Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K7/00—Use of ingredients characterised by shape
  • C08K7/22—Expanded, porous or hollow particles
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
  • B29C67/0007—Manufacturing coloured articles not otherwise provided for, e.g. by colour change
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
  • B01J13/02—Making microcapsules or microballoons
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
  • B01J13/02—Making microcapsules or microballoons
  • B01J13/06—Making microcapsules or microballoons by phase separation
  • B01J13/14—Polymerisation; cross-linking
• • 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
  • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/02—Elements
  • C08K3/04—Carbon
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L25/00—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 an aromatic carbocyclic ring; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2021/00—Use of unspecified rubbers as moulding material
  • B29K2021/003—Thermoplastic elastomers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2029/00—Use of polyvinylalcohols, polyvinylethers, polyvinylaldehydes, polyvinylketones or polyvinylketals or derivatives thereof as moulding material
  • B29K2029/04—PVOH, i.e. polyvinyl alcohol
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
  • B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
  • B29K2105/0032—Pigments, colouring agents or opacifiyng agents
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2507/00—Use of elements other than metals as filler
  • B29K2507/04—Carbon
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
  • B29K2995/0018—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular optical properties, e.g. fluorescent or phosphorescent
  • B29K2995/002—Coloured
• • 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
  • C08J2300/00—Characterised by the use of unspecified polymers
  • C08J2300/22—Thermoplastic resins
• • 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
  • C08J2300/00—Characterised by the use of unspecified polymers
  • C08J2300/26—Elastomers
• • 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
  • C08J2329/00—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 alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
  • C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
  • C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
• • 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
  • C08J2429/00—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 alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
  • C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
  • C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K2201/00—Specific properties of additives
  • C08K2201/002—Physical properties
  • C08K2201/005—Additives being defined by their particle size in general
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
  • C08L2205/18—Spheres
  • C08L2205/20—Hollow spheres

Definitions

• the present invention relates to a molded article.
• Hollow particles with voids inside the particles are lightweight, light diffusion, pore-forming, heat insulation, sound insulation, low dielectric, impact resistance, improved rigidity, texture, anti-sink, and improved paintability. It is used in a wide range of fields, including various molded products such as injection molded products, injection compression molded products, extrusion molded products, and hollow molded products, as well as wallpaper, paints, sealants, adhesives, and diffusion materials.
• thermoplastic hollow resin particles have superior light diffusivity compared to spherical resin particles that do not have a hollow structure, so they are said to produce excellent effects when used as light diffusion materials such as light diffusion plates.
• An object of the present invention is to provide a molded article that is less likely to suffer from poor appearance due to surface irregularities or whitening and has high strength.
• the present disclosure (1) is a molded product containing hollow particles containing a resin and a black material in the shell, the hollow particles having an average particle diameter of 3 to 200 ⁇ m.
• the present disclosure (2) is the molded article according to the present disclosure (1), wherein the black material is a black pigment or a black dye.
• the present disclosure (3) is the molded article according to the present disclosure (2), wherein the black pigment is at least one selected from the group consisting of a carbon-based black pigment and an oxide-based black pigment.
• the present disclosure (4) is the molded article according to the present disclosure (2), wherein the black dye is an organic black dye.
• the present disclosure (5) is the molded article according to any one of the present disclosure (1) to (4), wherein the content of the black material is 0.01 to 30% by weight based on the entire hollow particles.
• the present disclosure (6) is the molded article according to any one of the present disclosure (1) to (5), wherein the molded article further contains a coloring material. The present invention will be explained in detail below.
• a molded article that is an embodiment of the present invention includes hollow particles whose shells contain a resin and a black material.
• the core portion of the hollow particle may be a void, or the core portion may contain a liquid or the like, but it is preferable that the core portion be a void.
• Such voids have the advantage that the dimensions of the molded body are less likely to change even when heat is applied to the molded body, and that volatile matter from the liquid is small.
• the specific gravity may not be sufficiently reduced due to the presence of unexpanded particles, but when using hollow particles, all the particles will be affected by the specific gravity. The specific gravity of the molded body can be effectively lowered.
• the hollow particles constituting the molded article that is one embodiment of the present invention contain a black material in the shell.
• the black material exhibits black color by absorbing all light rays of sunlight including the visible light region.
• Common black pigments exhibit black color by absorbing light in the visible light range (approximately 380 to 780 nm), but in reality, they absorb light in the near-infrared wavelength range of 800 to 1,400 nm, which contributes to heat. It also absorbs light in the area.
• the dispersibility of the hollow particles in the molded body is improved, and white spots on the surface of the molded body become less noticeable. Furthermore, by containing the above-mentioned black material, the heat retention power of the molded body is increased, and temperature changes in the molded body can be reduced. In addition, by containing the above-mentioned black material, the shell strength of the hollow particles increases, and the hollow particles become less likely to be destroyed during kneading.
• the preferable lower limit of the OD value of the black material is 1.5, and the preferable upper limit is 5.0. By setting it within the above range, it is possible to obtain a molded article that has both high light-shielding properties and jet-black properties. That is, the OD value of the black material is preferably 1.5 to 5.0.
• the OD value of the above-mentioned black material refers to the OD value when an acrylic resin (coating film thickness: 1 ⁇ m) containing 50% by weight of the above-mentioned black material is measured.
• black material examples include black pigments, black dyes, black conductive polymers, and the like.
• black pigments are preferred.
