WO2022181349A1 - 樹脂微粒子及び樹脂微粒子含有組成物 - Google Patents
樹脂微粒子及び樹脂微粒子含有組成物 Download PDFInfo
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- WO2022181349A1 WO2022181349A1 PCT/JP2022/005278 JP2022005278W WO2022181349A1 WO 2022181349 A1 WO2022181349 A1 WO 2022181349A1 JP 2022005278 W JP2022005278 W JP 2022005278W WO 2022181349 A1 WO2022181349 A1 WO 2022181349A1
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- resin
- meth
- particles
- vinyl
- fine particles
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- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- XUGNVMKQXJXZCD-UHFFFAOYSA-N isopropyl palmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC(C)C XUGNVMKQXJXZCD-UHFFFAOYSA-N 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- MDYPDLBFDATSCF-UHFFFAOYSA-N nonyl prop-2-enoate Chemical compound CCCCCCCCCOC(=O)C=C MDYPDLBFDATSCF-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QUPCNWFFTANZPX-UHFFFAOYSA-M paramenthane hydroperoxide Chemical compound [O-]O.CC(C)C1CCC(C)CC1 QUPCNWFFTANZPX-UHFFFAOYSA-M 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- RCMHUQGSSVZPDG-UHFFFAOYSA-N phenoxybenzene;phosphoric acid Chemical class OP(O)(O)=O.C=1C=CC=CC=1OC1=CC=CC=C1 RCMHUQGSSVZPDG-UHFFFAOYSA-N 0.000 description 1
- FURYAADUZGZUGQ-UHFFFAOYSA-N phenoxybenzene;sulfuric acid Chemical compound OS(O)(=O)=O.C=1C=CC=CC=1OC1=CC=CC=C1 FURYAADUZGZUGQ-UHFFFAOYSA-N 0.000 description 1
- 229930015698 phenylpropene Natural products 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000012802 pre-warming Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- WREHAFOLOOKAOW-UHFFFAOYSA-N propane-1,2,3-triol prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(O)CO.OCC(O)CO.OCC(O)CO.OCC(O)CO.OCC(O)CO WREHAFOLOOKAOW-UHFFFAOYSA-N 0.000 description 1
- 229940080818 propionamide Drugs 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 235000019337 sorbitan trioleate Nutrition 0.000 description 1
- 229960000391 sorbitan trioleate Drugs 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- GZXOHHPYODFEGO-UHFFFAOYSA-N triglycine sulfate Chemical class NCC(O)=O.NCC(O)=O.NCC(O)=O.OS(O)(=O)=O GZXOHHPYODFEGO-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 238000001195 ultra high performance liquid chromatography Methods 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000019156 vitamin B Nutrition 0.000 description 1
- 239000011720 vitamin B Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/006—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to block copolymers containing at least one sequence of polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- 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
- C08F22/00—Homopolymers and 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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
- C08F22/10—Esters
- C08F22/1006—Esters of polyhydric alcohols or polyhydric phenols, e.g. ethylene glycol dimethacrylate
-
- 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
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- 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
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L35/02—Homopolymers or copolymers of esters
-
- 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
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/08—Homopolymers or copolymers of acrylic acid esters
Definitions
- the present invention relates to resin fine particles and resin fine particle-containing compositions obtained by polymerizing vinyl-based monomers.
- additives for resin films include optical members such as light diffusion films and anti-glare films, additives for resin films used for electronic device applications, anti-blocking agents for various resin films, and additives for various resin films.
- Applications such as modifiers can be mentioned.
- Resin films used in applications such as optical members and electronic devices are required to have sophisticated properties. Typical examples of such properties include sticking prevention, high transparency, high durability, scratch resistance (scratch resistance), and the like. These properties are imparted directly to the substrate film, or imparted in a post-process such as coating. Among these properties, the anti-sticking property prevents the resin films from sticking to each other at the overlapping portions when the resin films are stored in roll form, and prevents deterioration of the slipperiness and peelability of the resin films. is an important characteristic for Addition of fine resin particles or inorganic particles as an anti-sticking agent is known as a solution to the problem of imparting anti-sticking properties to resin films.
- the anti-sticking agent examples include inorganic particles such as silica, and resin fine particles such as (meth)acrylic resin fine particles.
- Silica has the advantage of being high in hardness, and can impart anti-sticking properties with the addition of a small amount. However, due to the material, there is a demerit that a difference in refractive index occurs with the resin film, which is a factor that impairs transparency.
- resin fine particles have the advantage of being able to maintain the transparency of the resin film and impart sticking prevention properties, so that they can be used in resin films that require high quality. It was weaker in strength compared to
- Patent Literature 1 describes crosslinked resin fine particles obtained using a technique for improving strength by devising a crosslinked structure.
- Patent Literature 2 describes applying core-shell type lubricating particles to an optical film to impart anti-sticking performance while maintaining transparency.
- Patent Document 3 a matrix resin and a It is described to improve the affinity of
- An object of the present invention is to provide a resin fine particle and a resin fine particle-containing composition which are resin fine particles prepared by a simple method, which prevent falling off from a base material or a binder, and which can impart scratch resistance to a film. That is.
- the present inventors have found that resin fine particles produced by a simple method have an absorbance ratio of the maximum absorbance in a specific wavenumber range in the infrared spectrum to a specific range. By doing so, the inventors have found that the fine resin particles can be prevented from falling off from the base material and the binder, and the resin fine particles can be provided with scratch resistance to the film.
- the present invention is as follows.
- the resin fine particles of the present invention are resin fine particles that can be prepared by a simple method, yet are capable of preventing detachment from the base material or binder, and can impart scratch resistance to the film, and resin fine particles are contained.
- a composition can be provided.
- a (meth)acrylic acid ester monomer means an acrylic acid ester monomer or a methacrylic acid ester monomer
- (meth)acrylic acid means acrylic acid or methacrylic acid
- the resin fine particles of the present invention are obtained by polymerizing one or more vinyl monomers.
- the vinyl-based monomer one selected from monofunctional vinyl-based monomers having one or more vinyl groups in one molecule and polyfunctional vinyl-based monomers having two or more vinyl groups in the molecule, or Two or more types are mentioned.
- Monofunctional vinyl monomers include, for example, monofunctional (meth)acrylic monomers, monofunctional aromatic vinyl monomers, fatty acid vinyl ester monomers, halogenated olefin monomers, cyanide Vinylide-based monomers, unsaturated carboxylic acid-based monomers, unsaturated polycarboxylic acid ester-based monomers, unsaturated carboxylic acid amide-based monomers, unsaturated carboxylic acid amide-based methylol monomers, etc. is mentioned.
- These monofunctional vinyl-based monomers may be used singly or in combination of two or more.
- Examples of monofunctional (meth)acrylic acid ester monomers include methyl (meth)acrylate (methyl methacrylate, methyl acrylate), ethyl (meth)acrylate, propyl (meth)acrylate, (meth)acrylate, Isopropyl acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, (meth)acrylic acid isopentyl, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, (meth)acrylic isononyl acid, decyl (meth)acrylate, iso
- An alicyclic structure such as (meth)acrylic acid alkyl ester having 1 to 20 carbon atoms in the alkyl group, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, etc.
- examples include (meth)acrylic acid esters having a hydroxyl group in the ester portion such as acrylate, dimethylaminoethyl (meth)acrylate, and (meth)acrylic acid esters having an amino group in the ester portion such as diethylaminoethyl (meth)acrylate. .
- These monofunctional (meth)acrylic acid ester monomers may be used singly or in combination of two or more.
- the alkyl group bonded to the ester has 1 to 10 carbon atoms, methyl (meth)acrylate, ethyl (meth)acrylate, (meth) ) propyl acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, (meth)acrylic pentyl acid, isopentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, (meth)acrylate Nonyl acrylate, isononyl (meth)acrylate, and decyl acrylate, methyl (meth)acrylate, eth
- Monofunctional aromatic vinyl monomers include, for example, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene (vinyltoluene), ethylvinylbenzene, ⁇ -methylstyrene, sodium styrenesulfonate, styrene Examples include styrenesulfonates such as ammonium sulfonate, vinylnaphthalene, and allylbenzene. Among these, styrene, ⁇ -methylstyrene and sodium styrenesulfonate are preferred. These monofunctional styrene-based monomers may be used singly or in combination of two or more.
- fatty acid vinyl ester monomers examples include vinyl acetate and vinyl propionate. These fatty acid vinyl ester monomers may be used singly or in combination of two or more.
- halogenated olefinic monomers examples include vinyl chloride, vinylidene chloride, tetrafluoroethylene, and vinylidene fluoride. These halogenated olefinic monomers may be used singly or in combination of two or more.
- Vinyl cyanide-based monomers include, for example, (meth)acrylonitrile.
- Unsaturated carboxylic acid-based monomers include unsaturated carboxylic acids, their salts or anhydrides, such as (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, their ammonium and metal salts. , maleic anhydride, and the like. These unsaturated carboxylic acid-based monomers may be used singly or in combination of two or more.
- the unsaturated polycarboxylic acid ester monomers include unsaturated dicarboxylic acid monoesters, salts thereof, and unsaturated dicarboxylic acid diesters. Examples include monobutyl maleic acid, their ammonium and metal salts, maleic acid dimethyl and the like. These unsaturated polycarboxylic acid ester-based monomers may be used singly or in combination of two or more. Examples of unsaturated carboxylic acid amide-based monomers include (meth)acrylamide and diacetone (meth)acrylamide. These unsaturated carboxylic acid amide-based monomers may be used singly or in combination of two or more.
- unsaturated carboxylic acid amide methylolated monomers examples include N-methylolacrylamide, N-methylolmethacrylamide, methylolated diacetoneacrylamide, and these monomers and alcohols having 1 to 8 carbon atoms. and the like. These unsaturated carboxylic acid amide methylol compound monomers may be used singly or in combination of two or more.
- polyfunctional vinyl-based monomers examples include polyfunctional (meth)acrylic monomers, polyfunctional aromatic vinyl-based monomers, and polyfunctional allyl-based monomers. These polyfunctional vinyl-based monomers may be used singly or in combination of two or more.
- polyfunctional (meth)acrylic monomers examples include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and decaethylene glycol.
- ethylene glycol di(meth)acrylate and allyl(meth)acrylate are preferred.
- These polyfunctional (meth)acrylic monomers may be used singly or in combination of two or more.
- polyfunctional aromatic vinyl-based monomers examples include divinylbenzene, divinylnaphthalene, and derivatives thereof in which the aromatic ring is substituted with a substituent. These polyfunctional aromatic vinyl-based monomers may be used singly or in combination of two or more.
- polyfunctional allylic monomers examples include diallyl phthalate and triallyl cyanurate. These polyfunctional allylic monomers may be used singly or in combination of two or more.
- the vinyl-based monomer constituting the fine resin particles contains a polyfunctional vinyl-based monomer.
- the vinyl-based monomer constituting the fine resin particles contains a (meth)acrylic acid ester-based monomer.
- the (meth)acrylic acid ester monomer is one or more selected from the group consisting of monofunctional (meth)acrylic monomers and polyfunctional (meth)acrylic monomers.
- the vinyl-based monomer constituting the fine resin particles is preferably a mixture of a monofunctional vinyl-based monomer and a polyfunctional vinyl-based monomer.
- the resin fine particles of the present invention are preferably composed of at least one resin selected from (meth)acrylic resins, styrene resins, and (meth)acrylic-styrene resins. Thereby, resin fine particles having high light transmittance can be formed.
- the (meth)acrylic resin is a resin obtained by polymerizing one or more of (meth)acrylic acid ester monomers, or one or two (meth)acrylic acid ester monomers. It is a resin obtained by polymerizing at least one species and one or more vinyl monomers other than (meth)acrylic acid ester monomers and styrene monomers.
- the styrene resin is a resin obtained by polymerizing one or more styrene monomers, or one or more styrene monomers and a (meth)acrylic acid ester monomer. It is a resin obtained by polymerizing one or more of vinyl-based monomers other than vinyl monomers and styrene-based monomers.
- (Meth)acrylic-styrene-based resin is a resin obtained by polymerizing one or more of (meth)acrylic acid ester-based monomers and one or more of styrene-based monomers, or (meth) 1 or 2 or more acrylic acid ester monomers, 1 or 2 or more styrene monomers, and 1 or 2 or more other vinyl monomers It is a resin obtained by polymerization.
- the content of the polyfunctional vinyl-based monomer in 100 parts by mass of the vinyl-based monomer constituting the fine resin particles is not particularly limited.
- the content of the polyfunctional vinyl monomer is 51 parts by mass or more, preferably 60 parts by mass or more, more preferably 70 parts by mass or more, for example 100 parts by mass or less. , preferably 95 parts by mass or less.
- the degree of cross-linking of the resin fine particles becomes low, and when the resin fine particles are mixed with a binder and/or a solvent, the resin particles swell, and the viscosity increases and the coating workability, etc. deteriorates; Since the degree of cross-linking becomes low, there is a possibility that the fine resin particles are easily deformed and dissolved when the fine resin particles and the binder are mixed and heated for molding.
- the resin fine particles of the present invention may contain various additives.
- it may contain an antioxidant.
- Antioxidants are not particularly limited, but include, for example, sulfur-based antioxidants, phosphorus-based antioxidants, hindered phenol-based antioxidants, and lactone-based antioxidants. The antioxidant can be added during the polymerization of the fine resin particles.
