WO2020105671A1 - Fluorine-containing polymer particles - Google Patents
Fluorine-containing polymer particlesInfo
- Publication number
- WO2020105671A1 WO2020105671A1 PCT/JP2019/045401 JP2019045401W WO2020105671A1 WO 2020105671 A1 WO2020105671 A1 WO 2020105671A1 JP 2019045401 W JP2019045401 W JP 2019045401W WO 2020105671 A1 WO2020105671 A1 WO 2020105671A1
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- fluorine
- meth
- polymer particles
- mass
- structural unit
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/22—Esters containing halogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
- C08L33/16—Homopolymers or copolymers of esters containing halogen atoms
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
- C09D133/16—Homopolymers or copolymers of esters containing halogen atoms
Definitions
- 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 property, chemical resistance, adhesion, and particle non-fusing property.
- Fluorine-containing polymers have the advantage of being excellent in properties such as heat resistance, oxidation resistance, light resistance, and chemical resistance, and various fluorine-containing polymers have been proposed in the past. Fluorine-containing polymers are used, for example, as water- and oil-repellent agents and antifouling agents, by taking advantage of the low free energy of fluorine-containing polymers, that is, the difficulty of adhering to other substances. References 1-3). However, if the fluorine-containing polymer is added too much, the chemical resistance is lowered and the cost is increased, and the production cost is a problem.
- the polymer particles are used for the purpose of improving the physical properties of the resin molded product such as light diffusivity, blocking resistance and slipperiness, and imparting further properties, and also for the spacers and electrical properties between minute parts of electronic devices. It is used as a base particle of conductive fine particles for connection. Therefore, the polymer particles are required to have various characteristics depending on the intended use, and various proposals have been made to satisfy such requirements (see Patent Documents 4 to 6, for example).
- fluorine-containing polymer particles which form a coating film having excellent adhesion to other materials while suppressing thermal fusion between particles and having excellent water repellency, antifouling property, and chemical resistance have not yet been obtained. Not established.
- Japanese Patent Laid-Open No. 2012-92316 Japanese Patent Laid-Open No. 2012-82414 Japanese Patent No. 3002764 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 form a coating film excellent in water repellency, antifouling property, chemical resistance, adhesiveness and particle non-fusing property by mixing in a small amount into a coating film, fluorine-containing polymer particles, Is to provide.
- 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), derived from the (meth) acrylic acid ester monomer (B).
- structural unit (Y) of 30% by mass or more, wherein the structural unit derived from the fluorine-containing (meth) acrylic acid ester monomer (A) is represented by the following general formula (1):
- the structural unit derived from the (meth) acrylic acid ester monomer (B) is represented by the following general formula (2).
- R 1 is hydrogen or a methyl group
- R 2 is a hydrocarbon group containing fluorine and having 1 to 10 carbon atoms
- R 3 is a benzyl group and a cyclic hydrocarbon group having 5 to 10 carbon atoms.
- a and b each represent a degree of polymerization.
- the fluorine-containing polymer particles of the present invention are added to the coating film in a small amount, and by making the most of the low surface free energy of fluorine itself, the characteristics of the other particles contained in the coating film are maintained and the coating film is maintained.
- the characteristics of fluorine can be developed on the surface.
- the fluorine-containing polymer particles are structural units (X) derived from a fluorine-containing (meth) acrylic acid ester monomer (A) having a low surface free energy, and (meth) acrylic having excellent chemical resistance, light resistance and adhesion. Since the structural unit derived from the acid ester monomer (B) is contained, the characteristics of fluorine can be easily exhibited on the surface of the coated article.
- the fluorine-containing polymer particle of the present invention is formed of a copolymer composed of the structural unit (X) and the structural unit (Y).
- the structural unit (X) is a repeating unit derived from the fluorine-containing (meth) acrylic acid ester monomer (A) and is represented by the following general formula (1).
- R 1 represents hydrogen or a methyl group
- R 2 represents a hydrocarbon group containing 1 to 10 carbon atoms containing fluorine
- a represents a degree of polymerization.
- R 1's each independently represent hydrogen or a methyl group.
- a monomer in which R 1 is hydrogen represents an acrylate, and a monomer in which R 1 is a methyl group represents a methacrylate.
- R 2 is a hydrocarbon group containing 1 to 10 carbon atoms containing fluorine, preferably a hydrocarbon group containing 2 to 10 carbon atoms containing fluorine.
- the hydrocarbon group may have an unsaturated bond, and may be either a straight chain hydrocarbon group or a branched chain hydrocarbon group.
- at least a part of hydrogen of the hydrocarbon group is replaced with fluorine.
- R 2 may have all the hydrogen atoms in the hydrocarbon group replaced with fluorine.
- R 2 examples include —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 can be mentioned.
- the fluorine-containing (meth) acrylic acid ester monomer (A) is a hydrocarbon group (R 2 ) having an ester portion containing fluorine and having 1 to 10 carbon atoms.
- R 2 hydrocarbon group
- 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
- 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
- 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).
- 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
- b represents the degree of polymerization.
- 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 composed of a single or plural units, and preferably 1 to 3 types of structural units different from each other are preferably contained.
- the different structural units are different in R 3 and / or different in acrylate and methacrylate.
- Examples of the cyclic hydrocarbon group having 5 to 10 carbon atoms include a monocyclic group, a polycyclic group and a bridged ring group.
- the cyclic hydrocarbon group may be saturated or unsaturated.
- Examples of the cyclic hydrocarbon group having 5 to 10 carbon atoms include cyclohexyl group, t-butylcyclohexyl group, dicyclopentanyl group, dicyclopentenyl group, isobonyl group and the like.
- 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 (meth). It is preferable that at least one selected from the group consisting of acrylate and isobornyl (meth) acrylate.
- the structural unit (X) derived from the fluorine-containing (meth) acrylic acid ester monomer (A) is 30% by mass. % And 30% by mass or more of the structural unit (Y) composed of structural units derived from structural units derived from the (meth) acrylic acid ester monomer (B).
- the amount of the structural unit derived from the (meth) acrylic acid ester monomer (B) is the total of structural units derived from one or more kinds of the monomer (B).
- a and b are the degree 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% in 100% by mass of the monomer unit. It is at least mass%, more preferably at least 40 mass%.
- 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, in 100% by mass of the monomer unit. It is preferably 60% or less, more preferably 50% by mass or less, and particularly preferably less than 50% by mass.
- 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 in 100% by mass of the monomer unit. , More preferably 40% by mass or more, further preferably 45% by mass or more, particularly preferably 50% by mass or more.
- the upper limit of the structural unit (Y) derived from the (meth) acrylic acid ester monomer (B) is 75 mass% or less, more preferably 70 mass% or less, and further preferably 68 mass% in 100 mass% of the monomer unit. % Or less, more preferably 66% by mass or less, still more preferably 64% by mass or less, and particularly preferably 62% by mass or less.
- 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 unit. It is preferably 90% by mass or more, more preferably 90% by mass or more, and particularly preferably 95% by 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 unit.
- the copolymer forming the fluorine-containing polymer particles contains, 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. Can be included. By containing the structural unit (Z) derived from the (meth) acrylic acid ester monomer (C) having a hydroxyl group, polymer particles having excellent stability after particle formation can be obtained.
- the lower limit of the structural unit (Z) is preferably 1% by mass or more and more preferably 2% by mass or more in 100% by mass of the monomer unit.
- the upper limit of the structural unit (Z) is preferably 10% by mass or less, more preferably 8% by mass or less in 100% by mass of the monomer unit.
- the structural unit (Z) is represented by the following formula (3).
- R 1 represents hydrogen or a methyl group
- R 4 represents a hydrocarbon group containing a hydroxyl group and having 1 to 10 carbon atoms
- c represents the degree of polymerization.
- R 1 represents hydrogen or a methyl group.
- R 4 is a hydrocarbon group containing a hydroxyl group and having 1 to 10 carbon atoms, and preferably a hydrocarbon group containing a hydroxyl group and having 2 to 6 carbon atoms.
- the hydrocarbon group may have an unsaturated bond. It may be either a straight chain hydrocarbon group or a branched chain hydrocarbon group.
- At least one hydrogen atom of the hydrocarbon group of R 4 is substituted with a hydroxyl group. Examples of R 4 include hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, hydroxyhexyl, hydroxyhepticyl, hydroxyoctyl, and the like.
- the structural unit (Z) is a repeating unit derived from the (meth) acrylic acid ester monomer (C) having a hydroxyl group, and c is its degree of polymerization.
- the (meth) acrylic acid ester monomer (C) having a hydroxyl group include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth).
- Acrylate 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 7-hydroxyhepticyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, and the like.
- the copolymer forming the fluorine-containing polymer particles can further contain a cross-linking agent (D) in an amount of 1 to 10% by mass based on 100% by mass of the monomer unit.
- a cross-linking agent (D) in an amount of 1 to 10% by mass based on 100% by mass of the monomer unit.
- the lower limit of the cross-linking agent (D) is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably more than 2% by mass, still more preferably 3% by mass or more, in 100% by mass of the monomer unit. It is preferably 5% by mass or more, and particularly preferably 7% by mass or more.
- the upper limit of the cross-linking agent (D) is preferably 10% by mass or less, more preferably less than 10% by mass, even more preferably 9% by mass or less, still more preferably less than 9% by mass, particularly preferably 100% by mass in 100% by mass of the monomer unit. It is preferably 8% by mass or less.
- the cross-linking agent (D) a monomer that can form a cross-linked structure when polymerized can be used.
- the cross-linking agent include a monomer having two or more reactive groups per molecule. More specifically, a monofunctional monomer having a thermally crosslinkable crosslinkable group and one olefinic double bond per molecule, and a polyfunctional having two or more olefinic double bonds per molecule.
- the monomer include a polymerizable monomer.
- the thermally crosslinkable crosslinkable group contained in the monofunctional monomer include an epoxy group, an N-methylolamide group, an oxetanyl group, an oxazoline group, and a combination thereof.
- crosslinkable monomer having an epoxy group as a thermally crosslinkable crosslinkable group and having an olefinic double bond examples include vinyl glycidyl ether, allyl glycidyl ether, butenyl glycidyl ether, and o-allylphenyl glycidyl.
- Unsaturated glycidyl ethers such as ethers; butadiene monoepoxide, chloroprene monoepoxide, 4,5-epoxy-2-pentene, 3,4-epoxy-1-vinylcyclohexene, 1,2-epoxy-5,9-cyclododecadiene
- Monoepoxides of dienes or polyenes such as; alkenyl epoxides such as 3,4-epoxy-1-butene, 1,2-epoxy-5-hexene, 1,2-epoxy-9-decene; and glycidyl acrylate, glycidyl methacrylate, Glycidyl crotonate, glycidyl-4-heptenoate, glycidyl sorbate, glycidyl linoleate, glycidyl-4-methyl-3-pentenoate, glycidyl ester of 3-cyclohex
- crosslinkable monomer having an N-methylolamide group as a thermally crosslinkable crosslinkable group and having an olefinic double bond examples include a methylol group such as N-methylol (meth) acrylamide (meth ) Examples include acrylamides.
- crosslinkable monomer having an oxetanyl group as a thermally crosslinkable crosslinkable group and having an olefinic double bond examples include 3-((meth) acryloyloxymethyl) oxetane and 3-((meth) Acryloyloxymethyl) -2-trifluoromethyloxetane, 3-((meth) acryloyloxymethyl) -2-phenyloxetane, 2-((meth) acryloyloxymethyl) oxetane, and 2-((meth) acryloyloxymethyl ) -4-Trifluoromethyloxetane.
- crosslinkable monomer having an oxazoline group as a heat-crosslinkable crosslinkable group and having an olefinic double bond examples include 2-vinyl-2-oxazoline and 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 may be mentioned.
- polyfunctional monomers having two or more olefinic double bonds per molecule examples include allyl (meth) acrylate, ethylene di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth).
- alkylene glycol di (meth) acrylate and urethane acrylate can be preferably used.
- the copolymer forming the fluorine-containing polymer particles contains a repeating unit derived from a radically polymerizable compound as a structural unit other than the structural unit (X), the structural unit (Y) and the structural unit (Z).
- a radically polymerizable compound that can serve as another structural unit include (meth) acrylic acid esters other than the above-mentioned (meth) acrylic acid ester monomers (A) to (C), and vinyl compounds.
- Examples of the radically polymerizable compound include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, ( (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) 2-ethylhexyl acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-diethylaminoethyl (meth) acrylate, (meth) acrylic acid-2 -Dipropylaminoethyl, 2-dip
- 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, even more preferably 30 ° C. or higher, even more preferably 40 ° C. or higher, especially It is preferably 50 ° C. or higher.
- the glass transition temperature (Tg) of the copolymer forming the fluorine-containing polymer particles has an upper limit of 100 ° C. or lower, more preferably 80 ° C. or lower, and further preferably 70 ° C. or lower. By setting the Tg of the copolymer to 20 ° C. or higher, fusion of particles can be suppressed. Further, if the Tg is 100 ° C. or less, the production becomes easy.
- the glass transition temperature (Tg) of the copolymer can be adjusted by changing the type and composition ratio of the monomers.
- Tg of copolymer is calculated from the type and composition ratio of the monomers contained in the monomer mixture, using the Fox equation.
- the Fox equation is for calculating the Tg of the copolymer based on the Tg of the homopolymer of the individual monomers forming the copolymer, The details are described in Bulletin of the American Physical Society, Series 2 (Bulletin of the American Physical Society, Series 2) Vol. 1, No. 3, 123 (1956).
- Tg of a monomer as a basis for evaluating the Tg of a copolymer according to Fox's formula is, for example, New Polymer Bunko, Volume 7, Introduction to Synthetic Resins for Paints (Kyozo Kitaoka, Polymer The numerical values described in Table 10-2 (main raw material monomers of acrylic resin for paints) on pages 168 to 169 (publishing society, Kyoto, 1974) can be adopted.
- the volume average particle diameter of the fluorine-containing polymer particles is preferably 100 to 500 nm, and the particle size distribution (volume average particle diameter / number average particle diameter) is 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, and further preferably 400 nm or less.
- the volume average particle diameter is less than 100 nm, the viscosity of the dispersion liquid in which the fluorine-containing polymer particles are dispersed in water increases, and it may be difficult to obtain a high solid content aqueous dispersion liquid. Further, when mixed with other particles, it becomes difficult to unevenly distribute the fluorine-containing polymer particles on the surface of the dispersion liquid. Further, if the volume average particle diameter exceeds 500 nm, the storage stability of the aqueous dispersion of the fluorine-containing polymer particles may be lowered, and this may cause the uniformity of the formed coating film to be lowered.
- the volume average particle size 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.
- the ratio is preferably 1.05 or less, more preferably 1.05 or less, and particularly preferably 1.03 or less.
- the particle size distribution of the fluorine-containing polymer particles can be adjusted by changing the type of monomer, emulsifier, composition ratio and polymerization conditions.
- the average particle size of the fluorine-containing polymer particles can be measured by using a particle size distribution measuring device having a dynamic light scattering method as a measurement principle.
- a particle size distribution measuring device having a dynamic light scattering method as a measurement principle.
- examples of such a particle size distribution measuring device include HORIBA LB-550, SZ-100 series (above, manufactured by Horiba Ltd.), FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.) and the like.
- a dispersion liquid can be prepared by mixing the fluorine-containing polymer particles with water.
- this dispersion liquid can also be mixed with inorganic particles such as alumina and titania.
- the pH of the dispersion liquid is preferably 5 to 10, more preferably 6 to 9.5. By controlling the pH of the dispersion within such a range, the dispersion stability can be improved.
- the dispersion containing the fluorine-containing polymer particles can be used for a film, that is, applied to the film to form a coating film, whereby 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 base material, and a conductive film.
- the fluorine-containing polymer particles have a fluorine-containing (meth) acrylic acid ester monomer (A), a (meth) acrylic acid ester monomer (B), and optionally a hydroxyl group (meth). ) It is obtained by emulsion-polymerizing a monomer mixture of an acrylic acid ester monomer (C) and other radically polymerizable compounds in an aqueous medium.
- the fluorine-containing (meth) acrylic acid ester monomer (A) is preferably 30% by mass or more
- the (meth) acrylic acid ester monomer (B) and styrene are preferably 30% by mass.
- the total of the fluorine-containing (meth) acrylic acid ester monomer (A), the (meth) acrylic acid ester monomer (B), and styrene is preferably 90% by mass or more.
- the content is preferably 1 to 10% by mass in 100% by mass of the monomer mixture.
- the conditions for emulsion polymerization of the monomer mixture are not particularly limited, and for example, 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 about 1 to 30 hours. All you have to do is react.
- a chain transfer agent, a chelating agent, a pH adjusting agent, a solvent and the like may be added if necessary.
- an anionic surfactant As the emulsifier, an anionic surfactant, a nonionic surfactant, a combination of an anionic surfactant and a nonionic surfactant, etc. are used, and in some cases, an amphoteric surfactant or a cationic surfactant. Can also be used.
- anionic surfactant examples include alkyl sulfate sodium salt, alkylbenzene sulfonic acid sodium salt, succinic acid dialkyl ester sulfonic acid sodium salt, alkyldiphenyl ether disulfonic acid sodium salt, polyoxyethylene alkyl ether sulfate sodium salt, polyoxyethylene.
- examples thereof include sodium alkylphenyl ether sulfate. Among these, sodium lauryl sulfate ester, sodium dodecylbenzenesulfonate, sodium polyoxyethylene alkyl ether sulfate, sodium lauryl sulfate and the like are preferable.
- nonionic surfactant examples include polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester and the like.
- polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether and the like are used.
- amphoteric surfactant examples include lauryl betaine, hydroxyethyl imidazoline sulfate sodium salt, imidazoline sulfonic acid sodium salt, and the like.
- cationic surfactant examples include alkylpyridinium chloride, alkyltrimethylammonium chloride, dialkyldimethylammonium chloride, alkyldimethylbenzylammonium chloride and the like.
- a fluorine-based interface such as perfluoroalkyl carboxylate, perfluoroalkyl sulfonate, perfluoroalkyl phosphate ester, perfluoroalkyl polyoxyethylene, perfluoroalkyl betaine, ammonium perfluoroalkoxyfluorocarboxylate, etc.
- Activators can also be used.
- reactive emulsifiers that can be copolymerized with the above monomers, such as sodium styrenesulfonate, sodium allylalkylsulfonate, ammonium polyoxyethylenealkylallylphenylether sulfate, polyoxyethylenealkylallylphenylether, etc.
- sodium styrenesulfonate sodium allylalkylsulfonate
- ammonium polyoxyethylenealkylallylphenylether sulfate polyoxyethylenealkylallylphenylether, etc.
- 2- (1-allyl) -4-nonylphenoxy polyethylene glycol sulfate ammonium salt 2- (1-allyl) -4-nonylphenoxy polyethylene glycol in combination.
- 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.
- a water-soluble polymerization initiator such as sodium persulfate, potassium persulfate, ammonium persulfate, hydrogen peroxide, or a redox-based polymerization initiator in which these water-soluble polymerization initiators and reducing agents are combined is used.
- a redox-based polymerization initiator in which these water-soluble polymerization initiators and reducing agents are combined is used.
- potassium persulfate and ammonium persulfate are preferable.
- 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, glucose and the like.
- L-ascorbic acid or its salt is preferable.
- an oil-soluble polymerization initiator can be used by dissolving it in a monomer or a solvent.
- the oil-soluble polymerization initiator include 2,2'-azobisisobutyronitrile, 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile) and 2,2'-azobis.
- 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.
- chain transfer agent examples include halogenated hydrocarbons (eg, carbon tetrachloride, chloroform, bromoform, etc.), mercaptans (eg, n-dodecyl mercaptan, t-dodecyl mercaptan, n-octyl mercaptan, n-hexadecyl mercaptan, etc.), xanthogens.
- halogenated hydrocarbons eg, carbon tetrachloride, chloroform, bromoform, etc.
- mercaptans eg, n-dodecyl mercaptan, t-dodecyl mercaptan, n-octyl mercaptan, n-hexadecyl mercaptan, etc.
- xanthogens examples include xanthogenated hydrocarbons (eg, carbon tetrachloride,
- terpenes eg, dipentene, terpinolene, etc.
- thiuram sulfides eg, tetramethylthiuram monosulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, dipentamethyl
- thiuram disulfide eg, tetramethylthiuram monosulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, dipentamethyl
- 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.
- Examples of the pH adjusting agent include sodium carbonate, potassium carbonate, sodium hydrogen carbonate, ammonia and the like.
- the amount of the pH adjusting agent used is preferably about 0 to 3 parts by mass per 100 parts by mass of the monomer mixture.
- the monomer mixture can be added by various methods.
- a method of adding the whole amount of the monomer mixture at once a method of charging a part of the monomer mixture and reacting, and a method of charging the remaining monomer mixture continuously or in a divided manner, the reaction
- a method of charging the remaining monomer mixture continuously or dividedly a method of charging the whole amount of the monomer mixture continuously or sequentially, and the like.
- the remaining monomer mixture is continuously or dividedly charged, or after charging a part of the reacted particles, the remaining monomer mixture is continuously or divided.
- the method of charging by charging is preferable.
- % and part represent “mass%” and “part by mass”.
- the measurement methods used in this example are shown below.
- (1) Dispersion stability Fluorine-containing polymer particles and inorganic particles (alumina, particle diameter 0.5 ⁇ m) were mixed in water at a mass ratio of 1: 1 so that the solid content concentration was 10 mass%, It was dispersed for 10 minutes with a sonic dispersing machine. The average particle size of the initial particles was measured with a concentrated particle size analyzer (FPAR-1000 manufactured by Otsuka Electronics Co., Ltd.).
- a contact angle of 90 ° or more is “excellent”, a contact angle of 80 ° or more and less than 90 ° is “good”, a contact angle of 50 ° or more and less than 80 ° is “slightly poor”, and a contact angle is 50. If the contact angle is less than 80 °, the water repellency is determined to be good. “Water repellency” described in Tables 1 to 3 is the value of the contact angle.
- NMP N-methyl-2-pyrrolidone
- Example 1 First stage polymerization> 300 parts of ion-exchanged water and 0.2 part of sodium lauryl sulfate were charged into the reactor, and stirring was started. To this, 0.5 part of ammonium persulfate was added at 80 ° C. under a nitrogen atmosphere, and 35 parts of 2,2,2-trifluoroethyl methacrylate (3FMA), 63 parts of cyclohexyl methacrylate (CHMA), and hydroxyethyl methacrylate (HEMA) 2 were added.
