JP2014009316A - Emboss decorative sheet and emboss decorative integrally-molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an emboss decorative sheet allowing suppression of disappearance of a projection and being excellent in followability (vacuum moldability) to projection or recess surfaces of a type for vacuum molding, when an emboss decorative integrally-molded article is obtained by injection molding; and an emboss decorative integrally-molded article comprising an emboss decorative sheet as a surface part.SOLUTION: The present invention is an emboss decorative sheet with a projection consisting of a thermoplastic resin composition obtained by melting and kneading a material comprising (A) a rubber-modified aromatic vinyl resin and (B) a polyamide resin, where (A) consists of a graft copolymer obtained by polymerization of a vinyl monomer x comprising an aromatic vinyl compound and a vinyl cyanide compound in the presence of a rubbery polymer, or consists of a mixture of this graft copolymer with a (co) polymer of a vinyl monomer y; at least one of the vinyl monomers x and y contains a functional group-containing monomer such as a carboxyl group-containing unsaturated compound; and the content of a structural unit from a functional group-containing monomer is 0.1-1.2 mass% relative to (A).

Description

  The present invention relates to an embossed decorative sheet having a three-dimensional design feeling of a concavo-convex pattern, and an embossed decorative integrally molded product obtained using this embossed decorative sheet.

A decorative molded product in which a decorative resin sheet as a skin material is laminated and integrated on the surface of a resin molded product as an adherend is an interior material of a vehicle such as an automobile, a base material, a construction member such as a skirt, a window, etc. Frames, door frames and other fittings, walls, floors, ceilings and other building interior materials, game machines, mobile phones, computers, washing machines, refrigerators, vacuum cleaners, rice cookers, microwave ovens, television receivers, air conditioners, Widely used as housings, surface materials, containers, and the like for home appliances such as audio equipment, video equipment, lighting equipment, and musical instruments. In particular, a decorative molded product having a concavo-convex pattern (also referred to as “texture pattern”) such as a dot tone, a satin surface, a line texture, a leather texture, a hairline tone, a wood grain tone on its surface has, for example, a low gloss appearance. It is said that it may be preferable for automobile interior materials (door trims, instrument panels, console boxes, sun visors, glove boxes, etc.), and home appliances (game machines, mobile phones, computers, etc.).
As a method for producing such a decorative molded product, for example, after arranging a decorative resin sheet having a wrinkle pattern inside the injection mold, toward the surface on one side of the decorative resin sheet, By injecting and filling a melt of a predetermined thermoplastic resin composition into a mold, a resin molded product having the same shape as the cavity is formed, and at the same time, a decorative resin sheet is adhered to the surface of this resin molded product and integrated. The method of making is common.

  Patent Document 1 discloses an embossed decorative integrally formed product composed of a skin material and a core material integrally formed with the skin material by injection molding, and the skin material is an olefin-based thermoplastic elastomer, styrene-based resin, chloride It is composed of an embossed decorative sheet mainly composed of at least one resin selected from the group consisting of vinyl resins and chlorinated polyethylene thermoplastic elastomers, and the core material is styrene resin and polycarbonate. Embossing, characterized in that the residual three-dimensional surface roughness of the surface of the skin material in the embossed decorative integrally molded product is in the range of 4 to 100 μm, comprising at least one resin selected from the group consisting of resin A decorative integrated molded product is disclosed.

  Patent Document 2 discloses a styrenic resin 20 to 70% by weight, a polyolefin 5 to 40% by weight, and an embossed decorative sheet that can simultaneously solve both embossing crushing and sheet whitening during injection molding, and And a composition containing 5 to 40% by weight of a thermoplastic elastomer, which does not whiten in a bending test and has an embossing residual ratio of 70% or more after injection molding measured using a 60-degree reflectivity, An embossed decorative sheet is disclosed in which the gate damage area ratio of the decorative surface is 20% or less.

JP 2010-89359 A JP 2011-25610 A

  An object of the present invention is a decorative resin sheet which has a convex portion on at least one surface side and reveals a concavo-convex pattern, and is formed as a skin material on the surface of a resin molded article as an adherend by injection molding. When the decorative resin sheet is laminated and integrated to obtain an embossed decorative integrated molded product, deformation or disappearance of the convex portion is suppressed, and the followability to the surface of the convex portion or concave portion (groove portion) of the vacuum forming mold (vacuum) It is to provide an embossed decorative sheet excellent in moldability) and an embossed decorative integrally formed product obtained by using this embossed decorative sheet.

