JP2014195997A - Decorative sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet using a specific film, having no heating defect, excellent in adhesiveness with a resin molded article and its film production property as a substrate film.SOLUTION: There is provided a decorative sheet in which a pattern layer 2 is arranged between a transparent resin film 1 and a substrate film 4 and the substrate film 1 is constituted by a rubber reinforced styrenic resin. [rubber reinforced styrenic resin] A resin containing a rubber-containing styrenic graft polymer (I) having a graft ratio of 50 to 200% and rubber content of 5 to 55 mass% and a styrenic (co)polymer (II) as needed, and having rubber content of 5 to 40 mass% and an intrinsic viscosity of a component soluble to acetone of 0.05 to 0.80 dl/g. A resin which is a graft copolymer (e.g. ABS resin) obtained by polymerizing the rubber-containing styrenic graft polymer (I) and a vinyl monomer containing an aromatic vinyl compound and a vinyl cyanide compound in a presence of a conjugated diene polymer.

Description

  The present invention relates to a decorative sheet, and more particularly, to a decorative sheet for insert molding used for surface decoration such as a resin molded product.

  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 used, and a design is also expressed, so that a design layer is often used between the front surface layer and the back surface layer.

  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).

  However, the decorative sheet as described above has a defect (heating defect) in that a convex film or the like is generated on the base film (base sheet) when heated. Such a heating defect causes a defect such as distortion in the design of the decorative molded product when the decorative sheet is laminated on the resin molded product to obtain a decorative molded product.

Japanese Patent Laid-Open No. 11-91041 JP 2003-170546 A

  The present invention has been made in view of the above circumstances, and its purpose is not to have a heating defect as a base film, and is excellent in adhesion to a resin molded product, and further, has its own film forming property. Another object of the present invention is to provide a decorative sheet using a specific film.

  That is, the gist of the present invention is a decorative sheet in which a pattern layer is disposed between a transparent resin film and a base film, and the base film is composed of the rubber-reinforced styrene resin described below. It exists in the decorative sheet characterized by being made.

[Rubber reinforced styrene resin]
Contains 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, a rubber content of 5 to 40% by mass and acceptable for acetone. Resin whose intrinsic viscosity of a soluble component is 0.05-0.80 dl / g.

  According to the present invention, the above-described problems are achieved.

FIG. 1 is a schematic sectional view showing an example of the decorative sheet of the present invention. FIG. 2 is a schematic sectional view showing another example of the decorative sheet of the present invention. FIG. 3 is a schematic cross-sectional view showing an example of a decorative molded product.

  Hereinafter, the present invention will be described in detail with reference to the accompanying drawings. As illustrated in FIG. 1, the decorative sheet of the present invention has a configuration in which a design layer (2) is disposed between a transparent resin film (1) and a base film (4). If desired, an adhesive layer (3) can be disposed between the base film (4) and the design layer (2) as illustrated in FIG.

  In a preferred embodiment of the present invention, the base film is a colored film. Thereby, there exists an advantage which can conceal the color of the resin molding which is a to-be-adhered body of an insert film, or can represent the base color of the design expression by a design layer.

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

  Examples of the transparent resin include an acrylic resin, a polyester resin, a polycarbonate resin, a styrene resin, and a polyolefin resin, and an acrylic resin is 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). Examples thereof include 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.

  In the transparent resin film, as long as the 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.

[Design layer]
The symbol layer is formed by printing or the like in order to express a symbol or a pattern. The material of the pattern layer is mainly composed of a colorant and a resin binder, and a dispersant and a wax are added as necessary.

  Examples of the colorant include color pigments such as carbon black, iron oxide, and monoazo yellow; metallic pigments made of metal powder such as aluminum, zinc, silver, and copper; and colorants such as quinacridone red, isoindolinone, and phthalocyanine blue. .

  Examples of the resin binder include acrylic resins, vinyl resins, olefin resins, cellulose resins, urethane resins, melamine resins, epoxy resins, styrene resins, and polyamide resins.

  Examples of the method for forming the pattern layer include a method for printing on a transparent resin film and a method for coating. Examples of the printing method include gravure printing, silk printing, and offset printing. Examples of the coating method include lip coater, reverse coater, and gravure coater.

  The thickness of the pattern layer is usually 0.2 to 50 μm, preferably 0.3 to 30 μm, and more preferably 0.5 to 20 μm. If the pattern layer thickness is too thin, it is difficult to form a print with a desired hue, and if it is too thick, it takes time to dry. Moreover, a design layer can also be formed partially as needed.

[Adhesive layer]
Examples of the resin constituting the adhesive layer include acrylic resins, vinyl resins, olefin resins, cellulose resins, urethane resins, melamine resins, epoxy resins, styrene resins, and polyamide resins.