• the black pigment include inorganic black pigments such as carbon black pigments and oxide black pigments, as well as organic black pigments.
• at least one selected from the group consisting of carbon-based black pigments and oxide-based black pigments is preferred.
• the carbon-based black pigment include carbon black, graphite, activated carbon, graphene, and the like.
• the carbon black include furnace black, channel black, acetylene black, thermal black, lamp black, and bone black.
• carbon nanotubes, carbon nanofibers, fullerenes, graphite, etc. may also be used.
• the above oxide-based black pigments mainly include titanium black, iron oxide, magnetite, cuprous oxide (cuprous oxide), copper and chromium, copper and manganese, copper and iron and manganese, cobalt, chromium and iron.
• Examples include complex oxide black pigments containing metal components.
• the above-mentioned inorganic black pigments include titanium black, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver, and other metal oxides, composite oxides, metal sulfides, metal sulfates, and metal carbonates. Salt etc. can also be used.
• the organic black pigment include aniline black (C.I. Pigment Black 1). Among these, carbon black is more preferable because it has excellent heat resistance, excellent dispersibility in resin, and can provide a homogeneous black color.
• black dye examples include inorganic black dyes and organic black dyes. Among them, organic black dyes are preferred.
• examples of the inorganic black dye include metal complex azo black dyes.
• Examples of the metal complex azo black dye include Neo Super Black C-832 (trade name: Solvent Black 27, manufactured by Chuo Gosei Kagaku Co., Ltd.).
• Examples of the organic black dyes include disazo black dyes, azine black dyes, phthalocyanine black dyes, anthraquinone black dyes, and indigoid black dyes.
• Examples of the disazo black dye include OIL BLACK860 (trade name: Solvent Black 3, manufactured by Orient Kagaku Co., Ltd.).
• Examples of the azine-based black dye include NUBIAN BLACK TH-807 (trade name: Solvent Black 7, manufactured by Orient Chemical Co., Ltd.).
• black conductive polymer examples include polythiophene, polydopamine, polypyrrole, polyaniline, polyphenylene vinylene, polyphenylene, polyacetylene, polyquinoxaline, polyoxadiazole, polybenzothiadiazole, and polymers having multiple of these conductive skeletons. It will be done.
• polythiophene and its derivatives are preferred, such as poly(3,4-ethylenedioxythiophene) [PEDOT], poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonate) [PEDOT/PSS], Particularly preferred is polythienothiophene.
• black fine particles fine particulate black materials
• the black fine particles preferably have an average particle diameter of 1 ⁇ m or less, more preferably 10 to 500 nm. By setting it within the above range, black fine particles are dispersed in the resin, and the hue (black) becomes uniform.
• the above average particle diameter can be measured, for example, by observation using a particle size distribution measuring device (ELSZ-2000ZS, manufactured by Otsuka Electronics Co., Ltd.), or by forming a thin film so as to pass around the center of the hollow particles dispersed in the embedding resin. It can be measured by observation using a transmission electron microscope or the like.
• the preferable lower limit of the content of the black material is 0.01% by weight, and the preferable upper limit is 30% by weight based on the entire hollow particles.
• the content By setting the content to 0.01% by weight or more, it is possible to suppress fusion of hollow particles in the resin during molding.
• the strength of the shell against melt kneading during molding can be increased, and the appearance performance can be further improved.
• a more preferred lower limit is 0.3% by weight, a more preferred upper limit is 15% by weight, an even more preferred upper limit is 10% by weight, and an even more preferred upper limit is 7% by weight.
• the content of the black material is preferably 0.01 to 30% by weight, more preferably 0.3 to 15% by weight, even more preferably 0.3 to 10% by weight, Particularly preferred is 0.3 to 7% by weight.
• the content of the black material can be determined by, for example, heating the hollow particles to 600°C in a nitrogen atmosphere at a rate of 10°C/min, holding the temperature for 10 minutes, then lowering the temperature to 400°C at a rate of 10°C/min, and holding the temperature for 10 minutes. Then, the atmosphere was changed to air, the temperature was raised to 1000°C under air, and the temperature was maintained at 1000°C for 10 minutes. It can be determined from the weight loss from 400°C to 1000°C at this time. Further, the content of the black material can also be determined by calculating from the amounts of the black material and other components added in the manufacturing process.
• the black material preferably has a specific surface area of 500 m 2 /g or less, more preferably 5 to 300 m 2 /g. By setting it within the above range, the black material is dispersed in the resin, and the hue (black) becomes uniform.
• the above specific surface area is determined by measuring the nitrogen adsorption isotherm using a surface area/pore size analyzer (NOVA4200e, manufactured by Quantachrome Instruments). Based on the measurement results, the specific surface area of the black material is determined according to the BET method. It can be measured by calculating .
• the black material preferably has a DBP (dibutyl phthalate) oil absorption of 30 cm 3 /100g or more and 140 cm 3 /100g or less.
• DBP dibutyl phthalate
• a more preferable lower limit of the DBP oil absorption amount is 45 cm 3 /100g, and a more preferable upper limit is 110 cm 3 /100g. Note that the above DBP oil absorption amount can be measured in accordance with JIS K 6221.