The present invention is as follows.
1. It is used as a skin material in a molding method by injection molding, an embossed decorative sheet having a convex portion on the surface on at least one surface side,
(A) A thermoplastic resin composition obtained by melt-kneading a raw material containing a rubber-modified aromatic vinyl resin and (B) a polyamide resin,
The rubber-modified aromatic vinyl resin (A) was obtained by polymerizing a vinyl monomer (b1) containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of the rubbery polymer (a). The graft copolymer (A1) or a mixture of the graft copolymer (A1) and a vinyl (co) polymer (A2) of a vinyl monomer (b2),
At least one of the vinyl monomer (b1) and the vinyl monomer (b2) is a hydroxyl group-containing unsaturated compound, an epoxy group-containing unsaturated compound, a substituted or unsubstituted amino group-containing unsaturated compound, Including at least one functional group-containing vinyl monomer selected from the group consisting of a carboxyl group-containing unsaturated compound, an acid anhydride group-containing unsaturated compound, and an oxazoline group-containing unsaturated compound,
The vinyl-based (co) polymer (A2) has a weight average molecular weight of less than 500,000,
The content of the structural unit derived from the functional group-containing vinyl monomer contained in the rubber-modified aromatic vinyl resin (A) is from 0.1 to the rubber-modified aromatic vinyl resin (A). 1.2% by weight,
The ratios of the rubber-modified aromatic vinyl resin (A) and the polyamide resin (B) are 35 to 75% by mass and 25 to 65% by mass, respectively, when the total of both is 100% by mass,
The content of the rubber polymer (a) is 5 to 30% by mass when the total of the rubber-modified aromatic vinyl resin (A) and the polyamide resin (B) is 100% by mass. Characteristic embossed decorative sheet.
2. A graft copolymer (A11) obtained by polymerizing a vinyl monomer comprising an aromatic vinyl compound and a vinyl cyanide compound in the rubber-modified aromatic vinyl resin (A) in the presence of a rubbery polymer. And a graft copolymer (A12) obtained by polymerizing a vinyl monomer composed of an aromatic vinyl compound, a vinyl cyanide compound and a carboxyl group-containing unsaturated compound in the presence of a rubbery polymer. The embossed decorative sheet according to 1 above, comprising
3. The thermoplastic resin composition further includes a vinyl (co) polymer (C) having a weight average molecular weight of 1,500,000 to 5,000,000, and the vinyl (co) polymer (C) is an aromatic vinyl compound. At least one of structural units derived from (meth) acrylic acid alkyl ester compounds, and the content ratio of the vinyl (co) polymer (C) is the above-mentioned rubber-modified aromatic vinyl resin ( The embossed decorative sheet according to 1 or 2 above, which is 0.1 to 5 parts by mass with respect to 100 parts by mass in total of A) and the polyamide resin (B).
4). The thermoplastic resin composition further includes an inorganic filler, and the content of the inorganic filler is 100 parts by mass in total of the rubber-modified aromatic vinyl resin (A) and the polyamide resin (B). The embossed decorative sheet according to any one of 1 to 3 above, which is 1 to 10 parts by mass.
5. 5. The embossed decorative sheet according to 4 above, wherein the inorganic filler is talc.
6). An embossed decorative integral molded product obtained using the embossed decorative sheet according to any one of 1 to 5 above and a thermoplastic resin composition (Z),
An embossed decorative integrally molded product in which a skin part made of the embossed decorative sheet and a core part made of the thermoplastic resin composition (Z) are joined and has a convex part on the surface of the skin part.
7). 7. The embossing according to 6 above, wherein the thermoplastic resin composition (Z) comprises at least one resin selected from the group consisting of an aromatic vinyl resin containing a structural unit derived from an aromatic vinyl compound and a polycarbonate resin. Decorative integrated molded product.

