WO2010067851A1 - 型内被覆組成物及び型内被覆成形体 - Google Patents
型内被覆組成物及び型内被覆成形体 Download PDFInfo
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- WO2010067851A1 WO2010067851A1 PCT/JP2009/070709 JP2009070709W WO2010067851A1 WO 2010067851 A1 WO2010067851 A1 WO 2010067851A1 JP 2009070709 W JP2009070709 W JP 2009070709W WO 2010067851 A1 WO2010067851 A1 WO 2010067851A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- 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
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/16—Making multilayered or multicoloured articles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
- C08G59/1461—Unsaturated monoacids
- C08G59/1466—Acrylic or methacrylic acids
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- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
- C09D167/07—Unsaturated polyesters having carbon-to-carbon unsaturation having terminal carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- 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
- C08K2201/001—Conductive additives
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- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
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- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31511—Of epoxy ether
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31609—Particulate metal or metal compound-containing
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31786—Of polyester [e.g., alkyd, etc.]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
Definitions
- the present invention relates to an in-mold coating composition and an in-mold coating. More specifically, a thermoplastic molding material or a thermosetting plastic molding material is molded in a mold by an injection molding method, injection compression molding method, injection press molding method, compression molding method or reaction injection molding method. An in-mold coating composition is injected between the surface of the molded body and the cavity surface of the mold, and the in-mold coating composition is cured in the mold, so that the in-mold coating composition is formed on the surface of the plastic molded body.
- the present invention relates to an in-mold coated molded body obtained by a so-called in-mold coating molding method (also referred to as an IMC method or an in-mold coating method), which produces an integrally molded body having a close contact.
- the surface of the moldings is coated.
- Application has been widely used.
- electrostatic coating has become common in order to improve the coating efficiency during top coating and to reduce the emission of volatile organic compounds (VOC) to the atmosphere.
- VOC volatile organic compounds
- the volume specific resistance value of the plastic molded body is usually 10 10 ⁇ / cm 2 or more, it is difficult to uniformly apply the paint even if an electrostatic coating method is used for this. Therefore, when performing electrostatic coating on these molded bodies, a conductive primer coating is spray-coated for the purpose of forming a conductive coating film.
- VOCs volatile organic compounds
- the paint is cured in the mold to form a coating film on the surface of the plastic molded body.
- An in-mold coating forming method for producing an intimate integral molded body has attracted attention.
- In-mold coating molding method forms a coating film in the mold, so the coating composition is solvent-free and 100% coating film in the mold, so there is no release of VOC to the atmosphere and waste This is a construction method that has little impact on the environment.
- the coating film is also cured by radical reaction due to the heat of the mold and the heat of plasticization of the thermoplastic resin and the reaction heat of the thermosetting resin. Compared with the reaction caused by UV irradiation or ultraviolet irradiation, the coating film formation consumes less energy and can be said to be an excellent coating method.
- the paint used for in-mold coating molding is difficult to develop compared to ordinary paints because it is required to cure in a short time without solvent because it forms a coating film in the mold.
- Carbon black is used as a conductive material that has already been developed as a conductive paint used in the inner coating molding method (see, for example, Patent Documents 1 and 2).
- the white conductive paint is generally a paint containing an organic solvent (see, for example, Patent Documents 4 to 8).
- a large amount of VOC is released into the atmosphere at the time of painting, and development of a solvent-free paint is desired from the viewpoint of environmental response in recent years.
- JP 60-212467 A Japanese Patent Laid-Open No. 04-226116 Japanese Patent Laid-Open No. 06-320681 JP 2004-75735 A JP 2004-217872 A Japanese Patent Laid-Open No. 2004-262988 Japanese Patent Laid-Open No. 2005-171024 Japanese Patent Laid-Open No. 2006-232828
- an object of the present invention is to provide SMC (sheet molding compound), BMC (bulk molding compound), or thermosetting molding resin mainly composed of dicyclopentadiene, ABS resin, polyamide resin, PPE resin, PC / PET, In-mold coating composition having excellent adhesion to thermoplastic molding resins such as PC / PBT and PC / ABS alloy, and in-mold coating in which a white conductive coating is effectively coated in the mold
- SMC sheet molding compound
- BMC bulk molding compound
- thermosetting molding resin mainly composed of dicyclopentadiene, ABS resin, polyamide resin, PPE resin, PC / PET, In-mold coating composition having excellent adhesion to thermoplastic molding resins such as PC / PBT and PC / ABS alloy, and in-mold coating in which a white conductive coating is effectively coated in the mold
- the object is to provide a molded body.
- An in-mold coating composition is provided.
- any one of an injection molding method, an injection compression molding method, an injection press molding method, a compression molding method or a reaction injection molding method is used.
- An in-mold coating product is provided, wherein the in-mold coating composition is the above-mentioned in-mold coating composition.
- the in-mold coating composition is cured in a mold to have a light-colored conductive film, and has excellent adhesion.
- An in-mold coated molded body having a coating film can be provided, and subsequent top coating electrostatic coating enables coloring of a top coating film having excellent lightness.
- the mold surface can be faithfully transferred by the in-mold coating molding method, effectively reducing sink marks and weld lines generated in the ribs and bosses due to molding resin shrinkage that cannot be solved by normal coating. It becomes possible.
- the in-mold coated molded body according to the present invention comprises a molded body made of a thermosetting molding resin or a thermoplastic molding resin and a coating of the in-mold coating composition formed on the surface thereof.
- thermosetting molding resin conventionally known molding materials can be used, for example, fiber reinforced plastic molding material called SMC or BMC with unsaturated polyester resin, epoxy acrylate resin, or phenol resin as a matrix, unsaturated.
- fiber reinforced plastic molding material called SMC or BMC with unsaturated polyester resin, epoxy acrylate resin, or phenol resin as a matrix, unsaturated.
- examples thereof include an RTM molding material using a polyester resin, an epoxy acrylate resin or an epoxy resin as a matrix, an RIM molding material using dicyclopentadiene, urethane, or the like.
- thermoplastic molding resin conventionally known various molding materials can be used, for example, polycarbonate, polymethyl methacrylate, polystyrene, polyamide, polyethylene terephthalate, polybutylene terephthalate, polyphenylene ether, ABS resin or these resins.
- An alloy material is mentioned.
- Such a molding material contains, for example, a reinforcing material such as glass fiber, carbon fiber or calcium carbonate whisker, an ultraviolet absorber, an antioxidant, a release agent, or the like so as to satisfy characteristics according to the application. be able to.
- a reinforcing material such as glass fiber, carbon fiber or calcium carbonate whisker, an ultraviolet absorber, an antioxidant, a release agent, or the like so as to satisfy characteristics according to the application. be able to.
- Certain inorganic particles such as titanium dioxide, diallyl phthalate oligomers, low shrinkage agents such as saturated polyester resins, polyvinyl acetate resins, polymethyl methacrylate resins, mold release agents, ultraviolet absorbers, antioxidants, antifoaming agents , And an optional component such as an antistatic agent, a polymerization inhibitor, or a curing accelerator.
- the component (A) used in the in-mold coating composition used in the present invention is a urethane oligomer, epoxy oligomer, polyester oligomer, polyether oligomer or non-polymer having a (meth) acryloyl group. It is at least one selected from saturated polyester resins.
