WO2021039798A1 - 樹脂微粒子及びその製造方法 - Google Patents
樹脂微粒子及びその製造方法 Download PDFInfo
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- WO2021039798A1 WO2021039798A1 PCT/JP2020/032051 JP2020032051W WO2021039798A1 WO 2021039798 A1 WO2021039798 A1 WO 2021039798A1 JP 2020032051 W JP2020032051 W JP 2020032051W WO 2021039798 A1 WO2021039798 A1 WO 2021039798A1
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- Prior art keywords
- resin fine
- fine particles
- vinyl
- based monomer
- monomer
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- 229920000058 polyacrylate Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 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
- 238000002360 preparation method Methods 0.000 description 1
- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 description 1
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 description 1
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- QEVHRUUCFGRFIF-MDEJGZGSSA-N reserpine Chemical compound O([C@H]1[C@@H]([C@H]([C@H]2C[C@@H]3C4=C(C5=CC=C(OC)C=C5N4)CCN3C[C@H]2C1)C(=O)OC)OC)C(=O)C1=CC(OC)=C(OC)C(OC)=C1 QEVHRUUCFGRFIF-MDEJGZGSSA-N 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 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
- 238000005507 spraying Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 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
- 238000000967 suction filtration Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 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
- 238000002834 transmittance Methods 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- XOALFFJGWSCQEO-UHFFFAOYSA-N tridecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C=C XOALFFJGWSCQEO-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- RRLMGCBZYFFRED-UHFFFAOYSA-N undecyl prop-2-enoate Chemical compound CCCCCCCCCCCOC(=O)C=C RRLMGCBZYFFRED-UHFFFAOYSA-N 0.000 description 1
- 235000019156 vitamin B Nutrition 0.000 description 1
- 239000011720 vitamin B Substances 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
- 239000007883 water-soluble azo polymerization initiator Substances 0.000 description 1
Classifications
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/001—Multistage polymerisation processes characterised by a change in reactor conditions without deactivating the intermediate polymer
-
- 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
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying 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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
-
- 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
- C08F212/00—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 an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- 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
- C08F220/08—Anhydrides
-
- 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
- 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
-
- 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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/04—Azo-compounds
-
- 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
- C08F6/00—Post-polymerisation treatments
- C08F6/14—Treatment of polymer emulsions
- C08F6/22—Coagulation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
- C08J3/122—Pulverisation by spraying
-
- 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
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/24—Polymer with special particle form or size
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2333/12—Homopolymers or copolymers of methyl methacrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2425/00—Characterised by the use 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 an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2425/02—Homopolymers or copolymers of hydrocarbons
- C08J2425/04—Homopolymers or copolymers of styrene
- C08J2425/08—Copolymers of styrene
Definitions
- the present invention relates to resin fine particles and a method for producing the same.
- a method for producing resin fine particles there are methods such as suspension polymerization, seed polymerization, emulsion polymerization, soap-free polymerization, and dispersion polymerization.
- emulsion polymerization is suitable for producing resin fine particles having a fine particle size such as submicrons, and the obtained fine particles are light diffusing plates, anti-blocking agents for various film films, various film modifiers, and various electronic devices. It is widely used as a spacer between minute parts, a pore-forming agent for various battery members, and core particles of conductive fine particles that are responsible for electrical connection.
- (meth) acrylic monomer or styrene monomer should be used as the particle composition.
- Resin fine particles obtained by polymerization have been preferably used.
- crosslinked fine particles have high resistance to solvents and heat, and are preferably used.
- Patent Document 1 and the like can be mentioned as an example of producing crosslinked fine particles.
- Patent Document 2 describes particles obtained by a production method that maintains solvent resistance and has good productivity, but all of them use a non-reactive surfactant during emulsion polymerization. If the particles obtained by the method described in Patent Document 2 are dried and used as they are, free residual surfactant will be present in the solvent or resin, and foaming will occur during dispersion, so that the particles will aggregate or settle. , It becomes a factor such as particles falling off from the base material.
- the present invention has been made in view of the above-mentioned problems, has solvent resistance that can withstand a heating step after solvent dispersion, generates less bubbles during dispersion, and is excellent in dispersibility in a solvent.
- An object of the present invention is to provide resin fine particles and a method for producing the same.
- the present invention has the following aspects.
- Resin fine particles obtained by polymerizing a vinyl-based monomer characterized by having a gel fraction of 93% or more and a solvent resistance index of 50 or less.
- Resin fine particles obtained by polymerizing a vinyl-based monomer wherein the vinyl-based monomer contains a reactive surfactant having a polyoxyalkylene chain in the molecule, and the resin fine particles are vinyl.
- a resin comprising a step, a vinyl-based monomer, an aqueous medium, and a second polymerization step of absorbing a monomer emulsion containing a reactive surfactant having a polyoxyalkylene chain in the molecule into the seed particles and then polymerizing.
- Method for producing fine particles [10]
- the vinyl-based monomer is a monofunctional (meth) acrylic monomer, a monofunctional aromatic vinyl-based monomer, a polyfunctional (meth) acrylic monomer, and a polyfunctional aromatic vinyl-based monomer.
- the method for producing resin fine particles according to [9] which comprises one or more selected from the monomers.
- the resin fine particles obtained in the second polymerization step are spray-dried under the conditions of an inlet temperature of 80 to 220 ° C. and an outlet temperature of 50 to 100 ° C. to obtain an aggregate.
- the method for producing resin fine particles according to [11] which comprises a crushing step of crushing the aggregate to disperse the resin fine particles.
- the method for producing resin fine particles according to any one of [9] to [12] which comprises a classification step for classifying resin fine particles.
- the present invention provides resin fine particles having solvent resistance that can withstand a heating step after solvent dispersion, less generation of bubbles during dispersion, and excellent dispersibility in a solvent, and a method for producing the same.
- the resin fine particles of the present invention are particles that do not easily swell even when heated in a state of being dispersed in a solvent and have a small variation in particle size.
- the amount of free surfactant is small, a cleaning step is not required and the productivity is excellent.
- the resin fine particles of the present invention are resin fine particles obtained by polymerizing a vinyl-based monomer, and are characterized by having a gel content of 93% or more and a solvent resistance index of 50 or less. Is. Further, it is a resin fine particle obtained by polymerizing a vinyl-based monomer, and the vinyl-based monomer is a monofunctional vinyl-based monomer, a polyfunctional vinyl-based monomer, and a polyoxyalkylene chain in the molecule. It is a resin fine particle characterized by containing a reactive surfactant having a above-mentioned substance and containing a hydroxyl group at the end of the vinyl polymerized chain of the resin fine particle.
- the resin fine particles of the present invention are obtained by polymerizing a vinyl-based monomer.
- the vinyl-based monomer in the present invention is selected from a monofunctional vinyl-based monomer having one vinyl group in one molecule and a polyfunctional vinyl-based monomer having two or more vinyl groups in one molecule. More than a seed.
- Examples of the monofunctional vinyl-based monomer include a monofunctional (meth) acrylic-based monomer and a monofunctional aromatic vinyl-based monomer.
- the polyfunctional vinyl-based monomer include a polyfunctional (meth) acrylic-based monomer and a polyfunctional aromatic vinyl-based monomer.
- (meth) acrylic refers to acrylic or methacrylic
- (meth) acrylate” refers to acrylate or methacrylate.
- Examples of the monofunctional (meth) acrylic monomer include methyl (meth) acrylic acid (methyl methacrylate, methyl acrylate), ethyl (meth) acrylic acid, propyl (meth) acrylic acid, and (meth) acrylic acid.
- Alicyclic structure such as (meth) acrylic acid alkyl ester having 1 to 20 carbon atoms of alkyl group, cyclohexyl (meth) acrylic acid, isobornyl (meth) acrylic acid, dicyclopentanyl (meth) acrylic acid, etc.
- examples include the (meth) acrylic acid ester possessed by.
- Examples of the monofunctional aromatic vinyl-based monomer include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, ⁇ -methylstyrene, t-butylstyrene, vinylnaphthalene, styrenesulfonic acid, and styrenesulfone.
- Examples thereof include acid salts (sodium styrene sulfonate, ammonium styrene sulfonate, etc.), vinyl benzoic acid, hydroxystyrene, and the like.
- styrene, ⁇ -methylstyrene, and sodium styrene sulfonate are preferable.
- One of these monofunctional aromatic vinyl-based monomers may be used alone, or two or more thereof may be mixed and used.
- Examples of the polyfunctional (meth) acrylic monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, decaethylene glycol di (meth) acrylate, and pentadeca.
- ethylene glycol di (meth) acrylate ethylene glycol dimethacrylate
- allyl (meth) acrylate allyl methacrylate
- One of these polyfunctional (meth) acrylic monomers may be used alone, or two or more thereof may be mixed and used.
- polyfunctional aromatic vinyl-based monomer examples include divinylbenzene and divinylnaphthalene.
- One of these polyfunctional aromatic vinyl-based monomers may be used alone, or two or more thereof may be mixed and used.
- the mass ratio of the monofunctional vinyl monomer to the polyfunctional vinyl monomer in the vinyl monomer is the monofunctional vinyl monomer / polyfunctional vinyl monomer, preferably 1/30. It can be ⁇ 30/1, more preferably 1/20 to 20/1, and even more preferably 1/10 to 10/1.
- the content of the monofunctional (meth) acrylic monomer in the vinyl-based monomer is preferably 2 to 95% by mass, more preferably 5 to 90% by mass, and further preferably 10 to 85% by mass. Can be done.
- the content of the monofunctional aromatic vinyl-based monomer in the vinyl-based monomer is preferably 0 to 25% by mass, more preferably 0 to 20% by mass, and further preferably 0 to 18% by mass. it can.
- the mass ratio of the monofunctional aromatic vinyl monomer to the monofunctional (meth) acrylic monomer in the monofunctional vinyl monomer is the monofunctional aromatic vinyl monomer / monofunctional (meth).