- Absorbance (A) means the maximum absorbance between 1700 cm -1 and 1800 cm -1 with a straight line connecting 1700 cm -1 and 1800 cm -1 as a baseline.
- Absorbance (B) means the maximum absorbance between 1600 cm -1 and 1700 cm -1 with a straight line connecting 1600 cm -1 and 1700 cm -1 as a baseline.
- absorbance (A) and absorbance (B) can be obtained, for example, using the method described in the section [Examples].
- the absorbance ratio of the resin fine particles of the present invention is 0.020 or more, preferably 0.025 or more, and 0.060 or less, preferably 0.055 or less. If the absorbance ratio is less than 0.020, the fine resin particles may fall off from the substrate or the binder, making it impossible to impart scratch resistance to the film. If the absorbance ratio exceeds 0.060, the fine resin particles may agglomerate, and the fine resin particles may fall off from the base material or the binder, making it impossible to impart scratch resistance to the film.
- the absorbance (B) of the resin fine particles of the present invention is not particularly limited, but is, for example, 0.0040 or more, preferably 0.0045 or more, and for example, 0.0120 or less, preferably 0.0100 or less.
- the amount of unreacted vinyl-based monomer in the fine resin particles is not particularly limited. For example, it is 1.0% by mass or less, preferably 0.9% by mass or less, and more preferably 0.8% by mass or less, based on 100% by mass of the total amount of vinyl-based monomers used in the preparation of the fine resin particles. If the amount of the unreacted vinyl monomer exceeds 1.0% by mass, problems such as deterioration of optical properties, generation of residual odor, environmental pollution, and generation of foreign substances (resin scum, etc.) when using fine resin particles occur. There is a risk.
- the amount of unreacted vinyl-based monomer in the fine resin particles can be determined, for example, by the method described in the section [Examples].
- the amount of water contained in the fine resin particles is not particularly limited, but it is preferable that the fine resin particles are dried with a low water content. For example, it is 2.0% by mass or less, preferably 1.0% by mass or less, more preferably 0.5% by mass or less, based on 100% by mass of the entire fine resin particles. If the water content exceeds 2.0% by mass, unevenness may occur during molding of the fine resin particle-containing composition or formation of a coating film, and problems such as deterioration of optical properties may occur.
- the water content of the fine resin particles can be obtained, for example, by using the method described in the section [Examples].
- the volume average particle diameter of the resin fine particles is not particularly limited. For example, it is 0.01 ⁇ m or more, preferably 0.1 ⁇ m or more, and for example, 20 ⁇ m or less, preferably 15 ⁇ m or less, more preferably 10 ⁇ m or less. By setting the volume average particle size within such a range, optical properties can be improved when used as an additive for a film.
- the volume-average particle diameter of the fine resin particles refers to, for example, the arithmetic mean of the volume-based particle size distribution obtained by the method described in the [Examples] section.
- the coefficient of variation of particle size is not particularly limited. For example, it is 35.0% or less, preferably 33.0% or less. By setting the variation coefficient of the particle size of the resin fine particles within this range, the dispersion uniformity of the resin fine particles can be further improved.
- the amount of residual surfactant in the resin fine particles of the present invention with respect to 100 parts by mass of the resin fine particles is not particularly limited, and is appropriately set according to the purpose and application. For example, 0.01 parts by mass or more, preferably 0.03 parts by mass or more, more preferably 0.05 parts by mass or more, for example 1 part by mass or less, preferably 0.7 parts by mass or less, more preferably 0.5 parts by mass The range is set to parts by mass or less.
- a surfactant is used during polymerization, if the amount of the residual surfactant is less than 0.01 part by mass, the process becomes complicated and there is a risk of being disadvantageous in terms of cost and the like.
- the residual surfactant amount can be determined, for example, using the method described in the section [Examples].
- the method for producing the resin fine particles of the present invention is not particularly limited. for example, (i) a polymerization step of polymerizing a vinyl-based monomer in a liquid medium in the presence of a surfactant and a polymerization initiator to obtain a crude product containing resin fine particles containing the surfactant and the medium; , (ii) a solid-liquid separation step of removing the medium contained in the crude product using a filter medium; (iii) a cleaning step of removing the cleaning liquid after contacting the fine resin particles with the cleaning liquid; (iv) optionally, a drying step and/or a classification step; is preferred.
- a polymerization step of polymerizing a vinyl-based monomer in a liquid medium in the presence of a surfactant and a polymerization initiator to obtain a crude product containing resin fine particles containing the surfactant and the medium
- a solid-liquid separation step of removing the medium contained in the crude product using a filter medium
- the polymerization method in the polymerization step is not particularly limited.
- suspension polymerization, seed polymerization, seed emulsion polymerization, emulsion polymerization, soap-free polymerization, mini-emulsion polymerization, using a vinyl monomer, a polymerization initiator and a liquid medium, and optionally using a surfactant, and Polymerization methods such as dispersion polymerization can be used.
- the number of remaining reactive groups tends to decrease. This is probably because the frequency of contact with radicals increases, but is not limited to this.
- the vinyl-based monomer used in the polymerization of the resin fine particles of the present invention include the vinyl-based monomers described in [Resin Fine Particles].
- Polymerization initiator There are no particular restrictions on the polymerization initiator used when the resin fine particles of the present invention are produced by a polymerization method such as emulsion polymerization, seed emulsion polymerization, or soap-free polymerization.
- a thermally decomposable water-soluble polymerization initiator is used.
- heat-decomposable water-soluble polymerization initiators include persulfates such as potassium persulfate, ammonium persulfate, lithium persulfate and sodium persulfate, hydrogen peroxide, and water-soluble azo polymerization initiators.
- water-soluble azo polymerization initiator polymerization initiators that have been generally used for emulsion polymerization and the like can be used, and newly developed polymerization initiators that are used for emulsion polymerization and the like can also be used.
- water-soluble azo polymerization initiators include, for example, VA-080 (2,2′-azobis(2-methyl-N-(1,1-bis(hydroxymethyl)-2-hydroxyethyl)propionamide) ), VA-086 (2,2′-azobis(2-methyl-N-(2-hydroxyethyl)-propionamide)), VA-057 (2,2′-azobis(2-(N-(2- carboxyethyl)amidino)propane)), VA-058 (2,2′-azobis(2-(3,4,5,6-tetrahydropyrimidin-2-yl)propane)dihydrochloride), VA-060 (2 , 2′-azobis(2-(1-(2-hydroxyethyl)-2-imidazolin-2-yl)propane) dihydrochloride), V-50 (2,2′-azobis(2-amidinopropane) dihydrochloride ), V-501 (4,4'-azobis (4-cyanopentanoic
- a water-soluble azo polymerization initiator is preferable because it has little effect on the slurry pH after polymerization and can suppress the aggregation of particles and the generation of coarse particles due to a decrease in dispersibility, and further from the viewpoint of improving the dispersibility of resin fine particles. Therefore, it is preferable that the hydroxyl group is present at the terminal of the polymerization initiator. Further, among the water-soluble azo polymerization initiators, from the viewpoint of reducing the electrical conductivity of the fine resin particle dispersion, halogen-free initiators are more preferable, and VA-086 and VA-057 are particularly preferable because of their good water solubility. .
- a known polymerization initiator can be used without particular limitation, but a thermally decomposable oil-soluble polymerization initiator is preferably used. is good.
- cumene hydroperoxide di-tert-butyl peroxide, dicumyl peroxide, benzoyl peroxide, lauroyl peroxide, dimethylbis(tert-butylperoxy)hexane, dimethylbis(tert-butylperoxy)hexyne- 3, bis(tert-butylperoxyisopropyl)benzene, bis(tert-butylperoxy)trimethylcyclohexane, butyl-bis(tert-butylperoxy)valerate, tert-butyl 2-ethylhexaneperoxyate, dibenzoyl peroxide , organic peroxides such as paramenthane hydroperoxide and tert-butyl peroxybenzoate; 2,2′-azobisisobutyronitrile, 2,2′-azobis(2-methylbutyronitrile), 2,2 '-azobis(2-isopropylbutyronitrile), 2,2'
- the amount of the polymerization initiator used can be appropriately determined according to its type, and is not particularly limited. For example, 0.1 parts by mass or more, preferably 0.3 parts by mass or more, for example 5 parts by mass or less, preferably 3 parts by mass or less, relative to 100 parts by mass of the total amount of all monomers used during polymerization. is within the range of
- An anionic surfactant can be used in the polymerization of the resin fine particles of the present invention.
- Anionic surfactants are classified into reactive surfactants having a reactive group such as a vinyl group and non-reactive surfactants having no reactive group.
- the anionic non-reactive surfactant any of known anionic surfactants such as fatty acid salt type, sulfate type, sulfonate type, and phosphate type can be used.
- alkylsulfuric acid ester salts such as sodium lauryl sulfate and ammonium lauryl sulfate
- alkylbenzenesulfonates such as sodium dodecylbenzenesulfonate
- dialkylsulfosuccinates such as sodium dioctylsulfosuccinate and sodium di(2-ethylhexyl)sulfosuccinate
- sodium oleate castor oil potash soap
- fatty acid soaps such as castor oil potash soap
- alkylnaphthalenesulfonates alkanesulfonates
- phosphate ester-based anionic surfactant for example, AL, A210G, A208F, etc. of Plysurf (registered trademark) manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
- Plysurf registered trademark
- Phosphanol registered trademark manufactured by Toho Chemical Industry Co., Ltd.
- anionic reactive surfactants include JS-20 and RS-3000 of Eleminol (registered trademark) manufactured by Sanyo Kasei Co., Ltd., and KH-10 and KH of Aqualon (registered trademark) manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
- Kao Corporation registered one or two selected from the group consisting of S-120, S-180A, S-180, PD-104 of ADEKA Corporation, SR-1025, SE-10N of Adekaria Soap (registered trademark) manufactured by ADEKA, etc.
- Kao Corporation registered one or two selected from the group consisting of S-120, S-180A, S-180, PD-104 of ADEKA Corporation, SR-1025, SE-10N of Adekaria Soap (registered trademark) manufactured by ADEKA,
- a nonionic surfactant can be used in the polymerization of the resin fine particles of the present invention.
- Nonionic surfactants are classified into reactive surfactants having a reactive group such as a vinyl group and non-reactive surfactants having no reactive group.
- any of known nonionic surfactants such as ester type, ether type and ester/ether type can be used.
- polyoxyalkylene alkyl ether such as polyoxyalkylene tridecyl ether in which the alkylene group has 3 or more carbon atoms; fatty acid ester such as sorbitan fatty acid ester, glycerin fatty acid ester, isopropyl palmitate, sorbitan trioleate; polyoxyethylene Styrenated phenyl ether; Polyoxyethylene styrenated phenyl ether (for example, Noigen EA series manufactured by Daiichi Kogyo Seiyaku Co., Ltd.); Polyoxyethylene alkyl ethers such as polyoxyethylene tridecyl ether; Oxyethylene alkylphenyl ether series; polyoxyethylene fatty acid esters; polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate; polyoxyethylene alkylamines; oxyethylene-oxypropylene block polymers; One or two or more selected from the group consisting of polyoxyethylene alkylphenyl
- nonionic reactive surfactants include alkyl ether-based surfactants (e.g., ADEKA ADEKA ARISOAP ER-10, ER-20, ER-30, ER-40, Kao Corporation Latemul PD-420, PD -430, PD-450, etc.); 20, AN-30, AN-5065, ADEKA Adekaria Soap NE-10, NE-20, NE-30, NE-40, etc.); 564, RMA-568, RMA-1114, etc.).
- alkyl ether-based surfactants e.g., ADEKA ADEKA ARISOAP ER-10, ER-20, ER-30, ER-40, Kao Corporation Latemul PD-420, PD -430, PD-450, etc.
- 564, RMA-568, RMA-1114, etc. those having
- the amount of the surfactant used is not particularly limited, but is, for example, 0.01 to 10 parts by mass with respect to 100 parts by mass of the vinyl monomer. If the total amount of the surfactant is less than the above range, the polymerization stability may be lowered, and it may be difficult to adjust the amount of the surfactant contained in the fine resin particles. Further, if the amount of the surfactant used is larger than the above range, it is uneconomical in terms of cost, and it becomes difficult to adjust the amount of each surfactant contained in the resin fine particles within the specified range. There is a risk.
- liquid medium used to prepare the resin fine particles of the present invention is not particularly limited.
- water, organic solvents, and mixtures thereof can be used.
- an aqueous medium is preferable, and for example, water, lower alcohols having 5 or less carbon atoms such as methyl alcohol and ethyl alcohol, mixtures of water and lower alcohols, and the like can be used.
- a method for polymerizing the vinyl-based monomer is not particularly limited. Examples include known polymerization methods such as suspension polymerization, emulsion polymerization, seed polymerization, seed emulsion polymerization, soap-free polymerization, miniemulsion polymerization, and dispersion polymerization. Suspension polymerization makes it possible to obtain fine resin particles having a small particle size and a small variation in particle size (the particle size is relatively uniform). Emulsion polymerization can reduce the variation in particle size of the obtained resin fine particles. Resin fine particles obtained by seed polymerization have little variation in particle size, and when used for optical members such as antiglare films and light diffusion films, can improve optical properties such as antiglare properties and light diffusion properties of optical members.
- Suspension polymerization, emulsion polymerization, or seed polymerization is preferred, and seed polymerization is most preferred, since the resulting resin fine particles have little variation in particle size.
- a general method of seed polymerization will be described below, but the polymerization method in the production method of the present invention is not limited to this method.
