JP2012223922A - Decorative resin sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative resin sheet which has a transparent protective layer excellent in scratch resistance on a surface thereof and is excellent in flexibility.SOLUTION: The decorative resin sheet is a laminate sheet including a first resin layer 11, a second resin layer 13 and a pattern layer 15. The first resin layer is the transparent protective layer containing a thermoplastic resin or a curable resin. The second resin layer is a support layer comprising a thermoplastic composition which contains: 5-50 mass% of a rubber-reinforced graft resin (1) that is obtained by polymerizing a polymerizable unsaturated monomer in the presence of a rubbery polymer and has a volume-average particle size of 80-250 nm and a graft rate of 50-150%; 50-95 mass% of a polymer (2) that comprises at least one of (co)polymers obtained by using the polymerizable unsaturated monomer and contains ≥50 mass% (meth)acrylate unit, wherein the content of the rubbery polymer is 5-40 mass% of the total of component (1) and (2).

Description

  The present invention relates to a decorative resin sheet provided with a transparent protective layer, a design layer, and a support layer. More specifically, the decorative resin sheet is arranged on the surface and integrated to form a design layer (decoration layer). The present invention relates to a decorative resin sheet suitable for the production of a resin molded product (decorated molded product) in which characters, numbers, pictures, and the like indicated by the above appear through a transparent protective layer.

  Conventionally, decorative molded products in which the surface of a resin molded product is decorated include interior materials or exterior materials for vehicles such as automobiles, construction members such as baseboards, and fringes, joinery such as window frames and door frames, and walls. It is widely used as interior materials for buildings such as floors and ceilings, casings and surface materials for home appliances such as television receivers and air conditioners, and containers. As a method for producing such a decorative molded product, for example, a decorative resin sheet comprising a transparent protective layer, a pattern layer on which a pattern showing letters, numbers, pictures, etc. is formed, and a support layer in this order. A thermoplastic resin composition containing an acrylic resin, a polycarbonate resin, an ABS resin, and the like toward the surface on the support layer side after being placed inside an injection mold (sometimes called an insert film) A method is known in which a molten resin is injected and filled into a mold to form a resin molding having the same shape as the cavity, and at the same time, a decorative resin sheet is bonded and integrated on the surface (see FIG. 6). ).

An example of a decorative resin sheet used in the case where a decorative molded product is manufactured by a method using injection molding as described above is shown below.
Patent Document 1 discloses an insert film with a picture in which a pattern is provided on a transparent acrylic film and an acrylonitrile butadiene styrene film (base film) is laminated thereon.
Patent Document 2 discloses a pattern ink layer in which a binder resin is a mixture of an acrylic resin and a vinyl chloride / vinyl acetate copolymer on the back surface of a top sheet made of a transparent acrylic resin, an acrylic resin and vinyl chloride / vinyl acetate. Adhesive layer composed of a mixture with a copolymer, and a base sheet composed of an acrylonitrile / butadiene / styrene copolymer resin with a butadiene component ratio of less than 20% by mass for injection molding and simultaneous decorating A sheet is disclosed.

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

A decorative molded product in which letters, numbers, pictures and the like shown by the design layer (decorative layer) are visually recognized through the transparent protective layer is manufactured by a method using injection molding as shown in FIG. In the case, the flexibility of the decorative resin sheet and the scratch resistance when the transparent protective layer in the decorative resin sheet contacts the inner surface of the mold are required, for example. Furthermore, the scratch resistance of the transparent protective layer in the decorative molded product integrated by injection molding is also required.
This invention is made | formed in view of the said situation, has a transparent protective layer excellent in the scratch resistance in the surface, and aims at providing the decorative resin sheet excellent in flexibility.

The inventors of the present invention have completed the present invention by using a sheet comprising a support layer containing a thermoplastic resin composition containing a specific ABS resin or the like.
The present invention is as follows.
1. In the laminated decorative resin sheet including the first resin layer, the second resin layer, and the design layer, the first resin layer is a transparent protective layer containing a thermoplastic resin or a cured resin, and the second resin layer is A rubber having a volume average particle diameter of 80 to 250 nm and a graft ratio of 50 to 150% obtained by polymerizing the polymerizable unsaturated monomer (b1) in the presence of a rubbery polymer. Polymer Copolymer-Reinforced Graft Resin (Q1) (hereinafter, also referred to as “Component (Q1)”) and Polymerizable Unsaturated Monomer (b2) (Co) polymer (Q2) (hereinafter also referred to as “component (Q2)”) comprising at least a species, and the (meth) acrylic acid alkyl ester compound is added to the entire component (Q2). Containing 50 to 100% by mass of the derived structural unit, component (Q1) and component (Q ) Are 5 to 50% by mass and 50 to 95% by mass, respectively, when the total of both is 100% by mass, and the content of the rubbery polymer is component (Q1) and component ( When the total of Q2) is 100% by mass, the support layer is made of a thermoplastic resin composition that is 5 to 40% by mass, and the stacking order is the first resin layer, the design layer, and the second resin. It is a layer, or it is the said 1st resin layer, the said 2nd resin layer, and the said design layer, The decorative resin sheet characterized by the above-mentioned.
2. The component (Q2) contains 50 to 100% by mass of the (co) polymer containing 80 to 100% by mass of the structural unit derived from the (meth) acrylic acid alkyl ester compound relative to the whole of the component (Q2). The decorative resin sheet according to 1 above.
3. 3. The decorative resin sheet according to 1 or 2 above, wherein the polymerizable unsaturated monomer (b1) contains an aromatic vinyl compound and a vinyl cyanide compound.
4). 4. The decorative resin sheet according to any one of 1 to 3, wherein the second resin layer is a colored layer.
5. 4. The decorative resin sheet according to any one of 1 to 3, wherein the second resin layer is a transparent layer.
6). The decorative resin sheet according to any one of 1 to 5, further comprising an adhesive layer between the first resin layer and the second resin layer.
7). The decorative resin sheet according to any one of 1 to 6 above, wherein the thickness is 50 to 1,500 μm.

The decorative resin sheet of the present invention has a transparent protective layer excellent in scratch resistance and hardness (pencil hardness) on the surface thereof, and is excellent in flexibility as a whole, so that it is easy to handle and is decorated using injection molding or the like. The production of the molded body can proceed without any problems. Moreover, in the decorative resin sheet, characters and the like of the decorative layer are clearly seen through the transparent protective layer, and the same visibility can be obtained in the resulting decorative molded body.
The component (Q2) contained in the second resin layer contains a (co) polymer containing 80 to 100% by mass of a structural unit derived from a (meth) acrylic acid alkyl ester compound, with respect to the whole component (Q2), When it contains 50-100 mass%, it can be set as the decorating resin sheet excellent in the scratch resistance in the surface of a transparent protective layer. Therefore, the decorative resin sheet of the present invention is a vehicle such as an automobile, an interior material or an exterior material such as a ship or an aircraft, a construction material such as a baseboard or a rounded edge, a window frame, a door frame or other fitting, a wall, a floor, Interior materials for buildings such as ceilings, household electrical appliances such as TV receivers and air conditioners, housing and surface materials for OA equipment, electrical and electronic equipment, containers and other household goods, sports equipment, stationery, etc. It is suitable for forming a decorative molded product.

It is a schematic sectional drawing which shows an example of the decorating resin sheet of this invention. It is a schematic sectional drawing which shows the other example of the decorating resin sheet of this invention. It is a schematic sectional drawing which shows the other example of the decorating resin sheet of this invention. It is a schematic sectional drawing which shows the other example of the decorating resin sheet of this invention. It is a schematic sectional drawing which shows the composite structure (decoration molded product) by which the surface of the side which is not the 1st resin layer in the decorating resin sheet of this invention and the other member (resin molded product) were joined. It is a schematic sectional drawing explaining the method of manufacturing a composite structure (decoration molded product) using the decorating resin sheet of this invention.

The present invention will be described in detail below.
In this specification, “(meth) acryl” refers to acryl and methacryl, “(meth) acrylate” refers to acrylate and methacrylate, “(meth) acryloyl group” refers to acryloyl group or methacryloyl group, “Polymer” means homopolymers and copolymers.

The decorative resin sheet of the present invention includes a first resin layer that is a transparent protective layer, a second resin layer that is a support layer, and a pattern layer that is formed with a pattern showing characters, numbers, pictures, and the like. It is a mold sheet. Then, the stacking order of these layers is the first resin layer 11, the design layer 15 and the second resin layer 13 as shown in FIGS. 1 to 3, or as shown in FIG. The resin layer 11, the second resin layer 13, and the design layer 15.
As shown in FIG. 5, the decorated resin sheet of the present invention is suitable as a raw material for producing a composite structure (decorated molded product) 5 in which the first resin layer 11 is disposed on the surface side.

  The first resin layer is a protective layer in which scratches on the surface thereof are suppressed due to friction with a surface of the surface by cloth, a brush, or the like, or contact with an article or the like. Moreover, the haze (based on JIS K7136) in the single layer film constituting the first resin layer is preferably 20% or less, more preferably 15% or less, and even more preferably 10% or less, regardless of the production raw material. It is a transparent layer. In addition, "transparent" includes those in which the appearance of the single-layer film is translucent from the viewpoint of designability in the decorative resin sheet if the design layer is recognized via the single-layer film. .

  The resin contained in the first resin layer may be either a thermoplastic resin or a cured resin. The first resin layer has 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, a charging agent, as long as the transparency is not lowered. It may contain an inhibitor, a flame retardant, an antifogging agent, an antibacterial agent, a fungicide, an antifouling agent, a tackifier, and the like.

Examples of the thermoplastic resin include acrylic resin, polyester resin, polycarbonate resin, aromatic vinyl resin, polyolefin resin, and norbornene resin. These may be used alone or in combination of two or more.
In the present invention, an acrylic resin is preferable. For example, poly (meth) methyl acrylate, poly (meth) ethyl acrylate, poly (meth) butyl acrylate, methyl (meth) acrylate / butyl (meth) acrylate Examples thereof include a polymer, an ethyl (meth) acrylate / butyl (meth) acrylate copolymer, and a methyl (meth) acrylate / styrene copolymer.

  When the said 1st resin layer is a layer containing a thermoplastic resin, the 1st resin layer in the decorating resin sheet of this invention can be formed using the single layer film containing a thermoplastic resin. The surface of this single-layer film is subjected to easy adhesion treatment such as corona discharge treatment, plasma treatment, and primer coating for the purpose of improving the adhesion with other layers directly or via an adhesive layer. It may be given.

