JP5715902B2 - Black decorative sheet - Google Patents

Description

  The present invention relates to a black decorative sheet, and more particularly, to a black decorative sheet used for surface decoration of a resin molded product or the like.

  Conventionally, a decorative molded product that decorated the surface of a resin molded product, after placing a decorative sheet in an injection mold, inject a molten resin such as acrylic resin, polycarbonate resin, ABS resin into the cavity By filling and solidifying, a decorative sheet is bonded and laminated on the surface at the same time as molding of the resin molded product, and the method is integrated.

  Usually, the same resin is used on the back side (surface that is in close contact with the resin molded product) of the decorative sheet from the viewpoint of adhesion to the resin to be injection-molded and moldability, and the design side is on the front side. In view of the above, a transparent resin such as an acrylic resin is often used.

  As such a decorative sheet, for example, a picture insert film in which a pattern is provided on an acrylic film and an acrylonitrile butadiene styrene film (base film) is laminated thereon is proposed, and the butadiene content ratio of the film is It is said that 20 to 50 weight% is preferable (patent document 1).

  Also, on the back side of the front sheet made of transparent acrylic resin, the binder ink is a pattern ink layer made of a mixture of acrylic resin and vinyl chloride-vinyl acetate copolymer, and a mixture of acrylic resin and vinyl chloride-vinyl acetate copolymer. A sheet for simultaneous injection molding is proposed, in which a base material sheet made of an acrylonitrile-butadiene-styrene copolymer resin having a butadiene component ratio of less than 20% by mass is laminated in this order. (Patent Document 2).

  A resin composition comprising an inorganic filler in a first resin layer made of an acrylic resin, and a butadiene-containing resin having an aromatic vinyl compound, a vinyl cyanide compound, and butadiene as essential monomers. A laminated film is proposed in which a second resin layer having a filler content of 1 to 40% by weight and an acetone insoluble resin content of 5 to 40% by weight is laminated, and when the laminated film is preshaped It is said that the occurrence of curling is effectively prevented (Patent Document 3).

  However, the conventional decorative sheet has excellent jetness, and also has a black decoration excellent in surface hardness, total light transmittance, weather resistance, heating defect, vacuum formability, film forming property and extrudability. It was difficult to obtain a sheet. In addition, when heated, the substrate film (substrate sheet) is prone to have convex defects (heating defects), which is caused by laminating a decorative sheet on a resin molded product. When it is set as a decorative molded product, it causes a defect such as distortion in the design of the decorative molded product.

Japanese Patent Laid-Open No. 11-91041 Japanese Patent Laid-Open No. 2003-170546 Japanese Patent Laid-Open No. 2003-285399

  The present invention has been made in view of the above circumstances, and its purpose is excellent in jet blackness, and also in surface hardness, total light transmittance, weather resistance, heating defects, vacuum formability, film forming property and extrudability. The object is to provide an excellent black decorative sheet.

  That is, the gist of the present invention is a black decorative sheet in which a transparent resin layer and a base material layer are arranged, and the base material layer has a particle diameter of 20 to 100 parts by weight of rubber-reinforced styrene resin. The black decorative sheet is composed of a resin composition containing 0.3 to 1 part by weight of carbon black of 50 nm and 0.1 to 1 part by weight of polycaprolactone.

  According to the present invention, it is possible to provide a black decorative sheet which is excellent in jet blackness, and which is excellent in surface hardness, total light transmittance, weather resistance, heating defects, vacuum formability, film forming property and extrudability.

FIG. 1 is a schematic sectional view showing an example of the black decorative sheet of the present invention. FIG. 2 is a schematic cross-sectional view showing an example of a black decorative molded product.

  Hereinafter, the present invention will be described in detail with reference to the accompanying drawings. As illustrated in FIG. 1, the black decorative sheet (3) of the present invention has a configuration in which a transparent resin layer (1) and a base material layer (2) are arranged. As illustrated in FIG. 2, the black decorative molded product (5) has a configuration in which the black decorative sheet (3) is laminated on the surface of the resin molded product (4), and the black decorative sheet (3). The base material layer (2) side is laminated on the resin molded product (4).

[Transparent resin layer]
The transparency of the transparent resin layer can be represented by haze. The haze of the transparent resin layer is usually 20% or less, preferably 15% or less, more preferably 10% or less. The thickness of the transparent resin layer is usually 20 to 500 μm, preferably 30 to 400 μm, and more preferably 40 to 300 μm. If the transparent resin layer is too thin, it is difficult to obtain a deep transparency, and if it is too thick, it is difficult to produce a wound roll. The transparent resin layer is usually uncolored, but can be colored and transparent if necessary.

  Examples of the transparent resin include acrylic resins, polyester resins, polycarbonate resins, styrene resins, polyolefin resins, and the like, and acrylic resins are preferable. Examples of the acrylic resin include polymethyl (meth) acrylate, polyethyl (meth) acrylate, polybutyl (meth) acrylate, methyl (meth) acrylate-butyl (meth) acrylate copolymer, ethyl (meth) acrylate-butyl (meth) ) Acrylic resins such as acrylate copolymers and methyl (meth) acrylate-styrene copolymers. These can also be used as a mixture of two or more. In addition, said "(meth) acrylate" means an acrylate or a methacrylate.

  When the rubber particles are contained in the acrylic resin, the rubber particles are preferably acrylic, and specific examples include an acrylic polymer having a core-shell structure including a rubber elastic layer. Here, as an acrylic polymer having a core-shell structure including a rubber elastic layer, the inner layer is a rubber elastic layer made of a copolymer of an alkyl acrylate having 4 to 8 carbon atoms and a polyfunctional monomer. , An acrylic polymer having a two-layer structure in which the outer layer is a hard polymer mainly composed of methyl methacrylate, and the innermost layer is a hard polymer composed mainly of methyl methacrylate, and the intermediate layer is a carbon having an alkyl portion. It is a rubber elastic layer made of a copolymer of an alkyl acrylate of 4 to 8 and a polyfunctional monomer, and the outermost layer is a hard polymer mainly composed of methyl methacrylate. Examples include coalescence.

  In the transparent resin layer, as long as transparency is not impaired, a lubricant, a filler, an ultraviolet absorber, a light stabilizer, an antioxidant, an anti-aging agent, a plasticizer, a fluorescent whitening agent, a weathering agent, Various additives such as an antistatic agent, a flame retardant, an antifogging agent, an antibacterial agent, an antifungal agent, an antifouling agent, and a tackifier may be blended.