- (A-1) Oligomer having (meth) acryloyl group examples include urethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, and polyether (meth). Mention may be made of acrylates.
- the mass average molecular weight of these oligomers may vary depending on the type of the oligomer, but is generally about 300 to 30,000, preferably 500 to 10,000.
- the oligomer having the (meth) acryloyl group suitably has at least 2 to 8, preferably 2 to 6, (meth) acryloyl groups in one molecule.
- Urethane (meth) acrylate oligomer As an oligomer used in the present invention is, for example, (1) an organic diisocyanate compound; (2) an organic polyol compound, and (3) a hydroxyalkyl (meth) acrylate,
- the NCO / OH ratio is 0.8 to 1.0, preferably 0.9 to 1.0.
- An oligomer having a large number of hydroxyl groups can be obtained by using excessive hydroxyl groups or using a large amount of hydroxyalkyl (meth) acrylate.
- an organic diisocyanate compound and (2) an organic polyol compound are reacted in the presence of a urethanization catalyst such as dibutyltin laurate to obtain an isocyanate-terminated polyurethane prepolymer.
- a urethanization catalyst such as dibutyltin laurate
- the urethane (meth) acrylate oligomer can be produced by reacting (3) hydroxyalkyl (meth) acrylate until almost the free isocyanate group is reacted.
- the ratio of (2) organic polyol compound and (3) hydroxyalkyl (meth) acrylate is, for example, about 0.1 to 0.5 mol for the former with respect to 1 mol of the latter.
- organic diisocyanate compounds used in the above reaction include 1,2-diisocyanatoethane, 1,2-diisocyanatopropane, 1,3-diisocyanatopropane, hexamethylene diisocyanate, and lysine.
- Diisocyanate trimethylhexamethylene diisocyanate, tetramethylene diisocyanate, bis (4-isocyanatocyclohexyl) methane, methylcyclohexane-2,4-diisocyanate, methylcyclohexane-2,6-diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane 1,3-bis (isocyanatoethyl) cyclohexane, 1,3-bis (isocyanatomethyl) benzene, 1,3-bis (isocyanato-1-methylethyl) benzene, etc.
- These organic diisocyanate compounds can be used alone or as a mixture of two or more thereof.
- the organic polyol compound (2) used in the above reaction preferably includes, as the organic diol compound, for example, alkyl diol, polyether diol, polyester diol and the like.
- alkyl diol include ethylene glycol, 1,3-propanediol, propylene glycol, 2,3-butanediol, 1,4-butanediol, 2-ethylbutane-1,4-diol, and 1,5-pentanediol.
- 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,4-cyclohexanediol, 1,4-dimethylolcyclohexane, 4,8-dihydroxytri it can be exemplified cyclopropyl [5.2.1.0 2,6] decane, and 2,2-bis (4-hydroxycyclohexyl) propane or the like as typical.
- the polyether diol as the organic diol compound can be synthesized, for example, by polymerization of aldehyde, alkylene oxide, glycol or the like by a known method.
- polyether diol can be obtained by addition polymerization of formaldehyde, ethylene oxide, propylene oxide, tetramethylene oxide, epichlorohydrin or the like to alkyl diol under appropriate conditions.
- polyester diol as the organic diol compound include esterification reaction products obtained by reacting saturated or unsaturated dicarboxylic acids and / or their acid anhydrides with excess alkyl diols, and alkyl diols.
- An esterification reaction product obtained by polymerizing hydroxycarboxylic acid and / or lactone which is an intramolecular ester thereof and / or lactide which is an intermolecular ester can be used.
- These organic polyol compounds can be used alone or in combination of two or more thereof.
- the (3) hydroxyalkyl (meth) acrylate examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate.
- the urethane (meth) acrylate oligomer as an oligomer used in the present invention is a compound having a (meth) acryloyl group and a hydroxyl group in one molecule and an organic diisocyanate compound, and the NCO / OH ratio is, for example, It can also be produced by reacting at a ratio of 0.9 to 1.0 in the presence of a urethanization catalyst such as dibutyltin dilaurate.
- polyester (meth) acrylate oligomer The polyester (meth) acrylate as an oligomer used in the present invention is produced, for example, by reacting a polyester polyol having a hydroxyl group at the terminal with an unsaturated carboxylic acid. be able to.
- a polyester polyol can be typically produced by esterifying a saturated or unsaturated dicarboxylic acid or an acid anhydride thereof with an excess amount of an alkylene diol.
- dicarboxylic acid used include oxalic acid, succinic acid, adipic acid, phthalic acid, and maleic acid.
- alkylene diol examples include ethylene glycol, propylene glycol, butane diol, and pentane diol.
- unsaturated carboxylic acid acrylic acid, methacrylic acid, etc. can be mentioned as a typical thing, for example.
- Epoxy (meth) acrylate oligomer as an oligomer used in the present invention comprises, for example, an epoxy compound and an unsaturated carboxylic acid as described above.
- a carboxyl group equivalent per equivalent is used, for example, at a ratio of 0.5 to 1.5, and is produced by a general ring-opening addition reaction of an acid to an epoxy group.
- an epoxy compound used here bisphenol A type epoxy, phenolic novolak type epoxy, etc. can be mentioned suitably, for example.
- polyether (meth) acrylate oligomer As an oligomer used in the present invention includes, for example, a polyether polyol such as polyethylene glycol or polypropylene glycol, and the unsaturated carboxylic acid described above. It can be produced by reaction with an acid.
- a polyether polyol such as polyethylene glycol or polypropylene glycol
- unsaturated carboxylic acid described above. It can be produced by reaction with an acid.
- the unsaturated polyester resin used as the component (A) is obtained by, for example, reacting an organic polyol compound and an unsaturated carboxylic acid by a known method, Further, if necessary, it can be produced by reacting a saturated polycarboxylic acid.
- the organic polyol to be used include ethylene glycol, propylene glycol, triethylene glycol, trimethylolpropane, glycerin, and bisphenol A.
- an unsaturated polycarboxylic acid to be used (anhydrous) maleic acid, (anhydrous) fumaric acid, (anhydrous) itaconic acid etc. can be mentioned as a typical thing, for example.
- the (meth) acryloyl group-containing oligomer and an unsaturated polyester resin may be used in combination.
- the (B) component used by this invention is an unsaturated monomer which can be copolymerized with the said (A) component.
- unsaturated monomers examples include styrene, ⁇ -methylstyrene, chlorostyrene, vinyltoluene, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2- Ethylhexyl (meth) acrylate, ethylene glycol (meth) acrylate, cyclohexyl (meth) acrylate, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) acrylic amide, 2 Acrylamide-2-methylpropanesulfonic acid, (meth) acrylic acid, ⁇ - (meth) acryloyloxyethyl hydrogen phthalate, ⁇ - (meth) acryloyloxyethyl hydrogen succine N-vinyl-2-pyrrol
- an aliphatic (meth) acrylate monomer such as tripropylene glycol diacrylate (TPGDA) and 1,6-hexanediol diacrylate (1,6-HDDA), and an alicyclic structure such as cyclohexyl methacrylate.