According to the embossed decorative sheet of the present invention, it is excellent in followability (vacuum formability) with respect to convex portions or concave portions (groove portions) formed on the surface of a vacuum forming mold or the like, and is molded as an adherend by injection molding. When a decorative resin sheet as a skin material is laminated and integrated on the surface of an object, an embossed decorative integrated molded product having an excellent appearance can be produced with a clear concavo-convex pattern. The resin composition for forming a resin molded part (injection resin) supplied to the mold cavity at the time of injection molding is usually heated and melted to be in a fluid state, and the temperature may reach 200 ° C. or more. However, even with such a high-temperature resin composition, it is possible to produce an embossed decorative integrally molded article having excellent shape stability without deformation or disappearance of the convex portion of the embossed decorative sheet. it can.
According to the embossed decorative integrally formed product of the present invention, the uneven pattern of the embossed decorative sheet is reflected on the surface without any defects, and the appearance is excellent.

It is a schematic sectional drawing which shows an example of the embossed decorative integral molded product of this invention. It is a schematic perspective view which shows the type | mold used for the evaluation of the vacuum formability with respect to the embossed decorative sheet obtained in the Example and the comparative example. It is a schematic sectional drawing explaining the evaluation method of the vacuum formability with respect to the embossed decorative sheet obtained in the Example and the comparative example. It is a schematic sectional drawing explaining the film forming property evaluation method before setting it as an embossed decorative sheet in an Example and a comparative example. It is explanatory drawing which shows the criteria of evaluation of film forming property using FIG. It is a schematic sectional drawing which shows an example of the method of manufacturing an embossing decorating integrally molded article using the embossing decorating 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.
Further, the “weight average molecular weight” is a standard polystyrene conversion value by gel permeation chromatography (GPC).

1. Embossed decorative sheet The embossed decorative sheet of the present invention comprises a thermoplastic resin composition obtained by melt-kneading a raw material containing (A) a rubber-modified aromatic vinyl resin and (B) a polyamide resin. A rubber-modified aromatic vinyl resin (A) is a graft obtained by polymerizing a vinyl monomer (b1) containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of a rubbery polymer (a). The vinyl monomer comprising a copolymer (A1) or a mixture of the graft copolymer (A1) and a vinyl (co) polymer (A2) of a vinyl monomer (b2). At least one of (b1) and the vinyl monomer (b2) is a hydroxyl group-containing unsaturated compound, an epoxy group-containing unsaturated compound, a substituted or unsubstituted amino group-containing unsaturated compound, or a carboxyl group-containing unsaturated compound. ,acid A weight average of the vinyl (co) polymer (A2) comprising at least one functional group-containing vinyl monomer selected from the group consisting of an anhydride group-containing unsaturated compound and an oxazoline group-containing unsaturated compound. The molecular weight is less than 500,000, and the content of the structural unit derived from the functional group-containing vinyl monomer contained in the rubber-modified aromatic vinyl resin (A) is the rubber-modified aromatic vinyl resin ( The proportion of the rubber-modified aromatic vinyl resin (A) and the polyamide resin (B) is 0.1 to 1.2% by mass with respect to A), and when the total of both is 100% by mass, The content of the rubber-like polymer (a) is 35 to 75% by mass and 25 to 65% by mass, respectively, and the total content of the rubber-modified aromatic vinyl resin (A) and the polyamide resin (B) is 100. When mass% Characterized in that from 5 to 30 wt%.

The rubber-modified aromatic vinyl resin (A) was obtained by polymerizing a vinyl monomer (b1) containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of the rubbery polymer (a). It consists of a graft copolymer (A1) or a mixture of the graft copolymer (A1) and a vinyl (co) polymer (A2) of a vinyl monomer (b2). The vinyl (co) polymer (A2) is obtained by polymerizing the vinyl monomer (b2) in the absence of the rubbery polymer (a).
In the present invention, at least the vinyl monomer (b1) used for forming the graft copolymer (A1) and the vinyl monomer (b2) used for forming the vinyl (co) polymer (A2) On the other hand, the compatibility of the component (A) and the component (B) according to the present invention can be improved by containing the functional group-containing vinyl monomer.