- an emulsion (suspension) containing an aqueous medium, a vinyl monomer, and a surfactant is prepared.
- the aqueous medium is water or a mixture of water and organic solvent.
- a known method can be used to prepare the emulsion (suspension).
- an emulsified liquid can be obtained by adding a vinyl-based monomer and a surfactant to an aqueous medium and dispersing the mixture with a fine emulsifier such as a homogenizer, an ultrasonic processor, or Nanomizer (registered trademark). It is preferable that the particle size of the droplets of the vinyl-based monomer present in the obtained emulsion is smaller than the particle size of the seed particles to be added next, because the droplets are efficiently absorbed by the seed particles.
- seed particles are added to the resulting emulsion (suspension).
- the seed particles may be added to the emulsion as they are, or may be added to the emulsion in the form of being dispersed in an aqueous medium.
- the seed particles absorb the vinyl-based monomer.
- a method for allowing the seed particles to absorb the vinyl-based monomer a method of stirring the emulsified liquid at room temperature (about 20° C.) for 1 to 12 hours is usually mentioned.
- the emulsion may be heated to about 30 to 50° C. in order to promote the absorption of the vinyl-based monomer into the seed particles.
- the seed particles When the seed particles absorb the vinyl-based monomer, the seed particles swell.
- the mixing ratio of the vinyl-based monomer and the seed particles is preferably in the range of, for example, 5 to 300 parts by mass of the vinyl-based monomer per 1 part by mass of the seed particles.
- the end of the absorption of the vinyl-based monomer into the seed particles can be determined by observing the particle diameter with an optical microscope.
- the vinyl-based monomer absorbed by the seed particles is polymerized to obtain fine resin particles.
- the resin fine particles may be obtained by repeating the step of allowing the seed particles to absorb the vinyl-based monomers and polymerizing them a plurality of times.
- a polymerization initiator may be used in the polymerization of the vinyl-based monomer.
- the polymerization initiator may be mixed in advance with the vinyl-based monomer and then dispersed in the aqueous medium, or both the polymerization initiator and the vinyl-based monomer may be separately dispersed in the aqueous
- the polymerization temperature and polymerization time for seed polymerization can be appropriately selected depending on the type of vinyl monomer and the type of polymerization initiator used as necessary.
- the polymerization temperature is, for example, 25 to 110° C.
- the polymerization time is, for example, 1 to 12 hours.
- the polymerization reaction of seed polymerization may be carried out under an atmosphere of an inert gas (for example, nitrogen) that is inert to the polymerization.
- the polymerization reaction of the seed polymerization is preferably carried out by raising the temperature after the vinyl-based monomer and optionally used polymerization initiator are completely absorbed by the seed particles. .
- a polymer dispersion stabilizer may be added to the polymerization reaction system in order to improve the dispersion stability of the fine resin particles.
- Polymer dispersion stabilizers include, for example, polyvinyl alcohol, polycarboxylic acids, celluloses, polyvinylpyrrolidone, and the like.
- the polymer dispersion stabilizer may be used in combination with an inorganic water-soluble polymer compound such as sodium tripolyphosphate.
- an inorganic water-soluble polymer compound such as sodium tripolyphosphate.
- the amount of polymer dispersion stabilizer to be added is preferably in the range of 1 to 10 parts by weight per 100 parts by weight of the vinyl monomer.
- nitrites such as sodium nitrite, sulfites, hydroquinones, ascorbic acids, water-soluble vitamin B
- a water-soluble polymerization inhibitor such as citric acid, polyphenols, etc. may be added to the aqueous medium.
- the amount added is preferably in the range of 0.02 to 0.2 parts by weight per 100 parts by weight of the vinyl monomer.
- the method for producing seed particles used for seed polymerization is not particularly limited, and dispersion polymerization, emulsion polymerization, soap-free emulsion polymerization (emulsion polymerization that does not use a surfactant as an emulsifier), seed polymerization, suspension polymerization, etc. may be used. can be done.
- Solid-liquid separation step for producing the resin fine particles of the present invention, the medium and the like are removed from the crude product containing the resin fine particles, the surfactant and the medium obtained in the polymerization step using a filter equipped with a filter medium. is a step of solid-liquid separation of the resin fine particles.
- a filter is not specifically limited.
- a pressurized filter that includes a pressure vessel, a filter medium arranged at the inner bottom of the pressure vessel, and a compressed gas feeder that supplies compressed gas into the pressure vessel.
- the filter medium is not particularly limited as long as it can reliably collect resin fine particles.
- filter cloth such as woven fabric or non-woven fabric made of natural fiber, synthetic fiber, etc., wire mesh made of sintered metal, non-woven fabric made of sintered metal, filter plate (perforated plate) made of natural fiber, glass fiber, etc., synthetic
- One or more selected from the group consisting of a net made of resin, filter paper, glass fiber filter, etc., is preferred, and filter cloth is particularly preferred.
- the amount of medium passing through the filter medium per unit time by controlling the amount of medium passing through the filter medium per unit time, the pressurization conditions, the dewatering speed when removing the medium, etc., the amount of residual surfactant in the resin fine particles and the non-volatile
- the amount of ingredients can be easily adjusted.
- the washing step in producing the resin microparticles of the present invention is a step of contacting the resin microparticles after the solid-liquid separation step with the washing liquid and then removing the washing liquid to obtain the washed resin microparticles.
- the resin fine particle cake obtained in the solid-liquid separation step is immersed in a cleaning liquid having a volume of 10 times or less, preferably 1.5 to 7 times the volume of the resin fine particle cake, and then removing the cleaning liquid.
- a means for removing the washing liquid for example, a means of repeating the washing treatment of removing the washing liquid by centrifugation using a centrifuge as necessary can be mentioned.
- a means for washing by contacting a cake of fine resin particles on a filter medium with a washing liquid using a pressure filter eliminates the short pass of the washing liquid, suppresses the amount of washing liquid used, and performs washing efficiently. be able to.
- the cleaning liquid can be removed by, for example, introducing a compressed gas into the pressurized filter and pressurizing it to bring the cake into contact with the cleaning liquid, and discharging the cleaning liquid after cleaning as filtrate.
- the amount of residual surfactant and the amount of non-volatile components contained in the resin fine particles can be adjusted by adjusting the number of centrifugal separations, the amount of washing liquid added, the amount of medium that passes through the filter media (ejection amount), etc. .
- the washing liquid used in the washing step is preferably an aqueous medium, and examples thereof include water, lower alcohols having 5 or less carbon atoms such as methyl alcohol and ethyl alcohol, and mixtures thereof. In particular, it is preferable to use the same medium as used in the polymerization step.
- the weight of the washing liquid used in the washing step is 10 times or less, preferably 1.5 to 7 times the weight of the fine resin particles to be washed. Thereby, it is possible to prevent the surfactant from eluting more than necessary in the washing process.
- the filtration rate of the washing liquid is not particularly limited, and is, for example, in the range of 0.025 to 0.095 kg/min ⁇ m 2 .
- the temperature of the washing liquid used for washing is a temperature at which the surfactant used in the polymerization is sufficiently eluted, and is, for example, in the range of 40 to 80.degree.
- the conductivity of the washing liquid that passed through the filter medium was 2.0 times or less that of the washing liquid before being put into the filter, and the internal pressure of the pressurized filter was 2/3 or less of the pressure during pressurization. It is preferable to terminate when
- the fine resin particles obtained in the washing step are preferably dried in a drier to remove the washing liquid and, if necessary, classified.
- the dryer is not particularly limited, but for example, a spray dryer (spray dryer), a freeze dryer, or a vacuum stirring dryer (crushing dryer) incorporating stirring blades is preferable, and suitable drying is performed according to the particle size and composition. You can choose your device.
- the washing liquid is almost completely removed, and if necessary, the particles are classified (preferably by airflow classification) to obtain fine resin particles that can be used as products.
- the drying conditions in the present invention are appropriately adjusted according to the capacity, performance, etc. of the dryer to be used. For example, the degree of vacuum (vs.
- the drying step the surfactant is eluted from the surface of the fine resin particles into water, and then a crushing dryer can be used to remove non-volatile components together with water. This makes it possible to adjust the amount of residual surfactant in the fine resin particles and the like. For example, by pre-warming the resin fine particle cake after washing, it is possible to easily adjust the surfactant on the particle surface to a specified amount. In addition, the crushing drying process shears the non-volatile components so that most of them are fractionated.
- the surface of the fine resin particles is effectively modified by the residual surfactant, and fine resin particles having excellent dispersion uniformity and improved dispersibility can be obtained.
- an appropriate amount of the residual surfactant attached to the fine resin particles in the polymerization process can be removed together with the medium and the cleaning liquid, and the content (residual amount) of the non-volatile component can also be adjusted to an appropriate amount. becomes possible.
- the resin fine particle-containing composition of the present invention contains the resin fine particles of the present invention, a photopolymerization initiator and an ultraviolet curable resin.
- the photopolymerization initiator contained in the resin fine particle-containing composition of the present invention is particularly limited as long as it is a compound capable of generating radicals in the composition by irradiation with light or ultraviolet rays and initiating polymerization of the ultraviolet curable resin. not. It is preferable to use a photopolymerization initiator suitable for the ultraviolet curable resin to be used.
- photopolymerization initiators include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, ⁇ -hydroxyalkylphenones, ⁇ -aminoalkylphenones, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds, fluoroamine compounds, aromatic sulfoniums, onium salts, borate salts, active halogen compounds, ⁇ -acyl oxime esters, etc. Two or more kinds can be used.
- the amount of the photopolymerization initiator used is, for example, 0.5 parts by mass or more, preferably 1.0 parts by mass or more, and for example, 20.0 parts by mass or less, preferably 5.0 parts by mass or more, relative to 100 parts by mass of the ultraviolet polymerizable resin. It is 0 mass part or less.
- the ultraviolet curable resin contained in the resin fine particle-containing composition of the present invention is appropriately selected according to required properties such as transparency, dispersibility of resin fine particles, light resistance, moisture resistance and heat resistance. , is not particularly limited.
- one or more selected from the group consisting of polyfunctional (meth)acrylate resins, polyfunctional urethane (meth)acrylate resins, polyfunctional polyester (meth)acrylate resins, epoxy (meth)acrylate resins, alkyd resins, etc. includes.
- the UV-curable resin preferably contains a polyfunctional (meth)acrylate resin, and more preferably contains a polyhydric alcohol polyfunctional (meth)acrylate having 3 or more (meth)acryloyl groups in one molecule.
- Polyhydric alcohol polyfunctional (meth)acrylates having 3 or more (meth)acryloyl groups in one molecule include, for example, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, 1,2 , 4-cyclohexane tri(meth)acrylate, pentaglycerol triacrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetra(meth) One or two or more selected from the group consisting of acrylates, dipentaeryth
- the resin fine particle-containing composition may contain components other than the resin fine particles, the photopolymerization initiator, and the ultraviolet curable resin, if necessary.
- resin fine particles and resins other than ultraviolet curable resins (vinyl resins such as cellulose resins, vinyl acetate resins, vinyl chloride resins, vinylidene chloride resins, acetal resins, (meth)acrylic resins, polystyrene resins, etc.) one or more selected from the group consisting of resins, polyamide resins, linear polyester resins, polycarbonate resins, etc.).
- It may also contain, for example, a reactive diluent as a solvent. Examples of the reactive diluent include one or more vinyl monomers.
- the vinyl monomer used as the reactive diluent is selected from, for example, monofunctional (meth)acrylic monomers and polyfunctional (meth)acrylic monomers used in the polymerization of the fine resin particles of the present invention. 1 type or 2 types or more are mentioned. Furthermore, it may contain inorganic particles such as silica, a coloring agent, an organic solvent, and the like. In addition, it is preferable that the amount of the organic solvent is very small, and usually it is preferable not to use the organic solvent.
- the amount of resin fine particles in the resin fine particle-containing composition is not particularly limited.
- 100 parts by mass of the solid content of the ultraviolet curable resin for example, 2 parts by mass or more, preferably 4 parts by mass or more, more preferably 6 parts by mass or more, 300 parts by mass or less, preferably 200 parts by mass or less, more Preferably, it is 100 parts by mass or less.
- optical properties such as matte properties of the layer (coating film) formed by the resin composition containing the resin fine particles can be improved.
- the properties can be exhibited sufficiently, and optical properties such as anti-glare property and light diffusion property of the optical member obtained by coating the resin composition containing resin fine particles on the substrate can be made sufficient.
- the content is 300 parts by mass or less, the layer (coating film) formed from the fine resin particle-containing composition tends to have sufficient linear transmittance.
- the method of applying the resin fine particle-containing composition onto the substrate is not particularly limited.
- known coating methods such as bar coating, blade coating, spin coating, reverse coating, die coating, spray coating, roll coating, gravure coating, micro gravure coating, lip coating, air knife coating, and dip coating can be used. can.
- the resin fine particle-containing composition After applying the resin fine particle-containing composition to form a layer of the resin composition on the substrate, it can be dried and cured by irradiation with active energy rays.
- active energy rays include ultraviolet rays and infrared rays emitted from light sources such as LEDs and high-pressure mercury lamps, electron rays emitted from electron beam accelerators, ⁇ rays, ⁇ rays, and ⁇ rays.
- the thickness (dry thickness) of the layer (coating film) formed from the resin composition containing fine resin particles is not particularly limited, and can be appropriately adjusted according to the purpose, desired properties, and the like. For example, it is 1 ⁇ m or more, preferably 3 ⁇ m or more, and for example, 10 ⁇ m or less, preferably 7 ⁇ m or less.