  Examples of the cured resin include cured products such as acrylic resin, phenol resin, furan resin, acrylic silicon resin, urethane resin, melamine resin, epoxy resin, and vinyl acetate resin. This curable resin can be produced by subjecting an uncured composition containing a curable resin (such as a prepolymer) and a curing agent (such as a polymerization initiator) to heat treatment, light irradiation, and the like.

  In this invention, the hardened | cured material of an acrylic resin is preferable and can be formed using the coating agent composition which is a conventionally well-known material for hard-coat layer formation. When this coating agent composition is an ultraviolet curable coating agent composition containing a polyfunctional acrylic prepolymer, it is particularly preferable because a film excellent in transparency and scratch resistance can be easily obtained. Used.

The UV-curable coating composition containing an acrylic prepolymer further comprises a monofunctional monomer, a photopolymerization initiator, an activator, a polymerization inhibitor, an antioxidant, fine particles, a wax, a non-reactive polymer, An organic solvent or the like may be included.
Examples of the acrylic prepolymer include epoxy acrylate, urethane acrylate, polyester acrylate, and polyether acrylate.
Examples of the monofunctional monomer include (meth) acrylic acid alkyl ester compounds, fatty acid esters having a hydroxyl group and a (meth) acryloyl group.
Examples of the photopolymerization initiator include benzoins, acetophenones, benzyl ketals, anthraquinones, and thioxanthones.
As the fine particles, particles mainly composed of an inorganic oxide of at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium can be used. The number average particle diameter of the fine particles is preferably 1 to 200 nm, more preferably 5 to 150 nm.
Examples of the organic solvent include aromatic hydrocarbons, alcohols, ketones, esters, ethers, amides and the like.

When the first resin layer is a layer containing a cured resin, the coating agent composition is applied to the surface of the second resin layer forming film and the like, and the coating film is subjected to heat treatment, light irradiation, and the like. Thereby, the 1st resin layer in the decorating resin sheet of this invention can be formed.
In the case where the coating agent composition is the above-mentioned UV curable coating agent composition, for example, the composition is applied to a direct gravure roll coating method, a gravure roll coating method, a kiss coating method, a reverse roll coating method, a transfer roll. Apply to the surface of the second resin layer forming film, etc. by the coating method, dipping coating method, spray coating method, flow coating method, shower coating method, spin coating method, brush coating method, etc. (Approx. 0.1 to 10 g / m ² ), and then the coating film is irradiated with ultraviolet rays (wavelength: 200 to 400 nm) using a mercury lamp, a metal halide lamp, or the like, thereby polymerizing the prepolymer and tough and transparent. Can form excellent coating .

  The thickness of the first resin layer is appropriately selected depending on the constituent material or the forming material. When the first resin layer is formed by using a single layer film containing a thermoplastic resin, the thickness of the first resin layer is preferably 10 to 500 μm, more preferably 12 to 300 μm, and still more preferably 15 to 200 μm. is there. Moreover, when the 1st resin layer is formed by use of a coating agent composition, the thickness of the 1st resin layer becomes like this. Preferably it is 0.1-100 micrometers, More preferably, it is 0.5-70 micrometers, More preferably, it is 1- 40 μm.

  The second resin layer is obtained by polymerizing the polymerizable unsaturated monomer (b1) in the presence of a rubbery polymer, and has a volume average particle diameter of 80 to 250 nm and a graft ratio of 50. It is composed of one or more of (co) polymers obtained by using ~ 150% rubbery polymer reinforced graft resin (Q1) and polymerizable unsaturated monomer (b2) (co) A polymer (Q2) comprising a component (Q2) containing 50 to 100% by mass of a structural unit derived from a (meth) acrylic acid alkyl ester compound based on the whole of the component (Q2); The proportion of Q1) and (Q2) is 5 to 50% by mass and 50 to 95% by mass, respectively, when the total of both is 100% by mass, and the content of the rubbery polymer is component (Q1). ) And (Q2) in the total amount of 100% by mass, 5 to 40% by mass A layer comprising a thermoplastic resin composition is. The type of the polymerizable unsaturated monomer (b1) and the type of the polymerizable unsaturated monomer (b2) may be the same or different in all cases. Some of the compounds may be the same.

The component (Q1) is a resin composition (hereinafter referred to as “the graft polymerization”) obtained by polymerizing the polymerizable unsaturated monomer (b1) in the presence of a rubbery polymer. Rubber-reinforced polymer-reinforced graft resin (hereinafter referred to as “graft resin”). This graft resin is a resin in which a (co) polymer containing a structural unit derived from the polymerizable unsaturated monomer (b1) is grafted to a rubbery polymer. It comprises a (co) polymer part (graft part) containing a structural unit derived from the polymerizable unsaturated monomer (b1).
The rubber-reinforced resin obtained by graft polymerization is usually a rubber-polymer-reinforced graft resin (graft resin) or a (co) polymer not grafted to a rubber-like polymer (hereinafter referred to as “ungrafted”). Polymer))). The structure of the ungrafted polymer depends on the type of the polymerizable unsaturated monomer (b1) used, and the ungrafted polymer is usually contained in the component (Q2) in the composition of the present invention.

  The rubbery polymer may be a homopolymer or a copolymer as long as it is rubbery at 25 ° C., but may be a diene polymer (hereinafter referred to as “diene rubber”). ) And a non-diene polymer (hereinafter referred to as “non-diene rubber”). Further, the rubbery polymer may be a crosslinked polymer or a non-crosslinked polymer. These can be used alone or in combination of two or more.

  Examples of the diene rubber include homopolymers such as polybutadiene, polyisoprene and polychloroprene; styrene / butadiene copolymers, styrene / butadiene / styrene copolymers, acrylonitrile / butadiene copolymers, acrylonitrile / styrene / butadiene copolymers. Styrene / butadiene copolymer rubbers such as styrene / isoprene copolymers, styrene / isoprene / styrene copolymers, styrene / isoprene copolymer rubbers such as acrylonitrile / styrene / isoprene copolymers, natural rubber, etc. Is mentioned. These copolymers may be block copolymers or random copolymers. These copolymers are hydrogenated (however, the hydrogenation rate is less than 50%). For example, hydrogenated polybutadiene, hydrogenated styrene / butadiene rubber, styrene / ethylene butylene / olefin crystal block polymer, olefin It may be a crystal / ethylene butylene / olefin crystal block polymer, a styrene / ethylene butylene / styrene block polymer, a hydrogenated product of a butadiene / acrylonitrile copolymer, or the like. The diene rubber can be used singly or in combination of two or more.

  Examples of the non-diene rubber include acrylic rubber; silicone rubber; silicone / acrylic composite rubber; ethylene / α-olefin copolymer containing an ethylene unit and a unit composed of an α-olefin having 3 or more carbon atoms. Examples include rubber, urethane rubber, and a polymer obtained by hydrogenating a (co) polymer containing a unit composed of a conjugated diene compound. These copolymers may be block copolymers or random copolymers. These copolymers may be hydrogenated (however, the hydrogenation rate is 50% or more). The non-diene rubber can be used alone or in combination of two or more.

  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 can be used alone or 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. For example, a polyorganosiloxane rubber produced by the method described in US Pat. No. 2,891,920, US Pat. No. 3,294,725, etc. Can be used.

  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. For example, the silicone / acrylic composite rubber described in JP-A-4-239010, JP-A-4-100812, and the like can be used.

  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 / nonconjugated diene copolymer include an ethylene / propylene / nonconjugated diene copolymer, an ethylene / butene-1 / nonconjugated diene copolymer, and the like.

  The rubbery polymer is preferably a diene rubber from the viewpoint of impact resistance, and from the viewpoint of weather resistance, acrylic rubber, silicone rubber, silicone / acryl composite rubber, ethylene / α-olefin copolymer. Rubber and hydrogenated conjugated diene rubber are preferred.

  The shape of the rubbery polymer used in the graft polymerization 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 50 to 250 nm, preferably 60 to 230 nm, more preferably 70 to 210 nm, from the viewpoint of mechanical properties and molding 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 particle diameter of the graft resin obtained by subjecting the rubber polymer having the volume average particle diameter to graft polymerization generally tends to be larger than that of the raw rubber polymer. Depending on the formulation, it may be approximately the same size as that of the raw rubber polymer.

  In the present invention, the component (Q1) is preferably a rubbery polymer reinforced graft resin obtained using a diene rubber as the rubbery polymer.

  The polymerizable unsaturated monomer (b1) is preferably a vinyl monomer. The vinyl monomers include aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid alkyl ester compounds, maleimide compounds, unsaturated acid anhydrides, carboxyl group-containing unsaturated compounds, hydroxyl group-containing unsaturated compounds. Compounds, oxazoline group-containing unsaturated compounds, and the like. The polymerizable unsaturated monomer (b1) preferably contains an aromatic vinyl compound.

  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. However, it shall not have a substituent such as a functional group. Examples thereof include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, β-methylstyrene, ethylstyrene, p-tert-butylstyrene, vinyltoluene, vinylxylene, vinylnaphthalene and the like. These compounds can be used alone or 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 and the like. These compounds can be used alone or in combination of two or more. Of these, acrylonitrile is preferred.

  The said (meth) acrylic-acid alkylester compound will not be specifically limited if it has a (meth) acryloyl group and the ester part contains a hydrocarbon group. Examples include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate. , Sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, hexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate , Phenyl (meth) acrylate, benzyl (meth) acrylate, and the like. These compounds can be used alone or in combination of two or more.

  As described above, since the rubber-reinforced resin obtained by graft polymerization usually contains an ungrafted polymer, the polymerizable unsaturated monomer (b1) contains a (meth) acrylic acid alkyl ester compound. In some cases, the ungrafted polymer may contain a (co) polymer containing a structural unit derived from a (meth) acrylic acid alkyl ester compound. It is a component related to Q2).

  Examples of the maleimide compound include maleimide, N-methylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-dodecylmaleimide, N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (4-methyl). Phenyl) maleimide, N- (2,6-dimethylphenyl) maleimide, N- (2,6-diethylphenyl) maleimide, N-benzylmaleimide, N-naphthylmaleimide, N-cyclohexylmaleimide and the like. These compounds can be used alone or in combination of two or more.

  In addition, as another method of introducing the structural unit derived from the maleimide compound into the graft resin, for example, a method of imidizing after unsaturated dicarboxylic anhydride of maleic anhydride is copolymerized may be used.