• the black material may be present on the shell surface of the hollow particle, may be present inside the shell, or may be present on the inner surface of the shell. It is preferable that the black material is present on the shell surface of the hollow particle. When the black material is present on the shell surface, the appearance of the molded product can be improved. Further, it is preferable that the hollow particles have an outermost layer, and the outermost layer contains a black material. With such a configuration, it is possible to further improve the dispersibility in the resin during molding. In addition, the black material may be present both on the shell surface and inside the shell, that is, a part of the black material may be exposed and a part may be present inside the shell. It can be further suppressed. The location of the black material can be confirmed using a transmission electron microscope or the like after forming a thin film so as to pass near the center of the hollow particles dispersed in the embedding resin.
• the shell constituting the hollow particle contains resin.
• the resin it is preferable to use, for example, a polymer of a monomer composition such as an unsaturated carboxylic acid monomer, a nitrile monomer, a polyfunctional monomer, a conjugated diene monomer, or a vinyl monomer. Furthermore, two or more of these may be used in combination as a copolymer. In particular, it is preferable to use a polyfunctional monomer alone or to use an unsaturated carboxylic acid monomer and a nitrile monomer together.
• (meth)acrylic acid esters and unsaturated carboxylic acids are preferred.
• the above (meth)acrylic esters include methacrylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate, and n-butyl methacrylate, or alicyclic and aromatic esters such as cyclohexyl methacrylate, benzyl methacrylate, and isobornyl methacrylate. Ring/heterocycle-containing methacrylic esters are preferred.
• unsaturated carboxylic acids examples include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, and cinnamic acid, maleic acid, itaconic acid, fumaric acid, citraconic acid, and chloromaleic acid. .
• monoesters of the above-mentioned unsaturated dicarboxylic acids may be used.
• the monoester of the unsaturated dicarboxylic acid include monomethyl maleate, monoethyl maleate, monobutyl maleate, monomethyl fumarate, monoethyl fumarate, monomethyl itaconate, monoethyl itaconate, monobutyl itaconate, and the like.
• acrylic acid, methacrylic acid, maleic acid, maleic anhydride, and itaconic acid are particularly preferred.
• the nitrile monomer is not particularly limited, and examples thereof include acrylonitrile, methacrylonitrile, ⁇ -chloroacrylonitrile, ⁇ -ethoxyacrylonitrile, fumaronitrile, and mixtures thereof. Among these, acrylonitrile and methacrylonitrile are particularly preferred. These may be used alone or in combination of two or more.
• polyfunctional monomer examples include monomers having two or more radically polymerizable double bonds, and specific examples include divinylbenzene, di(meth)acrylate, and trifunctional or higher-functional (meth)acrylates. It will be done.
• di(meth)acrylate examples include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, and 1,4-butanediol di(meth)acrylate. Examples include (meth)acrylate.
• polyethylene glycol di(meth)acrylate having a weight average molecular weight of 200 to 600 may be used.
• trifunctional (meth)acrylates examples include trimethylolpropane tri(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and triallyl formal tri(meth)acrylate. Can be mentioned. Further, examples of the above-mentioned (meth)acrylate having four or more functional functions include pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and the like.
• trifunctional ones such as trimethylolpropane tri(meth)acrylate, and difunctional (meth)acrylates such as polyethylene glycol
• trifunctional ones such as trimethylolpropane tri(meth)acrylate, and difunctional (meth)acrylates such as polyethylene glycol
• the strength of the shell can be strengthened.
• conjugated diene monomer examples include butadiene, isoprene, chloroprene, and the like.
• vinyl monomer examples include vinyl chloride, vinylidene chloride, vinyl acetate, and styrene. These may be used alone or in combination of two or more.
• the resin may contain a thermosetting resin.
• thermosetting resin examples include epoxy resin, phenol resin, melamine resin, urea resin, polyimide resin, and bismaleimide resin. Among these, epoxy resins and phenol resins are preferred.
• the above-mentioned epoxy resin is not particularly limited, and examples thereof include bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin, cresol novolak epoxy resin, dicyclopentadiene epoxy resin, glycidylamine epoxy resin, etc. Can be mentioned.
• examples of the above-mentioned phenolic resins include novolac type phenolic resins, resol type phenolic resins, benzylic ether type phenolic resins, and the like. Among these, novolac type phenolic resins are preferred.
• the thermosetting resin preferably has two or more functional groups in one molecule that react with carboxyl groups.
• the curability of the thermosetting resin can be made stronger.
• the above monomer composition contains a monomer having a carboxyl group
• the heat during heating and foaming causes the carboxyl group and the thermosetting resin to bond more firmly, significantly improving heat resistance and durability. It becomes possible to do so.
• the said thermosetting resin does not have a radically polymerizable double bond.
• Examples of the functional group that reacts with the carboxyl group include a glycidyl group, a phenol group, a methylol group, and an amino group. Among these, a glycidyl group is preferred.
• the functional groups that react with the carboxyl group the same type of functional groups may be used, or two or more types of functional groups may be used.
• a polymerization initiator is added to the monomer composition in order to polymerize the monomers.
• the polymerization initiator for example, dialkyl peroxide, diacyl peroxide, peroxy ester, peroxydicarbonate, azo compound, etc. are suitably used. Specific examples include dialkyl peroxides such as methyl ethyl peroxide, di-t-butyl peroxide, dicumyl peroxide; isobutyl peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, 3,5 , diacyl peroxides such as 5-trimethylhexanoyl peroxide, and the like.
• t-butyl peroxy pivalate t-hexyl peroxy pivalate, t-butyl peroxy neodecanoate, t-hexyl peroxy neodecanoate, 1-cyclohexyl-1-methylethyl peroxy neodecanoate, Noate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, and the like.
