WO2011152449A1 - Composition de résine et produit moulé associé - Google Patents

Composition de résine et produit moulé associé Download PDF

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Publication number
WO2011152449A1
WO2011152449A1 PCT/JP2011/062587 JP2011062587W WO2011152449A1 WO 2011152449 A1 WO2011152449 A1 WO 2011152449A1 JP 2011062587 W JP2011062587 W JP 2011062587W WO 2011152449 A1 WO2011152449 A1 WO 2011152449A1
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resin
weight
carbon black
acrylic resin
resin composition
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PCT/JP2011/062587
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English (en)
Japanese (ja)
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金田　豊
哲雄 目加田
青山　泰三
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株式会社カネカ
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Application filed by 株式会社カネカ filed Critical 株式会社カネカ
Priority to KR1020127031446A priority Critical patent/KR20130113316A/ko
Priority to CN201180026826XA priority patent/CN102918104A/zh
Priority to JP2012518426A priority patent/JP5898072B2/ja
Publication of WO2011152449A1 publication Critical patent/WO2011152449A1/fr
Priority to US13/689,268 priority patent/US20130183536A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • 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

Definitions

  • the present invention relates to a resin composition containing carbon black and a molded body thereof.
  • Acrylic resin mainly composed of polymethyl methacrylate has excellent weather resistance, gloss and transparency, but there is nothing that satisfies weather resistance, impact resistance and jet blackness at the same time. It has been.
  • Patent Document 1 As a method for imparting jetness, Patent Document 1 has a good matte appearance and jetness, excellent printability, surface hardness, molding whitening resistance, and trimming processability during molding.
  • an acrylic resin laminated film an acrylic resin laminated film obtained by laminating an acrylic resin layer (A) and an acrylic resin layer (B) is disclosed.
  • the film has an arithmetic mean roughness of the surface of the acrylic resin layer (A) on which the acrylic resin layer (B) is not laminated, of 0.01 ⁇ m or more and less than 0.1 ⁇ m, and the acrylic resin layer (B) has an acrylic
  • the 60 ° surface glossiness of the surface on which the resin layer (A) is not laminated is less than 60%, and the rubber content of the acrylic resin composition constituting the acrylic resin layer (A) is 25% by mass or more and 40% by mass. %, And the gel content is 45% by mass or more and less than 70% by mass, an acrylic resin laminated film, a method for producing the same, and a laminate obtained by laminating the same, and used as a pillar member for an automobile Is disclosed.
  • Patent Document 1 in order to obtain a pillar member having a jet black appearance, a process such as laminating a film on a structural resin is performed, which is expensive, and when a screw hole is cut. There was a problem of damage in the tapping process.
  • Patent Document 2 As methods for making the material itself jet black, a heat ray shielding plate (Patent Document 2) in which an infrared absorber and carbon black are added to methacrylic resin, and a heat ray shielding methacrylic resin composition in which specific carbon black is added to methacrylic resin are known.
  • Patent Document 3 As a skin material for an olefin-based resin molded base material, it is also known to produce a black transparent (smoke) film in which a dye is mixed (Patent Document 4).
  • Patent Documents 2 and 3 use carbon black having a very large particle diameter, which deteriorates the appearance of the molded product.
  • the shielding plate of Patent Document 2 has a problem with the light resistance of the infrared absorber. Moreover, in patent document 4, since the particle diameter of the dye to be used is small, there existed a problem that the weather resistance of dye itself was very low and the weather resistance of a film was also low.
  • Patent Document 5 discloses that a hydroxyl group-containing copolymer acrylic resin is laminated as a first layer on at least one surface of a transparent plastic substrate surface such as an acrylic resin, and the hydroxyl group 1 With respect to 100 parts by weight of the polyisocyanate compound and / or polyisocyanate compound precursor coating resin having a total isocyanate group content of 0.7 to 5 equivalents and an isocyanate group content of 5.0 to 60% by weight with respect to equivalents An organosiloxane resin comprising a hydrolyzed condensate of colloidal silica and trialkoxysilane, wherein an acrylic resin layer obtained by thermally curing a coating composition comprising 10 to 50 parts by weight of an ultraviolet absorber is laminated.
  • thermosetting coating layer of the composition is laminated.
  • Patent Document 5 A transparent plastic molded body in which a thermosetting coating layer of the composition is laminated.
  • the molded body disclosed in Patent Document 5 has significantly improved durability and excellent performance in wear resistance and hot water resistance, the number of manufacturing processes of the wear-resistant plastic molded body is large and expensive. There was a problem that there was.
  • the present invention is simple and low-cost, has weather resistance and gloss, and even with a large injection molded member, it has excellent blackness, that is, excellent black appearance, and excellent impact resistance. And it makes it a subject to provide the resin composition for obtaining the molded object which has high boss
  • an object of the present invention is to provide a resin composition that gives a molded article excellent in all of weather resistance, wear resistance, and jetness. Furthermore, this invention makes it a subject to provide the resin composition for obtaining the molded object which is useful, for example as a motor vehicle member, and has the outstanding black external appearance and smoke property.
  • the present inventors have intensively and researched, and by adding a carbon black having a number average particle diameter within a certain range to the thermoplastic resin, not only blackness and weather resistance, but also The present inventors have found that a resin composition excellent in molding processability, boss strength, wear resistance, and smoke properties can be obtained, and completed the present invention.
  • the present invention relates to a resin composition
  • a resin composition comprising an acrylic resin (A) and carbon black (B) having a number average particle size of 10 to 40 nm.
  • the carbon black (B) is preferably dispersed with a number average particle diameter of 10 to 40 nm.
  • the carbon black (B) is preferably primarily dispersed in a state where the number average particle diameter is 10 to 40 nm.
  • the resin composition further contains an organic phosphorus stabilizer having a melting point of 120 to 250 ° C.
  • the resin composition preferably further contains one or more lubricants selected from the group consisting of esters of C10 to C30 fatty acids and amides of C10 to C30 fatty acids.