- the acrylic monomer can be preferably 0 to 1, more preferably 0 to 0.5, and even more preferably 0 to 0.25.
- the content of the polyfunctional (meth) acrylic monomer in the vinyl-based monomer is preferably 0.4 to 98% by mass, more preferably 0.5 to 95% by mass, still more preferably 0.5 to 0.5 to It can be 91% by mass.
- the content of the polyfunctional aromatic vinyl-based monomer in the vinyl-based monomer is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, and further preferably 0 to 15% by mass. it can.
- the mass ratio of the polyfunctional aromatic vinyl-based monomer to the polyfunctional (meth) acrylic-based monomer in the polyfunctional vinyl-based monomer is the polyfunctional aromatic vinyl-based monomer / polyfunctional (meth).
- the acrylic monomer can be preferably 0 to 33, more preferably 0 to 30, and even more preferably 0 to 28.
- the monofunctional vinyl monomer / polyfunctional vinyl monomer is 2/1 to 8/1, and the content of the monofunctional (meth) acrylic monomer in the vinyl monomer is 60 to 60 to 1.
- content of monofunctional aromatic vinyl monomer in vinyl monomer is 1 to 18% by mass, monofunctional aromatic vinyl monomer / monofunctional (meth) acrylic monomer 0.005 to 0.25, the content of the polyfunctional (meth) acrylic monomer in the vinyl monomer is 0.3 to 30% by mass, and the polyfunctional aromatic vinyl in the vinyl monomer.
- the content of the system monomer can be 0 to 8% by mass, and the polyfunctional aromatic vinyl-based monomer / polyfunctional (meth) acrylic-based monomer can be 0 to 30.
- the monofunctional vinyl monomer / polyfunctional vinyl monomer is 1/20 to 4/1, and the content of the monofunctional (meth) acrylic monomer in the vinyl monomer is set.
- the content of the monofunctional aromatic vinyl monomer in the vinyl monomer is 0 to 5% by mass
- the monofunctional aromatic vinyl monomer / monofunctional (meth) acrylic monomer The weight is 0 to 0.05
- the content of the polyfunctional (meth) acrylic monomer in the vinyl monomer is 85 to 98% by mass
- the polyfunctional aromatic vinyl mono in the vinyl monomer The content of the weight can be 0 to 5% by mass
- the polyfunctional aromatic vinyl-based monomer / polyfunctional (meth) acrylic-based monomer can be 0 to 5.
- vinyl-based monomers include unsaturated carboxylic acid-based monomers such as (meth) acrylic acid and hydroxyalkyl (meth) acrylate-based monomers such as hydroxyethyl (meth) acrylate. , (Meta) acrylamide monomer, (meth) acrylonitrile monomer, vinyl halide monomer such as vinyl chloride, vinyl carboxylate monomer such as vinyl acetate, olefin monomer such as ethylene
- unsaturated imide-based monomer, vinyl alcohol and the like can also be used.
- the resin fine particles of the present invention may have a gel fraction of 93% or more, preferably 95% or more, and more preferably 96% or more.
- the gel fraction of the resin fine particles of the present invention means the abundance ratio of the crosslinked portion expressing solvent insolubility in the resin fine particles.
- the resin fine particles can be stably dispersed in an organic solvent such as toluene. Moreover, even if it is heated after that, the resin fine particles do not dissolve.
- the resin fine particles of the present invention may have a solvent resistance index of 50 or less, preferably 25 or less, and more preferably 10 or less.
- the lower limit of the solvent resistance index is not particularly limited.
- the solvent resistance index of the resin fine particles in the present invention was obtained by the following measuring method.
- volume average particle size of the heated resin fine particles is measured by the particle size distribution measuring device, and the solvent resistance index is obtained according to the following formula.
- Solvent resistance index (%) 100 ⁇ (volume average particle size of resin fine particles after heating (nm) -volume average particle size of resin fine particles (nm)) / volume average particle size of resin fine particles (nm)
- the resin fine particles of the present invention may be obtained by polymerizing a vinyl-based monomer containing a reactive surfactant having a polyoxyalkylene chain in the molecule.
- a reactive surfactant having a polyoxyalkylene chain in the molecule is an interface having a double bond capable of copolymerizing with a monomer in the polymerization system and a polyoxyalkylene chain which is a polymer of oxyalkylene in the molecule. It is an activator.
- a reactive surfactant By using such a reactive surfactant, the mechanical stability of the resin fine particles can be enhanced without the surfactant being desorbed from the surface of the resin fine particles. Further, even if the amount used is reduced, the polymerization can be carried out without impairing the polymerization stability.
- Examples of the monomer constituting the polyoxyalkylene chain include oxyalkylenes such as ethylene oxide, propylene oxide and butylene oxide. Further, the reactive surfactant having a polyoxyalkylene chain may be used alone or in combination of two or more.
- the reactive surfactant examples include polyoxyethylene-1- (allyloxymethyl) alkyl ether sulfate ammonium salt (“Aqualon KH1025” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), polyoxyethylene nonylpropenyl ether sulfate. Salts ("Aqualon HS1025", "Aqualon BC-10", etc.
- Anionic reactive emulsifier having a reactive group such as a group, an acrylate group, or a methacrylate group;
- Polyoxyethylene nonylpropenyl ether (“Aqualon RN” manufactured by Daiichi Kogyo Seiyaku Co., Ltd., etc.), polyoxyethylene allylglycidyl nonylphenyl ether (“Adecaria Soap NE” manufactured by ADEKA, etc.), polyoxyalkylene glycol monoacrylate (Nippon Oil) Lauroxypolyethylene glycol monoacrylate (Nichiyu's "Blemmer ALE”, etc.), Lauroxypolyethylene glycol monomethacrylate (Nichiyu's "Blemmer PLE", etc.), manufactured by Blemmer AET, Blemmer APT, etc.) , Stearoxy Polyethylene Glycol Monomethacrylate (Nichiyu Co., Ltd.
- Blemmer PSE Stearoxy Polyethylene Glycol-Polypropylene Glycol Monoacrylate (Nichiyu Co., Ltd. "Blemmer ASEP”, etc.) "Blemmer PNEP”, “Blemmer PNPE”, etc.), Nonylphenoxypolyoxyalkylene glycol monoacrylate (Nippon Oil Co., Ltd.
- the amount of the reactive surfactant used is preferably 0.1 to 20 parts by mass, more preferably 0.3 to 15 parts by mass, and further preferably 0.5 to 0.5 parts by mass with respect to 100 parts by mass of the vinyl-based monomer.
- the range is 10 parts by mass.
- the resin fine particles of the present invention may contain a hydroxyl group derived from a polymerization initiator at the end of the vinyl polymerization chain.
- Such resin fine particles can be obtained by using a polymerization initiator containing a hydroxyl group when polymerizing a vinyl-based monomer.
- a polymerization initiator containing a hydroxyl group for example, an azo-based polymerization initiator containing a hydroxyl group and the like can be mentioned as preferable.
- Examples of the azo polymerization initiator containing a hydroxyl group include 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide] (trade name "VA-086”), 2,2'-. Azobis ⁇ 2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide ⁇ (trade name "VA-080”), 2,2'-azobis ⁇ 2-methyl-N- [1,1-bis (hydroxymethyl) ethyl] propionamide ⁇ (trade name "VA-082”), 2,2'-azobis ⁇ 2-methyl-N- [2- (1-hydroxybutyl)]-propion Amide ⁇ (trade name "VA-085") (both manufactured by Fujifilm Wako Junyaku Co., Ltd.) and the like.
- the azo-based polymerization initiator containing these hydroxyl groups one type may be used alone, or two or more types may be mixed and used.
- the amount of the polymerization initiator used is preferably 0.1 to 2 parts by mass, more preferably 0.2 to 1 part by mass, and even more preferably 0.3 to 0 parts by mass with respect to 100 parts by mass of the vinyl-based monomer.
- the range is 8 parts by mass.
- the volume average particle diameter of the resin fine particles of the present invention is not particularly limited, and is appropriately set according to the purpose and application.
- the range is preferably 10 to 1000 nm, more preferably 30 to 750 nm, and even more preferably 50 to 500 nm.
- the coefficient of variation of the volume average particle size of the resin fine particles of the present invention is not particularly limited.
- the range is preferably 25% or less, more preferably 23% or less, still more preferably 21% or less.
- the amount of the residual surfactant with respect to 100 parts by mass of the resin fine particles of the resin fine particles of the present invention is not particularly limited and is appropriately set according to the purpose and application.
- the range is preferably 0.01 to 1 part by mass, more preferably 0.03 to 0.7 parts by mass, and further preferably 0.05 to 0.5 parts by mass.
- setting the amount of the residual surfactant to less than 0.01 parts by mass may complicate the process and may be disadvantageous in terms of cost and the like. If the amount of the residual surfactant is 1 part by mass or more, foaming may occur when the resin fine particles are dispersed in the medium.
- the amount of residual surfactant of the present invention can be determined, for example, as follows.
- the resin fine particles were extracted with a solvent and measured using a liquid chromatograph linear ion trap type mass spectrometer (LC / MS / MS apparatus).
- LC / MS / MS apparatus As the LC / MS / MS apparatus, "ULHPLC ACCELA” manufactured by Thermo Fisher Scientific and "Linear Ion Trap LC / MSn LXQ" manufactured by Thermo Fisher Scientific can be used.
- the content of the surfactant is measured by the method shown below.
- the extract After precisely weighing about 0.01 g of resin fine particles into a centrifuge tube, the extract is poured, the resin fine particles and the extract are mixed well, ultrasonic extraction is performed, and then the mixture is mixed again and centrifuged to obtain the obtained product.
- the obtained supernatant was filtered and used as a test solution.