[Base material layer]
In the black decorative sheet of the present invention, the base layer is 0.3 to 1 part by weight of carbon black having a particle diameter of 20 to 40 nm and 0.1 to 1 part by weight of polycaprolactone with respect to 100 parts by weight of the rubber-reinforced styrene resin. It is characterized by being comprised with the resin composition containing these. By blending specific amounts of carbon black and polycaprolactone each with a particle size in a specific range, it is excellent in jet blackness, and also has surface hardness, total light transmittance, weather resistance, vacuum formability, film-forming property and extrudability. An excellent black decorative sheet is obtained.

  In the present invention, the carbon black has a particle diameter of 20 to 50 nm, and if the carbon black particle diameter is less than 20 nm, the extrudability is insufficient, and if the particle diameter exceeds 50 nm, the jet blackness is insufficient. Inferior to heating defects. The particle size of carbon black is preferably 22 to 45 nm. Carbon black is a carbon-based fine particle, which is manufactured by incomplete combustion of oil or gas, and is produced by a channel method, an oil furnace method, or the like.

  As the carbon black having a particle diameter of 20 to 50 nm, commercially available carbon black can be used. For example, Mitsubishi Carbon Black # 45, # 33, # 260 manufactured by Mitsubishi Chemical, Talker Black # 7360SB, # 7350 manufactured by Tokai Carbon Etc. In addition, the measurement of the particle diameter of carbon black is obtained by observing the carbon black particles with an electron microscope and calculating the arithmetic average diameter.

The polycaprolactone is a polymer of caprolactone, particularly ε-caprolactone, that is, a repeating unit represented by (—CH ₂ —CH ₂ —CH ₂ —CH ₂ —CH ₂ —CO—O—). A part of hydrogen atoms in the methylene chain of polycaprolactone may be substituted with a halogen atom or a hydrocarbon group. The terminal of polycaprolactone may be subjected to terminal treatment by esterification, etherification or the like. The number average molecular weight of polycaprolactone is preferably about 2000 to 40000. Such polycaprolactone can be produced by ring-opening polymerization of caprolactone in the presence of a catalyst such as an acid, a base, or an organometallic compound. As the polycaprolactone, a commercially available product can be used, and examples thereof include “PLACCEL H1P” (manufactured by Daicel Corporation), “SOLPLUS330” (manufactured by Nippon Lubrizol Corporation), and the like.

  In the resin composition constituting the base material layer, the carbon black content is 0.3 to 1 part by weight with respect to 100 parts by weight of the rubber-reinforced styrene resin. When the content of the carbon black having a particle diameter of 20 to 50 nm is less than 0.3 parts by weight, the total light transmittance, extrudability, and heating defects are insufficient. Dispersion, extrudability, and heating defects are insufficient. The content of carbon black having a particle diameter of 20 to 50 nm is preferably 0.32 to 0.8 parts by weight with respect to 100 parts by weight of the rubber-reinforced styrene resin.

  In the resin composition constituting the base material layer, the content of polycaprolactone is 0.1 to 1 part by weight with respect to 100 parts by weight of the rubber-reinforced styrene resin. When the content of polycaprolactone is less than 0.1 parts by weight, the total light transmittance, extrudability, and heating defects are insufficient, and when it exceeds 1 part by weight, the dispersion of carbon black becomes insufficient. The content of polycaprolactone is preferably 0.12 to 0.8 parts by weight with respect to 100 parts by weight of the rubber-reinforced styrene resin.

  The ratio of the carbon black to the polycaprolactone is preferably 5/1 to 1/2, preferably 4/1 to 1 / 1.5, from the viewpoints of total light transmittance, weather resistance, extrudability, and the like. It is.

  In addition to polycaprolactone, for example, a small amount of other dispersant can be added to the resin composition in order to improve dispersion stability. Examples of the dispersant include anionic compounds such as fatty acid salts, sulfates, sulfonates and phosphates, cationic compounds such as aliphatic amine salts, nonionic compounds, polymer compounds, amphoteric compounds, and fluorine compounds. Can be mentioned.

  For the base material layer, as in the case of the transparent resin layer described above, known lubricants, fillers, flame retardants, antioxidants, stabilizers, antistatic agents, plasticizers, anti-aging agents, and the like as necessary. Various additives can be blended.

  Examples of the method for producing the raw material composition for the base material layer include a method in which carbon black, polycaprolactone and, if necessary, the above-mentioned additives and the like are blended into a rubber-reinforced styrene resin and melt-kneaded with a melt-kneader. Examples of the apparatus used for melt kneading include a single screw extruder, a twin screw extruder, a Banbury mixer, a kneader, and a continuous kneader. The temperature of melt kneading is usually about 190 to 260 ° C. The temperature of extrusion molding for obtaining the base film is usually about 190 to 260 ° C.

  The thickness of a base material layer is 20-1000 micrometers normally from points, such as a moldability, Preferably it is 30-800 micrometers, More preferably, it is 50-700 micrometers. In order to improve the adhesion to the other layer, the surface of the base material layer such as the front surface or the back surface may be subjected to easy adhesion treatment such as corona discharge treatment, plasma treatment, and primer coating.

  In a preferred embodiment of the present invention, the base material layer is made of a specific rubber-reinforced styrene resin. Such a rubber-reinforced styrene-based resin includes a rubber-containing styrene-based graft polymer (I) having a graft ratio of 50 to 200% and a rubber content of 5 to 55% by mass, and, if desired, a styrene-based (co) This resin contains polymer (II), has a rubber content of 5 to 40% by mass, and has an intrinsic viscosity of 0.05 to 0.80 dl / g of a component soluble in acetone. When the base material layer is composed of the rubber-reinforced styrene resin, there are few heating defects.

  Examples of the rubber-reinforced styrene resin include a rubber-containing styrene-based graft polymer obtained by polymerizing a vinyl monomer (b1) containing an aromatic vinyl compound in the presence of the rubber-like polymer (a), and a rubber-containing polymer. Examples thereof include a mixture of a styrene-based (co) polymer obtained by polymerizing a styrene-based graft polymer and a vinyl monomer (b2) containing an aromatic vinyl compound.

  The rubber-containing styrene-based graft polymer (I) usually includes a graft copolymer in which a vinyl monomer (b1) containing an aromatic vinyl compound is graft-copolymerized with the rubber-like polymer (a), and rubber The ungrafted component which is not grafted to the polymer (a), that is, the (co) polymer by the remaining vinyl monomer (b1) is included. Two or more rubber-containing styrene-based graft polymers (I) can be used in combination.