  • the molded product obtained by molding the resin composition preferably has an extinction coefficient of 0.02 to 0.04 ppm ⁇ 1 cm ⁇ 1 .
  • the acrylic resin (A) is preferably an acrylic resin in which the total light transmittance of a 3 mm-thick molded product obtained from the acrylic resin is 85% or more.
  • the acrylic resin (A) preferably contains a rubber-modified acrylic resin.
  • this invention relates to the resin molding obtained by shape
  • this invention relates to the motor vehicle member using the resin molding of this invention.
  • the resin composition of the present invention is dispersed in a state where the number average particle diameter is 10 to 40 nm, and further, an organic phosphorus stabilizer having a melting point of 120 to 250 ° C., an ester of a C10 to C30 fatty acid, or C10 Since it contains an amide of a fatty acid of C30, it is a resin molded product excellent in jet blackness, weather resistance, molding processability, boss strength, abrasion resistance, smoke resistance, etc., and a resin composition for obtaining the same Can be obtained.
  • FIG. 1 is an electron microscope (TEM) photograph of the molded body produced in Example 4.
  • FIG. FIG. 2 is an electron microscope (TEM) photograph of a sample of the composition (CB-4) containing the carbon black masterbatch (CB-3).
  • FIG. 3 is an electron microscope (TEM) photograph of a sample of the composition (CB-5).
  • the resin composition of the present invention contains an acrylic resin (A) and carbon black (B) having a number average particle size of 10 to 40 nm.
  • an acrylic resin (A) which is a thermoplastic resin is used.
  • the acrylic resin has particularly excellent transparency and excellent impact resistance, and the resin molded body can be a molded body having a particularly excellent black appearance.
  • the acrylic resin may include a partially modified resin, for example, a resin modified with an imide such as a maleimide-modified acrylic resin.
  • the total light transmittance of the 3 mm-thick molded product obtained from the acrylic resin (A) is preferably 85% or more and 90% or more from the viewpoint of imparting excellent jet blackness or excellent smoke properties. It is more preferable that Here, the wavelength of light used for measuring the total light transmittance is 380 to 780 nm.
  • the acrylic resin preferably contains a rubber-modified acrylic resin from the viewpoint of developing excellent impact resistance and the like.
  • the acrylic resin has a total amount of 100% by weight, rubber-containing acrylic graft copolymer (A1) 5 to 100% by weight, and acrylic resin (A2) 95 to 0%. It is preferable to contain% by weight.
  • the contents of the rubber-containing acrylic graft copolymer (A1) and the acrylic resin (A2) are more preferably 10 to 50% by weight and 90 to 50% by weight, respectively.
  • the rubber-modified acrylic resin is composed of 10 to 40% by weight of the rubber-containing acrylic graft copolymer (A1), acrylic resin (A2) 60 to It is preferably 90% by weight and other materials 0 to 5% by weight.
  • the rubber-containing acrylic graft copolymer (A1), acrylic resin (A2) 60 to It is preferably 90% by weight and other materials 0 to 5% by weight.
  • ultraviolet absorbers and light stabilizers described later, various antioxidants, colorants other than carbon black, and the like can be used.
  • the rubber-containing acrylic graft copolymer (A1) comprises an inner layer of the rubber copolymer (A1c) and an outer layer of the graft component (A1s) covering the inner layer.
  • a multilayer structure graft copolymer is preferably included so that the weight ratio of A1c: A1s is 5:95 to 85:15.
  • the weight ratio of A1c: A1s is more preferably 25:75 to 80:20 from the viewpoint of further improving the impact strength.
  • the innermost layer polymer (A1a) is further made to have a weight ratio of A1a: (total amount of A1c and A1s) of 10:90 to 40:60.
  • a multilayer structure graft copolymer having at least a three-layer structure in which the monomer of the rubber copolymer (A1c) is polymerized in the presence of the innermost layer polymer (A1a). More preferably, they are combined.
  • the rubber copolymer (A1c) is composed of 50 to 99.9% by weight of an acrylic acid alkyl ester and a copolymerizable vinyl monomer other than the acrylic acid alkyl ester.
  • the polymer is preferably a polymer of a rubber copolymer monomer consisting of 49.9% by weight and a polyfunctional monomer of 0.1 to 10% by weight, an acrylic acid alkyl ester of 70 to 99% by weight, This is a polymer of a rubber copolymer monomer comprising 0 to 29% by weight of a copolymerizable vinyl monomer other than alkyl acrylate and 0.1 to 5% by weight of a polyfunctional monomer. It is more preferable.
  • the number average molecular weight of the rubber copolymer (A1c) is usually 500 to 100,000.
  • the rubber copolymer (A1c) is a component mainly responsible for the impact resistance improving effect due to its rubber elasticity. Further, the closer the refractive index of the rubber copolymer (A1c) is to the refractive index of the graft component (A1s) or the acrylic resin (A2), and the smaller the particle diameter, the easier it is to become transparent.
  • alkyl acrylate ester those having 1 to 8 carbon atoms in the alkyl group are preferable from the viewpoint of the reaction rate at the time of polymerization.
  • methyl acrylate, ethyl acrylate, propyl acrylate, acrylic acid Butyl (BA), 2-ethylhexyl acrylate (2EHA), acrylate-n-octyl (nOA), and the like but from the viewpoint of improving impact resistance, selected from the group consisting of BA, 2EHA, and nOA
  • BA is particularly preferable.
  • the alkyl group of the acrylic acid alkyl ester may be linear or branched.
  • copolymerizable vinyl monomers other than the above alkyl acrylate esters include aromatic vinyl such as styrene, ⁇ -methylstyrene, and vinyl toluene, methyl methacrylate, ethyl methacrylate, propyl methacrylate, and methacrylic.
  • examples include methacrylic acid alkyl esters such as butyl acid, non-alkyl (meth) acrylates such as phenyl (meth) acrylate, cyclohexyl (meth) acrylate, and benzyl (meth) acrylate, (meth) acrylonitrile, and (meth) acrylic acid. .