• peroxy esters such as cumyl peroxyneodecanoate, ( ⁇ , ⁇ -bis-neodecanoylperoxy) diisopropylbenzene; bis(4-t-butylcyclohexyl) peroxydicarbonate, di-n-propyl -oxydicarbonate, diisopropyl peroxydicarbonate, etc.
• peroxydicarbonates such as di(2-ethylethylperoxy)dicarbonate, dimethoxybutylperoxydicarbonate, and di(3-methyl-3-methoxybutylperoxy)dicarbonate.
• the preferable lower limit of the weight average molecular weight of the resin constituting the shell is 50,000, and the preferable upper limit is 2,000,000. That is, the weight average molecular weight of the resin constituting the shell is preferably 50,000 to 2,000,000. When it is 50,000 or more, the strength of the shell can be improved, and when it is 2,000,000 or less, the strength of the shell can be made moderate.
• the above weight average molecular weight is a value determined by gel permeation chromatography (GPC) using DMF as a solvent and converted into polymethyl methacrylate.
• Examples of columns for measuring the weight average molecular weight in terms of polymethyl methacrylate by GPC include HSPgel RT MB-H (manufactured by Waters), and molecular weight standards include M-75 (manufactured by Shodex). ) etc.
• the shell may contain metal cations.
• the metal cation reacts with the carboxyl group and the copolymer undergoes ionic crosslinking, improving heat resistance. , it becomes possible to form hollow particles that do not rupture or shrink for a long time in a high-temperature region.
• the elastic modulus of the shell does not easily decrease even in high-temperature ranges, hollow particles can be No rupture or contraction will occur.
• the above-mentioned ionic crosslinking means that a crosslink is formed between free carboxyl groups present as side chains of the copolymer. Note that the number of carboxyl groups arranged per monovalent metal cation differs depending on the metal species.
• the metal cation is not particularly limited as long as it reacts with the carboxyl group of the copolymer to cause ionic crosslinking of the copolymer, and examples include Li, Na, K, Zn, Mg, Ca, Examples include ions such as Ba, Sr, Mn, Al, Ti, Ru, Fe, Ni, Cu, Cs, Sn, Cr, and Pb. These may be used alone or in combination of two or more. Among these, Ca, Zn, and Al ions are preferred, and Zn ions are particularly preferred. Note that the combination when two or more of the above metal cations are used is not particularly limited, but it is preferable to use a combination of an alkali metal ion and a metal cation other than the above alkali metal.
• alkali metal ion By having the alkali metal ion, functional groups such as carboxyl groups are activated, and the reaction between metal cations other than the alkali metal and the carboxyl groups of the copolymer can be promoted.
• the alkali metal include Na, K, Li, and the like.
• the shell may further contain a stabilizer, an ultraviolet absorber, an antioxidant, an antistatic agent, a flame retardant, a silane coupling agent, a coloring agent, etc., as necessary.
• the lower limit of the average particle diameter of the hollow particles is 3 ⁇ m, and the upper limit is 200 ⁇ m.
• the porosity of the molded body can be increased, and by setting it to 200 ⁇ m or less, the appearance of the molded body can be improved.
• a preferable lower limit of the above average particle diameter is 5 ⁇ m, a more preferable lower limit is 15 ⁇ m, a preferable upper limit is 150 ⁇ m, a more preferable upper limit is 100 ⁇ m, an even more preferable upper limit is 80 ⁇ m, an especially preferable upper limit is 60 ⁇ m, and an especially more preferable upper limit is 50 ⁇ m.
• the average particle diameter of the hollow particles is 3 to 200 ⁇ m, preferably 5 to 150 ⁇ m, more preferably 15 to 100 ⁇ m, even more preferably 15 to 80 ⁇ m, and even more preferably 15 to 60 ⁇ m.
• the thickness is particularly preferably 15 to 50 ⁇ m, particularly more preferably 15 to 50 ⁇ m.
• the CV value (coefficient of variation) of the average particle diameter of the hollow particles is preferably 40% or less, more preferably 30% or less, and even more preferably 20% or less. When it is 40% or less, the air bubbles in the obtained molded product will be uniform, and the thickness can be made uniform. Furthermore, since the bubbles present on the surface of the molded product are uniform, the molded product has an excellent appearance.
• the preferable lower limit is not particularly limited, but is preferably 0%.
• the average particle diameter of the hollow particles means the number average particle diameter, and the number average particle diameter of the hollow particles is determined by measuring the particle diameter of at least 50 hollow particles in a cross section obtained by cutting the molded product using SEM etc. It can be measured by calculating the average value. Furthermore, the CV value can also be calculated at the time of the measurement. In addition, when the cross section of the hollow particle is not a perfect circle, the average value of (maximum diameter + minimum diameter)/2 is taken as the particle diameter.
• the hollow particles preferably have a ratio (A/B) of the average particle diameter of the black material (A) to the thickness of the shell (B) of 0.01 to 20. By keeping it within the above range, both the strength and appearance of the shell can be achieved. A more preferable lower limit is 0.2, and a more preferable upper limit is 5. Further, the thickness of the shell is preferably 0.01 ⁇ m or more and 1 ⁇ m or less. Further, the hollow particles preferably have a ratio (B/C) of the thickness of the shell (B) to the average particle diameter (C) of the hollow particles of 0.001 to 0.01. In addition, the thickness of the above-mentioned shell is determined by measuring the thickness of the shell of 10 hollow particles in the cross section obtained by cutting the molded body at five arbitrary points per particle using SEM etc., and calculating the average value. It can be measured by measuring the thickness of the shell of 10 hollow particles in the cross section obtained by cutting the molded body at five arbitrary points per particle using SEM etc., and calculating the average value.