- TPGDA tripropylene glycol diacrylate
- 1,6-hexanediol diacrylate (1,6-HDDA) 1,6-hexanediol diacrylate
- an alicyclic structure such as cyclohexyl methacrylate.
- TMPT trimethylolpropane triacrylate
- the above unsaturated monomers may be used alone or as a mixture thereof.
- the hardness of the formed film is increased and scratches are less likely to occur.
- the component (C) used in the present invention comprises conductive particles obtained by coating the surface of inorganic particles such as acicular titanium dioxide, potassium titanate whisker or mica with conductive metal oxide particles. Can be mentioned.
- the inorganic particles coated with the conductive metal oxide particles (C) are preferably at least one selected from titanium dioxide, zinc oxide, alumina, silica, alkali titanate or mica.
- the conductive metal oxide particles are acicular titanium dioxide, potassium titanate whisker or scaly mica coated with either tin oxide, antimony-doped tin oxide or tin-doped indium oxide.
- the antimony-doped tin oxide preferably contains 0.1 to 5% by mass of at least one of phosphorus, aluminum or molybdenum as an oxide.
- the conductive particles (C) have an aspect ratio of 3 to 200 in order to develop the conductivity of the cured coating film.
- the component (D) used in the present invention generates free radicals, and is an organic peroxide polymerization initiator used for polymerizing the components (A) and (B). It is.
- the organic peroxide polymerization initiator preferably contains an organic peroxide polymerization initiator having a one-minute half-life temperature of 85 ° C. or more and less than 95 ° C. and an organic peroxide polymerization initiator of 95 ° C. or more and less than 170 ° C.
- Examples of the organic peroxide polymerization initiator having a one-minute half-life temperature of 85 ° C. or more and less than 95 ° C. include isobutyryl peroxide, 1,1,3,3-tetramethylbutylperoxyneodecanoate, ⁇ -Cumyl peroxyneodecanoate, di-3-methoxybutyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, and di-isopropyl peroxy Examples include dicarbonate, and bis (4-t-butylcyclohexyl) peroxydicarbonate is particularly preferable.
- Organic peroxide polymerization initiators having a 1 minute half-life temperature of 95 ° C. or higher and lower than 170 ° C. include t-butyl peroxybenzoate, t-butyl peroxyisobutyrate, t-butyl peroxy 2-ethylhexano And organic peroxides such as t-butylperoxy 2-ethylhexanoate, t-butylperoxyisopropyl carbonate, lauroyl peroxide, and benzoyl peroxide. Oxybenzoate and t-amylperoxy 2-ethylhexanoate are preferred.
- the blending ratio of the organic peroxide polymerization initiator as the component (D) is less than 0.1 / 100, the reaction of the components (A) and (B) does not proceed well, resulting in poor curing and a normal coating film is obtained. I can't. On the other hand, if it exceeds 5/100, the pot life of the coating composition is remarkably shortened.
- the in-mold coating composition used in the present invention further contains at least one inorganic particle having an average particle size of 0.1 ⁇ m or more and 20 ⁇ m or less, such as calcium carbonate or talc, if necessary. Can do. Preferred examples of such materials include calcium carbonate, talc, barium sulfate, aluminum hydroxide, and clay. These inorganic particles are blended for the purpose of dispersing shrinkage stress associated with film hardening, improving adhesion to the molded body, smoothing the surface irregularities, and improving the appearance of the molded body surface.
- inorganic particle having an average particle size of 0.1 ⁇ m or more and 20 ⁇ m or less, such as calcium carbonate or talc, if necessary. Can do. Preferred examples of such materials include calcium carbonate, talc, barium sulfate, aluminum hydroxide, and clay.
- the in-mold coating composition used in the present invention can further contain at least one coloring pigment as required.
- the color pigment various color pigments conventionally used for plastics and paints can be used.
- colored pigments such as titanium dioxide and zinc oxide can be used for white pigments, and titanium yellow can be used for yellow pigments.
- These light-colored coloring pigments color the cured coating film of the in-mold coating composition white to light-colored, have poor hiding power, and develop the desired color even when a light-colored top coat is applied. Mix for the purpose.
- a release agent can be optionally used in combination to smoothly release the cured coating film from the mold.
- Release agents include, for example, stearates such as stearic acid, hydroxystearic acid, zinc stearate, aluminum stearate, magnesium stearate, or calcium stearate, soybean oil lecithin, silicone oil, fatty acid esters, and fatty acid alcohol dibasic Examples include acid esters.
- the compounding amount of these release agents is preferably 0.1 to 5 parts by mass, and more preferably 0.2 to 2 parts by mass with respect to 100 parts by mass in total of the ⁇ (A) + (B) ⁇ components. It is preferable that Within this range, the effect of releasing from the mold is suitably exhibited.
- a modified resin can be blended for the purpose of improving adhesion to various base resin.
- the modified resin used for such a purpose include chlorinated polyolefin, maleic acid-modified polyolefin, acrylic oligomer, polyvinyl acetate, polymethyl methacrylate, and allyl ester oligomer.
- the in-mold coating composition used in the present invention may further include an antistatic agent, an antioxidant, a polymerization inhibitor, an ultraviolet absorber, a curing accelerator, a pigment dispersant, an antifoaming agent, or a plastic as necessary. You may mix
- FIG. 1 shows an apparatus for performing a compression molding method using a glass fiber reinforced thermosetting molding material called SMC, for example.
- SMC glass fiber reinforced thermosetting molding material
- the upper mold 1 and the lower mold 2 of the split mold are molding mold members facing each other.
- the upper mold 1 and the lower mold 2 are fixed to a movable platen 3 and a fixed platen 4 of the mold clamping device, respectively, and the movable platen 3 is configured to move forward and backward by a mold clamping cylinder 5.
- a split mold cavity 6 having a required shape can be formed by the upper mold 1 and the lower mold 2, and the cavity can be expanded in the direction of the surface of the in-mold molded body covered by the mold by moving the upper mold 1. .
- the surface to be coated in the mold may be one surface or two or more surfaces.
- the extension of the cavity in the direction of the surface to be coated in the mold may be one direction or more than two directions. May be.
- the above glass fiber reinforced plastic molding material is put between the upper mold 1 and the lower mold 2, the mold clamping cylinder 5 is operated, and the upper mold 1 and the lower mold 2 are brought close to each other to mold the molding material into the shape of the cavity. Then, it is cured by applying a clamping pressure.
- an injector 7 having a shut-off pin 7A which is an injection means for the in-mold coating composition, and a measuring cylinder 8 for supplying a predetermined amount of the in-mold coating composition to the injector 7 And a supply pump 9 for supplying the composition for in-mold coating from the storage unit 10 to the measuring cylinder 8 is provided.
- the measuring cylinder 8 is provided with a plunger regulator 8A for injecting the composition for in-mold coating.
- the clamping cylinder 5 is operated to separate the upper mold 1 from the lower mold 2, the glass fiber reinforced plastic molding material is placed on the lower mold 2, and then the clamping cylinder 5 is operated.
- the upper mold 1 and the lower mold 2 are brought close to each other to mold the molding material into a cavity shape, and a mold clamping pressure is applied.