  • the polyfunctional monomer is a monomer having two or more non-conjugated double bonds per molecule, and is a component that functions as a crosslinking agent or a graft crossing agent.
  • One or more selected from the group consisting of glycol di (meth) acrylates, vinyl group-containing polyfunctional monomers, and allyl group-containing polyfunctional monomers are preferred.
  • the alkylene glycol di (meth) acrylates include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, and dibutylene glycol di (meth) acrylate.
  • Examples of the vinyl group-containing polyfunctional monomers include divinylbenzene and divinyl adipate.
  • examples of the allyl group-containing polyfunctional monomers include allyl (meth) acrylate, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, and the like.
  • the graft component (A1s) is composed of 50 to 100% by weight of a methacrylic acid alkyl ester and a copolymerizable vinyl monomer other than the methacrylic acid alkyl ester. It is preferably a polymer of a monomer for a graft component consisting of 0 to 50% by weight of a monomer, 80 to 100% by weight of an alkyl methacrylate and a copolymerizable vinyl monomer other than the alkyl methacrylate More preferably, it is a polymer of a monomer for graft components comprising 20 to 0% by weight.
  • the mercaptan compound such as dodecyl mercaptan and octyl mercaptan is further added to 0.01 parts by weight of the graft component monomer. It is preferable to add ⁇ 5 parts by weight.
  • the graft component (A1s) itself may have a multilayer structure as necessary.
  • the alkyl methacrylate is preferably one having 1 to 4 carbon atoms in the alkyl group from the viewpoint of the reaction rate during polymerization.
  • methyl methacrylate, ethyl methacrylate, propyl methacrylate, methacrylic acid Although butyl etc. are mentioned, From a viewpoint of improving workability, methyl methacrylate is preferred.
  • the alkyl group of the methacrylic acid alkyl ester may be linear or branched.
  • copolymerizable vinyl monomers other than methacrylic acid alkyl esters include aromatic vinyl such as styrene, ⁇ -methylstyrene, vinyltoluene, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, etc.
  • Non-alkyl (meth) acrylates such as alkyl acrylate ester, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, and benzyl (meth) acrylate, (meth) acrylonitrile, (meth) acrylic acid, and the like.
  • the innermost layer polymer (A1a) is composed of 40 to 99.9% by weight of one or more monomers selected from the group consisting of alkyl methacrylates and aromatic vinyl compounds, and other vinyl monomers that can be copolymerized. It is preferably a polymer of the innermost layer polymer monomer consisting of 59.9 to 0% by weight, and 0.1 to 5% by weight of the polyfunctional monomer. One or more selected from the group consisting of vinyl 55 to 90% by weight, 45 to 10% by weight of other copolymerizable vinyl monomers, and 0.1 to 5% by weight of polyfunctional monomers More preferably, it is a polymer of the monomer for the innermost layer polymer.
  • the rubber copolymer monomer is polymerized in the presence of the innermost layer polymer (A1a), whereby the innermost layer polymer (A1a) becomes the rubber-containing acrylic graft copolymer (A1).
  • the layer is distributed almost in the center.
  • the aromatic vinyl compound is preferably one or more selected from the group consisting of styrene, ⁇ -methylstyrene and vinyltoluene, and more preferably styrene.
  • methacrylic acid alkyl ester the other copolymerizable vinyl monomer, and the polyfunctional monomer, those described above can be used.
  • (Meth) acrylate means acrylate and / or methacrylate.
  • (Meth) acrylonitrile means acrylonitrile and / or methacrylonitrile
  • (meth) acrylic acid means acrylic acid and / or methacrylic acid.
  • the number average particle size of such a rubber-containing acrylic graft copolymer (A1) is preferably 30 to 400 nm, and preferably 40 to 300 nm, from the viewpoint of the balance between impact resistance and transparency. More preferred.
  • the method for producing such a rubber-containing acrylic graft copolymer (A1) is not particularly limited, and for example, a suspension polymerization method or an emulsion polymerization method can be used, but the particle diameters of the copolymer particles are made uniform. Therefore, it is preferable to produce the emulsion by an emulsion polymerization method.
  • the acrylic resin (A2) is a continuous layer resin that wraps the rubber-containing acrylic graft copolymer (A1) and the carbon black (B) according to the present invention as a base resin of the resin composition of the present invention, that is, a matrix. Functions as a resin. From the viewpoint of obtaining excellent transparency, it is preferably a polymer of acrylic resin monomers comprising 0 to 50% by weight of acrylic acid alkyl ester and 100 to 50% by weight of methacrylic acid alkyl ester.
  • the number average molecular weight of the acrylic resin (A2) is preferably 5000 to 150,000, and more preferably 9000 to 120,000.
  • an acrylic resin (A2) there is no limitation in particular in the manufacturing method of such an acrylic resin (A2),
  • a suspension polymerization method, an emulsion polymerization method, etc. can be used, but methacrylic acid alkylester and acrylic acid alkylester are efficiently used. From the viewpoint of copolymerization, the suspension polymerization method is preferred.
  • acrylic acid alkyl ester and methacrylic acid alkyl ester those described above can be used.
  • the resin composition according to the present invention contains carbon black (B) having a number average particle size of 10 to 40 nm.
  • the number average particle diameter is more preferably 10 to 30 nm, more preferably 10 to 25 nm from the viewpoint of imparting sufficient jet blackness to the rubber-modified acrylic resin composition of the present invention. More preferably, the thickness is 10 to 20 nm. Those having a number average particle diameter of more than 40 nm may not exhibit sufficient jetness, and those having a number average particle diameter of less than 10 nm are excellent in ability to impart jetness but are likely to aggregate. There is a problem and generally that particle size separation is difficult and difficult to obtain.
  • the resin molding which has the specific light absorption coefficient which concerns on this invention it is carbon black (B so that a molded object may have a specific light absorption coefficient from a viewpoint which provides the resin composition with the outstanding black appearance.