Examples of the unsaturated acid anhydride include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. These compounds can be used alone or 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, cinnamic acid and the like. These compounds can be used alone or 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, 3-hydroxypropyl (meth) acrylate, (Meth) acrylic acid 2-hydroxybutyl, (meth) acrylic acid 3-hydroxybutyl, (meth) acrylic acid 4-hydroxybutyl, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, (meth) acrylic Compound obtained by adding ε-caprolactone to 2-hydroxyethyl acid, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-hydroxy-α-methylstyrene, m-hydroxy-α-methylstyrene P-hydroxy α-methylstyrene, 2-hydroxymethyl-α-methylstyrene, 3-hydroxymethyl-α-methylstyrene, 4-hydroxymethyl-α-methylstyrene, 4-hydroxymethyl-1-vinylnaphthalene, 7-hydroxymethyl- 1-vinylnaphthalene, 8-hydroxymethyl-1-vinylnaphthalene, 4-hydroxymethyl-1-isopropenylnaphthalene, 7-hydroxymethyl-1-isopropenylnaphthalene, 8-hydroxymethyl-1-isopropenylnaphthalene, p- Vinylbenzyl alcohol, 3-hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene, trans-4-hydroxy-2-butene, 3-hydroxy-2-methyl-1- And propene. These compounds can be used alone or 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 compounds can be used alone or in combination of two or more.

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

  In a preferred embodiment of the present invention, the polymerizable unsaturated monomer (b1) may be composed only of an aromatic vinyl compound, and the aromatic vinyl compound and other single monomers copolymerizable with this compound. It may consist of a polymer. Other monomers are preferably vinyl cyanide compounds and (meth) acrylic acid alkyl ester compounds.

When the polymerizable unsaturated monomer (b1) contains an aromatic vinyl compound and a vinyl cyanide compound, the total amount used is molding processability, chemical resistance, hydrolysis resistance, dimensional stability, molding From the viewpoint of appearance and the like, it is usually 70 to 100% by mass, preferably 80 to 100% by mass, based on the total amount of the polymerizable unsaturated monomer (b1). 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 such a case, it is preferably 5 to 95% by mass and 5 to 95% by mass, more preferably 50 to 95% by mass and 5 to 50% by mass, still more preferably 60 to 95% by mass and 5 to 40% by mass, respectively.
Moreover, when the said polymerizable unsaturated monomer (b1) contains an aromatic vinyl compound and a (meth) acrylic-acid alkylester compound, the total usage-amount is moldability, chemical resistance, hydrolysis resistance. From the viewpoints of dimensional stability, molded appearance, etc., it is usually 70 to 100% by mass, preferably 80 to 100% by mass, based on the total amount of the polymerizable unsaturated monomer (b1). Further, the use ratio of the aromatic vinyl compound and the (meth) acrylic acid alkyl ester compound is 100 in total from the viewpoint of molding processability, chemical resistance, hydrolysis resistance, dimensional stability, molding appearance, and the like. When it is defined as mass%, it is preferably 5 to 95 mass% and 5 to 95 mass%, more preferably 50 to 95 mass% and 5 to 50 mass%, still more preferably 60 to 95 mass% and 5 to 40 mass%, respectively. %. In addition, when transparency is required for the second resin layer, the use ratio of the aromatic vinyl compound and the (meth) acrylic acid alkyl ester compound is preferably 5 when the total of these is 100% by mass. It is -95 mass% and 5-95 mass%, More preferably, it is 5-50 mass% and 50-95 mass%, More preferably, it is 5-30 mass% and 70-95 mass%.

As the component (Q1), preferred graft resins are as follows.
(Q1-1) Graft resin (q1-2) diene obtained by polymerizing a polymerizable unsaturated monomer (b1) comprising an aromatic vinyl compound and a vinyl cyanide compound in the presence of a diene rubber Presence of graft resin (q1-3) diene rubber obtained by polymerizing polymerizable unsaturated monomer (b1) comprising an aromatic vinyl compound and a (meth) acrylic acid alkyl ester compound in the presence of rubber A graft resin (q1-4) diene rubber obtained by polymerizing a polymerizable unsaturated monomer (b1) comprising an aromatic vinyl compound, a vinyl cyanide compound and a (meth) acrylic acid alkyl ester compound. A graft resin obtained by polymerizing a polymerizable unsaturated monomer (b1) comprising an aromatic vinyl compound, a vinyl cyanide compound and a maleimide compound in the presence of

  The volume average particle diameter of the component (Q1) contained in the second resin layer is 80 to 250 nm, preferably 85 to 230 nm, and more preferably 90 to 210 nm. When the volume average particle diameter is in the above range, the scratch resistance and hardness on the surface of the first resin layer in the decorative resin sheet of the present invention are excellent. In addition, when the volume average particle diameter is too small, the flexibility and appearance of the decorative resin sheet are inferior. On the other hand, if the volume average particle size is too large, the scratch resistance, hardness and flexibility are poor. The volume average particle diameter can be obtained by image analysis using an electron micrograph.

  The method for producing the component (Q1) is not particularly limited, and a known method can be applied. As a polymerization method, emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, or a combination of these can be used.

  In the production of the component (Q1), the polymerization may be started by supplying the polymerizable unsaturated monomer (b1) all together in the reaction system in the presence of the total amount of the rubbery polymer. Alternatively, the polymerization may be performed while being divided or continuously fed. In addition, in the presence or absence of a part of the rubbery polymer, the polymerizable unsaturated monomer (b1) may be supplied all at once to initiate polymerization, or may be supplied separately or continuously. May be. At this time, the remainder of the rubbery polymer may be supplied in a batch, divided or continuously in the middle of the reaction.

  When performing emulsion polymerization, a polymerization initiator, a chain transfer agent (molecular weight regulator), an emulsifier, water, and the like are used.

  Examples of the polymerization initiator include organic peroxides, azo compounds, inorganic peroxides, and redox polymerization initiators.

  Examples of the organic peroxide include tert-butyl hydroperoxide, tert-amyl-tert-butyl peroxide, tert-butyl-tert-hexyl peroxide, tert-amyl-tert-hexyl peroxide, di (tert-hexyl). ) Peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1- Bis (tert-butylperoxy) cyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydropa Oxide, 1,3-bis (tert-butylperoxy) -m-isopropyl) benzene, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, diisopropylbenzene peroxide, tert-butyl kumi Ruperoxide, decanoyl peroxide, lauroyl peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxylaurate, tert-butylperoxymonocarbonate, bis (tert-butylcyclohexyl) peroxy Examples include dicarbonate, tert-butyl peroxybenzoate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, and the like.

  Examples of the azo compound include 2,2′-azobis (isobutyronitrile), 1,1-azobis (cyclohexane-1-carbonitrile), azocumene, and 2,2′-azobis (2-methylbutyronitrile). 2,2′-azobisdimethylvaleronitrile, 4,4′-azobis (4-cyanovaleric acid), 2- (tert-butylazo) -2-cyanopropane, 2,2′-azobis (2,4,4) 4-trimethylpentane), 2,2′-azobis (2-methylpropane), dimethyl 2,2′-azobis (2-methylpropionate) and the like.

Examples of the inorganic peroxide include potassium persulfate, sodium persulfate, and ammonium persulfate.
Further, as a redox type polymerization initiator, sodium sulfite, sodium thiosulfate, sodium formaldehyde sulfoxylate, ascorbic acid, ferrous sulfate and the like are used as reducing agents, potassium peroxodisulfate, hydrogen peroxide, cumene hydroperoxide, What used tert-butyl hydroperoxide etc. as the oxidizing agent can be used.

The usage-amount of the said polymerization initiator is 0.1-1.5 mass% normally with respect to the whole quantity of the said polymerizable unsaturated monomer (b1).
The polymerization initiator can be supplied to the reaction system all at once or continuously.

  Examples of the chain transfer agent include mercaptans such as octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, n-hexyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, tert-tetradecyl mercaptan; Examples include α-methylstyrene dimers. These can be used alone or in combination of two or more.

The amount of the chain transfer agent used is usually 0.05 to 2.0% by mass with respect to the total amount of the polymerizable unsaturated monomer.
The chain transfer agent can be supplied 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, aliphatic phosphates, etc. Is mentioned. Examples of nonionic surfactants include polyethylene glycol alkyl ester compounds and alkyl ether compounds. These can be used alone or in combination of two or more.

  The usage-amount of the said emulsifier is 0.3-5 mass% normally with respect to the whole quantity of the said polymerizable unsaturated monomer (b1).

Emulsion polymerization can be carried out under known conditions depending on the type of polymerizable unsaturated monomer, polymerization initiator and the like. The latex obtained by this emulsion polymerization is usually subjected to coagulation of the resin component with a coagulant to form a powder or the like. Thereafter, it is purified by washing with water, etc., dried and collected. For coagulation, conventionally known coagulants are used, and 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 are used.
In addition, when two or more types of graft resins are contained in the thermoplastic resin composition, these resins may be mixed after isolating the graft resins from the respective latexes. There is a method of coagulating the mixture obtained in this way.

  When the component (Q1) is produced by solution polymerization, bulk polymerization, and bulk-suspension polymerization, a known method can be applied.

  When the component (Q1) and the ungrafted polymer are separated from the rubber-reinforced resin containing the component (Q1) obtained as described above, for example, 10 g of the rubber-reinforced resin is added to 100 to 200 ml of acetone (rubber If the polymer is an acrylic rubber, use acetonitrile) and shake it at 25 ° C for 2 to 3 hours using a shaker etc. to separate the insoluble and soluble components produced. The method of recovery is applied. The acetone-soluble component (acetonitrile-soluble component) corresponds to the ungrafted polymer and is included in the component (Q2) as described above.

  The graft ratio in the component (Q1) is from 50 to 150%, preferably from 55 to 120%, more preferably from 60 to 100%, from the viewpoints of moldability, impact resistance of the molded product, molded appearance, and the like. It is. If this graft ratio is too low, the impact resistance and molded appearance of the molded product may be lowered. On the other hand, if the graft ratio is too high, the moldability is not sufficient and the impact resistance may be lowered.

The graft ratio can be determined by the following formula.
Graft rate (%) = {(S−T) / T} × 100
In the formula, S represents 1 gram of rubber-reinforced resin obtained by graft polymerization in 20 ml of acetone (acetonitrile is used when the rubbery polymer is an acrylic rubber), and is shaken using a shaker. (Temperature 25 ° C., 2 hours), then centrifuge using a centrifuge (temperature 5 ° C., rotation speed 23,000 rpm, 1 hour) to separate the insoluble matter and the soluble matter. The mass (g) of the minute, and T is the mass (g) of the rubbery polymer contained in 1 gram of the rubber-reinforced resin. The mass of the rubbery polymer 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.