• the hollow particles preferably have an optical density (OD value) of 0.5 or more.
• OD value optical density
• a more preferable lower limit is 0.8
• a more preferable upper limit is 1.6. That is, the OD value of the hollow particles is preferably 0.5 to 1.6, more preferably 0.8 to 1.6.
• the optical density (OD value) can be measured using a Macbeth densitometer or the like.
• the method for producing the hollow particles is not particularly limited, but includes, for example, a step of preparing an aqueous dispersion medium containing a dispersant, a step of adding a monomer composition, a black material, and a hollowing agent, and a step of polymerizing the monomer. It can be manufactured by performing the step of
• an aqueous dispersion medium containing a dispersant is prepared by adding water, a dispersant, and, if necessary, a co-stabilizer to a polymerization reaction vessel.
• the dispersant in addition to an emulsifier such as polyvinyl alcohol, it is preferable to use at least one inorganic compound selected from the group consisting of Si-based compounds and Mg-based compounds.
• an emulsifier such as polyvinyl alcohol
• the Si-based compound and Mg-based compound preferably contain an oxide, hydroxide, carbonate, or hydrogen carbonate of silicon or magnesium. These Si-based compounds and Mg-based compounds may be used alone or in combination of two or more.
• Examples of the Si-based compound include colloidal silica, silicate sol, etc., as well as No. 3 water glass, sodium orthosilicate, sodium metasilicate, and the like. Among them, colloidal silica is preferred.
• Examples of the Mg-based compounds include magnesium oxide, magnesium hydroxide, magnesium hydroxide oxide, hydrotalcite, dihydrotalcite, magnesium carbonate, basic magnesium carbonate, magnesium calcium carbonate, magnesium phosphate, magnesium hydrogen phosphate, and pyrroline. Examples include magnesium acid, magnesium borate, and the like. Among them, magnesium hydroxide is preferred.
• inorganic compounds that may be added include, for example, calcium phosphate, aluminum hydroxide, ferric hydroxide, barium sulfate, calcium sulfate, sodium sulfate, calcium oxalate, calcium carbonate, barium carbonate, and the like.
• inorganic salts such as sodium chloride and sodium sulfate, alkali metal nitrites, stannous chloride, stannic chloride, potassium dichromate, and the like may be added as necessary.
• the above-mentioned inorganic compound is preferably in the form of fine particles.
• the primary particle size is preferably 0.5 ⁇ m or less, more preferably 5 to 100 nm (0.1 ⁇ m). By setting it within the above range, it is possible to suppress fusion of hollow particles in the resin during molding.
• the primary particle diameter can be measured by observation using a scanning electron microscope (Regulus 8220, manufactured by Hitachi High-Technologies).
• the preferable lower limit of the amount of the dispersant added is 0.5% by weight and the preferable upper limit is 30% by weight based on the entire monomer composition.
• the content By setting the content to 0.5% by weight or more, agglomeration during hollow particle creation can be suppressed. By controlling the content to 30% by weight or less, dispersibility can be further improved.
• a more preferable lower limit is 1% by weight, and a more preferable upper limit is 25% by weight. That is, the amount of the dispersant added is preferably 0.5 to 30% by weight, more preferably 1 to 25% by weight.
• the costabilizer examples include a condensation product of diethanolamine and an aliphatic dicarboxylic acid, a condensation product of urea and formaldehyde, and the like.
• Other examples include polyvinylpyrrolidone, polyethylene oxide, polyethyleneimine, tetramethylammonium hydroxide, gelatin, methylcellulose, dioctyl sulfosuccinate, sorbitan ester, and various emulsifiers.
• condensation product in addition to the co-stabilizer, a condensation product or a water-soluble nitrogen compound may be added.
• the condensation product is preferably a condensation product of diethanolamine and an aliphatic dicarboxylic acid, particularly a condensation product of diethanolamine and adipic acid or a condensation product of diethanolamine and itaconic acid.
• water-soluble nitrogen compound examples include polyvinylpyrrolidone, polyethyleneimine, polyoxyethylenealkylamine, polydialkylaminoalkyl (meth)acrylate represented by polydimethylaminoethyl methacrylate and polydimethylaminoethyl acrylate.
• polyvinylpyrrolidone is preferably used.
• the aqueous dispersion medium containing the above dispersant and, if necessary, a co-stabilizer is prepared by blending it with deionized water, and the pH of the aqueous phase at this time is adjusted as appropriate depending on the type of dispersant and co-stabilizer used. It can be decided. For example, when using a Si-based compound such as colloidal silica as a dispersant, polymerization is performed using an acidic aqueous dispersion medium. To make the aqueous dispersion medium acidic, an acid such as hydrochloric acid may be added as necessary. In addition, the pH of the system is adjusted to 3-4. On the other hand, when an Mg-based compound such as magnesium hydroxide or calcium phosphate is used as an inorganic compound, an alkaline aqueous dispersion medium adjusted to a pH of 8 to 11 is used for polymerization.
• an Mg-based compound such as magnesium hydroxide or calcium phosphate
• a step of adding a monomer composition, a black material, and a hollowing agent is performed.
• the monomer composition, black material, and hollowing agent may be added separately to the aqueous dispersion medium to prepare an oily mixture in the aqueous dispersion medium, but usually, the two are mixed in advance and the oily The mixture may be prepared and then added to the aqueous dispersion medium.