  • the number average particle diameter is more preferably from 10 to 30 nm, and further preferably from 10 to 20 nm. If the number average particle diameter exceeds 40 nm, it may be difficult for the molded product to have a specific extinction coefficient, and a resin molded product having blackness and smoke without color tone unevenness may be obtained. It may be difficult. In addition, those having a number average particle diameter of less than 10 nm are generally difficult to obtain, although they have excellent ability to impart smoke properties.
  • Carbon black (B) is preferably dispersed in the resin composition with a number average particle size of 10 to 40 nm.
  • the dispersion state of carbon black is more preferably primary dispersion in that black is developed.
  • the primary dispersion refers to a state in which the carbon black particles are primary particles, that is, the unit particles are dispersed without being aggregated with other particles.
  • the particles themselves are not perfectly spherical, but it can be confirmed by TEM observation whether they are primary dispersed.
  • the number average particle diameter when carbon black is dispersed in the resin composition is more preferably 10 to 30 nm for the same reason as above. It is more preferably from ⁇ 25 nm, most preferably from 10 to 20 nm.
  • the dispersed particle diameter of carbon black is more preferably 10 to 30 nm, and more preferably 10 to 20 nm for the same reason as described above. Further preferred.
  • the carbon black is preferably a carbon black having a blackness (MCF: High Color Furnace) or HCC: High Color Channel, which is a general name for carbon black for coloring, and Mitsubishi Carbon.
  • the carbon black is supplied in powder form or granular form.
  • a so-called master batch obtained by pre-kneading and pulverizing an acrylic resin and high-concentration carbon black. It is preferable to use a pigment from the viewpoint of dispersibility of carbon black.
  • the molecular weight of the acrylic resin used for preparing the masterbatch is preferably 50,000 to 150,000, more preferably 90000 to 120,000. If it is less than 50000, there exists a tendency for the molecular weight fall by a masterbatch manufacturing process and a pellet manufacturing process to generate
  • the carbon black concentration is lowered over two or more stages, that is, the step of preliminary kneading and then pulverizing is repeated. Therefore, it is preferable to use a master batch having a low carbon black concentration in the final molding from the viewpoint of smoke quality stability and carbon black dispersibility, measurement, and quality stability.
  • the addition amount of carbon black is preferably 0.05 to 10 parts by weight, and 0.1 to 5 parts by weight with respect to 100 parts by weight of the acrylic resin (A) from the viewpoint of imparting sufficient jet blackness. More preferably, it is a part. If it exceeds 10 parts by weight, the jetness is saturated, which is not economical.
  • it is preferably 0.001 to 0.1 parts by weight with respect to 100 parts by weight of the acrylic resin (A).
  • it is more preferably 0.001 to 0.05 parts by weight, that is, 10 to 500 ppm by weight, more preferably 20 to 300 ppm by weight, and further 40 to 250 ppm by weight. More preferred is 40 to 100 ppm by weight.
  • the pigment in order to obtain a resin molded body having an excellent black appearance, it is preferable to color only with carbon black (B), but the range in which the required weather resistance can be maintained (sunshine weather meter (with rain, black panel)
  • the pigment may be further colored with a pigment or a dye within a range in which ⁇ E can be maintained below 3 under the condition that the temperature is 63 ° C. for 2000 hours.
  • ⁇ E can be maintained below 3 under the condition that the temperature is 63 ° C. for 2000 hours.
  • an excessive amount of pigment or dye is added, the weather resistance of the pigment or dye itself, or the weather resistance of the base resin due to the presence of the pigment or dye, will decrease, resulting in a resin molded product with excellent black appearance over the long term. There is a risk of not being able to.
  • the resin composition of the present invention preferably further contains an organic phosphorus stabilizer having a melting point (mp) of 120 to 250 ° C. This is because when the resin molded product of the present invention is obtained from the resin composition, the resin composition is molded at a high temperature in order to improve processability, or the residence time of the resin composition becomes long because a large molding machine is used. This is because, in particular, the heat stability during processing can be further improved, and a molded article having an excellent jetness can be obtained. Further, from the viewpoint of exerting the above-described effects during processing and from the viewpoint of preventing bleeding out, it is more preferable that the melting point of the organophosphorus stabilizer is 140 ° C. to 200 ° C.
  • organophosphorous stabilizers examples include 2,2′-methylenebis (4,6-di-t-butylphenyl) octyl phosphite (mp 146 to 152 ° C., for example, HP-10 manufactured by Adeka Corporation), tris ( 2,4-di-t-butylphenyl) phosphite (mp 180-190 ° C., for example, Irgaphos 168 manufactured by BASF, Adeka Stub 2112 manufactured by Adeka), bis (2,6-di-t-butyl-4-methylphenyl) ) Pentaerystole diphosphite (mp 234 to 240 ° C., for example, PEP-36 manufactured by ADEKA CORPORATION), 2-[[2,4,8,10-tetrakis (1,1-dimethylether) dibenzo [d, f] [1,3,2] dioxaphosphepin-6-yl] oxy] -N, N-
  • the organophosphorus stabilizer is preferably added in an amount of 0.01 to 3 parts by weight, more preferably 0.05 to 1 part by weight, based on 100 parts by weight of the acrylic resin (A). It is more preferable to add 1 to 0.5 parts by weight.
  • the resin composition of the present invention has a good compatibility with the acrylic resin (A) from the viewpoint of excellent wear resistance while maintaining the jet blackness of the molded body, and has a certain degree of external slip. From the standpoint of exhibiting a balance of properties, it is preferable to further contain one or more lubricants selected from the group consisting of esters of C10 to C30 fatty acids and amides of C10 to C30 fatty acids.
  • Fatty acid esters include montanic acid ester, butyl oleate, butyl stearate, hydrogenated castor oil, ethylene glycol monostearate, glyceryl monooleate, glycerin monostearate, sorbitan mono Examples thereof include laurate.
  • fatty acid amide examples include oleic acid amide, stearic acid amide, palmitic acid amide, methylene bisstearamide, ethylene bisstearamide, and the like.
