cyclic hydrocarbon group having 5 to 10 carbon atoms. The (meth)acrylic acid ester monomer (B) is benzyl (meth)acrylate, cyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl ( What is necessary is just to be at least 1 selected from the group which consists of meth)acrylate and isobornyl (meth)acrylate.

When the monomer unit of the copolymer forming the fluorine-containing polymer particles is 100 mass%, the structural unit (X) derived from the fluorine-containing (meth)acrylic acid ester monomer (A) is 30 mass% or more and (meth)acrylic acid ester The structural unit (Y) which consists of a structural unit derived from the structural unit derived from a monomer (B) consists of 30 mass % or more. In addition, let the quantity of the structural unit derived from a (meth)acrylic acid ester monomer (B) be the sum total of the structural unit derived from 1 or more types of monomer (B). In formulas (1) and (2), a and b are the degrees of polymerization of each repeating unit, and are real numbers matching the above mass ratio.

The lower limit of the structural unit (X) derived from the fluorine-containing (meth)acrylic acid ester monomer (A) is 30% by mass or more, preferably more than 30% by mass, more preferably 35% by mass or more, in 100% by mass of the monomer units, More preferably, it is 40 mass % or more. The upper limit of the structural unit (X) derived from the fluorine-containing (meth)acrylic acid ester monomer (A) is preferably 70% by mass or less, more preferably less than 70% by mass, still more preferably 60% by mass in 100% by mass of the monomer units. % or less, more preferably 50 mass % or less, and particularly preferably less than 50 mass %. When the structural unit (X) derived from the fluorine-containing (meth)acrylic acid ester monomer (A) is 30 mass % or more, polymer particles excellent in heat resistance, oxidation resistance, chemical resistance, light resistance, etc. can be obtained.

The lower limit of the structural unit (Y) derived from the (meth)acrylic acid ester monomer (B) is 30% by mass or more, preferably more than 30%, more preferably 35% by mass or more, still more preferably, in 100% by mass of the monomer units. is 40 mass % or more, More preferably, 45 mass % or more, Especially preferably, it is 50 mass % or more. The upper limit of the structural unit (Y) derived from the (meth)acrylic acid ester monomer (B) is 75% by mass or less, more preferably 70% by mass or less, further preferably 68% by mass or less, in 100% by mass of the monomer units. More preferably, it is 66 mass % or less, More preferably, it is 64 mass % or less, Especially preferably, it is 62 mass % or less. By making the structural unit (Y) into 30 mass % or more, the polymer particle excellent in chemical-resistance, light resistance, adhesiveness, etc. can be obtained.

The lower limit of the total of the structural unit (X) and the structural unit (Y) is preferably 80% by mass or more, more preferably more than 80% by mass, still more preferably 85% by mass or more, in 100% by mass of the monomer units. More preferably, it is 90 mass % or more, More preferably, it is 90 mass % or more, Especially preferably, it is 95 mass % or more. The upper limit of the total of the structural unit (X) and the structural unit (Y) is preferably 99.5% by mass or less, more preferably 99% by mass or less in 100% by mass of the monomer units. When the total of the structural unit (X) and the structural unit (Y) is more than 80% by mass, it is possible to obtain polymer particles having more excellent chemical resistance and light resistance characteristics.

The copolymer forming the fluorine-containing polymer particles may contain, in addition to the structural unit (X) and the structural unit (Y), a structural unit (Z) derived from a (meth)acrylic acid ester monomer (C) having a hydroxyl group. By containing the structural unit (Z) derived from the (meth)acrylic acid ester monomer (C) which has a hydroxyl group, the polymer particle excellent in stability after particle|grain formation can be obtained. The lower limit of the structural unit (Z) is preferably 1% by mass or more, more preferably 2% by mass or more in 100% by mass of the monomer units. The upper limit of the structural unit (Z) is 10 mass % or less in 100 mass % of monomeric units, More preferably, what is necessary is just 8 mass % or less.

The structural unit (Z) is represented by the following formula (3).

(In formula (3), R ¹ is hydrogen or a methyl group, R ⁴ is a hydrocarbon group having 1 to 10 carbon atoms including a hydroxyl group, and c represents a degree of polymerization)

In Formula (3), R<^1> represents hydrogen or a methyl group.

R ⁴ is a hydrocarbon group having 1 to 10 carbon atoms including a hydroxyl group, preferably a hydrocarbon group having 2 to 6 carbon atoms including a hydroxyl group. The hydrocarbon group may have an unsaturated bond. Moreover, any of a linear hydrocarbon group and a branched hydrocarbon group may be sufficient. In R ⁴ , at least one of hydrogens in the hydrocarbon group is substituted with a hydroxyl group. Examples of R ⁴ include hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, hydroxyhexyl, hydroxyheptyl, and hydroxyoctyl.

The structural unit (Z) is a repeating unit derived from the (meth)acrylic acid ester monomer (C) having a hydroxyl group, and c is the polymerization degree thereof. As the (meth)acrylic acid ester monomer (C) having a hydroxyl group, for example, hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4- Hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 7-hydroxyheptyl (meth) acrylate, 8-hydroxyoctyl (meth) Acrylates etc. are mentioned.

The copolymer forming the fluorine-containing polymer particles can further contain 1 to 10 mass% of a crosslinking agent (D) when the monomer unit is 100 mass%. By containing a crosslinking agent (D), the polymer particle excellent in solvent resistance after particle formation can be obtained. The lower limit of the crosslinking agent (D) is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably more than 2% by mass, even more preferably 3% by mass or more, in 100% by mass of the monomer units, Still more preferably, it is 5 mass % or more, Especially preferably, it is 7 mass % or more. The upper limit of the crosslinking agent (D) is preferably 10% by mass or less, more preferably less than 10% by mass, still more preferably 9% by mass or less, still more preferably less than 9% by mass in 100% by mass of the monomer units, Especially preferably, what is necessary is just 8 mass % or less.