- the resin fine particles of the present invention can be used in various applications other than the resin fine particle-containing composition.
- a molding resin composition containing fine resin particles and a resin is formed and used to obtain an optical film such as an antiglare film or a light diffusion film or an optical member such as a light diffuser, particularly an antiglare member. be able to.
- a resin molded article can be obtained by molding the resin fine particles themselves or a mixture of the resin particles and the resin.
- an optical member can be formed by providing a layer on a base material by coating the resin fine particle-containing composition.
- the optical member include a light diffusion film or an antiglare film for light diffusion or antiglare.
- the substrate is preferably transparent.
- transparent substrates include glass, polyester-based resins, cellulose-based resins, polycarbonate-based resins, (meth)acrylic-based resins, cyclic polyolefin-based resins, mixtures containing one or more of these resins, and these. can be used as a base material. Among these, those having a particularly low birefringence are preferably used.
- those substrates provided with an easy-adhesion layer of (meth)acrylic resin, polyurethane resin, or the like on at least one surface of these substrates can be used as the substrate.
- the thickness of the base material can be determined as appropriate, but is generally within the range of 10 to 500 ⁇ m from the viewpoints of strength, workability such as handling, and thinness. It is preferably 20 to 300 ⁇ m, more preferably 30 to 200 ⁇ m.
- the substrate may contain additives. Examples of additives include ultraviolet absorbers, infrared absorbers, antistatic agents, refractive index modifiers, enhancers, and the like.
- the resin fine particles of the present invention can be used alone or mixed with other resins to prepare resin moldings by various molding methods.
- a transparent resin can be preferably used, and the fine resin particles can function as light diffusion particles in the resin molding.
- the resin molded body functions as a light diffuser such as a light diffusion plate, and can be used as an LED lighting cover or the like.
- transparent resins include (meth)acrylic resins, polycarbonate resins, polystyrene resins, (meth)acrylic-styrene resins (copolymers of (meth)acrylic acid esters and styrene), and the like. 1 type or 2 or more types selected can be used.
- the amount of the resin fine particles contained in the resin molding is in the range of 0.01 to 5 parts by mass, preferably in the range of 0.01 to 5 parts by mass with respect to 100 parts by mass of the transparent resin. It can be in the range of 0.1 to 5 parts by mass.
- the resin molding may contain additives such as ultraviolet absorbers, antioxidants, heat stabilizers, light stabilizers, and fluorescent brighteners, if necessary.
- the thickness, shape, etc. of the resin molding can be appropriately selected depending on the application.
- the resin molding can be obtained by melt-kneading the transparent resin and the fine resin particles using a single-screw extruder, a twin-screw extruder, or the like.
- the resin composition obtained by melt-kneading may be molded into a plate shape through a T-die and a roll unit to obtain a resin molding.
- the resin composition obtained by melt-kneading may be pelletized, and the pellets may be molded by injection molding, press molding, or the like to obtain a resin molding.
- the resin molding containing the fine resin particles of the present invention is excellent in the uniformity of dispersion of the fine resin particles, and exhibits optical properties such as uniform light diffusion and anti-glare properties.
- the intensity of the infrared absorption spectrum obtained by measurement changes depending on the degree of adhesion between the sample and the high-refractive-index crystal.
- the measurement was performed with The infrared absorption spectrum obtained under the above conditions is peak-processed as follows, and the maximum peak height (maximum absorbance) (A) at a wave number of 1700 cm -1 to 1800 cm -1 and a wave number of 1600 cm -1 to 1700 cm -1
- the maximum peak height (maximum absorbance) (B) of was determined.
- the maximum absorbance (A) at a wave number of 1700 cm ⁇ 1 to 1800 cm ⁇ 1 obtained from the infrared absorption spectrum was the absorbance corresponding to the absorption spectrum derived from the C ⁇ O stretching vibration of the ester group. In this absorbance measurement, peak separation was not performed even when other absorption spectra overlapped from 1700 cm ⁇ 1 to 1800 cm ⁇ 1 .
- Absorbance (A) means the maximum absorbance between 1700 cm -1 and 1800 cm -1 with the straight line connecting 1700 cm -1 and 1800 cm -1 as the baseline.
- Absorbance (B) means the maximum absorbance between 1600 cm -1 and 1700 cm -1 with a straight line connecting 1600 cm -1 and 1700 cm -1 as a baseline.
- the maximum peak height (maximum absorbance) (B) from ⁇ 1 to 1700 cm ⁇ 1 was used, and the absorbance ratio was calculated from (Equation 1).
- (Formula 1) absorbance ratio (B) / (A)
- Coulometric titration was performed by the Karl Fischer method according to JIS K0113 using a trace moisture measuring device (Mitsubishi Chemical Analytech CA-310 type) to measure the moisture content of the resin fine particles.
- ⁇ Amount of unreacted vinyl-based monomer in fine resin particles > 5 mL of methanol is added to 0.01 g of the fine resin particles, and the mixture is thoroughly mixed and left to stand for 24 hours to obtain a dispersion liquid. Then, the dispersion is treated with a centrifuge at a stirring speed of 18500 rpm for 30 minutes to precipitate insoluble matter. By analyzing 2 ⁇ L of the obtained supernatant with an ultra-high performance liquid chromatogram La Chrom Ultra (manufactured by Hitachi High-Technologies Corporation), the residual monomer amount relative to the resin microparticles is measured. As for the measurement conditions, a La Chrom Ultra C18 2 ⁇ m column is used, and the column temperature is 40°C. The solvent used was a mixture of 0.05% aqueous trifluoroacetic acid and acetonitrile (50/50 w/w) with a flow rate of 0.6 mL/min.
- the resin fine particles were extracted with a solvent and measured using a liquid chromatograph linear ion trap mass spectrometer (LC/MS/MS device).
- LC/MS/MS device liquid chromatograph linear ion trap mass spectrometer
- UHPLC ACCELA manufactured by Thermo SCIENTIFIC
- Linear Ion Trap LC/MSn LXQ manufactured by Thermo SCIENTIFIC
- the surfactant content is measured by the method described below. After accurately weighing about 0.01 g of the fine resin particles into a centrifuge tube, the extract is added, the resin fine particles and the extract are well mixed, ultrasonically extracted, mixed again, and centrifuged. The obtained supernatant was filtered and used as the test solution.
- the method for preparing a calibration curve is as follows.
- volume-average particle size and number-average particle size of the fine resin particles were measured with a laser diffraction scattering type particle size distribution analyzer (model number “LS230”, manufactured by Beckman Coulter, Inc.). Specifically, 0.1 g of resin fine particle aqueous dispersion (solid content: 20%) and 20 ml of 2 mass % anionic surfactant solution were put into a test tube.
- the refractive index of the resin fine particles is the average value obtained by weighting and averaging the refractive indices of the homopolymers of each monomer by the amount of each monomer used. was used. From the measurement results, a volume-based particle size distribution of the fine resin particles was obtained. The arithmetic mean of the volume-based particle size distribution was taken as the volume-average particle size of the fine resin particles.
- Variation coefficient of volume average particle size of resin fine particles [(standard deviation of volume-based particle size distribution of resin fine particles)/(volume average particle diameter of resin fine particles)] ⁇ 100
- Example 1 ⁇ Production of fine resin particles> 320 parts of ion-exchanged water and 0.2 parts of Aqualon AR-1025 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) were mixed in a polymerization vessel equipped with a stirrer, a thermometer and a cooling mechanism. In another container, 3.8 parts of methyl methacrylate and 0.2 parts of ethylene glycol dimethacrylate were mixed, charged into a polymerization vessel, and stirred at 8000 rpm for 10 minutes with a TK homomixer (manufactured by Primix) to obtain a single polymer. A polymer mixture was obtained.
- TK homomixer manufactured by Primix
- ethylene glycol dimethacrylate was mixed well, added to the surfactant solution, and stirred at 8000 rpm for 10 minutes with a TK homomixer (manufactured by Primix) to obtain a monomer mixture (2 ).
- the monomer mixed solution (2) was charged into the slurry (1) maintained at 85° C. in the polymerization vessel over a period of 2 hours in 8 divided portions. Then, after an aging process for 1 hour, the temperature was raised to 100° C., held for 3 hours, and then cooled to prepare a slurry containing fine resin particles.
- the resin fine particle-containing slurry was passed through a nylon mesh of 400 mesh to classify the resin fine particles, thereby obtaining a classified resin fine particle slurry.
- the classified resin fine particle slurry is spray-dried using a spray dryer (manufactured by Sakamoto Giken Co., Ltd., machine name: spray dryer, model: atomizer take-up method, model number: TRS-3WK) under the following equipment conditions. , an aggregate of fine resin particles was obtained.
- a spray dryer manufactured by Sakamoto Giken Co., Ltd., machine name: spray dryer, model: atomizer take-up method, model number: TRS-3WK
- Example 2 In the production conditions of the resin fine particles described in Example 1, except that 36 parts of ethylene glycol dimethacrylate used in preparing the monomer mixture (2) was changed to 34 parts of ethylene glycol dimethacrylate and 2 parts of styrene, By treating under the same conditions as in Example 1, the desired resin fine particles were obtained. Table 1 shows the physical properties and evaluation results of the obtained resin fine particles.
- Example 3 Except for changing the 36 parts of ethylene glycol dimethacrylate used in preparing the monomer mixture (2) to 24 parts of ethylene glycol dimethacrylate and 12 parts of methyl methacrylate under the conditions for producing resin fine particles described in Example 1. was treated under the same conditions as in Example 1 to obtain the desired resin fine particles. Table 1 shows the physical properties and evaluation results of the obtained resin fine particles.
- Example 4 6 parts of magnesium pyrophosphate and 0.04 part of sodium lauryl sulfate were mixed with 70 parts of ion-exchanged water in a polymerization vessel equipped with a stirrer, a thermometer and a cooling mechanism. In another container, 20 parts of ethylene glycol dimethacrylate and 0.12 parts of 2,2′-azobis(2,4-dimethylvaleronitrile) were mixed well, charged into the polymerization vessel, and TK homomixer (manufactured by Primix Co., Ltd.) ) at 7,000 rpm for 5 minutes to obtain a monomer mixture.
- TK homomixer manufactured by Primix Co., Ltd.
- the resulting monomer mixed solution was treated with a microfluidizer at 20 MPa and charged again into the polymerization vessel. After purging the polymerization vessel with nitrogen for 5 minutes, the temperature was raised to 55° C. and the reaction was carried out for 4 hours. After aging for 1 hour, the temperature was raised to 100° C. and polymerization was carried out for 3 hours. After cooling and taking out the resulting resin fine particle-containing slurry, the particles and the supernatant were separated by a centrifugal separator, and only the supernatant was removed.
- the washing process of similarly separating the particles with a centrifuge and removing the supernatant was repeated, and the washing was finished when the conductivity of the supernatant became 15 ⁇ S or less. .
- the resulting particles were dried in a vacuum oven to obtain a dry powder.
- the obtained dry powder was subjected to an air classification treatment by a turbo classifier (manufactured by Nisshin Engineering Co., Ltd.) to obtain the target resin fine particles.
- Table 1 shows the physical properties and evaluation results of the obtained resin fine particles.
- Example 5 Under the conditions for producing fine resin particles described in Example 4, 20 parts of ethylene glycol dimethacrylate used in preparing the monomer mixture (2) was added to 18 parts of ethylene glycol dimethacrylate and 2 parts of pentaerythritol tetrakisthioglycolate. Except for the change, the treatment was carried out under the same conditions as in Example 4 to obtain the desired resin fine particles. Table 1 shows the physical properties and evaluation results of the obtained resin fine particles.