  The rubber-reinforced styrene-based resin rubber content is 5 to 40% by mass, preferably 8 to 38% by mass, more preferably 15 to 36% by mass, from the viewpoints of prevention of heating defects, adhesion, mechanical properties, and the like. Most preferably, it is 21-35 mass%. In both cases where the rubber-reinforced styrene resin is made of a rubber-containing styrene-based graft polymer and a mixture of a rubber-containing styrene-based graft polymer and a styrene-based (co) polymer, the rubber-reinforced styrene-based resin is used. The rubber content of the resin (I) is calculated from the polymerization prescription conditions and the polymerization conversion rate of the rubber-containing styrene-based graft polymer (I). Further, the rubber-containing styrene-based graft polymer (I) and the styrene-based (co-polymer) ) Obtained from the blending ratio with the polymer (II), obtained by pyrolysis gas chromatography (PyGC), obtained by infrared absorption spectrum (IR), and the like.

  The intrinsic viscosity [η] (measured in methyl ethyl ketone at 30 ° C.) of the rubber-reinforced styrene resin-soluble component is 0.05 to 0.80 dl / from the viewpoint of extrudability, molding processability, adhesion and the like. g, preferably 0.07 to 0.70 dl / g, more preferably 0.09 to 0.60 dl / g, and particularly preferably 0.12 to 0.55 dl / g.

  The intrinsic viscosity [η] can be determined in the following manner. In both cases where the rubber-reinforced styrene resin is made of a rubber-containing styrene-based graft polymer and a mixture of a rubber-containing styrene-based graft polymer and a styrene-based (co) polymer, the rubber-reinforced styrene-based resin is used. Dissolve the resin in acetone, dissolve the acetone-soluble matter recovered after centrifugation in methyl ethyl ketone, prepare 5 samples with different concentrations, and measure the reduced viscosity at each concentration at 30 ° C from the Ubbelohde viscosity tube. Determine the intrinsic viscosity [η].

  The intrinsic viscosity [η] of the rubber-reinforced styrene resin-soluble component is the polymerization initiator, chain transfer agent, emulsifier, solvent used in the production of the graft copolymer and styrene (co) polymer. It is possible to control by adjusting the kind and amount of the above, and the polymerization time and polymerization temperature. The intrinsic viscosity [η] of the rubber-reinforced styrene resin can be adjusted by appropriately selecting rubber-containing styrene graft polymers and styrene (co) polymers having different intrinsic viscosities [η].

  The rubber content of the rubber-containing styrene-based graft polymer (I) is 5 to 55% by mass, preferably 7 to 53% by mass, and more preferably 9 to 51% by mass from the viewpoint of preventing the occurrence of heating defects and mechanical properties. %. The rubber content of the rubber-containing styrene-based graft polymer (I) can be obtained by a method of calculating from a polymerization prescription and a polymerization conversion rate, a method of obtaining by pyrolysis gas chromatography (PyGC), infrared absorption spectrum (IR), and the like. I can do it.

  The rubbery polymer (a) used for forming the rubber-containing styrene-based graft polymer (I) is not particularly limited as long as it is rubbery at room temperature, and may be either a homopolymer or a copolymer. The rubbery polymer (a) may be a crosslinked polymer or a non-crosslinked polymer.

  Examples of the rubbery polymer (a) include conjugated diene rubber, hydrogenated conjugated diene rubber, ethylene / α-olefin copolymer rubber, acrylic rubber, silicone rubber, and silicone / acrylic composite rubber. It is done. These may be used in combination of two or more. From the viewpoint of impact resistance, conjugated diene rubbers are preferred, and from the viewpoint of weather resistance, acrylic rubber, silicone rubber, silicone / acrylic composite rubber, ethylene / α-olefin copolymer rubber and hydrogenated conjugated diene are used. System rubber is preferred.

  The shape of the rubber polymer (a) can be, for example, particulate (spherical or substantially spherical), linear, curved or the like. When it is in the form of particles, the volume average particle diameter is usually 5 to 2,000 nm, preferably 10 to 1,500 nm, more preferably 50 to 1,200 nm, from the viewpoint of mechanical properties and processability. The volume average particle diameter can be measured by image analysis using an electron micrograph, a laser diffraction method, a light scattering method, or the like.

  The volume average particle size of the rubber polymer (a) is, for example, a combination of a rubber polymer having a relatively small particle size of about 100 to 400 nm and a rubber polymer having a relatively large particle size of about 400 to 1200 nm. You can also adjust it. When used in combination, the blending ratio of the rubber polymer having a relatively small particle diameter and the rubber polymer having a relatively large particle diameter is usually 60 to 99/40 to 1, preferably 70 to 95/30 to 5. is there.

  Examples of the conjugated diene rubber include polybutadiene, butadiene / styrene random copolymer, butadiene / styrene block copolymer, butadiene / acrylonitrile copolymer, and the like. These can be used in combination of two or more. The glass transition temperature of the conjugated diene rubber is usually −20 ° C. or less from the viewpoints of flexibility, low temperature impact property and the like.

  The hydrogenated conjugated diene rubber is not particularly limited as long as it is a (co) polymer obtained by hydrogenating a (co) polymer containing a structural unit derived from a conjugated diene compound, for example, hydrogenated polybutadiene. Hydrogenated styrene / butadiene rubber, styrene / ethylene butylene / olefin crystal block polymer, olefin crystal / ethylene butylene / olefin crystal block polymer, styrene / ethylene butylene / styrene block polymer, hydrogenated butadiene / acrylonitrile copolymer, etc. Can be mentioned.

  As an acrylic rubber, the proportion of structural units derived from an alkyl acrylate ester having 2 to 8 carbon atoms in the alkyl group is 80% by mass or more based on the total amount of structural units constituting the acrylic rubber (both ) A polymer is preferred.

  Examples of the alkyl acrylate having 2 to 8 carbon atoms in the alkyl group include ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, hexyl acrylate, n-octyl acrylate, and 2-ethylhexyl acrylate. Preferred are n-butyl acrylate, isobutyl acrylate and 2-ethylhexyl acrylate. These may be used in combination of two or more.