As a crosslinking agent (D), the monomer which can form a crosslinked structure when superposed|polymerized can be used. Examples of the crosslinking agent include monomers having two or more reactive groups per molecule. More specifically, a monofunctional monomer having a heat-crosslinkable crosslinkable group and one olefinic double bond per molecule and a polyfunctional monomer having two or more olefinic double bonds per molecule are exemplified. Examples of the thermally crosslinkable crosslinkable group contained in the monofunctional monomer include an epoxy group, N-methylolamide group, oxetanyl group, oxazoline group, and combinations thereof.

Examples of the crosslinkable monomer having an epoxy group as the thermally crosslinkable crosslinkable group and further having an olefinic double bond include vinyl glycidyl ether, allyl glycidyl ether, butenyl glycidyl ether, o-allylphenyl glycidyl ether, etc. of unsaturated glycidyl ether; dienes such as butadiene monoepoxide, chloroprene monoepoxide, 4,5-epoxy-2-pentene, 3,4-epoxy-1-vinylcyclohexene, 1,2-epoxy-5,9-cyclododecadiene, or monoepoxides of polyenes; alkenyl epoxides such as 3,4-epoxy-1-butene, 1,2-epoxy-5-hexene, and 1,2-epoxy-9-decene; and glycidyl acrylate, glycidyl methacrylate, glycidyl crotonate, glycidyl-4-heptenoate, glycidyl sorbate, glycidyl linoleate, glycidyl-4-methyl Glycidyl esters of unsaturated carboxylic acids such as -3-pentenoate, glycidyl ester of 3-cyclohexene carboxylic acid, and glycidyl ester of 4-methyl-3-cyclohexene carboxylic acid are listed. do.

Examples of the crosslinkable monomer having an N-methylolamide group as the thermally crosslinkable crosslinkable group and having an olefinic double bond include (meth)acrylamides having a methylol group such as N-methylol (meth)acrylamide. .

Examples of the crosslinkable monomer having an oxetanyl group as the thermally crosslinkable crosslinkable group and having an olefinic double bond include 3-((meth)acryloyloxymethyl)oxetane, 3-((meth)acryloyloxymethyl )-2-trifluoromethyloxetane, 3-((meth)acryloyloxymethyl)-2-phenyl oxetane, 2-((meth)acryloyloxymethyl)oxetane and 2-((meth) ) acryloyloxymethyl)-4-trifluoromethyloxetane.

Examples of the crosslinkable monomer having an oxazoline group as the thermally crosslinkable crosslinkable group and having an olefinic double bond include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5 -Methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-methyl-2-oxazoline and 2 -isopropenyl-5-ethyl-2-oxazoline is listed.

Examples of the polyfunctional monomer having two or more olefinic double bonds per molecule include allyl (meth) acrylate, ethylene di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylic Late, tetraethylene glycol di(meth)acrylate, trimethylolpropane-tri(meth)acrylate, dipropylene glycol diallyl ether, polyglycol diallyl ether, triethylene glycol divinyl ether, hydroquinone diallyl ether, tetraallyl Oxyethane, trimethylolpropane-diallyl ether, allyl or vinyl ether of polyfunctional alcohols other than the above, triallylamine, methylenebisacrylamide, divinylbenzene, alkylene glycol di(meth)acrylate, urethane acrylate are listed

As a crosslinking agent (D), alkylene glycol di(meth)acrylate and a urethane acrylate can be used especially preferably.

The copolymer forming the fluorine-containing polymer particles may contain, as structural units other than the structural unit (X), the structural unit (Y), and the structural unit (Z), a repeating unit derived from a radically polymerizable compound. As the radically polymerizable compound that can be another structural unit, (meth)acrylic acid esters and vinyl compounds are exemplified except for the above-described (meth)acrylic acid ester monomers (A) to (C). As the radically polymerizable compound, for example, methyl (meth)acrylate, ethyl (meth)acrylate, (meth)acrylic acid-n-propyl, (meth)acrylic acid isopropyl, (meth)acrylic acid-n-butyl, (meth)acrylic acid -sec-butyl, (meth)acrylic acid-tert-butyl, (meth)acrylic acid pentyl, (meth)acrylic acid neopentyl, (meth)acrylic acid isoamyl, (meth)acrylic acid hexyl, (meth)acrylic acid 2-ethylhexyl, ( Lauryl (meth)acrylic acid, dodecyl (meth)acrylic acid, (meth)acrylic acid-2-dimethylaminoethyl, (meth)acrylic acid-2-diethylaminoethyl, (meth)acrylic acid-2-dipropylaminoethyl, (meth)acrylic acid ) Acrylic acid-2-diphenylaminoethyl, (meth)acrylic acid 3-(N,N-dimethylamino)propyl, N-(meth)acryloylphthalimide, styrene, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl acetate, and the like. Among these, methyl (meth)acrylate and styrene are preferable.

The lower limit of the glass transition temperature (Tg) of the copolymer forming the fluorine-containing polymer particles is preferably 20°C or higher, more preferably 25°C or higher, still more preferably 30°C or higher, still more preferably 40°C or higher. , particularly preferably 50°C or higher. The upper limit of the glass transition temperature (Tg) of the copolymer forming the fluorine-containing polymer particles is 100°C or less, more preferably 80°C or less, and still more preferably 70°C or less. By setting the Tg of the copolymer to 20°C or higher, it is possible to suppress the fusion of particles. Moreover, it becomes easy to manufacture by making Tg into 100 degrees C or less. The glass transition temperature (Tg) of the copolymer can be controlled by changing the type and composition ratio of the monomer.