- FMA 2,2,2-trifluoroethyl methacrylate
- CHMA cyclohexyl methacrylate
- HEMA hydroxyethyl methacrylate
- FMA 2,2,2-trifluoroethyl methacrylate
- CHMA cyclohexyl methacrylate
- HEMA hydroxyethyl methacrylate
- 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 concentrated particle size analyzer FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.).
- the calculated Tg of the obtained polymer particles was 71 ° C.
- the composition ratio of the monomers shown in Table 1 is the ratio of each component to the total amount of the monomer components.
- the heating residue when the obtained polymer particles were heated at 140 ° C. for 60 minutes was 22.7% by mass.
- HEMA hydroxyethyl methacrylate (in the formula (3), R 1 : —CH 3 , R 4 : hydroxyethyl group)
- 4HBA 4-hydroxybutyl acrylate (R 1 : -H, R 4 : 4-hydroxybutyl group in the above formula (3))
- ⁇ MMA methyl methacrylate
- Example 2 300 parts of ion-exchanged water and 0.2 part of sodium lauryl sulfate were charged into the reactor, and stirring was started. To this, 0.5 part of ammonium persulfate was added at 80 ° C. under a nitrogen atmosphere to obtain 50 parts of 2,2,2-trifluoroethyl methacrylate (3FMA), 24 parts of cyclohexyl methacrylate (CHMA) and 24 parts of cyclohexyl acrylate (CHA). , 4-hydroxybutyl acrylate (4HBA) (2 parts), sodium lauryl sulfate (2 parts), ion-exchanged water (50 parts) were continuously added dropwise over 4 hours, and polymerization was performed for 3 hours after completion of the addition. It was The pH was adjusted to about 8 with aqueous ammonia. The polymer particles obtained were as shown in Table 1.
- Example 3 Polymer particles were obtained in the same manner as in Example 1 except that the composition ratio of the monomer mixture was changed to the composition shown in Table 1. The polymer particles obtained were as shown in Table 1.
- Example 4 300 parts of ion-exchanged water and 0.2 part of ADEKA RearSorb SR-1025 (emulsifier manufactured by ADEKA CORPORATION) were charged into the reactor and stirring was started. To this, 0.5 part of ammonium persulfate was added at 80 ° C. under a nitrogen atmosphere to obtain 50 parts of 2,2,2-trifluoroethyl methacrylate (3FMA), 24 parts of cyclohexyl methacrylate (CHMA) and 24 parts of cyclohexyl acrylate (CHA).
- 3FMA 2,2,2-trifluoroethyl methacrylate
- CHMA cyclohexyl methacrylate
- CHA cyclohexyl acrylate
- HEMA hydroxyethyl methacrylate
- ADEKA RIASORB SR-1025 Emmulsifier manufactured by ADEKA CORPORATION
- 50 parts of ion-exchanged water were continuously added dropwise over 4 hours, and the addition was completed. Polymerization was carried out for the next 3 hours. The pH was adjusted to about 8 with aqueous ammonia.
- the polymer particles obtained were as shown in Table 1.
- Example 5 300 parts of ion-exchanged water and 0.5 part of sodium lauryl sulfate were charged into the reactor, and stirring was started. 0.5 parts of ammonium persulfate was added thereto at 80 ° C. under a nitrogen atmosphere, and CF 3 CF 2 — (CF 2 CF 2 ) 2 —CH 2 CH 2 OCOC (CH 3 ) ⁇ CH 2 (13FMA) 50 parts, A monomer mixture consisting of 48 parts of isobornyl methacrylate (IBOMA), 2 parts of hydroxyethyl methacrylate (HEMA), 2 parts of sodium lauryl sulfate and 50 parts of ion-exchanged water was continuously added dropwise over 4 hours, and after the addition was completed. Polymerization was performed for 3 hours. The pH was adjusted to about 8 with aqueous ammonia. The polymer particles obtained were as shown in Table 1.
- Example 6 Polymer particles were obtained in the same manner as in Example 2 except that the pH was not adjusted with aqueous ammonia. The polymer particles obtained were as shown in Table 1.
- Example 7 120 parts of ion-exchanged water and 1 part of ADEKA RIASORB SR-1025 (emulsifier manufactured by ADEKA CORPORATION) were charged into the reactor and stirring was started. 2,2'-azobis (2- (2-imidazolin-2-yl) propane) (Wako Pure Chemical Industries, Ltd.) 0.4 part was added to this under a nitrogen atmosphere, and 2,2,2-tri 40 parts of fluoroethyl methacrylate (3FMA), 20 parts of dicyclopentanyl acrylate (TCDA), 38 parts of cyclohexyl acrylate (CHA), 2 parts of hydroxyethyl methacrylate (HEMA), ADEKA REASORB SR-1025 (emulsifier manufactured by ADEKA CORPORATION) A monomer mixture consisting of 5 parts and 115 parts of ion-exchanged water was continuously added dropwise at 60 ° C. over 2 hours, and a polymerization treatment was carried out for 4 hours after completion of the addition.
- Example 8 Polymer particles were obtained in the same manner as in Example 7, except that the composition ratio of the monomer mixture was changed to the composition shown in Table 1. The polymer particles obtained were as shown in Table 1.
- Example 9 Polymer particles were obtained in the same manner as in Example 7, except that the composition ratio of the monomer mixture was changed to the composition shown in Table 1. The polymer particles obtained were as shown in Table 1.
- Example 10 120 parts of ion-exchanged water and 1 part of ADEKA RIASORB SR-1025 (emulsifier manufactured by ADEKA CORPORATION) were charged into the reactor and stirring was started. 2,2'-azobis (2- (2-imidazolin-2-yl) propane) (Wako Pure Chemical Industries, Ltd.) 0.4 part was added to this under a nitrogen atmosphere, and 2,2,2-tri 40 parts of fluoroethyl methacrylate (3FMA), 20 parts of dicyclopentanyl acrylate (TCDA), 35 parts of cyclohexyl acrylate (CHA), 2 parts of hydroxyethyl methacrylate (HEMA), urethane acrylate DP-600BU (manufactured by NOF Corporation) 3 Part, 9 parts of ADEKA RIASORB SR-1025 (emulsifier manufactured by ADEKA Corporation), and 115 parts of ion-exchanged water were continuously added dropwise at 60 ° C. over 2 hours, and polymer
- Example 11 Polymer particles were obtained in the same manner as in Example 10 except that the composition ratio of the monomer mixture was changed to the composition shown in Table 2. The polymer particles obtained were as shown in Table 2.
- Example 12 Polymer particles were obtained in the same manner as in Example 10 except that the composition ratio of the monomer mixture was changed to the composition shown in Table 2. The polymer particles obtained were as shown in Table 2.
- Example 13 Polymer particles were obtained in the same manner as in Example 10 except that the composition ratio of the monomer mixture was changed to the composition shown in Table 2. The polymer particles obtained were as shown in Table 2.
- Example 14 Polymer particles were obtained in the same manner as in Example 10 except that the composition ratio of the monomer mixture was changed to the composition shown in Table 2. The polymer particles obtained were as shown in Table 2.
- Example 15 120 parts of ion-exchanged water and 1 part of ADEKA RIASORB SR-1025 (emulsifier manufactured by ADEKA CORPORATION) were charged into the reactor and stirring was started. 2,2'-azobis (2- (2-imidazolin-2-yl) propane) (Wako Pure Chemical Industries, Ltd.) 0.4 part was added to this under a nitrogen atmosphere, and 2,2,2-tri A unit consisting of 40 parts of fluoroethyl methacrylate (3FMA), 58 parts of cyclohexyl acrylate (CHA), 2 parts of hydroxyethyl methacrylate (HEMA), 9 parts of ADEKA REASORB SR-1025 (emulsifier manufactured by ADEKA CORPORATION), and 115 parts of ion-exchanged water. The monomer mixture was continuously added dropwise at 60 ° C. over 2 hours, and a polymerization treatment was performed for 4 hours after the completion of the addition. The polymer particles obtained were as shown in Table 2.
- Example 16 Polymer particles were obtained in the same manner as in Example 15 except that the composition ratio of the monomer mixture was changed to the composition shown in Table 2. The polymer particles obtained were as shown in Table 2.
- Example 17 Polymer particles were obtained in the same manner as in Example 15, except that the composition ratio of the monomer mixture was changed to the composition shown in Table 2. The polymer particles obtained were as shown in Table 2.
- Example 18 120 parts of ion-exchanged water and 1 part of ADEKA RIASORB SR-1025 (emulsifier manufactured by ADEKA CORPORATION) were charged into the reactor and stirring was started. 2,2'-azobis (2- (2-imidazolin-2-yl) propane) (Wako Pure Chemical Industries, Ltd.) 0.4 part was added to this 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 Rearsorb SR-1025 (Adeka Corporation) A monomer mixture consisting of 9 parts of an emulsifier manufactured by the company) and 115 parts of ion-exchanged water was continuously added dropwise at 60 ° C. for 2 hours, and a poly
- Example 19 Polymer particles were obtained in the same manner as in Example 18 except that the urethane acrylate UF-07DF (manufactured by Kyoeisha Chemical Co., Ltd.) was used as the crosslinking agent (D). The polymer particles obtained were as shown in Table 3.
- Example 20 Polymer particles were obtained in the same manner as in Example 18, except that the urethane acrylate UF-C012 (manufactured by Kyoeisha Chemical Co., Ltd.) was used as the crosslinking agent (D). The polymer particles obtained were as shown in Table 3.
- Example 21 Polymer particles were obtained in the same manner as in Example 18, except that the urethane acrylate UF-C052 (manufactured by Kyoeisha Chemical Co., Ltd.) was used as the crosslinking agent (D). The polymer particles obtained were as shown in Table 3.
- Example 22 Polymer particles were obtained in the same manner as in Example 18, except that the urethane acrylate UF-0146 (manufactured by Kyoeisha Chemical Co., Ltd.) was used as the crosslinking agent (D). The polymer particles obtained were as shown in Table 3.
- Example 23 Polymer particles were obtained in the same manner as in Example 18, except that the cross-linking agent (D) was changed to alkylene glycol dimethacrylate PDE-600 (manufactured by Kyoeisha Chemical Co., Ltd.). The polymer particles obtained were as shown in Table 3.
- Example 24 Polymer particles were obtained in the same manner as in Example 18 except that the cross-linking agent (D) was changed to alkylene glycol diacrylate ADP-400 (manufactured by Kyoeisha Chemical Co., Ltd.). The polymer particles obtained were as shown in Table 3.
- Comparative Example 1 Polymer particles were obtained in the same manner as in Example 1 except that the composition ratio of the monomer mixture was changed to the composition shown in Table 3. The polymer particles obtained were as shown in Table 3.
- Comparative example 2 300 parts of ion-exchanged water and 0.2 part of sodium lauryl sulfate were charged into the reactor, and stirring was started. Under nitrogen atmosphere, 0.5 part of ammonium persulfate was added at 80 ° C., 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 added for 4 hours. Was continuously added dropwise, and the polymerization treatment was carried out for 3 hours after the completion of the addition. The pH was adjusted to about 8 with aqueous ammonia. The polymer particles obtained were as shown in Table 3.
- IBOMA isobornyl methacrylate
- Comparative Example 3 Polymer particles were obtained in the same manner as in Example 1 except that the composition ratio of the monomer mixture was changed to the composition shown in Table 3. The polymer particles obtained were as shown in Table 3.
- the fluorine-containing polymer particles of the present invention are added to a coating film on a film in a small amount, and by making the most of the low surface free energy of fluorine itself, the characteristics of other particles contained in the coating film on the film can be obtained.
- the characteristics of fluorine can be developed on the surface of the coating film while it is held.
- the application as a coating agent that modifies the surface of the separator film used in a lithium-ion battery is particularly advanced, and it can be expected to contribute to the reduction of global warming gas emissions by promoting the spread of EV / PHEV.
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Abstract
Provided are fluorine-containing polymer particles that can form a coating film having excellent water repellency, antifouling properties, chemical resistance, adhesion properties, and particle non-fusibility, by mixing a small amount of the fluorine-containing polymer particles with other particles. The fluorine-containing polymer particles are formed of a copolymer containing 30 mass% or more of a structural unit (X) derived from a fluorine-containing (meth)acrylic acid ester monomer (A), and 30 mass% or more of a structural unit (Y) derived from a (meth)acrylic acid ester monomer (B), and are characterized in that the structural unit derived from the fluorine-containing (meth)acrylic acid ester monomer (A) is represented by general formula (1), and the structural unit derived from the (meth)acrylic acid ester monomer (B) is represented by general formula (2). (In formulas (1) and (2), R1 represents hydrogen or a methyl group, R2 represents a fluorine-containing hydrocarbon group having 1-10 carbon atoms, R3 represents a group selected from the group consisting of a benzyl group and cyclic hydrocarbon groups having 5-10 carbon atoms, and a and b represent the degree of polymerization.)
Description
本発明は、フッ素含有重合体粒子に関し、撥水性、防汚性、耐薬品性、密着性、粒子非融着性に優れた塗膜を形成し得る、フッ素含有重合体粒子に関する。
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 property, chemical resistance, adhesion, and particle non-fusing property.
フッ素含有重合体には、耐熱性、耐酸化性、耐光性、耐薬品性などの特性に優れているという利点があり、従来、種々のフッ素含有重合体が提案されている。フッ素含有重合体の自由エネルギーが低い、すなわち、他の物に付着し難いという特性を利用して、フッ素含有重合体は、例えば、撥水撥油剤および防汚剤として使用されている（例えば特許文献１～３を参照）。ただし、フッ素含有重合体を入れすぎると耐薬品性の低下や、コストアップにつながり、製造コストを下げることが課題となっている。
Fluorine-containing polymers have the advantage of being excellent in properties such as heat resistance, oxidation resistance, light resistance, and chemical resistance, and various fluorine-containing polymers have been proposed in the past. Fluorine-containing polymers are used, for example, as water- and oil-repellent agents and antifouling agents, by taking advantage of the low free energy of fluorine-containing polymers, that is, the difficulty of adhering to other substances. References 1-3). However, if the fluorine-containing polymer is added too much, the chemical resistance is lowered and the cost is increased, and the production cost is a problem.
また、重合体粒子は、樹脂成形品の光拡散性、耐ブロッキング性および滑り性などの物性の向上や更なる特性の付与を目的として、また、電子機器類の微小部位間のスペーサや電気的接続を担う導電性微粒子の基材粒子として用いられている。したがって、重合体粒子は用いられる用途に応じて様々な特性が要求されており、かかる要求を満足すべく様々な提案がなされている（例えば特許文献４～６を参照）。
Further, the polymer particles are used for the purpose of improving the physical properties of the resin molded product such as light diffusivity, blocking resistance and slipperiness, and imparting further properties, and also for the spacers and electrical properties between minute parts of electronic devices. It is used as a base particle of conductive fine particles for connection. Therefore, the polymer particles are required to have various characteristics depending on the intended use, and various proposals have been made to satisfy such requirements (see Patent Documents 4 to 6, for example).
しかし、粒子同士の熱融着を抑制しながら他の物への密着性を有し、かつ撥水性、防汚性、耐薬品性に優れた塗膜を形成するフッ素含有重合体粒子は、未だ確立されていない。
However, fluorine-containing polymer particles which form a coating film having excellent adhesion to other materials while suppressing thermal fusion between particles and having excellent water repellency, antifouling property, and chemical resistance have not yet been obtained. Not established.
本発明の目的は、塗膜に少量混合することにより、撥水性、防汚性、耐薬品性、密着性、粒子非融着性に優れた塗膜を形成し得る、フッ素含有重合体粒子を提供することである。
An object of the present invention is to form a coating film excellent in water repellency, antifouling property, chemical resistance, adhesiveness and particle non-fusing property by mixing in a small amount into a coating film, fluorine-containing polymer particles, Is to provide.
本発明のフッ素含有重合体粒子は、フッ素含有（メタ）アクリル酸エステル単量体（Ａ）由来の構造単位（Ｘ）を３０質量％以上、（メタ）アクリル酸エステル単量体（Ｂ）由来の構造単位（Ｙ）を３０質量％以上含む共重合体で形成された粒子であって、前記フッ素含有（メタ）アクリル酸エステル単量体（Ａ）由来の構造単位が下記一般式（１）、前記（メタ）アクリル酸エステル単量体（Ｂ）由来の構造単位が下記一般式（２）で表されることを特徴とすることを特徴とする。
（式（１）（２）中、Ｒ1は水素またはメチル基、Ｒ2はフッ素を含む炭素数１～１０の炭化水素基、Ｒ3はベンジル基および炭素数５～１０の環状炭化水素基からなる群から選ばれる基、ａ，ｂは重合度を表す。）
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), derived from the (meth) acrylic acid ester monomer (B). Of the structural unit (Y) of 30% by mass or more, wherein the structural unit derived from the fluorine-containing (meth) acrylic acid ester monomer (A) is represented by the following general formula (1): The structural unit derived from the (meth) acrylic acid ester monomer (B) is represented by the following general formula (2).
(In the formulas (1) and (2), R 1 is hydrogen or a methyl group, R 2 is a hydrocarbon group containing fluorine and having 1 to 10 carbon atoms, R 3 is a benzyl group and a cyclic hydrocarbon group having 5 to 10 carbon atoms. And a and b each represent a degree of polymerization.
本発明のフッ素含有重合体粒子は、塗膜に少量添加し、フッ素自体の表面自由エネルギーの低さを最大限に活かすことにより、塗膜に含まれる他粒子の特性を保持したまま、塗膜表面へフッ素の特徴を発現させることができる。フッ素含有重合体粒子は、表面自由エネルギーの低いフッ素含有（メタ）アクリル酸エステル単量体（Ａ）由来の構造単位（Ｘ）および耐薬品性、耐光性、密着性に優れた（メタ）アクリル酸エステル単量体（Ｂ）由来の構造単位を含有するため、塗装物の表面へフッ素の特徴を発現し易くすることができる。
The fluorine-containing polymer particles of the present invention are added to the coating film in a small amount, and by making the most of the low surface free energy of fluorine itself, the characteristics of the other particles contained in the coating film are maintained and the coating film is maintained. The characteristics of fluorine can be developed on the surface. The fluorine-containing polymer particles are structural units (X) derived from a fluorine-containing (meth) acrylic acid ester monomer (A) having a low surface free energy, and (meth) acrylic having excellent chemical resistance, light resistance and adhesion. Since the structural unit derived from the acid ester monomer (B) is contained, the characteristics of fluorine can be easily exhibited on the surface of the coated article.
以下、本発明に係る好適な実施形態について詳細に説明する。なお、本発明は、下記に記載された実施形態のみに限定されるものではなく、本発明の要旨を変更しない範囲において実施される各種の変形例も含むものとして理解されるべきである。なお、本明細書における「～（メタ）アクリレート」とは、「～アクリレート」および「～メタクリレート」の双方を包括する概念である。
Hereinafter, preferred embodiments according to the present invention will be described in detail. The present invention is not limited to the embodiments described below, and should be understood as including various modifications that are carried out within the scope without changing the gist of the present invention. The term "-(meth) acrylate" as used herein is a concept including both "-acrylate" and "-methacrylate".
本発明のフッ素含有重合体粒子は、構造単位（Ｘ）および構造単位（Ｙ）からなる共重合体で形成される。
構造単位（Ｘ）は、フッ素含有（メタ）アクリル酸エステル単量体（Ａ）由来の繰り返し単位であり、下記一般式（１）で表される。
（式（１）中、Ｒ1は水素またはメチル基、Ｒ2はフッ素を含む炭素数１～１０の炭化水素基、ａは重合度を表す。）
The fluorine-containing polymer particle of the present invention is formed of a copolymer composed of the structural unit (X) and the structural unit (Y).
The structural unit (X) is a repeating unit derived from the fluorine-containing (meth) acrylic acid ester monomer (A) and is represented by the following general formula (1).
(In the formula (1), R 1 represents hydrogen or a methyl group, R 2 represents a hydrocarbon group containing 1 to 10 carbon atoms containing fluorine, and a represents a degree of polymerization.)
構造単位（Ｘ）は、フッ素含有（メタ）アクリル酸エステル単量体（Ａ）由来の繰り返し単位であり、下記一般式（１）で表される。
The structural unit (X) is a repeating unit derived from the fluorine-containing (meth) acrylic acid ester monomer (A) and is represented by the following general formula (1).
式（１）において、Ｒ1は互いに独立して水素またはメチル基である。Ｒ1が水素の単量体はアクリレート、Ｒ1がメチル基の単量体はメタクリレートを表す。
In the formula (1), R 1's each independently represent hydrogen or a methyl group. A monomer in which R 1 is hydrogen represents an acrylate, and a monomer in which R 1 is a methyl group represents a methacrylate.
Ｒ2はフッ素を含む炭素数１～１０の炭化水素基であり、好ましくはフッ素を含む炭素数２～１０の炭化水素基である。炭化水素基は、不飽和結合を有してもよく、また直鎖状炭化水素基、分岐鎖状炭化水素基のいずれでもよい。Ｒ2は炭化水素基の少なくとも１部の水素がフッ素に置換されている。Ｒ2は炭化水素基のすべての水素がフッ素に置換されてもよい。
R 2 is a hydrocarbon group containing 1 to 10 carbon atoms containing fluorine, preferably a hydrocarbon group containing 2 to 10 carbon atoms containing fluorine. The hydrocarbon group may have an unsaturated bond, and may be either a straight chain hydrocarbon group or a branched chain hydrocarbon group. In R 2 , at least a part of hydrogen of the hydrocarbon group is replaced with fluorine. R 2 may have all the hydrogen atoms in the hydrocarbon group replaced with fluorine.
Ｒ2として、例えば、－ＣＨ2ＣＦ3、－ＣＨ2ＣＦ2ＣＦ2Ｈ、－ＣＨ2ＣＦ2ＣＦ3、－ＣＨ2ＣＦ2ＣＦＨＣＦ3、－ＣＨ2（ＣＦ2）3ＣＦ2Ｈ、－ＣＨ2ＣＨ2（ＣＦ2）3ＣＦ3、－ＣＨ2（ＣＦ2）5ＣＦ2Ｈ、－ＣＨ2ＣＨ2（ＣＦ2）5ＣＦ3、－ＣＨ2ＣＨ2（ＣＦ2）7ＣＦ3、－ＣＨ（ＣＦ3）2、－ＣＨ2ＣＣＨ3（ＣＦ3）2等が挙げられる。
Examples of R 2 include —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 can be mentioned.