- the concentration of the surfactant in this test solution was calculated from the calibration curve prepared in advance from the peak area value on the obtained chromatogram using an LC / MS / MS apparatus. Then, from the measured concentration of the surfactant in the test solution, the weight of the resin fine particles used as the sample (sample weight), and the amount of the extract, the content of the surfactant in the resin fine particles is calculated by the following formula. Asked.
- solvent dispersibility The solvent dispersibility of the resin fine particles of the present invention is evaluated on the basis of good when the solvent resistance index is 50 or less. When the solvent resistance index is 50 or less, it means that the change in the volume average particle size of the resin fine particles after heating is small, and the resin fine particles are not swollen and dispersed without agglomeration in the solvent. Means that you are.
- Number average particle size The number average particle size of the resin fine particles of the present invention is not particularly limited, and is appropriately set according to the purpose and application. It is preferably in the range of 10 to 1000 nm, more preferably 30 to 750 nm, and even more preferably 50 to 350 nm.
- the monodispersity of the resin fine particles of the present invention is not particularly limited, and is appropriately set according to the purpose and application.
- the range is preferably 1.2 or less, more preferably 1.15 or less, and even more preferably 1.12 or less.
- the resin fine particles of the present invention include plasticizers, anti-bonding agents, bubble modifiers, cross-linking agents, fillers, lubricants, colorants, fusion promoters, spreading agents, etc., as long as the effects of the present invention are not impaired. Additives such as antioxidants, flame retardants and flame retardants may be included.
- the resin fine particles can be produced by polymerizing a vinyl-based monomer in the presence of a polymerization initiator or a surfactant (emulsifier), if necessary.
- the polymerization initiator used in the polymerization of the resin fine particles of the present invention is not particularly limited, but it is preferable to use a thermally decomposable water-soluble polymerization initiator.
- the thermodegradable water-soluble polymerization initiator include persulfates such as ammonium persulfate, potassium persulfate, and sodium persulfate, and 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propion.
- it since it has little effect on the slurry pH after polymerization, it is preferably a water-soluble azo polymerization initiator, and from the viewpoint of improving the dispersibility of the resin fine particles, it has a hydroxyl group in the molecule and the resin fine particles are vinyl. Those capable of introducing a hydroxyl group derived from a polymerization initiator into the terminal of the polymerization chain are preferable.
- a polymerization initiator other than the water-soluble polymerization initiator can also be used.
- examples of such a polymerization initiator include cumenehydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, benzoyl peroxide, lauroyl peroxide, dimethylbis (tert-butylperoxy) hexane, and dimethylbis.
- persulfates and organic peroxide polymerization initiators sodium sulfoxylate formaldehyde, sodium hydrogen sulfite, ammonium hydrogen sulfite, sodium thiosulfite, ammonium thiosulfate, hydrogen peroxide, sodium hydroxymethanesulfite,
- a redox-based initiator that is a combination of L-ascorbic acid and a reducing agent such as a salt thereof, a ferrous salt, and a ferrous salt may be used as the polymerization initiator. Only one kind of these polymerization initiators may be used, or two or more kinds thereof may be mixed and used.
- these polymerization initiators are preferably 0.1 to 2 parts by mass, more preferably 0.2 to 1 part by mass, and further preferably 0.3 to 0 with respect to 100 parts by mass of the vinyl-based monomer. . Used in the range of 8 parts by mass.
- the surfactant for producing the resin fine particles of the present invention is not particularly limited, but it is preferable to use a reactive surfactant.
- a reactive surfactant examples include JS-20 and RS-3000 of Eleminor (registered trademark) manufactured by Sanyo Kasei Kogyo Co., Ltd., and KH-10 of Aqualon (registered trademark) manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
- KH-1025, KH-05, HS-10, HS-1025, BC-0515, BC-10, BC-1025, BC-20, BC-2020, AR-1025, AR-2025, Kao's Latemuru examples thereof include S-120, S-180A, S-180, PD-104 of (registered trademark), SR-1025, SE-10N of ADEKA Corporation's Adecaria Soap (registered trademark).
- the nonionic reactive surfactant include alkyl ethers (commercially available products include, for example, ADEKA ADEKA Adecaria Soap ER-10, ER-20, ER-30, ER-40, and Kao Latemul.
- PD-420, PD-430, PD-450, etc. Alkylphenyl ether type or alkylphenyl ester type (Commercially available products include, for example, Aqualon RN-10, RN-20, RN-30, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. RN-50, AN-10, AN-20, AN-30, AN-5065, ADEKA Adecaria Soap NE-10, NE-20, NE-30, NE-40, etc.); (Meta) acrylate sulfate ester (Commercial products include, for example, RMA-564, RMA-568, RMA-1114, etc. manufactured by Nippon Ester Co., Ltd.) and the like. Among these reactive surfactants, those having a polyoxyalkylene chain in the molecule are preferable from the viewpoint of particle dispersibility, dispersion stability and the like.
- a surfactant other than the reactive surfactant can also be used.
- a surfactant any of an anionic surfactant, a cationic surfactant, an amphoteric ionic surfactant and a nonionic surfactant can be used.
- anionic surfactant examples include sodium oleate; fatty acid soap such as castor oil potassium soap; alkyl sulfate ester salts such as sodium lauryl sulfate and ammonium lauryl sulfate; alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate; alkylnaphthalene.
- nonionic surfactant examples include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxysorbitan fatty acid ester, polyoxyethylene alkyl amine, glycerin fatty acid ester, and oxy.
- examples thereof include ethylene-oxypropylene block polymer.
- Examples of the cationic surfactant include alkylamine salts such as laurylamine acetate and stearylamine acetate; and quaternary ammonium salts such as lauryltrimethylammonium chloride.
- Examples of the amphoteric ion surfactant include lauryldimethylamine oxide, a phosphate ester-based surfactant, and a phosphite ester-based surfactant.
- One of these surfactants may be used alone, or two or more thereof may be mixed and used.
- the type of surfactant is appropriately selected and the amount used is appropriately adjusted in consideration of the particle size of the obtained resin fine particles, the dispersion stability of the polymerizable monomer during polymerization, and the like.
- the amount of the surfactant used is preferably 0.3 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, and further preferably 0.7 to 10 parts by mass with respect to 100 parts by mass of the vinyl-based monomer. Used in the range of parts by mass.
- an aqueous medium As the medium used at the time of polymerization, either an aqueous medium or a non-aqueous medium can be used. In the present invention, it is preferable to use an aqueous medium.
- the aqueous medium include water (ion-exchanged water and the like) and a mixed solvent of water and a water-soluble solvent (lower alcohol such as ethanol).
- a dispersant may be used to stabilize the dispersibility of the droplets of the vinyl-based monomer and the seed particles.
- examples of such dispersants include organic dispersants such as partially saponified polyvinyl alcohol, polyacrylate, polyvinylpyrrolidone, carboxymethylcellulose, and methylcellulose; magnesium pyrophosphate, calcium pyrophosphate, calcium phosphate, calcium carbonate, magnesium phosphate, etc.
- examples thereof include inorganic dispersants such as magnesium carbonate and magnesium oxide. When an inorganic dispersant is used, it is preferable to use a surfactant in combination.
- the polymerization method of the vinyl-based monomer is not particularly limited as long as it is a known polymerization method. If necessary, a polymerization initiator or a surfactant (emulsifier) is used. For example, methods such as seed polymerization, emulsion polymerization, and suspension polymerization can be mentioned.
- resin fine particles composed of a polymer of vinyl-based monomers are used as seed particles, the vinyl-based monomers are absorbed by the seed particles in an aqueous medium, and the vinyl-based monomers are polymerized in the seed particles. It is a method to make it. In this method, by growing the seed particles, resin fine particles having a particle size larger than that of the original seed particles can be obtained.
- emulsion polymerization an aqueous medium, a vinyl-based monomer that is difficult to dissolve in this medium, and a surfactant (emulsifier) are mixed, and a polymerization initiator that is soluble in the aqueous medium is added thereto to carry out polymerization. The method.
- Emulsion polymerization is characterized in that the particle size of the obtained resin fine particles does not vary much.
- Suspension polymerization is a polymerization method in which a vinyl-based monomer and an aqueous medium are mechanically stirred to suspend the vinyl-based monomer in an aqueous medium for polymerization.
- Suspension polymerization is characterized in that resin fine particles having a small particle size and a relatively uniform particle size can be obtained. In the present invention, seed polymerization is most preferable.
- the method for polymerizing the vinyl-based monomer for obtaining seed particles used for seed polymerization is not particularly limited, but is limited to dispersion polymerization, emulsion polymerization, soap-free emulsion polymerization (emulsion polymerization without using a surfactant as an emulsifier), and the like. Seed polymerization, suspension polymerization and the like can be used. In order to obtain resin fine particles having a substantially uniform particle size by seed polymerization, it is necessary to first use seed particles having a substantially uniform particle size and to grow these seed particles substantially uniformly.
- the seed particles having a substantially uniform particle size as a raw material are polymerization methods such as soap-free emulsion polymerization of vinyl-based monomers (emulsion polymerization without using a surfactant), polymerization using a reactive surfactant, and dispersion polymerization. It can be made by polymerizing with.
- the reactive surfactant is not particularly limited, but it is preferable to use a reactive surfactant having a polyoxyalkylene chain in the molecule. Therefore, emulsion polymerization, soap-free emulsion polymerization, seed polymerization and dispersion polymerization are preferable as the polymerization method for polymerizing the vinyl-based monomer to obtain seed particles.
- a polymerization initiator is also used as necessary in the polymerization for obtaining seed particles.
- the polymerization initiator the above-mentioned polymerization initiator can be used.
- the amount of the polymerization initiator used is preferably in the range of 0.1 to 2 parts by mass with respect to 100 parts by mass of the vinyl-based monomer used to obtain the seed particles.
- the weight average molecular weight of the obtained seed particles can be adjusted by the amount of the polymerization initiator used.