In addition, in this specification, "Tg of a copolymer" is computed from the kind and composition ratio of the monomer contained in a monomer mixture using Fox formula. Here, for each monomer forming the copolymer, the Fox formula is for calculating the Tg of the copolymer based on the Tg of the homopolymer of the monomer, and the details are Bulletin of the American Physical Society Series 2 (Bulletin). of the American Physical Society, Series 2) Volume 1 · No. 3 · page 123 (1956).

In addition, the Tg regarding the monomer which is the basis for evaluating the Tg of the copolymer by the Fox formula is, for example, New Molecular Library, Vol. 7, Introduction to Synthetic Resins for Paints (Kyojo Kitaoka, Polymers Publishing Society, Kyoto, 1974) Year) The numerical values described in Table 10-2 (Main raw material monomer of acrylic resin for paint) on pages 168 to 169 can be adopted.

The fluorine-containing polymer particles preferably have a volume average particle diameter of 100 to 500 nm, and a particle size distribution (volume average particle diameter/number average particle diameter) of preferably 1.30 or less.

The lower limit of the volume average particle diameter of the fluorine-containing polymer particles is preferably 100 nm or more, more preferably 120 nm or more, still more preferably 150 nm or more. The upper limit of the volume average particle diameter of the fluorine-containing polymer particles is preferably 500 nm or less, more preferably 450 nm or less, still more preferably 400 nm or less. When the volume average particle diameter is less than 100 nm, the viscosity of the dispersion in which the fluorine-containing polymer particles are dispersed in water increases, and there is a fear that it becomes difficult to obtain an aqueous dispersion of high solid content. In addition, when mixed with other particles, it becomes difficult to make the fluorine-containing polymer particles unevenly distributed on the surface of the dispersion. Moreover, when a volume average particle diameter exceeds 500 nm, there exists a possibility that the storage stability of the aqueous dispersion of a fluorine-containing polymer particle|grains may fall, and also causes the uniformity of the coating film to be formed to fall. The volume average particle diameter of the fluorine-containing polymer particles can be adjusted by changing the type and composition ratio of the emulsifier.

The particle size distribution (volume average particle diameter/number average particle diameter) of the fluorine-containing polymer particles is preferably 1.30 or less, more preferably 1.20 or less, still more preferably 1.15 or less, still more preferably 1.10 or less, even more preferably Preferably it is 1.05 or less, Especially preferably, what is necessary is just 1.03 or less. When a particle size distribution exceeds 1.20, it will become a cause of the uniformity of the coating film containing a fluorine-containing polymer particle falling, and it will become difficult to extract the performance peculiar to fluorine. The particle size distribution of the fluorine-containing polymer particles can be controlled by changing the monomer, the type of the emulsifier, the composition ratio, and the polymerization conditions.

In addition, the average particle diameter of a fluorine-containing polymer particle can measure an average particle diameter and a particle size distribution using the particle size distribution measuring apparatus which makes a dynamic light scattering method a measuring principle. As such a particle size distribution measuring apparatus, HORIBA LB-550, SZ-100 series (above, HORIBA, Ltd. make), FPAR-1000 (made by OTSUKA ELECTRONICS CO., LTD.) etc. are mentioned, for example.

A dispersion liquid can be prepared by mixing a fluorine-containing polymer particle with water. In addition to the fluorine-containing polymer particles, the dispersion can also contain inorganic particles such as alumina and titania. The pH of the dispersion is preferably 5 to 10, more preferably 6 to 9.5. When the pH of the dispersion is within this range, dispersion stability can be improved.

The dispersion liquid containing the fluorine-containing polymer particles is used for a film, that is, by applying it to a film to form a coating film, the surface properties of the film can be modified. The film is not particularly limited, and examples thereof include a plastic film, a metal film, paper, a porous film, a porous substrate, and a conductive film.

Method for producing fluorine-containing polymer particles

The fluorine-containing polymer particles include a fluorine-containing (meth)acrylic acid ester monomer (A), a (meth)acrylic acid ester monomer (B), a (meth)acrylic acid ester monomer optionally having a hydroxyl group (C), and other radically polymerizable compounds. It is obtained by emulsion polymerization of a mixture in an aqueous medium. In 100 mass % of the monomer mixture, the fluorine-containing (meth) acrylic acid ester monomer (A) is preferably 30 mass % or more, the (meth) acrylic acid ester monomer (B) and styrene are preferably 30 mass % or more, and fluorine The total amount of containing (meth)acrylic acid ester monomer (A), (meth)acrylic acid ester monomer (B), and styrene should just be 90 mass % or more. Moreover, when a (meth)acrylic acid ester monomer (C) which has a hydroxyl group is included, in 100 mass % of monomer mixtures, Preferably it is just 1-10 mass %.

The conditions for the emulsion polymerization of the monomer mixture are not particularly limited, and for example, the reaction may be carried out in an aqueous medium in the presence of an emulsifier and a polymerization initiator, preferably at a temperature of about 50 to 100° C. for 1 to 30 hours. Moreover, you may add a chain transfer agent, a chelating agent, a pH adjuster, a solvent, etc. as needed.

As the emulsifier, anionic surfactants, nonionic surfactants, combinations of anionic surfactants and nonionic surfactants, etc. are used, and in some cases, amphoteric surfactants and cationic surfactants can also be used.