  The thickness of the adhesive layer is usually 0.1 to 30 μm, preferably 0.2 to 20 μm, more preferably 0.5 to 10 μm. If the thickness of the adhesive layer is too thin, it is difficult to obtain adhesiveness, and if it is too thick, it takes time to dry. In addition, productivity is reduced. The adhesive layer can be partially formed as necessary.

[Base film]
The decorative sheet of the present invention is characterized in that the base film is composed of a specific rubber-reinforced styrene resin. That is, the base film has 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) weight. It is composed of a resin containing the coalescence (II), having a rubber content of 5 to 40% by mass, and an intrinsic viscosity of a component soluble in acetone of 0.05 to 0.80 dl / g. About the rubber-reinforced styrene-based resin, including its production method, described later,

  Examples of the colorant used when the base film is a colored film include black pigments and white pigments. Examples of the black pigment include carbon black and iron black. Examples of the white pigment include titanium white, zinc white, and antimony trioxide. Further, if necessary, a colorant that becomes the base color of the design of the design layer can be added. As this colorant, various known pigments and dyes described in the design layer can be used.

  For example, a small amount of a wetting / dispersing agent can be added to the colorant such as carbon black in order to enhance the dispersion stability of the colorant. Wetting / dispersing agents 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. Etc.

  For the base film, as in the case of the transparent resin film 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.

  When the base film is a colored film, the raw material composition can be produced by using a rubber-containing styrene-based graft polymer (I) or styrene-based (co) polymer (II), a colorant, and if necessary. The method of mix | blending the said additive and melt-kneading with a melt-kneading apparatus is mentioned. 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 the base film is usually 20 to 1000 μm, preferably 30 to 800 μm, and more preferably 50 to 600 μm from the viewpoint of moldability. In order to improve the adhesion with the other layer, the surface of the base film such as the front surface and the back surface can be subjected to easy adhesion treatment such as corona discharge treatment, plasma treatment, and primer coating.

[Rubber reinforced styrene resin]
In the present invention, as described above, the 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) A resin containing the polymer (II), having a rubber content of 5 to 40% by mass, and having an intrinsic viscosity of a component soluble in acetone of 0.05 to 0.80 dl / g is used.

  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 decorative sheet]
As a method for obtaining a decorative sheet, for example, in the case of a layer structure as shown in FIG. 1, a printing film having a pattern layer (2) printed on the back surface of a transparent resin film (1) is prepared. And a method of laminating a printed surface and a colored or non-colored base film (4) made of a rubber-reinforced styrene resin. Also, for example, in the case of a layer structure as shown in FIG. 2, the design layer (2) is printed on the back surface of the transparent resin film (1), and then the adhesive layer (3) is applied or printed. And a method of laminating a colored or non-colored base film (4) made of a rubber-reinforced styrene resin by heat-sealing the adhesive layer (3) of the printed film. It is done.

  The thickness of the decorative sheet (5) 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.

[Decorative products]
As illustrated in FIG. 3, the decorative molded product (7) has a configuration in which a decorative sheet (5) is laminated on the surface of a resin molded product (6), and the decorative sheet (5) is a base material thereof. The film (4) side is laminated.

  The decorative molded product (7) can be obtained by applying the decorative sheet (5) to an insert injection molding method and laminating the resin molded product (6) as an adherend. The shape of the resin molded product (6) is preferably such that at least the decorative surface can make use of the moldability of the decorative sheet (5), but the overall shape is the decorative sheet (5). The shape may be any shape that can be laminated on the decorative surface, and may be a plate shape (flat plate, curved plate), a column shape, a three-dimensional solid object, or the like.

  Examples of the thermoplastic resin used for the resin molded product (6) include styrene resins (polystyrene, high impact polystyrene, AS resin, ABS resin, MBS resin, AES resin, AAS resin, etc.); polyester resins (polyethylene terephthalate, poly Butylene terephthalate, polynaphthalene terephthalate, etc.); Olefin resins (polyethylene, polypropylene, etc.); Polycarbonate resins; Polyamide resins; Polyarylate resins; Polyacetal resins; Vinyl chloride resins such as polyvinyl chloride; Polymethyl methacrylate (PMMA) Acrylic resins such as (co) polymers using one or more of (meth) acrylic acid esters such as: polyphenylene ether; polyphenylene sulfide; imide resin; polyether ketone, polyether ether Ketone resins such as Teruketon; polysulfone, sulfonated resins polyether sulfone; biodegradable plastic and the like. These may be used in combination of two or more.

  In the above-mentioned insert molding method, an insert film (decorative sheet) is placed between both male and female molds for injection molding, and then a molten resin is injected and filled into the mold. This is a method of laminating films. During insert molding, the decorative sheet may be preformed or not. Further, the preheating of the decorative sheet may or may not be performed, but is preferably performed.