- a molecular weight adjusting agent may be used to adjust the weight average molecular weight of the obtained seed particles.
- the molecular weight modifier include mercaptans such as n-octyl mercaptan and tert-dodecyl mercaptan; ⁇ -methylstyrene dimer; terpenes such as ⁇ -terpinene and dipentene; halogenated hydrocarbons such as chloroform and carbon tetrachloride. Etc. can be used.
- the weight average molecular weight of the obtained seed particles can be adjusted by adjusting the amount of the molecular weight adjusting agent used.
- the volume average particle size of the seed particles can be appropriately adjusted according to the average particle size of the resin fine particles. It is preferably in the range of 1 to 300 nm, and its average mass is 1 to 100 mg / 100 grains.
- the shape thereof may be a true sphere, an elliptical sphere (egg-shaped), or the like.
- seed particles are added to an emulsion containing a vinyl-based monomer and an aqueous medium.
- the emulsion can be prepared by a known method.
- an emulsion can be obtained by adding a vinyl-based monomer to an aqueous medium and dispersing it with a fine emulsifier such as a homogenizer, an ultrasonic processor, or a nanomizer (registered trademark).
- a surfactant In seed polymerization, it is preferable to use 0.3 to 15 parts by mass of a surfactant with respect to 100 parts by mass of the vinyl-based monomer.
- the surfactant the above-mentioned surfactant can be used. If the amount of the surfactant used is less than the above range, the polymerization stability may be lowered. Further, when the amount of the surfactant used is larger than the above range, it is uneconomical in terms of cost.
- 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 vinyl-based monomer is absorbed by the seed particles. This absorption can usually be carried out by stirring the emulsion at room temperature (about 25 ° C.) for 1-12 hours. Further, in order to promote the absorption of the vinyl-based monomer into the seed particles, the emulsion may be heated to about 30 to 50 ° C.
- Seed particles swell by absorbing vinyl-based monomers.
- the mixing ratio of the vinyl-based monomer and the seed particles is preferably in the range of 1 to 100 parts by mass with respect to 1 part by mass of the seed particles, and is in the range of 5 to 50 parts by mass. It is more preferable to be inside.
- the mixing ratio of the vinyl-based monomers is smaller than the above range, the increase in particle size due to polymerization is small, so that the production efficiency is lowered.
- the mixing ratio of the vinyl-based monomer is larger than the above range, the vinyl-based monomer is not completely absorbed by the seed particles and is independently emulsion-polymerized in the aqueous medium, resulting in an unintended abnormal particle size. Resin fine particles may be produced.
- the completion of absorption of the vinyl-based monomer into the seed particles can be determined by confirming the enlargement of the particle size by observing with an optical microscope.
- a resin fine particle dispersion is obtained by polymerizing the vinyl-based monomer absorbed by the seed particles.
- the resin fine particle dispersion may be obtained by repeating the steps of absorbing the vinyl-based monomer into the seed particles and polymerizing them a plurality of times.
- a polymerization initiator When polymerizing the vinyl-based monomer absorbed by the seed particles, a polymerization initiator may be added if necessary. After mixing the polymerization initiator with the vinyl-based monomer, the obtained mixture may be dispersed in an aqueous medium, or both the polymerization initiator and the vinyl-based monomer are separately dispersed in the aqueous medium. May be mixed. 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 because the vinyl-based monomer is efficiently absorbed by the seed particles.
- the above-mentioned polymerization initiator can be used.
- the polymerization initiator is preferably used in the range of 0 to 3 parts by mass with respect to 100 parts by mass of the vinyl-based monomer.
- the polymerization temperature of the seed polymerization can be appropriately selected depending on the type of the vinyl-based monomer and the type of the polymerization initiator used as needed. For example, it is 25 to 110 ° C, preferably 50 to 100 ° C.
- the polymerization time of the seed polymerization can be appropriately selected depending on the type of the vinyl-based monomer and the type of the polymerization initiator used as needed. For example, 1 to 12 hours.
- the seed polymerization may be carried out in an atmosphere of a gas (for example, nitrogen) which is inert to the polymerization.
- the seed polymerization is preferably carried out by raising the temperature after the vinyl-based monomer and the polymerization initiator used as necessary are completely absorbed by the seed particles.
- the above-mentioned dispersant may be added to the polymerization reaction system as a dispersion stabilizer in order to improve the dispersion stability of the resin fine particles.
- a dispersion stabilizer polyvinyl alcohol and polyvinylpyrrolidone are preferable.
- the amount of the dispersion stabilizer added is preferably in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the vinyl-based monomer.
- nitrites such as sodium nitrite, nitrites, hydroquinones, ascorbic acids, and water-soluble vitamin B
- a water-soluble polymerization inhibitor such as nitrite, polyphenols, etc. may be added to the aqueous medium.
- the amount of the polymerization inhibitor added is, for example, in the range of 0.002 to 0.2 parts by mass with respect to 100 parts by mass of the vinyl-based monomer.
- a monomer emulsion containing a vinyl-based monomer, an aqueous medium, and a reactive surfactant having a polyoxyalkylene chain in the molecule is used as a water-soluble polymerization initiator.
- a monomer emulsion containing a vinyl-based monomer, an aqueous medium, and a reactive surfactant having a polyoxyalkylene chain in the molecule was absorbed into the seed particles.
- a method for producing resin fine particles having a second polymerization step of subsequent polymerization can be mentioned.
- a vinyl-based monomer, ion-exchanged water, and a polyoxyalkylene chain in the molecule are provided in the same polymerizer substituted with nitrogen.
- a method for producing resin fine particles which comprises a second polymerization step of dividing or dropping a monomer emulsion composed of a surfactant such as a reactive surfactant having a chain and absorbing it in the seed particles to polymerize it. Be done.
- the resin fine particles are made into a cake containing an aqueous medium (hydrous cake) by a method such as suction filtration, centrifugation, pressure separation, etc., and if necessary, after undergoing a washing step with water and / or a solvent, dried and required. It is isolated as a dry powder through crushing and classification steps.
- the drying method is not particularly limited, but a spray drying method using a spray dryer, a freeze drying method, a drying method of adhering to a heated rotating drum such as a drum dryer, or the like can be used.
- a spray drying step is used in which the resin fine particles obtained in the second polymerization step are spray-dried under the conditions of an inlet temperature of 80 to 220 ° C. and an outlet temperature of 50 to 100 ° C. to obtain an aggregate.
- the obtained aggregate has good handleability during handling.
- the resin fine particles crushed and dispersed have good dispersibility in a solvent.
- a classification step of classifying the resin fine particles for example, it is preferable to include at least one of a classification step of classifying the resin fine particles obtained in the second polymerization step and a classification step of classifying the resin fine particles obtained in the crushing step. Classification can be performed by known means.
- the resin fine particles of the present invention can be used for various purposes. For example, additives for light diffusing plates, anti-blocking agents for various film films, various film modifiers, spacer applications between minute parts of various electronic devices, pore-forming agents for various battery members, conductive fine particles responsible for electrical connection. Core particles and the like.
- the resin fine particles of the present invention can maintain the target particle size without swelling of the resin fine particles even when a heating step is applied after the resin fine particles are dispersed in a solvent during use.
- ⁇ Gel fraction> After collecting the resin fine particles and precisely weighing them to measure the weight (W 1 g), the resin particles are immersed in 100 parts by mass of toluene, stirred at 130 ° C. for 24 hours under reflux, and then cooled. The obtained resin fine particle dispersion is centrifuged at 18,000 rpm for 30 minutes in a centrifuge, the supernatant is removed, and the mixture is dried in a vacuum dryer at 60 ° C. for 12 hours to measure the weight of the insoluble matter (W 2 g). .. Further, the gel fraction of the resin fine particles is obtained from the formula of W 2 / W 1 ⁇ 100.
- ⁇ Solvent resistance index Put 1 part by mass of resin fine particles and 50 parts by mass of toluene in a 100 mL plastic container with a lid, and defoam stirrer (Sinky, rotating / revolving mixer (atmospheric pressure type) AR-100 (trade name: Awatori Rentaro AR-100) ) (THINKY MIXER (Non Vacuum) AR-100)) for 3 minutes, and a "resin fine particle toluene dispersion" by a light turbulent light scattering method concentrated nanoparticle size distribution measuring device (CORDOUAN, "VASCO”). "Volume average particle size” is measured.
- the obtained resin fine particle toluene dispersion is placed in a glass flask equipped with a reflux tube, refluxed at 130 ° C. for 24 hours, and cooled.
- the "volume average particle size of the heated resin fine particle toluene dispersion" is measured by the particle size distribution measuring device, and the solvent resistance index is obtained according to the following formula.
- Solvent resistance index (%) 100 ⁇ (volume average particle size of resin fine particles after heating (nm) -volume average particle size of resin fine particles (nm)) / volume average particle size of resin fine particles (nm)
- ⁇ Solvent resistance> Based on the gel fraction and solvent resistance index, the solvent resistance was evaluated according to the following criteria. ⁇ : Gel fraction is 93% or more, solvent resistance index is 10 or less ⁇ : Gel fraction is 93% or more, solvent resistance index is more than 10 and 25 or less ⁇ : Gel fraction is 93% or more, solvent resistance Index exceeds 25 and 50 or less ⁇ : Gel fraction is less than 93%, solvent resistance index exceeds 50
- volume average particle size and the number average particle size of the resin fine particles were measured by a laser diffraction / scattering type particle size distribution measuring device (model number "LS230", manufactured by Beckman Coulter, Inc.). Specifically, 0.1 g of a resin fine particle aqueous dispersion (solid content 20%) and 20 ml of a 2% by mass anionic surfactant solution were put into a test tube. After that, it was dispersed over 5 minutes using a test tube mixer (manufactured by AS ONE Corporation, "Test tube mixer TRIO HM-1N”) and an ultrasonic cleaner (manufactured by AS ONE Corporation, "ULTRASONIC CLEANER VS-150").