The rubbery polymer (a) used for forming the graft copolymer (A1) may be a homopolymer or a copolymer as long as it is rubbery at 25 ° C. The rubbery polymer (a1) may be a crosslinked polymer or a non-crosslinked polymer.
Examples of the rubber polymer (a) include conjugated diene rubber polymers and non-conjugated diene rubber polymers. Examples of the conjugated diene rubbery polymer include polybutadiene, butadiene / styrene copolymer, butadiene / acrylonitrile copolymer, and hydrogenated products thereof. Examples of the non-conjugated diene rubber polymer include, for example, ethylene / propylene copolymer, ethylene / propylene / non-conjugated diene copolymer, ethylene / 1-butene copolymer, ethylene / 1-butene / non-conjugated. Ethylene / α-olefin copolymer rubber such as diene copolymer, ethylene / 1-octene copolymer, ethylene / 1-octene / non-conjugated diene copolymer; acrylic rubber; silicone rubber; silicone acrylic System IPN rubber and the like.
These rubbery polymers may be used alone or in combination of two or more.
In the present invention, a conjugated diene rubbery polymer is preferably used.

The vinyl monomer (b1) used for the formation of the graft copolymer (A1) includes an aromatic vinyl compound and a vinyl cyanide compound. In addition, (meth) acrylic acid alkyl ester, maleimide compound, hydroxyl Including group-containing unsaturated compounds, epoxy group-containing unsaturated compounds, substituted or unsubstituted amino group-containing unsaturated compounds, carboxyl group-containing unsaturated compounds, acid anhydride group-containing unsaturated compounds, oxazoline group-containing unsaturated compounds, etc. But you can.
The vinyl monomer (b1) may be a hydroxyl group-containing unsaturated compound, an epoxy group-containing unsaturated compound, a substituted or unsubstituted amino group-containing unsaturated compound, a carboxyl group-containing unsaturated compound, an acid, if necessary. A vinyl monomer containing a functional group having reactivity with an amino group selected from an anhydride group-containing unsaturated compound and an oxazoline group-containing unsaturated compound (hereinafter referred to as “functional group-containing vinyl monomer”). It is referred to as a “mer”.
When the vinyl monomer (b2) does not contain a functional group-containing vinyl monomer, the vinyl monomer (b1) needs to contain a functional group-containing vinyl monomer. In the following, the vinyl monomer (b1) not containing the functional group-containing vinyl monomer is referred to as “vinyl monomer (b1-1)”, and the vinyl monomer containing the functional group-containing vinyl monomer. The monomer (b1) may be described as “vinyl monomer (b1-2)”.

  Examples of the aromatic vinyl compound include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, vinyltoluene, vinylxylene, ethylstyrene, dimethylstyrene, p-tert-butylstyrene, vinylnaphthalene, methoxystyrene, Examples thereof include monobromostyrene, dibromostyrene, tribromostyrene, and fluorostyrene. Of these, styrene and α-methylstyrene are preferred. Moreover, these compounds may be used independently and may be used in combination of 2 or more.

  Examples of the vinyl cyanide compound include acrylonitrile, methacrylonitrile, ethacrylonitrile, α-ethylacrylonitrile, α-isopropylacrylonitrile, α-chloro (meth) acrylonitrile and the like. Of these, acrylonitrile is preferred. Moreover, these compounds may be used independently and may be used in combination of 2 or more.

  Examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, Isobutyl (meth) acrylate, tert-butyl (meth) acrylate, sec-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n- (meth) acrylate Heptyl, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, n-decyl (meth) acrylate, n-dodecyl (meth) acrylate, (meth) Examples include cyclohexyl acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, and the like. These compounds may be used alone or in combination of two or more.

  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 may be used alone or in combination of two or more.

  Examples of the hydroxyl group-containing unsaturated compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, Ε-Caprolactone is added to 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and 2-hydroxyethyl (meth) acrylate. Compound obtained by addition, 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-propene and the like. These compounds may be used alone or in combination of two or more.

  Examples of the epoxy group-containing unsaturated compound include glycidyl (meth) acrylate and allyl glycidyl ether. These compounds may be used alone or in combination of two or more.

Examples of substituted or unsubstituted amino group-containing unsaturated compounds include aminoethyl acrylate, aminoethyl methacrylate, aminopropyl methacrylate, propylaminoethyl acrylate, dimethylaminoethyl methacrylate, phenylaminoethyl methacrylate, and N-vinyl. Diethylamine, N-acetylvinylamine, acrylic amine, methacrylamine, N
-Methylacrylamine, acrylamide, N-methylacrylamide, p-aminostyrene, etc. are mentioned. These compounds may be used alone or in combination of two or more.