- This clamping pressure is usually 4 to 15 MPa.
- the molding temperature is arbitrarily determined according to the molding time, the type of molding material, etc., but usually 120 to 180 ° C. is appropriate, and the mold is set to the above temperature in advance before the molding material is added. It is desirable to maintain the temperature until a cured coating is obtained.
- an in-mold coating composition is coated from the injector 7 to the inner wall of the upper mold 1 and the molded body in an amount sufficient to obtain a desired film thickness, preferably a cured film of 20 to 1,000 ⁇ m. Inject between the surface.
- the injection port is closed with the shut-off pin 7A, and the clamping cylinder 5 is operated as necessary to perform the clamping operation, and the mold is formed on the surface of the molded body in the cavity 6
- the coating composition is cured.
- the pressure is usually (re) pressed to about 1 to 10 MPa, and the pressure is usually maintained for about 10 to 300 seconds until a cured coating is formed. .
- the clamping cylinder 5 is operated to separate the upper mold 1 and the lower mold 2 and take out the molded body having the cured film from the mold.
- FIG. 2 shows a mode in the case of an injection molding method of a thermoplastic resin molding material.
- reference numeral 11 denotes a stationary platen of a mold clamping device of an injection molding machine
- 12 denotes a movable platen, each having a stationary mold part 13 and a movable mold part 14 which are molding members facing each other.
- the movable platen 12 is configured to be moved back and forth by the mold clamping cylinder 15.
- a cavity 16 having a required shape is formed at a fitting portion of the fixed mold portion 13 and the movable mold portion 14, and a molten or soft thermoplastic resin molding material is injected and filled into the cavity 16. It is then solidified.
- the resin molding material can be injected into the cavity 16 from an injection cylinder 17 having a screw through a nozzle 18 and a sprue 19.
- reference numeral 20 denotes a rib part (boss part), and 21 denotes an ejector pin at the time of mold release.
- the in-mold coating composition injection means includes an injector 22 having a shut-off pin 22A, a measuring cylinder 23 for supplying a predetermined amount of the in-mold coating composition to the injector 22, and an in-mold coating.
- a supply pump 25 is provided for supplying the composition from the reservoir 24 to the metering cylinder 23.
- the measuring cylinder 23 is provided with a plunger regulator 23A for injecting the mold coating composition.
- the clamping cylinder 15 is first operated to close the fixed mold part 13 and the movable mold part 14 and apply a clamping pressure.
- This clamping pressure needs to be able to counter the injection pressure of the resin molding material. Normally, this injection pressure is 40 to 250 MPa at the nozzle 18 portion.
- the supply pump operates to supply a necessary amount of coating material to the measuring cylinder 23.
- the molten or softened resin molding material is injected from the injection cylinder 17 into the cavity 16 through the nozzle 18 and the sprue 19.
- the mold clamping pressure is reduced or less than the desired cured film thickness described below.
- the movable mold part 14 is moved backward by a distance that does not release the fitting between the fixed mold part 13 and the movable mold part 14, and preferably by 0.2 to 5 mm.
- the shutoff pin 22A is operated to open the injection port of the injector 22.
- the plunger regulator 23A for injecting the in-mold coating composition of the measuring cylinder 23 is operated, and a desired space is formed between the cavity 16, that is, the inner wall of the fixed mold portion 13 and the surface of the resin molding to be coated in the mold.
- An in-mold coating composition is injected in such an amount that a cured film having a thickness of preferably 20 to 1,000 ⁇ m can be obtained.
- the injection port is closed again with the shut-off pin 22A, and the clamping cylinder 15 is operated as necessary to perform the clamping operation, and the in-mold coating composition is pushed in the mold.
- the spread molding surface is coated, and the in-mold coating composition is cured on the surface of the cavity 16 molding.
- the clamping cylinder 15 is operated, the fixed mold part 13 and the movable mold part 14 are separated from each other, and the molded body having the cured coating is taken out from the mold.
- FIG. 3 shows an aspect of the RIM molding method of urethane or dicyclopentadiene molding material.
- reference numerals 26 and 27 denote molding members that oppose each other.
- Mold member 26 (fixed mold) and 27 (movable mold) are fixed to a fixed plate and a movable plate of the mold clamping device, respectively, and the movable plate is configured to be advanced and retracted by a mold clamping cylinder.
- the fixed plate, the movable plate, and the mold closing cylinder of the mold clamping device are not shown.
- a cavity 28 having a required shape is formed by the molding members 26 and 27, and a molding material mainly composed of dicyclopentadiene is filled in the cavity 28 and cured.
- a raw material mainly composed of liquid A composed of dicyclopentadiene and a catalyst and liquid B composed of dicyclopentadiene and an activator are respectively stored in a storage tank 29 and After the temperature is adjusted at 30, the pressure is increased to 50 to 200 bar by the hydraulic cylinders 35 and 36 by the measuring cylinders 31 and 32, ejected from the opposed nozzles in the mixing head 38, and mixed by colliding with each other.
- an injector 39 provided with a shut-off pin 39 ⁇ / b> A, a coating metering cylinder 40 for supplying a predetermined amount of coating material to the injector 39, and a coating agent in its storage portion 41.
- a supply pump 42 for supplying to the measuring cylinder 40 from above.
- the measuring cylinder 40 is provided with a plunger regulator 40A for injecting a coating material.
- the mold clamping cylinder is operated to close the mold (molding mold members 26 and 27) and apply mold clamping pressure. This clamping pressure is usually 0.5 to 1 MPa.
- a molding material containing dicyclopentadiene as a main raw material is injected from the mixing head 38 into the cavity 28.
- the supply pump 42 is operated to supply a necessary amount of coating material to the metering cylinder 40.
- the injector 39 operates its shut-off pin 39A to open its injection port.
- the plunger regulator 40A for injecting the coating material of the measuring cylinder 40 is operated to fill the space between the cavity 28, that is, the inner wall of the mold member 26 and the surface of the molded product.
- the mold clamping cylinder is operated to perform the mold clamping operation, and the coating agent is cured in the mold.
- the mold clamping cylinder is operated, the mold members 26 and 27 are separated, and the coated molded product is taken out from the mold.
- Urethane oligomers can be prepared by polymerization by various known methods.
- component (A) in the amount shown in Table 1 is charged with 0.02 parts by mass of dibutyltin dilaurate per 100 parts by mass of components (A) to (C), and kept at 40 ° C.
- the component (B) in the amount shown in Table 1 was added dropwise and allowed to react for a sufficient time
- the component (C) shown in Table 1 was added to the component (A) to (C) in an amount of 0.00 per 100 parts by mass.
- a solution in which hydroquinone in an amount of 1 part by mass was dissolved was dropped, and the mixture was further heated and stirred at 75 ° C. for a sufficient time to obtain urethane oligomers UAC-1 to UAC-3.
- the conductive particles (C) can be produced by various known methods.
- conductive particles EC-1 100 g of rutile type titanium dioxide powder (trade name: R-310, manufactured by Sakai Chemical Industry Co., Ltd.) (TiO 2 97% or more, average primary particle size 0.20 ⁇ m) Disperse in 3 liters, and add 16 g of trichloroacetic acid and 19 g of sodium trichloroacetate as a pH buffer.