- a test tube mixer manufactured by AS ONE Corporation, "Test tube mixer TRIO HM-1N
- ultrasonic cleaner manufactured by AS ONE Corporation, "ULTRASONIC CLEANER VS-150
- a dispersion was obtained.
- the volume average particle size and the number average particle size of the resin fine particles in the dispersion were measured while irradiating the obtained dispersion with ultrasonic waves using a laser diffraction / scattering type particle size distribution measuring device.
- the measurement conditions of the laser diffraction / scattering type particle size distribution measuring device are as follows.
- Refractive index of solid Refractive index of resin fine particles PIDS relative concentration: 40-55%
- the optical model at the time of measurement was matched with the refractive index of the produced resin fine particles.
- the refractive index of the homopolymer of the monomer was used as the refractive index of the resin fine particles.
- the refractive index of the homopolymer of each monomer is a weighted average value of the refractive index of each monomer as the refractive index of the resin fine particles.
- a volume-based particle size distribution of the resin fine particles was obtained. The arithmetic mean of the volume-based particle size distribution was taken as the volume average particle diameter of the resin fine particles.
- the content of the surfactant in the resin fine particles was measured by extracting the resin fine particles with a solvent and using a liquid chromatograph linear ion trap type mass spectrometer (LC / MS / MS apparatus).
- LC / MS / MS apparatus liquid chromatograph linear ion trap type mass spectrometer
- UHPLC ACCELA manufactured by Thermo Fisher Scientific
- UHPLC ACCELA manufactured by Thermo Fisher Scientific
- Linear Ion Trap LC / MSn LXQ was used.
- the resin fine particles in Examples and Comparative Examples described later are, as surfactants, Aqualon AR-1025 (pure content 25%, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) and AN-5065 (pure content 65%, Dai-ichi Kogyo Co., Ltd.). (Manufactured by Pharmaceutical Co., Ltd.) was used, and the content of the surfactant in the resin fine particles of Examples and Comparative Examples was measured by the method shown below. About 0.01 g of the resin fine particles as a sample was precisely weighed into a centrifuge tube, and 5 mL of methanol as an extract was poured with a whole pipette to mix the resin fine particles and the extract well.
- the concentrations of the surfactants AR-1025 and AN-5065 in this test solution were measured using an LC / MS / MS apparatus. Then, the measured concentration of the surfactant in the test solution ( ⁇ g / mL), the weight of the resin fine particles used as the sample (sample weight (g)), and the amount of the extract (extract amount (mL)) Therefore, the content ( ⁇ g / g) of the surfactant in the resin fine particles was determined by the following calculation formula. The amount of the extract is 5 mL.
- the surfactant concentration was calculated from the calibration curve prepared in advance from the peak area value on the obtained chromatogram using an LC / MS / MS apparatus.
- the method for creating a calibration curve is as follows. An intermediate standard solution (methanol solution) of about 1000 ppm of the surfactant is prepared, and then diluted stepwise with methanol to prepare standard solutions for preparing calibration curves of 20 ppm, 10 ppm, 5 ppm, and 2.5 ppm.
- the LC measurement conditions are as follows.
- Measuring device UHPLC ACCELA (manufactured by Thermo Fisher Scientific) Column: Hypersil GOLD C18 1.9 ⁇ m (inner diameter 2.1 mm, length 100 mm) (manufactured by Thermo Fisher Scientific) Column temperature: 40 ° C
- Example 1 In a polymerizer having a stirrer, a thermometer and a cooling mechanism, 320 parts by mass of ion-exchanged water and 0.08 parts by mass of the reactive surfactant Aqualon AR-1025 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) were mixed. Mix 3.8 parts by mass of methyl methacrylate and 0.2 parts by mass of ethylene glycol dimethacrylate in a separate container, put them into a polymerizer, and stir with a TK homomixer (manufactured by Primix Corporation) at 8000 rpm for 10 minutes. To obtain a monomer mixed solution.
- TK homomixer manufactured by Primix Corporation
- a slurry (1) was obtained by adding (manufactured by Yakuhin Co., Ltd.) and reacting for 1 hour.
- the resin fine particle-containing slurry was passed through a 400 Mesh nylon net to classify the resin fine particles, thereby obtaining a classified resin fine particle slurry.
- the classified resin fine particle slurry is spray-dried under the following equipment conditions using a spray dryer (manufactured by Sakamoto Giken Co., Ltd., machine name: spray dryer, model: atomizer take-up method, model number: TRS-3WK). To obtain an aggregate of resin fine particles.
- the desired resin fine particles were obtained. Obtained.
- the volume average particle diameter of the obtained resin fine particles was 212 nm, and the coefficient of variation was 19.3%.
- the volume average particle size of the toluene dispersion was 215 nm
- the volume average particle size of the toluene dispersion after heating was 228 nm
- the solvent resistance index was 6. Met.
- the amount of residual surfactant in the obtained resin fine particles was measured and found to be 0.1% by mass.
- the gel fraction of the obtained resin fine particles was measured and found to be 96%, confirming that it has solvent resistance.