フッ素含有（メタ）アクリル酸エステル単量体（Ａ）は、そのエステル部分がフッ素を含む炭素数１～１０の炭化水素基（Ｒ2）である。
フッ素含有（メタ）アクリル酸エステル単量体（Ａ）として、
ＣＨ2＝ＣＨＣＯＯＣＨ2ＣＦ3（３ＦＡ）、
ＣＨ2＝ＣＨＣＯＯＣＨ2ＣＦ2ＣＦ2Ｈ（４ＦＡ）、
ＣＨ2＝ＣＨＣＯＯＣＨ2ＣＦ2ＣＦ3（５ＦＡ）、
ＣＨ2＝ＣＨＣＯＯＣＨ2ＣＦ2ＣＦＨＣＦ3（６ＦＡ）、
ＣＨ2＝ＣＨＣＯＯＣＨ2（ＣＦ2）3ＣＦ2Ｈ（８ＦＡ）、
ＣＨ2＝ＣＨＣＯＯＣＨ2ＣＨ2（ＣＦ2）3ＣＦ3（９ＦＡ）、
ＣＨ2＝ＣＨＣＯＯＣＨ2（ＣＦ2）5ＣＦ2Ｈ（１２ＦＡ）、
ＣＨ2＝ＣＨＣＯＯＣＨ2ＣＨ2（ＣＦ2）5ＣＦ3（１３ＦＡ）、
ＣＨ2＝ＣＨＣＯＯＣＨ2ＣＨ2（ＣＦ2）7ＣＦ3（１７ＦＡ）、
ＣＨ2＝ＣＨＣＯＯＣＨ（ＣＦ3）2（ＨＦＩＰ－Ａ）、
ＣＨ2＝ＣＨＣＯＯＣＨ2ＣＣＨ3（ＣＦ3）2（６ＦＮＰ－Ａ）、
ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯＣＨ2ＣＦ3（３ＦＭＡ）、
ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯＣＨ2ＣＦ2ＣＦ2Ｈ（４ＦＭＡ）、
ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯＣＨ2ＣＦ2ＣＦ3（５ＦＭＡ）、
ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯＣＨ2ＣＦ2ＣＦＨＣＦ3（６ＦＭＡ）、
ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯＣＨ2（ＣＦ2）3ＣＦ2Ｈ（８ＦＭＡ）、
ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯＣＨ2ＣＨ2（ＣＦ2）3ＣＦ3（９ＦＭＡ）、
ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯＣＨ2（ＣＦ2）5ＣＦ2Ｈ（１２ＦＭＡ）、
ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯＣＨ2ＣＨ2（ＣＦ2）5ＣＦ3（１３ＦＭＡ）、
ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯＣＨ2ＣＨ2（ＣＦ2）7ＣＦ3（１７ＦＭＡ）、
ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯＣＨ（ＣＦ3）2（ＨＦＩＰ－ＭＡ）、
ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯＣＨ2ＣＣＨ3（ＣＦ3）2（６ＦＮＰ－ＭＡ）
等の化合物が例示される。 The fluorine-containing (meth) acrylic acid ester monomer (A) is a hydrocarbon group (R 2 ) having an ester portion containing fluorine and having 1 to 10 carbon atoms.
As the 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)
Compounds such as
フッ素含有（メタ）アクリル酸エステル単量体（Ａ）として、
ＣＨ2＝ＣＨＣＯＯＣＨ2ＣＦ3（３ＦＡ）、
ＣＨ2＝ＣＨＣＯＯＣＨ2ＣＦ2ＣＦ2Ｈ（４ＦＡ）、
ＣＨ2＝ＣＨＣＯＯＣＨ2ＣＦ2ＣＦ3（５ＦＡ）、
ＣＨ2＝ＣＨＣＯＯＣＨ2ＣＦ2ＣＦＨＣＦ3（６ＦＡ）、
ＣＨ2＝ＣＨＣＯＯＣＨ2（ＣＦ2）3ＣＦ2Ｈ（８ＦＡ）、
ＣＨ2＝ＣＨＣＯＯＣＨ2ＣＨ2（ＣＦ2）3ＣＦ3（９ＦＡ）、
ＣＨ2＝ＣＨＣＯＯＣＨ2（ＣＦ2）5ＣＦ2Ｈ（１２ＦＡ）、
ＣＨ2＝ＣＨＣＯＯＣＨ2ＣＨ2（ＣＦ2）5ＣＦ3（１３ＦＡ）、
ＣＨ2＝ＣＨＣＯＯＣＨ2ＣＨ2（ＣＦ2）7ＣＦ3（１７ＦＡ）、
ＣＨ2＝ＣＨＣＯＯＣＨ（ＣＦ3）2（ＨＦＩＰ－Ａ）、
ＣＨ2＝ＣＨＣＯＯＣＨ2ＣＣＨ3（ＣＦ3）2（６ＦＮＰ－Ａ）、
ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯＣＨ2ＣＦ3（３ＦＭＡ）、
ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯＣＨ2ＣＦ2ＣＦ2Ｈ（４ＦＭＡ）、
ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯＣＨ2ＣＦ2ＣＦ3（５ＦＭＡ）、
ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯＣＨ2ＣＦ2ＣＦＨＣＦ3（６ＦＭＡ）、
ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯＣＨ2（ＣＦ2）3ＣＦ2Ｈ（８ＦＭＡ）、
ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯＣＨ2ＣＨ2（ＣＦ2）3ＣＦ3（９ＦＭＡ）、
ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯＣＨ2（ＣＦ2）5ＣＦ2Ｈ（１２ＦＭＡ）、
ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯＣＨ2ＣＨ2（ＣＦ2）5ＣＦ3（１３ＦＭＡ）、
ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯＣＨ2ＣＨ2（ＣＦ2）7ＣＦ3（１７ＦＭＡ）、
ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯＣＨ（ＣＦ3）2（ＨＦＩＰ－ＭＡ）、
ＣＨ2＝Ｃ（ＣＨ3）ＣＯＯＣＨ2ＣＣＨ3（ＣＦ3）2（６ＦＮＰ－ＭＡ）
等の化合物が例示される。 The fluorine-containing (meth) acrylic acid ester monomer (A) is a hydrocarbon group (R 2 ) having an ester portion containing fluorine and having 1 to 10 carbon atoms.
As the 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)
Compounds such as
構造単位（Ｙ）は、（メタ）アクリル酸エステル単量体（Ｂ）由来の繰り返し単位であり、下記一般式（２）で表される。
（式（２）中、Ｒ1は水素またはメチル基、Ｒ3はベンジル基および炭素数５～１０の環状炭化水素基からなる群から選ばれる基、ｂは重合度を表す。）
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 the 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 the degree of polymerization.)
式（２）において、Ｒ1は水素またはメチル基を表す。
Ｒ3はベンジル基および炭素数５～１０の環状炭化水素基からなる群から選ばれる基である。Ｒ3を有する構造単位は、単数または複数で構成することができ、好ましくは互いに異なる構造単位を１～３種の有するとよい。なお、異なる構造単位とは、Ｒ3が互いに相違するもの、および／または、アクリレートとメタクリレートとで相違するものとする。 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 composed of a single or plural units, and preferably 1 to 3 types of structural units different from each other are preferably contained. The different structural units are different in R 3 and / or different in acrylate and methacrylate.
Ｒ3はベンジル基および炭素数５～１０の環状炭化水素基からなる群から選ばれる基である。Ｒ3を有する構造単位は、単数または複数で構成することができ、好ましくは互いに異なる構造単位を１～３種の有するとよい。なお、異なる構造単位とは、Ｒ3が互いに相違するもの、および／または、アクリレートとメタクリレートとで相違するものとする。 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 composed of a single or plural units, and preferably 1 to 3 types of structural units different from each other are preferably contained. The different structural units are different in R 3 and / or different in acrylate and methacrylate.
炭素数５～１０の環状炭化水素基として、単環基、多環基、橋かけ環基を例示することができる。また環状炭化水素基は、飽和、不飽和のいずれでもよい。炭素数５～１０の環状炭化水素基として、例えば、シクロヘキシル基、ｔ－ブチルシクロヘキシル基、ジシクロペンタニル基、ジシクロペンテニル基、イソボニル基、等を挙げることができる。
Examples of the cyclic hydrocarbon group having 5 to 10 carbon atoms include a monocyclic group, a polycyclic group and a bridged ring group. The cyclic hydrocarbon group may be saturated or unsaturated. Examples of the cyclic hydrocarbon group having 5 to 10 carbon atoms include cyclohexyl group, t-butylcyclohexyl group, dicyclopentanyl group, dicyclopentenyl group, isobonyl group and the like.
（メタ）アクリル酸エステル単量体（Ｂ）は、ベンジル基および炭素数５～１０の環状炭化水素基からなる群から選ばれる基（Ｒ3）を有する（メタ）アクリレートである。（メタ）アクリル酸エステル単量体（Ｂ）は、ベンジル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ｔ－ブチルシクロヘキシル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、イソボニル（メタ）アクリレートからなる群から選ばれる少なくとも１つであるとよい。
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 (meth). It is preferable that at least one selected from the group consisting of acrylate and isobornyl (meth) acrylate.
フッ素含有重合体粒子を形成する共重合体は、その単量体単位を１００質量％とするとき、フッ素含有（メタ）アクリル酸エステル単量体（Ａ）由来の構造単位（Ｘ）が３０質量％以上、および（メタ）アクリル酸エステル単量体（Ｂ）由来の構造単位由来の構造単位からなる構造単位（Ｙ）が３０質量％以上からなる。なお、（メタ）アクリル酸エステル単量体（Ｂ）由来の構造単位の量は、１種以上の単量体（Ｂ）由来の構造単位の合計とする。式（１）,（２）のａ，ｂは、各繰り返し単位の重合度であり、上記の質量割合に整合する実数である。
In the copolymer forming the fluorine-containing polymer particles, when the monomer unit is 100% by mass, the structural unit (X) derived from the fluorine-containing (meth) acrylic acid ester monomer (A) is 30% by mass. % And 30% by mass or more of the structural unit (Y) composed of structural units derived from structural units derived from the (meth) acrylic acid ester monomer (B). The amount of the structural unit derived from the (meth) acrylic acid ester monomer (B) is the total of structural units derived from one or more kinds of the monomer (B). In the formulas (1) and (2), a and b are the degree of polymerization of each repeating unit, and are real numbers matching the above mass ratio.
フッ素含有（メタ）アクリル酸エステル単量体（Ａ）由来の構造単位（Ｘ）の下限は、単量体単位１００質量％中、３０質量％以上、好ましくは３０質量％超、より好ましくは３５質量％以上、さらに好ましくは４０質量％以上である。フッ素含有（メタ）アクリル酸エステル単量体（Ａ）由来の構造単位（Ｘ）の上限は、単量体単位１００質量％中、好ましくは７０質量％以下、より好ましくは７０質量％未満、さらに好ましくは６０％以下、一層好ましくは５０質量％以下、特に好ましくは５０質量％未満である。フッ素含有（メタ）アクリル酸エステル単量体（Ａ）由来の構造単位（Ｘ）を３０質量％以上にすることにより、耐熱性、耐酸化性、耐薬品性、耐光性などに優れた重合体粒子を得ることができる。
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% in 100% by mass of the monomer unit. It is at least mass%, more preferably at least 40 mass%. 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, in 100% by mass of the monomer unit. It is preferably 60% or less, more preferably 50% by mass or less, and particularly preferably less than 50% by mass. A polymer having excellent heat resistance, oxidation resistance, chemical resistance, light resistance, etc. by containing 30% by mass or more of the structural unit (X) derived from the fluorine-containing (meth) acrylic acid ester monomer (A). Particles can be obtained.
（メタ）アクリル酸エステル単量体（Ｂ）由来の構造単位（Ｙ）の下限は、単量体単位１００質量％中、３０質量％以上、好ましくは３０％超、より好ましくは３５質量％以上、さらに好ましくは４０質量％以上、一層好ましくは４５質量％以上、特に好ましくは５０質量％以上である。（メタ）アクリル酸エステル単量体（Ｂ）由来の構造単位（Ｙ）の上限は、単量体単位１００質量％中、７５質量％以下、より好ましくは７０質量％以下、さらに好ましくは６８質量％以下、一層好ましくは６６質量％以下、なお好ましくは６４質量％以下、特に好ましくは６２質量％以下である。構造単位（Ｙ）を３０質量％以上にすることにより、耐薬品性、耐光性、密着性などに優れた重合体粒子を得ることができる。
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 in 100% by mass of the monomer unit. , More preferably 40% by mass or more, further preferably 45% by mass or more, particularly preferably 50% by mass or more. The upper limit of the structural unit (Y) derived from the (meth) acrylic acid ester monomer (B) is 75 mass% or less, more preferably 70 mass% or less, and further preferably 68 mass% in 100 mass% of the monomer unit. % Or less, more preferably 66% by mass or less, still more preferably 64% by mass or less, and particularly preferably 62% by mass or less. When the structural unit (Y) is 30% by mass or more, polymer particles excellent in chemical resistance, light resistance, adhesion and the like can be obtained.
構造単位（Ｘ）および構造単位（Ｙ）の合計の下限は、単量体単位１００質量％中、好ましくは８０質量％以上、より好ましくは８０質量％超、さらに好ましくは８５質量％以上、一層好ましくは９０質量％以上、なお好ましくは９０質量％以上、特に好ましくは９５質量％以上である。構造単位（Ｘ）および構造単位（Ｙ）の合計の上限は、単量体単位１００質量％中、好ましくは９９．５質量％以下、さらに好ましくは９９質量％以下であるとよい。構造単位（Ｘ）および構造単位（Ｙ）の合計を８０質量％超にすることにより、耐薬品性、耐光性の特性により優れた重合体粒子を得ることができる。
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 unit. It is preferably 90% by mass or more, more preferably 90% by mass or more, and particularly preferably 95% by 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 unit. When the total amount of the structural unit (X) and the structural unit (Y) exceeds 80% by mass, polymer particles excellent in chemical resistance and light resistance can be obtained.
フッ素含有重合体粒子を形成する共重合体は、構造単位（Ｘ）および構造単位（Ｙ）に加え、水酸基を有する（メタ）アクリル酸エステル単量体（Ｃ）由来の構造単位（Ｚ）を含有することができる。水酸基を有する（メタ）アクリル酸エステル単量体（Ｃ）由来の構造単位（Ｚ）を含有することにより、粒子形成後の安定性に優れた重合体粒子を得ることができる。構造単位（Ｚ）の下限は、単量体単位１００質量％中、好ましくは１質量％以上、より好ましくは２質量％以上である。構造単位（Ｚ）の上限は、単量体単位１００質量％中、１０質量％以下、より好ましくは８質量％以下であるとよい。
The copolymer forming the fluorine-containing polymer particles contains, 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. Can be included. By containing the structural unit (Z) derived from the (meth) acrylic acid ester monomer (C) having a hydroxyl group, polymer particles having excellent stability after particle formation can be obtained. The lower limit of the structural unit (Z) is preferably 1% by mass or more and more preferably 2% by mass or more in 100% by mass of the monomer unit. The upper limit of the structural unit (Z) is preferably 10% by mass or less, more preferably 8% by mass or less in 100% by mass of the monomer unit.
構造単位（Ｚ）は、下記式（３）で表される。
（式（３）中、Ｒ1は水素またはメチル基、Ｒ4は水酸基を含む炭素数１～１０の炭化水素基、ｃは重合度を表す。）
The structural unit (Z) is represented by the following formula (3).
(In the formula (3), R 1 represents hydrogen or a methyl group, R 4 represents a hydrocarbon group containing a hydroxyl group and having 1 to 10 carbon atoms, and c represents the degree of polymerization.)
式（３）において、Ｒ1は水素またはメチル基を表す。
Ｒ4は水酸基を含む炭素数１～１０の炭化水素基であり、好ましくは水酸基を含む炭素数２～６の炭化水素基である。炭化水素基は、不飽和結合を有してもよい。また直鎖状炭化水素基、分岐鎖状炭化水素基のいずれでもよい。Ｒ4は炭化水素基の水素の少なくとも１つが水酸基に置換されている。Ｒ4として、例えば、ヒドロキシメチル、ヒドロキシエチル、ヒドロキシプロピル、ヒドロキシブチル、ヒドロキシペンチル、ヒドロキシヘキシル、ヒドロキシヘプチシル、ヒドロキシオクチル、等を挙げることができる。 In the formula (3), R 1 represents hydrogen or a methyl group.
R 4 is a hydrocarbon group containing a hydroxyl group and having 1 to 10 carbon atoms, and preferably a hydrocarbon group containing a hydroxyl group and having 2 to 6 carbon atoms. The hydrocarbon group may have an unsaturated bond. It may be either a straight chain hydrocarbon group or a branched chain hydrocarbon group. At least one hydrogen atom of the hydrocarbon group of R 4 is substituted with a hydroxyl group. Examples of R 4 include hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, hydroxyhexyl, hydroxyhepticyl, hydroxyoctyl, and the like.
Ｒ4は水酸基を含む炭素数１～１０の炭化水素基であり、好ましくは水酸基を含む炭素数２～６の炭化水素基である。炭化水素基は、不飽和結合を有してもよい。また直鎖状炭化水素基、分岐鎖状炭化水素基のいずれでもよい。Ｒ4は炭化水素基の水素の少なくとも１つが水酸基に置換されている。Ｒ4として、例えば、ヒドロキシメチル、ヒドロキシエチル、ヒドロキシプロピル、ヒドロキシブチル、ヒドロキシペンチル、ヒドロキシヘキシル、ヒドロキシヘプチシル、ヒドロキシオクチル、等を挙げることができる。 In the formula (3), R 1 represents hydrogen or a methyl group.
R 4 is a hydrocarbon group containing a hydroxyl group and having 1 to 10 carbon atoms, and preferably a hydrocarbon group containing a hydroxyl group and having 2 to 6 carbon atoms. The hydrocarbon group may have an unsaturated bond. It may be either a straight chain hydrocarbon group or a branched chain hydrocarbon group. At least one hydrogen atom of the hydrocarbon group of R 4 is substituted with a hydroxyl group. Examples of R 4 include hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, hydroxyhexyl, hydroxyhepticyl, hydroxyoctyl, and the like.
構造単位（Ｚ）は、水酸基を有する（メタ）アクリル酸エステル単量体（Ｃ）に由来する繰り返し単位であり、ｃはその重合度である。水酸基を有する（メタ）アクリル酸エステル単量体（Ｃ）として、例えば、ヒドロキシメチル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、３－ヒドロキシプロピル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、５－ヒドロキシペンチル（メタ）アクリレート、６－ヒドロキシヘキシル（メタ）アクリレート、７－ヒドロキシヘプチシル（メタ）アクリレート、８－ヒドロキシオクチル（メタ）アクリレート、等を挙げることができる。
The structural unit (Z) is a repeating unit derived from the (meth) acrylic acid ester monomer (C) having a hydroxyl group, and c is its degree of polymerization. Examples of the (meth) acrylic acid ester monomer (C) having a hydroxyl group include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth). ) Acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 7-hydroxyhepticyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, and the like.
フッ素含有重合体粒子を形成する共重合体は、その単量体単位を１００質量％とするとき、更に架橋剤（Ｄ）を１～１０質量％含有することができる。架橋剤（Ｄ）を含有することにより、粒子形成後の耐溶剤性に優れた重合体粒子を得ることができる。架橋剤（Ｄ）の下限は、単量体単位１００質量％中、好ましくは１質量％以上、より好ましくは２質量％以上、さらに好ましくは２質量％超、一層好ましくは３質量％以上、なお好ましくは５質量％以上、特に好ましくは７質量％以上である。架橋剤（Ｄ）の上限は、単量体単位１００質量％中、好ましくは１０質量％以下、より好ましくは１０質量％未満、さらに好ましくは９質量％以下、一層好ましくは９質量％未満、特に好ましくは８質量％以下であるとよい。
The copolymer forming the fluorine-containing polymer particles can further contain a cross-linking agent (D) in an amount of 1 to 10% by mass based on 100% by mass of the monomer unit. By containing the crosslinking agent (D), polymer particles having excellent solvent resistance after particle formation can be obtained. The lower limit of the cross-linking agent (D) is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably more than 2% by mass, still more preferably 3% by mass or more, in 100% by mass of the monomer unit. It is preferably 5% by mass or more, and particularly preferably 7% by mass or more. The upper limit of the cross-linking agent (D) is preferably 10% by mass or less, more preferably less than 10% by mass, even more preferably 9% by mass or less, still more preferably less than 9% by mass, particularly preferably 100% by mass in 100% by mass of the monomer unit. It is preferably 8% by mass or less.
架橋剤（Ｄ）としては、重合した際に架橋構造を形成しうる単量体を用いることができる。架橋剤の例としては、１分子あたり２以上の反応性基を有する単量体を挙げることができる。より具体的には、熱架橋性の架橋性基及び１分子あたり１つのオレフィン性二重結合を有する単官能性単量体、及び１分子あたり２つ以上のオレフィン性二重結合を有する多官能性単量体が挙げられる。単官能性単量体に含まれる熱架橋性の架橋性基の例としては、エポキシ基、Ｎ－メチロールアミド基、オキセタニル基、オキサゾリン基、及びこれらの組み合わせが挙げられる。
As the cross-linking agent (D), a monomer that can form a cross-linked structure when polymerized can be used. Examples of the cross-linking agent include a monomer having two or more reactive groups per molecule. More specifically, a monofunctional monomer having a thermally crosslinkable crosslinkable group and one olefinic double bond per molecule, and a polyfunctional having two or more olefinic double bonds per molecule. Examples of the monomer include a polymerizable monomer. Examples of the thermally crosslinkable crosslinkable group contained in the monofunctional monomer include an epoxy group, an N-methylolamide group, an oxetanyl group, an oxazoline group, and a combination thereof.