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Abstract
Description
このうち、樹脂フィルム用の添加剤としては、光拡散フィルムや防眩フィルム等の光学部材や電子デバイス用途に使用される樹脂フィルム用の添加剤、各種樹脂フィルムのアンチブロッキング剤、各種樹脂フィルムの改質剤等の用途が挙げられる。
これらの特性のうち、貼り付き防止性は、樹脂フィルムをロール状で保管した際に、重なり部分に生じる樹脂フィルム同士の貼り付きを防止し、樹脂フィルムの滑り性や剥離性の悪化を防止するために重要な特性である。樹脂フィルムに貼り付き防止性を付与する課題に対して、貼り付き防止剤として樹脂微粒子や無機粒子を添加することが知られている。
シリカは、硬度が高いことがメリットであり、少量の添加で貼り付き防止性を付与できる。しかしながら、その材質上、樹脂フィルムとの間に屈折率差が生じてしまい、透明性を損なう要因となるデメリットが存在する。
一方、樹脂微粒子は、樹脂フィルムの透明性を維持して、かつ貼り付き防止性を付与できる点から、高度な品質を要求される樹脂フィルム等においても使用できる点がメリットであるが、無機粒子と比較すると強度に劣っていた。
特許文献2には、コアシェル型の滑性粒子を光学フィルムに適用して、透明性を維持しつつ貼り付き防止性能を付与することが記載されている。
特許文献3には、ヒドロキシル基、エポキシ基、カルボキシル基、及びアルコキシシリル基から選ばれる少なくとも1つの反応性官能基と、エチレン性不飽和基とを有する樹脂微粒子を使用することで、マトリックス樹脂との親和性を向上させることが記載されている。
すなわち、本発明は、具体的には以下のとおりである。
[1] ビニル系単量体の1種又は2種以上を重合して得られ、
赤外分光光度計によるATR法で測定した赤外分光スペクトルにおいて、波数1700cm-1~1800cm-1の最大ピーク高さ(極大吸光度)(A)と波数1600cm-1~1700cm-1の最大ピーク高さ(極大吸光度)(B)との吸光度比(B)/(A)が0.020~0.060の範囲にある、樹脂微粒子。
[2] 前記ビニル系単量体が、多官能ビニル系単量体を含む、[1]に記載の樹脂微粒子。
[3] 前記ビニル系単量体が、(メタ)アクリル酸エステル系単量体を含む、[1]又は[2]に記載の樹脂微粒子。
[4] 前記ビニル系単量体100質量部中、多官能ビニル系単量体の含有量が51質量部~100質量部の範囲である、[1]~[3]のいずれか1項に記載の樹脂微粒子。
[5] 前記樹脂微粒子中の未反応のビニル系単量体量が1.0質量%以下である、[1]~[4]のいずれか1項に記載の樹脂微粒子。
[6] 前記樹脂微粒子が、含有水分量2.0質量%以下の乾燥粉体である、[1]~[5]のいずれか1項に記載の樹脂微粒子。
[7] [1]~[6]のいずれか1項に記載の樹脂微粒子、光重合開始剤及び紫外線硬化型樹脂を含む、樹脂微粒子含有組成物。
本明細書において、(メタ)アクリル酸エステル系単量体は、アクリル酸エステル系単量体又はメタクリル酸エステル系単量体を、(メタ)アクリル酸は、アクリル酸又はメタクリル酸を意味する。
本発明の樹脂微粒子は、ビニル系単量体の1種又は2種以上を重合して得られる。ビニル系単量体としては、1分子中にビニル基を1つ以上有する単官能ビニル系単量体及び分子中にビニル基を2つ以上有する多官能ビニル系単量体から選ばれる1種又は2種以上が挙げられる。
単官能ビニル系単量体としては、例えば、単官能(メタ)アクリル系単量体、単官能芳香族ビニル系単量体、脂肪酸ビニルエステル系単量体、ハロゲン化オレフィン系単量体、シアン化ビニル系単量体、不飽和カルボン酸系単量体、不飽和ポリカルボン酸エステル系単量体、不飽和カルボン酸アミド系単量体、不飽和カルボン酸アミド類メチロール化物系単量体等が挙げられる。
これら単官能(メタ)アクリル酸エステル系単量体は、1種を単独で用いてもよく、2種以上を混合して用いてもよい。
ハロゲン化オレフィン系単量体としては、例えば、塩化ビニル、塩化ビニリデン、テトラフルオロエチレン、フッ化ビニリデン等が挙げられる。これらハロゲン化オレフィン系単量体は、1種を単独で用いてもよく、2種以上を混合して用いてもよい。
シアン化ビニル系単量体としては、例えば、(メタ)アクリロニトリル等が挙げられる。
不飽和カルボン酸系単量体としては、不飽和カルボン酸、その塩又は無水物を含むものであり、例えば、(メタ)アクリル酸、クロトン酸、マレイン酸、フマル酸、それらのアンモニウムや金属塩、無水マレイン酸等が挙げられる。これら不飽和カルボン酸系単量体は、1種を単独で用いてもよく、2種以上を混合して用いてもよい。
不飽和カルボン酸アミド系単量体としては、例えば、(メタ)アクリルアミド、ジアセトン(メタ)アクリルアミド等が挙げられる。これら不飽和カルボン酸アミド系単量体は、1種を単独で用いてもよく、2種以上を混合して用いてもよい。
不飽和カルボン酸アミド類メチロール化物系単量体としては、例えば、N-メチロールアクリルアミド、N-メチロールメタクリルアミド、メチロール化ジアセトンアクリルアミド、及び、これら単量体と炭素数1~8のアルコール類とのエーテル化物等が挙げられる。これら不飽和カルボン酸アミド類メチロール化物系単量体は、1種を単独で用いてもよく、2種以上を混合して用いてもよい。
多官能ビニル系単量体としては、例えば、多官能(メタ)アクリル系単量体、多官能芳香族ビニル系単量体、多官能アリル系単量体等が挙げられる。
これら多官能ビニル系単量体は、1種を単独で用いてもよく、2種以上を混合して用いてもよい。
多官能アリル系単量体としては、例えば、ジアリルフタレート、トリアリルシアヌレート等が挙げられる。これらの多官能アリル系単量体は、1種を単独で用いてもよく、2種以上を混合して用いてもよい。
本発明においては、樹脂微粒子を構成するビニル系単量体が多官能ビニル系単量体を含むことが好ましい。
本発明においては、樹脂微粒子を構成するビニル系単量体が、(メタ)アクリル酸エステル系単量体を含むことが好ましい。ここで、(メタ)アクリル酸エステル系単量体は、単官能(メタ)アクリル系単量体及び多官能(メタ)アクリル系単量体からなる群より選ばれる1種又は2種以上である。
また、本発明においては、樹脂微粒子を構成するビニル系単量体が、単官能ビニル系単量体と多官能ビニル系単量体との混合物であることが好ましい。
(メタ)アクリル系樹脂は、(メタ)アクリル酸エステル系単量体の1種又は2種以上を重合して得られる樹脂、又は、(メタ)アクリル酸エステル系単量体の1種又は2種以上と、(メタ)アクリル酸エステル系単量体及びスチレン系単量体以外のビニル系単量体の1種又は2種以上とを重合して得られる樹脂である。
スチレン系樹脂は、スチレン系単量体の1種又は2種以上を重合して得られる樹脂、又は、スチレン系単量体の1種又は2種以上と、(メタ)アクリル酸エステル系単量体及びスチレン系単量体以外のビニル系単量体の1種又は2種以上を重合して得られる樹脂である。
(メタ)アクリル-スチレン系樹脂は、(メタ)アクリル酸エステル系単量体の1種又は2種以上とスチレン系単量体の1種又は2種以上を重合して得られる樹脂、又は、(メタ)アクリル酸エステル系単量体の1種又は2種以上と、スチレン系単量体の1種又は2種以上と、それら以外のビニル系単量体の1種又は2種以上とを重合して得られる樹脂である。
樹脂微粒子を構成するビニル系単量体100質量部中の多官能ビニル系単量体の含有量が少ない場合、(i)基材やバインダーからの樹脂微粒子の脱落を防止できない、(ii)フィルムに耐傷付き性を付与できない、(iii)赤外分光光度計によるATR法で測定した赤外分光スペクトルにおいて、波数1600cm-1~1700cm-1の最大ピーク高さ(極大吸光度)(B)が大きくならない、(iv)樹脂微粒子の架橋度が低くなり、樹脂微粒子をバインダー及び/又は溶剤と混合した際に膨潤し、粘度が上昇して塗工作業性等が低下する、(v)樹脂微粒子の架橋度が低くなるため、樹脂微粒子とバインダーとを混合し加熱して成形する際に、樹脂微粒子が変形、溶解しやすくなるおそれがある。
酸化防止剤としては特に限定されないが、例えば硫黄系酸化防止剤、リン系酸化防止剤、ヒンダードフェノール系酸化防止剤、及びラクトン系酸化防止剤等が挙げられる。酸化防止剤は、樹脂微粒子の重合時に添加できる。
吸光度比は、樹脂微粒子を赤外分光光度計によるATR法で測定した赤外分光スペクトルより得られる波数1700cm-1~1800cm-1の最大ピーク高さ(極大吸光度)(A)(以下、「吸光度(A)」という場合がある。)、波数1600cm-1~1700cm-1の最大ピーク高さ(極大吸光度)(B)(以下、「吸光度(B)」という場合がある。)を求めた後に、その吸光度比を(式1)より算出したものである。
(式1)吸光度比=(B)/(A)
吸光度(B)は、主としてアルケンC=C伸縮振動に由来する吸収スペクトルに対応する吸光度である。なお、1600cm-1~1700cm-1で他の吸収スペクトルが重なっている場合でも、ピーク分離を実施していない。また、吸光度(B)は、1600cm-1と1700cm-1を結ぶ直線をベースラインとして、1600cm-1と1700cm-1間の最大吸光度を意味する。
本発明において、吸光度(A)及び吸光度(B)は、例えば、[実施例]の項において記載した方法を用いて求めることができる。
本発明の樹脂微粒子の吸光度(B)は、特に限定されないが、例えば0.0040以上、好ましくは0.0045以上であり、例えば0.0120以下、好ましくは0.0100以下である。
樹脂微粒子中の未反応のビニル系単量体量は、特に限定されない。例えば、樹脂微粒子の調製に使用した全ビニル系単量体量を100質量%として、1.0質量%以下、好ましくは0.9質量%以下、より好ましくは0.8質量%以下である。未反応のビニル系単量体量が1.0質量%を超えると、光学特性の低下、残存臭気の発生、環境汚染、樹脂微粒子使用時の異物(樹脂メヤニ等)の発生等の問題が生じるおそれがある。
本発明において、樹脂微粒子における未反応のビニル系単量体量は、例えば、[実施例]の項において記載した方法を用いて求めることができる。
樹脂微粒子中の含有水分量は、特に限定されないが、水分量が低い乾燥したものであることが好ましい。例えば、樹脂微粒子全体を100質量%として、2.0質量%以下、好ましくは1.0質量%以下、より好ましくは0.5質量%以下である。水分含有量が2.0質量%を超えると、樹脂微粒子含有組成物の成形時や塗膜形成時にムラ等が生じ、光学特性の低下等の問題が生じるおそれがある。
本発明において、樹脂微粒子の含有水分量は、例えば、[実施例]の項において記載した方法を用いて求めることができる。
本発明において、樹脂微粒子の体積平均粒子径は、特に限定されない。例えば0.01μm以上、好ましくは0.1μm以上であり、例えば20μm以下、好ましくは15μm以下、より好ましくは10μm以下である。体積平均粒子径をこのような範囲とすることで、フィルムの添加剤として使用した場合に、光学特性を向上させることができる。
本発明において、樹脂微粒子の体積平均粒子径は、例えば、[実施例]の項において記載した方法により得られた、体積基準の粒度分布の算術平均を指すものとする。
本発明において、粒子径の変動係数は、特に限定されない。例えば35.0%以下、好ましくは33.0%以下である。樹脂微粒子の粒子径の変動係数をこの範囲とすることで、樹脂微粒子の分散均一性をさらに向上できる。
本発明の樹脂微粒子の粒子径の変動係数は、下記の式により求められる。
樹脂微粒子の粒子径の変動係数=(樹脂微粒子の体積基準の粒度分布の標準偏差÷樹脂微粒子の体積平均粒子径)×100
本発明の樹脂微粒子の樹脂微粒子100質量部に対する残存界面活性剤量は、特に限定されず、目的や用途に応じて適宜設定される。例えば0.01質量部以上、好ましくは0.03質量部以上、より好ましくは0.05質量部以上であり、例えば1質量部以下、好ましくは0.7質量部以下、より好ましくは0.5質量部以下の範囲とされる。
重合時に界面活性剤を用いる場合において、残存界面活性剤量を0.01質量部未満とすることは、工程が煩雑となりコスト等の点で不利となるおそれがある。残存界面活性剤量が1質量部を超えると、樹脂微粒子をコーティング組成物に配合した際に、フリーの界面活性剤が存在することとなり、粒子が脱落しやすくなる傾向にある。
本発明において、残存界面活性剤量は、例えば、[実施例]の項において記載した方法を用いて求めることができる。
本発明の樹脂微粒子の製造方法は、特に限定されない。例えば、
(i)液状媒体中、界面活性剤及び重合開始剤の存在下で、ビニル系単量体を重合させて、前記界面活性剤を含む樹脂微粒子と前記媒体とを含む粗生成物を得る重合工程、
(ii)粗生成物に含まれる媒体を、濾材を用いて除去する固液分離工程、
(iii)樹脂微粒子と洗浄液とを接触させた後に、洗浄液を除去する洗浄工程、
(iv)必要に応じて、乾燥工程及び/又は分級工程、