• the oily mixture and the aqueous dispersion medium are prepared in advance in separate containers, and the oily mixture is dispersed in the aqueous dispersion medium by mixing with stirring in the separate container, and then transferred to the polymerization reaction vessel. May be added.
• a dispersant can be present at the interface between the oil droplets of the oily mixture and the aqueous dispersion medium.
• a polymerization initiator is used to polymerize the above monomer, but the polymerization initiator may be added to the oily mixture in advance, or the aqueous dispersion medium and the oily mixture may be mixed in a polymerization reaction vessel. It may be added after stirring and mixing. Note that the black material and the dispersant may be added to the aqueous dispersion medium or may be added later.
• the average particle diameter of the hollow particles obtained can be adjusted. can be controlled.
• the adjustment of the reaction process includes, for example, sufficient pre-stirring before emulsifying and dispersing the oily mixture into the aqueous dispersion medium, and emulsifying and dispersing the oily mixture into the aqueous dispersion medium with a predetermined particle size. Examples include:
• the amount of the hollowing agent added is preferably 50 to 2,800 parts by weight per 10 parts by weight of the monomer composition.
• Methods for emulsifying and dispersing the above-mentioned oily mixture in an aqueous dispersion medium with a predetermined particle size include stirring with a homomixer (for example, manufactured by Tokushu Kika Kogyo Co., Ltd.), a homogenizer, etc., a line mixer, an element type static type, etc. Examples include a method of passing through a stationary dispersion device such as a dispersion device. Moreover, the average particle diameter of the hollow particles obtained can also be controlled by adjusting the stirring force (rotation speed, etc.) during the stirring. Note that the aqueous dispersion medium and the monomer composition may be supplied separately to the static dispersion device, or a dispersion liquid that has been mixed and stirred in advance may be supplied.
• a homomixer for example, manufactured by Tokushu Kika Kogyo Co., Ltd.
• a homogenizer for example, manufactured by Tokushu Kika Kogyo Co., Ltd.
• a line mixer
• the hollowing agent is a substance for forming a hollow portion that becomes a core.
• the hollowing agent is preferably an organic solvent with a boiling point of -50 to 100°C, since it is easy to handle when drying is performed in the hollowing process.
• hollowing agent examples include n-butane, isobutane, butane, butene, isobutene, n-pentane, isopentane, neopentane, n-hexane, cyclohexane, heptane, petroleum ether, isooctane, octane, decane, isododecane, and dodecane.
• low molecular weight hydrocarbons such as hexanedecane, and the like.
• Further examples include ethyl acetate, methyl ethyl ketone, acetone, methylene chloride, chloroform, and carbon tetrachloride.
• cyclohexane, isobutane, n-butane, n-pentane, isopentane, n-hexane, isooctane, isododecane, and mixtures thereof are preferred.
• These hollowing agents may be used alone or in combination of two or more. Further, as the hollowing agent, a pyrolyzable compound that is thermally decomposed by heating to become gaseous may be used.
• the hollow particles can be produced by subjecting the dispersion obtained through the steps described above to a step of polymerizing monomers by heating and pressurizing the dispersion, and a step of washing.
• the average particle diameter of the hollow particles obtained can be controlled by controlling the temperature during heating to 40 to 100°C and the pressure during pressurization to 0.2 to 1.0 MPa. I can do it.
• a molded article that is an embodiment of the present invention contains a base resin in addition to the hollow particles described above.
• the base resin is preferably a thermoplastic resin.
• the thermoplastic resins include, for example, polyolefins such as low density polyethylene (LDPE) and polypropylene (PP), ethylene-vinyl acetate copolymers (EVA), vinyl chloride, polystyrene, thermoplastic elastomers, and olefin-based resins.
• LDPE low density polyethylene
• PP polypropylene
• EVA ethylene-vinyl acetate copolymers
• vinyl chloride vinyl chloride
• polystyrene thermoplastic elastomers
• olefin-based resins examples include thermoplastic elastomer (TPV), ethylene-methyl methacrylate copolymer (EMMA), and the like.
• LDPE, EVA, EMMA, etc. are preferred because they have a low melting point and are easy to process.
• the content of the hollow particles in the molded article that is an embodiment of the present invention is not particularly limited, but the preferable lower limit is 1 part by weight and the preferable upper limit is 90 parts by weight based on 100 parts by weight of the base resin.
• the molded article which is an embodiment of the present invention, further contains a coloring material.
• a coloring material general dyes, organic pigments, and inorganic pigments can be used, but it is preferable to use organic pigments.
• organic pigment include pigments of various colors such as blue pigment, red pigment, yellow pigment, green pigment, purple pigment, and orange pigment.
• the structures of the above organic pigments include phthalocyanine pigments, monoazo pigments, diazo pigments, azo pigments such as condensed diazo pigments, diketopyrrolopyrrole pigments, isoindolinone pigments, isoindoline pigments, and quinacridone pigments.
• polycyclic pigments such as indigo pigments, thioindigo pigments, quinophthalone pigments, dioxazine pigments, anthraquinone pigments, perylene pigments, and perinone pigments.
• indigo pigments thioindigo pigments
• quinophthalone pigments dioxazine pigments
• anthraquinone pigments perylene pigments
• perinone pigments perinone pigments.