熱架橋性の架橋性基としてエポキシ基を有し、且つオレフィン性二重結合を有する架橋性単量体の例としては、ビニルグリシジルエーテル、アリルグリシジルエーテル、ブテニルグリシジルエーテル、ｏ－アリルフェニルグリシジルエーテルなどの不飽和グリシジルエーテル；ブタジエンモノエポキシド、クロロプレンモノエポキシド、４，５－エポキシ－２－ペンテン、３，４－エポキシ－１－ビニルシクロヘキセン、１，２－エポキシ－５，９－シクロドデカジエンなどのジエンまたはポリエンのモノエポキシド；３，４－エポキシ－１－ブテン、１，２－エポキシ－５－ヘキセン、１，２－エポキシ－９－デセンなどのアルケニルエポキシド；並びにグリシジルアクリレート、グリシジルメタクリレート、グリシジルクロトネート、グリシジル－４－ヘプテノエート、グリシジルソルベート、グリシジルリノレート、グリシジル－４－メチル－３－ペンテノエート、３－シクロヘキセンカルボン酸のグリシジルエステル、４－メチル－３－シクロヘキセンカルボン酸のグリシジルエステルなどの不飽和カルボン酸のグリシジルエステル類が挙げられる。
Examples of the crosslinkable monomer having an epoxy group as a thermally crosslinkable crosslinkable group and having an olefinic double bond include vinyl glycidyl ether, allyl glycidyl ether, butenyl glycidyl ether, and o-allylphenyl glycidyl. Unsaturated glycidyl ethers such as ethers; butadiene monoepoxide, chloroprene monoepoxide, 4,5-epoxy-2-pentene, 3,4-epoxy-1-vinylcyclohexene, 1,2-epoxy-5,9-cyclododecadiene Monoepoxides of dienes or polyenes such as; alkenyl epoxides such as 3,4-epoxy-1-butene, 1,2-epoxy-5-hexene, 1,2-epoxy-9-decene; and glycidyl acrylate, glycidyl methacrylate, Glycidyl crotonate, glycidyl-4-heptenoate, glycidyl sorbate, glycidyl linoleate, glycidyl-4-methyl-3-pentenoate, glycidyl ester of 3-cyclohexenecarboxylic acid, glycidyl ester of 4-methyl-3-cyclohexenecarboxylic acid, etc. And unsaturated carboxylic acid glycidyl esters.
熱架橋性の架橋性基としてＮ－メチロールアミド基を有し、且つオレフィン性二重結合を有する架橋性単量体の例としては、Ｎ－メチロール（メタ）アクリルアミドなどのメチロール基を有する（メタ）アクリルアミド類が挙げられる。
Examples of the crosslinkable monomer having an N-methylolamide group as a thermally crosslinkable crosslinkable group and having an olefinic double bond include a methylol group such as N-methylol (meth) acrylamide (meth ) Examples include acrylamides.
熱架橋性の架橋性基としてオキセタニル基を有し、且つオレフィン性二重結合を有する架橋性単量体の例としては、３－（（メタ）アクリロイルオキシメチル）オキセタン、３－（（メタ）アクリロイルオキシメチル）－２－トリフロロメチルオキセタン、３－（（メタ）アクリロイルオキシメチル）－２－フェニルオキセタン、２－（（メタ）アクリロイルオキシメチル）オキセタン、及び２－（（メタ）アクリロイルオキシメチル）－４－トリフロロメチルオキセタンが挙げられる。
Examples of the crosslinkable monomer having an oxetanyl group as a thermally crosslinkable crosslinkable group and having an olefinic double bond include 3-((meth) acryloyloxymethyl) oxetane and 3-((meth) Acryloyloxymethyl) -2-trifluoromethyloxetane, 3-((meth) acryloyloxymethyl) -2-phenyloxetane, 2-((meth) acryloyloxymethyl) oxetane, and 2-((meth) acryloyloxymethyl ) -4-Trifluoromethyloxetane.
熱架橋性の架橋性基としてオキサゾリン基を有し、且つオレフィン性二重結合を有する架橋性単量体の例としては、２－ビニル－２－オキサゾリン、２－ビニル－４－メチル－２－オキサゾリン、２－ビニル－５－メチル－２－オキサゾリン、２－イソプロペニル－２－オキサゾリン、２－イソプロペニル－４－メチル－２－オキサゾリン、２－イソプロペニル－５－メチル－２－オキサゾリン、及び２－イソプロペニル－５－エチル－２－オキサゾリンが挙げられる。
Examples of the crosslinkable monomer having an oxazoline group as a heat-crosslinkable crosslinkable group and having an olefinic double bond include 2-vinyl-2-oxazoline and 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 may be mentioned.
１分子あたり２つ以上のオレフィン性二重結合を有する多官能性単量体の例としては、アリル（メタ）アクリレート、エチレンジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、トリメチロールプロパン－トリ（メタ）アクリレート、ジプロピレングリコールジアリルエーテル、ポリグリコールジアリルエーテル、トリエチレングリコールジビニルエーテル、ヒドロキノンジアリルエーテル、テトラアリルオキシエタン、トリメチロールプロパン－ジアリルエーテル、前記以外の多官能性アルコールのアリルまたはビニルエーテル、トリアリルアミン、メチレンビスアクリルアミド、ジビニルベンゼン、アルキレングリコールジ（メタ）アクリレート、ウレタンアクリレートが挙げられる。
Examples of polyfunctional monomers 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). ) Acrylate, tetraethylene glycol di (meth) acrylate, trimethylolpropane-tri (meth) acrylate, dipropylene glycol diallyl ether, polyglycol diallyl ether, triethylene glycol divinyl ether, hydroquinone diallyl ether, tetraallyloxyethane, trimethylol Examples thereof include propane-diallyl ether, allyl or vinyl ethers of polyfunctional alcohols other than the above, triallylamine, methylenebisacrylamide, divinylbenzene, alkylene glycol di (meth) acrylate, and urethane acrylate.
架橋剤（Ｄ）としては、特に、アルキレングリコールジ（メタ）アクリレート、及びウレタンアクリレートを好ましく用いることができる。
As the cross-linking agent (D), alkylene glycol di (meth) acrylate and urethane acrylate can be preferably used.
フッ素含有重合体粒子を形成する共重合体は、構造単位（Ｘ）、構造単位（Ｙ）、構造単位（Ｚ）以外の他の構造単位として、ラジカル重合性化合物由来の繰り返し単位を含有することができる。他の構造単位となり得るラジカル重合性化合物として、上述した（メタ）アクリル酸エステル単量体（Ａ）～（Ｃ）を除く（メタ）アクリル酸エステル、ビニル化合物が例示される。ラジカル重合性化合物として、例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸－ｎ－プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸－ｎ－ブチル、（メタ）アクリル酸－ｓｅｃ－ブチル、（メタ）アクリル酸－ｔｅｒｔ－ブチル、（メタ）アクリル酸ペンチル、（メタ）アクリル酸ネオペンチル、（メタ）アクリル酸イソアミル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸２－エチルヘキシル、（メタ）アクリル酸ラウリル、（メタ）アクリル酸ドデシル、（メタ）アクリル酸－２－ジメチルアミノエチル、（メタ）アクリル酸－２－ジエチルアミノエチル、（メタ）アクリル酸－２－ジプロピルアミノエチル、（メタ）アクリル酸－２－ジフェニルアミノエチル、（メタ）アクリル酸３－（Ｎ，Ｎ－ジメチルアミノ）プロピル、Ｎ－（メタ）アクリロイルフタルイミド、スチレン、塩化ビニル、塩化ビニリデン、フッ化ビニル、フッ化ビニリデン、Ｎ－ビニルピロリドン、ビニルピリジン、酢酸ビニルなどを挙げることができる。なかでも（メタ）アクリル酸メチル、スチレンが好ましい。
The copolymer forming the fluorine-containing polymer particles contains a repeating unit derived from a radically polymerizable compound as a structural unit other than the structural unit (X), the structural unit (Y) and the structural unit (Z). You can Examples of the radically polymerizable compound that can serve as another structural unit include (meth) acrylic acid esters other than the above-mentioned (meth) acrylic acid ester monomers (A) to (C), and vinyl compounds. Examples of the radically polymerizable compound include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, ( (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) 2-ethylhexyl acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-diethylaminoethyl (meth) acrylate, (meth) acrylic acid-2 -Dipropylaminoethyl, 2-diphenylaminoethyl (meth) acrylate, 3- (N, N-dimethylamino) propyl (meth) acrylate, N- (meth) acryloylphthalimide, styrene, vinyl chloride, vinylidene chloride , Vinyl fluoride, vinylidene fluoride, N-vinyl pyrrolidone, vinyl pyridine, vinyl acetate and the like. Of these, methyl (meth) acrylate and styrene are preferable.
フッ素含有重合体粒子を形成する共重合体のガラス転移温度（Ｔｇ）の下限は、好ましくは２０℃以上、より好ましくは２５℃以上、さらに好ましくは３０℃以上、一層好ましくは４０℃以上、特に好ましくは５０℃以上であるとよい。フッ素含有重合体粒子を形成する共重合体のガラス転移温度（Ｔｇ）の上限は、１００℃以下、より好ましくは８０℃以下、さらに好ましくは７０℃以下であるとよい。共重合体のＴｇを２０℃以上にすることにより、粒子の融着を抑制可能にする。またＴｇを１００℃以下にすることにより、製造し易くなる。共重合体のガラス転移温度（Ｔｇ）は、単量体の種類および組成比を変更することにより調節することができる。
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, even more preferably 30 ° C. or higher, even more preferably 40 ° C. or higher, especially It is preferably 50 ° C. or higher. The glass transition temperature (Tg) of the copolymer forming the fluorine-containing polymer particles has an upper limit of 100 ° C. or lower, more preferably 80 ° C. or lower, and further preferably 70 ° C. or lower. By setting the Tg of the copolymer to 20 ° C. or higher, fusion of particles can be suppressed. Further, if the Tg is 100 ° C. or less, the production becomes easy. The glass transition temperature (Tg) of the copolymer can be adjusted by changing the type and composition ratio of the monomers.
なお、本明細書において、「共重合体のＴｇ」とは、フォックスの式を用いて、単量体混合物中に含まれる単量体の種類および組成比から算出したものである。ここで、フォックスの式とは、共重合体を形成する個々の単量体について、その単量体の単独重合体のＴｇに基づいて、共重合体のＴｇを算出するためのものであり、その詳細は、ブルテン・オブ・ザ・アメリカン・フィジカル・ソサエティー，シリーズ２（Ｂｕｌｌｅｔｉｎ ｏｆ ｔｈｅ Ａｍｅｒｉｃａｎ Ｐｈｙｓｉｃａｌ Ｓｏｃｉｅｔｙ，Ｓｅｒｉｅｓ ２）１巻・３号・１２３頁（１９５６年）に記載されている。
In the present specification, “Tg of copolymer” is calculated from the type and composition ratio of the monomers contained in the monomer mixture, using the Fox equation. Here, the Fox equation is for calculating the Tg of the copolymer based on the Tg of the homopolymer of the individual monomers forming the copolymer, The details are described in Bulletin of the American Physical Society, Series 2 (Bulletin of the American Physical Society, Series 2) Vol. 1, No. 3, 123 (1956).
また、フォックスの式による共重合体のＴｇを評価するための基礎となる単量体についてのＴｇは、例えば、新高分子文庫・第７巻・塗料用合成樹脂入門（北岡協三著、高分子刊行会、京都、１９７４年）１６８～１６９頁の表１０－２（塗料用アクリル樹脂の主な原料単量体）に記載されている数値を採用することができる。
In addition, Tg of a monomer as a basis for evaluating the Tg of a copolymer according to Fox's formula is, for example, New Polymer Bunko, Volume 7, Introduction to Synthetic Resins for Paints (Kyozo Kitaoka, Polymer The numerical values described in Table 10-2 (main raw material monomers of acrylic resin for paints) on pages 168 to 169 (publishing society, Kyoto, 1974) can be adopted.
フッ素含有重合体粒子の体積平均粒子径は、好ましくは１００～５００ｎｍ、粒度分布（体積平均粒子径／数平均粒子径）は、好ましくは１．３０以下であるとよい。
フッ素含有重合体粒子の体積平均粒子径の下限は、好ましくは１００ｎｍ以上、より好ましくは１２０ｎｍ以上、さらに好ましくは１５０ｎｍ以上であるとよい。フッ素含有重合体粒子の体積平均粒子径の上限は、好ましくは５００ｎｍ以下、より好ましくは４５０ｎｍ以下、さらに好ましくは４００ｎｍ以下であるとよい。体積平均粒子径が１００ｎｍ未満であると、フッ素含有重合体粒子を水に分散させた分散液の粘度が上昇し、高固形分の水性分散液が得られ難くなる虞がある。また他の粒子と混合したときに、分散液の表面へフッ素含有重合体粒子を偏在させるのが困難になる。また体積平均粒子径が５００ｎｍを超えると、フッ素含有重合体粒子の水分散液の貯蔵安定性が低下する虞があり、さらに形成される塗膜の均一性が低下する原因になる。フッ素含有重合体粒子の体積平均粒子径は、乳化剤の種類および組成比を変更することにより調節することができる。 The volume average particle diameter of the fluorine-containing polymer particles is preferably 100 to 500 nm, and the particle size distribution (volume average particle diameter / number average particle diameter) is 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, and further preferably 400 nm or less. When the volume average particle diameter is less than 100 nm, the viscosity of the dispersion liquid in which the fluorine-containing polymer particles are dispersed in water increases, and it may be difficult to obtain a high solid content aqueous dispersion liquid. Further, when mixed with other particles, it becomes difficult to unevenly distribute the fluorine-containing polymer particles on the surface of the dispersion liquid. Further, if the volume average particle diameter exceeds 500 nm, the storage stability of the aqueous dispersion of the fluorine-containing polymer particles may be lowered, and this may cause the uniformity of the formed coating film to be lowered. The volume average particle size of the fluorine-containing polymer particles can be adjusted by changing the type and composition ratio of the emulsifier.
フッ素含有重合体粒子の体積平均粒子径の下限は、好ましくは１００ｎｍ以上、より好ましくは１２０ｎｍ以上、さらに好ましくは１５０ｎｍ以上であるとよい。フッ素含有重合体粒子の体積平均粒子径の上限は、好ましくは５００ｎｍ以下、より好ましくは４５０ｎｍ以下、さらに好ましくは４００ｎｍ以下であるとよい。体積平均粒子径が１００ｎｍ未満であると、フッ素含有重合体粒子を水に分散させた分散液の粘度が上昇し、高固形分の水性分散液が得られ難くなる虞がある。また他の粒子と混合したときに、分散液の表面へフッ素含有重合体粒子を偏在させるのが困難になる。また体積平均粒子径が５００ｎｍを超えると、フッ素含有重合体粒子の水分散液の貯蔵安定性が低下する虞があり、さらに形成される塗膜の均一性が低下する原因になる。フッ素含有重合体粒子の体積平均粒子径は、乳化剤の種類および組成比を変更することにより調節することができる。 The volume average particle diameter of the fluorine-containing polymer particles is preferably 100 to 500 nm, and the particle size distribution (volume average particle diameter / number average particle diameter) is 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, and further preferably 400 nm or less. When the volume average particle diameter is less than 100 nm, the viscosity of the dispersion liquid in which the fluorine-containing polymer particles are dispersed in water increases, and it may be difficult to obtain a high solid content aqueous dispersion liquid. Further, when mixed with other particles, it becomes difficult to unevenly distribute the fluorine-containing polymer particles on the surface of the dispersion liquid. Further, if the volume average particle diameter exceeds 500 nm, the storage stability of the aqueous dispersion of the fluorine-containing polymer particles may be lowered, and this may cause the uniformity of the formed coating film to be lowered. The volume average particle size of the fluorine-containing polymer particles can be adjusted by changing the type and composition ratio of the emulsifier.
フッ素含有重合体粒子の粒度分布（体積平均粒子径／数平均粒子径）は、好ましくは１．３０以下、より好ましくは１．２０以下、さらに好ましくは１．１５以下、一層好ましくは１．１０以下、なお好ましくは１．０５以下、特に好ましくは１．０３以下であるとよい。粒度分布が１．２０を超えると、フッ素含有重合体粒子を含む塗膜の均一性が低下する原因となり、フッ素特有の性能を引き出すことが困難となる。フッ素含有重合体粒子の粒度分布は、単量体、乳化剤の種類、組成比および重合条件を変更することにより調節することができる。
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. The ratio is preferably 1.05 or less, more preferably 1.05 or less, and particularly preferably 1.03 or less. When the particle size distribution exceeds 1.20, the uniformity of the coating film containing the fluorine-containing polymer particles is deteriorated, and it becomes difficult to bring out the performance peculiar to fluorine. The particle size distribution of the fluorine-containing polymer particles can be adjusted by changing the type of monomer, emulsifier, composition ratio and polymerization conditions.
なお、フッ素含有重合体粒子の平均粒子径は、動的光散乱法を測定原理とする粒度分布測定装置を用いて、平均粒子径、粒度分布を測定することができる。このような粒度分布測定装置としては、例えば、ＨＯＲＩＢＡ ＬＢ－５５０、ＳＺ－１００シリーズ（以上、株式会社堀場製作所製）、ＦＰＡＲ－１０００（大塚電子株式会社製）等が挙げられる。
Note that the average particle size of the fluorine-containing polymer particles can be measured by using a particle size distribution measuring device having a dynamic light scattering method as a measurement principle. Examples of such a particle size distribution measuring device include HORIBA LB-550, SZ-100 series (above, manufactured by Horiba Ltd.), FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.) and the like.
フッ素含有重合体粒子は、水と混合することにより、分散液を調製することができる。この分散液は、フッ素含有重合体粒子の他に、アルミナやチタニアなどの無機粒子も混合することができる。分散液のｐＨは、好ましくは５～１０、より好ましくは６～９．５であるとよい。分散液のｐＨをこのような範囲内にすることにより、分散安定性を改善することができる。
A dispersion liquid can be prepared by mixing the fluorine-containing polymer particles with water. In addition to the fluorine-containing polymer particles, this dispersion liquid can also be mixed with inorganic particles such as alumina and titania. The pH of the dispersion liquid is preferably 5 to 10, more preferably 6 to 9.5. By controlling the pH of the dispersion within such a range, the dispersion stability can be improved.
フッ素含有重合体粒子を含む分散液は、フィルム用に使用すること、すなわちフィルムに塗布し塗膜を形成することにより、フィルムの表面特性を改質することができる。フィルムは、特に制限されるものではなく、例えば、プラスチックフィルム、金属フィルム、紙、多孔質フィルム、多孔質基材、導電フィルム、等が挙げられる。
The dispersion containing the fluorine-containing polymer particles can be used for a film, that is, applied to the film to form a coating film, whereby 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 base material, and a conductive film.
フッ素含有重合体粒子の製造方法
フッ素含有重合体粒子は、フッ素含有（メタ）アクリル酸エステル単量体（Ａ）、（メタ）アクリル酸エステル単量体（Ｂ）、任意に水酸基を有する（メタ）アクリル酸エステル単量体（Ｃ）、その他のラジカル重合性化合物からなる単量体混合物を水性媒体中で乳化重合することにより得られる。単量体混合物１００質量％中、フッ素含有（メタ）アクリル酸エステル単量体（Ａ）が好ましくは３０質量％以上、（メタ）アクリル酸エステル単量体（Ｂ）およびスチレンが好ましくは３０質量％以上であるとよく、フッ素含有（メタ）アクリル酸エステル単量体（Ａ）、（メタ）アクリル酸エステル単量体（Ｂ）およびスチレンの合計が、９０質量％以上であるとよい。また水酸基を有する（メタ）アクリル酸エステル単量体（Ｃ）を含むとき、単量体混合物１００質量％中、好ましくは１～１０質量％であるとよい。 Method for Producing Fluorine-Containing Polymer Particles The fluorine-containing polymer particles have a fluorine-containing (meth) acrylic acid ester monomer (A), a (meth) acrylic acid ester monomer (B), and optionally a hydroxyl group (meth). ) It is obtained by emulsion-polymerizing a monomer mixture of an acrylic acid ester monomer (C) and other radically polymerizable compounds in an aqueous medium. In 100% by mass of the monomer mixture, the fluorine-containing (meth) acrylic acid ester monomer (A) is preferably 30% by mass or more, and the (meth) acrylic acid ester monomer (B) and styrene are preferably 30% by mass. % Or more, and the total of the fluorine-containing (meth) acrylic acid ester monomer (A), the (meth) acrylic acid ester monomer (B), and styrene is preferably 90% by mass or more. Further, when the (meth) acrylic acid ester monomer (C) having a hydroxyl group is contained, the content is preferably 1 to 10% by mass in 100% by mass of the monomer mixture.
フッ素含有重合体粒子は、フッ素含有（メタ）アクリル酸エステル単量体（Ａ）、（メタ）アクリル酸エステル単量体（Ｂ）、任意に水酸基を有する（メタ）アクリル酸エステル単量体（Ｃ）、その他のラジカル重合性化合物からなる単量体混合物を水性媒体中で乳化重合することにより得られる。単量体混合物１００質量％中、フッ素含有（メタ）アクリル酸エステル単量体（Ａ）が好ましくは３０質量％以上、（メタ）アクリル酸エステル単量体（Ｂ）およびスチレンが好ましくは３０質量％以上であるとよく、フッ素含有（メタ）アクリル酸エステル単量体（Ａ）、（メタ）アクリル酸エステル単量体（Ｂ）およびスチレンの合計が、９０質量％以上であるとよい。また水酸基を有する（メタ）アクリル酸エステル単量体（Ｃ）を含むとき、単量体混合物１００質量％中、好ましくは１～１０質量％であるとよい。 Method for Producing Fluorine-Containing Polymer Particles The fluorine-containing polymer particles have a fluorine-containing (meth) acrylic acid ester monomer (A), a (meth) acrylic acid ester monomer (B), and optionally a hydroxyl group (meth). ) It is obtained by emulsion-polymerizing a monomer mixture of an acrylic acid ester monomer (C) and other radically polymerizable compounds in an aqueous medium. In 100% by mass of the monomer mixture, the fluorine-containing (meth) acrylic acid ester monomer (A) is preferably 30% by mass or more, and the (meth) acrylic acid ester monomer (B) and styrene are preferably 30% by mass. % Or more, and the total of the fluorine-containing (meth) acrylic acid ester monomer (A), the (meth) acrylic acid ester monomer (B), and styrene is preferably 90% by mass or more. Further, when the (meth) acrylic acid ester monomer (C) having a hydroxyl group is contained, the content is preferably 1 to 10% by mass in 100% by mass of the monomer mixture.
単量体混合物の乳化重合の条件は特に制限されるものではなく、例えば、水性媒体中に、乳化剤および重合開始剤の存在下で、好ましくは５０～１００℃程度の温度で１～３０時間程度反応を行えばよい。なお、必要に応じて連鎖移動剤、キレート化剤、ｐＨ調整剤、溶媒等を添加してもよい。
The conditions for emulsion polymerization of the monomer mixture are not particularly limited, and for example, 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 about 1 to 30 hours. All you have to do is react. In addition, a chain transfer agent, a chelating agent, a pH adjusting agent, a solvent and the like may be added if necessary.