を含む方法が好ましい。
以下、本発明の樹脂微粒子の製造方法の各工程について、詳述する。
本発明の樹脂微粒子の製造方法において、重合工程における重合方法としては、特に制限されない。例えば、ビニル系単量体、重合開始剤及び液状媒体を用い、必要に応じて界面活性剤を用いる、懸濁重合、シード重合、シード乳化重合、乳化重合、ソープフリー重合、ミニエマルション重合、及び分散重合等の重合方法が挙げられる。
これらの重合方法においては種々の有機溶剤を添加して重合することで、樹脂微粒子の構造制御等が可能であることが公知の技術となっているが、本発明においては、有機溶剤非存在下での重合が好ましい。有機溶剤が存在している系での重合の場合、残存する反応性基数が減少する傾向にあり、これは重合中の高分子鎖が溶剤に膨潤することにより駆動性が向上し、系内のラジカルと接触する頻度が増加するためと考えられるが、この限りではない。
本発明の樹脂微粒子の重合に際して使用されるビニル系単量体としては、[樹脂微粒子]において記載したビニル系単量体が挙げられる。
本発明の樹脂微粒子を、乳化重合やシード乳化重合、ソープフリー重合等の重合方法で作成する場合に用いられる重合開始剤としては、特に限定されない。例えば、熱分解性の水溶性重合開始剤が用いられる。熱分解性の水溶性重合開始剤としては、例えば、過硫酸カリウム、過硫酸アンモニウム、過硫酸リチウム、過硫酸ナトリウム等の過硫酸塩、過酸化水素、水溶性アゾ系重合開始剤が用いられる。水溶性アゾ系重合開始剤としては、従来から乳化重合等に汎用的に用いられている重合開始剤を使用でき、また、新規に開発された乳化重合等に用いられる重合開始剤も使用できる。水溶性アゾ系重合開始剤の例としては、例えば、VA-080(2,2’-アゾビス(2-メチル-N-(1,1-ビス(ヒドロキシメチル)-2-ヒドロキシエチル)プロピオンアミド))、VA-086(2,2’-アゾビス(2-メチル-N-(2-ヒドロキシエチル)-プロピオンアミド))、VA-057(2,2’-アゾビス(2-(N-(2-カルボキシエチル)アミジノ)プロパン))、VA-058(2,2’-アゾビス(2-(3,4,5,6,-テトラヒドロピリミジン-2-イル)プロパン)ジヒドロクロライド)、VA-060(2,2’-アゾビス(2-(1-(2-ヒドロキシエチル)-2-イミダゾリン-2-イル)プロパン)ジヒドロクロライド)、V-50(2,2’-アゾビス(2-アミジノプロパン)ジヒドロクロライド)、V-501(4,4’-アゾビス(4-シアノペンタノン酸))、VA-082(2,2’-アゾビス(2-メチル-N-(1,1-ビス(ヒドロキシメチル)エチル)プロピオンアミド))、VA-085(2,2’-アゾビス(2-メチル-N-(2-(1-ヒドロキシブチル))-プロピオンアミド))、VA-044(2,2’-アゾビス(2-(2-イミダゾリン-2-イル)プロパン)2塩酸塩)、VA-046B(2,2’-アゾビス(2-(2-イミダゾリン-2-イル)プロパン)2硫酸塩2水和物)、VA-061(2,2’-アゾビス(2-(2-イミダゾリン-2-イル)プロパン))(いずれも、富士フイルム和光純薬社製)、2,2’-アゾビス(2-アミジノプロパン)二塩酸塩、2,2’-アゾビス(2-(1-(2-ヒドロキシエチル)-2-イミダゾリン-2-イル)プロパン)二塩酸塩、2,2’-アゾビス(1-イミノ-1-ピロリジノ-2-エチルプロパン)二塩酸塩、2,2’-アゾビス(1-イミノ-1-ピロリジノ-2-メチルプロパン)二塩酸塩、2,2’-アゾビス(2-メチル-N-(1,1-ビス(ヒドロキシメチル)-2-ヒドロキシエチル)プロピオンアミド)等からなる群より選ばれる1種又は2種以上が挙げられる。
重合後のスラリーpHへ与える影響が少なく、分散性低下による粒子の凝集や粗大粒子の発生を抑制できることから、水溶性アゾ系重合開始剤であることが好ましく、さらに樹脂微粒子の分散性向上の観点から、重合開始剤の末端に水酸基が存在しているものが好ましい。
また、水溶性アゾ系重合開始剤の中でも、樹脂微粒子分散体の導電率を低減する観点から、ハロゲンを有しないものがより好ましく、更に水溶性の良さからVA-086、VA-057が特に好ましい。
本発明の樹脂微粒子を作成するために必要に応じて用いられる界面活性剤としては、特に限定されない。
本発明の樹脂微粒子の重合に際しては、アニオン性界面活性剤を用いることができる。アニオン性界面活性剤は、ビニル基などの反応性基を有する反応性界面活性剤と、反応性基を有さない非反応性界面活性剤に分類される。
アニオン性の非反応性界面活性剤としては、脂肪酸塩型、硫酸エステル塩型、スルホン酸塩型、リン酸エステル塩型等の公知のアニオン性界面活性剤をいずれも用いることができる。例えばラウリル硫酸ナトリウム、ラウリル硫酸アンモニウム等のアルキル硫酸エステル塩;ドデシルベンゼンスルホン酸ナトリウム等のアルキルベンゼンスルホン酸塩;ジオクチルスルホコハク酸ナトリウム、ジ(2-エチルヘキシル)スルホコハク酸ナトリウム等のジアルキルスルホコハク酸塩;オレイン酸ナトリウム、ヒマシ油カリ石鹸等の脂肪酸石鹸;アルキルナフタレンスルホン酸塩;アルカンスルホン酸塩;アルケニルコハク酸(モノ又はジ)ナトリウム等のアルケニルコハク酸塩;アルキルリン酸エステル塩;ナフタレンスルホン酸ホルマリン縮合物;ポリオキシエチレンアルキルフェニルエーテル硫酸エステル塩;ポリオキシエチレンラウリルエーテル硫酸ナトリウム等のポリオキシエチレンアルキルエーテル硫酸塩;ポリオキシエチレンアルキル硫酸エステル;ポリオキシエチレンスチレン化フェニルエーテル硫酸エステルアンモニウム等のポリオキシエチレンスチレン化フェニルエーテル硫酸エステル塩;ポリオキシエチレンノニルフェニルエーテルリン酸塩(例えばポリオキシエチレンノニルフェニルエーテルリン酸ナトリウム)等のポリオキシエチレンアルキルフェニルエーテルリン酸塩;等からなる群より選ばれる1種または2種以上が挙げられる。このうち、リン酸エステル系アニオン系界面活性剤としては、例えば、第一工業製薬社製のプライサーフ(登録商標)のAL、A210G、A208F等、東邦化学工業社製のフォスファノール(登録商標)のLO-529等の市販品及びそれらの塩から選ばれる1種以上を用いることができる。
アニオン性の反応性界面活性剤としては、例えば、三洋化成社製のエレミノール(登録商標)のJS-20やRS-3000、第一工業製薬社製のアクアロン(登録商標)のKH-10、KH-1025、KH-05、HS-10、HS-1025、BC-0515、BC-10、BC-1025、BC-20、BC-2020、AR-1025、AR-2025、花王社製のラテムル(登録商標)のS-120、S-180A、S-180、PD-104、ADEKA社製のアデカリアソープ(登録商標)のSR-1025、SE-10N等からなる群より選ばれる1種又は2種以上が挙げられる。中でも分子鎖中にオキシアルキレン鎖を有するものが、粒子の分散性向上の観点から好ましい。
ノニオン性の非反応性界面活性剤としては、エステル型、エーテル型、エステル・エーテル型等の公知のノニオン性界面活性剤をいずれも用いることができる。例えば、アルキレン基の炭素数が3以上であるポリオキシアルキレントリデシルエーテル等のポリオキシアルキレンアルキルエーテル;ソルビタン脂肪酸エステル、グリセリン脂肪酸エステル、パルミチン酸イソプロピル、トリオレイン酸ソルビタン等の脂肪酸エステル;ポリオキシエチレンスチレン化フェニルエーテル;ポリオキシエチレンスチレン化フェニルエーテル(例えば、第一工業製薬社製ノイゲンEAシリーズ);ポリオキシエチレントリデシルエーテル等のポリオキシエチレンアルキルエーテル系;ポリオキシエチレンオクチルフェニルエーテル等のポリオキシエチレンアルキルフェニルエーテル系;ポリオキシエチレン脂肪酸エステル;モノラウリン酸ポリオキシエチレンソルビタン等のポリオキシエチレンソルビタン脂肪酸エステル;ポリオキシエチレンアルキルアミン;オキシエチレン-オキシプロピレンブロック重合体;ポリオキシエチレンノニルフェニルエーテルリン酸エステル等のポリオキシエチレンアルキルフェニルエーテルリン酸エステル;ポリオキシエチレンスチレン化フェニルエーテルリン酸エステル;ポリオキシエチレンアルキルエーテルリン酸エステル;等からなる群より選ばれる1種または2種以上が挙げられる。
ノニオン性の反応性界面活性剤としては、例えば、アルキルエーテル系(例えば、ADEKA社製アデカリアソープER-10、ER-20、ER-30、ER-40、花王社製ラテムルPD-420、PD-430、PD-450等);アルキルフェニルエーテル系もしくはアルキルフェニルエステル系(例えば、第一工業製薬社製アクアロンRN-10、RN-20、RN-30、RN-50、AN-10、AN-20、AN-30,AN-5065、ADEKA社製アデカリアソープNE-10、NE-20、NE-30、NE-40等);(メタ)アクリレート硫酸エステル系(例えば、日本乳化剤社製RMA-564、RMA-568、RMA-1114等)等からなる群より選ばれる1種以上が挙げられる。中でも分子鎖中にオキシアルキレン鎖を有するものが、粒子の分散安定性の観点から好ましい。
本発明の樹脂微粒子を作成するために用いられる液状媒体としては、特に限定されない。例えば、水、有機溶剤、及びこれらの混合物のいずれを用いることができる。本発明においては、水性媒体が好ましく、例えば、水、メチルアルコール、エチルアルコール等の炭素数5以下の低級アルコール、水と低級アルコールとの混合物等を用いることができる。
ビニル系単量体の重合方法は、特に限定されない。例えば、懸濁重合、乳化重合、シード重合、シード乳化重合、ソープフリー重合、ミニエマルション重合、及び分散重合などの、公知の重合方法が挙げられる。
懸濁重合により、粒子径が小さく、かつ粒子径のばらつきが小さい(粒子径が比較的整った)樹脂微粒子を得ることができる。
乳化重合により、得られる樹脂微粒子の粒子径のばらつきを小さくすることができる。
シード重合により得られる樹脂微粒子は、粒子径のばらつきが少なく、防眩フィルムや光拡散フィルム等の光学部材用とした場合に、光学部材の防眩性や光拡散性等の光学特性を向上できる。
得られる樹脂微粒子の粒子径のばらつきが少ないことから、懸濁重合、乳化重合又はシード重合が好ましく、シード重合が最も好ましい。
以下、シード重合の一般的な方法を述べるが、本発明の製造方法における重合方法は、この方法に限定されるものではない。
乳化液(懸濁液)の調製は、公知の方法を用いることができる。例えば、ビニル系単量体と界面活性剤とを水性媒体に添加し、ホモジナイザー、超音波処理機、ナノマイザー(登録商標)等の微細乳化機により分散させることで、乳化液を得ることができる。
なお、得られた乳化液中に存するビニル系単量体の液滴の粒子径は、次に添加する種粒子の粒子径よりも小さい方が、種粒子に効率よく吸収されるので好ましい。
種粒子は、そのままで乳化液に添加されてもよく、水性媒体に分散された形態で乳化液に添加されてもよい。種粒子が乳化液へ添加されると、種粒子にビニル系単量体が吸収される。種粒子にビニル系単量体を吸収させる方法としては、通常、乳化液を、室温(約20℃)で1~12時間撹拌する方法が挙げられる。また、種粒子にビニル系単量体が吸収されるのを促進するため、乳化液を30~50℃程度に加温してもよい。
種粒子にビニル系単量体が吸収されると、種粒子は膨潤する。ビニル系単量体と種粒子との混合比率は、種粒子1質量部に対して、例えばビニル系単量体が5~300質量部の範囲内が好ましい。なお、種粒子へのビニル系単量体の吸収の終了判定は、光学顕微鏡の観察で粒子径を確認することで行うことができる。
次いで、種粒子に吸収されたビニル系単量体を重合して、樹脂微粒子が得られる。なお、種粒子にビニル系単量体を吸収させて重合させる工程を複数回繰り返すことにより樹脂微粒子を得てもよい。
ビニル系単量体の重合に際しては、必要に応じて重合開始剤を使用してもよい。重合開始剤は、あらかじめビニル系単量体と混合した後、水性媒体中に分散させてもよく、重合開始剤とビニル系単量体との両者を別々に水性媒体に分散させてもよい。
シード重合の重合反応は、重合に対して不活性な不活性ガス(例えば窒素)の雰囲気下で行ってもよい。
本発明の樹脂微粒子の製造において、シード重合の重合反応は、ビニル系単量体及び必要に応じて用いられる重合開始剤が種粒子に完全に吸収された後に、昇温して行うことが好ましい。
重合反応における水性媒体中での乳化重合生成物(粒子径の小さすぎる樹脂微粒子)の発生を抑えるために、亜硝酸ナトリウム等の亜硝酸塩類、亜硫酸塩類、ハイドロキノン類、アスコルビン酸類、水溶性ビタミンB類、クエン酸、ポリフェノール類等の水溶性の重合禁止剤を水性媒体に添加してもよい。重合禁止剤を使用する場合の添加量は、例えばビニル系単量体100質量部に対して0.02~0.2質量部の範囲内が好ましい。