Examples of the anionic surfactant include alkyl sulfate sodium salt, alkylbenzenesulfonic acid sodium salt, succinic acid dialkyl estersulfonic acid sodium salt, alkyldiphenyl ether disulfonic acid sodium salt, polyoxyethylene alkyl ether sulfate sodium salt, polyoxyethylene alkylphenyl ether sulfate sodium salt and the like. Among these, sodium lauryl sulfate, sodium dodecylbenzenesulfonic acid, sodium polyoxyethylene alkyl ether sulfate, sodium lauryl sulfate, etc. are preferable.

Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene fatty acid ester, and polyoxyethylene sorbitan fatty acid ester. Generally, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, etc. are used.

Examples of the amphoteric surfactant include lauryl betaine, hydroxyethylimidazoline sulfate sodium salt, and imidazolinesulfonic acid sodium salt.

Examples of the cationic surfactant include alkylpyridinium chloride, alkyltrimethylammonium chloride, dialkyldimethylammonium chloride, and alkyldimethylbenzylammonium chloride.

Further, as the emulsifier, perfluoroalkylcarboxylate, perfluoroalkylsulfonate, perfluoroalkylphosphoric acid ester, perfluoroalkylpolyoxyethylene, perfluoroalkylbetaine, perfluoroalkoxyfluorocarboxyl Fluorine surfactants, such as ammonium acid, can also be used.

In addition, a so-called reactive emulsifier copolymerizable with the above monomers, for example, styrene sulfonic acid sodium salt, allyl alkyl sulfonic acid sodium salt, polyoxyethylene alkyl allyl phenyl ether ammonium sulfate salt, polyoxyethylene alkyl allyl phenyl ether, etc. can be used, In particular, the combined use of 2-(1-allyl)-4-nonylphenoxypolyethylene glycol sulfate ammonium salt and 2-(1-allyl)-4-nonylphenoxypolyethylene glycol is preferable.

The amount of the emulsifier used is preferably about 0.05 to 10 parts by mass per 100 parts by mass of the total amount of the monomer mixture.

As the polymerization initiator, a water-soluble polymerization initiator such as sodium persulfate, potassium persulfate, ammonium persulfate or hydrogen peroxide, or a redox polymerization initiator obtained by combining these water-soluble polymerization initiators with a reducing agent can be used. Among these, potassium persulfate and ammonium persulfate are preferable. Examples of the reducing agent include sodium pyrobisulfite, sodium hydrogen sulfite, sodium sulfite, sodium thiosulfate, L-ascorbic acid or a salt thereof, sodium formaldehyde sulfoxylate, ferrous sulfate, and glucose. Among these, L-ascorbic acid or its salt is preferable.

Moreover, an oil-soluble polymerization initiator can also be used melt|dissolved in a monomer or a solvent. Examples of the oil-soluble polymerization initiator include 2,2'-azobisisobutyronitrile, 2,2'-azobis-(4-methoxy-2,4-dimethylvaleronitrile), 2,2'- Azobis-2,4-dimethylvaleronitrile, 1,1'-azobiscyclohexane-1-carbonitrile, 2,2'-azobisisovaleronitrile, 2,2'-azobisisocapuronitrile , 2,2'-azobis (phenylisobutyronitrile), benzoyl peroxide, di-t-butyl peroxide, dilauroyl peroxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, par Ramentane hydroperoxide, t-butylhydroperoxide, 3,5,5-trimethylhexanolperoxide, t-butylperoxy(2-ethylhexanoate) and the like are exemplified. Among these, 2,2'-azobisisobutyronitrile, benzoyl peroxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramentane hydroperoxide, t-butyl hydroperoxide, 3,5,5-trimethylhexanolperoxide and t-butylperoxy(2-ethylhexanoate) are preferred.

The amount of the polymerization initiator used is preferably about 0.1 to 3 parts by mass per 100 parts by mass of the monomer mixture.

As the chain transfer agent, halogenated hydrocarbons (eg, carbon tetrachloride, chloroform, bromoform, etc.), mercaptans (eg, n-dodecyl mercaptan, t-dodecyl mercaptan, n-octyl mercaptan, n -hexadecyl mercaptan, etc.), xanthogens (eg, dimethyl xanthogen disulfide, diethyl xanthogen disulfide, diisopropyl xanthogen disulfide, etc.), terpenes (eg dipeptide) , terpinolene, etc.), thiuram sulfides (eg, tetramethylthiuram monosulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, dipentamethylthiuram disulfide, etc.) are listed. .

The amount of the chain transfer agent used is preferably about 0 to 10 parts by mass per 100 parts by mass of the monomer mixture.

As a pH adjuster, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, ammonia, etc. are mentioned, for example. In addition, the usage-amount of a pH adjuster is per 100 mass parts of monomer mixtures, Preferably it is about 0-3 mass parts.

When emulsion polymerization of a monomer mixture in an aqueous medium, the monomer mixture can be added in a number of ways. Examples of the addition method include a method in which the entire amount of the monomer mixture is added at once, a method in which a part of the monomer mixture is added and reacted, and the remaining monomer mixture is continuously or dividedly added, and a part of the reacted particles is added and then the remainder There are methods such as a method of continuously or dividedly introducing the monomer mixture, and a method of introducing the whole amount of the monomer mixture continuously or sequentially, but after adding a part of the monomer mixture and reacting, the remaining monomer mixture is continuously or dividedly added A method of adding a part of the reacted particles and then continuously or dividing the remaining monomer mixture is preferable.

Example

Hereinafter, although an Example demonstrates this invention in more detail, this invention is not limited by this. In addition, in the following description, "%" and "part" represent "mass %" and "mass part". The measuring method used in this Example is shown below.