乳化剤としては、アニオン性界面活性剤、非イオン性界面活性剤、アニオン性界面活性剤と非イオン性界面活性剤との組み合わせ等が使用され、場合によっては両性界面活性剤、カチオン性界面活性剤も用いることができる。
As the emulsifier, an anionic surfactant, a nonionic surfactant, a combination of an anionic surfactant and a nonionic surfactant, etc. are used, and in some cases, an amphoteric surfactant or a cationic surfactant. Can also be used.
アニオン性界面活性剤としては、例えば、アルキル硫酸エステルナトリウム塩、アルキルベンゼンスルホン酸ナトリウム塩、コハク酸ジアルキルエステルスルホン酸ナトリウム塩、アルキルジフェニルエーテルジスルホン酸ナトリウム塩、ポリオキシエチレンアルキルエーテル硫酸ナトリウム塩、ポリオキシエチレンアルキルフェニルエーテル硫酸ナトリウム塩等が挙げられる。これらの中でも、ラウリル硫酸エステルナトリウム塩、ドデシルベンゼンスルホン酸ナトリウム塩、ポリオキシエチレンアルキルエーテル硫酸ナトリウム塩、ラウリル硫酸ナトリウム等が好ましい。
Examples of the anionic surfactant include alkyl sulfate sodium salt, alkylbenzene sulfonic acid sodium salt, succinic acid dialkyl ester sulfonic acid sodium salt, alkyldiphenyl ether disulfonic acid sodium salt, polyoxyethylene alkyl ether sulfate sodium salt, polyoxyethylene. Examples thereof include sodium alkylphenyl ether sulfate. Among these, sodium lauryl sulfate ester, sodium dodecylbenzenesulfonate, sodium polyoxyethylene alkyl ether sulfate, sodium lauryl sulfate and the like are preferable.
非イオン性界面活性剤としては、例えば、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルアリールエーテル、ポリオキシエチレン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル等が挙げられる。一般的には、ポリオキシエチレンノニルフェニルエーテル、ポリオキシエチレンオクチルフェニルエーテル等が使用される。
Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester and the like. Generally, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether and the like are used.
両性界面活性剤としては、例えば、ラウリルベタイン、ヒドロキシエチルイミダゾリン硫酸エステルナトリウム塩、イミダゾリンスルホン酸ナトリウム塩等が挙げられる。
Examples of the amphoteric surfactant include lauryl betaine, hydroxyethyl imidazoline sulfate sodium salt, imidazoline sulfonic acid sodium salt, and the like.
カチオン性界面活性剤としては、例えば、アルキルピリジニウムクロライド、アルキルトリメチルアンモニウムクロライド、ジアルキルジメチルアンモニウムクロライド、アルキルジメチルベンジルアンモニウムクロライド等が挙げられる。
Examples of the cationic surfactant include alkylpyridinium chloride, alkyltrimethylammonium chloride, dialkyldimethylammonium chloride, alkyldimethylbenzylammonium chloride and the like.
また、乳化剤として、パーフルオロアルキルカルボン酸塩、パーフルオロアルキルスルホン酸塩、パーフルオロアルキルリン酸エステル、パーフルオロアルキルポリオキシエチレン、パーフルオロアルキルベタイン、パーフルオロアルコキシフルオロカルボン酸アンモニウム等のフッ素系界面活性剤を使用することもできる。
Further, as an emulsifier, a fluorine-based interface such as perfluoroalkyl carboxylate, perfluoroalkyl sulfonate, perfluoroalkyl phosphate ester, perfluoroalkyl polyoxyethylene, perfluoroalkyl betaine, ammonium perfluoroalkoxyfluorocarboxylate, etc. Activators can also be used.
さらに、上記の単量体と共重合可能な、いわゆる反応性乳化剤、例えばスチレンスルホン酸ナトリウム塩、アリルアルキルスルホン酸ナトリウム塩、ポリオキシエチレンアルキルアリルフェニルエーテル硫酸アンモニウム塩、ポリオキシエチレンアルキルアリルフェニルエーテル等を使用することができ、特に２－（１－アリル）－４－ノニルフェノキシポリエチレングリコール硫酸エステルアンモニウム塩と２－（１－アリル）－４－ノニルフェノキシポリエチレングリコールとの併用が好ましい。
Furthermore, so-called reactive emulsifiers that can be copolymerized with the above monomers, such as sodium styrenesulfonate, sodium allylalkylsulfonate, ammonium polyoxyethylenealkylallylphenylether sulfate, polyoxyethylenealkylallylphenylether, etc. Can be used, and it is particularly preferable to use 2- (1-allyl) -4-nonylphenoxy polyethylene glycol sulfate ammonium salt and 2- (1-allyl) -4-nonylphenoxy polyethylene glycol in combination.
乳化剤の使用量は、単量体混合物の合計量１００質量部当たり、好ましくは０．０５～１０質量部程度である。
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.
重合開始剤としては、過硫酸ナトリウム、過硫酸カリウム、過硫酸アンモニウム、過酸化水素等の水溶性重合開始剤、あるいはこれらの水溶性重合開始剤と還元剤とを組み合わせたレドックス系重合開始剤を使用することができる。これらの中でも、過硫酸カリウム、過硫酸アンモニウムが好ましい。還元剤としては、例えば、ピロ重亜硫酸ナトリウム、亜硫酸水素ナトリウム、亜硫酸ナトリウム、チオ硫酸ナトリウム、Ｌ－アスコルビン酸またはその塩、ナトリウムホルムアルデヒドスルホキシレート、硫酸第一鉄、グルコース等が挙げられる。これらの中でも、Ｌ－アスコルビン酸またはその塩が好ましい。
As the polymerization initiator, a water-soluble polymerization initiator such as sodium persulfate, potassium persulfate, ammonium persulfate, hydrogen peroxide, or a redox-based polymerization initiator in which these water-soluble polymerization initiators and reducing agents are combined is used. can do. 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, glucose and the like. Among these, L-ascorbic acid or its salt is preferable.
また、油溶性重合開始剤も単量体あるいは溶媒に溶解して使用することができる。この油溶性重合開始剤としては、例えば、２，２’－アゾビスイソブチロニトリル、２，２’－アゾビス－（４－メトキシ－２，４－ジメチルバレロニトリル）、２，２’－アゾビス－２，４－ジメチルバレロニトリル、１，１’－アゾビスシクロヘキサン－１－カルボニトリル、２，２’－アゾビスイソバレロニトリル、２，２’－アゾビスイソカプロニトリル、２，２’－アゾビス（フェニルイソブチロニトリル）、ベンゾイルパーオキシド、ジ－ｔ－ブチルパーオキシド、ジラウロイルパーオキシド、クメンハイドロパーオキシド、ジイソプロピルベンゼンハイドロパーオキシド、パラメンタンハイドロパーオキシド、ｔ－ブチルハイドロパーオキシド、３，５，５－トリメチルヘキサノールパーオキシド、ｔ－ブチルパーオキシ（２－エチルヘキサノエート）等が挙げられる。これらの中でも、２，２’－アゾビスイソブチロニトリル、ベンゾイルパーオキシド、クメンハイドロパーオキシド、ジイソプロピルベンゼンハイドロパーオキシド、パラメンタンハイドロパーオキシド、ｔ－ブチルハイドロパーオキシド、３，５，５－トリメチルヘキサノールパーオキシド、ｔ－ブチルパーオキシ（２－エチルヘキサノエート）が好ましい。
Also, an oil-soluble polymerization initiator can be used by dissolving it 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) and 2,2'-azobis. -2,4-Dimethylvaleronitrile, 1,1'-azobiscyclohexane-1-carbonitrile, 2,2'-azobisisovaleronitrile, 2,2'-azobisisocapronitrile, 2,2 ' -Azobis (phenylisobutyronitrile), benzoyl peroxide, di-t-butyl peroxide, dilauroyl peroxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramenthane hydroperoxide, t-butyl hydroperoxide , 3,5,5-trimethylhexanol peroxide, t-butylperoxy (2-ethylhexanoate) and the like. Among these, 2,2′-azobisisobutyronitrile, benzoyl peroxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramenthane hydroperoxide, t-butyl hydroperoxide, 3,5,5- Trimethylhexanol peroxide and t-butylperoxy (2-ethylhexanoate) are preferred.
重合開始剤の使用量は、単量体混合物１００質量部当たり、好ましくは０．１～３質量部程度である。
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.
連鎖移動剤としては、ハロゲン化炭化水素（例えば四塩化炭素、クロロホルム、ブロモホルム等）、メルカプタン類（例えばｎ－ドデシルメルカプタン、ｔ－ドデシルメルカプタン、ｎ－オクチルメルカプタン、ｎ－ヘキサデシルメルカプタン等）、キサントゲン類（例えばジメチルキサントゲンジスルフィド、ジエチルキサントゲンジスルフィド、ジイソプロピルキサントゲンジスルフィド等）、テルペン類（例えばジペンテン、ターピノーレン等）、チウラムスルフィド類（例えばテトラメチルチウラムモノスルフィド、テトラエチルチウラムジスルフィド、テトラブチルチウラムジスルフィド、ジペンタメチルチウラムジスルフィド等）が挙げられる。
Examples of the chain transfer agent include 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, dimethylxanthogen disulfide, diethylxanthogen disulfide, diisopropylxanthogen disulfide, etc.), terpenes (eg, dipentene, terpinolene, etc.), thiuram sulfides (eg, tetramethylthiuram monosulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, dipentamethyl) And thiuram disulfide).
連鎖移動剤の使用量は、単量体混合物１００質量部当たり、好ましくは０～１０質量部程度である。
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.
ｐＨ調整剤としては、例えば炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、アンモニア等が挙げられる。また、ｐＨ調整剤の使用量は、単量体混合物１００質量部当たり、好ましくは０～３質量部程度である。
Examples of the pH adjusting agent include sodium carbonate, potassium carbonate, sodium hydrogen carbonate, ammonia and the like. The amount of the pH adjusting agent used is preferably about 0 to 3 parts by mass per 100 parts by mass of the monomer mixture.
水性媒体中で単量体混合物を乳化重合する際には、単量体混合物は種々の方法で添加することができる。添加方法としては、単量体混合物の全量を一括して添加する方法、単量体混合物の一部を仕込んで反応させた後、残りの単量体混合物を連続または分割して仕込む方法、反応させた粒子の一部を仕込んだ後、残りの単量体混合物を連続または分割して仕込む方法、単量体混合物の全量を連続または逐次分割して仕込む方法などがあるが、単量体混合物の一部を仕込んで反応させた後、残りの単量体混合物を連続または分割して仕込む方法もしくは、反応させた粒子の一部を仕込んだ後、残りの単量体混合物を連続または分割して仕込む方法が好ましい。
When emulsion-polymerizing a monomer mixture in an aqueous medium, the monomer mixture can be added by various methods. As the addition method, a method of adding the whole amount of the monomer mixture at once, a method of charging a part of the monomer mixture and reacting, and a method of charging the remaining monomer mixture continuously or in a divided manner, the reaction After charging a part of the allowed particles, there is a method of charging the remaining monomer mixture continuously or dividedly, a method of charging the whole amount of the monomer mixture continuously or sequentially, and the like. After charging a part of the mixture and reacting, the remaining monomer mixture is continuously or dividedly charged, or after charging a part of the reacted particles, the remaining monomer mixture is continuously or divided. The method of charging by charging is preferable.
以下、本発明を実施例により詳細に説明するが、これにより本発明が制限されるものではない。なお、以下の記載において「％」および「部」は、「質量％」および「質量部」を表わす。本実施例で用いた測定法を以下に示す。
（１）分散安定性
フッ素含有重合体粒子と無機粒子（アルミナ、粒子径０．５μｍ）とを１：１の質量比で水に固形分濃度が１０質量％となるように、混合し、超音波分散機にて１０分間分散させた。濃厚系粒径アナライザー（大塚電子社製ＦＰＡＲ－１０００）にて初期の粒子の平均粒子径を測定した。１日間静置した後に、遠心加速速度お２０，０００Ｇ、３０分で遠心分離した粒子の平均粒子径を測定した。増加率が１０％未満のとき「優」、増加率が１０％以上２０％未満のとき「良」、増加率が２０％以上５０％未満のとき「やや劣る」、増加率が５０％以上のとき「劣る」とし、増加率が２０％未満のとき分散安定性が良好と判定する。表１～３に記載の「分散安定性」は、上記増加率の値である。 Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto. In the following description, “%” and “part” represent “mass%” and “part by mass”. The measurement methods used in this example are shown below.
(1) Dispersion stability Fluorine-containing polymer particles and inorganic particles (alumina, particle diameter 0.5 μm) were mixed in water at a mass ratio of 1: 1 so that the solid content concentration was 10 mass%, It was dispersed for 10 minutes with a sonic dispersing machine. The average particle size of the initial particles was measured with a concentrated particle size analyzer (FPAR-1000 manufactured by Otsuka Electronics Co., Ltd.). After standing for 1 day, the average particle size of the particles centrifuged at 20,000 G for 30 minutes was measured. When the rate of increase is less than 10%, it is "excellent"; when the rate of increase is 10% or more and less than 20%, it is "good"; when the rate of increase is 20% or more and less than 50%, "somewhat inferior"; When the increase rate is less than 20%, the dispersion stability is determined to be good. “Dispersion stability” described in Tables 1 to 3 is the value of the above-mentioned increase rate.
（１）分散安定性
フッ素含有重合体粒子と無機粒子（アルミナ、粒子径０．５μｍ）とを１：１の質量比で水に固形分濃度が１０質量％となるように、混合し、超音波分散機にて１０分間分散させた。濃厚系粒径アナライザー（大塚電子社製ＦＰＡＲ－１０００）にて初期の粒子の平均粒子径を測定した。１日間静置した後に、遠心加速速度お２０，０００Ｇ、３０分で遠心分離した粒子の平均粒子径を測定した。増加率が１０％未満のとき「優」、増加率が１０％以上２０％未満のとき「良」、増加率が２０％以上５０％未満のとき「やや劣る」、増加率が５０％以上のとき「劣る」とし、増加率が２０％未満のとき分散安定性が良好と判定する。表１～３に記載の「分散安定性」は、上記増加率の値である。 Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto. In the following description, “%” and “part” represent “mass%” and “part by mass”. The measurement methods used in this example are shown below.
(1) Dispersion stability Fluorine-containing polymer particles and inorganic particles (alumina, particle diameter 0.5 μm) were mixed in water at a mass ratio of 1: 1 so that the solid content concentration was 10 mass%, It was dispersed for 10 minutes with a sonic dispersing machine. The average particle size of the initial particles was measured with a concentrated particle size analyzer (FPAR-1000 manufactured by Otsuka Electronics Co., Ltd.). After standing for 1 day, the average particle size of the particles centrifuged at 20,000 G for 30 minutes was measured. When the rate of increase is less than 10%, it is "excellent"; when the rate of increase is 10% or more and less than 20%, it is "good"; when the rate of increase is 20% or more and less than 50%, "somewhat inferior"; When the increase rate is less than 20%, the dispersion stability is determined to be good. “Dispersion stability” described in Tables 1 to 3 is the value of the above-mentioned increase rate.
（２）粒子融着性
フッ素含有重合体粒子を水にて濃度０．０１質量％に希釈した分散液をアルミホイル上に滴下し、室温乾燥させた試料と、５０℃の熱をかけ乾燥させた試料を調製した。その後、走査型電子顕微鏡（Ｈｉｔａｃｈｉ，ＳＵ８０００）を用いて、加速電圧２．０ｋＶ，５０，０００倍で２視野観察した。無作為に１００個の粒子の算術平均粒子径を測定した。室温乾燥させた試料の算術平均粒子径に対する、５０℃で乾燥させた試料の算術平均粒子径の変化率［変化率＝５０℃で乾燥させた試料の算術平均粒子径／室温乾燥させた試料の算術平均粒子径］を分析した。変化率が１．５未満であれば「融着なし」、変化率が１．５以上２．０未満であれば「融着少ない」、変化率が２．０以上３．０未満であれば「融着がある」、変化率が３．０以上であれば「融着多い」と評価し、変化率が２．０未満のとき良好な粒子融着性と判定する。表１～３に記載の「粒子融着性」は、上記変化率の値である。 (2) Particle Fusing Property A dispersion liquid obtained by diluting fluorine-containing polymer particles with water to a concentration of 0.01% by mass was dropped on aluminum foil, dried at room temperature, and dried by applying heat at 50 ° C. Prepared samples. Then, two fields of view were observed using a scanning electron microscope (Hitachi, SU8000) at an acceleration voltage of 2.0 kV and 50,000 times. The arithmetic mean particle size of 100 particles was measured at random. Change rate of the arithmetic mean particle size of the sample dried at 50 ° C. with respect to the arithmetic mean particle size of the sample dried at room temperature [change rate = arithmetic mean particle size of sample dried at 50 ° C./of room temperature dried sample Arithmetic mean particle size] was analyzed. If the rate of change is less than 1.5, "no fusion", if the rate of change is 1.5 or more and less than 2.0, "low fusion", if the rate of change is 2.0 or more and less than 3.0 If there is "fusion" and the change rate is 3.0 or more, it is evaluated as "a lot of fusion", and if the change rate is less than 2.0, it is judged as good particle fusion property. The “particle fusion property” described in Tables 1 to 3 is the value of the above change rate.
フッ素含有重合体粒子を水にて濃度０．０１質量％に希釈した分散液をアルミホイル上に滴下し、室温乾燥させた試料と、５０℃の熱をかけ乾燥させた試料を調製した。その後、走査型電子顕微鏡（Ｈｉｔａｃｈｉ，ＳＵ８０００）を用いて、加速電圧２．０ｋＶ，５０，０００倍で２視野観察した。無作為に１００個の粒子の算術平均粒子径を測定した。室温乾燥させた試料の算術平均粒子径に対する、５０℃で乾燥させた試料の算術平均粒子径の変化率［変化率＝５０℃で乾燥させた試料の算術平均粒子径／室温乾燥させた試料の算術平均粒子径］を分析した。変化率が１．５未満であれば「融着なし」、変化率が１．５以上２．０未満であれば「融着少ない」、変化率が２．０以上３．０未満であれば「融着がある」、変化率が３．０以上であれば「融着多い」と評価し、変化率が２．０未満のとき良好な粒子融着性と判定する。表１～３に記載の「粒子融着性」は、上記変化率の値である。 (2) Particle Fusing Property A dispersion liquid obtained by diluting fluorine-containing polymer particles with water to a concentration of 0.01% by mass was dropped on aluminum foil, dried at room temperature, and dried by applying heat at 50 ° C. Prepared samples. Then, two fields of view were observed using a scanning electron microscope (Hitachi, SU8000) at an acceleration voltage of 2.0 kV and 50,000 times. The arithmetic mean particle size of 100 particles was measured at random. Change rate of the arithmetic mean particle size of the sample dried at 50 ° C. with respect to the arithmetic mean particle size of the sample dried at room temperature [change rate = arithmetic mean particle size of sample dried at 50 ° C./of room temperature dried sample Arithmetic mean particle size] was analyzed. If the rate of change is less than 1.5, "no fusion", if the rate of change is 1.5 or more and less than 2.0, "low fusion", if the rate of change is 2.0 or more and less than 3.0 If there is "fusion" and the change rate is 3.0 or more, it is evaluated as "a lot of fusion", and if the change rate is less than 2.0, it is judged as good particle fusion property. The “particle fusion property” described in Tables 1 to 3 is the value of the above change rate.
（３）撥水性
フッ素含有重合体粒子と無機粒子（アルミナ、粒子径０．５μｍ）とを１：１の質量比で、固形分濃度が１０質量％となるように水に分散させた分散液を調製した。この分散液を親水性アンダーコート付ＰＥＴ基材上にバーコーター（＃３番手）で塗布し６０℃で１０分乾燥し塗膜層を形成した。室温２５℃、相対湿度５０％の雰囲気下で、塗膜層表面に１～４μＬの水をシリンジで滴下した。接触角計（協和界面科学（株）製、接触角計ＣＡ－Ｘ型）を用いて、液滴を水平断面から観察し、液滴端部の接線と塗膜層平面とのなす接触角を求めた。接触角が９０°以上であれば「優」、接触角が８０°以上９０°未満であれば「良」、接触角が５０°以上８０°未満であれば「やや劣る」、接触角が５０未満であれば「劣る」と評価し、接触角が８０°より大きければ撥水性が良好であると判定する。表１～３に記載の「撥水性」は、上記接触角の値である。 (3) Water repellent A dispersion liquid in which fluorine-containing polymer particles and inorganic particles (alumina, particle diameter 0.5 μm) are dispersed in water at a mass ratio of 1: 1 so that the solid content concentration is 10% by mass. Was prepared. This dispersion was applied on a PET substrate with hydrophilic undercoat by a bar coater (# 3 count) and dried at 60 ° C. for 10 minutes to form a coating layer. In an atmosphere of room temperature of 25 ° C. and relative humidity of 50%, 1 to 4 μL of water was dropped on the surface of the coating layer with a syringe. Using a contact angle meter (Kyowa Interface Science Co., Ltd., contact angle meter CA-X type), the droplet was observed from a horizontal cross section, and the contact angle between the tangent line of the droplet edge and the coating layer plane was measured. I asked. A contact angle of 90 ° or more is “excellent”, a contact angle of 80 ° or more and less than 90 ° is “good”, a contact angle of 50 ° or more and less than 80 ° is “slightly poor”, and a contact angle is 50. If the contact angle is less than 80 °, the water repellency is determined to be good. “Water repellency” described in Tables 1 to 3 is the value of the contact angle.