- the foaming property test was carried out with the obtained resin fine particles, no foaming was observed.
- AR-1025 Anionic reactive surfactant having a polyoxyalkylene chain in the molecule
- MMA Methyl methacrylate
- EGDMA Ethylene glycol dimethacrylate
- VA-086 Water-soluble azo-based polymerization initiator (2,2'-azobis [2,2'-azobis 2-Methyl-N- (2-hydroxyethyl) propionamide])
- AN-5065 Nonionic reactive surfactant having a polyoxyalkylene chain in the molecule St: Styrene
- DVB Divinylbenzene
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Abstract
Description
本発明は、前述の課題に鑑みてなされたものであり、溶剤分散後の加熱工程にも耐えうる耐溶剤性を有し、分散時に気泡の発生が少なく、溶剤中での分散性に優れた樹脂微粒子ならびにその製造方法を提供することを目的とする。
[1] ビニル系単量体を重合して得られる樹脂微粒子であって、ゲル分率が93%以上、耐溶剤性指数が50以下であることを特徴とする樹脂微粒子。
[2] ビニル系単量体を重合して得られる樹脂微粒子であって、前記ビニル系単量体が、分子中にポリオキシアルキレン鎖を有する反応性界面活性剤を含有し、樹脂微粒子のビニル重合鎖の末端に重合開始剤由来の水酸基を含むことを特徴とする樹脂微粒子。
[3] ゲル分率が93%以上、耐溶剤性指数が50以下であることを特徴とする[2]の樹脂微粒子。
[4] 体積平均粒子径が10~1000nmであることを特徴とする[1]~[3]いずれかの樹脂微粒子。
[5] 体積平均粒子径の変動係数が25%以下であることを特徴とする[1]~[4]いずれかの樹脂微粒子。
[6] 樹脂微粒子100質量部に対して、残存界面活性剤量が0.01~1質量部であることを特徴とする[1]~[5]いずれかの樹脂微粒子。
[7] 前記ビニル系単量体が、単官能(メタ)アクリル系単量体及び/又は単官能芳香族ビニル系単量体を含むことを特徴とする[1]~[6]いずれかの樹脂微粒子。
[8] 前記ビニル系単量体が、多官能(メタ)アクリル系単量体及び/又は多官能芳香族ビニル系単量体を含むことを特徴とする[1]~[7]いずれかの樹脂微粒子。
[9] ビニル系単量体、水性媒体、分子内にポリオキシアルキレン鎖を有する反応性界面活性剤を含む単量体エマルジョンを水溶性重合開始剤によって重合してシード粒子を得る第一の重合工程、ビニル系単量体、水性媒体、分子内にポリオキシアルキレン鎖を有する反応性界面活性剤を含む単量体エマルジョンを前記シード粒子に吸収したのち重合する第二の重合工程、を有する樹脂微粒子の製造方法。
[10] 前記ビニル系単量体が、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、多官能(メタ)アクリル系単量体及び多官能芳香族ビニル系単量体から選ばれる1種以上を含むことを特徴とする[9]の樹脂微粒子の製造方法。
[11] 前記第二の重合工程で得られた樹脂微粒子を、入口温度が80~220℃及び出口温度が50~100℃の条件で、噴霧乾燥して集合体を得る噴霧乾燥工程を有することを特徴とする[9]又は[10]の樹脂微粒子の製造方法。
[12] 前記集合体を解砕して樹脂微粒子を分散させる解砕工程を有することを特徴とする[11]の樹脂微粒子の製造方法。
[13] 樹脂微粒子を分級する分級工程を有することを特徴とする[9]~[12]いずれかの樹脂微粒子の製造方法。
[14] 樹脂フィルムのアンチブロッキング剤として使用されることを特徴とする[1]~[8]のいずれかに記載の樹脂微粒子。
[15] 光拡散板用添加剤として使用されることを特徴とする[1]~[8]のいずれかに記載の樹脂微粒子。
[16] 電子デバイスのスペーサーとして使用されることを特徴とする[1]~[8]のいずれかに記載の樹脂微粒子。
本発明の樹脂微粒子は、溶剤に分散させた状態で加熱しても膨潤しにくく、粒子径の変動が小さい粒子である。また、フリーの界面活性剤量が少ないため洗浄工程を要さず、生産性に優れる。
[樹脂微粒子]
本発明の樹脂微粒子は、ビニル系単量体を重合して得られる樹脂微粒子であって、ゲル分率が93%以上であり、耐溶剤性指数が50以下であることを特徴とする樹脂微粒子である。また、ビニル系単量体を重合して得られる樹脂微粒子であって、前記ビニル系単量体が、単官能ビニル系単量体、多官能ビニル系単量体及び分子中にポリオキシアルキレン鎖を有する反応性界面活性剤を含有し、樹脂微粒子のビニル重合鎖の末端に水酸基を含むことを特徴とする樹脂微粒子である。
本発明の樹脂微粒子は、ビニル系単量体を重合して得られる。
本発明におけるビニル系単量体は、1分子中にビニル基を1個有する単官能ビニル系単量体及び1分子中にビニル基を2個以上有する多官能ビニル系単量体から選ばれる1種以上である。
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等があげられる。
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等があげられる。
なお、本明細書において、「(メタ)アクリル」は、アクリル又はメタクリルを、「(メタ)アクリレート」は、アクリレート又はメタクリレートを指す。
これらの中でも、エステルに結合しているアルキル基の炭素数が1~10である、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸プロピル、(メタ)アクリル酸イソプロピル、(メタ)アクリル酸n-ブチル、(メタ)アクリル酸イソブチル、(メタ)アクリル酸s-ブチル、(メタ)アクリル酸t-ブチル、(メタ)アクリル酸ペンチル、(メタ)アクリル酸イソペンチル、(メタ)アクリル酸ヘキシル、(メタ)アクリル酸ヘプチル、(メタ)アクリル酸オクチル、(メタ)アクリル酸2-エチルヘキシル、(メタ)アクリル酸イソオクチル、(メタ)アクリル酸ノニル、(メタ)アクリル酸イソノニル、(メタ)アクリル酸デシルが汎用的で好ましく、特に耐熱性が求められる用途においては、(メタ)アクリル酸シクロヘキシル、(メタ)アクリル酸イソボルニル、(メタ)アクリル酸ジシクロペンタニルが好ましい。これら(メタ)アクリル酸アルキルエステルは、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。
ビニル系単量体中の単官能(メタ)アクリル系単量体の含有量は、好ましくは2~95質量%、より好ましくは5~90質量%、さらに好ましくは10~85質量%とすることができる。
ビニル系単量体中の単官能芳香族ビニル系単量体の含有量は、好ましくは0~25質量%、より好ましくは0~20質量%、さらに好ましくは0~18質量%とすることができる。
単官能ビニル系単量体中の単官能芳香族ビニル系単量体と単官能(メタ)アクリル系単量体との質量比は、単官能芳香族ビニル系単量体/単官能(メタ)アクリル系単量体として、好ましくは0~1、より好ましくは0~0.5、さらに好ましくは0~0.25とすることができる。
ビニル系単量体中の多官能(メタ)アクリル系単量体の含有量は、好ましくは0.4~98質量%、より好ましくは0.5~95質量%、さらに好ましくは0.5~91質量%とすることができる。
ビニル系単量体中の多官能芳香族ビニル系単量体の含有量は、好ましくは0~30質量%、より好ましくは0~20質量%、さらに好ましくは0~15質量%とすることができる。
多官能ビニル系単量体中の多官能芳香族ビニル系単量体と多官能(メタ)アクリル系単量体との質量比は、多官能芳香族ビニル系単量体/多官能(メタ)アクリル系単量体として、好ましくは0~33、より好ましくは0~30、さらに好ましくは0~28とすることができる。
例えば、上記単官能ビニル系単量体/多官能ビニル系単量体を2/1~8/1、ビニル系単量体中の単官能(メタ)アクリル系単量体の含有量を60~85質量%、ビニル系単量体中の単官能芳香族ビニル系単量体の含有量を1~18質量%、単官能芳香族ビニル系単量体/単官能(メタ)アクリル系単量体を0.005~0.25、ビニル系単量体中の多官能(メタ)アクリル系単量体の含有量を0.3~30質量%、ビニル系単量体中の多官能芳香族ビニル系単量体の含有量を0~8質量%、多官能芳香族ビニル系単量体/多官能(メタ)アクリル系単量体を0~30とすることができる。
また、例えば、上記単官能ビニル系単量体/多官能ビニル系単量体を1/20~4/1、ビニル系単量体中の単官能(メタ)アクリル系単量体の含有量を5~15質量%、ビニル系単量体中の単官能芳香族ビニル系単量体の含有量を0~5質量%、単官能芳香族ビニル系単量体/単官能(メタ)アクリル系単量体を0~0.05、ビニル系単量体中の多官能(メタ)アクリル系単量体の含有量を85~98質量%、ビニル系単量体中の多官能芳香族ビニル系単量体の含有量を0~5質量%、多官能芳香族ビニル系単量体/多官能(メタ)アクリル系単量体を0~5とすることができる。
本発明の樹脂微粒子は、ゲル分率が93%以上、好ましくは95%以上、より好ましくは96%以上であってもよい。
本発明の樹脂微粒子のゲル分率は、樹脂微粒子中に存在する、溶剤不溶性を発現する架橋部分の存在割合を意味する。
ゲル分率が93%以上であると、樹脂微粒子をトルエン等の有機溶剤に安定して分散させることができる。また、その後に加熱しても、樹脂微粒子が溶解することがない。
本発明の樹脂微粒子は、耐溶剤性指数が50以下、好ましくは25以下、より好ましくは10以下であってもよい。耐溶剤性指数の下限値は、特に限定されない。
本発明における樹脂微粒子の耐溶剤性指数は、以下の測定方法で得られたものである。
-耐溶剤性指数の測定方法-
樹脂微粒子1質量部とトルエン50質量部を100mL蓋付プラスチック容器に入れ、脱泡攪拌機(シンキー社製、自転・公転ミキサー(大気圧タイプ)AR-100(商品名:あわとり練太郎 AR-100(THINKYMIXER(Non Vacuum) AR-100)))にて3分間攪拌し、動的光散乱方式 濃厚系ナノ粒子径分布測定装置(CORDOUAN社製、「VASCO」)により「樹脂微粒子の体積平均粒子径」を測定する。続いて、得られた樹脂微粒子トルエン分散体を還流管付きガラスフラスコに入れ、130℃で24時間還流を行い、冷却する。得られた加熱後の樹脂微粒子トルエン分散体について、前記粒子径分布測定装置にて「加熱後の樹脂微粒子の体積平均粒子径」を測定し、下式に従って耐溶剤性指数を求める。
耐溶剤性指数(%)=100×(加熱後の樹脂微粒子の体積平均粒子径(nm)-樹脂微粒子の体積平均粒子径(nm))/樹脂微粒子の体積平均粒子径(nm)
本発明の樹脂微粒子は、分子中にポリオキシアルキレン鎖を有する反応性界面活性剤を含有しているビニル系単量体を重合して得られるものでもよい。
ポリオキシアルキレン鎖を構成する単量体としては、エチレンオキサイド、プロピレンオキサイド及びブチレンオキサイドのようなオキシアルキレンがあげられる。また、ポリオキシアルキレン鎖を有する反応性界面活性剤は単独で使用してもよく、2種以上を併用しても良い。
反応性界面活性剤の使用量は、ビニル系単量体100質量部に対して、好ましくは0.1~20質量部、より好ましくは0.3~15質量部、さらに好ましくは0.5~10質量部の範囲とされる。
本発明の樹脂微粒子は、ビニル重合鎖の末端に重合開始剤由来の水酸基を含むものでもよい。
このような樹脂微粒子は、ビニル系単量体の重合に際して、水酸基を含む重合開始剤を用いることで得ることができる。
水酸基を含む重合開始剤としては、例えば、水酸基を含むアゾ系重合開始剤等を好ましいものとしてあげることができる。
水酸基を含むアゾ系重合開始剤としては、例えば、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](商品名「VA-086」)、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}(商品名「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)エチル]プロピオンアミド}(商品名「VA-082」)、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}(商品名「VA-085」)(いずれも、富士フイルム和光純薬社製)等があげられる。これらの水酸基を含むアゾ系重合開始剤は、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。