• the blue pigment examples include organic pigments containing organic compounds as a main component, such as phthalocyanine pigments, anthraquinone pigments, and dioxazine pigments. Among them, phthalocyanine pigments are preferred, and metal phthalocyanine pigments and monohalogenated metal phthalocyanine pigments (halogenated metal phthalocyanine pigments having one halogen atom in the molecule) are more preferred. As the phthalocyanine pigment, a copper phthalocyanine pigment or a monohalogenated copper phthalocyanine pigment is preferable.
• C.I. Color Index
• C.I. I. Pigment Blue 1 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, 16, 17, 17:1, 19, 22, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79, 80, etc.
• phthalocyanine pigments include C.I. I.
• Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 17:1, and 75 are preferred, and as the copper phthalocyanine pigment and monohalogenated copper phthalocyanine pigment, C.I. I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, and 17:1 are preferred.
• C.I. I. Pigment Blue 60 is preferred.
• dioxazine pigment C.I. I. Pigment Blue 80 is preferred.
• C.I. I. Pigment Green 1 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58, 59, 62, 63,
• C.I. I. Pigment Violet 1 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50, etc.
• C.I. I. Pigment Orange 1 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 78, 79 and the like.
• the inorganic pigment examples include barium sulfate, lead sulfate, titanium oxide (rutile type, anatase type, etc.), yellow lead, red iron oxide, chromium oxide, and the like.
• a molded article having high appearance quality such as an uneven shape can be obtained, and can be suitably used for applications such as wallpaper for houses and interior materials for automobiles.
• the method for molding the molded article that is an embodiment of the present invention is not particularly limited, and examples thereof include kneading molding, calendar molding, extrusion molding, injection molding, and the like.
• a molded article that is less likely to suffer from poor appearance due to surface irregularities or whitening and has high strength can be obtained.
• Example 1 Preparation of hollow particles
• PVA polyvinyl alcohol
• GH-20 GH-20, viscosity 40 to 46 mPa s, degree of saponification 86.5 to 89.0 mol%
• ion-exchanged water 250 parts by weight of ion-exchanged water.
• aqueous medium 250 parts by weight of ion-exchanged water.
• a mixed solution After adding 26 parts by weight and performing a dispersion treatment by ultrasonic irradiation, 200 parts by weight of cyclohexane was added to prepare a mixed solution. To this mixed solution, 0.8 parts by weight of a polymerization initiator (2,2'-azobisisobutyronitrile) was added and mixed in an autoclave. As the carbon black, MA100 (manufactured by Mitsubishi Chemical Corporation, primary average particle diameter 24 nm, specific surface area 110 m 2 /g, DBP oil absorption 100 cm 3 /100 g) was used. Thereafter, it was added to an aqueous medium and suspended to prepare a dispersion.
• MA100 manufactured by Mitsubishi Chemical Corporation, primary average particle diameter 24 nm, specific surface area 110 m 2 /g, DBP oil absorption 100 cm 3 /100 g
• the resulting dispersion was stirred and mixed using a homogenizer, charged into a pressure polymerization vessel purged with nitrogen, and reacted at 60° C. for 20 hours under pressure (0.5 MPa) to obtain a reaction product.
• the obtained reaction product was repeatedly filtered and washed with water, and then dried to obtain hollow particles.
• the content of the black material was calculated from the amounts of the added black material and other components. Note that the obtained hollow particles were added to an embedding resin (Technovit 4000, manufactured by Kulzer) and dispersed to prepare a hollow particle embedding resin.
• a thin film was made using a microtome (EM UC7, manufactured by LEICA) so as to pass near the center of the hollow particles dispersed in the embedding resin, and the location of the black material was observed using a transmission electron microscope (JEM-2100, manufactured by JEOL Ltd.). Upon checking, it was confirmed that one part was exposed and the other part existed inside the shell of the particle (existed on the surface and inside).
• EM UC7 microtome
• LEICA transmission electron microscope
• Example 2 Hollow particles and molded bodies were produced in the same manner as in Example 1 except that the amount of cyclohexane added was changed from 200 parts by weight to 500 parts by weight.
• Example 3 Hollow particles and molded bodies were produced in the same manner as in Example 1, except that the amount of cyclohexane added was changed from 200 parts by weight to 800 parts by weight.
• Example 4 Hollow particles and molded bodies were prepared in the same manner as in Example 2, except that the carbon black was changed to #2350 (manufactured by Mitsubishi Chemical Corporation, primary average particle size 15 nm, specific surface area 320 m 2 /g, DBP oil absorption 65 cm 3 /100 g). was created.
• #2350 manufactured by Mitsubishi Chemical Corporation, primary average particle size 15 nm, specific surface area 320 m 2 /g, DBP oil absorption 65 cm 3 /100 g.
• Example 5 Hollow particles and molded bodies were prepared in the same manner as in Example 2, except that the carbon black was changed to MA14 (manufactured by Mitsubishi Chemical Corporation, primary average particle size 40 nm, specific surface area 56 m 2 /g, DBP oil absorption 73 cm 3 /100 g). Created.
• MA14 manufactured by Mitsubishi Chemical Corporation, primary average particle size 40 nm, specific surface area 56 m 2 /g, DBP oil absorption 73 cm 3 /100 g.
• Example 6 Hollow particles and molded bodies were prepared in the same manner as in Example 2, except that the carbon black was changed to MA220 (manufactured by Mitsubishi Chemical Corporation, primary average particle size 55 nm, specific surface area 36 m 2 /g, DBP oil absorption 93 cm 3 /100 g). Created.