  The graft ratio is, for example, the type of polymerization initiator used in the production of component (Q1) and the amount thereof used, the type and amount of chain transfer agent used, the method for supplying the polymerizable unsaturated monomer (b1), and The supply time, polymerization temperature, and the like can be adjusted by appropriately selecting them.

The thermoplastic resin composition constituting the second resin layer includes components (Q1) and (Q2), and the component (Q2) is the same as the polymerizable unsaturated monomer (b1). It is composed of one or more of (co) polymers obtained by using a good polymerizable unsaturated monomer (b2), and is derived from a (meth) acrylic acid alkyl ester compound for the whole. It is a component containing 50-100 mass% of structural units.
Therefore, when this component (Q2) consists of only one kind of the (co) polymer obtained by using the polymerizable unsaturated monomer (b2), a structure derived from the (meth) acrylic acid alkyl ester compound It is a (co) polymer containing 50 to 100% by mass of units.
When this component (Q2) is composed of two or more kinds of (co) polymers obtained using the polymerizable unsaturated monomer (b2), all (co) polymers are (meth) It is not necessary to include a structural unit derived from an acrylic acid alkyl ester compound, and at least one (co) polymer includes a structural unit derived from a (meth) acrylic acid alkyl ester compound. The content rate of the structural unit originating in the (meth) acrylic-acid alkylester compound should just be 50-100 mass% with respect to the whole.
The content ratio of the structural unit derived from the (meth) acrylic acid alkyl ester compound in the component (Q2) is preferably 75 to 100% by mass, more preferably 80 to 100% by mass.
In the present invention, a preferable component (Q2) is a (co) polymer (polymethyl methacrylate) in which the component (Q2) contains 80 to 100% by mass of a structural unit derived from a (meth) acrylic acid alkyl ester compound. Etc.), and the total amount of these (co) polymers is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, based on the total amount of the component (Q2). %, Particularly preferably 85 to 100% by mass.

As a (co) polymer containing a structural unit derived from a (meth) acrylic acid alkyl ester compound, it can be used as a polymerizable unsaturated monomer (b1) used for forming the component (Q1) (meth). It can be set as the (co) polymer containing the structural unit derived from the acrylic acid alkylester compound. Preferable (meth) acrylic acid alkyl ester compounds are compounds in which the ester portion is a hydrocarbon group having 1 to 4 carbon atoms. Specific examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, (meth ) Propyl acrylate and butyl (meth) acrylate.
The monomer that can be copolymerized with this (meth) acrylic acid alkyl ester compound and gives other structural units includes aromatic vinyl compounds, vinyl cyanide compounds, maleimide compounds, unsaturated acid anhydrides. , Carboxyl group-containing unsaturated compounds, hydroxyl group-containing unsaturated compounds, oxazoline group-containing unsaturated compounds, and the like.

  The component (Q2) can be produced by polymerizing the polymerizable unsaturated monomer (b2) 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 these polymerization methods may be combined. On the other hand, when no polymerization initiator is used, thermal polymerization can be applied.

  When using a polymerization initiator, the compound illustrated by description of the manufacturing method of the said component (Q1) can be used. At this time, the usage-amount of a polymerization initiator is 0.1-1.5 mass% normally with respect to the polymerizable unsaturated monomer (b2) whole quantity. If necessary, a chain transfer agent or an emulsifier that can be used at the time of producing the rubber-reinforced resin can be used.

  In the production of the component (Q2), the polymerization may be started in a state where the total amount of the polymerizable unsaturated monomer (b2) is accommodated in the reaction system, and arbitrarily selected monomer components are added in portions or continuously. Polymerization may be performed by adding. Furthermore, when using said polymerization initiator, it can add to a reaction system collectively or continuously.

The component (Q2) is exemplified below.
(Q2-1) Copolymers obtained by polymerizing a polymerizable unsaturated monomer (b2) comprising an aromatic vinyl compound and a (meth) acrylic acid alkyl ester compound (styrene / methyl methacrylate copolymer, etc.) )
(Q2-2) a copolymer obtained by polymerizing a polymerizable unsaturated monomer (b2) composed of an aromatic vinyl compound, a vinyl cyanide compound and a (meth) acrylic acid alkyl ester compound (styrene / acrylonitrile / Methyl methacrylate copolymer, etc.)
(Q2-3) (Co) polymer (polymethyl methacrylate, etc.) obtained by polymerizing polymerizable unsaturated monomer (b2) comprising (meth) acrylic acid alkyl ester compound

The thermoplastic resin composition constituting the second resin layer is a rubber obtained by polymerizing the polymerizable unsaturated monomer (b1) in the presence of a rubbery polymer in order to obtain the component (Q1). It is a reinforced resin, and the rubber reinforced resin containing the components (Q1) and (Q2) according to the present invention can be used as it is. In this case, if necessary, the (co) polymer corresponding to the component (Q2), for example, the polymers shown in the above (q2-1) to (q2-3) may be further blended. In addition, as long as the structural unit derived from the (meth) acrylic acid alkyl ester compound is 50% by mass as the whole component (Q2), (q2-4): (meth) acrylic acid alkyl ester compound is not included. You may further mix | blend the (co) polymer obtained using the polymerizable unsaturated monomer (b2).
Therefore, in the present invention, the preferred component (Q2) is at least one of the polymers shown in (q2-1) to (q2-3), or (q2-1) to (q2-3). It is a combination of at least one polymer and the polymer shown in (q2-4).

  The intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) of the component (Q2) is preferably 0 from the viewpoint of molding processability and extrudability of the thermoplastic resin composition, and adhesion to the first resin layer. 0.05 to 0.80 dl / g, more preferably 0.07 to 0.70 dl / g, still 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.
By dissolving the above component (Q2) in methyl ethyl ketone, preparing 5 samples with different concentrations, and measuring the reduced viscosity of each concentration solution at 30 ° C. using an Ubbelohde viscosity tube, the intrinsic viscosity [η] is Desired.
In addition, as a method of obtaining a component (Q2) from a thermoplastic resin composition, the method etc. which put a predetermined amount of composition in acetone or acetonitrile, and collect | recover soluble components are mentioned.

  The proportions of the components (Q1) and (Q2) contained in the thermoplastic resin composition are 5 to 50% by mass and 50 to 95% by mass, respectively, when the total of both is 100% by mass, preferably Is 10 to 40% by mass and 60 to 90% by mass, more preferably 13 to 30% by mass and 70 to 87% by mass. When the ratio of components (Q1) and (Q2) is in the above range, the scratch resistance and hardness on the surface of the first resin layer in the decorative resin sheet of the present invention are excellent.

Moreover, in the said thermoplastic resin composition, content of the rubber-like polymer derived from a component (Q1) is 5-40 mass% when the sum total of a component (Q1) and (Q2) is 100 mass%. Preferably, it is 6-30 mass%, More preferably, it is 7-20 mass%. When the content of the rubbery polymer is in the above range, the scratch resistance and hardness on the surface of the first resin layer in the decorative resin sheet of the present invention are excellent.
In addition, when calculating | requiring content of a rubbery polymer from a thermoplastic resin composition, it can calculate | require using pyrolysis gas chromatography (PyGC), an infrared absorption spectrum (IR), etc.

The said thermoplastic resin composition may contain the other polymer (resin) which has thermoplasticity as needed.
Examples of other polymers include polyolefin resins, polyvinyl chloride resins, polyvinylidene chloride resins, polyester resins, polyamide resins, and fluororesins.
When the composition of the present invention contains other resins, the upper limit of the content is preferably 20 parts by mass, more preferably 10 parts with respect to 100 parts by mass in total of the components (Q1) and (Q2). Part by mass.

  The thermoplastic resin composition further comprises a filler, a plasticizer, an antioxidant, an ultraviolet absorber, an anti-aging agent, a flame retardant, a lubricant, a weather stabilizer, a light stabilizer, a heat, depending on the purpose and application. It may contain additives such as a stabilizer, an antistatic agent, a water repellent, an oil repellent, an antifoaming agent, an antibacterial agent, an antiseptic, a colorant, a fluorescent whitening agent, and a conductivity imparting agent.

The usage method of the decorative resin sheet of this invention joins the decorative resin sheet 1 to the surface of the resin molding part 3 so that the 1st resin layer 11 may be arrange | positioned on the surface, as shown in FIG. is there. In order that the decorative resin sheet of the present invention is in the form shown in FIGS. 1 to 3 and the pattern layer visually recognized through the first resin layer shows a target image, resin molding The second resin layer is preferably a colored layer for the purpose of not being influenced by the color of the portion 3.
Moreover, when the decorative resin sheet of this invention is an aspect shown in FIG. 4, it is preferable that a 2nd resin layer is a transparent layer.

  Examples of the filler include heavy calcium carbonate, colloidal calcium carbonate, light calcium carbonate, magnesium carbonate, zinc carbonate, aluminum hydroxide, magnesium hydroxide, clay, talc, fumed silica, calcined silica, precipitated silica, ground silica, Fused silica, kaolin, diatomaceous earth, zeolite, titanium oxide, quicklime, iron oxide, zinc oxide, barium oxide, aluminum oxide, magnesium oxide, aluminum sulfate, glass fiber, carbon fiber, glass balloon, shirasu balloon, saran balloon, phenol Examples include balloons. These can be used alone or in combination of two or more.

  Examples of the plasticizer include phthalic acid ester, trimellitic acid ester, pyromellitic acid ester, aliphatic monobasic acid ester, aliphatic dibasic acid ester, phosphoric acid ester, polyhydric alcohol ester, epoxy plasticizer, high Examples include molecular plasticizers and chlorinated paraffins. These can be used alone or in combination of two or more.

  Examples of the antioxidant include hindered amine compounds, hydroquinone compounds, hindered phenol compounds, sulfur-containing compounds, and phosphorus-containing compounds. These can be used alone or in combination of two or more.

  Examples of the ultraviolet absorber include benzophenone compounds, benzotriazole compounds, and triazine compounds. These can be used alone or in combination of two or more.

  Examples of the anti-aging agent include naphthylamine compounds, diphenylamine compounds, p-phenylenediamine compounds, quinoline compounds, hydroquinone derivative compounds, monophenol compounds, bisphenol compounds, trisphenol compounds, polyphenol compounds, thiols. Examples thereof include bisphenol compounds, hindered phenol compounds, phosphite compounds, imidazole compounds, nickel dithiocarbamate salts, phosphoric compounds, and the like. These can be used alone or in combination of two or more.

  Examples of the flame retardant include organic flame retardants, inorganic flame retardants, and reactive flame retardants. These can be used alone or in combination of two or more.