  When the acrylic rubber contains a structural unit derived from another monomer, the other monomer may be a monofunctional unit such as acrylonitrile, vinyl ester, methacrylic acid alkyl ester, (meth) acrylic acid, styrene, etc. Body: Mono- or polyethylene glycol di (meth) acrylate such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, divinylbenzene, diallyl Examples thereof include crosslinkable monomers such as di- or triallyl compounds such as phthalate, diallyl maleate, diallyl succinate and triallyl triazine. Content of the structural unit derived from a crosslinkable monomer is about 0.01-10 mass% normally with respect to the whole quantity of a structural unit. A preferred method for producing the acrylic rubber is an emulsion polymerization method.

  The silicone rubber is preferably a latex rubber, and examples thereof include polyorgano produced by the methods described in US Pat. No. 2,891,920, US Pat. No. 3,294,725, and the like. A siloxane rubber is mentioned.

  Silicone / acrylic composite rubber is a rubbery polymer containing polyorganosiloxane rubber and polyalkyl (meth) acrylate rubber. A preferable silicone-acrylic composite rubber is a composite rubber having a structure in which polyorganosiloxane rubber and polyalkyl (meth) acrylate rubber are intertwined with each other so that they cannot be separated.

  Silicone / acrylic composite rubber can be produced, for example, by the methods described in JP-A-4-239010, JP-A-4-100812, and the like.

  The ethylene / α-olefin copolymer rubber is a copolymer including an ethylene unit and a unit composed of an α-olefin having 3 or more carbon atoms, and includes an ethylene / α-olefin copolymer, an ethylene / α-olefin copolymer, Non-conjugated diene copolymers are exemplified.

  Examples of the ethylene / α-olefin copolymer include an ethylene / propylene copolymer and an ethylene / butene-1 copolymer. Examples of the ethylene / α-olefin / non-conjugated diene copolymer include an ethylene / propylene / non-conjugated diene copolymer and an ethylene / butene-1 / non-conjugated diene copolymer.

  The vinyl monomer (b1) used for the production of the rubber-containing styrene graft polymer (I) contains an aromatic vinyl compound. That is, the vinyl monomer (b1) may be composed only of an aromatic vinyl compound, or composed of an aromatic vinyl compound and another monomer copolymerizable with this compound. Also good. Other monomers include vinyl cyanide compounds, (meth) acrylic acid ester compounds, maleimide compounds, unsaturated acid anhydrides, carboxyl group-containing unsaturated compounds, hydroxyl group-containing unsaturated compounds, and epoxy group-containing unsaturated compounds. Compounds, oxazoline group-containing unsaturated compounds, and the like. These may be used in combination of two or more.

  The aromatic vinyl compound is not particularly limited as long as it is a compound having at least one vinyl bond and at least one aromatic ring. Examples thereof include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, β-methylstyrene, ethylstyrene, p-tert-butylstyrene, vinyltoluene, vinylxylene, vinylnaphthalene, monochlorostyrene, dichloromethane. Examples thereof include styrene, monobromostyrene, dibromostyrene, tribromostyrene, and fluorostyrene. These may be used in combination of two or more. Of these, styrene and α-methylstyrene are preferable, and styrene is particularly preferable.

  Examples of the vinyl cyanide compound include acrylonitrile, methacrylonitrile, ethacrylonitrile, α-ethylacrylonitrile, α-isopropylacrylonitrile, α-chloroacrylonitrile, α-fluoroacrylonitrile and the like. These can also be used in combination of two or more. Of these, acrylonitrile is preferred.

  Examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, ( (Meth) acrylic acid isobutyl, (meth) acrylic acid sec-butyl, (meth) acrylic acid tert-butyl, (meth) acrylic acid hexyl, (meth) acrylic acid n-octyl, (meth) acrylic acid 2-ethylhexyl, ( Examples thereof include cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, and the like. These may be used in combination of two or more.

  As maleimide compounds, maleimide, N-methylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-dodecylmaleimide, N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (4-methylphenyl) ) Maleimide, N- (2,6-dimethylphenyl) maleimide, N- (2,6-diethylphenyl) maleimide, N- (2-methoxyphenyl) maleimide, N-benzylmaleimide, N- (4-hydroxyphenyl) Maleimide, N-naphthylmaleimide, N-cyclohexylmaleimide and the like can be mentioned. These may be used in combination of two or more. Of these, N-phenylmaleimide is preferred.

  In addition, as another method for introducing a structural unit derived from a maleimide compound into the rubber-reinforced aromatic vinyl resin, for example, an unsaturated dicarboxylic anhydride of maleic anhydride is copolymerized and then imidized. The method may be used.

  Examples of the unsaturated acid anhydride include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. These may be used in combination of two or more.

  Examples of the carboxyl group-containing unsaturated compound include (meth) acrylic acid, ethacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, and cinnamic acid. These may be used in combination of two or more.

  Examples of the hydroxyl group-containing unsaturated compound include 2-hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene etc. are mentioned. These may be used in combination of two or more.

  Examples of the epoxy group-containing unsaturated compound include glycidyl (meth) acrylate, 3,4-oxycyclohexyl (meth) acrylate, vinyl glycidyl ether, allyl glycidyl ether, and methallyl glycidyl ether. These may be used in combination of two or more.

  Examples of the oxazoline group-containing unsaturated compound include vinyl oxazoline.

  In the present invention, the vinyl monomer (b1) preferably contains an aromatic vinyl compound and a vinyl cyanide compound, and the total amount used thereof is molding processability, chemical resistance, hydrolysis resistance, dimensions. From the viewpoint of stability, molded appearance, etc., the content is usually 70 to 100% by mass, preferably 80 to 100% by mass, based on the total amount of the vinyl monomer (b1). In addition, the use ratio of the aromatic vinyl compound and the vinyl cyanide compound was 100% by mass in total from the viewpoint of molding processability, chemical resistance, hydrolysis resistance, dimensional stability, molding appearance, and the like. In this case, it is usually 5 to 95% by mass and 5 to 95% by mass, preferably 50 to 95% by mass and 5 to 50% by mass, and more preferably 60 to 95% by mass and 5 to 40% by mass, respectively.

  As the rubber-containing styrene-based graft polymer (I), a vinyl monomer (b1) containing an aromatic vinyl compound and a vinyl cyanide compound is preferably polymerized in the presence of the rubber-like polymer (a). The graft copolymer obtained in this way.

  Examples of the polymerization method of the rubber-containing styrene-based graft polymer (I) include emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, or a polymerization method combining these. In the production of the rubber-containing styrene-based graft polymer (I), the rubber-like polymer (a) and the vinyl-type monomer (b1) are present in the reaction system in the presence of the total amount of the rubber-like polymer (a). The vinyl monomer (b1) may be added all at once to initiate the polymerization, or the polymerization may be carried out while being divided or continuously added. Further, in the presence or absence of part of the rubber polymer (a), the vinyl monomer (b1) may be added all at once to initiate polymerization, or may be divided or continuously. May be added. Under the present circumstances, you may add the remainder of the said rubber-like polymer (a) collectively, divided | segmented or continuously in the middle of reaction.