  A decorative molded product is, for example, an interior or exterior material of a vehicle such as an automobile, a construction material such as a baseboard or a rim, a fitting such as a window frame or a door frame, an interior material of a building such as a wall, floor, or ceiling. It is used for housings and containers of household electrical appliances such as 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.

(1) Evaluation method

(1-1) Number of heating defects of the colored base film:
The colored substrate film was cut into a 300 mm (MD) × 210 mm (TD) test piece and attached and fixed to a small vacuum molding machine (“300X” manufactured by Seiko Sangyo Co., Ltd.). The colored base film was heated for 10 seconds using a heater that was 40 mm away from the colored base film surface and heated to 450 ° C. in advance, and the film was drawn down. The number of defects such as blisters having a size of 0.2 mm × 0.2 mm or more in the range of the central portion of the colored base film that was drawn down, which was 100 mm × 100 mm, was measured using a contaminant measurement chart.

(1-2) Evaluation of film forming property:
The thickness of the colored base film is measured by using a thickness gauge (“ID-C1112C” manufactured by Mitutoyo Corporation), cutting the colored base film one hour after the start of the production of the colored base film, and the width direction of the colored base film. 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 the colored base film was removed from the calculation of the average value. And, when the thickness difference of the colored substrate film is less than 20 μm, the film forming property is ◎, when it is 20 μm or more and less than 30 μm, the film forming property is ◯, and when it is 30 μm or more and less than 40 μm, the film forming property is Is Δ, and when it is 40 μm or more, the film forming property is x.

(1-3) Adhesiveness with resin molding:
The colored base film is cut into a 700 mm (MD) × 400 mm (TD) test piece, fixed in a mold of an injection molding machine, and then the mold is closed, and a heat-resistant ABS resin (“Techno MUH E1500, manufactured by Techno Polymer Co., Ltd.) is used. ]) Was injected and molded. An integrally molded product of the colored substrate film and the resin molded product was taken out from the mold, and after adjusting the state at a temperature of 23 ° C. and a humidity of 50% for 24 hours, the adhesion between the colored substrate film and the resin molded product was evaluated. And, when the colored base film is not peeled off from the resin molded product and the film is broken, ◯, and when the colored base film is slightly peeled from the resin molded product and the adhesion surface, the film is broken halfway, and Δ The case where the colored base film peeled off from the resin molded product at the contact surface and the film did not break was marked as x.

(1-4) The number of heating defects of the decorative sheet:
The 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.) with the printing film side as the lower side. Using a heater that was 40 mm away from the surface of the decorative sheet and heated to 450 ° C. in advance, the decorative sheet was heated for 10 seconds to draw down the decorative sheet. Measure the number of defects, such as looseness of 0.2 mm x 0.2 mm or more, present on the printed film side in the range of 100 mm x 100 mm pieces in the center of the decorative sheet that has been drawn down, using a measurement table for impurities. did.

(2) Manufacturing method

(2-1) Production of rubber-containing styrene-based graft polymer

(2-1-1) 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.

(2-1-2) 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.

(2-1-3) 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.

(2-1-4) Production of graft polymer (G4):
In a glass reactor equipped with a stirrer, 75 parts of ion-exchanged water, 0.1 part of t-dodecyl mercaptan, 48 parts of polybutadiene latex (average particle size: 300 nm, gel content 80%) as a rubber polymer (solid content) Conversion) and 12 parts of styrene-butadiene latex (styrene / butadiene = 30/70, average particle size 600 nm, gel content 0%) (converted to solid content), 9.5 parts of styrene and 4 parts of acrylonitrile, in a nitrogen stream The temperature was raised with stirring. 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, 0.2 part of potassium rosinate, 19 parts of styrene, 7.5 parts of acrylonitrile, 0.25 part of t-dodecyl mercaptan, and 0.2 part of cumene hydroperoxide are continuously added over 2 hours. Added to. 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 (G4) was obtained by washing with water and further drying. The graft ratio was 57%, and the intrinsic viscosity of the acetone-soluble component was 0.35.

(2-1-5) Production of graft polymer (G5):
In a glass reactor equipped with a stirrer, 75 parts of ion exchange water, 0.35 part of potassium rosinate, 0.24 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. Subsequently, 50 parts of ion-exchanged water, 0.7 part of potassium rosinate, 29 parts of styrene, 11 parts of acrylonitrile, 0.2 part of t-dodecyl mercaptan and 0.11 part of cumene hydroperoxide are continuously added over 1 hour and 30 minutes. Added to. 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 (G5) was obtained by washing with water and further drying. The graft ratio was 45%, and the intrinsic viscosity of the acetone-soluble component was 0.39.

(2-2) Styrene (co) polymer:
The styrene-acrylonitrile resin (AS resin) described below was used as the styrene-based (co) polymer.