  Organic flame retardants include brominated epoxy compounds, brominated alkyltriazine compounds, brominated bisphenol epoxy resins, brominated bisphenol phenoxy resins, brominated bisphenol polycarbonate resins, brominated polystyrene resins, brominated crosslinked polystyrene resins Halogenated flame retardants such as brominated bisphenol cyanurate resin, brominated polyphenylene ether, decabromodiphenyl oxide, tetrabromobisphenol A and oligomers thereof; trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, tripentyl phosphate Hexyl phosphate, tricyclohexyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate Phosphate esters such as phosphate, cresyl diphenyl phosphate, dicresyl phenyl phosphate, dimethyl ethyl phosphate, methyl dibutyl phosphate, ethyl dipropyl phosphate, hydroxyphenyl diphenyl phosphate, modified compounds thereof, condensed phosphate ester compounds, phosphorus Phosphorus flame retardants such as phosphazene derivatives containing elements and nitrogen elements; polytetrafluoroethylene, guanidine salts, silicone compounds, phosphazene compounds, and the like.

Examples of the inorganic flame retardant include aluminum hydroxide, antimony oxide, magnesium hydroxide, zinc borate, zirconium compound, molybdenum compound, and zinc stannate.
Examples of the reactive flame retardant include tetrabromobisphenol A, dibromophenol glycidyl ether, brominated aromatic triazine, tribromophenol, tetrabromophthalate, tetrachlorophthalic anhydride, dibromoneopentyl glycol, poly (pentabromobenzyl poly). Acrylate), chlorendic acid (hett acid), chlorendic anhydride (hett acid anhydride), brominated phenol glycidyl ether, dibromocresyl glycidyl ether, and the like.

Examples of the colorant include pigments and dyes. These can be used alone or in combination.
When the second resin layer is a white colored layer, a white pigment such as titanium oxide, zinc oxide, or antimony trioxide is preferably used.
When the second resin layer is a dark colored layer, carbon black, black iron oxide or the like is preferably used. In addition, if necessary, a colorant that serves as a base color of the design of the design layer may be used in combination. This colorant is exemplified in the description of the design layer.

  When carbon black is used as the colorant, for example, a small amount of a wetting / dispersing agent can be added to improve 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.

  The thickness of the second resin layer is preferably 20 to 1,000 μm, more preferably 30 to 800 μm, and still more preferably 50 to 600 μm. The surface of the second resin layer can be easily subjected to corona discharge treatment, plasma treatment, primer coating, etc. for the purpose of improving the adhesion with other layers directly or via an adhesive layer. Adhesion treatment may be performed.

The thermoplastic resin composition constituting the second resin layer is a composition having film-forming properties. Accordingly, a film obtained by subjecting a composition containing essential components such as the above components (Q1) and (Q2) to T-die molding, calendar molding, inflation molding, etc., is used as the second resin layer forming film. Can be used. The extrusion temperature of the molten resin in these molding methods is usually about 190 ° C to 260 ° C.
The thermoplastic resin composition is prepared by melt-kneading a rubber-reinforced resin, a (co) polymer corresponding to the component (Q2), an additive and the like with a known melt-kneading apparatus. 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 ° C to 260 ° C.

  Next, the pattern layer is a layer including an image portion formed by printing, coating, vapor deposition, sputtering, or the like, and is a layer that displays characters, numbers, pictures, and the like through the first resin layer. This design layer may be a layer over the entire surface as shown in FIG. 1, or may be a partially formed layer as shown in FIGS.

  The constituent material of the design layer is usually a component excluding a medium contained in a known printing or paint ink, or a metal component. The main components of the former (hereinafter referred to as “ink”) are a resin binder, a colorant and the like, and if necessary, a dispersant, a wax and the like are contained. The latter metal component may be aluminum, nickel, gold, platinum, chromium, iron, copper, tin, indium, silver, titanium, lead, zinc, an alloy containing these metal elements, or a compound thereof. it can.

  Examples of the resin binder for the ink include acrylic resin, vinyl ester resin, polyolefin resin, cellulose resin, urethane resin, melamine resin, alkyd resin, polyester resin, epoxy resin, aromatic vinyl resin, and polyamide resin. .

  Examples of the colorant for the ink include inorganic pigments such as carbon black, iron oxide and phosphorescent pigments; metallic pigments made of metal powder such as aluminum, zinc, silver and copper; soluble azo pigments, insoluble azo pigments, condensed azo Pigment, quinacridone pigment, isoindoline pigment, isoindolinone pigment, anthraquinone pigment, diketopyrrolopyrrole pigment, nitro pigment, quinophthalone pigment, perylene pigment, perinone pigment, phthalocyanine pigment, dioxazine pigment, metal Examples thereof include organic pigments such as complex pigments and organic white pigments.

  Since the desired hue is reflected, the thickness of the design layer is usually 0.2 to 50 μm, preferably 0.3 to 30 μm, and more preferably 0.5 to 20 μm.

The pattern layer forming method using the ink is appropriately selected from the printing method and the coating method depending on the layer structure of the decorative resin sheet of the present invention, the configuration of the image portion, and the like. Examples of the printing method include gravure printing, silk printing, offset printing, and screen printing. Examples of the coating method include a method using a lip coater, a reverse coater, a gravure coater, and the like.
The pattern layer may be formed on any surface of the first resin layer forming film or the second resin layer forming film.

When the decorative resin sheet of the present invention is in the order of the first resin layer, the design layer, and the second resin layer, an adhesive layer 17 can be provided between the first resin layer 11 and the second resin layer 13 ( 2 and 3). 2 and 3, the design layer 15 is partially bonded and formed on the surface of the first resin layer 11 side or the second resin layer 13 side, respectively. In this embodiment, the resin layer 11 and the second resin layer 13 are joined by the adhesive layer 17. In FIG. 2 and FIG. 3, the adhesive layer 17 is also formed between the second resin layer 13 or the first resin layer 11 and the design layer 15. If sufficient adhesion between the resin layer 11 and the second resin layer 13 is obtained, the adhesive layer 17 is not formed between the second resin layer 13 or the first resin layer 11 and the design layer 15. It is good (not shown).
The present invention is not limited to these embodiments, and the design layer is formed over the entire surface between the first resin layer and the second resin layer, and the first resin layer side and the second resin layer side. An adhesive layer can be provided between the first resin layer and the second resin layer, even if it is formed on any surface on the resin layer side. In this aspect, the adhesive layer is correctly formed between the first resin layer or the second resin layer and the design layer (not shown).

  Furthermore, although the decorative resin sheet 1 in FIG. 4 shows an aspect in the order of the first resin layer 11, the second resin layer 13, and the design layer 15, it is between the first resin layer 11 and the second resin layer 13. Can be provided with an adhesive layer (not shown).

  The constituent material of the adhesive layer is preferably a material that gives a transparent film. For example, acrylic resin, vinyl ester resin, polyolefin resin, cellulose resin, urethane resin, melamine resin, alkyd resin, polyester resin, epoxy resin , Aromatic vinyl resins, polyamide resins and the like.

  The upper limit of the thickness of the adhesive layer is usually 30 μm, preferably 20 μm, and more preferably 10 μm, from the viewpoint of flexibility of the decorative resin sheet. In addition, a lower limit is 0.1 micrometer normally, Preferably it is 0.2 micrometer, More preferably, it is 0.5 micrometer.

  The decorative resin sheet of the present invention has flexibility, and the thickness thereof is 50 to 1,500 μm, preferably 80 to 1,200 μm, and more preferably 100 to 1,000 μm.

The method for producing the decorative resin sheet of the present invention is appropriately selected depending on the purpose, application, etc., and is not particularly limited.
In the case where the decorative resin sheet shown in FIG. 1 is manufactured, and the first resin layer is a layer containing a cured resin, the second resin layer-forming thermoplastic resin composition is used. A method of forming the first resin layer by applying the above-mentioned coating agent composition as the first resin layer forming material after forming the pattern layer 15 by printing or the like on the surface of the two resin layer forming film Is mentioned.

  In the case of producing the decorative resin sheet shown in FIG. 2, when the first resin layer is a layer containing a thermoplastic resin, it was obtained using the first resin layer forming thermoplastic resin composition. After the pattern layer 15 is formed on the surface of the first resin layer forming film by printing or the like, the surface of the pattern layer 15 and a second resin layer obtained separately using the second resin layer forming thermoplastic resin composition are used. The method of joining the film for resin layer formation with an adhesive composition is mentioned.

  In the case of producing the decorative resin sheet shown in FIG. 3, when the first resin layer is a layer containing a thermoplastic resin, it was obtained using the second resin layer forming thermoplastic resin composition. After the pattern layer 15 is formed on the surface of the second resin layer forming film by printing or the like, the surface of the pattern layer 15 is separately obtained from the first resin layer-forming thermoplastic resin composition. The method of joining the film for resin layer formation with an adhesive composition is mentioned.

When the decorative resin sheet shown in FIG. 4 is manufactured, and the first resin layer is a layer containing a thermoplastic resin, the first resin layer forming thermoplastic resin composition and the second resin layer A laminated film composed of the first resin layer 11 and the second resin layer 13 is produced by co-extrusion with the forming thermoplastic resin composition, and then, on the surface of the laminated film on the second resin layer 13 side. A method of forming the pattern layer 15 by printing or the like; a first resin layer forming film obtained by using the first resin layer forming thermoplastic resin composition, and a second resin layer forming thermoplastic resin composition. The film for forming a second resin layer obtained by using is bonded with an adhesive composition to produce a laminated film, and then the pattern layer is printed on the surface of the laminated film on the second resin layer 13 side by printing or the like. 15 and the like .
In addition, when the decorative resin sheet shown in FIG. 4 is manufactured and the first resin layer is a layer containing a cured resin, the decorative resin sheet is obtained using the second resin layer forming thermoplastic resin composition. The first resin layer is formed on one side of the second resin layer-forming film by applying the above-mentioned coating agent composition, which is the first resin layer-forming material, and dried, and on the other side by printing or the like. A method of forming the pattern layer 15 is exemplified.