  • ethylene glycol esters of C10 to C30 fatty acids and C10 to C30 alcohol esters of C10 to C30 fatty acids is more preferable, and ethylene glycol esters of C10 to C30 fatty acids are Further preferred.
  • ethylene glycol esters of C10 to C30 fatty acids include ethylene glycol esters of montanic acid and ethylene glycol esters of stearic acid, with ethylene glycol esters of montanic acid being more preferred.
  • the addition amount of the lubricant is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the acrylic resin. If the amount is less than 0.1 parts by weight, the effect of addition is hardly exhibited, and if the amount exceeds 10 parts by weight, the jetness and physical properties of the molded article are deteriorated.
  • aliphatic hydrocarbons for example, aliphatic hydrocarbons, aliphatic alcohols, fatty acids, metal soaps, silicone oils and the like may be used in combination.
  • aliphatic hydrocarbon include liquid paraffin, natural paraffin, synthetic paraffin, microwax (microcrystalline wax), polyethylene wax, and partial oxides, fluorides, chlorides, and the like thereof.
  • aliphatic alcohol include cetyl alcohol, lauryl alcohol, stearyl alcohol, oleyl alcohol, mixed aliphatic alcohol, and the like.
  • fatty acids examples include lauric acid, stearic acid, mixed fatty acids (fatty acids from beef tallow, fish oil, coconut oil, soybean oil, rapeseed oil, rice bran oil, etc.) and the like.
  • metal soap examples include barium stearate, zinc stearate, calcium stearate, lead stearate, aluminum stearate, magnesium stearate and the like.
  • silicone oil examples include silicone oils mainly composed of polydimethylsiloxane, and among the silicone oils, silicone oils containing carboxylic acid groups, modified silicone oils such as silicone oils containing hydroxyl groups, and the like.
  • the ultraviolet absorber is preferably at least one selected from the group consisting of benzotriazole-based, triazine-based, and benzophenone-based ultraviolet absorbers from the viewpoint of ultraviolet absorbing ability.
  • benzotriazole UV absorbers include 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- [2-hydroxy-5- (1,1,3,3-tetramethylbutyl) phenyl ] Benzotriazole, 2- [2-hydroxy-3,5-bis ( ⁇ , ⁇ -dimethylbenzyl) phenyl] benzotriazole, 2- (2′-hydroxy-3-tert-butyl-5′-methylphenyl)- 5-chlorobenzotriazole, 2- (2-hydroxy-3,5-di-tert-amylphenyl) benzotriazole, 2- (2-hydroxy-3-sec-butyl-5-tert-butylphenyl) benzotriazole, 2,2′-methylenebis [6- (2H-benzotria
  • triazine ultraviolet absorbers examples include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol.
  • benzophenone UV absorbers examples include 2-hydroxy-4-phenylmethoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydrate benzophenone, 2-hydroxy-4-phenylpropoxybenzophenone, and the like. It is done.
  • an ultraviolet absorber to the resin composition in an amount that does not affect the total light transmittance of the molded product.
  • 0.1 to 15 parts by weight is preferably added with respect to 100 parts by weight of the acrylic resin (A), more preferably 0.2 to 5 parts by weight.
  • the light stabilizer is not particularly limited, and a known light stabilizer can be used.
  • a known light stabilizer can be used.
  • a light stabilizer it is preferable to add 0.1 to 3 parts by weight of a light stabilizer to the resin composition with respect to 100 parts by weight of the acrylic resin (A).
  • the resin molded body of the present invention is obtained by molding the resin composition of the present invention, and has excellent blackness, that is, excellent black appearance.
  • a molded article having excellent jetness refers to a molded article having an L value specified in JISZ-8729 of 6.5 or less.
  • the L value is more preferably 6 or less.
  • the L value is evaluated by irradiating the measurement surface of the resin molded body with light from directly above (90 °) and measuring the light reflected in the direction of 45 ° from the measurement surface.
  • the resin molded body obtained by molding the resin composition of the present invention is 0.02 to 0.04 ppm ⁇ 1 cm ⁇ 1 , the resin molded body has an excellent black appearance and excellent Exhibits smoke.
  • Equation 1 The extinction coefficient is defined by Equation 1 below.
  • Equation 1 C is the weight concentration (ppm) of the carbon black (B) in the resin (A), I is the parallel light transmittance of the resin molding, I 0 is the same shape as the resin molding, and carbon
  • L is the thickness (cm) of the resin molded product in the direction of incidence of the parallel light on the resin molded product.
  • the acrylic resin (A) is a rubber-modified acrylic resin, it is dispersed so as to have the above-described specific extinction coefficient due to excellent appearance such as glass unique to the acrylic resin, such as transparency and gloss.
  • excellent weather resistance, gloss, and impact resistance can be imparted to the resin molded body of the present invention.
  • the resin molded body having the above-mentioned specific extinction coefficient has an excellent light semi-transmission, that is, its total light transmittance from the viewpoint of having a deep appearance while having an excellent smoke property. Is preferably 1% to 80%, more preferably 30% to 80%.
  • the resin molded body having the above-described specific extinction coefficient is a flat plate composed of two main planes and four side planes, one main surface is a mirror surface, and the other main surface and 4
  • the side planes By forming the side planes into a shape having a satin surface, a molded body having a small L value can be obtained.
  • the resin composition of the present invention has an excellent black appearance and is excellent in molding processability, it can be used for housing and building materials, automobile members by a known thermoplastic resin molding method, such as an injection molding method or an extrusion molding method. It can be suitably used for electrical / electronic parts, sundries, films and the like.
  • This molded article is not only excellent in weather resistance, impact resistance, and appearance, but also excellent in blackness and gloss, so it is suitable as an appearance member that requires a high-grade appearance, for example. It is suitable for vehicle members, household electrical appliance members, furniture parts, OA housing applications, and film applications.
  • the resin formed body of the present invention can be used as an automobile member of the present invention, and can be used for either an exterior member or an interior member.