(1) dispersion stability

Fluorine-containing polymer particles and inorganic particles (alumina, particle diameter 0.5 µm) are mixed in a mass ratio of 1:1 so that the solid content concentration is 10% by mass in water, and dispersed in an ultrasonic disperser for 10 minutes. The average particle diameter of the initial particles was measured with a thick particle size analyzer (manufactured by OTSUKA ELECTRONICS CO., LTD., FPAR-1000). After standing still for 1 day, the average particle diameter of the particle|grains centrifuged by the centrifugal acceleration speed of 20,000 G and 30 minutes was measured. When the increase rate is less than 10%, it is “excellent”, when the increase rate is 10% or more and less than 20%, “good”, when the increase rate is 20% or more and less than 50%, “slightly poor”, when the increase rate is 50% or more, “poor” , it is judged that dispersion stability is good when the increase rate is less than 20%. "Dispersion stability" described in Tables 1-3 is the value of the said increase rate.

(2) particle fusion properties

A dispersion liquid obtained by diluting fluorine-containing polymer particles in water to a concentration of 0.01% by mass was added dropwise onto aluminum foil to prepare a sample dried at room temperature and a sample dried by applying heat at 50°C. Then, using the scanning electron microscope (Hitachi, SU8000), two-field observation was carried out at the acceleration voltage of 2.0 kV, 50,000 times. The arithmetic mean particle diameter of 100 particles was measured at random. Rate of change of the arithmetic mean particle diameter of the sample dried at 50 ° C with respect to the arithmetic mean particle diameter of the sample dried at room temperature [the rate of change = the arithmetic mean particle diameter of the sample dried at 50 ° C / the arithmetic mean particle diameter of the sample dried at room temperature] analyzed. If the rate of change is less than 1.5, it is evaluated as “no fusion”, if the rate of change is 1.5 or more and less than 2.0, “there is little fusion”, when the rate of change is 2.0 or more and less than 3.0, “there is fusion”, and if the rate of change is 3.0 or more, it is evaluated as “high fusion”. , when the change rate is less than 2.0, it is judged as good particle adhesion. "Particle fusion property" described in Tables 1-3 is the value of the said change rate.

(3) water repellency

A dispersion liquid was prepared in which fluorine-containing polymer particles and inorganic particles (alumina, particle diameter 0.5 µm) were dispersed in water at a mass ratio of 1:1 so that the solid content concentration was 10% by mass. This dispersion was applied on a PET substrate with a hydrophilic undercoat with a bar coater (#3) and dried at 60° C. for 10 minutes to form a coating layer. In an atmosphere of room temperature of 25°C and a relative humidity of 50%, 1-4 µL of water was dripped onto the surface of the coating layer with a syringe. Using a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., contact angle meter CA-X type), the droplet was observed from a horizontal cross section, and the contact angle formed between the tangent of the droplet end and the plane of the coating film layer was determined. If the contact angle is more than 90°, it is evaluated as “excellent”, if the contact angle is more than 80° and less than 90°, it is “good”, if the contact angle is more than 50° and less than 80°, it is “slightly poor”, and if the contact angle is less than 50, it is evaluated as “poor” and if the contact angle is larger than 80°, it is determined that the water repellency is good. "Water repellency" described in Tables 1-3 is the value of the said contact angle.

(4) chemical resistance

It was mixed with N-methyl-2-pyrrolidone (henceforth NMP) so that the solid content concentration of a fluorine-containing polymer particle might be 10 mass %, and it stirred for 10 minutes, and the dispersion liquid was prepared. A sample solution obtained by diluting each dispersion to a solid content concentration of 0.01% by mass of the fluorine-containing polymer particles was dropped onto an aluminum foil, dried at room temperature, and then accelerated using a scanning electron microscope (Hitachi, SU8000) at an acceleration voltage of 2.0 kV, 50,000 Observation was carried out at 2 o'clock by boat. The arithmetic mean particle diameter when 100 particles were randomly measured was calculated|required. The rate of change of the arithmetic mean particle diameter of the sample dispersed in NMP with respect to the arithmetic mean particle diameter of the sample in which the aqueous dispersion was dried at room temperature, determined by the particle fusion property of (2) above [rate of change = arithmetic mean particle size of the sample dispersed in NMP] The diameter/arithmetic mean particle diameter of the sample dispersed in water] was calculated. If the rate of change is less than 1.5, it is evaluated as “excellent”, if the rate of change is 1.5 or more and less than 2.0, it is “good”, if the rate of change is 2.0 or more and less than 3.0, it is evaluated as “slightly poor”, if the rate of change is 3.0 or more, it is evaluated as “poor”, and the rate of change is 2.0 When it is less than, it is judged as good chemical resistance. "Chemical resistance" of Tables 1-3 is the value of the said change rate.

Example 1

<Polymerization of 1st stage>

300 parts of ion-exchanged water and 0.2 parts of sodium lauryl sulfate were put into a reactor, and stirring was started. 0.5 parts of ammonium persulfate was added thereto at 80°C under a nitrogen atmosphere, 35 parts of 2,2,2-trifluoroethyl methacrylate (3FMA), 63 parts of cyclohexyl methacrylate (CHMA), and hydroxyethyl methacrylate A monomer mixture consisting of 2 parts of acrylate (HEMA), 2 parts of sodium lauryl sulfate, and 50 parts of ion-exchanged water is continuously added dropwise over 4 hours, and polymerization is performed over 3 hours after the completion of the dropping, and the polymer particles in the first stage are got it