• MA220 manufactured by Mitsubishi Chemical Corporation, primary average particle size 55 nm, specific surface area 36 m 2 /g, DBP oil absorption 93 cm 3 /100 g.
• Example 7 After adding 75 parts by weight of sodium chloride, 30 parts by weight of colloidal silica which is 20% by weight of the active ingredient, 2.0 parts by weight of polyvinylpyrrolidone and 0.6 parts by weight of ethylenediaminetetraacetic acid/4Na salt to 250 parts by weight of ion-exchanged water, The pH of the resulting mixture was adjusted to 2.0 to 3.0 to prepare an aqueous dispersion medium. Separately, 500 parts by weight of cyclohexane and the active ingredient were added to a monomer composition of 0.2 parts by weight of acrylonitrile, 5.5 parts by weight of methacrylonitrile, 4 parts by weight of methacrylic acid, and 0.3 parts by weight of methyl acrylate.
• An oily mixture was prepared by mixing 1.6 parts by weight of a liquid containing 50% di-sec-butyl peroxydicarbonate. To this oily mixture, 0.2 parts by weight of an amine salt of polyether ester acid (Disparon-234, manufactured by Kusumoto Kasei Co., Ltd.) and carbon black (MA100, manufactured by Mitsubishi Chemical Corporation, primary average particle diameter 24 nm, specific surface area) as a black material were added. After adding 0.39 parts by weight (110 m 2 /g) and dispersing the mixture by ultrasonic irradiation, the mixture was charged into an autoclave and mixed. Thereafter, it was added to an aqueous medium and suspended to prepare a dispersion.
• an amine salt of polyether ester acid Dispersing the mixture by ultrasonic irradiation
• the resulting dispersion was stirred and mixed using a homogenizer, charged into a pressure polymerization vessel purged with nitrogen, and reacted at 60° C. for 20 hours under pressure (0.5 MPa) to obtain a reaction product.
• the obtained reaction product was repeatedly filtered and washed with water, and then dried to obtain hollow particles. Furthermore, a molded body was produced in the same manner as in Example 1 using the obtained hollow particles.
• Example 8 Hollow particles were prepared in the same manner as in Example 8, except that 3.3 parts by weight of acrylonitrile, 2.5 parts by weight of methacrylonitrile, 3 parts by weight of methacrylic acid, and 1.2 parts by weight of methyl methacrylate were used as the monomer composition. And a molded body was produced.
• Example 9 As a dispersant, 30 parts by weight of colloidal silica (manufactured by Asahi Denka Co., Ltd., primary average particle diameter: 20 nm) and 2.0 parts by weight of polyvinylpyrrolidone (manufactured by BASF), which are 20% by weight of active ingredients, were added to 250 parts by weight of ion-exchanged water. The mixture was added and mixed to prepare an aqueous dispersion medium. 2 parts by weight of acrylonitrile, 3 parts by weight of methacrylonitrile, 4 parts by weight of methacrylic acid, and 1 part by weight of methyl methacrylate were mixed to form a monomer composition in the form of a homogeneous solution.
• colloidal silica manufactured by Asahi Denka Co., Ltd., primary average particle diameter: 20 nm
• polyvinylpyrrolidone manufactured by BASF
• the mixture was added and mixed in an autoclave. Thereafter, it was added to an aqueous medium and suspended to prepare a dispersion.
• the resulting dispersion was stirred and mixed using a homogenizer, charged into a pressure polymerization vessel purged with nitrogen, and reacted at 60° C. for 20 hours under pressure (0.5 MPa) to obtain a reaction product.
• the obtained reaction product was repeatedly filtered and washed with water, and then dried to obtain hollow particles.
• Example 10 Hollow particles and molded bodies were produced in the same manner as in Example 1 except that the amount of cyclohexane added was changed from 200 parts by weight to 100 parts by weight.
• Example 11 Hollow particles and molded bodies were produced in the same manner as in Example 1, except that the amount of cyclohexane added was changed from 200 parts by weight to 2,700 parts by weight.
• Example 12 Hollow particles and molded bodies were produced in the same manner as in Example 2, except that the amount of cyclohexane added was changed from 200 parts by weight to 3,500 parts by weight.
• Example 13 Hollow particles and molded bodies were produced in the same manner as in Example 2, except that the amount of carbon black added was changed from 0.26 parts by weight to 0.52 parts by weight.
• Example 14 Hollow particles and molded bodies were produced in the same manner as in Example 2, except that the amount of carbon black added was changed from 0.26 parts by weight to 1.12 parts by weight.
• Example 15 Hollow particles and molded bodies were prepared in the same manner as in Example 2, except that 0.26 parts by weight of Solvent Black 3 (black dye, OIL BLACK860, manufactured by Orient Chemical Co., Ltd.) was added instead of 0.26 parts by weight of carbon black. Created.
• Solvent Black 3 black dye, OIL BLACK860, manufactured by Orient Chemical Co., Ltd.
• Example 16 Hollow particles and molded bodies were produced in the same manner as in Example 1, except that the amount of cyclohexane added was changed from 200 parts by weight to 250 parts by weight.
• Example 17 Hollow particles and molded bodies were produced in the same manner as in Example 1, except that the amount of cyclohexane added was changed from 200 parts by weight to 90 parts by weight.
• the surface roughness (Rz value) of the surface of the molded article was measured using a 3D shape measuring machine (manufactured by Keyence Corporation). The measured Rz values were evaluated based on the following criteria.

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