  • an exterior member or an interior member for example, if it is a jet-black molded body, covers such as a pillar cover, pillar garnish, rear garnish, rear spoiler, switch cover, garnish such as interior garnish used in the vicinity of the console, hood peripheral parts such as a food upper, It can be suitably used as a radiator grill or the like.
  • it is a light semipermeable resin molding which has the above-mentioned specific light absorption coefficient, it can be used conveniently as a side visor, a roof visor, a sunroof, etc.
  • the resin molded body of the present invention not only has excellent weather resistance and gloss, but also has a uniform and excellent blackness even with a large injection molded member, that is, an excellent black appearance, And it can be set as the motor vehicle member which is excellent in impact resistance and has high boss strength.
  • the resin molded body of the present invention is suitable as an automobile member that requires a high-grade appearance and that requires excellent wear resistance.
  • Acrylic resin 3 Delpet 80NE manufactured by Asahi Kasei Chemicals Corporation (catalog value: deflection temperature under load (ISO75-1, 75-2) 97 ° C., melt flow rate (ISO1133 cond13) 2.3 g / 10 min) (3 mm thick molded product) Total light transmittance: 92%)
  • Acrylic resin 4 Delpet 720V manufactured by Asahi Kasei Chemicals Corporation (catalog value: deflection temperature under load (ISO75-1, 75-2) 93 ° C., melt flow rate (ISO1133 cond13) 21 g / 10 min) (all 3 mm thick molded product) (Light transmittance: 92%)
  • Carbon black Carbon black (Mitsubishi Chemical Co., Ltd. # 2600, particle diameter measured by TEM: 10 nm) Carbon black 40 parts by weight, acrylic resin 2: 59 parts by weight, antioxidant (BASF Irganox 1010) 0.5 parts by weight, and dispersant 0.5 parts by weight using a 44 mm twin screw extruder. Then, it is pelletized twice at 260 ° C. (a mixture of carbon black and acrylic resin is pelletized, and other pellets are mixed into the pellet for the second pelletization), and then pulverized to obtain a master of carbon black. Batch (CB-1) was manufactured, and the resin composition was manufactured using a master batch instead of using carbon black itself.
  • PEP-36 bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite
  • ADEKA CORPORATION HP-10 manufactured by Adeka Corporation
  • Adeka Corporation (2,2'-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite
  • Tinuvin 234 (benzotriazole UV absorber) manufactured by BASF
  • Adekastab LA-63 hindered amine light stabilizer
  • Irganox 1010 manufactured by BASF (Hinder) 0.5 parts by weight of each was used.
  • Example 1 Comparative Example 1 According to the composition shown in Table 1, compounding, extrusion by an extruder, molding, and evaluation were performed.
  • the residence heat stability during injection molding was evaluated.
  • the cooling time was set to 18 seconds, which is the standard cooling time
  • the time cycle was 37 seconds, which is the standard time cycle.
  • the residence time at the time of evaluation was a format in which the cooling time was extended by the set amount. For example, when the residence time is 60 seconds, the cooling time is set to 78 seconds which is the standard cooling time + the residence time, and the time cycle is 97 seconds which is the standard time cycle + the residence time.
  • a molding method that extends the residence time every two shots was adopted.
  • the organophosphorus stabilizer when added, high residence heat stability was observed.
  • 2,2′-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite when used, it can withstand a long residence time of 3 minutes even at a high molding temperature of 290 ° C. I found it.
  • the melting point of the organophosphorus stabilizer is in a range that matches the processing region of the acrylic resin, that is, the melting point and the processing temperature of the resin have a sufficient width. That is, in both extrusion kneading and injection molding, it is considered that the phosphorus stabilizer is required to be sufficiently dissolved at the processing temperature and adapted to the composition.
  • the melting point of the phosphorus stabilizer is too high with respect to the processing temperature, it does not sufficiently dissolve at the processing temperature and does not perform its function. Conversely, if the melting point of the phosphorus stabilizer is too low Although dissolution is not a problem, it is considered that a defective phenomenon such as bleed out is caused when the molded body is used.
  • Examples 4 to 6, Comparative Examples 2 and 3 According to the composition shown in Table 3, blending, extrusion with an extruder, molding, and evaluation were performed. In Comparative Examples 2 and 3, the acrylic resin as a raw material was molded as it was.
  • the molded article of the composition of the present application is also excellent in practical strength.
  • Examples 7 to 11, Comparative Examples 4 and 5 Samples were prepared using the raw materials and methods described below, and various evaluations were performed.
  • Carbon black Carbon black (Mitsubishi Chemical Corporation # 2600, TEM measured particle size is 10 nm)
  • carbon black is a copolymer of 40 parts by weight of carbon black, an acrylic plasticizer resin (87% by weight of methyl methacrylate and 13% by weight of methyl acrylate, melt flow rate (JIS K7210, 230 ° C., 37.3 N) is 15 g / 10 min) 60 parts by weight and antioxidant (BASF Irganox 1010) 0.5 part by weight using a 44 mm twin screw extruder, A carbon black masterbatch (CB-2) was produced by pelletizing twice at 240 ° C. and then pulverizing.
  • the amount of lubricant was 0.5 parts by weight of Tinuvin 234 (benzotriazole UV absorber) manufactured by BASF, 0.5 part by weight of Adeka Stab LA-63 (hindered amine light stabilizer) manufactured by Adeka Corporation, and BASF 0.5 parts by weight of Irganox 1010 (hindered phenol antioxidant) manufactured by dry blending was carried out, and pelletized at 240 ° C. using a 44 mm twin screw extruder. Using the pellets, a 150 ⁇ 150 ⁇ 3 mm flat plate, a 50 ⁇ 90 ⁇ 3 mm color plate (CP), and a 63.5 ⁇ 12.7 ⁇ 6.3 mm bar were molded and evaluated.
  • L value which is an index of jetness
  • SE2000 Denshoku Kogyo Co., JISZ8722 compliant, 0-45 degree spectroscopic system
  • the evaluation was performed by irradiating the measurement surface of the resin molded body with light from directly above (90 °) and measuring the light reflected in the direction of 45 ° from the measurement surface.