重合開始剤の使用量は、ビニル系単量体100質量部に対して、好ましくは0.1~2質量部、より好ましくは0.2~1質量部、さらに好ましくは0.3~0.8質量部の範囲とされる。
(体積平均粒子径及びその変動係数)
本発明の樹脂微粒子の体積平均粒子径は、特に限定されず、目的や用途に応じて適宜設定される。好ましくは10~1000nm、より好ましくは30~750nm、さらに好ましくは50~500nmの範囲とされる。
本発明の樹脂微粒子の体積平均粒子径の変動係数は、特に限定されない。好ましくは25%以下、より好ましくは23%以下、さらに好ましくは21%以下の範囲とされる。
樹脂微粒子の体積平均粒子径の変動係数(CV値)は、以下の数式から算出される。
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
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。好ましくは0.01~1質量部、より好ましくは0.03~0.7質量部、さらに好ましくは0.05~0.5質量部の範囲とされる。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質量部以上であると、樹脂微粒子を媒体に分散させた場合に泡立ちが発生してしまうおそれがある。
本発明の残存界面活性剤量は、例えば以下のようにして求めることができる。
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 Fisher Scientific社製の「UHPLC ACCELA」及びThermo Fisher Scientific社製の「Linear Ion Trap LC/MSn LXQ」を用いることができる。
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。
本発明の樹脂微粒子の溶剤分散性は、前記の耐溶剤性指数が50以下である場合に良好との基準で評価される。耐溶剤性指数が50以下であることは、加熱後の樹脂微粒子の体積平均粒子径の変化が小さいことを意味し、樹脂微粒子が膨潤していないとともに、溶剤内で凝集することなく分散していることを意味する。
(個数平均粒子径)
本発明の樹脂微粒子の個数平均粒子径は、特に限定されず、目的や用途に応じて適宜設定される。好ましくは10~1000nm、より好ましくは30~750nm、さらに好ましくは50~350nmの範囲とされる。
本発明の樹脂微粒子の単分散度は、特に限定されず、目的や用途に応じて適宜設定される。好ましくは1.2以下、より好ましくは1.15以下、さらに好ましくは1.12以下の範囲とされる。
単分散度は、以下の数式から算出される。
単分散度=(樹脂微粒子の体積平均粒子径)/(樹脂微粒子の個数平均粒子径)
本発明の樹脂微粒子には、本発明による効果を損なわない範囲内において、可塑剤、結合防止剤、気泡調整剤、架橋剤、充填剤、滑剤、着色剤、融着促進剤、展着剤、酸化防止剤、難燃剤及び難燃助剤等の添加剤が含まれていてもよい。
樹脂微粒子は、ビニル系単量体を、必要に応じて重合開始剤や界面活性剤(乳化剤)の存在下で重合させて製造することができる。
本発明の樹脂微粒子の重合に際して用いられる重合開始剤は、特に限定されないが、熱分解性の水溶性重合開始剤を用いるのが好ましい。熱分解性の水溶性重合開始剤としては、例えば、過硫酸アンモニウム、過硫酸カリウム、過硫酸ナトリウム等の過硫酸塩類、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](商品名「VA-086」)、2,2’-アゾビス[2-(2-イミダゾリン-2-イル)プロパン](商品名「VA-061」)、2,2’-アゾビス[2-(2-イミダゾリン-2-イル)プロパン]二塩酸塩(商品名「VA-044」)、2,2’-アゾビス[2-(2-イミダゾリン-2-イル)プロパン]二硫酸塩二水和物(商品名「VA-046B」)、2,2’-アゾビス(2-メチルプロピオンアミジン)二塩酸塩(商品名「V-50」)、2,2’-アゾビス[N-(2-カルボキシエチル)-2-メチルプロピオンアミジン]水和物(商品名「VA-057」)、4,4’-アゾビス(4-シアノバレリン酸)(商品名「V-501」)、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}(商品名「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)エチル]プロピオンアミド}(商品名「VA-082」)、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}(商品名「VA-085」)、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}等のアゾ化合物類があげられる。特に重合後のスラリーpHへ与える影響が少ないことから、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、分子中に水酸基を有し、樹脂微粒子のビニル重合鎖の末端に重合開始剤由来の水酸基を導入できるものが好ましい。
これらの重合開始剤は、1種のみ使用していてもよく、2種以上を混合して用いてもよい。また、これらの重合開始剤は、ビニル系単量体100質量部に対して、好ましくは0.1~2質量部、より好ましくは0.2~1質量部、さらに好ましくは0.3~0.8質量部の範囲で使用される。
本発明の樹脂微粒子を作成するための界面活性剤としては、特に制限されないが、反応性界面活性剤を用いるのが好ましい。
アニオン性の反応性界面活性剤としては、例えば、三洋化成工業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等があげられる。
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(市販品としては、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など);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(市販品としては、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など);(メタ)アクリレート硫酸エステル系(市販品としては、例えば、日本乳化剤社製RMA-564、RMA-568、RMA-1114など)などがあげられる。
これらの反応性界面活性剤の中でも、分子中にポリオキシアルキレン鎖を有するものが、粒子の分散性、分散安定性等の観点から好ましい。
両性イオン界面活性剤としては、ラウリルジメチルアミンオキサイド、リン酸エステル系界面活性剤、亜リン酸エステル系界面活性剤等があげられる。
重合時に用いられる媒体としては、水性媒体、非水性媒体のいずれも用いることができる。本発明においては、水性媒体を用いることが好ましい。水性媒体としては、水(イオン交換水等)、水と水溶性溶媒(エタノール等の低級アルコール)との混合溶媒があげられる。
重合時に水性媒体を用いる場合には、ビニル系単量体の液滴や種粒子の分散性を安定させるために分散剤を用いてもよい。このような分散剤としては、例えば、部分けん化ポリビニルアルコール、ポリアクリル酸塩、ポリビニルピロリドン、カルボキシメチルセルロース、メチルセルロース等の有機系分散剤;ピロリン酸マグネシウム、ピロリン酸カルシウム、リン酸カルシウム、炭酸カルシウム、リン酸マグネシウム、炭酸マグネシウム、酸化マグネシウム等の無機系分散剤があげられる。無機系分散剤を用いる場合には、界面活性剤を併用することが好ましい。
樹脂微粒子の製造に際して、ビニル系単量体の重合方法は、公知の重合方法であれば特に限定されるものではない。必要に応じて重合開始剤や界面活性剤(乳化剤)を用いる。例えば、シード重合、乳化重合、懸濁重合等の方法があげられる。
乳化重合は、水性媒体と、この媒体に溶解し難いビニル系単量体と、界面活性剤(乳化剤)とを混合し、そこに水性媒体に溶解可能な重合開始剤を加えて重合を行う重合方法である。乳化重合は、得られる樹脂微粒子の粒子径のばらつきが少ないという特徴がある。
懸濁重合は、ビニル系単量体と水性媒体とを機械的に攪拌して、ビニル系単量体を水性媒体中に懸濁させて重合させる重合方法である。懸濁重合は、粒子径が小さく、かつ粒子径が比較的整った樹脂微粒子を得ることができるという特徴がある。
本発明においては、シード重合が最も好ましい。
シード重合に用いる種粒子を得るためのビニル系単量体の重合方法については、特に限定されないが、分散重合、乳化重合、ソープフリー乳化重合(乳化剤としての界面活性剤を用いない乳化重合)、シード重合、懸濁重合等を用いることができる。シード重合によって略均一な粒子径の樹脂微粒子を得るためには、最初に略均一の粒子径の種粒子を使用し、これらの種粒子を略一様に成長させることが必要になる。原料となる略均一な粒子径の種粒子は、ビニル系単量体のソープフリー乳化重合(界面活性剤を使用しない乳化重合)、反応性界面活性剤を用いた重合及び分散重合等の重合方法で重合することによって作ることができる。反応性界面活性剤としては、特に限定されないが、分子内にポリオキシアルキレン鎖を有する反応性界面活性剤を用いることが好ましい。したがって、ビニル系単量体を重合して種粒子を得るための重合方法としては、乳化重合、ソープフリー乳化重合、シード重合及び分散重合が好ましい。
種粒子の体積平均粒子径は、樹脂微粒子の平均粒子径に応じて適宜調整できる。好ましくは1~300nmの範囲であり、その平均質量は1~100mg/100粒である。また、その形状は、真球状、楕円球状(卵状)等があげられる。
シード重合の重合時間は、ビニル系単量体の種類や、必要に応じて用いられる重合開始剤の種類に応じて適宜選択できる。例えば1~12時間である。
シード重合は、重合に対して不活性なガス(例えば窒素)の雰囲気下で行ってもよい。
シード重合に際しては、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、昇温して行われるのが好ましい。
また、本発明の樹脂微粒子の製造方法の好ましい別の実施態様としては、窒素置換された同一の重合器内にて、ビニル系単量体、イオン交換水、分子内にポリオキシアルキレン鎖を有する反応性界面活性剤等の界面活性剤からなる単量体エマルジョンを水溶性重合開始剤によって重合する第一のシード粒子重合工程、ならびにビニル系単量体、イオン交換水、分子内にポリオキシアルキレン鎖を有する反応性界面活性剤等の界面活性剤からなる単量体エマルジョンを、分割又は滴下して前記シード粒子に吸収させて重合する第二の重合工程を経てなる樹脂微粒子の製造方法があげられる。
樹脂微粒子は、重合完了後、吸引濾過、遠心分離、加圧分離等の方法により水性媒体を含むケーキ(含水ケーキ)とし、必要により水及び/又は溶剤による洗浄工程を経た後に、乾燥し、必要により解砕、分級工程を経て乾燥粉体として単離される。
乾燥法は、特に限定されないが、スプレードライヤーによる噴霧乾燥法、凍結乾燥法、ドラムドライヤー等の加熱回転ドラムに付着させる乾燥法等を用いることができる。
本発明においては、前記第二の重合工程で得られた樹脂微粒子を入口温度が80~220℃及び出口温度が50~100℃の条件で、噴霧乾燥して集合体を得る噴霧乾燥工程を用いることが好ましい。得られた集合体は取り扱い時のハンドリング性が良い。
本発明においては、得られた集合体を解砕して樹脂微粒子を分散させる解砕工程を含むことが好ましい。解砕して分散された樹脂微粒子は、溶剤への分散性が良い。
また、本発明においては、樹脂微粒子を分級する分級工程を含むことが好ましい。例えば、前記第二の重合工程で得られた樹脂微粒子を分級する分級工程、及び前記解砕工程で得られた樹脂微粒子を分級する分級工程の少なくとも一方を含むことが好ましい。分級は、公知の手段で行うことができる。
本発明の樹脂微粒子は、種々の用途に用いることができる。例えば、光拡散板用の添加剤、各種フィルム膜のアンチブロッキング剤、各種フィルム改質剤、各種電子デバイスの微小部位間のスペーサー用途、各種電池部材の造孔剤、電気接続を担う導電性微粒子のコア粒子等があげられる。
本発明の樹脂微粒子は、使用に際して溶剤に分散させた後に加熱工程が加わる場合であっても、樹脂微粒子が膨潤することなく、目的の粒子径を維持することができる。