- the solution is kept at 90 ° C., and an acidic aqueous solution of hydrochloric acid containing 14 g of stannic chloride and 5 g of antimony (III) chloride and an aqueous sodium hydroxide solution (75 g / liter) are brought to a pH of 2-4.
- the mixture was dropped simultaneously over 30 minutes, and the hydrated coprecipitate of tin and antimony was coated on the powder having the tin hydrate coating.
- the obtained powder was filtered, washed with water and dried, and then calcined at 550 ° C. for 1 hour.
- 111 g of the obtained white powder (covering amount: 11% by mass), the whiteness was 83 and the volume resistivity was 370 ⁇ ⁇ cm.
- conductive particles EC-3 100 g of rutile needle-like titanium dioxide powder (trade name: FTL-100, manufactured by Ishihara Sangyo Co., Ltd.) (fiber length 1.68 ⁇ m, fiber diameter 0.13 ⁇ m) Disperse in 3 liters, and add 16 g of trichloroacetic acid and 19 g of sodium trichloroacetate as a pH buffer. While maintaining at 90 ° C., an acidic aqueous hydrochloric acid solution containing 17 g of stannic chloride and 2.5 g of antimony (III) chloride and an aqueous sodium hydroxide solution (75 g / liter) were simultaneously added over 30 minutes, Antimony oxide co-precipitate was coated.
- FTL-100 rutile needle-like titanium dioxide powder
- the obtained 110 g of white powder (covering amount: 10% by mass) had a whiteness of 88 and a volume resistivity of 6 ⁇ ⁇ cm.
- a white powder was prepared using an aqueous sodium hydroxide solution containing 0.3 g of sodium aluminate. 120 g of the obtained white powder (a coating amount of 20 mass% including 0.8 mass% of aluminum) had a whiteness of 86 and a volume resistivity of 2 ⁇ ⁇ cm.
- Examples 1 to 4 and Comparative Examples 1 to 5 Using a mold having a cavity for obtaining a resin molded body having a product shape having a length of 800 mm, a width of 300 mm, a height of 50 mm, and a plate thickness of 3 mm, in-mold coating was performed on the molded body according to the embodiment shown in FIG. In this case, the mold temperature was set to 150 ° C. for the upper mold and 135 ° C. for the lower mold. First, the SMC molding material was placed on the lower mold, clamped with a mold clamping pressure of 2400 KN, and held for 80 seconds.
- the surface of the SMC compact was cured to such an extent that it could withstand the injection and flow pressure of the in-mold coating composition.
- 36 cm 3 of each of the in-mold coating compositions having the composition shown in Table 3 was injected between the mold surface and the surface of the molded article over about 1.5 seconds. did.
- the mold clamping pressure was increased to 1440 KN over 1 second and held for 10 seconds, then the mold clamping pressure was reduced to 960 KN and held for 80 seconds to cure the in-mold coating composition.
- the obtained molded body was electrostatically coated under the conditions shown in Table 2, and the appearance of the coating film after the top coating was evaluated.
- the top coat used was Delicon # 1500 White (Dai Nippon Paint Co., Ltd.).
- the surface resistance value of the coating film was measured using a Hiresta UP MCP-HT450 type measuring instrument (manufactured by Mitsubishi Chemical Corporation) after being left in a room of 23 ⁇ 2 ° C. and 50 ⁇ 5% RH for 24 hours.
- Adhesion between substrate and coating film According to JIS K 5600-5-6: Adhesion (cross-cut method), an initial coating adhesion test was performed. The adhesion of the coating film was evaluated in the following 6 grades from 0 to 5 based on the classification of the test results described in JIS K 5600-5-6. ⁇ 6-level evaluation> 0: The edges of the cut are completely smooth, and there is no peeling of any lattice. 1 ... Small peeling of the coating film at the intersection of cuts. It is clearly not more than 5% that the crosscut is affected. 2 ... The coating is peeled along the edge of the cut and / or at the intersection. The cross-cut part is clearly affected by more than 5% but not more than 15%. 3 ...
- the coating film is partially or completely peeled along the edge of the cut, and / or various parts of the eye are partially or completely peeled off.
- the cross-cut portion is clearly affected by more than 15% but not more than 35%. 4 ...
- the coating film is partially or completely peeled along the edge of the cut, and / or some eyes are partially or completely peeled off.
- the cross-cut portion is clearly affected by more than 35% but not more than 65%. 5 ... When the degree of peeling exceeds Category 4.
- Examples 5 and 6> Using a mold having a cavity for obtaining a box-shaped resin molded body having a length of 300 mm, a width of 200 mm, a height of 30 mm, and a plate thickness of 2.5 mm, in-mold coating was performed on the molded body according to the embodiment shown in FIG. .
- the mold temperature is set to 100 ° C for the fixed mold, 80 ° C for the movable mold, and the barrel temperature is heated to 180 ° C.
- the rubber-modified polypropylene resin is heated and melted in the injection cylinder, and the 3000KN mold Injection was performed in a mold clamped with a clamping pressure over about 1.5 seconds, and a holding pressure of 40 MPa was applied for 5 seconds.
- the mold was cooled for 40 seconds in a state in which the mold clamping pressure was applied, and the surface of the obtained molded body was solidified to such an extent that it could withstand the injection and flow pressure of the in-mold coating composition.
- 9 cm 3 of each coating composition described in Table 5 was injected between the mold surface and the surface of the molded body over about 0.5 seconds. After completion of the injection, the mold clamping pressure was increased to 200 KN over 1 second and held for 120 seconds to cure the in-mold coating composition.
- the obtained molded body was electrostatically coated under the same conditions as described above, and the appearance of the coating film after the top coating was evaluated.
- the top coat used was Planit # 3600PA White (Dainippon Paint Co., Ltd.).
- Examples 7 to 13 and Comparative Examples 6 to 8> Using a mold having a cavity for obtaining a box-shaped resin molded body having a length of 300 mm, a width of 200 mm, a height of 30 mm, and a plate thickness of 2.5 mm, in-mold coating was performed on the molded body according to the embodiment shown in FIG. .
- the mold temperature is set to 95 ° C for the fixed mold, 75 ° C for the movable mold, the barrel temperature is heated to 200 ° C, and ABS resin is first heated and melted in the injection cylinder, and the mold clamping pressure is 3,500KN. It was injected into the mold clamped in step 1 for about 1 second, cooled for 30 seconds, and the surface of the obtained molded body was solidified to such an extent that it could withstand the injection of the composition for in-mold coating and the flow pressure.
- each coating composition 13 cm 3 described in Table 7 was injected between the mold surface and the surface of the molded body over about 0.5 seconds. After completion of the injection, the mold clamping pressure was increased to 200 KN over 1 second and held for 60 seconds to cure the in-mold coating composition.
- the obtained molded body was electrostatically coated under the same conditions as described above, and the appearance of the coating film after the top coating was evaluated.
- the top coat used was Planit # 3600PA White (Dainippon Paint Co., Ltd.).