  • the sample for L value measurement was manufactured using the metal mold
  • the cloth of Kanakin No. 3 was attached by quadruple winding, and fixed with a stopper of an ASTM jig.
  • the abrasion test was performed while the cloth and the sample were in contact with each other in an area of about 4 cm 2 and the load was correctly transmitted to the sample.
  • the front is the normal direction of the observer perpendicular to the flat plate of the sample.
  • a scratch was observed from the front, it was evaluated as 3 if it was between 2, 4 and 2 and the scratch was difficult to see when viewed from the front, but was visible when viewed from an oblique direction.
  • Table 4 summarizes the types and compositions of the lubricants of each example and comparative example, the L value and the abrasion resistance test results.
  • Example 9 since excellent abrasion resistance exceeding Example 8 and excellent jetness comparable to Example 8 are shown, ester lubricants other than montanic acid esters are also preferable as lubricants. It turns out that it is a thing.
  • the type of lubricant is an amide type, it is comparable to those of the ester type lubricants used in Examples 7 to 9, although they are clearly different in nature. It can be seen that both jetness and wear resistance are compatible, and amide type lubricants are also preferable as lubricants.
  • the result of the abrasion test of Example 11 was between 3 and 4. It can be seen that even when stearamide is used, the change in L value is small and the wear resistance is good.
  • Comparative Example 5 since the wear resistance is not improved in spite of the poor jetness, it is understood that the selection of the type of lubricant, particularly the selection focusing on the melting point and polarity of the lubricant is important. .
  • a copolymer of monomers for acrylic resin comprising 87% by weight of methyl methacrylate and 13% by weight of methyl acrylate, with a melt flow rate (JIS K7210, 230 ° C., 37.3N).
  • Composition (CB-4) 15 g / 10 min (total light transmittance of molded product with 3 mm thickness: 92%) (Composition (CB-4)
  • carbon black Mitsubishi Chemical Corporation # 2600, particle diameter measured by TEM is 10 nm
  • BASF antioxidant
  • a carbon black masterbatch (CB-3) was manufactured by pulverizing 0.5 parts by weight of Irganox 1010) manufactured by the company, using a 44-mm twin screw extruder at 240 ° C. and then pulverizing twice. .
  • Carbon black masterbatch (CB-3) was blended with rubber-modified acrylic resin (A) composed of rubber-containing acrylic graft copolymer (A1) and acrylic resin (A2) with the composition shown in Table 5. Furthermore, 0.5 parts by weight of Tinuvin 234 (benzotriazole-based UV absorber) manufactured by BASF, 0.5 parts by weight of Adeka Stab LA-63 (hindered amine light stabilizer) manufactured by Adeka Co., Ltd., and Irganox manufactured by BASF The compound added with 0.5 part by weight of 1010 (hindered phenol antioxidant) was pelletized at 240 ° C. using a 44 mm twin screw extruder to produce a composition (CB-4).
  • composition (CB-5) For comparison, a commercially available carbon black masterbatch having a composition shown in Table 5 and a rubber-modified acrylic resin (A) comprising a rubber-containing acrylic graft copolymer (A1) and an acrylic resin (A2).
  • SPAB-8K500 carbon concentration 45% by weight
  • Tinuvin 234 0.5 part by weight
  • Adeka Stub LA-63 0.5 part by weight
  • Irganox The composition to which 1010 (0.45 parts by weight) was added was pelletized at 240 ° C. using a 44 mm twin screw extruder to produce a composition (CB-5).
  • Rubber-modified acrylic comprising 15 parts by weight of rubber-containing acrylic graft copolymer (A1) and 85 parts by weight of acrylic resin (A2) comprising 50 parts by weight of (A2-3) and 35 parts by weight of (A2-4) Dry blend by adding Tinuvin 234 (0.5 parts by weight), Adeka Stub LA-63 (0.5 parts by weight) and Irganox 1010 (0.5 parts by weight) to 100 parts by weight of the resin (A) And pelletized at 240 ° C. using a 44 mm twin screw extruder. Using the pellets, a 150 ⁇ 150 ⁇ 3 mm flat plate, a 50 ⁇ 90 ⁇ 3 mm color plate, and a 63.5 ⁇ 12.7 ⁇ 6.3 mm bar were formed.
  • Example 12 to 15 The composition (CB-4) was added to 101.5 parts by weight of the rubber-modified acrylic resin composition of Reference Example 1, 2.5 parts by weight in Example 12, 5 parts by weight in Example 13, and 10 parts by weight in Example 14. Parts, 20 parts by weight in Example 15, were added, and this composition was molded in the same manner as in Reference Example 1 to obtain flat plates, color plates (CP) and bars.
  • Comparative Examples 6-9 Samples of Comparative Examples 6 to 9 were prepared and evaluated in the same manner as in Examples 12 to 15, except that the composition (CB-4) was replaced with the composition (CB-5). That is, the composition (CB-5) was added to 101.5 parts by weight of the rubber-modified acrylic resin composition of Reference Example 1, 2.5 parts by weight in Comparative Example 6, 5 parts by weight in Comparative Example 7, and 10 parts by weight and 20 parts by weight in Comparative Example 9 were added, and the composition was molded in the same manner as in Reference Example 1 to obtain a flat plate, a color plate, and a bar.
  • the L value was measured for a flat plate sample and a color plate (CP) sample by using SE2000 manufactured by Nippon Denshoku Industries Co., Ltd. (JISZ8722 compliant, 0-45 degree spectroscopic system) as a color difference meter. That is, the evaluation was performed by irradiating the measurement surface of the resin molded body with light from directly above (90 °) and measuring the light reflected in the direction of 45 ° from the measurement surface.
  • the sample for L value measurement was manufactured using the metal mold
  • the total light transmittance and the haze value are average transmission values at wavelengths of 380 to 780 nm measured in accordance with JIS K7105 using NDH-300A manufactured by Nippon Denshoku Industries Co., Ltd. for flat plate samples.