本発明の樹脂微粒子を製造する際の固液分離工程は、重合工程で得られた樹脂微粒子、界面活性剤及び媒体を含む粗生成物から、濾材を備える濾過器を用いて媒体等を除去し、樹脂微粒子を固液分離する工程である。
濾材は、樹脂微粒子を確実に捕集できるものであれば特に限定されない。例えば、天然繊維、合成繊維等からなる、織布、不織布等の濾布、焼結金属からなる金網、焼結金属からなる不織布、天然繊維、ガラス繊維等からなる濾過板(多孔板)、合成樹脂からなる網、濾紙、ガラス繊維フィルター等よりなる群から選ばれる1種又は2種以上が挙げられ、特に濾布が好ましい。
固液分離工程では、濾材を通過する媒体の単位時間当たりの量、加圧条件、媒体を除去する際の脱液速度等を制御することで、樹脂微粒子中の残存界面活性剤量及び非揮発成分量を容易に調整できる。
本発明の樹脂微粒子を製造する際の洗浄工程は、固液分離工程後の樹脂微粒子と洗浄液とを接触させた後に洗浄液を除去し、洗浄された樹脂微粒子を得る工程である。
洗浄工程において、固液分離工程で得られた樹脂微粒子のケーキを、樹脂微粒子ケーキ体積の10倍以下、好ましくは1.5~7倍の洗浄液中に浸漬後、洗浄液を除去する洗浄処理を、必要に応じて繰り返すことで、樹脂微粒子における残存界面活性剤量等を制御できる。
洗浄液を除去する手段としては、例えば、遠心分離機を用い、洗浄液を遠心分離除去する洗浄処理を、必要に応じて繰り返す手段が挙げられる。
また、例えば、加圧濾過器を用い、濾材上の樹脂微粒子のケーキと洗浄液を接触させて洗浄する手段は、洗浄液のショートパスがなくなり、洗浄液の使用量が抑制され、効率的な洗浄を行うことができる。洗浄液の除去は、例えば、加圧濾過器内に圧縮気体を導入して加圧することで、ケーキと洗浄液を接触させるとともに、洗浄後の洗浄液を濾液として排出する方法が挙げられる。
洗浄工程では、遠心分離の回数、洗浄液の添加量、濾材を通過する媒体の量(排出量)等を調整することで、樹脂微粒子に含まれる残存界面活性剤量や非揮発成分量を調整できる。
洗浄工程で用いる洗浄液の重量は、洗浄する樹脂微粒子の重量の10倍以下、好ましくは1.5~7倍である。これにより、洗浄工程において、界面活性剤が必要以上に溶出することを防止できる。
洗浄に用いる洗浄液の温度は、重合時に用いた界面活性剤が十分に溶出する温度であり、例えば40~80℃の範囲である。
洗浄工程は、濾材を通過した洗浄液の導電率が、濾過器投入前の洗浄液の導電率の2.0倍以下、加圧濾過器内圧が、加圧時の圧力の2/3以下になったときに終了することが好ましい。
洗浄工程で得られた樹脂微粒子は、乾燥機で乾燥して洗浄液を除去するとともに必要に応じて分級することが好ましい。乾燥機としては、特に限定されないが、例えば、噴霧乾燥装置(スプレードライヤー)やフリーズドライ、撹拌羽を組み込んだ真空撹拌ドライヤー(解砕乾燥機)が好ましく、粒子径、組成に応じて適切な乾燥装置を選択することができる。乾燥によって、洗浄液をほぼ完全に除去し、必要に応じて分級(好ましくは、気流分級)し、製品として利用可能な樹脂微粒子とできる。
本発明における乾燥条件としては、使用する乾燥機の容量・能力等に応じて適宜調整される。例えば、真空度(対大気圧)を-0.001~-0.5MPaに、乾燥温度を40~80℃に、乾燥時間を4~10時間(hr)とできる。
本発明においては、乾燥工程において、界面活性剤を樹脂微粒子表面から水中へ溶出させ、その後、解砕乾燥機を使用して、水分と共に非揮発成分を除去できる。これにより、樹脂微粒子の残存界面活性剤量等を調整できる。
例えば、洗浄後の樹脂微粒子ケーキを、予め温めておくことにより、粒子表面の界面活性剤を容易に規定量に調整することが可能となる。さらに、解砕乾燥プロセスにより、非揮発成分がせん断されてほとんどが分取されることとなる。そして、残存界面活性剤により樹脂微粒子表面が効果的に修飾され、分散均一性に優れ、分散性が向上した樹脂微粒子を得ることができる。
このような樹脂微粒子の製造方法によれば、重合工程において樹脂微粒子に付着した残存界面活性剤を、媒体及び洗浄液と共に適量除去でき、さらに、非揮発成分の含有量(残存量)も適量にすることが可能となる。
本発明の樹脂微粒子含有組成物は、前記本発明の樹脂微粒子、光重合開始剤及び紫外線硬化型樹脂を含むものである。
本発明の樹脂微粒子含有組成物に含まれる光重合開始剤としては、光又は紫外線の照射により組成物内にラジカルを発生させ、紫外線硬化型樹脂の重合を開始させ得る化合物であれば、特に限定されない。光重合開始剤は、使用する紫外線硬化型樹脂にあったものを用いることが好ましい。
光重合開始剤としては、例えば、アセトフェノン類、ベンゾイン類、ベンゾフェノン類、ホスフィンオキシド類、ケタール類、α-ヒドロキシアルキルフェノン類、α-アミノアルキルフェノン、アントラキノン類、チオキサントン類、アゾ化合物、過酸化物類、2,3-ジアルキルジオン化合物類、ジスルフィド化合物類、フルオロアミン化合物類、芳香族スルホニウム類、オニウム塩類、ボレート塩、活性ハロゲン化合物、α-アシルオキシムエステル等よりなる群から選ばれる1種又は2種以上を用いることができる。
光重合開始剤の使用量は、紫外線重合型樹脂100質量部に対し、例えば0.5質量部以上、好ましくは1.0質量部以上であり、例えば20.0質量部以下、好ましくは5.0質量部以下である。
本発明の樹脂微粒子含有組成物に含まれる紫外線硬化型樹脂としては、透明性、樹脂微粒子の分散性、耐光性、耐湿性及び耐熱性等の要求される特性に応じて適宜選択されるもので、特に限定されない。例えば多官能(メタ)アクリレート樹脂、多官能ウレタン(メタ)アクリレート樹脂、多官能ポリエステル(メタ)アクリレート樹脂、エポキシ(メタ)アクリレート樹脂、アルキッド樹脂等からなる群より選ばれる1種又は2種以上を含むものが挙げられる。
紫外線硬化型樹脂としては、多官能(メタ)アクリレート樹脂を含むものが好ましく、1分子中に3個以上の(メタ)アクリロイル基を有する多価アルコール多官能(メタ)アクリレートを含むものがより好ましい。1分子中に3個以上の(メタ)アクリロイル基を有する多価アルコール多官能(メタ)アクリレートとしては、例えば、トリメチロールプロパントリ(メタ)アクリレート、トリメチロールエタントリ(メタ)アクリレート、1,2,4-シクロヘキサントリ(メタ)アクリレート、ペンタグリセロールトリアクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、ジペンタエリスリトールトリアクリレート、ジペンタエリスリトールペンタアクリレート、ジペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、トリペンタエリスリトールトリアクリレート、トリペンタエリスリトールヘキサアクリレート等からなる群より選ばれる1種又は2種以上が挙げられる。
例えば、樹脂微粒子及び紫外線硬化型樹脂以外の樹脂(セルロース系樹脂、酢酸ビニル系樹脂、塩化ビニル系樹脂、塩化ビニリデン系樹脂等のビニル系樹脂、アセタール系樹脂、(メタ)アクリル系樹脂、ポリスチレン系樹脂、ポリアミド樹脂、線状ポリエステル樹脂、ポリカーボネート樹脂等からなる群より選ばれる1種又は2種以上)を含んでいてもよい。
また、例えば、反応性希釈剤を溶媒として含んでいてもよい。反応性希釈剤としては、ビニル系単量体の1種又は2種以上が挙げられる。反応性希釈剤として用いられるビニル系単量体としては、例えば、本発明の樹脂微粒子の重合に際して用いられる単官能(メタ)アクリル系単量体や多官能(メタ)アクリル系単量体から選ばれる1種又は2種以上が挙げられる。
さらに、シリカ等の無機粒子、着色剤、有機溶剤等を含んでいてもよい。なお、有機溶媒は微量であることが好ましく、通常は有機溶剤を用いないことが好ましい。
樹脂微粒子の量を、紫外線硬化型樹脂の固形分100質量部に対して2質量部以上とすることで、樹脂微粒子含有樹脂組成物によって形成される層(塗膜)の艶消し性等の光学特性を十分発揮させることができ、樹脂微粒子含有樹脂組成物を基材上に塗工してなる光学部材の防眩性や光拡散性等の光学特性を十分なものにできる。また、300質量部以下とすることで、樹脂微粒子含有組成物によって形成される層(塗膜)の直線透過性を十分なものにし易くなる。
活性エネルギー線としては、例えば、LED、高圧水銀灯等の光源から発せられる紫外線、赤外線、電子線加速器から発せられる電子線、α線、β線、γ線等を用いることができる。
樹脂微粒子含有樹脂組成物によって形成される層(塗膜)の厚さ(乾燥厚さ)は、特に限定されず、目的や求める特性等に応じて適宜調整できる。例えば1μm以上、好ましくは3μm以上であり、例えば10μm以下、好ましくは7μm以下である。
本発明の樹脂微粒子は、前記樹脂微粒子含有組成物以外に、各種の用途に供することができる。例えば、樹脂微粒子と樹脂とを含む成形用樹脂組成物を形成し、これを用いて、防眩フィルムや光拡散フィルム等の光学フィルムや光拡散体等の光学部材、特に、防眩部材を得ることができる。
さらに、樹脂微粒子自体又はそれと樹脂との混合物を成形して、樹脂成形体を得ることができる。
基材は、透明であることが好ましい。透明の基材としては、例えば、ガラス、ポリエステル系樹脂、セルロース系樹脂、ポリカーボネート系樹脂、(メタ)アクリル系樹脂、環状ポリオレフィン系樹脂、これらの樹脂の1種又は2種以上を含む混合物、これらの樹脂の積層物等を基材とすることができる。これらの中でも、特に複屈折率の少ないものが好適に用いられる。
さらに、これらの基材の少なくとも一方の面に、(メタ)アクリル系樹脂、ポリウレタン系樹脂等の易接着層を設けたものを基材として用いることができる。
基材の厚さは、適宜に決定し得るが、一般には、強度や取り扱い等の作業性、薄層性等の点より10~500μmの範囲内である。好ましくは20~300μm、より好ましくは30~200μmである。
基材は、添加剤を含んでいてもよい。添加剤としては、例えば、紫外線吸収剤、赤外線吸収剤、帯電防止剤、屈折率調整剤、増強剤等が挙げられる。
上記樹脂成形体は、光拡散板等の光拡散体として機能し、LED照明カバー等として利用できる。
透明樹脂としては、例えば、(メタ)アクリル系樹脂、ポリカーボネート樹脂、ポリスチレン系樹脂、(メタ)アクリル-スチレン系樹脂((メタ)アクリル)酸エステルとスチレンとの共重合体)等よりなる群から選ばれる1種又は2種以上を用いることができる。それらの中でも、ポリスチレン系樹脂又は(メタ)アクリル-スチレン系樹脂が好ましい。
本発明の樹脂微粒子と透明樹脂とから樹脂成形体を調製する際、樹脂成形体に含まれる樹脂微粒子の量は、透明樹脂100質量部に対して0.01~5質量部の範囲、好ましくは0.1~5質量部の範囲とできる。樹脂成形体は、必要に応じて、紫外線吸収剤、酸化防止剤、熱安定剤、光安定剤、蛍光増白剤等の添加剤を含んでいてもよい。
樹脂成形体の厚み及び形状等は、用途によって適宜選択できる。
本発明の樹脂微粒子を含む樹脂成形体は、樹脂微粒子の分散均一性に優れたものであり、むらのない均一な光拡散性や防眩性等の光学特性を発揮する。
<極大吸光度及び吸光度比>
Thermo SCIENTIFIC社製フーリエ変換赤外分光光度計「Nicolet iS10」に、ATRアクセサリーとしてThermo SCIENTIFIC社製「Smart-iTR」を接続して測定した。
赤外分光分析ATR測定の条件は以下のとおりである。
・測定装置:フーリエ変換赤外分光光度計 Nicolet iS10(Thermo SCIENTIFIC社製)及び一回反射型水平状ATR Smart-iTR(Thermo SCIENTIFIC社製)
・ATRクリスタル:Diamond with ZnSe lens、角度=42°
・測定方法:一回ATR法
・測定波数領域:4000cm-1~650cm-1
・測定深度の波数依存性:補正せず
・検出器:重水素化硫酸トリグリシン(DTGS)検出器及びKBrビームスプリッター・分解能:4cm-1
・積算回数:16回(バックグラウンド測定時も同様)
以上の条件で得られた赤外線吸収スペクトルは、次のようにピーク処理をして波数1700cm-1~1800cm-1の最大ピーク高さ(極大吸光度)(A)と波数1600cm-1~1700cm-1の最大ピーク高さ(極大吸光度)(B)を求めた。
赤外吸収スペクトルから得られる波数1700cm-1~1800cm-1での極大吸光度(A)は、エステル基のC=O伸縮振動に由来する吸収スペクトルに対応する吸光度であった。この吸光度の測定では、1700cm-1~1800cm-1で他の吸収スペクトルが重なっている場合でもピーク分離を実施しなかった。吸光度(A)は、1700cm-1と1800cm-1を結ぶ直線をベースラインとして、1700cm-1と1800cm-1間の最大吸光度を意味する。
また、1600cm-1~1700cm-1での極大吸光度(B)は、アルケンC=C伸縮振動に由来する吸収スペクトルに対応する吸光度であった。この吸光度の測定では、1600cm-1~1700cm-1で他の吸収スペクトルが重なっている場合でもピーク分離を実施しなかった。吸光度(B)は、1600cm-1と1700cm-1を結ぶ直線をベースラインとして、1600cm-1と1700cm-1間の最大吸光度を意味する。