Using the decorative resin sheet of the present invention, a composite structure (decorative molded product) 5 in which the first resin layer 11 is disposed on the surface side thereof can be manufactured (see FIG. 5). The part shown with the code | symbol 3 in FIG. 5 shows the resin molding part formed with the thermoplastic resin composition which may contain additives, such as a coloring agent. The thermoplastic resin composition is not particularly limited, and is a rubber-reinforced resin (ABS resin, AES resin, ASA resin, MBS resin) obtained by polymerizing a polymerizable unsaturated monomer in the presence of a rubbery polymer. ), (Co) polymers obtained by polymerizing polymerizable unsaturated monomers containing aromatic vinyl compounds in the absence of rubbery polymers (polystyrene, styrene / acrylonitrile copolymers, styrene / acrylonitrile)・ Methyl methacrylate copolymer, styrene / acrylonitrile / N-phenylmaleimide copolymer, etc.), acrylic resin (polymethyl methacrylate, etc.), polyolefin resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyester resin (polyethylene terephthalate) , Polybutylene terephthalate, polynaphthalene terephthalate, etc.), polycarbonate tree , Polyarylate resin, polyacetal resin, polyamide resin, fluorine resin, polyphenylene ether, polyphenylene sulfide, imide resin, ketone resin such as polyether ketone and polyether ether ketone, sulfone resin such as polysulfone and polyethersulfone, It can be set as the composition containing the at least 1 sort (s) of thermoplastic resin chosen from degradable plastics. In the present invention, among these, the same or the same kind of thermoplastic resin is preferable when included in the second resin layer forming thermoplastic resin composition.
In addition, it is a case where the composite structure (decorative molded product) 5 is obtained using the decorative resin sheet of FIGS. 1 to 3, and the thermoplastic resin contained in the resin molded portion 3 is the second resin. When the same or the same kind of thermoplastic resin is contained in the layer-forming thermoplastic resin composition, in this composite structure (decorated molded article) 5, the second resin layer 13 in the decorative resin sheet, Since it is integrated with the resin molding part 3, the boundary may not be distinguished unless there is a difference in color or the like between the compositions.

  The shape of the resin molded body constituting the resin molded portion 3 is selected depending on the purpose, application, etc., and is not particularly limited. For example, it may be a plate shape (flat plate, curved plate), a column shape, a three-dimensional solid object, or the like. it can. In these shapes, you may provide a recessed part, a convex part, etc.

  Hereinafter, an example of the manufacturing method of the composite structure (decorative molded product) 5 will be described with reference to FIG. In the form shown in FIG. 6, a composite structure (decorative molded product) 5 is manufactured using an injection mold including a male mold 71 and a female mold 72.

  First, as shown in FIG. 6A, the decorative resin sheet 1 is disposed between the male mold 71 and the female mold 72. After that, as shown in FIG. 6B, the decorative resin sheet 1 is placed inside the female mold 72 with the first resin layer side surface using suction means such as a suction hole 75 arranged in the female mold 72. Adhere to the surface. Since the decorative resin sheet 1 has flexibility, it can be easily brought into close contact with the inner surface of the female mold 72. Although not shown, the decorative resin sheet 1 may be fixed by, for example, a frame-shaped sheet clamp.

  Next, as shown in FIG. 6C, the male mold 71 and the female mold 72 are clamped, and the cavity formed by both molds is heated and melted, that is, in a fluid state, for forming the second resin layer. A thermoplastic resin composition 2 is supplied. At this time, the decorative resin sheet 1 may be preheated. Thereafter, the resin composition is solidified by cooling or the like, and the mold is opened to take out an integrated resin molded product. At this time, if there is an unnecessary portion of the decorative resin sheet, it is trimmed appropriately. Through the above steps, a resin molded product (decorative molded product) 5 shown in FIG. 6D is obtained.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples as long as the gist of the present invention is not exceeded. In the following, “part” and “%” are based on mass unless otherwise specified.

1. Evaluation method First, the evaluation method or measurement method employed in the following examples will be described.
1-1. Pencil Hardness The pencil hardness of the surface of the second resin layer forming film (single layer film) and the surface of the decorative resin sheet on the first resin layer side was measured according to JIS K5400.
1-2. Scratch resistance The scratch resistance was evaluated by two methods.
(1) Using a reciprocating friction tester manufactured by Toko Seimitsu Kogyo Co., Ltd., under the condition of cotton canvas Kanakin No. 3 and a vertical load of 500 g, the surface of the first resin layer in the decorative resin sheet is subjected to 500 reciprocating frictions, The surface was visually observed and evaluated according to the following criteria.
○: Scratches are not observed.
Δ: Slight scratches are observed.
X: Scratches are clearly observed.
(2) A brass brush (0.15 mm, hair length 16 mm, 4 lines) manufactured by TRUSCO NAKAYAMA CO., LTD. Is dropped 5 times from the height of 10 cm to the same location on the surface of the first resin layer in the decorative resin sheet with a load of 100 g. After being lowered, the surface was visually observed and evaluated according to the following criteria.
○: Scratches are not observed.
Δ: Slight scratches are observed.
X: Scratches are clearly observed.

1-3. Flexibility of second resin layer forming film (single layer film) and decorative resin sheet The size of the test piece is 100 mm (MD direction) × 100 mm (TD direction) and is bent along the axis of symmetry in the MD direction. After that, it was bent along the axis of symmetry in the TD direction. In addition, about the decorative resin sheet, it bent so that the 1st resin layer might come inside. Then, the test piece in a folded state was reciprocated twice on each crease at a speed of 5 mm / second using a manual crimping roll (2,000 g) in accordance with JIS Z0237, and then the crease was spread to the original. It returned to the state, the crease | fold was observed visually, and the following reference | standard determined. Those in which the folds are not broken are excellent in flexibility.
○: The crease was not cracked, and the crease did not break even when folded and expanded again.
(Triangle | delta): Although the crease | fold is not cracked, when it was folded again and spread, the crease | fold was cracked.
X: The crease was broken.
1-4. The image visibility of the design layer in the decorative resin sheet Whether or not the image of the design layer can be recognized through the first resin layer of the decorative resin sheet was visually observed and evaluated according to the following criteria.
○: The pattern layer image is clearly recognized.
(Triangle | delta): The image of a design layer is recognizable although it is unclear.
X: The image of a design layer is hardly recognized.

2. Production raw materials 2-1. First resin layer forming material A curable composition and a transparent film were used as materials for forming the first resin layer, which is a transparent protective layer. Details are as follows.

2-1-1. Curable composition (C1)
An ultraviolet curable composition obtained by the following method was used. The haze (based on JIS K7136) in the film formed using this composition is 0.2%.
When forming the first resin layer using this curable composition (C1), directly on the second resin layer forming film obtained using the second resin layer forming thermoplastic resin composition, or The composition (C1) was applied to the surface of the pattern layer formed on the surface of the second resin layer forming film, and then the coating film was irradiated with ultraviolet rays and cured. The thickness of the 1st resin layer in the decorative resin sheet manufactured using the curable composition (C1) is shown in Tables 3 to 8 and Table 10.

<Method for producing curable composition (C1)>
To a solution consisting of 221 parts of mercaptopropyltrimethoxysilane and 1 part of dibutyltin dilaurate in dry air, 222 parts of isophorone diisocyanate was added dropwise at 50 ° C. over 1 hour with stirring, followed by heating and stirring at 70 ° C. for 3 hours. . To this, 549 parts of a polyfunctional monomer “NK Ester A-TMM-3LM-N” (trade name) consisting of 60% pentaerythritol triacrylate and 40% pentaerythritol tetraacrylate manufactured by Shin-Nakamura Chemical Co., Ltd. was added at 30 ° C. (Among these, only pentaerythritol triacrylate having a hydroxyl group is involved in the reaction.) Subsequently, the particle modifier containing a polymerizable unsaturated group was obtained by heating and stirring at 60 ° C. for 10 hours. As a result, a composition containing 773 parts of a particle modifier and 220 parts of pentaerythritol tetraacrylate was obtained.
Thereafter, a silica particle dispersion “Methanol Silica Sol” (manufactured by Nissan Chemical Industries, Ltd.) having a solid content of 31% containing silica particles having an average particle diameter of 13 nm is added to 6.06 parts of this composition (including 4.72 parts of particle modifier) ( (Trade name) 61.95 parts, 0.05 mol / l sulfuric acid aqueous solution 0.02 part and p-hydroxyphenyl monomethyl ether 0.01 part were added, and the mixture was stirred at 60 ° C. After stirring for 4 hours, 0.98 part of methyltrimethoxysilane was added, and the mixture was further heated and stirred at the same temperature for 1 hour to obtain a reactive particle dispersion.
Next, to this reactive particle dispersion, dipentaerythritol hexaacrylate “KAYARAD DPHA” (trade name) 22.11 parts manufactured by Nippon Kayaku Co., Ltd., photopolymerization initiator “Irgacure 184” (trade name) manufactured by BASF Japan Ltd. 1.26 parts, 0.76 parts of BASF Japan photopolymerization initiator “Irgacure 907” (trade name) and 56.86 parts of propylene glycol monomethyl ether are added and concentrated to a solid content of 50%. Thus, a curable composition (C1) was obtained.

2-1-2. Transparent film (F1)
It is a film having a thickness of 30 μm and 100 μm obtained by subjecting a methacrylic resin “Acrypet IRL409” (trade name) manufactured by Mitsubishi Rayon Co., Ltd. to the following calendar molding. The haze according to JIS K7136 of this film is 0.2%.
<Method for producing transparent film (F1)>
Using a film forming machine equipped with a T-die having a die width of 1,600 mm and a lip interval of 1 mm and an extruder having a screw diameter of 115 mm, pellets made of the methacrylic resin were supplied to the extruder. Then, a resin melted at a temperature of 260 ° C. was discharged from the T die to obtain a soft film. Then, this soft film was cooled and solidified with an air knife while being in surface contact with a cast roll whose surface temperature was controlled at 70 ° C., to obtain a transparent film (F1) having the above thickness.

2-2. Second Resin Layer Forming Materials The raw materials for producing the thermoplastic resin compositions (S1) to (S18) used for forming the second resin layer are as follows. The measurement of the graft ratio, intrinsic viscosity [η], etc. was performed according to the method described above.
2-2-1. Raw material [P]
This raw material [P] is a copolymer obtained by using a rubber-reinforced aromatic vinyl resin and a polymerizable unsaturated monomer. The former is a resin comprising a rubbery polymer reinforced graft resin (Q1) and an ungrafted (co) polymer (which may include a polymer (Q2)).