  When producing a rubber-containing styrene-based graft polymer by emulsion polymerization, a polymerization initiator, a chain transfer agent (molecular weight regulator), an emulsifier, water, and the like are used.

  As a polymerization initiator, a redox system in which an organic peroxide such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramentane hydroperoxide and a reducing agent such as a sugar-containing pyrophosphate formulation and a sulfoxylate formulation are combined. Initiators; persulfates such as potassium persulfate; peroxides such as benzoyl peroxide (BPO), lauroyl peroxide, tert-butyl peroxylaurate, and tert-butyl peroxymonocarbonate. These may be used in combination of two or more. Moreover, the usage-amount of the said polymerization initiator is 0.1-1.5 mass% normally with respect to the said vinylic monomer (b11) whole quantity. The polymerization initiator can be added to the reaction system all at once or continuously.

  Examples of chain transfer agents include mercaptans such as octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, n-hexyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, tert-tetradecyl mercaptan; terpinolenes, α -A dimer of methylstyrene or the like. These may be used in combination of two or more. The usage-amount of a chain transfer agent is 0.05-2.0 mass% normally with respect to the said vinylic monomer (b1) whole quantity. The chain transfer agent can be added to the reaction system all at once or continuously.

  Examples of the emulsifier include anionic surfactants and nonionic surfactants. Anionic surfactants include higher alcohol sulfates; alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate; aliphatic sulfonates such as sodium lauryl sulfate; higher aliphatic carboxylates and aliphatic phosphates. Is mentioned. Examples of nonionic surfactants include polyethylene glycol alkyl ester compounds and alkyl ether compounds. These may be used in combination of two or more. The usage-amount of an emulsifier is 0.3-5.0 mass% normally with respect to the said vinylic monomer (b11) whole quantity.

  Emulsion polymerization can be carried out under known conditions depending on the type of vinyl monomer (b1), polymerization initiator, and the like. The latex obtained by this emulsion polymerization is usually purified by coagulation with a coagulant to form a polymer component in powder form, and then washing and drying the polymer component. Examples of the coagulant used at this time include inorganic salts such as calcium chloride, magnesium sulfate, magnesium chloride and sodium chloride; inorganic acids such as sulfuric acid and hydrochloric acid; organic acids such as acetic acid and lactic acid.

  When two or more kinds of rubber-containing styrene-based graft polymers are contained in the rubber-reinforced styrene-based resin, the resins may be mixed after being isolated from each latex. There are methods such as coagulating a latex mixture. A known method can be applied to the method for producing a rubber-containing styrene-based graft polymer by solution polymerization, bulk polymerization, and bulk-suspension polymerization.

  The graft ratio of the rubber-containing styrene-based graft polymer (I) is 50 to 200%, preferably 51 to 190%, more preferably 52 to 180%, from the viewpoint of preventing the occurrence of heating defects and extrudability. .

The graft ratio can be determined by the following formula.
[Equation 1]
Graft rate (%) = {(S−T) / T} × 100

  In the above formula, S represents 1 gram of rubber-containing styrene-based graft polymer (I) in 20 ml of acetone (acetonitrile when the rubbery polymer (a) is an acrylic rubber) and shaken at 25 ° C. Insoluble matter obtained by shaking for 2 hours with a shaker and then centrifuging for 60 minutes in a centrifuge (rotation speed: 23,000 rpm) under a temperature condition of 5 ° C. to separate insolubles and solubles. T is the mass (g) of the rubbery polymer (a) contained in 1 gram of the rubber-containing styrene-based graft polymer (I). The mass of the rubbery polymer (a) can be obtained by a method of calculating from a polymerization prescription and a polymerization conversion rate, a method of obtaining from an infrared absorption spectrum (IR), and the like.

  When the rubber-reinforced styrene resin is a mixture of the rubber-containing styrene graft polymer (I) and the styrene (co) polymer (II), the styrene (co) polymer (II) is a homopolymer and a copolymer. Any of these may be combined, or a combination thereof may be used.

  The graft ratio of the rubber-containing styrene-based graft polymer (I) is determined based on the type and amount of a polymerization initiator, a chain transfer agent, an emulsifier, etc. used when the rubber-containing styrene-based graft polymer (I) is produced. It can be controlled by adjusting the charging time, charging time, polymerization temperature, polymerization time and the like.

  The vinyl monomer (b2) used for the polymerization of the styrene (co) polymer (II) may be only an aromatic vinyl compound, or the aromatic vinyl compound and other monomers. It may be a combination. Other monomers include vinyl cyanide compounds, (meth) acrylic acid ester compounds, maleimide compounds, unsaturated acid anhydrides, carboxyl group-containing unsaturated compounds, hydroxyl group-containing unsaturated compounds, and epoxy group-containing unsaturated compounds. Compounds, oxazoline group-containing unsaturated compounds, and the like. These may be used in combination of two or more. As each of the above compounds, the compounds exemplified in the vinyl monomer (b1) are applied.

  The styrenic (co) polymer (II) is preferably a copolymer, and the vinyl monomer (b2) is preferably composed of an aromatic vinyl compound and another monomer. Other monomers are preferably vinyl cyanide compounds and maleimide compounds, and more preferably vinyl cyanide compounds.

  When the vinyl monomer (b2) contains an aromatic vinyl compound and a vinyl cyanide compound, the total amount thereof is usually 40 to 100% by mass, preferably with respect to the whole vinyl monomer (b2). It is 50-100 mass%. In addition, the use ratio of the aromatic vinyl compound and the vinyl cyanide compound is usually 5 to 95 masses each when the total is 100 mass% from the viewpoint of molding processability, chemical resistance, and molding appearance. % And 5 to 95% by mass, preferably 40 to 95% by mass and 5 to 60% by mass, more preferably 50 to 90% by mass and 10 to 50% by mass.

  The styrene (co) polymer (II) can be produced by polymerizing the vinyl monomer (b2) containing an aromatic vinyl compound in the presence or absence of a polymerization initiator. When a polymerization initiator is used as the polymerization method, solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization and the like are suitable, and a method combining these polymerization methods may be used. In the case where no polymerization initiator is used, thermal polymerization can be employed.