- Examples 14 to 17 and Comparative Example 9> Using a mold having a cavity for obtaining a resin-molded product made of box-shaped dicyclopentadiene having a length of 400 mm, a width of 400 mm, and a height of 30 mm as a main raw material, in-mold coating on the molded body according to the embodiment shown in FIG. Carried out.
- the mold temperature is set to 95 ° C. for the upper mold and 60 ° C. for the lower mold.
- a molding material mainly composed of dicyclopentadiene is injected into the mold clamped with a mold clamping pressure of 160 KN. And cured for 60 seconds.
- the obtained molded body was electrostatically coated under the same conditions as described above, and the appearance of the coating film after the top coating was evaluated.
- the top coat used was Planit # 3600PA White (Dainippon Paint Co., Ltd.).
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Abstract
Description
金型内被覆成形方法は金型内で塗膜を形成するため、被覆組成物は無溶剤であり、金型内で100%塗膜となるため、VOCの大気への放出がなく、廃棄物も少なく、環境に対する負荷が少ない工法である。また、塗膜の形成も金型の熱及び熱可塑性樹脂が持っている樹脂可塑化の熱、熱硬化性樹脂が持っている反応熱によってラジカル反応で硬化するため、一般的な乾燥炉の熱や紫外線照射による反応に比べて塗膜形成のエネルギー消費も少なく、優れた塗装方法と言える。
(A)(メタ)アクリロイル基を有するウレタンオリゴマー、エポキシオリゴマー、ポリエステルオリゴマー、ポリエーテルオリゴマーあるいは不飽和ポリエステル樹脂から選ばれる少なくとも1種と、
(B)前記(A)成分と共重合可能なモノマーと、
(C)導電性金属酸化物粒子を無機粒子表面に被覆した導電性粒子と、及び
(D)有機過酸化物重合開始剤と、
を含有してなり、かつ、
前記(A)成分と前記(B)成分との質量割合が、(A)/(B)=20/80~80/20であり、
前記(C)成分の質量割合が、(C)/{(A)+(B)}=5/100~50/100であり、及び
前記(D)成分の質量割合が、(D)/{(A)+(B)}=0.1/100~5/100であることを特徴とする型内被覆組成物が提供される。
固定金型部と可動金型部からなる金型を型締めする工程と、
金型キャビティ内で樹脂を成形する工程と、
キャビティ内へ型内被覆組成物を注入する工程と、
注入した型内被覆組成物を硬化させる工程と、及び
型内被覆組成物が硬化した後に被覆された成形体を金型から取り出す工程
により製造される型内被覆成形体において、
該型内被覆組成物が、上記型内被覆組成物であることを特徴とする型内被覆成形体が提供される。
(A)(メタ)アクリロイル基を有するウレタンオリゴマー、エポキシオリゴマー、ポリエステルオリゴマー、ポリエーテルオリゴマーあるいは不飽和ポリエステル樹脂から選ばれる少なくとも1種と、
(B)前記(A)成分と共重合可能なモノマーと、
(C)導電性金属酸化物粒子を無機粒子表面に被覆した導電性粒子と、及び
(D)有機過酸化物重合開始剤と、を含有してなり、
かつ、前記(A)成分と前記(B)成分との質量割合が、(A)/(B)=20/80~80/20であり、
前記(C)成分の質量割合が、(C)/{(A)+(B)}=5/100~50/100であり、及び
前記(D)成分の質量割合が、(D)/{(A)+(B)}=0.1/100~5/100である
ことを必須成分として含有し、更に必要に応じて炭酸カルシウムやタルク等の平均粒子径が0.1μm以上20μm以下である無機粒子、二酸化チタン等の着色顔料、ジアリルフタレートオリゴマー、飽和ポリエステル樹脂やポリ酢酸ビニル樹脂、ポリメチルメタアクリレート樹脂等の低収縮剤、離型剤、紫外線吸収剤、酸化防止剤、消泡剤、帯電防止剤、重合防止剤、又は硬化促進剤等の任意成分を含むものである。
本発明で用いられる型内被覆用組成物に使用される(A)成分は、(メタ)アクリロイル基を有するウレタンオリゴマー、エポキシオリゴマー、ポリエステルオリゴマー、ポリエーテルオリゴマーあるいは不飽和ポリエステル樹脂から選ばれる少なくとも1種である。
(メタ)アクリロイル基を有するオリゴマーとしては、例えば、ウレタン(メタ)アクリレート、ポリエステル(メタ)アクリレート、エポキシ(メタ)アクリレート、及びポリエーテル(メタ)アクリレートを挙げることができる。
本発明で使用されるオリゴマーとしてのウレタン(メタ)アクリレートオリゴマーは、例えば、
(1)有機ジイソシアネート化合物と、
(2)有機ポリオール化合物と、及び
(3)ヒドロシキアルキル(メタ)アクリレートとを、
NCO/OH比が、例えば、0.8~1.0、好ましくは0.9~1.0となるような存在比で混合し、通常の方法により製造することができる。水酸基が過剰に存在する場合や、ヒドロキシアルキル(メタ)アクリレートを多量に使用することにより、水酸基を多く有するオリゴマーが得られる。
本発明で使用されるオリゴマーとしてのポリエステル(メタ)アクリレートは、例えば、水酸基を末端に有するポリエステルポリオールと、不飽和カルボン酸との反応によって製造することができる。このようなポリエステルポリオールは、代表的には飽和又は不飽和のジカルボン酸又はその酸無水物と、過剰量のアルキレンジオールとをエステル化反応することによって製造することができる。使用されるジカルボン酸としては、例えば、シュウ酸、コハク酸、アジピン酸、フタル酸、及びマレイン酸等が代表的なものとして挙げられる。また、使用されるアルキレンジオールとしては、例えば、エチレングリコールや、プロピレングリコール、ブタンジオール、及びペンタンジオール等が代表的なものとして挙げることができる。ここで、不飽和カルボン酸としては、例えば、アクリル酸及びメタクリル酸等を代表的なものとして挙げることができる。
本発明で使用されるオリゴマーとしてのエポキシ(メタ)アクリレートオリゴマーは、例えば、エポキシ化合物と、上記のような不飽和カルボン酸とを、エポキシ基1当量当たりのカルボキシル基当量を、例えば、0.5~1.5となるような割合で用い、通常のエポキシ基への酸の開環付加反応によって製造させたものである。ここで使用されるエポキシ化合物としては、例えば、ビスフェノールA型エポキシ及びフェノール性ノボラック型エポキシ等を好適に挙げることができる。