上記のようにして、樹脂微粒子を赤外分光光度計によるATR法で測定した赤外分光スペクトルより得られる波数1700cm-1~1800cm-1の最大ピーク高さ(極大吸光度)(A)、波数1600cm-1~1700cm-1の最大ピーク高さ(極大吸光度)(B)とし、その吸光度比を(式1)より算出した。
(式1)吸光度比=(B)/(A)
電量滴定方式 微量水分測定装置(三菱ケミカルアナリテック社 CA-310型)を用いて、JIS K0113に準拠したカールフィッシャー法により電量滴定を行い、樹脂微粒子の含有水分量を測定した。
樹脂微粒子0.01gにメタノール5mLを加え、充分に混合させた後、24時間静置させることにより分散液を得る。次いで、遠心分離機で30分間、撹拌回転数18500rpmで分散液を処理することにより不溶物を沈殿させる。超高速液体クロマトグラムLa Chrom Ultra(日立ハイテクノロジーズ社製)で、得られる上澄液2μLを解析することにより、樹脂微粒子に対する残存モノマー量を測定する。
測定条件は、カラムとしてLa Chrom Ultra C18 2μmを用い、カラム温度を40℃とする。溶媒は0.05%トリフルオロ酢酸水溶液とアセトニトリルの混合物(50/50 w/w)を使用し、フロー速度を0.6mL/minとした。
樹脂微粒子2部を、バインダーとしてペンタエリスリトールトリアクリレート55部とアクリロイルモルフォリン38部の混合物に添加して攪拌、混合した。さらに光重合開始剤としてイルガキュア184を5部加え、PETフィルムにアプリケーターで膜厚が10μmになるように塗工し、メタルハライドランプで400mJ/cm2の紫外線を照射し、PETフィルム上に塗膜を有する塗工物を作製した。室温で1週間経過した後に、以下の固着性評価試験で固着性を評価した。
(固着性評価試験)
200gの荷重をかけながら#1000のスチールウールで塗膜を10往復させた後、塗膜上に出た粉を目視で観察し評価した。樹脂微粒子の脱離が確認されなかったものはA、樹脂微粒子の脱離が確認されたものはDとした。
樹脂微粒子を溶媒により抽出し、液体クロマトグラフリニアイオントラップ型質量分析計(LC/MS/MS装置)を用いて測定した。
LC/MS/MS装置としては、Thermo SCIENTIFIC社製の「UHPLC ACCELA」及びThermo SCIENTIFIC社製の「Linear Ion Trap LC/MSn LXQ」を用いた。
界面活性剤の含有量は、以下に示す方法により測定される。
樹脂微粒子約0.01gを遠沈管に精秤後、抽出液を注加して、樹脂微粒子と抽出液とをよく混合し、超音波抽出を行った後再度混合し、遠心分離を行い、得られた上澄み液を濾過したものを試験液とした。
この試験液中の界面活性剤の濃度をLC/MS/MS装置を用い、得られたクロマトグラム上のピーク面積値から予め作成した検量線より含有量を算出した。そして、測定された試験液中の界面活性剤濃度と、試料として用いた樹脂微粒子の重量(試料重量)と、抽出液量とから、下記算出式により、樹脂微粒子中の界面活性剤の含有量を求めた。
界面活性剤の含有量=試験液中の界面活性剤濃度×抽出液量÷試料重量
なお、検量線作成方法は、以下の通りである。
界面活性剤の約1000ppm中間標準液(メタノール溶液)を調製後、さらにメタノールで段階的に希釈して20ppm、10ppm、5ppm、2.5ppmの検量線作成用標準液を調製する。各濃度の検量線作成用標準液を下記条件にて測定し、モニターイオンm/z=730~830のクロマトグラム上のピーク面積値を得た。各濃度と面積値をプロットして最小二乗法により近似曲線(二次曲線)を求め、これを定量用の検量線とした。
樹脂微粒子の体積平均粒子径ならびに個数平均粒子径は、レーザー回折散乱方式粒度分布測定装置(型番「LS230」、ベックマン・コールター社製)で測定した。具体的には、樹脂微粒子水分散液(固形分20%)0.1gと2質量%アニオン性界面活性剤溶液20mlとを、試験管に投入した。その後、試験管ミキサー(アズワン社製、「試験管ミキサーTRIO HM-1N」)及び超音波洗浄器(アズワン社製、「ULTRASONIC CLEANER VS-150」)を用いて5分間かけて分散させ、分散液を得た。得られた分散液をレーザー回折散乱方式粒度分布測定装置(ベックマン・コールター社製、「LS230」)により、超音波を照射しながら、下記の測定条件により、分散液中の樹脂微粒子の体積平均粒子径ならびに個数平均粒子径を測定した。
(レーザー回折散乱方式粒度分布測定装置の測定条件)
媒体=水
媒体の屈折率=1.333
固体の屈折率=樹脂微粒子の屈折率
PIDS相対濃度:40~55%
測定時の光学モデルは、製造した樹脂微粒子の屈折率に合わせた。樹脂微粒子の製造に1種類の単量体を用いた場合には、樹脂微粒子の屈折率としてその単量体の単独重合体の屈折率を用いた。樹脂微粒子の製造に複数種類の単量体を用いた場合には、樹脂微粒子の屈折率として、各単量体の単独重合体の屈折率を各単量体の使用量で加重平均した平均値を用いた。
測定結果から、樹脂微粒子の体積基準の粒度分布を得た。当該体積基準の粒度分布の算術平均を樹脂微粒子の体積平均粒子径とした。
樹脂微粒子の体積平均粒子径の変動係数(CV値)を以下の数式によって算出した。
樹脂微粒子の体積平均粒子径の変動係数=[(樹脂微粒子の体積基準の粒度分布の標準偏差)/(樹脂微粒子の体積平均粒子径)]×100
<樹脂微粒子の製造>
攪拌装置と温度計と冷却機構を兼ね備えた重合器内で、イオン交換水320部とアクアロンAR-1025(第一工業製薬社製)0.2部を混合した。別の容器でメタクリル酸メチル3.8部とエチレングリコールジメタクリレート0.2部を混合して、重合器に投入し、TKホモミキサー(プライミクス社製)により8000rpmで10分間攪拌することにより、単量体混合液を得た。重合器の窒素パージを5分間実施した後85℃まで昇温し、85℃に到達した時点で、10部のイオン交換水に溶解させたVA-086(富士フィルム和光純薬社製)0.2部を投入し1時間反応させてスラリー(1)を得た。
次に先程使用したものとは別の容器でイオン交換水36部とアクアロンAR-1025(第一工業製薬社製)0.3部とアクアロンAN-5065(第一工業製薬社製)0.03部を混合して界面活性剤溶液を得た。さらに別の容器でエチレングリコールジメタクリレート36部をよく混合して、前記界面活性剤溶液に投入し、TKホモミキサー(プライミクス社製)により8000rpmで10分間攪拌して、単量体混合液(2)を得た。
前記単量体混合液(2)を、前記重合器内で85℃に保持されたスラリー(1)に2時間かけて8分割して投入した。その後1時間熟成工程を経て、100℃まで昇温し3時間保持してから冷却して、樹脂微粒子含有スラリーを作成した。
樹脂微粒子含有スラリーを400Meshのナイロン網に通過させて樹脂微粒子の分級を行い、分級された樹脂微粒子スラリーを得た。
分級された樹脂微粒子スラリーを、噴霧乾燥機(坂本技研社製、機械名:スプレードライヤー、型式:アトマイザーテイクアップ方式、型番:TRS-3WK)を用いて、以下の装置条件下、噴霧乾燥して、樹脂微粒子の集合体を得た。
樹脂微粒子を含むスラリー供給速度:25mL/min
アトマイザ回転数:12000rpm
風量:2m3/min
入口温度(スプレードライヤーに備えられた、樹脂微粒子を含むスラリーが噴霧されて導入される樹脂微粒子を含むスラリー投入口の温度):150℃
出口温度(スプレードライヤーに備えられた、ビニル系樹脂微粒子の集合体が排出される粉体出口温度):70℃
得られた樹脂微粒子集合体を、カレントジェットミル(日清エンジニアリング社製、商品名:CJ-10、粉砕空気圧:0.5MPa)を使用して解砕処理を行った結果、目的の樹脂微粒子を得た。
得られた樹脂微粒子の体積平均粒子径は183nmであり、変動係数は20.8%であった。また、得られた樹脂微粒子を赤外分光光度計によるATR法で測定した赤外分光スペクトルにて、波数1700cm-1~1800cm-1の最大ピーク高さ(極大吸光度)(A)=0.1921、波数1600cm-1~1700cm-1の最大ピーク高さ(極大吸光度)(B)=0.00965を確認し、吸光度比(B)/(A)は0.05023であった。
また、固着性試験の評価は、Aであった。
得られた樹脂微粒子の物性及び評価結果を、表1に示す。
実施例1に記載の樹脂微粒子の製造条件において、単量体混合液(2)の作成時に使用したエチレングリコールジメタクリレート36部を、エチレングリコールジメタクリレート34部及びスチレン2部に変更した以外は、実施例1と同条件で処理して、目的の樹脂微粒子を得た。
得られた樹脂微粒子の物性及び評価結果を、表1に示す。
実施例1に記載の樹脂微粒子の製造条件において、単量体混合液(2)の作成時に使用したエチレングリコールジメタクリレート36部を、エチレングリコールジメタクリレート24部及びメタクリル酸メチル12部に変更した以外は、実施例1と同条件で処理して、目的の樹脂微粒子を得た。
得られた樹脂微粒子の物性及び評価結果を、表1に示す。
攪拌装置と温度計と冷却機構を兼ね備えた重合器内で、イオン交換水70部にピロリン酸マグネシウム6部、ラウリル硫酸ナトリウム0.04部を混合した。別の容器にてエチレングリコールジメタクリレート20部と2,2´-アゾビス(2,4-ジメチルバレロニトリル)0.12部をよく混合し、重合器内に投入し、TKホモミキサー(プライミクス社製)により7,000rpmで5分間攪拌して、単量体混合液を得た。さらに得られた単量体混合液をマイクロフルイダイザーにて20MPaで処理し、重合器内に再度投入した。重合器の窒素パージを5分間実施した後55℃まで昇温し、4時間反応を行い、その後1時間熟成させた後、100℃まで昇温し3時間重合させた。得られた樹脂微粒子含有スラリーを冷却して取り出した後、遠心分離機にて粒子と上澄み液を分離し、上澄み液のみを除去した。得られた粒子をイオン交換水に再分散させたのち、同様に遠心分離機にて分離し上澄みを除去する洗浄工程を繰り返し、上澄み液の導電率が15μS以下になった時点で洗浄終点とした。得られた粒子を真空オーブンにて乾燥し、乾燥粉体を得た。得られた乾燥粉体をターボクラシファイア(日清エンジニアリング社製)にて気流分級処理して、目的の樹脂微粒子を得た。
得られた樹脂微粒子の物性及び評価結果を、表1に示す。
実施例4に記載の樹脂微粒子の製造条件において、単量体混合液(2)の作成時に使用したエチレングリコールジメタクリレート20部を、エチレングリコールジメタクリレート18部とペンタエリスリトールテトラキスチオグリコレート2部に変更した以外は、実施例4と同条件で処理して、目的の樹脂微粒子を得た。
得られた樹脂微粒子の物性及び評価結果を、表1に示す。
実施例1に記載の樹脂微粒子の製造条件において、単量体混合液(2)の作成時に使用したエチレングリコールジメタクリレート36部を、エチレングリコールジメタクリレート8部及びメタクリル酸メチル28部に変更した以外は、実施例1と同条件で処理して、目的の樹脂微粒子を得た。
得られた樹脂微粒子の物性及び評価結果を、表1に示す。
実施例4に記載の樹脂微粒子の製造条件において、単量体混合液(2)の作成時に使用したエチレングリコールジメタクリレート20部を、エチレングリコールジメタクリレート4部及びメタクリル酸メチル16部に変更した以外は、実施例4と同条件で処理して、目的の樹脂微粒子を得た。
得られた樹脂微粒子の物性及び評価結果を、表1に示す。
Claims (7)
- ビニル系単量体の1種又は2種以上を重合して得られ、
赤外分光光度計によるATR法で測定した赤外分光スペクトルにおいて、波数1700cm-1~1800cm-1の最大ピーク高さ(極大吸光度)(A)と波数1600cm-1~1700cm-1の最大ピーク高さ(極大吸光度)(B)との吸光度比(B)/(A)が0.020~0.060の範囲にある、樹脂微粒子。 - 前記ビニル系単量体が、多官能ビニル系単量体を含む、請求項1に記載の樹脂微粒子。
- 前記ビニル系単量体が、(メタ)アクリル酸エステル系単量体を含む、請求項1又は2に記載の樹脂微粒子。
- 前記ビニル系単量体100質量部中、多官能ビニル系単量体の含有量が51質量部~100質量部の範囲である、請求項1~3のいずれか1項に記載の樹脂微粒子。
- 前記樹脂微粒子中の未反応のビニル系単量体量が1.0質量%以下である、請求項1~4のいずれか1項に記載の樹脂微粒子。
- 前記樹脂微粒子が、含有水分量2.0質量%以下の乾燥粉体である、請求項1~5のいずれか1項に記載の樹脂微粒子。
- 請求項1~6のいずれか1項に記載の樹脂微粒子、光重合開始剤及び紫外線硬化型樹脂を含む、樹脂微粒子含有組成物。
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