  • C is the carbon black weight concentration (ppm) in the resin
  • L is the thickness (cm) in the direction parallel to the measurement light beam of each sample
  • I 0 is the parallel light beam of the sample of Reference Example 1 that does not contain carbon black.
  • Transmittance I is the parallel light transmittance of each sample in which carbon black is dispersed.
  • Izod impact test The Izod impact test was performed using a bar sample in accordance with ASTM D256 under the conditions of 1/4 inch, no notch, and 23 ° C.
  • Carbon black number average particle size A part of the flat plate sample was cut out with a microtome, and the ultrathin section was subjected to ruthenium staining, followed by TEM observation.
  • Table 6 shows the calculated values of carbon concentration, L value, total light transmittance, haze value, extinction coefficient, Izod impact strength, carbon black number average particle diameter, weather resistance, and appearance evaluation results for each sample.
  • the resin molded product of the present invention is excellent in blackness, smoke properties, impact resistance, weather resistance and appearance.
  • the obtained samples of Examples 12 to 15 all had an excellent black appearance.
  • the black appearances of the samples of Comparative Examples 6 to 9 obtained were not deep and were inferior to the black appearance of the samples of Examples 12 to 15.
  • FIG. 2 shows an electron micrograph of a sample of the composition (CB-4). It can be seen that the carbon black is in the form of primary particles, and the number average particle diameter is uniformly dispersed at 10 to 15 nm. The reason why the carbon black particles appear to be connected is that the front particles and the rear particles appear to overlap.
  • the particle having a particle diameter of 220 nm in the figure is a rubber-containing acrylic graft copolymer (A1).
  • FIG. 3 shows an electron micrograph of a sample of the composition (CB-5). It can be seen that a plurality of carbon blacks are aggregated and dispersed with a number average particle diameter of 50 nm. In addition, the particle
  • the resin molded body of the present invention is formed by dispersing the carbon black (B) in the acrylic resin (A) so as to have a specific absorption coefficient, the absorbance is lower than that of the conventional carbon black-dispersed resin molded body.
  • the resin molded body has high light transmittance, excellent blackness and smoke properties, and is excellent in black appearance.

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Abstract

L'invention porte sur un produit de résine moulé qui présente d'excellentes propriétés de noir profond, de résistance aux intempéries, d'aptitude à la mise en œuvre lors du moulage, de résistance au bossage, de résistance à l'usure, de dégagement de fumée, etc.; et sur une composition de résine pour sa production. La composition de résine comprend (A) une résine acrylique et (B) un noir de carbone ayant une granulométrie moyenne en nombre de 10 à 40 nm.
PCT/JP2011/062587 2010-06-01 2011-06-01 Composition de résine et produit moulé associé WO2011152449A1 (fr)

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US20150025175A1 (en) * 2012-03-12 2015-01-22 Iqap Masterbatch Group, S.L. Concentrated polymer composition ("masterbatch"), manufacturing method and use for adding it to polyester fibres and filaments
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WO2017170044A1 (fr) * 2016-03-30 2017-10-05 日本ゼオン株式会社 Composition de polymère acrylique
JPWO2018016473A1 (ja) * 2016-07-21 2018-07-26 三菱ケミカル株式会社 熱可塑性樹脂組成物、成形体及び車両材料
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JP2020105425A (ja) * 2018-12-28 2020-07-09 株式会社クラレ 不透明な弾球遊技用樹脂基盤とその製造方法、及び、印刷フィルム付き弾球遊技用樹脂基盤
JP2020125376A (ja) * 2019-02-01 2020-08-20 大日精化工業株式会社 樹脂組成物、樹脂成形体、及び樹脂組成物の製造方法

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EP2826808B1 (fr) * 2012-03-12 2018-09-26 Iqap Masterbatch Group, S.L. Fibres et filaments de polyester préparés par utilisation d'un masterbatch de pigment de pmma, procédé de fabrication et utilisation
US20150025175A1 (en) * 2012-03-12 2015-01-22 Iqap Masterbatch Group, S.L. Concentrated polymer composition ("masterbatch"), manufacturing method and use for adding it to polyester fibres and filaments
JP2014234508A (ja) * 2013-06-05 2014-12-15 旭化成ケミカルズ株式会社 熱可塑性樹脂組成物及び筐体
JP2016037518A (ja) * 2014-08-05 2016-03-22 旭化成ケミカルズ株式会社 メタクリル系樹脂組成物製成形品
WO2017170042A1 (fr) * 2016-03-30 2017-10-05 日本ゼオン株式会社 Composition de polymère acrylique
WO2017170044A1 (fr) * 2016-03-30 2017-10-05 日本ゼオン株式会社 Composition de polymère acrylique
JPWO2018016473A1 (ja) * 2016-07-21 2018-07-26 三菱ケミカル株式会社 熱可塑性樹脂組成物、成形体及び車両材料
JP2019135287A (ja) * 2018-02-05 2019-08-15 ユーエムジー・エービーエス株式会社 熱可塑性樹脂組成物及びその成形品
JP7110609B2 (ja) 2018-02-05 2022-08-02 テクノＵｍｇ株式会社 熱可塑性樹脂組成物及びその成形品
JP2020105425A (ja) * 2018-12-28 2020-07-09 株式会社クラレ 不透明な弾球遊技用樹脂基盤とその製造方法、及び、印刷フィルム付き弾球遊技用樹脂基盤
JP7082566B2 (ja) 2018-12-28 2022-06-08 株式会社クラレ 不透明な弾球遊技用樹脂基盤とその製造方法、及び、印刷フィルム付き弾球遊技用樹脂基盤
JP2020125376A (ja) * 2019-02-01 2020-08-20 大日精化工業株式会社 樹脂組成物、樹脂成形体、及び樹脂組成物の製造方法
JP7000366B2 (ja) 2019-02-01 2022-02-10 大日精化工業株式会社 樹脂組成物、樹脂成形体、及び樹脂組成物の製造方法

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