<Second-stage polymerization>

300 parts of ion-exchanged water, 10 parts (in terms of solid content) of the polymer particle obtained by the polymerization in the 1st stage, and 0.2 part of sodium lauryl sulfate were put into the reactor, and stirring was started. To this was added 0.5 parts of ammonium persulfate at 80°C under a nitrogen atmosphere, 35 parts of 2,2,2-trifluoroethyl methacrylate (3FMA), 63 parts of cyclohexyl methacrylate (CHMA), and hydroxyethyl methacrylate A monomer mixture consisting of 2 parts of acrylate (HEMA), 1 part of sodium lauryl sulfate, and 50 parts of ion-exchanged water was continuously dripped over 4 hours, and polymerization was performed over 3 hours after the completion of the dropping. The pH was adjusted to about 8 with aqueous ammonia. The obtained polymer particles had a volume average particle diameter of 256 nm and a number average particle diameter of 253 nm. The average particle size was measured using a thick particle size analyzer FPAR-1000 (manufactured by OTSUKA ELECTRONICS CO., LTD). Calculation Tg of the obtained polymer particle was 71 degreeC. In addition, the composition ratio of the monomer shown in Table 1 is the ratio of each component with respect to the total amount of monomer components. In addition, the heating residue at the time of heating the obtained polymer particle at 140 degreeC for 60 minutes was 22.7 mass %.

In addition, the abbreviation of each component in Tables 1-3 has the following meaning, respectively.

3FMA: 2,2,2-trifluoroethyl methacrylate (in Formula (1), R ¹ :-CH ₃ , R ² :-CH ₂ CF ₃ )

3FA: 2,2,2-trifluoroethyl acrylate (in Formula (1), R ¹ :-H, R ² :-CH ₂ CF ₃ )

13FMA: CF ₃ CF ₂ ^- (CF ₂ CF ₂ ) ₂ -CH ₂ CH ₂ OCOC(CH ₃ )=CH ₂ (in Formula (1), R ¹ :-H, R ² :-CH ₂ CH ₂ (CF ₂ ) ₅ CF ₃ )

·IBOMA: isobornyl methacrylate (in the formula (2), R ¹ :-CH ₃ , R ³ : isobornyl group)

CHMA: cyclohexyl methacrylate (in formula (2), R ¹ :-CH ₃ , R ³ :cyclohexyl group)

CHA: cyclohexyl acrylate (in formula (2), R ¹ :-H, R ³ : cyclohexyl group)

ST: Styrene

TCDA: dicyclopentanyl acrylate (in formula (2), R ¹ :-H, R ³ : dicyclofentanyl group)

·HEMA: hydroxyethyl methacrylate (in formula (3), R ¹ :-CH ₃ , R ⁴ :hydroxyethyl group)

4HBA: 4-hydroxybutyl acrylate (in the formula (3), R ¹ :-H, R ⁴ :4-hydroxybutyl group)

MMA: methyl methacrylate

Example 2

300 parts of ion-exchanged water and 0.2 parts of sodium lauryl sulfate were put into a reactor, and stirring was started. In a nitrogen atmosphere, 0.5 parts of ammonium persulfate is added at 80° C., 2,2,2-trifluoroethyl methacrylate (3FMA) 50 parts, cyclohexyl methacrylate (CHMA) 24 parts, cyclohexyl acrylate A monomer mixture comprising 24 parts of (CHA), 2 parts of 4-hydroxybutyl acrylate (4HBA), 2 parts of sodium lauryl sulfate, and 50 parts of ion-exchanged water is continuously added dropwise over 4 hours, and 3 hours after the completion of the dropping A polymerization treatment was performed. The pH was adjusted to about 8 with aqueous ammonia. The obtained polymer particle was as showing in Table 1.

Example 3

Except having changed the composition ratio of the monomer mixture into the composition shown in Table 1, it carried out similarly to Example 1, and obtained the polymer particle. The obtained polymer particle was as showing in Table 1.

Example 4

300 parts of ion-exchanged water and 0.2 parts of Adeka Resolve SR-1025 (made by ADEKA CORPORATION emulsifier) were put into the reactor, and stirring was started. In a nitrogen atmosphere, 0.5 parts of ammonium persulfate is added at 80° C., 2,2,2-trifluoroethyl methacrylate (3FMA) 50 parts, cyclohexyl methacrylate (CHMA) 24 parts, cyclohexyl acrylate 24 parts of (CHA), 2 parts of hydroxyethyl methacrylate (HEMA), 1 part of ADEKA Resolve SR-1025 (emulsifier manufactured by ADEKA CORPORATION), and 50 parts of ion-exchanged water were added dropwise continuously over 4 hours. , polymerization treatment was performed over 3 hours after completion of the dropwise addition. The pH was adjusted to about 8 with aqueous ammonia. The obtained polymer particle was as showing in Table 1.

Example 5

300 parts of ion-exchanged water and 0.5 part of sodium lauryl sulfate were put into a reactor, and stirring was started. To this was added 0.5 parts of ammonium persulfate at 80° C. under a nitrogen atmosphere, CF ₃ CF ₂ -(CF ₂ CF ₂ ) ₂ -CH ₂ CH ₂ OCOC(CH ₃ )=CH ₂ (13FMA) 50 parts, isobornyl A monomer mixture consisting of 48 parts of methacrylate (IBOMA), 2 parts of hydroxyethyl methacrylate (HEMA), 2 parts of sodium lauryl sulfate, and 50 parts of ion-exchanged water is continuously added dropwise over 4 hours, and 3 hours after completion of the dropping polymerization treatment was performed over the The pH was adjusted to about 8 with aqueous ammonia. The obtained polymer particle was as showing in Table 1.

Example 6

Except not having adjusted pH with aqueous ammonia, it carried out similarly to Example 2, and obtained the polymer particle. The obtained polymer particle was as showing in Table 1.