本発明で使用されるオリゴマーとしてのポリエーテル(メタ)アクリレートは、例えば、ポリエチレングリコール又はポリプロピレングリコール等のポリエーテルポリオールと、前述の不飽和カルボン酸との反応によって製造することができる。
一方、本発明において、(A)成分として使用される不飽和ポリエステル樹脂は、例えば、有機ポリオール化合物と、不飽和カルボン酸とを、公知の方法により反応させ、更に必要に応じて、飽和ポリカルボン酸を反応させて製造することができる。使用される有機ポリオールとしては、例えば、エチレングリコール、プロピレングリコール、トリエチレングリコール、トリメチロールプロパン、グリセリン、及びビスフェノールA等が代表的なものとして挙げることができる。また、使用される不飽和ポリカルボン酸としては、例えば、(無水)マレイン酸、(無水)フマル酸、及び(無水)イタコン酸等を代表的なものとして挙げることができる。
本発明で使用される(B)成分は、上記(A)成分と共重合することができる不飽和モノマーである。
本発明で使用される(C)成分は、導電性金属酸化物粒子で針状二酸化チタン、チタン酸カリウムウィスカー又は雲母等の無機粒子表面を被覆した導電性粒子を挙げることができる。
本発明で使用される(D)成分は、フリーラジカルを発生し、前記(A)成分及び(B)成分を重合させるために使用する有機過酸化物重合開始剤である。特に有機過酸化物重合開始剤として、1分間半減期温度が85℃以上95℃未満のものと、95℃以上170℃未満の有機過酸化物重合開始剤を含むことが好ましい。
本発明で使用される型内被覆組成物は、更に必要に応じ炭酸カルシウムやタルク等の平均粒子径が0.1μm以上20μm以下である無機粒子の少なくとも1種を含むことができる。このようなものとして、例えば、炭酸カルシウム、タルク、硫酸バリウム、水酸化アルミニウム、及びクレー等を好適に挙げることができる。これら無機粒子は、被膜硬化に伴う収縮応力を分散させ、成形体との付着性を向上させたり、表面の凹凸を平滑にしたり、成形体表面の外観を改良する目的で配合する。
以下、本発明の型内被覆成形体の製造方法について、それを実施するための成形機の構成、成形型及び被覆組成物注入装置を、図面を参照しながら具体的に説明するが、本発明の範囲はこのような具体的な成形機、成形型及び被覆組成物注入装置によって何ら限定されるものではない。
ウレタンオリゴマーは、各種公知の方法で重合して作製することができる。合成例として、表1に示す量の(A)成分に、(A)~(C)成分の合計量100質量部当たり0.02質量部となる量のジブチル錫ジラウレートを仕込み、40℃に保ちつつ、表1に示す量の(B)成分を滴下し、十分な時間反応させた後、表1に示す(C)成分に(A)~(C)成分の合計量100質量部当たり0.1質量部となる量のハイドロキノンを溶解させたものを滴下して、更に十分な時間75℃で加熱攪拌を続け、ウレタンオリゴマーUAC-1~UAC-3を得た。
エポキシ化合物(商品名:エピコート828(油化シェルエポキシ社製))1,000質量部、メタクリル酸490質量部、トリエチルアミン3質量部、ハイドロキノン0.01質量部を反応器中に入れ、125℃、3時間反応させ、エポキシオリゴマーEAC-1を得た。
導電性粒子(C)は、各種公知の方法で作製することができる。
ルチル型二酸化チタン粉末(商品名:R-310、堺化学工業(株)製)(TiO297%以上、平均一次粒子径0.20μm)100gを純水0.3リットルに分散し、これにpH緩衝材としてトリクロル酢酸16g、トリクロル酢酸ナトリウム19gを加える。
鱗片状フッ素雲母粉末(商品名:MK-100、コープケミカル(株)製)(白色度95、平均粒子径2μm、アスペクト比20~30)100gを純水0.3リットルに分散し、90℃に保持し、塩化第二錫3.5gを含む塩酸酸性水溶液を添加後、水酸化ナトリウム水溶液(75g/リットル)をpHが2~4になるように10分間かけて徐々に滴下し、加水分解させて前記粉末上に錫水和物の被膜を形成した。
ルチル型針状二酸化チタン粉末(商品名:FTL-100、石原産業(株)製)(繊維長1.68μm、繊維径0.13μm)100gを純水0.3リットルに分散し、これにpH緩衝材としてトリクロル酢酸16g、トリクロル酢酸ナトリウム19gを加える。
90℃に保持しながら塩化第二錫17gと塩化アンチモン(III)2.5gとを含む塩酸酸性水溶液と水酸化ナトリウム水溶液(75g/リットル)とを30分間に亘って同時に添加し、酸化錫、酸化アンチモンの水酸化共沈物を被覆した。水洗、ろ過、乾燥を行った後、550℃で1時間焼成した。得られた110gの白色粉末(被覆量10質量%)は白色度88、体積抵抗率6Ω・cmであった。
ルチル型二酸化チタン粉末(商品名:R-310、堺化学工業(株)製)(TiO297%以上、平均一次粒子径0.20μm)100gを純水0.3リットルに分散し、これを90℃に保持しながら塩化第二錫34gと三塩化アンチモン5gとを含む塩酸酸性水溶液と、ヘキサメタリン酸ナトリウム0.7gを含む水酸化ナトリウム水溶液(500g/リットル)50ミリリットルとを、30分間に亘って同時に滴下することにより、リンを含む酸化錫、酸化アンチモンの水酸化共沈物で被覆した。水洗、ろ過、乾燥を行った後、600℃で1時間焼成した。得られた121gの白色粉末(リン1質量%を含む被覆量20質量%)で、白色度87、体積抵抗率7Ω・cmであった。
導電性粒子C-3と同様に、アルミン酸ナトリウム0.3gを含む水酸化ナトリウム水溶液を用い白色粉末を作製した。得られた120gの白色粉末(アルミニウム0.8質量%を含む被覆量20質量%)は白色度86、体積抵抗率2Ω・cmであった。
長さ800mm、幅300mm、高さ50mm、板厚3mmの製品形状の樹脂成形体を得るためのキャビティを有する金型を用い、図1に示す態様に従って、成形体に対する型内被覆を実施した。この場合、金型温度を上型150℃、下型135℃に設定し、まずSMC成形材料を下型の上に置き、2400KNの型締め圧力で型締めし、80秒間保持し、得られたSMC成形体の表面が型内被覆用組成物の注入、流動圧力に耐え得る程度に硬化させた。次いで型締め圧力を360KNまで減圧した後、表3に記載した組成の各々の型内被覆用組成物36cm3を金型表面と成形体の表面との間に、約1.5秒かけて注入した。注入完了後、型締め圧力を1秒かけて1440KNまで加圧し10秒間保持し、次いで型締め圧力を960KNに減圧し、80秒間保持して型内被覆用組成物を硬化させた。
被覆膜のツヤ、流れスジ、均一性等を目視にて、以下に従い外観を評価した。
○…ツヤのムラ、流れスジがなく、外観が均一であるもの。
△…わずかにツヤのムラ、流れスジが見られるもの。
×…ツヤのムラ、流れスジが著しく、外観が不均一であるもの。
JIS Z 8729に規定されるL*a*b*表示系に基づくL*値を測定した。
被覆膜の表面抵抗値は、23±2℃、50±5%RHの室内に24時間放置後、ハイレスターUP MCP-HT450型測定器(三菱化学(株)製)を用いて測定した。
JIS K 5600-5-6:付着性(クロスカット法)に従って初期の塗膜付着性試験を実施した。塗膜の付着性はJIS K 5600-5-6に記載の試験結果の分類に基づき下記の0~5の6段階で評価した。
<6段階評価>
0…カットの縁が完全に滑らかで、どの格子の目にもはがれがない。