  As a polymerization initiator, the 1 type (s) or 2 or more types of the compound illustrated by description of the manufacturing method of rubber-containing styrene-type graft polymer (I) can be used. The usage-amount of a polymerization initiator is 0.1-1.5 mass% normally with respect to vinyl-type monomer (b2) whole quantity. If necessary, a chain transfer agent or an emulsifier that can be used when producing the rubber-containing styrene-based graft polymer can be used.

  In the production of the styrene-based (co) polymer (II), the polymerization may be started in a state where the total amount of the vinyl-based monomer (b2) is accommodated in the reaction system, and an arbitrarily selected monomer component is added. Polymerization may be carried out by divided addition or continuous addition. Furthermore, when using said polymerization initiator, it can add to a reaction system collectively or continuously. Styrenic (co) polymers (II) can be used in combination of two or more.

[Production method of black decorative sheet]
The black decorative sheet of the present invention is produced by a method of producing a composite by forming two or more layers at the time of film formation, a method of separately forming films for forming each layer, and laminating these films separately. Is preferred.

  Examples of the method for producing a multilayered state by compounding at the time of film formation include a method of co-extrusion of a resin for forming a transparent resin layer and a resin for forming a base material layer to produce a laminated sheet. For example, a multi-manifold method that uses a plurality of extruders to form a plurality of resin layers and then bonds the resins in a molten state. A merging device is used to form a plurality of resins after merging and bonding. And a feed block method, and an inflation method using a round die.

  As a method of separately forming a film for forming each layer in advance and laminating these films separately, a method for manufacturing a film for forming each layer in advance includes, for example, a melt casting method, a T-die method, an inflation method, etc. Examples of the melt extrusion method include: a calendar method.

  The resin melt-extruded from the T-die is formed into a film by a take-up machine equipped with a cooling roll. Examples of the method for cooling the molten resin include a method in which a film is formed in contact with one metal roll; a method in which a film is formed by being sandwiched between a plurality of metal rolls, non-metal rolls and / or metal belts.

  As a method of laminating the film forming each layer, for example, a dry laminating method in which an adhesive layer is provided between the films and bonded through a laminating roll, a plurality of films are preheated and then made of two metals and / or non-metals. Examples thereof include a roll press laminating method in which the film is sandwiched and adhered to a heating roll, and a belt press laminating method in which a plurality of films are preheated and then sandwiched between a plurality of metal belts to be adhered.

  The thickness of the decorative sheet (3) of the present invention is usually from 50 to 1500 μm, preferably from 80 to 1200 μm, more preferably from 100 to 1000 μm, from the viewpoint of moldability and workability.

[Black decorative molded product]
As a method of laminating the black decorative sheet of the present invention on the surface of an injection molded product and producing a black decorative molded product, for example, the black decorative sheet is laminated so that the base material layer is on the inside of the injection molded product surface. Method of lamination (lamination molding method): The black decorative sheet is processed into the shape of the injection-molded product in advance by vacuum / air pressure molding, push-up molding, etc. so that the transparent resin layer is on the outer surface, and this is processed into a gold for injection molding A method of molding a laminated injection-molded product at the same time as injection molding by performing injection molding after placement in the mold (insert molding method); a black decorative sheet in the mold cavity for injection molding and a transparent resin layer as the mold For example, a method (in-mold molding method) in which a molding resin is injection-molded in a mold cavity after being set so as to be on the wall surface and subjected to vacuum / pressure molding.

  In the insert molding method, an insert film (black decorative sheet) is placed between both male and female molds for injection molding, and then a molten resin is injected and filled in the mold, and at the same time as molding the resin molding, Although a film is laminated | stacked, in the case of insert molding, it does not need to perform preforming of a decoration sheet. In addition, the black decorative sheet may be preheated or not, but is preferably performed.

  The shape of the resin molded product is preferably such that at least the decorative surface can make use of the moldability of the black decorative sheet, but the overall shape is a shape that allows the black decorative sheet to be laminated on the decorative surface. The shape may be any plate shape (flat plate, curved plate), columnar shape, three-dimensional solid object, or the like.

  Examples of the thermoplastic resin used in the resin molding include styrene resins (polystyrene, high impact polystyrene, AS resin, ABS resin, MBS resin, AES resin, AAS resin, etc.); polyester resins (polyethylene terephthalate, polybutylene terephthalate, Polynaphthalene terephthalate, etc.); Olefin resins (polyethylene, polypropylene, etc.); Polycarbonate resins; Polyamide resins; Polyarylate resins; Polyacetal resins; Vinyl chloride resins such as polyvinyl chloride; (Methyl methacrylate (PMMA) etc.) Acrylic resins such as (co) polymers using one or more of (meth) acrylic acid ester; polyphenylene ether; polyphenylene sulfide; imide resin; polyether ketone, polyether ether Ketone resins tons like; polysulfone, sulfonated resins polyether sulfone; biodegradable plastic and the like. These may be used in combination of two or more.

  Black decorative molded products are, for example, interior and exterior materials for vehicles such as automobiles, construction members such as baseboards and rims, interior parts such as window frames and door frames, interiors of buildings such as walls, floors, and ceilings. Used for housings, containers, etc. of household appliances such as materials, television receivers, and air conditioners.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to a following example, unless the summary is exceeded. In the following, “part” and “%” are based on mass unless otherwise specified. The evaluation methods employed in the following examples are as follows.

<Evaluation method>

(1) Surface hardness:
The pencil hardness of the transparent resin layer side surface in the black decorative sheet was measured according to JIS K5400.

(2) Jetness:
Cut the black decorative sheet into 50 mm (MD) x 40 mm (TD) test pieces, and set the transparent resin layer side surface on the UV-Vis near-infrared spectrophotometer V-670 manufactured by JASCO Corporation on the measurement side. The L value was measured. A lower L value indicates better jetness.

(3) Total light transmittance:
The black decorative sheet was cut into a 50 mm (MD) × 40 mm (TD) test piece, and the total light transmittance was measured with a haze-gard plus made by BYK Gardner. The smaller the number, the higher the concealment and the better the jetness.

(4) Weather resistance:
Cut the black decorative sheet into a 50 mm (MD) x 40 mm (TD) test piece, and set it on a super long life weather meter manufactured by Suga Test Instruments Co., Ltd. with the acrylic side facing the irradiation side, with an irradiance of 255 W / m ² , BPT was treated at 63 ° C. for 1 hour (rain + irradiation 18 minutes, irradiation 102 minutes) for 2000 hours. Thereafter, the transparent resin layer surface is set on the measurement side on the UV-Vis near-infrared spectrophotometer V-670 manufactured by JASCO Corporation, and L, a, and b of each of the untreated product and the treated product are measured. ΔE was calculated. Those having a small ΔE value have good weather resistance.