Example 7

120 parts of ion-exchanged water and 1 part of Adeka Resolve SR-1025 (made by ADEKA CORPORATION emulsifier) were put into the reactor, and stirring was started. To this was added 0.4 parts of 2,2'-azobis(2-(2-imidazolin-2-yl)propane) (Wako Pure Chemicals Co., Ltd.) under a nitrogen atmosphere, and 2,2,2-tri Fluoroethyl methacrylate (3FMA) 40 parts, dicyclofentanyl acrylate (TCDA) 20 parts, cyclohexyl acrylate (CHA) 38 parts, hydroxyethyl methacrylate (HEMA) 2 parts, Adeca Resolve SR A monomer mixture consisting of 5 parts of -1025 (emulsifier manufactured by ADEKA CORPORATION) and 115 parts of ion-exchanged water was continuously added dropwise at 60° C. over 2 hours, and polymerization was performed over 4 hours after completion of the dropping. The obtained polymer particle was as showing in Table 1.

Example 8

Except having changed the composition ratio of the monomer mixture into the composition shown in Table 1, it carried out similarly to Example 7, and obtained the polymer particle. The obtained polymer particle was as showing in Table 1.

Example 9

Except having changed the composition ratio of the monomer mixture into the composition shown in Table 1, it carried out similarly to Example 7, and obtained the polymer particle. The obtained polymer particle was as showing in Table 1.

Example 10

120 parts of ion-exchanged water and 1 part of Adeka Resolve SR-1025 (made by ADEKA CORPORATION emulsifier) were put into the reactor, and stirring was started. To this was added 0.4 parts of 2,2'-azobis(2-(2-imidazolin-2-yl)propane) (Wako Pure Chemicals Co., Ltd.) under a nitrogen atmosphere, and 2,2,2-tri Fluoroethyl methacrylate (3FMA) 40 parts, dicyclopentanyl acrylate (TCDA) 20 parts, cyclohexyl acrylate (CHA) 35 parts, hydroxyethyl methacrylate (HEMA) 2 parts, urethane acrylate DP- A monomer mixture consisting of 3 parts of 600BU (manufactured by NOF CORPORATION), 9 parts of ADEKA Resolve SR-1025 (an emulsifier manufactured by ADEKA CORPORATION), and 115 parts of ion-exchanged water was continuously dripped at 60°C for 2 hours over 2 hours, and 4 hours after the completion of the dripping polymerization treatment was performed over the The obtained polymer particle was as showing in Table 2. In addition, the composition ratio of the monomer shown in Table 2 is the ratio of each component with respect to the total amount of monomer components.

Example 11

Except having changed the composition ratio of the monomer mixture into the composition shown in Table 2, it carried out similarly to Example 10, and obtained the polymer particle. The obtained polymer particle was as showing in Table 2.

Example 12

Except having changed the composition ratio of the monomer mixture into the composition shown in Table 2, it carried out similarly to Example 10, and obtained the polymer particle. The obtained polymer particle was as showing in Table 2.

Example 13

Except having changed the composition ratio of the monomer mixture into the composition shown in Table 2, it carried out similarly to Example 10, and obtained the polymer particle. The obtained polymer particle was as showing in Table 2.

Example 14

Except having changed the composition ratio of the monomer mixture into the composition shown in Table 2, it carried out similarly to Example 10, and obtained the polymer particle. The obtained polymer particle was as showing in Table 2.

Example 15

120 parts of ion-exchanged water and 1 part of Adeka Resolve SR-1025 (made by ADEKA CORPORATION emulsifier) were put into the reactor, and stirring was started. To this was added 0.4 parts of 2,2'-azobis(2-(2-imidazolin-2-yl)propane) (Wako Pure Chemicals Co., Ltd.) under a nitrogen atmosphere, and 2,2,2-tri Fluoroethyl methacrylate (3FMA) 40 parts, cyclohexyl acrylate (CHA) 58 parts, hydroxyethyl methacrylate (HEMA) 2 parts, ADEKA Resolve SR-1025 (an emulsifier manufactured by ADEKA CORPORATION) 9 parts, The monomer mixture consisting of 115 parts of ion-exchanged water was continuously dripped at 60 degreeC over 2 hours, and the polymerization process was performed over 4 hours after completion|finish of dripping. The obtained polymer particle was as showing in Table 2.

Example 16

Except having changed the composition ratio of a monomer mixture into the composition shown in Table 2, it carried out similarly to Example 15, and obtained the polymer particle. The obtained polymer particle was as showing in Table 2.

Example 17

Except having changed the composition ratio of a monomer mixture into the composition shown in Table 2, it carried out similarly to Example 15, and obtained the polymer particle. The obtained polymer particle was as showing in Table 2.

Example 18

120 parts of ion-exchanged water and 1 part of ADEKA Resolve SR-1025 (made by ADEKA CORPORATION emulsifier) were put into the reactor, and stirring was started. To this was added 0.4 parts of 2,2'-azobis(2-(2-imidazolin-2-yl)propane) (Wako Pure Chemicals Co., Ltd.) under a nitrogen atmosphere, and 2,2,2-tri 30 parts of fluoroethyl methacrylate (3FMA), 61 parts of cyclohexyl acrylate (CHA), 2 parts of hydroxyethyl methacrylate (HEMA), 7 parts of urethane acrylate DP-600BU (manufactured by NOF Corporation), ADEKA A monomer mixture comprising 9 parts of Resolve SR-1025 (an emulsifier manufactured by ADEKA CORPORATION) and 115 parts of ion-exchanged water was continuously dripped at 60° C. over 2 hours, and polymerization was performed over 4 hours after the dropping was completed. The obtained polymer particle was as showing in Table 2. In addition, the composition ratio of the monomer shown in Table 2 is the ratio of each component with respect to the total amount of monomer components.

Example 19

Except having changed the crosslinking agent (D) into urethane acrylate UF-07DF (made by KYOEISHA CHEMICAL Co., Ltd.), it carried out similarly to Example 18, and obtained the polymer particle. The obtained polymer particle was as showing in Table 3.