1…カットの交差点における塗膜の小さなはがれ。クロスカット部分で影響を受けるのは、明確に5%を上回ることはない。
2…塗膜がカットの縁に沿って、及び/又は交差点においてはがれている。クロスカット部分で影響を受けるのは明確に5%を超えるが15%を上回ることはない。
3…塗膜がカットの縁に沿って、部分的又は全面的に大はがれを生じており、及び又は目のいろいろな部分が、部分的又は全面的にはがれている。クロスカット部分で影響を受けるのは、明確に15%を超えるが35%を上回ることはない。
4…塗膜がカットの縁に沿って、部分的又は全面的に大はがれを生じており、及び又は数カ所の目が部分的又は全面的にはがれている。クロスカット部分で影響を受けるのは、明確に35%を超えるが65%を上回ることはない。
5…はがれの程度が分類4を超える場合。
○…下地のスケ、ツヤのムラがなく、外観が均一であるもの。
×…下地のスケ、ツヤのムラがあり、外観が不均一であるもの。
長さ300mm、幅200mm、高さ30mm、板厚2.5mmの箱形状の樹脂成形体を得るためのキャビティを有する金型を用い、図2に示す態様に従って成形体に対する型内被覆を実施した。金型温度は固定金型を100℃に、可動金型を80℃に設定し、バレル温度を180℃に加熱し、まずゴム変性ポリプロピレン樹脂を射出シリンダ内で加熱溶融させ、3,000KNの型締め圧力で型締めされた金型内に約1.5秒かけて射出し、40MPaの保圧を5秒間かけた。型締め圧力をかけた状態で40秒間冷却し、得られた成形体の表面が型内被覆用組成物の注入、流動圧力に耐えうる程度に固化させた。次いで、可動金型を約0.5mm離間させた後、表5に記載した各被覆用組成物9cm3を金型表面と成形体の表面との間に約0.5秒かけて注入した。注入完了後、型締め圧力を1秒間かけて200KNまで加圧し120秒間保持し、型内被覆用組成物を硬化させた。
長さ300mm、幅200mm、高さ30mm、板厚2.5mmの箱形状の樹脂成形体を得るためのキャビティを有する金型を用い、図2に示す態様に従って成形体に対する型内被覆を実施した。金型温度は固定金型を95℃に、可動金型を75℃に設定し、バレル温度を200℃に加熱し、まずABS樹脂を射出シリンダ内で加熱溶融させ、3,500KNの型締め圧力で型締めされた金型内に約1秒かけて射出し、30秒間冷却し、得られた成形体の表面が型内被覆用組成物の注入、流動圧力に耐えうる程度に固化させた。
長さ400mm、幅400mm、高さ30mmの箱形状のジシクロペンタジエンを主原料とする樹脂成形品を得るためのキャビティを有する金型を用い、図3に示す態様に従って、成形体に対する型内被覆を実施した。この場合、金型温度を上型95℃、下型60℃に設定して、先ずジシクロペンタジエンを主原料とする成形材料を、160KNの型締め圧力で型締めされた金型内に射出し、60秒間硬化させた。
Claims (9)
- (A)(メタ)アクリロイル基を有するウレタンオリゴマー、エポキシオリゴマー、ポリエステルオリゴマー、ポリエーテルオリゴマーあるいは不飽和ポリエステル樹脂から選ばれる少なくとも1種と、
(B)前記(A)成分と共重合可能なモノマーと、
(C)導電性金属酸化物粒子を無機粒子表面に被覆した導電性粒子と、及び
(D)有機過酸化物重合開始剤と、
を含有してなり、かつ、
前記(A)成分と前記(B)成分との質量割合が、(A)/(B)=20/80~80/20であり、
前記(C)成分の質量割合が、(C)/{(A)+(B)}=5/100~50/100であり、及び
前記(D)成分の質量割合が、(D)/{(A)+(B)}=0.1/100~5/100であることを特徴とする型内被覆組成物。 - 前記(C)成分の導電性金属酸化物粒子で被覆された無機粒子が、二酸化チタン、酸化亜鉛、アルミナ、シリカ、チタン酸アルカリ又は雲母から選ばれる少なくとも1種である請求項1に記載の型内被覆組成物。
- 前記(C)成分の無機粒子表面を被覆する導電性金属酸化物粒子が、酸化錫、アンチモンドープ酸化錫又は錫ドープ酸化インジウムから選ばれる少なくとも1種である請求項1又は2に記載の型内被覆組成物。
- 前記アンチモンドープ酸化錫が、リン、アルミニウム又はモリブデンの少なくとも1種を酸化物として0.1~5質量%含有する請求項3に記載の型内被覆組成物。
- 前記(C)成分の導電性粒子のアスペクト比が3~200である請求項1~4のいずれかに記載の型内被覆組成物。
- 前記(C)成分の導電性金属酸化物粒子で被覆された無機粒子が、針状二酸化チタン、チタン酸カリウムウィスカー又は鱗片状雲母である請求項1~5のいずれかに記載の型内被覆組成物。
- 前記(B)成分の前記(A)成分と共重合可能なモノマーにおいて、少なくともスチレンモノマーを含有し、その含有量が質量比で(スチレンモノマー)/{(A)+(B)}=0.2/100~5/100である請求項1~6のいずれかに記載の型内被覆組成物。
- 前記(D)成分の有機過酸化物重合開始剤として、1分間半減期温度が85℃以上95℃未満のものと、95℃以上170℃未満の有機過酸化物重合開始剤を含む請求項1~7のいずれかに記載の型内被覆組成物。
- 成形法として、射出成形法、射出圧縮成形法、射出プレス成形法、圧縮成形法又は反応射出成形法のいずれかを用いて、
固定金型部と可動金型部からなる金型を型締めする工程と、
金型キャビティ内で樹脂を成形する工程と、
キャビティ内へ型内被覆組成物を注入する工程と、
注入した型内被覆組成物を硬化させる工程と、及び
型内被覆組成物が硬化した後に被覆された成形体を金型から取り出す工程
により製造される型内被覆成形体において、
該型内被覆組成物が、請求項1~8のいずれかに記載の型内被覆組成物であることを特徴とする型内被覆成形体。
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JP2022099793A (ja) * | 2020-12-23 | 2022-07-05 | 関西ペイント株式会社 | 塗料組成物 |
JP7154721B2 (ja) | 2020-12-23 | 2022-10-18 | 関西ペイント株式会社 | 塗料組成物 |
JP7154725B2 (ja) | 2020-12-23 | 2022-10-18 | 関西ペイント株式会社 | 塗料組成物 |
CN116261508A (zh) * | 2020-12-23 | 2023-06-13 | 关西涂料株式会社 | 涂料组合物 |
Also Published As
Publication number | Publication date |
---|---|
JP4590473B2 (ja) | 2010-12-01 |
KR101651707B1 (ko) | 2016-08-26 |
JP2010138248A (ja) | 2010-06-24 |
US20110250457A1 (en) | 2011-10-13 |
EP2374826A1 (en) | 2011-10-12 |
CN102245660A (zh) | 2011-11-16 |
KR20110110155A (ko) | 2011-10-06 |
EP2374826B1 (en) | 2014-04-16 |
CN102245660B (zh) | 2013-11-13 |
EP2374826A4 (en) | 2012-08-15 |
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