実施例及び比較例においては、得られた樹脂微粒子を次のようにして評価した。
樹脂微粒子を採取して精密秤量し重量(W1g)を測定した後に、100質量部のトルエンに浸漬し、130℃で24時間還流下にて攪拌後冷却する。得られた樹脂微粒子分散液を遠心分離器にて18000rpmで30分間遠心分離し、上澄液を除去し60℃の真空乾燥機で12時間乾燥し不溶分の重量(W2g)を測定する。更に、W2/W1×100の式より樹脂微粒子のゲル分率を求める。
樹脂微粒子1質量部とトルエン50質量部を100mL蓋付プラスチック容器に入れ、脱泡攪拌機(シンキー社製、自転・公転ミキサー(大気圧タイプ)AR-100(商品名:あわとり練太郎 AR-100)(THINKYMIXER(Non Vacuum) AR-100))にて3分間攪拌し、光動乱動的光散乱方式 濃厚系ナノ粒子径分布測定装置(CORDOUAN社製、「VASCO」)により「樹脂微粒子トルエン分散体の体積平均粒子径」を測定する。続いて、得られた樹脂微粒子トルエン分散体を還流管付きガラスフラスコに入れ、130℃で24時間還流を行い、冷却する。得られた加熱後の樹脂微粒子トルエン分散体について、前記粒度分布測定装置にて「加熱後の樹脂微粒子トルエン分散体の体積平均粒子径」を測定し、下式に従って耐溶剤性指数を求める。
耐溶剤性指数(%)=100×(加熱後の樹脂微粒子の体積平均粒子径(nm)-樹脂微粒子の体積平均粒子径(nm))/樹脂微粒子の体積平均粒子径(nm)
ゲル分率及び耐溶剤性指数に基づき、下記の基準で耐溶剤性を評価した。
◎:ゲル分率が93%以上、耐溶剤性指数が10以下
〇:ゲル分率が93%以上、耐溶剤性指数が10を超え25以下
△:ゲル分率が93%以上、耐溶剤性指数が25を超え50以下
×:ゲル分率が93%未満、耐溶剤性指数が50を超える
前述した耐溶剤性指数の結果に基づき、下記の基準で溶剤への分散性を評価した。
○:耐溶剤性指数が50以下
×:耐溶剤性指数が50を超える
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・コールター株式会社製)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(アズワン株式会社製、「試験管ミキサーTRIO HM-1N」)及び超音波洗浄器(アズワン株式会社製、「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により、超音波を照射しながら、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は以下のとおりである。
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。
樹脂微粒子中の界面活性剤の含有量は、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。
なお、後述する実施例及び比較例の樹脂微粒子における界面活性剤の含有量の測定には、LC/MS/MS装置として、Thermo Fisher Scientific社製の「UHPLC ACCELA」及びThermo Fisher Scientific社製の「Linear Ion Trap LC/MSn LXQ」を用いた。
また、後述する実施例及び比較例における樹脂微粒子は、界面活性剤として、アクアロンAR-1025(純分25%、第一工業製薬株式会社製)ならびにAN-5065(純分65%、第一工業製薬株式会社製)を使用しており、実施例及び比較例の樹脂微粒子における界面活性剤の含有量は、以下に示す方法により、測定した。
試料としての樹脂微粒子約0.01gを遠沈管に精秤し、抽出液としてのメタノール5mLをホールピペットで注加して、樹脂微粒子と抽出液とをよく混合させた。15分間、超音波抽出を行った後再度良く混合し、3,500rpmで60分間遠心分離を行い、これにより得られた上澄み液をジーエルサイエンス社製GLクロマトディスク非水系0.20μmで濾過したものを試験液とした。
界面活性剤の含有量(μg/g)
=試験液中の界面活性剤濃度(μg/mL)×抽出液量(mL)÷試料重量(g)
なお、界面活性剤濃度は、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。
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。
LC測定条件は、以下の通りである。
測定装置:UHPLC ACCELA(Thermo Fisher Scientific社製)
カラム:Hypersil GOLD C18 1.9μm(内径2.1mm、長さ100mm )(Thermo Fisher Scientific社製)
カラム温度:40℃
移動相:(A:10mM酢酸アンモニウム/B:アセトニトリル)
移動相条件:0min=B濃度70%
0→0.5min=B濃度70%→80%
0.5→1.5min=B濃度80%
1.5→1.6min=B濃度80%→70%
1.6→4min=B濃度70%
流量:0.3mL/min
ポンプ温度:室温(25℃)
注入量:2μL
測定時間:4min
MS測定条件は、以下の通りである。
測定装置:Linear Ion Trap LC/MSn LXQ(Thermo Fisher Scientific社
製)
イオン化法(Ionization):(ESI/positive)
シースガス(Sheath Gas):45arb
補助ガス(AUX Gas):0arb
スイープガス(Sweep Gas):0arb
スプレー電圧(I Spray Voltage):4.0kV
キャピラリー温度(Capillary Temp):350℃
キャピラリー電圧(Capillary voltage):25V
チューブレンズ電圧(Tube lens Voltage):100V
Monitoring Mass(m/z):AR-1025(SIM=730~830)、
AN-5065(SIM=730~830)
樹脂微粒子の単分散度を以下の数式によって算出した。
単分散度=(樹脂微粒子の体積平均粒子径)/(樹脂微粒子の個数平均粒子径)
底部に攪拌子を置いた200mlのビーカーにイオン交換水80mlを投入した。各実施例、比較例の樹脂微粒子0.8gを水面に浮かべ、300rpmにて30分間攪拌を実施した後の、イオン交換水への起泡性を以下の基準により評価した。
泡立ちなし:起泡性試験後、液面に泡立ちが確認されなかった。
泡立ち発生:起泡性試験後、液面に泡立ちが確認された。
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質量部と反応性界面活性剤アクアロンAR-1025(第一工業製薬社製)0.08質量部を混合した。別の容器でメタクリル酸メチル3.8質量部とエチレングリコールジメタクリレート0.2質量部をよく混合して、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75℃まで昇温し、75℃に到達した時点で、10質量部のイオン交換水に溶解させた水溶性重合開始剤VA-086(富士フイルム和光純薬株式会社製)を投入し1時間反応させることで、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質量部とアクアロンAR-1025(第一工業製薬社製)0.3質量部と反応性界面活性剤アクアロンAN-5065(第一工業製薬株式会社製)0.03質量部を混合して界面活性剤溶液を得た。さらに別の容器でメタクリル酸メチル22質量部、スチレン6質量部、エチレングリコールジメタクリレート8質量部をよく混合して、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分間攪拌することにより、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75℃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することによって、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うことによって、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、噴霧乾燥することにより、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の体積平均粒子径は212nmであり、変動係数は19.3%であった。また、耐溶剤性指数の測定方法に従って評価を実施したところ、トルエン分散体の体積平均粒子径は215nmであり、加熱後トルエン分散体の体積平均粒子径は228nmであり、耐溶剤性指数は6であった。得られた樹脂微粒子の残存界面活性剤量を測定したところ、0.1質量%であった。得られた樹脂微粒子のゲル分率を測定したところ、96%であり、耐溶剤性があることが確認された。また、得られた樹脂微粒子で起泡性試験を実施したところ、泡立ちは見られなかった。
樹脂微粒子の製造条件を表1のとおりとしたほかは、実施例1と同様の手順にて樹脂微粒子を得た。得られた樹脂微粒子の各種物性を表1に併せて示す。
AR-1025:分子内にポリオキシアルキレン鎖を有するアニオン性反応
性界面活性剤
MMA:メタクリル酸メチル
EGDMA:エチレングリコールジメタクリレート
VA-086:水溶性アゾ系重合開始剤(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])
AN-5065:分子内にポリオキシアルキレン鎖を有するノニオン性反応
性界面活性剤
St:スチレン
DVB:ジビニルベンゼン
Claims (16)
- ビニル系単量体を重合して得られる樹脂微粒子であって、ゲル分率が93%以上、耐溶剤性指数が50以下であることを特徴とする樹脂微粒子。
- ビニル系単量体を重合して得られる樹脂微粒子であって、前記ビニル系単量体が、分子中にポリオキシアルキレン鎖を有する反応性界面活性剤を含有し、樹脂微粒子のビニル重合鎖の末端に重合開始剤由来の水酸基を含むことを特徴とする樹脂微粒子。
- ゲル分率が93%以上、耐溶剤性指数が50以下であることを特徴とする請求項2に記載の樹脂微粒子。
- 体積平均粒子径が10~1000nmであることを特徴とする請求項1~3のいずれかに記載の樹脂微粒子。
- 体積平均粒子径の変動係数が25%以下であることを特徴とする請求項1~4のいずれかに記載の樹脂微粒子。
- 樹脂微粒子100質量部に対して、残存界面活性剤量が0.01~1質量部であることを特徴とする請求項1~5のいずれかに記載の樹脂微粒子。
- 前記ビニル系単量体が、単官能(メタ)アクリル系単量体及び/又は単官能芳香族ビニル系単量体を含むことを特徴とする請求項1~6のいずれかに記載の樹脂微粒子。
- 前記ビニル系単量体が、多官能(メタ)アクリル系単量体及び/又は多官能芳香族ビニル系単量体を含むことを特徴とする請求項1~7のいずれかに記載の樹脂微粒子。
- ビニル系単量体、水性媒体、分子内にポリオキシアルキレン鎖を有する反応性界面活性剤を含む単量体エマルジョンを水溶性重合開始剤によって重合してシード粒子を得る第一の重合工程、ビニル系単量体、水性媒体、分子内にポリオキシアルキレン鎖を有する反応性界面活性剤を含む単量体エマルジョンを前記シード粒子に吸収したのち重合する第二の重合工程、を有する樹脂微粒子の製造方法。
- 前記ビニル系単量体が、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、多官能(メタ)アクリル系単量体及び多官能芳香族ビニル系単量体から選ばれる1種以上を含むことを特徴とする請求項9に記載の樹脂微粒子の製造方法。
- 前記第二の重合工程で得られた樹脂微粒子を、入口温度が80~220℃及び出口温度が50~100℃の条件で、噴霧乾燥して集合体を得る噴霧乾燥工程を有することを特徴とする請求項9又は10に記載の樹脂微粒子の製造方法。
- 前記集合体を解砕して樹脂微粒子を分散させる解砕工程を有することを特徴とする請求項11に記載の樹脂微粒子の製造方法。
- 樹脂微粒子を分級する分級工程を有することを特徴とする請求項9~12のいずれかに記載の樹脂微粒子の製造方法。
- 樹脂フィルムのアンチブロッキング剤として使用されることを特徴とする請求項1~8のいずれかに記載の樹脂微粒子。
- 光拡散板用添加剤として使用されることを特徴とする請求項1~8のいずれかに記載の樹脂微粒子。
- 電子デバイスのスペーサーとして使用されることを特徴とする請求項1~8のいずれかに記載の樹脂微粒子。
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