フッ素含有重合体粒子と無機粒子（アルミナ、粒子径０．５μｍ）とを１：１の質量比で、固形分濃度が１０質量％となるように水に分散させた分散液を調製した。この分散液を親水性アンダーコート付ＰＥＴ基材上にバーコーター（＃３番手）で塗布し６０℃で１０分乾燥し塗膜層を形成した。室温２５℃、相対湿度５０％の雰囲気下で、塗膜層表面に１～４μＬの水をシリンジで滴下した。接触角計（協和界面科学（株）製、接触角計ＣＡ－Ｘ型）を用いて、液滴を水平断面から観察し、液滴端部の接線と塗膜層平面とのなす接触角を求めた。接触角が９０°以上であれば「優」、接触角が８０°以上９０°未満であれば「良」、接触角が５０°以上８０°未満であれば「やや劣る」、接触角が５０未満であれば「劣る」と評価し、接触角が８０°より大きければ撥水性が良好であると判定する。表１～３に記載の「撥水性」は、上記接触角の値である。 (3) Water repellent A dispersion liquid in which fluorine-containing polymer particles and inorganic particles (alumina, particle diameter 0.5 μm) are dispersed in water at a mass ratio of 1: 1 so that the solid content concentration is 10% by mass. Was prepared. This dispersion was applied on a PET substrate with hydrophilic undercoat by a bar coater (# 3 count) and dried at 60 ° C. for 10 minutes to form a coating layer. In an atmosphere of room temperature of 25 ° C. and relative humidity of 50%, 1 to 4 μL of water was dropped on the surface of the coating layer with a syringe. Using a contact angle meter (Kyowa Interface Science Co., Ltd., contact angle meter CA-X type), the droplet was observed from a horizontal cross section, and the contact angle between the tangent line of the droplet edge and the coating layer plane was measured. I asked. A contact angle of 90 ° or more is “excellent”, a contact angle of 80 ° or more and less than 90 ° is “good”, a contact angle of 50 ° or more and less than 80 ° is “slightly poor”, and a contact angle is 50. If the contact angle is less than 80 °, the water repellency is determined to be good. “Water repellency” described in Tables 1 to 3 is the value of the contact angle.
（４）耐薬品性
フッ素含有重合体粒子の固形分濃度が１０質量％となるように、Ｎ-メチル-２-ピロリドン（以下、ＮＭＰ）に混合し、１０分間攪拌し分散液を調製した。それぞれの分散液をフッ素含有重合体粒子の固形分濃度０．０１質量％に希釈した試料液をアルミホイル上に滴下し、室温で乾燥した後、走査型電子顕微鏡（Ｈｉｔａｃｈｉ，ＳＵ８０００）を用いて、加速電圧２．０ｋＶ，５０，０００倍で２視野観察した。無作為に１００個の粒子を測定した際の算術平均粒子径を求めた。上記（２）の粒子融着性で求めた、水分散液を室温乾燥させた試料の算術平均粒子径に対する、ＮＭＰに分散させた試料の算術平均粒子径の変化率［変化率＝ＮＭＰに分散させた試料の算術平均粒子径／水に分散させた試料の算術平均粒子径］を算出した。変化率が１．５未満であれば「優」、変化率が１．５以上２．０未満であれば「良」、変化率が２．０以上３．０未満であれば「やや劣る」、変化率が３．０以上であれば「劣る」と評価し、変化率が２．０未満のとき良好な耐薬品性と判定する。表１～３に記載の「耐薬品性」は、上記変化率の値である。 (4) Chemical resistance N-methyl-2-pyrrolidone (hereinafter, NMP) was mixed so that the solid content concentration of the fluorine-containing polymer particles was 10% by mass, and the mixture was stirred for 10 minutes to prepare a dispersion liquid. A sample solution obtained by diluting each dispersion liquid to a solid content concentration of fluorine-containing polymer particles of 0.01 mass% was dropped on an aluminum foil and dried at room temperature, and then using a scanning electron microscope (Hitachi, SU8000). Two fields of view were observed at an acceleration voltage of 2.0 kV and 50,000 times. The arithmetic average particle diameter when 100 particles were measured at random was determined. The rate of change of the arithmetic mean particle size of the sample dispersed in NMP with respect to the arithmetic mean particle size of the sample obtained by drying the aqueous dispersion at room temperature, obtained by the particle fusion property of (2) [change rate = dispersed in NMP The arithmetic mean particle size of the sample thus obtained / the arithmetic mean particle size of the sample dispersed in water] was calculated. If the change rate is less than 1.5, it is "excellent", if the change rate is 1.5 or more and less than 2.0, it is "good", and if the change rate is 2.0 or more and less than 3.0, "somewhat inferior". When the rate of change is 3.0 or more, it is evaluated as "poor", and when the rate of change is less than 2.0, the chemical resistance is judged to be good. “Chemical resistance” described in Tables 1 to 3 is a value of the above change rate.
フッ素含有重合体粒子の固形分濃度が１０質量％となるように、Ｎ-メチル-２-ピロリドン（以下、ＮＭＰ）に混合し、１０分間攪拌し分散液を調製した。それぞれの分散液をフッ素含有重合体粒子の固形分濃度０．０１質量％に希釈した試料液をアルミホイル上に滴下し、室温で乾燥した後、走査型電子顕微鏡（Ｈｉｔａｃｈｉ，ＳＵ８０００）を用いて、加速電圧２．０ｋＶ，５０，０００倍で２視野観察した。無作為に１００個の粒子を測定した際の算術平均粒子径を求めた。上記（２）の粒子融着性で求めた、水分散液を室温乾燥させた試料の算術平均粒子径に対する、ＮＭＰに分散させた試料の算術平均粒子径の変化率［変化率＝ＮＭＰに分散させた試料の算術平均粒子径／水に分散させた試料の算術平均粒子径］を算出した。変化率が１．５未満であれば「優」、変化率が１．５以上２．０未満であれば「良」、変化率が２．０以上３．０未満であれば「やや劣る」、変化率が３．０以上であれば「劣る」と評価し、変化率が２．０未満のとき良好な耐薬品性と判定する。表１～３に記載の「耐薬品性」は、上記変化率の値である。 (4) Chemical resistance N-methyl-2-pyrrolidone (hereinafter, NMP) was mixed so that the solid content concentration of the fluorine-containing polymer particles was 10% by mass, and the mixture was stirred for 10 minutes to prepare a dispersion liquid. A sample solution obtained by diluting each dispersion liquid to a solid content concentration of fluorine-containing polymer particles of 0.01 mass% was dropped on an aluminum foil and dried at room temperature, and then using a scanning electron microscope (Hitachi, SU8000). Two fields of view were observed at an acceleration voltage of 2.0 kV and 50,000 times. The arithmetic average particle diameter when 100 particles were measured at random was determined. The rate of change of the arithmetic mean particle size of the sample dispersed in NMP with respect to the arithmetic mean particle size of the sample obtained by drying the aqueous dispersion at room temperature, obtained by the particle fusion property of (2) [change rate = dispersed in NMP The arithmetic mean particle size of the sample thus obtained / the arithmetic mean particle size of the sample dispersed in water] was calculated. If the change rate is less than 1.5, it is "excellent", if the change rate is 1.5 or more and less than 2.0, it is "good", and if the change rate is 2.0 or more and less than 3.0, "somewhat inferior". When the rate of change is 3.0 or more, it is evaluated as "poor", and when the rate of change is less than 2.0, the chemical resistance is judged to be good. “Chemical resistance” described in Tables 1 to 3 is a value of the above change rate.
実施例１
＜１段目の重合＞
イオン交換水３００部、ラウリル硫酸ナトリウム０．２部を反応器に仕込み、撹拌を開始した。これに窒素雰囲気下で過硫酸アンモニウム０．５部を８０℃で添加し、２，２，２－トリフルオロエチルメタクリレート（３ＦＭＡ）３５部、シクロヘキシルメタクリレート（ＣＨＭＡ）６３部、ヒドロキシエチルメタクリレート（ＨＥＭＡ）２部、ラウリル硫酸ナトリウム２部、イオン交換水５０部からなる単量体混合物を４時間かけて連続的に滴下し、滴下終了後３時間にわたり重合処理を行い、１段目の重合体粒子を得た。 Example 1
<First stage polymerization>
300 parts of ion-exchanged water and 0.2 part of sodium lauryl sulfate were charged into the reactor, and stirring was started. To this, 0.5 part of ammonium persulfate was added at 80 ° C. under a nitrogen atmosphere, and 35 parts of 2,2,2-trifluoroethyl methacrylate (3FMA), 63 parts of cyclohexyl methacrylate (CHMA), and hydroxyethyl methacrylate (HEMA) 2 were added. Part, 2 parts of sodium lauryl sulfate, and 50 parts of ion-exchanged water were continuously added dropwise over 4 hours, and after completion of the polymerization, polymerization treatment was carried out for 3 hours to obtain first-stage polymer particles. It was
＜１段目の重合＞
イオン交換水３００部、ラウリル硫酸ナトリウム０．２部を反応器に仕込み、撹拌を開始した。これに窒素雰囲気下で過硫酸アンモニウム０．５部を８０℃で添加し、２，２，２－トリフルオロエチルメタクリレート（３ＦＭＡ）３５部、シクロヘキシルメタクリレート（ＣＨＭＡ）６３部、ヒドロキシエチルメタクリレート（ＨＥＭＡ）２部、ラウリル硫酸ナトリウム２部、イオン交換水５０部からなる単量体混合物を４時間かけて連続的に滴下し、滴下終了後３時間にわたり重合処理を行い、１段目の重合体粒子を得た。 Example 1
<First stage polymerization>
300 parts of ion-exchanged water and 0.2 part of sodium lauryl sulfate were charged into the reactor, and stirring was started. To this, 0.5 part of ammonium persulfate was added at 80 ° C. under a nitrogen atmosphere, and 35 parts of 2,2,2-trifluoroethyl methacrylate (3FMA), 63 parts of cyclohexyl methacrylate (CHMA), and hydroxyethyl methacrylate (HEMA) 2 were added. Part, 2 parts of sodium lauryl sulfate, and 50 parts of ion-exchanged water were continuously added dropwise over 4 hours, and after completion of the polymerization, polymerization treatment was carried out for 3 hours to obtain first-stage polymer particles. It was
＜２段目の重合＞
イオン交換水３００部、第１段目の重合で得られた重合体粒子１０部（固形分換算）、ラウリル硫酸ナトリウム０．２部を反応器に仕込み、撹拌を開始した。これに窒素雰囲気下で過硫酸アンモニウム０．５部を８０℃で添加し、２，２，２－トリフルオロエチルメタクリレート（３ＦＭＡ）３５部、シクロヘキシルメタクリレート（ＣＨＭＡ）６３部、ヒドロキシエチルメタクリレート（ＨＥＭＡ）２部、ラウリル硫酸ナトリウム１部、イオン交換水５０部からなる単量体混合物を４時間かけて連続的に滴下し、滴下終了後３時間にわたり重合処理を行った。ｐＨはアンモニア水で約８に調整した。得られた重合体粒子は体積平均粒子径２５６ｎｍ、数平均粒子径２５３ｎｍであった。平均粒径は、濃厚系粒径アナライザー ＦＰＡＲ－１０００（大塚電子株式会社製）を用いて測定した。得られた重合体粒子の計算Ｔｇは７１℃であった。なお、表１に示した単量体の組成比は単量体成分の総量に対する各成分の割合である。なお、得られた重合体粒子を１４０℃、６０分間加熱したときの加熱残分は、２２．７質量％であった。 <Second-stage polymerization>
300 parts of ion-exchanged water, 10 parts of polymer particles obtained in the first stage polymerization (solid content conversion), and 0.2 part of sodium lauryl sulfate were charged into a reactor, and stirring was started. To this, 0.5 part of ammonium persulfate was added at 80 ° C. under a nitrogen atmosphere, and 35 parts of 2,2,2-trifluoroethyl methacrylate (3FMA), 63 parts of cyclohexyl methacrylate (CHMA), and hydroxyethyl methacrylate (HEMA) 2 were added. Part, 1 part of sodium lauryl sulfate and 50 parts of ion-exchanged water were continuously added dropwise over 4 hours, and a polymerization treatment was carried out for 3 hours after the completion of the addition. 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 concentrated particle size analyzer FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.). The calculated Tg of the obtained polymer particles was 71 ° C. The composition ratio of the monomers shown in Table 1 is the ratio of each component to the total amount of the monomer components. The heating residue when the obtained polymer particles were heated at 140 ° C. for 60 minutes was 22.7% by mass.
イオン交換水３００部、第１段目の重合で得られた重合体粒子１０部（固形分換算）、ラウリル硫酸ナトリウム０．２部を反応器に仕込み、撹拌を開始した。これに窒素雰囲気下で過硫酸アンモニウム０．５部を８０℃で添加し、２，２，２－トリフルオロエチルメタクリレート（３ＦＭＡ）３５部、シクロヘキシルメタクリレート（ＣＨＭＡ）６３部、ヒドロキシエチルメタクリレート（ＨＥＭＡ）２部、ラウリル硫酸ナトリウム１部、イオン交換水５０部からなる単量体混合物を４時間かけて連続的に滴下し、滴下終了後３時間にわたり重合処理を行った。ｐＨはアンモニア水で約８に調整した。得られた重合体粒子は体積平均粒子径２５６ｎｍ、数平均粒子径２５３ｎｍであった。平均粒径は、濃厚系粒径アナライザー ＦＰＡＲ－１０００（大塚電子株式会社製）を用いて測定した。得られた重合体粒子の計算Ｔｇは７１℃であった。なお、表１に示した単量体の組成比は単量体成分の総量に対する各成分の割合である。なお、得られた重合体粒子を１４０℃、６０分間加熱したときの加熱残分は、２２．７質量％であった。 <Second-stage polymerization>
300 parts of ion-exchanged water, 10 parts of polymer particles obtained in the first stage polymerization (solid content conversion), and 0.2 part of sodium lauryl sulfate were charged into a reactor, and stirring was started. To this, 0.5 part of ammonium persulfate was added at 80 ° C. under a nitrogen atmosphere, and 35 parts of 2,2,2-trifluoroethyl methacrylate (3FMA), 63 parts of cyclohexyl methacrylate (CHMA), and hydroxyethyl methacrylate (HEMA) 2 were added. Part, 1 part of sodium lauryl sulfate and 50 parts of ion-exchanged water were continuously added dropwise over 4 hours, and a polymerization treatment was carried out for 3 hours after the completion of the addition. 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 concentrated particle size analyzer FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.). The calculated Tg of the obtained polymer particles was 71 ° C. The composition ratio of the monomers shown in Table 1 is the ratio of each component to the total amount of the monomer components. The heating residue when the obtained polymer particles were heated at 140 ° C. for 60 minutes was 22.7% by mass.
なお、表１～３における各成分の略称は、それぞれ以下の意味である。
・３ＦＭＡ：２，２，２－トリフルオロエチルメタクリレート（前記式（１）中、Ｒ1：－ＣＨ3、Ｒ2：－ＣＨ2ＣＦ3）
・３ＦＡ：２，２，２－トリフルオロエチルアクリレート（前記式（１）中、Ｒ1：－Ｈ、Ｒ2：－ＣＨ2ＣＦ3）
・１３ＦＭＡ：ＣＦ3ＣＦ2-（ＣＦ2ＣＦ2）2-ＣＨ2ＣＨ2ＯＣＯＣ（ＣＨ3）=ＣＨ2（前記式（１）中、Ｒ1：－Ｈ、Ｒ2：－ＣＨ2ＣＨ2（ＣＦ2）5ＣＦ3）
・ＩＢＯＭＡ：イソボルニルメタクリレート（前記式（２）中、Ｒ1：－ＣＨ3、Ｒ3：イソボニル基）
・ＣＨＭＡ：シクロヘキシルメタクリレート（前記式（２）中、Ｒ1：－ＣＨ3、Ｒ3：シクロヘキシル基）
・ＣＨＡ：シクロヘキシルアクリレート（前記式（２）中、Ｒ1：－Ｈ、Ｒ3：シクロヘキシル基）
・ＳＴ：スチレン
・ＴＣＤＡ：ジシクロペンタニルアクリレート（前記式（２）中、Ｒ1：－Ｈ、Ｒ3：ジシクロペンタニル基）
・ＨＥＭＡ：ヒドロキシエチルメタクリレート（前記式（３）中、Ｒ1：－ＣＨ3、Ｒ4：ヒドロキシエチル基）
・４ＨＢＡ：４－ヒドロキシブチルアクリレート（前記式（３）中、Ｒ1：－Ｈ、Ｒ4：４－ヒドロキシブチル基）
・ＭＭＡ：メチルメタクリレート The abbreviations of the components in Tables 1 to 3 have the following meanings.
3FMA: 2,2,2-trifluoroethylmethacrylate (in the above formula (1), R 1 : -CH 3 , R 2 : -CH 2 CF 3 )
3FA: 2,2,2-trifluoroethyl acrylate (R 1 : -H, R 2 : -CH 2 CF 3 in the above formula (1))
· 13FMA: CF 3 CF 2 - (CF 2 CF 2) 2 -CH 2 CH 2 OCOC (CH 3) = CH 2 ( in the 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 is an isobornyl group)
CHMA: cyclohexyl methacrylate (in the formula (2), R 1 : —CH 3 , R 3 : cyclohexyl group)
CHA: cyclohexyl acrylate (in the formula (2), R 1 : -H, R 3 : cyclohexyl group)
-ST: styrene-TCDA: dicyclopentanyl acrylate (in the formula (2), R 1 : -H, R 3 : dicyclopentanyl group).
HEMA: hydroxyethyl methacrylate (in the formula (3), R 1 : —CH 3 , R 4 : hydroxyethyl group)
4HBA: 4-hydroxybutyl acrylate (R 1 : -H, R 4 : 4-hydroxybutyl group in the above formula (3))
・ MMA: methyl methacrylate
・３ＦＭＡ：２，２，２－トリフルオロエチルメタクリレート（前記式（１）中、Ｒ1：－ＣＨ3、Ｒ2：－ＣＨ2ＣＦ3）
・３ＦＡ：２，２，２－トリフルオロエチルアクリレート（前記式（１）中、Ｒ1：－Ｈ、Ｒ2：－ＣＨ2ＣＦ3）
・１３ＦＭＡ：ＣＦ3ＣＦ2-（ＣＦ2ＣＦ2）2-ＣＨ2ＣＨ2ＯＣＯＣ（ＣＨ3）=ＣＨ2（前記式（１）中、Ｒ1：－Ｈ、Ｒ2：－ＣＨ2ＣＨ2（ＣＦ2）5ＣＦ3）
・ＩＢＯＭＡ：イソボルニルメタクリレート（前記式（２）中、Ｒ1：－ＣＨ3、Ｒ3：イソボニル基）
・ＣＨＭＡ：シクロヘキシルメタクリレート（前記式（２）中、Ｒ1：－ＣＨ3、Ｒ3：シクロヘキシル基）
・ＣＨＡ：シクロヘキシルアクリレート（前記式（２）中、Ｒ1：－Ｈ、Ｒ3：シクロヘキシル基）
・ＳＴ：スチレン
・ＴＣＤＡ：ジシクロペンタニルアクリレート（前記式（２）中、Ｒ1：－Ｈ、Ｒ3：ジシクロペンタニル基）
・ＨＥＭＡ：ヒドロキシエチルメタクリレート（前記式（３）中、Ｒ1：－ＣＨ3、Ｒ4：ヒドロキシエチル基）
・４ＨＢＡ：４－ヒドロキシブチルアクリレート（前記式（３）中、Ｒ1：－Ｈ、Ｒ4：４－ヒドロキシブチル基）
・ＭＭＡ：メチルメタクリレート The abbreviations of the components in Tables 1 to 3 have the following meanings.
3FMA: 2,2,2-trifluoroethylmethacrylate (in the above formula (1), R 1 : -CH 3 , R 2 : -CH 2 CF 3 )
3FA: 2,2,2-trifluoroethyl acrylate (R 1 : -H, R 2 : -CH 2 CF 3 in the above formula (1))
· 13FMA: CF 3 CF 2 - (CF 2 CF 2) 2 -CH 2 CH 2 OCOC (CH 3) = CH 2 ( in the 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 is an isobornyl group)
CHMA: cyclohexyl methacrylate (in the formula (2), R 1 : —CH 3 , R 3 : cyclohexyl group)
CHA: cyclohexyl acrylate (in the formula (2), R 1 : -H, R 3 : cyclohexyl group)
-ST: styrene-TCDA: dicyclopentanyl acrylate (in the formula (2), R 1 : -H, R 3 : dicyclopentanyl group).
HEMA: hydroxyethyl methacrylate (in the formula (3), R 1 : —CH 3 , R 4 : hydroxyethyl group)
4HBA: 4-hydroxybutyl acrylate (R 1 : -H, R 4 : 4-hydroxybutyl group in the above formula (3))
・ MMA: methyl methacrylate
実施例２
イオン交換水３００部、ラウリル硫酸ナトリウム０．２部を反応器に仕込み、撹拌を開始した。これに窒素雰囲気下で過硫酸アンモニウム０．５部を８０℃で添加し、２，２，２－トリフルオロエチルメタクリレート（３ＦＭＡ）５０部、シクロヘキシルメタクリレート（ＣＨＭＡ）２４部、シクロヘキシルアクリレート（ＣＨＡ）２４部、４－ヒドロキシブチルアクリレート（４ＨＢＡ）２部、ラウリル硫酸ナトリウム２部、イオン交換水５０部からなる単量体混合物を４時間かけて連続的に滴下し、滴下終了後３時間にわたり重合処理を行った。ｐＨはアンモニア水で約８に調整した。得られた重合体粒子は表１に示す通りであった。 Example 2
300 parts of ion-exchanged water and 0.2 part of sodium lauryl sulfate were charged into the reactor, and stirring was started. To this, 0.5 part of ammonium persulfate was added at 80 ° C. under a nitrogen atmosphere to obtain 50 parts of 2,2,2-trifluoroethyl methacrylate (3FMA), 24 parts of cyclohexyl methacrylate (CHMA) and 24 parts of cyclohexyl acrylate (CHA). , 4-hydroxybutyl acrylate (4HBA) (2 parts), sodium lauryl sulfate (2 parts), ion-exchanged water (50 parts) were continuously added dropwise over 4 hours, and polymerization was performed for 3 hours after completion of the addition. It was The pH was adjusted to about 8 with aqueous ammonia. The polymer particles obtained were as shown in Table 1.
イオン交換水３００部、ラウリル硫酸ナトリウム０．２部を反応器に仕込み、撹拌を開始した。これに窒素雰囲気下で過硫酸アンモニウム０．５部を８０℃で添加し、２，２，２－トリフルオロエチルメタクリレート（３ＦＭＡ）５０部、シクロヘキシルメタクリレート（ＣＨＭＡ）２４部、シクロヘキシルアクリレート（ＣＨＡ）２４部、４－ヒドロキシブチルアクリレート（４ＨＢＡ）２部、ラウリル硫酸ナトリウム２部、イオン交換水５０部からなる単量体混合物を４時間かけて連続的に滴下し、滴下終了後３時間にわたり重合処理を行った。ｐＨはアンモニア水で約８に調整した。得られた重合体粒子は表１に示す通りであった。 Example 2
300 parts of ion-exchanged water and 0.2 part of sodium lauryl sulfate were charged into the reactor, and stirring was started. To this, 0.5 part of ammonium persulfate was added at 80 ° C. under a nitrogen atmosphere to obtain 50 parts of 2,2,2-trifluoroethyl methacrylate (3FMA), 24 parts of cyclohexyl methacrylate (CHMA) and 24 parts of cyclohexyl acrylate (CHA). , 4-hydroxybutyl acrylate (4HBA) (2 parts), sodium lauryl sulfate (2 parts), ion-exchanged water (50 parts) were continuously added dropwise over 4 hours, and polymerization was performed for 3 hours after completion of the addition. It was The pH was adjusted to about 8 with aqueous ammonia. The polymer particles obtained were as shown in Table 1.