AS1: 24% acrylonitrile content, intrinsic viscosity 0.10
AS2: Acrylonitrile content 29%, intrinsic viscosity 0.13
AS3: Acrylonitrile content 28%, intrinsic viscosity 0.15
AS4: Acrylonitrile content 27%, intrinsic viscosity 0.20
AS5: 27% acrylonitrile content, intrinsic viscosity 0.39
AS6: 27% acrylonitrile content, intrinsic viscosity 1.20

(2-3) Production of rubber-reinforced styrene resin:
Carbon black ("general-purpose color RCF # 45" manufactured by Mitsubishi Chemical Corporation) 0.15 parts by mass and heat stabilizer ("IRGANOX 1010" manufactured by Ciba Specialty Chemicals) in a total of 100 parts by mass of the graft polymer and AS resin shown in Table 1 ) After blending 0.4 parts by mass and 0.2 parts by mass of calcium stearate (manufactured by Nitto Kasei Kogyo Co., Ltd.) as a lubricant and uniformly mixing with a high-speed mixer, a φ58 mm vented twin screw extruder (L / D = 32) Were kneaded and pelletized by a strand cut method to obtain colored resin pellets shown in Table 1.

(2-4) Production of colored base film:
Production Examples 1 to 11:
Using a film forming machine equipped with a T die (die width: 1600 mm, lip interval 1 mm) and an extruder with a screw diameter of 115 mm, the pellets of colored resin shown in Table 1 are supplied to the extruder and the melting temperature is obtained from the T die. Resin was discharged at 230 ° C. to obtain a film. Then, this film is surface-adhered to a cast roll (roll surface temperature 70 ° C.) with an air knife, cooled and solidified, and the operating conditions of the extruder and the cast roll are adjusted, whereby the colored base material having the thickness described in Table 1 is obtained. Films were manufactured and evaluated for film forming properties, number of heating defects, and adhesion to resin molded products.

(2-5) Production of decorative sheet:
Example 1:
A colorless and transparent acrylic resin film (haze: 10% or less) having a thickness of 100 μm, which is mainly composed of polymethyl methacrylate (PMMA), is used as a transparent resin film. Using a mixed resin of 6 to 4 mass ratio of vinyl chloride-vinyl acetate copolymer and coloring ink using quinacridone red, isoindolinone, phthalocyanine blue, and carbon black as a colorant, An adhesive layer having a thickness of 5 μm is formed on the entire surface by a gravure roll coating method, which is formed by a gravure printing method, and further a coating liquid using a mixture of acrylic resin, vinyl chloride-vinyl acetate copolymer and 6 to 4 mass ratio is formed thereon. And a printed film was obtained. Next, the colored base film produced in Production Example 1 is overlapped with the adhesive layer side of the printing film, and both films are laminated by thermal welding with a rotary heat press to obtain a decorative sheet, and the number of heating defects is determined. evaluated. The results are shown in Table 2.

Example 2:
As a colored substrate film, a decorative sheet is obtained and heated in the same manner as in Example 1 except that the colored substrate film produced in Production Example 2 is used instead of the colored substrate film produced in Production Example 1. The number of defects was evaluated. The results are shown in Table 2.

Comparative Example 1:
As a colored substrate film, a decorative sheet is obtained in the same manner as in Example 1 except that the colored substrate film produced in Production Example 8 is used instead of the colored substrate film produced in Production Example 1.
The number of heating defects was evaluated. The results are shown in Table 2.

Comparative Example 2:
As a colored substrate film, a decorative sheet is obtained in the same manner as in Example 1 except that the colored substrate film produced in Production Example 9 is used instead of the colored substrate film produced in Production Example 1. The number of defects was evaluated. The results are shown in Table 2.

1: transparent resin film 2: design layer 3: adhesive layer 4: substrate film 5: resin molded product 6: decorative sheet 7: decorative molded product

Claims (5)

It is a decorative sheet in which a pattern layer is arranged between a transparent resin film and a base film, and the base film is composed of a conjugated diene rubber-reinforced styrene resin described below. A decorative sheet.
[Rubber reinforced styrene resin]
Containing a conjugated diene 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, a rubber content of 5 to 40% by mass and Resin whose intrinsic viscosity of components soluble in acetone is 0.05 to 0.80 dl / g.   The decorative sheet according to claim 1, wherein the base film is a colored film.   Graft copolymer obtained by polymerizing rubber-containing styrene-based graft polymer (I) with a vinyl monomer containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of a conjugated diene rubber-like polymer The decorative sheet according to claim 1 or 2.   The styrene-based (co) polymer (II) is a styrene-based copolymer obtained by polymerizing a vinyl monomer containing an aromatic vinyl compound and a vinyl cyanide compound. The decorative sheet described in 1.   The decorative sheet according to any one of claims 1 to 4, wherein an adhesive layer is disposed between the base film and the design layer.

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