(5) Number of heating defects:
The black decorative sheet was cut into a test piece of 300 mm (MD) × 210 mm (TD) and attached and fixed to a small vacuum molding machine (“300X” manufactured by Seiko Sangyo Co., Ltd.). The black decorative sheet was heated for 10 seconds using a heater that was 40 mm away from the surface of the black decorative sheet and heated in advance to 450 ° C., and the black decorative sheet was drawn down. The number of defects, such as blisters having a size of 0.2 mm × 0.2 mm or more, present in the range of the central part 100 mm × 100 mm piece of the black decorative sheet that was drawn down was measured using a foreign matter measurement chart.

(6) Vacuum formability:
The black decorative sheet was cut into a 300 mm (MD) × 210 mm (TD) test piece, and fixed using the small vacuum molding machine 300X manufactured by Seiko Sangyo Co., Ltd. with the acrylic surface on the upper side. Using a heater that is 40 mm away from the surface of the black decorative sheet and heated to 450 ° C. in advance, the black decorative sheet is heated for 20 seconds to form a tofu mold (the bottom is 15 cm long and 15 cm wide, and the top is 14 cm long horizontally) 14cm, height 4.5cm), and then vacuum forming by reducing the pressure from the bottom of the mold. The ability to follow the tofu mold was compared. In the case of good vacuum formability, the sheet part that hits the four corners of the mold cleanly follows the mold, but in the case of the poor one, wrinkles enter the four corners. Those that follow were marked with ○, and those with wrinkles were marked with ×.

(7) Evaluation of film forming property:
Thickness gauge ("ID-C1112C" manufactured by Mitutoyo Co., Ltd.) is used for the thickness of the black decorative sheet, and the black decorative sheet is cut out 1 hour after the start of black decorative sheet production. Measured at 10 mm intervals from the center and both ends from the center, and the average value was adopted. In addition, the value of the measurement point in the range of 20 mm from the edge part of a black decorating sheet was removed from calculation of the said average value. When the thickness difference of the black decorative sheet is less than 30 μm, the film forming property is ○, when it is 30 μm or more and less than 40 μm, the film forming property is Δ, and when it is 40 μm or more, the film forming property is ×. .

(8) Extrudability (resin pressure):
Using a 25 mm extruder made by Union Plastic Co., Ltd., set to die: 230 ° C, cylinder C3: 230 ° C, cylinder C2: 230 ° C, cylinder C1: 200 ° C. After raising the temperature, set 60 mesh / 500 mesh / 60 mesh in the die part. Pellets were flowed at a screw rotation of 60 rpm, and changes in the resin pressure after 1 hour and after 1 hour were confirmed, and the amount of change was calculated using the following equation. A resin pressure change amount of less than 10 was evaluated as ○, 10 or more and less than 15 as Δ, and 15 or more as ×.

[Equation 2]
{(Resin pressure after 1 hour-resin pressure at start) / resin pressure at start} × 100

<Production of rubber-containing styrene-based graft polymer>

(1) Production of graft polymer (G1):
In a glass reactor equipped with a stirrer, 75 parts of ion exchange water, 0.5 part of potassium rosinate, 0.3 part of t-dodecyl mercaptan, 8 parts of polybutadiene latex (average particle size: 300 nm, gel content 80%) (In terms of solid content) and styrene / butadiene latex (styrene / butadiene = 30/70, average particle size 600 nm, gel content 0%) 2 parts (in terms of solid content), 21.5 parts of styrene and 8.5 parts of acrylonitrile. The mixture was heated while stirring in a nitrogen stream. When the internal temperature reached 45 ° C., a solution prepared by dissolving 0.2 parts of sodium pyrophosphate, 0.01 parts of ferrous sulfate heptahydrate and 0.2 parts of glucose in 20 parts of ion-exchanged water was added. Thereafter, 0.07 part of cumene hydroperoxide was added to initiate polymerization, and polymerization was carried out for 1 hour. Next, 50 parts of ion-exchanged water, 0.7 part of potassium rosinate, 43 parts of styrene, 17 parts of acrylonitrile, 0.3 part of t-dodecyl mercaptan, 0.2 part of cumene hydroperoxide are continuously added over 5 hours. did. After polymerization for 1 hour, 0.2 part of 2,2′-methylene-bis (4-ethylene-6-t-butylphenol) was added to complete the polymerization. Magnesium sulfate was added to this latex to coagulate the resin component. Then, the graft polymer (G1) was obtained by washing with water and further drying. The graft ratio was 150%, and the intrinsic viscosity of the acetone-soluble component was 0.10.

(2) Production of graft polymer (G2):
In a glass reactor equipped with a stirrer, 75 parts of ion exchange water, 0.35 part of potassium rosinate, 0.2 part of t-dodecyl mercaptan, polybutadiene latex (average particle size: 300 nm, gel content) as a rubbery polymer 80%) 32 parts (solid content conversion) and styrene-butadiene latex (styrene / butadiene = 30/70, average particle diameter 600 nm, gel content 0%) 8 parts (solid content conversion), styrene 14 parts and acrylonitrile 6 parts The mixture was heated with stirring in a nitrogen stream. When the internal temperature reached 45 ° C., a solution prepared by dissolving 0.2 parts of sodium pyrophosphate, 0.01 parts of ferrous sulfate heptahydrate and 0.2 parts of glucose in 20 parts of ion-exchanged water was added. Thereafter, 0.07 part of cumene hydroperoxide was added to initiate polymerization, and polymerization was carried out for 1 hour. Next, 50 parts of ion-exchanged water, 0.7 part of potassium rosinate, 29 parts of styrene, 11 parts of acrylonitrile, 0.15 part of t-dodecyl mercaptan and 0.11 part of cumene hydroperoxide are continuously added over 3 hours. did. After polymerization for 1 hour, 0.2 part of 2,2′-methylene-bis (4-ethylene-6-t-butylphenol) was added to complete the polymerization. Magnesium sulfate was added to this latex to coagulate the resin component. Then, the graft polymer (G2) was obtained by washing with water and further drying. The graft ratio was 55%, and the intrinsic viscosity of the acetone-soluble component was 0.39.