実施例３
単量体混合物の組成比を、表１に示す組成に変更したこと以外は、実施例１と同様にして重合体粒子を得た。得られた重合体粒子は表１に示す通りであった。 Example 3
Polymer particles were obtained in the same manner as in Example 1 except that the composition ratio of the monomer mixture was changed to the composition shown in Table 1. The polymer particles obtained were as shown in Table 1.
単量体混合物の組成比を、表１に示す組成に変更したこと以外は、実施例１と同様にして重合体粒子を得た。得られた重合体粒子は表１に示す通りであった。 Example 3
Polymer particles were obtained in the same manner as in Example 1 except that the composition ratio of the monomer mixture was changed to the composition shown in Table 1. The polymer particles obtained were as shown in Table 1.
実施例４
イオン交換水３００部、アデカリアソーブＳＲ－１０２５（アデカ（株）社製乳化剤）０．２部を反応器に仕込み、撹拌を開始した。これに窒素雰囲気下で過硫酸アンモニウム０．５部を８０℃で添加し、２，２，２－トリフルオロエチルメタクリレート（３ＦＭＡ）５０部、シクロヘキシルメタクリレート（ＣＨＭＡ）２４部、シクロヘキシルアクリレート（ＣＨＡ）２４部、ヒドロキシエチルメタクリレート（ＨＥＭＡ）２部、アデカリアソーブＳＲ－１０２５（アデカ（株）社製乳化剤）１部、イオン交換水５０部からなる単量体混合物を４時間かけて連続的に滴下し、滴下終了後３時間にわたり重合処理を行った。ｐＨはアンモニア水で約８に調整した。得られた重合体粒子は表１に示す通りであった。 Example 4
300 parts of ion-exchanged water and 0.2 part of ADEKA RearSorb SR-1025 (emulsifier manufactured by ADEKA CORPORATION) were charged into the reactor and stirring was started. To this, 0.5 part of ammonium persulfate was added at 80 ° C. under a nitrogen atmosphere to obtain 50 parts of 2,2,2-trifluoroethyl methacrylate (3FMA), 24 parts of cyclohexyl methacrylate (CHMA) and 24 parts of cyclohexyl acrylate (CHA). , 2 parts of hydroxyethyl methacrylate (HEMA), 1 part of ADEKA RIASORB SR-1025 (Emulsifier manufactured by ADEKA CORPORATION), and 50 parts of ion-exchanged water were continuously added dropwise over 4 hours, and the addition was completed. Polymerization was carried out for the next 3 hours. The pH was adjusted to about 8 with aqueous ammonia. The polymer particles obtained were as shown in Table 1.
イオン交換水３００部、アデカリアソーブＳＲ－１０２５（アデカ（株）社製乳化剤）０．２部を反応器に仕込み、撹拌を開始した。これに窒素雰囲気下で過硫酸アンモニウム０．５部を８０℃で添加し、２，２，２－トリフルオロエチルメタクリレート（３ＦＭＡ）５０部、シクロヘキシルメタクリレート（ＣＨＭＡ）２４部、シクロヘキシルアクリレート（ＣＨＡ）２４部、ヒドロキシエチルメタクリレート（ＨＥＭＡ）２部、アデカリアソーブＳＲ－１０２５（アデカ（株）社製乳化剤）１部、イオン交換水５０部からなる単量体混合物を４時間かけて連続的に滴下し、滴下終了後３時間にわたり重合処理を行った。ｐＨはアンモニア水で約８に調整した。得られた重合体粒子は表１に示す通りであった。 Example 4
300 parts of ion-exchanged water and 0.2 part of ADEKA RearSorb SR-1025 (emulsifier manufactured by ADEKA CORPORATION) were charged into the reactor and stirring was started. To this, 0.5 part of ammonium persulfate was added at 80 ° C. under a nitrogen atmosphere to obtain 50 parts of 2,2,2-trifluoroethyl methacrylate (3FMA), 24 parts of cyclohexyl methacrylate (CHMA) and 24 parts of cyclohexyl acrylate (CHA). , 2 parts of hydroxyethyl methacrylate (HEMA), 1 part of ADEKA RIASORB SR-1025 (Emulsifier manufactured by ADEKA CORPORATION), and 50 parts of ion-exchanged water were continuously added dropwise over 4 hours, and the addition was completed. Polymerization was carried out for the next 3 hours. The pH was adjusted to about 8 with aqueous ammonia. The polymer particles obtained were as shown in Table 1.
実施例５
イオン交換水３００部、ラウリル硫酸ナトリウム０．５部を反応器に仕込み、撹拌を開始した。これに窒素雰囲気下で過硫酸アンモニウム０．５部を８０℃で添加し、ＣＦ3ＣＦ2-（ＣＦ2ＣＦ2）2-ＣＨ2ＣＨ2ＯＣＯＣ（ＣＨ3）=ＣＨ2（１３ＦＭＡ）５０部、イソボルニルメタクリレート（ＩＢＯＭＡ）４８部、ヒドロキシエチルメタクリレート（ＨＥＭＡ）２部、ラウリル硫酸ナトリウム２部、イオン交換水５０部からなる単量体混合物を４時間かけて連続的に滴下し、滴下終了後３時間にわたり重合処理を行った。ｐＨはアンモニア水で約８に調整した。得られた重合体粒子は表１に示す通りであった。 Example 5
300 parts of ion-exchanged water and 0.5 part of sodium lauryl sulfate were charged into the reactor, and stirring was started. 0.5 parts of ammonium persulfate was added thereto at 80 ° C. under a nitrogen atmosphere, and CF 3 CF 2 — (CF 2 CF 2 ) 2 —CH 2 CH 2 OCOC (CH 3 ) ═CH 2 (13FMA) 50 parts, A monomer mixture consisting of 48 parts of isobornyl methacrylate (IBOMA), 2 parts of hydroxyethyl methacrylate (HEMA), 2 parts of sodium lauryl sulfate and 50 parts of ion-exchanged water was continuously added dropwise over 4 hours, and after the addition was completed. Polymerization was performed for 3 hours. The pH was adjusted to about 8 with aqueous ammonia. The polymer particles obtained were as shown in Table 1.
イオン交換水３００部、ラウリル硫酸ナトリウム０．５部を反応器に仕込み、撹拌を開始した。これに窒素雰囲気下で過硫酸アンモニウム０．５部を８０℃で添加し、ＣＦ3ＣＦ2-（ＣＦ2ＣＦ2）2-ＣＨ2ＣＨ2ＯＣＯＣ（ＣＨ3）=ＣＨ2（１３ＦＭＡ）５０部、イソボルニルメタクリレート（ＩＢＯＭＡ）４８部、ヒドロキシエチルメタクリレート（ＨＥＭＡ）２部、ラウリル硫酸ナトリウム２部、イオン交換水５０部からなる単量体混合物を４時間かけて連続的に滴下し、滴下終了後３時間にわたり重合処理を行った。ｐＨはアンモニア水で約８に調整した。得られた重合体粒子は表１に示す通りであった。 Example 5
300 parts of ion-exchanged water and 0.5 part of sodium lauryl sulfate were charged into the reactor, and stirring was started. 0.5 parts of ammonium persulfate was added thereto at 80 ° C. under a nitrogen atmosphere, and CF 3 CF 2 — (CF 2 CF 2 ) 2 —CH 2 CH 2 OCOC (CH 3 ) ═CH 2 (13FMA) 50 parts, A monomer mixture consisting of 48 parts of isobornyl methacrylate (IBOMA), 2 parts of hydroxyethyl methacrylate (HEMA), 2 parts of sodium lauryl sulfate and 50 parts of ion-exchanged water was continuously added dropwise over 4 hours, and after the addition was completed. Polymerization was performed for 3 hours. The pH was adjusted to about 8 with aqueous ammonia. The polymer particles obtained were as shown in Table 1.
実施例６
ｐＨをアンモニア水で調整しなかったこと以外は、実施例２と同様にして重合体粒子を得た。得られた重合体粒子は表１に示す通りであった。 Example 6
Polymer particles were obtained in the same manner as in Example 2 except that the pH was not adjusted with aqueous ammonia. The polymer particles obtained were as shown in Table 1.
ｐＨをアンモニア水で調整しなかったこと以外は、実施例２と同様にして重合体粒子を得た。得られた重合体粒子は表１に示す通りであった。 Example 6
Polymer particles were obtained in the same manner as in Example 2 except that the pH was not adjusted with aqueous ammonia. The polymer particles obtained were as shown in Table 1.
実施例７
イオン交換水１２０部、アデカリアソーブＳＲ－１０２５（アデカ（株）社製乳化剤）１部を反応器に仕込み、撹拌を開始した。これに窒素雰囲気下で２，２’－アゾビス（２－（２－イミダゾリン－２－イル）プロパン）（和光純薬工業（株））０．４部を添加し、２，２，２－トリフルオロエチルメタクリレート（３ＦＭＡ）４０部、ジシクロペンタニルアクリレート（ＴＣＤＡ）２０部、シクロヘキシルアクリレート（ＣＨＡ）３８部、ヒドロキシエチルメタクリレート（ＨＥＭＡ）２部、アデカリアソーブＳＲ－１０２５（アデカ（株）社製乳化剤）５部、イオン交換水１１５部からなる単量体混合物を６０℃で２時間かけて連続的に滴下し、滴下終了後４時間にわたり重合処理を行った。得られた重合体粒子は表１に示す通りであった。 Example 7
120 parts of ion-exchanged water and 1 part of ADEKA RIASORB SR-1025 (emulsifier manufactured by ADEKA CORPORATION) were charged into the reactor and stirring was started. 2,2'-azobis (2- (2-imidazolin-2-yl) propane) (Wako Pure Chemical Industries, Ltd.) 0.4 part was added to this under a nitrogen atmosphere, and 2,2,2-tri 40 parts of fluoroethyl methacrylate (3FMA), 20 parts of dicyclopentanyl acrylate (TCDA), 38 parts of cyclohexyl acrylate (CHA), 2 parts of hydroxyethyl methacrylate (HEMA), ADEKA REASORB SR-1025 (emulsifier manufactured by ADEKA CORPORATION) A monomer mixture consisting of 5 parts and 115 parts of ion-exchanged water was continuously added dropwise at 60 ° C. over 2 hours, and a polymerization treatment was carried out for 4 hours after completion of the addition. The polymer particles obtained were as shown in Table 1.
イオン交換水１２０部、アデカリアソーブＳＲ－１０２５（アデカ（株）社製乳化剤）１部を反応器に仕込み、撹拌を開始した。これに窒素雰囲気下で２，２’－アゾビス（２－（２－イミダゾリン－２－イル）プロパン）（和光純薬工業（株））０．４部を添加し、２，２，２－トリフルオロエチルメタクリレート（３ＦＭＡ）４０部、ジシクロペンタニルアクリレート（ＴＣＤＡ）２０部、シクロヘキシルアクリレート（ＣＨＡ）３８部、ヒドロキシエチルメタクリレート（ＨＥＭＡ）２部、アデカリアソーブＳＲ－１０２５（アデカ（株）社製乳化剤）５部、イオン交換水１１５部からなる単量体混合物を６０℃で２時間かけて連続的に滴下し、滴下終了後４時間にわたり重合処理を行った。得られた重合体粒子は表１に示す通りであった。 Example 7
120 parts of ion-exchanged water and 1 part of ADEKA RIASORB SR-1025 (emulsifier manufactured by ADEKA CORPORATION) were charged into the reactor and stirring was started. 2,2'-azobis (2- (2-imidazolin-2-yl) propane) (Wako Pure Chemical Industries, Ltd.) 0.4 part was added to this under a nitrogen atmosphere, and 2,2,2-tri 40 parts of fluoroethyl methacrylate (3FMA), 20 parts of dicyclopentanyl acrylate (TCDA), 38 parts of cyclohexyl acrylate (CHA), 2 parts of hydroxyethyl methacrylate (HEMA), ADEKA REASORB SR-1025 (emulsifier manufactured by ADEKA CORPORATION) A monomer mixture consisting of 5 parts and 115 parts of ion-exchanged water was continuously added dropwise at 60 ° C. over 2 hours, and a polymerization treatment was carried out for 4 hours after completion of the addition. The polymer particles obtained were as shown in Table 1.
実施例８
単量体混合物の組成比を、表１に示す組成に変更したこと以外は、実施例７と同様にして重合体粒子を得た。得られた重合体粒子は表１に示す通りであった。 Example 8
Polymer particles were obtained in the same manner as in Example 7, except that the composition ratio of the monomer mixture was changed to the composition shown in Table 1. The polymer particles obtained were as shown in Table 1.
単量体混合物の組成比を、表１に示す組成に変更したこと以外は、実施例７と同様にして重合体粒子を得た。得られた重合体粒子は表１に示す通りであった。 Example 8
Polymer particles were obtained in the same manner as in Example 7, except that the composition ratio of the monomer mixture was changed to the composition shown in Table 1. The polymer particles obtained were as shown in Table 1.
実施例９
単量体混合物の組成比を、表１に示す組成に変更したこと以外は、実施例７と同様にして重合体粒子を得た。得られた重合体粒子は表１に示す通りであった。 Example 9
Polymer particles were obtained in the same manner as in Example 7, except that the composition ratio of the monomer mixture was changed to the composition shown in Table 1. The polymer particles obtained were as shown in Table 1.
単量体混合物の組成比を、表１に示す組成に変更したこと以外は、実施例７と同様にして重合体粒子を得た。得られた重合体粒子は表１に示す通りであった。 Example 9
Polymer particles were obtained in the same manner as in Example 7, except that the composition ratio of the monomer mixture was changed to the composition shown in Table 1. The polymer particles obtained were as shown in Table 1.
実施例１０
イオン交換水１２０部、アデカリアソーブＳＲ－１０２５（アデカ（株）社製乳化剤）１部を反応器に仕込み、撹拌を開始した。これに窒素雰囲気下で２，２’－アゾビス（２－（２－イミダゾリン－２－イル）プロパン）（和光純薬工業（株））０．４部を添加し、２，２，２－トリフルオロエチルメタクリレート（３ＦＭＡ）４０部、ジシクロペンタニルアクリレート（ＴＣＤＡ）２０部、シクロヘキシルアクリレート（ＣＨＡ）３５部、ヒドロキシエチルメタクリレート（ＨＥＭＡ）２部、ウレタンアクリレートＤＰ－６００ＢＵ（日油株式会社製）３部、アデカリアソーブＳＲ－１０２５（アデカ（株）社製乳化剤）９部、イオン交換水１１５部からなる単量体混合物を６０℃で２時間かけて連続的に滴下し、滴下終了後４時間にわたり重合処理を行った。得られた重合体粒子は表２に示す通りであった。なお、表２に示した単量体の組成比は単量体成分の総量に対する各成分の割合である。 Example 10
120 parts of ion-exchanged water and 1 part of ADEKA RIASORB SR-1025 (emulsifier manufactured by ADEKA CORPORATION) were charged into the reactor and stirring was started. 2,2'-azobis (2- (2-imidazolin-2-yl) propane) (Wako Pure Chemical Industries, Ltd.) 0.4 part was added to this under a nitrogen atmosphere, and 2,2,2-tri 40 parts of fluoroethyl methacrylate (3FMA), 20 parts of dicyclopentanyl acrylate (TCDA), 35 parts of cyclohexyl acrylate (CHA), 2 parts of hydroxyethyl methacrylate (HEMA), urethane acrylate DP-600BU (manufactured by NOF Corporation) 3 Part, 9 parts of ADEKA RIASORB SR-1025 (emulsifier manufactured by ADEKA Corporation), and 115 parts of ion-exchanged water were continuously added dropwise at 60 ° C. over 2 hours, and polymerization was carried out for 4 hours after completion of the addition. Processed. The polymer particles obtained were as shown in Table 2. The composition ratio of the monomers shown in Table 2 is the ratio of each component to the total amount of the monomer components.
イオン交換水１２０部、アデカリアソーブＳＲ－１０２５（アデカ（株）社製乳化剤）１部を反応器に仕込み、撹拌を開始した。これに窒素雰囲気下で２，２’－アゾビス（２－（２－イミダゾリン－２－イル）プロパン）（和光純薬工業（株））０．４部を添加し、２，２，２－トリフルオロエチルメタクリレート（３ＦＭＡ）４０部、ジシクロペンタニルアクリレート（ＴＣＤＡ）２０部、シクロヘキシルアクリレート（ＣＨＡ）３５部、ヒドロキシエチルメタクリレート（ＨＥＭＡ）２部、ウレタンアクリレートＤＰ－６００ＢＵ（日油株式会社製）３部、アデカリアソーブＳＲ－１０２５（アデカ（株）社製乳化剤）９部、イオン交換水１１５部からなる単量体混合物を６０℃で２時間かけて連続的に滴下し、滴下終了後４時間にわたり重合処理を行った。得られた重合体粒子は表２に示す通りであった。なお、表２に示した単量体の組成比は単量体成分の総量に対する各成分の割合である。 Example 10
120 parts of ion-exchanged water and 1 part of ADEKA RIASORB SR-1025 (emulsifier manufactured by ADEKA CORPORATION) were charged into the reactor and stirring was started. 2,2'-azobis (2- (2-imidazolin-2-yl) propane) (Wako Pure Chemical Industries, Ltd.) 0.4 part was added to this under a nitrogen atmosphere, and 2,2,2-tri 40 parts of fluoroethyl methacrylate (3FMA), 20 parts of dicyclopentanyl acrylate (TCDA), 35 parts of cyclohexyl acrylate (CHA), 2 parts of hydroxyethyl methacrylate (HEMA), urethane acrylate DP-600BU (manufactured by NOF Corporation) 3 Part, 9 parts of ADEKA RIASORB SR-1025 (emulsifier manufactured by ADEKA Corporation), and 115 parts of ion-exchanged water were continuously added dropwise at 60 ° C. over 2 hours, and polymerization was carried out for 4 hours after completion of the addition. Processed. The polymer particles obtained were as shown in Table 2. The composition ratio of the monomers shown in Table 2 is the ratio of each component to the total amount of the monomer components.
実施例１１
単量体混合物の組成比を、表２に示す組成に変更したこと以外は、実施例１０と同様にして重合体粒子を得た。得られた重合体粒子は表２に示す通りであった。 Example 11
Polymer particles were obtained in the same manner as in Example 10 except that the composition ratio of the monomer mixture was changed to the composition shown in Table 2. The polymer particles obtained were as shown in Table 2.
単量体混合物の組成比を、表２に示す組成に変更したこと以外は、実施例１０と同様にして重合体粒子を得た。得られた重合体粒子は表２に示す通りであった。 Example 11
Polymer particles were obtained in the same manner as in Example 10 except that the composition ratio of the monomer mixture was changed to the composition shown in Table 2. The polymer particles obtained were as shown in Table 2.
実施例１２
単量体混合物の組成比を、表２に示す組成に変更したこと以外は、実施例１０と同様にして重合体粒子を得た。得られた重合体粒子は表２に示す通りであった。 Example 12
Polymer particles were obtained in the same manner as in Example 10 except that the composition ratio of the monomer mixture was changed to the composition shown in Table 2. The polymer particles obtained were as shown in Table 2.
単量体混合物の組成比を、表２に示す組成に変更したこと以外は、実施例１０と同様にして重合体粒子を得た。得られた重合体粒子は表２に示す通りであった。 Example 12
Polymer particles were obtained in the same manner as in Example 10 except that the composition ratio of the monomer mixture was changed to the composition shown in Table 2. The polymer particles obtained were as shown in Table 2.
実施例１３
単量体混合物の組成比を、表２に示す組成に変更したこと以外は、実施例１０と同様にして重合体粒子を得た。得られた重合体粒子は表２に示す通りであった。 Example 13
Polymer particles were obtained in the same manner as in Example 10 except that the composition ratio of the monomer mixture was changed to the composition shown in Table 2. The polymer particles obtained were as shown in Table 2.
単量体混合物の組成比を、表２に示す組成に変更したこと以外は、実施例１０と同様にして重合体粒子を得た。得られた重合体粒子は表２に示す通りであった。 Example 13
Polymer particles were obtained in the same manner as in Example 10 except that the composition ratio of the monomer mixture was changed to the composition shown in Table 2. The polymer particles obtained were as shown in Table 2.
実施例１４
単量体混合物の組成比を、表２に示す組成に変更したこと以外は、実施例１０と同様にして重合体粒子を得た。得られた重合体粒子は表２に示す通りであった。 Example 14
Polymer particles were obtained in the same manner as in Example 10 except that the composition ratio of the monomer mixture was changed to the composition shown in Table 2. The polymer particles obtained were as shown in Table 2.
単量体混合物の組成比を、表２に示す組成に変更したこと以外は、実施例１０と同様にして重合体粒子を得た。得られた重合体粒子は表２に示す通りであった。 Example 14
Polymer particles were obtained in the same manner as in Example 10 except that the composition ratio of the monomer mixture was changed to the composition shown in Table 2. The polymer particles obtained were as shown in Table 2.