Example 20

Except having changed the crosslinking agent (D) into urethane acrylate UF-C012 (made by KYOEISHA CHEMICAL Co., Ltd.), it carried out similarly to Example 18, and obtained the polymer particle. The obtained polymer particle was as showing in Table 3.

Example 21

Except having changed the crosslinking agent (D) into urethane acrylate UF-C052 (made by KYOEISHA CHEMICAL Co., Ltd.), it carried out similarly to Example 18, and obtained the polymer particle. The obtained polymer particle was as showing in Table 3.

Example 22

Except having changed the crosslinking agent (D) into urethane acrylate UF-0146 (made by KYOEISHA CHEMICAL Co., Ltd.), it carried out similarly to Example 18, and obtained the polymer particle. The obtained polymer particle was as showing in Table 3.

Example 23

Except having changed the crosslinking agent (D) into alkylene glycol dimethacrylate PDE-600 (made by KYOEISHA CHEMICAL Co., Ltd.), it carried out similarly to Example 18, and obtained the polymer particle. The obtained polymer particle was as showing in Table 3.

Example 24

Except having changed the crosslinking agent (D) into alkylene glycol diacrylate ADP-400 (made by KYOEISHA CHEMICAL Co., Ltd.), it carried out similarly to Example 18, and obtained the polymer particle. The obtained polymer particle was as showing in Table 3.

Comparative Example 1

Except having changed the composition ratio of the monomer mixture into the composition shown in Table 3, it carried out similarly to Example 1, and obtained the polymer particle. The obtained polymer particle was as showing in Table 3.

Comparative Example 2

300 parts of ion-exchanged water and 0.2 parts of sodium lauryl sulfate were put into a reactor, and stirring was started. To this was added 0.5 parts of ammonium persulfate at 80°C under a nitrogen atmosphere, and a monomer mixture consisting of 100 parts of isobornyl methacrylate (IBOMA), 2 parts of sodium lauryl sulfate, and 50 parts of ion-exchanged water was continuously added dropwise over 4 hours. and superposition|polymerization process was performed over 3 hours after completion|finish of dripping. The pH was adjusted to about 8 with aqueous ammonia. The obtained polymer particle was as showing in Table 3.

Comparative Example 3

Except having changed the composition ratio of a monomer mixture into the composition shown in Table 3, it carried out similarly to Example 1, and obtained the polymer particle. The obtained polymer particle was as showing in Table 3.

Industrial Applicability

The fluorine-containing polymer particles of the present invention are added in a small amount to the coating film on the film, and by maximizing the low surface free energy of fluorine itself, fluorine is applied to the surface of the coating film while maintaining the properties of other particles contained in the coating film on the film. characteristics can be expressed. Moreover, since it has adhesiveness to another while suppressing thermal fusion of particle|grains, it becomes possible to provide the film which forms the coating film excellent in water repellency, antifouling property, chemical-resistance, and adhesiveness with high productivity. In particular, application as a coating agent for modifying the surface of a separator film used in lithium ion batteries is advanced by this, and contribution to reduction of global warming gas emission by promoting EV/PHEV spread can be expected.

Claims (9)

A copolymer comprising 30% by mass or more of the structural unit (X) derived from the fluorine-containing (meth)acrylic acid ester monomer (A) and 30% by mass or more of the structural unit (Y) derived from the (meth)acrylic acid ester monomer (B) As the formed particles, the structural unit derived from the fluorine-containing (meth)acrylic acid ester monomer (A) is represented by the following general formula (1), and the structural unit derived from the (meth)acrylic acid ester monomer (B) is represented by the following general formula (2) Fluorine-containing polymer particles characterized in that shown.

(in formula (1) (2), R ¹ is hydrogen or a methyl group, R ² is a fluorine-containing hydrocarbon group having 1 to 10 carbon atoms, R ³ is a benzyl group and a group consisting of a cyclic hydrocarbon group having 5 to 10 carbon atoms. A group selected from, a, b represents a degree of polymerization) The method of claim 1,
The fluorine-containing polymer particles in the copolymer, wherein the total of the structural unit (X) and the structural unit (Y) exceeds 80% by mass. 3. The method according to claim 1 or 2,
The (meth)acrylic acid ester monomer (B) is isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) ) Fluorine-containing polymer particles, characterized in that at least one selected from acrylate. 4. The method according to any one of claims 1 to 3,
The copolymer further contains 1 to 10% by mass of a structural unit (Z) derived from a (meth)acrylic acid ester monomer (C) having a hydroxyl group, wherein the structural unit (Z) is represented by the following formula (3) fluorine-containing polymer particles.

(In formula (3), R ¹ is hydrogen or a methyl group, R ⁴ is a hydrocarbon group having 1 to 10 carbon atoms including a hydroxyl group, and c represents a degree of polymerization) 5. The method according to any one of claims 1 to 4,
The said copolymer further contains 1-10 mass % of a crosslinking agent (D), The fluorine-containing polymer particle characterized by the above-mentioned. 6. The method according to any one of claims 1 to 5,
Fluorine-containing polymer particles having a volume average particle diameter of 100 to 500 nm and a particle size distribution (volume average particle diameter/number average particle diameter) of 1.20 or less. 7. The method according to any one of claims 1 to 6,
The fluorine-containing polymer particles having a glass transition temperature of 20°C to 100°C of the copolymer. A dispersion comprising the fluorine-containing polymer particles according to any one of claims 1 to 7 and water, the dispersion comprising the fluorine-containing polymer particles having a pH of 5 to 10. 9. The method of claim 8,
A dispersion comprising fluorine-containing polymer particles used for a film.