(3) Production of graft polymer (G3):
In a glass reactor equipped with a stirrer, 75 parts of ion exchange water, 0.2 part of potassium rosinate, 0.12 part of t-dodecyl mercaptan, polybutadiene latex (average particle size: 300 nm, gel content) as a rubbery polymer 80%) 40 parts (in terms of solid content) and 10 parts of styrene-butadiene latex (styrene / butadiene = 30/70, average particle size 600 nm, gel content 0%) (in terms of solid content), 12 parts of styrene and 5 parts of acrylonitrile The mixture was heated with stirring in a nitrogen stream. When the internal temperature reached 45 ° C., a solution prepared by dissolving 0.2 parts of sodium pyrophosphate, 0.01 parts of ferrous sulfate heptahydrate and 0.2 parts of glucose in 20 parts of ion-exchanged water was added. Thereafter, 0.07 part of cumene hydroperoxide was added to initiate polymerization, and polymerization was carried out for 1 hour. Subsequently, 50 parts of ion-exchanged water, 0.5 part of potassium rosinate, 24 parts of styrene, 9 parts of acrylonitrile, 0.4 part of t-dodecyl mercaptan, and 0.17 part of cumene hydroperoxide are continuously added over 4 hours. did. After polymerization for 1 hour, 0.2 part of 2,2′-methylene-bis (4-ethylene-6-t-butylphenol) was added to complete the polymerization. Magnesium sulfate was added to this latex to coagulate the resin component. Then, the graft polymer (G3) was obtained by washing with water and further drying. The graft ratio was 58%, and the intrinsic viscosity of the acetone-soluble component was 0.30.

<Styrene (co) polymer>
Styrene acrylonitrile resin (AS resin) described below was used.

(1) AS1: 24% acrylonitrile content, intrinsic viscosity 0.10
(2) AS2: Acrylonitrile content 29%, intrinsic viscosity 0.13
(3) AS3: 27% acrylonitrile content, intrinsic viscosity 0.20
(4) AS4: Acrylonitrile content 27%, intrinsic viscosity 0.39

<Transparent resin>
PMMA: “ACRYPET IRL409” (manufactured by Mitsubishi Rayon Co., Ltd.) was used.

<Carbon black>
The following carbon black was used.

(1) Mitsubishi Carbon Black # 45 (particle size 24 nm, manufactured by Mitsubishi Chemical Corporation)
(2) Mitsubishi Carbon Black # 33 (particle size 30 nm, manufactured by Mitsubishi Chemical Corporation)
(3) Mitsubishi Carbon Black # 260 (particle size 40 nm, manufactured by Mitsubishi Chemical Corporation)
(4) Mitsubishi Carbon Black # 960 (particle size 16 nm, manufactured by Mitsubishi Chemical Corporation)
(5) Mitsubishi Carbon Black # 5 (particle size 76 nm, manufactured by Mitsubishi Chemical Corporation)

<Dispersant>
The dispersants described below were used.

(1) Polycaprolactone (PLC) (“SOLPLUS DP330” manufactured by Nippon Lubrizol)
(2) Stearic acid amide ("SOLPLUS DP320" manufactured by Nippon Lubrizol)
(3) Magnesium stearate (“Mg-St” manufactured by Nitto Kasei Kogyo)

<Manufacture of resin composition>
In addition to the carbon black and dispersant shown in Table 1, 0.2 parts by mass of heat stabilizer (“IRGANOX1010” manufactured by BASF) are added to 100 parts by mass of the graft polymer and AS resin shown in Table 1. Stabilizer ("ADEKA STAB PEP-36" manufactured by Adeka) 0.4 parts by weight and 0.2 parts by mass of calcium stearate and magnesium stearate complex ("HT-00" manufactured by Nitto Kasei Kogyo Co., Ltd.) are blended at high speed. After uniform mixing with a machine, the mixture was kneaded using a φ58 mm vented twin screw extruder (L / D = 32) and pelletized by a strand cutting method to obtain pellets of the resin composition shown in Table 1.

Examples 1-10:
Using a co-extrusion sheet molding machine equipped with a T-die and a two-layer two-layer extruder with a screw diameter of 115 mm, the pellets of the resin composition shown in Table 1 were placed in one extruder (cylinder setting temperature 200 to 230 ° C.). PMMA is supplied to the other extruder (cylinder temperature setting 230 to 250 ° C.), the temperature of the junction block and the feed block is set to 240 to 250 ° C., respectively, from the T die (set temperature 250 to 260 ° C.) Molten resin was discharged to obtain a laminated sheet. The screen mesh used was 60 mesh / 120 mesh / 60 mesh. The extruder controlled the discharge amount so that the transparent resin layer and the base material layer each had a target film thickness. The roll temperature was controlled from 80 ° C. to 90 ° C., 80 ° C. to 90 ° C., 50 ° C. to 60 ° C. from the extruder side, the film was formed at a take-up speed of 5 to 15 m / min. A decorative sheet was manufactured and evaluated.

Comparative Examples 1-6:
In the same manner as in Example 1, a black decorative sheet having the thickness described in Table 2 was produced and evaluated.

1: Transparent resin layer 2: Base material layer 3: Black decorative sheet 4: Resin molded product 5: Decorative molded product

Claims (5)

  A black decorative sheet in which a transparent resin layer and a base material layer are arranged, and the base material layer is carbon black 0.3 having a particle diameter of 20 to 50 nm with respect to 100 parts by weight of the rubber-reinforced styrene resin. A black decorative sheet comprising a resin composition containing -1 part by weight and 0.1-1 part by weight of polycaprolactone.   A rubber-reinforced styrene-based resin comprising a rubber-containing styrene-based graft polymer (I) having a graft ratio of 50 to 200% and a rubber content of 5 to 55% by mass, and, if desired, a styrene (co) weight 2. The resin according to claim 1, wherein the resin contains a combination (II), the rubber content is 5 to 40% by mass, and the intrinsic viscosity of the component soluble in acetone is 0.05 to 0.80 dl / g. Black decorative sheet.   The rubber-containing styrene-based graft polymer (I) is a graft copolymer obtained by polymerizing a vinyl monomer containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of a rubbery polymer. Item 3. A black decorative sheet according to Item 2.   The styrenic (co) polymer (II) is a styrenic copolymer obtained by polymerizing a vinyl monomer containing an aromatic vinyl compound and a vinyl cyanide compound. Black decorative sheet.   The black decorative sheet according to any one of claims 1 to 4, wherein a ratio of carbon black to polycaprolactone is 5/1 to 1/2.

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