実施例１５
イオン交換水１２０部、アデカリアソーブＳＲ－１０２５（アデカ（株）社製乳化剤）１部を反応器に仕込み、撹拌を開始した。これに窒素雰囲気下で２，２’－アゾビス（２－（２－イミダゾリン－２－イル）プロパン）（和光純薬工業（株））０．４部を添加し、２，２，２－トリフルオロエチルメタクリレート（３ＦＭＡ）４０部、シクロヘキシルアクリレート（ＣＨＡ）５８部、ヒドロキシエチルメタクリレート（ＨＥＭＡ）２部、アデカリアソーブＳＲ－１０２５（アデカ（株）社製乳化剤）９部、イオン交換水１１５部からなる単量体混合物を６０℃で２時間かけて連続的に滴下し、滴下終了後４時間にわたり重合処理を行った。得られた重合体粒子は表２に示す通りであった。 Example 15
120 parts of ion-exchanged water and 1 part of ADEKA RIASORB SR-1025 (emulsifier manufactured by ADEKA CORPORATION) were charged into the reactor and stirring was started. 2,2'-azobis (2- (2-imidazolin-2-yl) propane) (Wako Pure Chemical Industries, Ltd.) 0.4 part was added to this under a nitrogen atmosphere, and 2,2,2-tri A unit consisting of 40 parts of fluoroethyl methacrylate (3FMA), 58 parts of cyclohexyl acrylate (CHA), 2 parts of hydroxyethyl methacrylate (HEMA), 9 parts of ADEKA REASORB SR-1025 (emulsifier manufactured by ADEKA CORPORATION), and 115 parts of ion-exchanged water. The monomer mixture was continuously added dropwise at 60 ° C. over 2 hours, and a polymerization treatment was performed for 4 hours after the completion of the addition. The polymer particles obtained were as shown in Table 2.
イオン交換水１２０部、アデカリアソーブＳＲ－１０２５（アデカ（株）社製乳化剤）１部を反応器に仕込み、撹拌を開始した。これに窒素雰囲気下で２，２’－アゾビス（２－（２－イミダゾリン－２－イル）プロパン）（和光純薬工業（株））０．４部を添加し、２，２，２－トリフルオロエチルメタクリレート（３ＦＭＡ）４０部、シクロヘキシルアクリレート（ＣＨＡ）５８部、ヒドロキシエチルメタクリレート（ＨＥＭＡ）２部、アデカリアソーブＳＲ－１０２５（アデカ（株）社製乳化剤）９部、イオン交換水１１５部からなる単量体混合物を６０℃で２時間かけて連続的に滴下し、滴下終了後４時間にわたり重合処理を行った。得られた重合体粒子は表２に示す通りであった。 Example 15
120 parts of ion-exchanged water and 1 part of ADEKA RIASORB SR-1025 (emulsifier manufactured by ADEKA CORPORATION) were charged into the reactor and stirring was started. 2,2'-azobis (2- (2-imidazolin-2-yl) propane) (Wako Pure Chemical Industries, Ltd.) 0.4 part was added to this under a nitrogen atmosphere, and 2,2,2-tri A unit consisting of 40 parts of fluoroethyl methacrylate (3FMA), 58 parts of cyclohexyl acrylate (CHA), 2 parts of hydroxyethyl methacrylate (HEMA), 9 parts of ADEKA REASORB SR-1025 (emulsifier manufactured by ADEKA CORPORATION), and 115 parts of ion-exchanged water. The monomer mixture was continuously added dropwise at 60 ° C. over 2 hours, and a polymerization treatment was performed for 4 hours after the completion of the addition. The polymer particles obtained were as shown in Table 2.
実施例１６
単量体混合物の組成比を、表２に示す組成に変更したこと以外は、実施例１５と同様にして重合体粒子を得た。得られた重合体粒子は表２に示す通りであった。 Example 16
Polymer particles were obtained in the same manner as in Example 15 except that the composition ratio of the monomer mixture was changed to the composition shown in Table 2. The polymer particles obtained were as shown in Table 2.
単量体混合物の組成比を、表２に示す組成に変更したこと以外は、実施例１５と同様にして重合体粒子を得た。得られた重合体粒子は表２に示す通りであった。 Example 16
Polymer particles were obtained in the same manner as in Example 15 except that the composition ratio of the monomer mixture was changed to the composition shown in Table 2. The polymer particles obtained were as shown in Table 2.
実施例１７
単量体混合物の組成比を、表２に示す組成に変更したこと以外は、実施例１５と同様にして重合体粒子を得た。得られた重合体粒子は表２に示す通りであった。 Example 17
Polymer particles were obtained in the same manner as in Example 15, except that the composition ratio of the monomer mixture was changed to the composition shown in Table 2. The polymer particles obtained were as shown in Table 2.
単量体混合物の組成比を、表２に示す組成に変更したこと以外は、実施例１５と同様にして重合体粒子を得た。得られた重合体粒子は表２に示す通りであった。 Example 17
Polymer particles were obtained in the same manner as in Example 15, except that the composition ratio of the monomer mixture was changed to the composition shown in Table 2. The polymer particles obtained were as shown in Table 2.
実施例１８
イオン交換水１２０部、アデカリアソーブＳＲ－１０２５（アデカ（株）社製乳化剤）１部を反応器に仕込み、撹拌を開始した。これに窒素雰囲気下で２，２’－アゾビス（２－（２－イミダゾリン－２－イル）プロパン）（和光純薬工業（株））０．４部を添加し、２，２，２－トリフルオロエチルメタクリレート（３ＦＭＡ）３０部、シクロヘキシルアクリレート（ＣＨＡ）６１部、ヒドロキシエチルメタクリレート（ＨＥＭＡ）２部、ウレタンアクリレートＤＰ－６００ＢＵ（日油株式会社製）７部、アデカリアソーブＳＲ－１０２５（アデカ（株）社製乳化剤）９部、イオン交換水１１５部からなる単量体混合物を６０℃で２時間かけて連続的に滴下し、滴下終了後４時間にわたり重合処理を行った。得られた重合体粒子は表２に示す通りであった。なお、表２に示した単量体の組成比は単量体成分の総量に対する各成分の割合である。 Example 18
120 parts of ion-exchanged water and 1 part of ADEKA RIASORB SR-1025 (emulsifier manufactured by ADEKA CORPORATION) were charged into the reactor and stirring was started. 2,2'-azobis (2- (2-imidazolin-2-yl) propane) (Wako Pure Chemical Industries, Ltd.) 0.4 part was added to this 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 Rearsorb SR-1025 (Adeka Corporation) A monomer mixture consisting of 9 parts of an emulsifier manufactured by the company) and 115 parts of ion-exchanged water was continuously added dropwise at 60 ° C. for 2 hours, and a polymerization treatment was carried out for 4 hours after the completion of the addition. The polymer particles obtained were as shown in Table 2. The composition ratio of the monomers shown in Table 2 is the ratio of each component to the total amount of the monomer components.
イオン交換水１２０部、アデカリアソーブＳＲ－１０２５（アデカ（株）社製乳化剤）１部を反応器に仕込み、撹拌を開始した。これに窒素雰囲気下で２，２’－アゾビス（２－（２－イミダゾリン－２－イル）プロパン）（和光純薬工業（株））０．４部を添加し、２，２，２－トリフルオロエチルメタクリレート（３ＦＭＡ）３０部、シクロヘキシルアクリレート（ＣＨＡ）６１部、ヒドロキシエチルメタクリレート（ＨＥＭＡ）２部、ウレタンアクリレートＤＰ－６００ＢＵ（日油株式会社製）７部、アデカリアソーブＳＲ－１０２５（アデカ（株）社製乳化剤）９部、イオン交換水１１５部からなる単量体混合物を６０℃で２時間かけて連続的に滴下し、滴下終了後４時間にわたり重合処理を行った。得られた重合体粒子は表２に示す通りであった。なお、表２に示した単量体の組成比は単量体成分の総量に対する各成分の割合である。 Example 18
120 parts of ion-exchanged water and 1 part of ADEKA RIASORB SR-1025 (emulsifier manufactured by ADEKA CORPORATION) were charged into the reactor and stirring was started. 2,2'-azobis (2- (2-imidazolin-2-yl) propane) (Wako Pure Chemical Industries, Ltd.) 0.4 part was added to this 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 Rearsorb SR-1025 (Adeka Corporation) A monomer mixture consisting of 9 parts of an emulsifier manufactured by the company) and 115 parts of ion-exchanged water was continuously added dropwise at 60 ° C. for 2 hours, and a polymerization treatment was carried out for 4 hours after the completion of the addition. The polymer particles obtained were as shown in Table 2. The composition ratio of the monomers shown in Table 2 is the ratio of each component to the total amount of the monomer components.
実施例１９
架橋剤（Ｄ）を、ウレタンアクリレートＵＦ－０７ＤＦ（共栄社化学株式会社製）に変更したこと以外は、実施例１８と同様にして重合体粒子を得た。得られた重合体粒子は表３に示す通りであった。 Example 19
Polymer particles were obtained in the same manner as in Example 18 except that the urethane acrylate UF-07DF (manufactured by Kyoeisha Chemical Co., Ltd.) was used as the crosslinking agent (D). The polymer particles obtained were as shown in Table 3.
架橋剤（Ｄ）を、ウレタンアクリレートＵＦ－０７ＤＦ（共栄社化学株式会社製）に変更したこと以外は、実施例１８と同様にして重合体粒子を得た。得られた重合体粒子は表３に示す通りであった。 Example 19
Polymer particles were obtained in the same manner as in Example 18 except that the urethane acrylate UF-07DF (manufactured by Kyoeisha Chemical Co., Ltd.) was used as the crosslinking agent (D). The polymer particles obtained were as shown in Table 3.
実施例２０
架橋剤（Ｄ）を、ウレタンアクリレートＵＦ－Ｃ０１２（共栄社化学株式会社製）に変更したこと以外は、実施例１８と同様にして重合体粒子を得た。得られた重合体粒子は表３に示す通りであった。 Example 20
Polymer particles were obtained in the same manner as in Example 18, except that the urethane acrylate UF-C012 (manufactured by Kyoeisha Chemical Co., Ltd.) was used as the crosslinking agent (D). The polymer particles obtained were as shown in Table 3.
架橋剤（Ｄ）を、ウレタンアクリレートＵＦ－Ｃ０１２（共栄社化学株式会社製）に変更したこと以外は、実施例１８と同様にして重合体粒子を得た。得られた重合体粒子は表３に示す通りであった。 Example 20
Polymer particles were obtained in the same manner as in Example 18, except that the urethane acrylate UF-C012 (manufactured by Kyoeisha Chemical Co., Ltd.) was used as the crosslinking agent (D). The polymer particles obtained were as shown in Table 3.
実施例２１
架橋剤（Ｄ）を、ウレタンアクリレートＵＦ－Ｃ０５２（共栄社化学株式会社製）に変更したこと以外は、実施例１８と同様にして重合体粒子を得た。得られた重合体粒子は表３に示す通りであった。 Example 21
Polymer particles were obtained in the same manner as in Example 18, except that the urethane acrylate UF-C052 (manufactured by Kyoeisha Chemical Co., Ltd.) was used as the crosslinking agent (D). The polymer particles obtained were as shown in Table 3.
架橋剤（Ｄ）を、ウレタンアクリレートＵＦ－Ｃ０５２（共栄社化学株式会社製）に変更したこと以外は、実施例１８と同様にして重合体粒子を得た。得られた重合体粒子は表３に示す通りであった。 Example 21
Polymer particles were obtained in the same manner as in Example 18, except that the urethane acrylate UF-C052 (manufactured by Kyoeisha Chemical Co., Ltd.) was used as the crosslinking agent (D). The polymer particles obtained were as shown in Table 3.
実施例２２
架橋剤（Ｄ）を、ウレタンアクリレートＵＦ－０１４６（共栄社化学株式会社製）に変更したこと以外は、実施例１８と同様にして重合体粒子を得た。得られた重合体粒子は表３に示す通りであった。 Example 22
Polymer particles were obtained in the same manner as in Example 18, except that the urethane acrylate UF-0146 (manufactured by Kyoeisha Chemical Co., Ltd.) was used as the crosslinking agent (D). The polymer particles obtained were as shown in Table 3.
架橋剤（Ｄ）を、ウレタンアクリレートＵＦ－０１４６（共栄社化学株式会社製）に変更したこと以外は、実施例１８と同様にして重合体粒子を得た。得られた重合体粒子は表３に示す通りであった。 Example 22
Polymer particles were obtained in the same manner as in Example 18, except that the urethane acrylate UF-0146 (manufactured by Kyoeisha Chemical Co., Ltd.) was used as the crosslinking agent (D). The polymer particles obtained were as shown in Table 3.
実施例２３
架橋剤（Ｄ）を、アルキレングリコールジメタクリレートＰＤＥ－６００（共栄社化学株式会社製）に変更したこと以外は、実施例１８と同様にして重合体粒子を得た。得られた重合体粒子は表３に示す通りであった。 Example 23
Polymer particles were obtained in the same manner as in Example 18, except that the cross-linking agent (D) was changed to alkylene glycol dimethacrylate PDE-600 (manufactured by Kyoeisha Chemical Co., Ltd.). The polymer particles obtained were as shown in Table 3.
架橋剤（Ｄ）を、アルキレングリコールジメタクリレートＰＤＥ－６００（共栄社化学株式会社製）に変更したこと以外は、実施例１８と同様にして重合体粒子を得た。得られた重合体粒子は表３に示す通りであった。 Example 23
Polymer particles were obtained in the same manner as in Example 18, except that the cross-linking agent (D) was changed to alkylene glycol dimethacrylate PDE-600 (manufactured by Kyoeisha Chemical Co., Ltd.). The polymer particles obtained were as shown in Table 3.
実施例２４
架橋剤（Ｄ）を、アルキレングリコールジアクリレートＡＤＰ－４００（共栄社化学株式会社製）に変更したこと以外は、実施例１８と同様にして重合体粒子を得た。得られた重合体粒子は表３に示す通りであった。 Example 24
Polymer particles were obtained in the same manner as in Example 18 except that the cross-linking agent (D) was changed to alkylene glycol diacrylate ADP-400 (manufactured by Kyoeisha Chemical Co., Ltd.). The polymer particles obtained were as shown in Table 3.
架橋剤（Ｄ）を、アルキレングリコールジアクリレートＡＤＰ－４００（共栄社化学株式会社製）に変更したこと以外は、実施例１８と同様にして重合体粒子を得た。得られた重合体粒子は表３に示す通りであった。 Example 24
Polymer particles were obtained in the same manner as in Example 18 except that the cross-linking agent (D) was changed to alkylene glycol diacrylate ADP-400 (manufactured by Kyoeisha Chemical Co., Ltd.). The polymer particles obtained were as shown in Table 3.
比較例１
単量体混合物の組成比を、表３に示す組成に変更したこと以外は、実施例１と同様にして重合体粒子を得た。得られた重合体粒子は表３に示す通りであった。 Comparative Example 1
Polymer particles were obtained in the same manner as in Example 1 except that the composition ratio of the monomer mixture was changed to the composition shown in Table 3. The polymer particles obtained were as shown in Table 3.
単量体混合物の組成比を、表３に示す組成に変更したこと以外は、実施例１と同様にして重合体粒子を得た。得られた重合体粒子は表３に示す通りであった。 Comparative Example 1
Polymer particles were obtained in the same manner as in Example 1 except that the composition ratio of the monomer mixture was changed to the composition shown in Table 3. The polymer particles obtained were as shown in Table 3.
比較例２
イオン交換水３００部、ラウリル硫酸ナトリウム０．２部を反応器に仕込み、撹拌を開始した。これに窒素雰囲気下で過硫酸アンモニウム０．５部を８０℃で添加し、イソボルニルメタクリレート（ＩＢＯＭＡ）１００部、ラウリル硫酸ナトリウム２部、イオン交換水５０部からなる単量体混合物を４時間かけて連続的に滴下し、滴下終了後３時間にわたり重合処理を行った。ｐＨはアンモニア水で約８に調整した。得られた重合体粒子は表３に示す通りであった。 Comparative example 2
300 parts of ion-exchanged water and 0.2 part of sodium lauryl sulfate were charged into the reactor, and stirring was started. Under nitrogen atmosphere, 0.5 part of ammonium persulfate was added at 80 ° C., 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 added for 4 hours. Was continuously added dropwise, and the polymerization treatment was carried out for 3 hours after the completion of the addition. The pH was adjusted to about 8 with aqueous ammonia. The polymer particles obtained were as shown in Table 3.
イオン交換水３００部、ラウリル硫酸ナトリウム０．２部を反応器に仕込み、撹拌を開始した。これに窒素雰囲気下で過硫酸アンモニウム０．５部を８０℃で添加し、イソボルニルメタクリレート（ＩＢＯＭＡ）１００部、ラウリル硫酸ナトリウム２部、イオン交換水５０部からなる単量体混合物を４時間かけて連続的に滴下し、滴下終了後３時間にわたり重合処理を行った。ｐＨはアンモニア水で約８に調整した。得られた重合体粒子は表３に示す通りであった。 Comparative example 2
300 parts of ion-exchanged water and 0.2 part of sodium lauryl sulfate were charged into the reactor, and stirring was started. Under nitrogen atmosphere, 0.5 part of ammonium persulfate was added at 80 ° C., 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 added for 4 hours. Was continuously added dropwise, and the polymerization treatment was carried out for 3 hours after the completion of the addition. The pH was adjusted to about 8 with aqueous ammonia. The polymer particles obtained were as shown in Table 3.
比較例３
単量体混合物の組成比を、表３に示す組成に変更したこと以外は、実施例１と同様にして重合体粒子を得た。得られた重合体粒子は表３に示す通りであった。 Comparative Example 3
Polymer particles were obtained in the same manner as in Example 1 except that the composition ratio of the monomer mixture was changed to the composition shown in Table 3. The polymer particles obtained were as shown in Table 3.
単量体混合物の組成比を、表３に示す組成に変更したこと以外は、実施例１と同様にして重合体粒子を得た。得られた重合体粒子は表３に示す通りであった。 Comparative Example 3
Polymer particles were obtained in the same manner as in Example 1 except that the composition ratio of the monomer mixture was changed to the composition shown in Table 3. The polymer particles obtained were as shown in Table 3.
本発明のフッ素含有重合体粒子は、フィルム上の塗膜に少量添加し、フッ素自体の表面自由エネルギーの低さを最大限に活かすことにより、フィルム上の塗膜に含まれる他粒子の特性を保持したまま、塗膜表面へフッ素の特徴を発現させることができる。また、粒子同士の熱融着を抑制しながら他の物への密着性を有すことから、撥水性、防汚性、耐薬品性および密着性に優れた塗膜を形成するフィルムを高い生産性で提供可能となる。これにより、特にリチウムイオン電池に用いられるセパレータフィルムの表面を改質するコート剤として適用が進み、ＥＶ／ＰＨＥＶ普及促進による地球温暖化ガス排出削減への貢献が期待できる。
The fluorine-containing polymer particles of the present invention are added to a coating film on a film in a small amount, and by making the most of the low surface free energy of fluorine itself, the characteristics of other particles contained in the coating film on the film can be obtained. The characteristics of fluorine can be developed on the surface of the coating film while it is held. In addition, since it has adhesion to other materials while suppressing thermal fusion of particles, it produces a film that forms a coating film excellent in water repellency, stain resistance, chemical resistance and adhesion. Can be provided by sex. As a result, the application as a coating agent that modifies the surface of the separator film used in a lithium-ion battery is particularly advanced, and it can be expected to contribute to the reduction of global warming gas emissions by promoting the spread of EV / PHEV.
Claims (9)
- フッ素含有（メタ）アクリル酸エステル単量体（Ａ）由来の構造単位（Ｘ）を３０質量％以上、（メタ）アクリル酸エステル単量体（Ｂ）由来の構造単位（Ｙ）を３０質量％以上含む共重合体で形成された粒子であって、前記フッ素含有（メタ）アクリル酸エステル単量体（Ａ）由来の構造単位が下記一般式（１）、前記（メタ）アクリル酸エステル単量体（Ｂ）由来の構造単位が下記一般式（２）で表されることを特徴とする、フッ素含有重合体粒子。
- 前記共重合体において、前記構造単位（Ｘ）および構造単位（Ｙ）の合計が８０質量％を超えることを特徴とする、請求項１に記載のフッ素含有重合体粒子。 The fluorine-containing polymer particles according to claim 1, wherein the total of the structural unit (X) and the structural unit (Y) in the copolymer exceeds 80% by mass.
- 前記（メタ）アクリル酸エステル単量体（Ｂ）が、イソボルニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ベンジル（メタ）アクリレートから選ばれる少なくとも１つであることを特徴とする、請求項１または２に記載のフッ素含有重合体粒子。 The (meth) acrylic acid ester monomer (B) is selected from isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, cyclohexyl (meth) acrylate and benzyl (meth) acrylate. The fluorine-containing polymer particles according to claim 1 or 2, which is at least one selected.
- 前記共重合体が、更に水酸基を有する（メタ）アクリル酸エステル単量体（Ｃ）由来の構造単位（Ｚ）を１～１０質量％含有し、前記構造単位（Ｚ）が下記式（３）で表されることを特徴とする、請求項１～３のいずれかに記載のフッ素含有重合体粒子。
- 前記共重合体が、更に架橋剤（Ｄ）を１～１０質量％含有することを特徴とする、請求項１～４のいずれかに記載のフッ素含有重合体粒子。 The fluorine-containing polymer particles according to any one of claims 1 to 4, wherein the copolymer further contains 1 to 10% by mass of a crosslinking agent (D).
- 体積平均粒子径が１００～５００ｎｍ、粒度分布（体積平均粒子径／数平均粒子径）が１．２０以下であることを特徴とする、請求項１～５のいずれかに記載のフッ素含有重合体粒子。 The fluorine-containing polymer according to any one of claims 1 to 5, which has 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. particle.
- 前記共重合体のガラス転移温度が２０℃～１００℃である、請求項１～６のいずれかに記載のフッ素含有重合体粒子。 The fluorine-containing polymer particles according to any one of claims 1 to 6, wherein the glass transition temperature of the copolymer is 20 ° C to 100 ° C.
- 請求項１～７いずれかに記載のフッ素含有重合体粒子と水からなる分散液であって、ｐＨが５～１０であることを特徴とする、フッ素含有重合体粒子を含む分散液。 A dispersion comprising the fluorine-containing polymer particles according to any one of claims 1 to 7 and water, wherein the dispersion has a pH of 5 to 10, containing the fluorine-containing polymer particles.
- フィルム用に使用される、請求項８に記載のフッ素含有重合体粒子を含む分散液。 A dispersion containing the fluorine-containing polymer particles according to claim 8, which is used for a film.
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| CN201980066513.3A CN112839970B (en) | 2018-11-22 | 2019-11-20 | Fluoropolymer particles |
| KR1020217006515A KR20210093845A (en) | 2018-11-22 | 2019-11-20 | Fluorine-containing polymer particles |
| JP2019564560A JP6773922B1 (en) | 2018-11-22 | 2019-11-20 | Fluorine-containing polymer particles |
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| JPWO2021235539A1 (en) * | 2020-05-22 | 2021-11-25 | ||
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| JPWO2020105671A1 (en) | 2021-02-15 |
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