2-2-1-1. Rubber-reinforced aromatic vinyl resin Resin obtained by Synthesis Examples 1 to 6 below.
Synthesis Example 1 (Synthesis of rubber-reinforced aromatic vinyl resin P-1)
In a glass reactor equipped with a stirrer, 110 parts of ion-exchanged water and 50 parts of polybutadiene latex (volume average particle size: 180 nm, gel content 80%) as a rubbery polymer (in terms of solid content) are placed in a nitrogen stream. The temperature was raised with stirring. When the internal temperature reached 70 ° C., a solution in which 0.2 parts of sodium pyrophosphate, 0.005 parts of ferrous sulfate heptahydrate and 0.2 parts of glucose were dissolved in 15 parts of ion-exchanged water was added, and styrene was added. 9.5 parts, acrylonitrile 3 parts, tert-dodecyl mercaptan 0.025 part, cumene hydroperoxide 0.07 part and sodium dodecylbenzenesulfonate 0.05 part dissolved in ion-exchanged water 1.2 parts Were continuously added over 1 hour. Next, 28 parts of styrene, 9.5 parts of acrylonitrile, 0.075 part of tert-dodecyl mercaptan, 0.2 part of cumene hydroperoxide and 0.15 part of sodium dodecylbenzenesulfonate were added to 3.5 parts of ion-exchanged water. The dissolved solution was added continuously over 3 hours. After completion of the addition, the mixture was further polymerized for 1 hour, and then 0.2 part of 2,2′-methylene-bis (4-ethylene-6-tert-butylphenol) was added to complete the polymerization. Magnesium sulfate was added to the obtained latex to coagulate the resin component. Then, rubber reinforced aromatic vinyl resin (P-1) was obtained by washing with water and further drying. The graft ratio in the graft resin (component (Q1)) contained in this resin (P-1) was 73.4%, and the volume average particle diameter of the rubber polymer constituting the graft resin was 182 nm. The content of the rubbery polymer, the structural unit derived from styrene and the structural unit derived from acrylonitrile contained in the rubber-reinforced aromatic vinyl resin (P-1) The intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) of the ungrafted (co) polymer (hereinafter also referred to as “acetone-soluble matter”) is 50%, 37% and 13%, respectively. It was 0.23 dl / g.

Synthesis Example 2 (Synthesis of rubber-reinforced aromatic vinyl resin P-2)
A rubber-reinforced aromatic vinyl resin (P-2) was prepared in the same manner as in Synthesis Example 1 except that polybutyl acrylate latex (volume average particle size: 100 nm, gel content 90%) was used as the rubber polymer. Obtained. The graft ratio in the graft resin (component (Q1)) contained in this resin (P-2) was 85.0%, and the volume average particle diameter of the rubber polymer constituting the graft resin was 105 nm. The content of the rubbery polymer, the structural unit derived from styrene and the structural unit derived from acrylonitrile contained in the rubber-reinforced aromatic vinyl resin (P-2) 50.4%, 37.5% and 12.1%, respectively, and the intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) of the ungrafted (co) polymer (acetone soluble component) is 0 .40 dl / g.

Synthesis Example 3 (Synthesis of rubber-reinforced aromatic vinyl resin P-3)
A rubber-reinforced aromatic vinyl resin (P-3) was obtained in the same manner as in Synthesis Example 1 except that polybutadiene latex (volume average particle size: 200 nm, gel content 82%) was used as the rubber polymer. . The graft ratio in the graft resin (component (Q1)) contained in this resin (P-3) was 60.0%, and the volume average particle diameter of the rubber polymer constituting the graft resin was 202 nm. In addition, the content of the rubbery polymer, the structural unit derived from styrene and the structural unit derived from methyl methacrylate contained in the rubber-reinforced aromatic vinyl resin (P-3) was 100%. And the intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) of the ungrafted (co) polymer (acetone solubles) is 0.26 dl / g, respectively, 18%, 20% and 62%. Met.

Synthesis Example 4 (Synthesis of rubber-reinforced aromatic vinyl resin P-4)
A rubber-reinforced aromatic vinyl resin (P-4) was obtained in the same manner as in Synthesis Example 1 except that polybutadiene latex (volume average particle size: 368 nm, gel content: 65%) was used as the rubber polymer. . The graft ratio in the graft resin (component (Q1)) contained in this resin (P-4) was 55.7%, and the volume average particle size of the rubbery polymer constituting the graft resin was 370 nm. The content of the rubbery polymer, the structural unit derived from styrene and the structural unit derived from acrylonitrile contained in the rubber-reinforced aromatic vinyl resin (P-4) The intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) of the ungrafted (co) polymer (acetone soluble component) was 0.45 dl / g, respectively. It was.

Synthesis Example 5 (Synthesis of rubber-reinforced aromatic vinyl resin P-5)
A rubber-reinforced aromatic vinyl resin (P-5) was obtained in the same manner as in Synthesis Example 1 except that polybutadiene latex (volume average particle size: 330 nm, gel content: 72%) was used as the rubber polymer. . The graft ratio in the graft resin (component (Q1)) contained in this resin (P-5) was 34.3%, and the volume average particle diameter of the rubber polymer constituting the graft resin was 332 nm. The content of the rubbery polymer, the structural unit derived from styrene and the structural unit derived from acrylonitrile contained in the rubber-reinforced aromatic vinyl resin (P-5) The intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) of the ungrafted (co) polymer (acetone soluble component) is 0.21 dl, respectively 60%, 11.3% and 28.7%. / G.

Synthesis Example 6 (Synthesis of rubber-reinforced aromatic vinyl resin P-6)
A rubber-reinforced aromatic vinyl resin (P-6) was obtained in the same manner as in Synthesis Example 1 except that polybutadiene latex (volume average particle size: 295 nm, gel content: 80%) was used as the rubber polymer. . The graft ratio in the graft resin (component (Q1)) contained in this resin (P-6) was 47.0%, and the volume average particle diameter of the rubber polymer constituting the graft resin was 300 nm. The content of the rubbery polymer contained in the rubber-reinforced aromatic vinyl resin (P-6), the structural unit derived from styrene and the structural unit derived from methyl methacrylate was 100% in total. And the intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) of the ungrafted (co) polymer (acetone solubles) is 0.26 dl / g, respectively, 18%, 20% and 62%. Met.

2-2-1-2. Copolymer (1) Copolymer P-8
Styrene / acrylonitrile copolymers having a content of structural units derived from styrene and structural units derived from acrylonitrile of 70.5% and 29.5%, respectively, were used. The intrinsic viscosity [η] (in methyl ethyl ketone, 30 ° C.) is 0.75 dl / g.
(2) Copolymer P-9
A methacrylic resin “Acrypet VH001” (trade name) manufactured by Mitsubishi Rayon Co., Ltd., which contains 99% and 1% of structural units derived from methyl methacrylate and structural units derived from methyl acrylate, respectively. The weight average molecular weight is 97,000.
(3) Copolymer P-10
A methacrylic resin “Acrypet VH5” (trade name) manufactured by Mitsubishi Rayon Co., Ltd., which contains 98% and 2% of structural units derived from methyl methacrylate and structural units derived from methyl acrylate, respectively. The weight average molecular weight is 69,000.

2-2-2. Colorant Titanium oxide “Taipaque CR60-2” (trade name) manufactured by Ishihara Sangyo Co., Ltd. was used.
2-2-3. Thermal Stabilizer Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] “IRGANOX1010” (trade name) manufactured by BASF Japan Ltd. was used.
2-2-4. Lubricant Calcium stearate manufactured by Nitto Kasei Kogyo Co., Ltd. was used.

The thermoplastic resin composition for forming the second resin layer is prepared by mixing the raw materials shown in Table 1 and Table 2 with a high-speed mixer, and then supplying it to a φ58 mm vented twin screw extruder (L / D = 32). It was prepared by kneading at 240 ° C. In producing the decorative resin sheet, pellets obtained by the strand cutting method were used.
Tables 1 and 2 show the results of pencil hardness and flexibility test (MD direction) in a single-layer film having a thickness of 125 μm.

2-3. Pattern layer forming material The ink used to form the pattern layer (hereinafter referred to as “pattern layer forming ink”) is a mixture of acrylic resin and vinyl chloride / vinyl acetate copolymer in a mass ratio of 6: 4. And a colorant composed of quinacridone red, isoindolinone, phthalocyanine blue, and carbon black.

2-4. Adhesive layer forming material The adhesive composition used for forming the adhesive layer is a composition that gives a transparent adhesive layer obtained by mixing acrylic resin and vinyl chloride / vinyl acetate copolymer in a mass ratio of 6: 4. It is a thing.

3. Production and evaluation of decorative resin sheets (1)
Example 1
A thermoplastic resin composition for forming a second resin layer shown in Table 1 is used in a film forming machine equipped with a T die having a die width of 1,600 mm and a lip interval of 1 mm and an extruder having a screw diameter of 115 mm. The pellet consisting of S1) was fed. Then, a resin melted at a temperature of 260 ° C. was discharged from the T die to obtain a soft film. Then, this soft film was cooled and solidified while being in surface contact with a cast roll whose surface temperature was controlled at 70 ° C. with an air knife, to obtain a second resin layer film having the thickness described in Table 3. It was.
Next, using the pattern layer forming ink, a gravure printing of woodgrain was performed on the surface of the second resin layer film to form a pattern layer. And the curable composition (C1) was apply | coated to the surface by the side of the design layer in the film for 2nd resin layers (bar coater: 13 mil and 20 mil), and after drying a coating film at 80 degreeC for 2 minutes, air | atmosphere A decorative resin sheet having the structure shown in FIG. 1 is obtained by curing by ultraviolet irradiation (irradiation amount: 1.0 J / cm ² ) with a high pressure mercury lamp and forming a first resin layer having a thickness shown in Table 3. Obtained.
About the obtained decorative resin sheet, the pencil hardness in the 1st resin layer surface, scratch resistance, the design visibility in the 1st resin layer side, and flexibility (folding to the 1st resin layer side) are evaluated. The results are shown in Table 3. Further, the volume average particle diameter of the component (Q1) contained in the second resin layer was determined by image analysis using an electron micrograph, and is shown together in Table 3.

Examples 2-9 and Comparative Examples 1-8
Instead of the second resin layer forming thermoplastic resin composition (S1), the second resin layer forming thermoplastic resin compositions (S2) to (S8) and (S10) shown in Table 1, and Table 2 A decorative resin sheet was produced in the same manner as in Example 1 except that the second resin layer forming thermoplastic resin compositions (S11) to (S18) shown were used, and various evaluations were performed. The results are shown in Tables 3 to 8.

  Examples 1-9 and Comparative Examples 1-8 are examples of decorative resin sheets in which the first resin layer is formed using the curable composition (C1). From Tables 3 to 8, the following is clear. Comparative Example 1 is an example using the second resin layer forming thermoplastic resin composition (S11) in which the volume average particle diameter of the component (Q1) is large outside the scope of the present invention, and the flexibility is not sufficient. It was. Comparative Example 2 is the formation of the second resin layer in which the volume average particle diameter of the component (Q1) is large outside the range of the present invention, and the content of the (meth) acrylic acid alkyl ester unit is 0% with respect to the entire component (Q2). This is an example using the thermoplastic resin composition (S12), and the scratch resistance and hardness on the surface on the first resin layer side were not sufficient. Comparative Example 3 is an example in which the second resin layer forming thermoplastic resin composition (S13) having a content of (meth) acrylic acid alkyl ester units of 0% with respect to the entire component (Q2) was used. The scratch resistance and hardness on the surface on the resin layer side were not sufficient. Comparative Example 4 is an example using the second resin layer forming thermoplastic resin composition (S14) in which the volume average particle size of the component (Q1) is outside the range of the present invention, and the flexibility is not sufficient. It was. Comparative Example 5 is an example using the thermoplastic resin composition for forming a second resin layer (S15) that does not contain the component (Q1), and the flexibility was not sufficient. Comparative Example 6 is an example using the thermoplastic resin composition (S16) for forming the second resin layer, in which the content of the rubber-like polymer with respect to the whole component (Q1) is low outside the scope of the present invention. Sex was not enough. Comparative Example 7 is an example using the thermoplastic resin composition for forming a second resin layer (S17) in which the ratio of the component (Q1) and the component (Q2) is outside the scope of the present invention, and the first resin layer side The surface scratch resistance and hardness were not sufficient. Comparative Example 8 is a thermoplastic resin composition for forming a second resin layer in which the content of the (meth) acrylic acid alkyl ester unit relative to the entire component (Q2) is as low as 40.5% outside the scope of the present invention ( This is an example using S18), and the scratch resistance and hardness on the surface on the first resin layer side were not sufficient. On the other hand, it turns out that Examples 1-9 are excellent in the balance of the flaw resistance in the surface by the side of the 1st resin layer, hardness, flexibility, and image visibility.

4). Production and evaluation of decorative resin sheets (2)
Example 10
A thermoplastic resin composition for forming a second resin layer shown in Table 1 is used in a film forming machine equipped with a T die having a die width of 1,600 mm and a lip interval of 1 mm and an extruder having a screw diameter of 115 mm. The pellet consisting of S2) was supplied. Then, a resin melted at a temperature of 260 ° C. was discharged from the T die to obtain a soft film. Thereafter, this soft film was cooled and solidified while being in surface contact with a cast roll whose surface temperature was controlled at 70 ° C. with an air knife, to obtain a second resin layer film having the thickness described in Table 9 It was.
On the other hand, wood gravure printing was performed on the surface on one side of the transparent film (F1) constituting the first resin layer to form a design layer, thereby obtaining a printed film. And the material for contact bonding layer (adhesive composition) was apply | coated to the surface by the side of the design layer in this printing film by the gravure roll coat method, and the printing film with a contact bonding layer was obtained.
Next, the second resin layer film is brought into contact with the surface on the adhesive layer side of the printed film with the adhesive layer, and these are thermally welded by a rotary heat press to obtain the structure shown in FIG. A decorative resin sheet was obtained.
About the obtained decorative resin sheet, the pencil hardness in the 1st resin layer surface, scratch resistance, the design visibility in the 1st resin layer side, and flexibility (folding to the 1st resin layer side) are evaluated. The results are also shown in Table 9.

Example 11 and Comparative Example 9
Instead of the second resin layer forming thermoplastic resin composition (S2), the second resin layer forming thermoplastic resin composition (S4) shown in Table 1 and the second resin layer forming shown in Table 2, respectively. A decorative resin sheet was produced in the same manner as in Example 10 except that the thermoplastic resin composition (S12) for use was used, and various evaluations were performed. The results are shown in Table 9.

  Examples 10 to 11 and Comparative Example 9 are examples of a decorative resin sheet in which the first resin layer is formed using a transparent film (F1). From Table 9, the following is clear. In Comparative Example 9, the volume average particle diameter of the component (Q1) is large outside the scope of the present invention, and the second resin layer formation in which the content of the (meth) acrylic acid alkyl ester unit is 0% with respect to the entire component (Q2) This is an example using the thermoplastic resin composition (S12), and the scratch resistance and hardness on the surface on the first resin layer side were not sufficient. On the other hand, it can be seen that Examples 10 and 11 are excellent in the balance of scratch resistance, hardness, flexibility and image visibility on the surface on the first resin layer side.

5. Production and evaluation of decorative resin sheets (3)
Example 12
A thermoplastic resin composition for forming a second resin layer shown in Table 1 is used in a film forming machine equipped with a T die having a die width of 1,600 mm and a lip interval of 1 mm and an extruder having a screw diameter of 115 mm. The pellet consisting of S9) was supplied. Then, a resin melted at a temperature of 260 ° C. was discharged from the T die to obtain a soft film. Then, this soft film was cooled and solidified while being in surface contact with a cast roll whose surface temperature was controlled at 70 ° C. with an air knife, and had a thickness described in Table 10 and a haze according to JIS K7136 of 1 A transparent second resin layer film of 9% was obtained.
Subsequently, the gravure printing of the wood grain tone was performed on the surface on the one surface side of the second resin layer film to form a design layer, thereby obtaining a printing film. Then, the curable composition (C1) was applied to the surface of the printed film that was not the design layer (bar coater: 13 mils), and the coating film was dried at 80 ° C. for 2 minutes. Was cured by UV irradiation (irradiation amount: 1.0 J / cm ² ) to form a first resin layer having a thickness shown in Table 10, thereby obtaining a decorated resin sheet having the structure shown in FIG.
About the obtained decorative resin sheet, the pencil hardness in the 1st resin layer surface, scratch resistance, the design visibility in the 1st resin layer side, and flexibility (folding to the 1st resin layer side) are evaluated. The results are also shown in Table 10.

Example 13
A thermoplastic resin composition for forming a second resin layer shown in Table 1 is used in a film forming machine equipped with a T die having a die width of 1,600 mm and a lip interval of 1 mm and an extruder having a screw diameter of 115 mm. The pellet consisting of S9) was supplied. Then, a resin melted at a temperature of 260 ° C. was discharged from the T die to obtain a soft film. Then, this soft film was cooled and solidified while being in surface contact with a cast roll whose surface temperature was controlled at 70 ° C. with an air knife, and had a thickness described in Table 10 and a haze according to JIS K7136 of 1 A transparent second resin layer film of 8% was obtained.
Subsequently, the gravure printing of the wood grain tone was performed on the surface on the one surface side of the second resin layer film to form a design layer, thereby obtaining a printing film.
On the other hand, a material for forming an adhesive layer (adhesive composition) was applied to the surface on one side of the transparent film (F1) constituting the first resin layer by a gravure roll coating method to obtain a transparent film with an adhesive layer. .
After that, the surface of the printed film that is not the pattern layer and the surface of the adhesive layer side of the transparent film with the adhesive layer are brought into contact with each other, and these are thermally welded by a rotary heat press. A decorative resin sheet having the structure shown in 4 was obtained.
About the obtained decorative resin sheet, the pencil hardness in the 1st resin layer surface, scratch resistance, the design visibility in the 1st resin layer side, and flexibility (folding to the 1st resin layer side) are evaluated. The results are also shown in Table 10.

  In Examples 12 and 13, the first resin layer and the second resin layer are transparent, and the design layer arranged on the second resin layer side is visually recognized from these layers through these layers. It is an example of the decorative resin sheet of the structure which is. From Table 10, the first resin layer is formed using the curable composition (C1) and the first resin layer is formed using the transparent film (F1). It turns out that it is excellent in the balance of the flaw resistance in the surface of 1 resin layer side, hardness, flexibility, and image visibility.

  In the present invention, a decorative resin sheet is arranged and integrated on the surface, and characters, numbers, pictures, etc. forming an image of a design layer (decorative layer) are displayed via a transparent protective layer. It is suitable for the production of the resin molded product (decorated molded product). And this decorative molded product includes vehicles such as automobiles, interior materials or exterior materials such as ships and aircraft, construction materials such as baseboards and fringes, fittings such as window frames and door frames, walls, floors, ceilings, etc. Interior materials for buildings, home appliances such as TV receivers and air conditioners, OA equipment, casings and surface materials for electric and electronic equipment, daily miscellaneous goods such as containers, sports equipment, stationery, etc. it can.

1: Decorative resin sheet 11: First resin layer (transparent protective layer)
13: Second resin layer (support layer)
15: Design layer 17: Adhesive layer 2: Thermoplastic resin composition for forming a second resin layer in a molten state 3: Resin molded part 5: Decorative molded product 71: Mold for injection molding (male)
72: Mold for injection molding (female)
75: Suction hole

Claims (7)

In the laminated decorative resin sheet comprising the first resin layer, the second resin layer and the design layer,
The first resin layer is a transparent protective layer containing a thermoplastic resin or a cured resin,
The second resin layer is obtained by polymerizing the polymerizable unsaturated monomer (b1) in the presence of a rubbery polymer, and has a volume average particle diameter of 80 to 250 nm and a graft ratio of 50. It is composed of one or more of (co) polymers obtained by using ~ 150% rubbery polymer reinforced graft resin (Q1) and polymerizable unsaturated monomer (b2) (co) The polymer (Q2) and 50 to 100% by mass of structural units derived from the (meth) acrylic acid alkyl ester compound with respect to the whole of the (co) polymer (Q2). ) And the ratio of the component (Q2) are 5 to 50% by mass and 50 to 95% by mass, respectively, when the total of both is 100% by mass, and the content of the rubbery polymer is the above When the sum of the component (Q1) and the component (Q2) is 100% by mass A support layer made of thermoplastic resin composition is 5 to 40 wt%,
The decorative resin is characterized in that the stacking order is the first resin layer, the design layer, and the second resin layer, or the first resin layer, the second resin layer, and the design layer. Sheet.   The component (Q2) contains 50 to 100% by mass of the (co) polymer containing 80 to 100% by mass of a structural unit derived from a (meth) acrylic acid alkyl ester compound based on the total of the component (Q2). The decorative resin sheet according to claim 1 comprising.   The decorative resin sheet according to claim 1 or 2, wherein the polymerizable unsaturated monomer (b1) contains an aromatic vinyl compound and a vinyl cyanide compound.   The decorative resin sheet according to any one of claims 1 to 3, wherein the second resin layer is a colored layer.   The decorative resin sheet according to any one of claims 1 to 3, wherein the second resin layer is a transparent layer.   The decorative resin sheet according to any one of claims 1 to 5, further comprising an adhesive layer between the second resin layer and the design layer.   The decorative resin sheet according to any one of claims 1 to 6, having a thickness of 50 to 1,500 µm.

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