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

Examples of the acid anhydride group-containing unsaturated compound include unsaturated carboxylic acid anhydrides such as maleic anhydride, itaconic anhydride, and citraconic anhydride. These compounds may be used alone or in combination of two or more.

  Examples of the oxazoline group-containing unsaturated compound include vinyl oxazoline. These compounds may be used alone or in combination of two or more.

In the present invention, the vinyl monomer (b1) includes an aromatic vinyl compound and a vinyl cyanide compound. The total amount of these monomers is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, and still more preferably 80 to 100% by mass with respect to the total amount of the vinyl monomer (b1). is there. Further, the use ratio of the aromatic vinyl compound and the vinyl cyanide compound is preferably 40 to 85% by mass and 15 to 60% by mass, more preferably 55 to 80% by mass, when the total of these is 100% by mass. % And 20 to 45% by mass.
When the vinyl monomer (b1) contains a functional group-containing vinyl monomer, the upper limit of the content is preferably 50% by mass, based on the total amount of the vinyl monomer (b1). Preferably it is 30 mass%, More preferably, it is 20 mass%.

  In the present invention, the graft copolymer (A1) is a vinyl monomer (b1-1) comprising an aromatic vinyl compound and a vinyl cyanide compound in the presence of the rubbery polymer (a) (provided that In the presence of the rubbery polymer (a), an aromatic vinyl compound and vinyl cyanide are obtained. Compound, hydroxyl group-containing unsaturated compound, epoxy group-containing unsaturated compound, substituted or unsubstituted amino group-containing unsaturated compound, carboxyl group-containing unsaturated compound, acid anhydride group-containing unsaturated compound, and oxazoline group-containing unsaturated compound Graft copolymer (A1-2) obtained by polymerizing vinyl monomer (b1-2) comprising at least one functional group-containing vinyl monomer selected from the group consisting of compounds A vinyl monomer (b1-1) comprising an aromatic vinyl compound and an alkyl (meth) acrylate in the presence of the rubbery polymer (a) (however, a functional group-containing vinyl monomer is contained) A graft copolymer (A1-3) obtained by polymerizing a vinyl polymer comprising an aromatic vinyl compound, a vinyl cyanide compound and a (meth) acrylic acid alkyl ester in the presence of the rubbery polymer (a). And a graft copolymer (A1-4) obtained by polymerizing a monomer (b1-1) (but not containing a functional group-containing vinyl monomer). These may be used alone or in combination. For these graft copolymers (A1-1) to (A1-4), a plurality of different types of graft copolymers may be used.

  In the present invention, the graft copolymer (A1) is a graft copolymer obtained by polymerizing a vinyl monomer comprising an aromatic vinyl compound and a vinyl cyanide compound in the presence of a rubbery polymer. Graft copolymer obtained by polymerizing vinyl monomer comprising aromatic vinyl compound, vinyl cyanide compound and carboxyl group-containing unsaturated compound in the presence of polymer (A11) and rubber polymer ( A12).

  A method for producing the graft copolymer (A1) will be described later.

Next, the vinyl (co) polymer (A2) is a (co) polymer obtained by using the vinyl monomer (b2). In the present invention, components used as necessary It is. When the graft copolymer (A1) includes the graft copolymer (A1-2), the vinyl-based (co) polymer (A2) may or may not be contained. Also good.
Examples of the vinyl monomer (b2) include aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid alkyl esters, maleimide compounds, hydroxyl group-containing unsaturated compounds, epoxy group-containing unsaturated compounds, substituted or Examples thereof include an unsubstituted amino group-containing unsaturated compound, a carboxyl group-containing unsaturated compound, an acid anhydride group-containing unsaturated compound, and an oxazoline group-containing unsaturated compound. These compounds may be used alone or in combination of two or more. In the present invention, the vinyl monomer (b2) preferably contains an aromatic vinyl compound and a vinyl cyanide compound.
The vinyl monomer (b2) may be a hydroxyl group-containing unsaturated compound, an epoxy group-containing unsaturated compound, a substituted or unsubstituted amino group-containing unsaturated compound, a carboxyl group-containing unsaturated compound, an acid, if necessary. At least one functional group-containing vinyl monomer selected from an anhydride group-containing unsaturated compound and an oxazoline group-containing unsaturated compound.
When the vinyl monomer (b1) does not contain a functional group-containing vinyl monomer, the vinyl monomer (b2) needs to contain a functional group-containing vinyl monomer. In the following, the vinyl monomer (b2) not containing the functional group-containing vinyl monomer is referred to as “vinyl monomer (b2-1)”, the vinyl monomer containing the functional group-containing vinyl monomer. The monomer (b2) may be referred to as “vinyl monomer (b2-2)”.

  Aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid alkyl esters, maleimide compounds, hydroxyl group-containing unsaturated compounds, epoxy group-containing unsaturated compounds that can be used as the vinyl monomer (b2), Examples of substituted or unsubstituted amino group-containing unsaturated compounds, carboxyl group-containing unsaturated compounds, acid anhydride group-containing unsaturated compounds, and oxazoline group-containing unsaturated compounds are the compounds exemplified for the vinyl monomer (b1). Can be used.

When the vinyl monomer (b2) contains an aromatic vinyl compound and a vinyl cyanide compound, the total amount of these monomers is preferably relative to the total amount of the vinyl monomer (b2). It is 50-100 mass%, More preferably, it is 70-100 mass%, More preferably, it is 80-100 mass%. The use ratio of the aromatic vinyl compound and the vinyl cyanide compound is preferably 40 to 95% by mass and 5 to 60% by mass, more preferably 50 to 90% by mass, when the total of these is 100% by mass. % And 10 to 50% by mass, more preferably 55 to 85% by mass and 15 to 45% by mass.
When the vinyl monomer (b2) contains a functional group-containing vinyl monomer, the upper limit of the content is preferably 50% by mass, based on the total amount of the vinyl monomer (b2). Preferably it is 30 mass%, More preferably, it is 20 mass%.

  In the present invention, the vinyl (co) polymer (A2) is a vinyl monomer (b2) comprising an aromatic vinyl compound and a vinyl cyanide compound in the absence of the rubbery polymer (a). -1) A vinyl copolymer (A2-1) obtained by polymerizing (but not containing a functional group-containing vinyl monomer); an aromatic compound in the absence of the rubbery polymer (a). Vinyl compound, vinyl cyanide compound, hydroxyl group-containing unsaturated compound, epoxy group-containing unsaturated compound, substituted or unsubstituted amino group-containing unsaturated compound, carboxyl group-containing unsaturated compound, acid anhydride group-containing unsaturated A vinyl copolymer obtained by polymerizing a vinyl monomer (b2-2) comprising at least one functional group-containing vinyl monomer selected from the group consisting of a compound and an oxazoline group-containing unsaturated compound Coalescence A2-2); in the absence of the rubbery polymer (a), a vinyl monomer (b2-1) comprising an aromatic vinyl compound and (meth) acrylic acid alkyl ester (however, a functional group-containing vinyl-based polymer) A vinyl copolymer (A2-3) obtained by polymerizing a monomer-free polymer) in the absence of the rubbery polymer (a), an aromatic vinyl compound, a vinyl cyanide compound, and (meth) Examples thereof include a vinyl copolymer (A2-4) obtained by polymerizing a vinyl monomer (b2-1) composed of an acrylic acid alkyl ester (but not containing a functional group-containing vinyl monomer). It is done. These may be used alone or in combination. Regarding these vinyl copolymers (A2-1) to (A2-4), a plurality of different types of vinyl copolymers may be used.

  The vinyl-based (co) polymer (A2) has a weight average molecular weight of less than 500,000, preferably 30,000 to 400,000, and more preferably 50,000 to 300,000.

  A method for producing the vinyl (co) polymer (A2) will be described later.

  The method for producing the graft copolymer (A1) may be a method including emulsion polymerization, solution polymerization, bulk polymerization, suspension polymerization and the like. As the polymerization method, emulsion polymerization is preferred. The rubber polymer (a) and the vinyl monomer (b1) are used in a proportion of preferably 5 to 80% by mass and 20 to 95% by mass, respectively, when the total of these is 100% by mass. More preferably, they are 5-70 mass% and 30-95 mass%, More preferably, they are 10-65 mass% and 35-90 mass%.

  When the graft copolymer (A1) is produced by emulsion polymerization, a polymerization initiator, an emulsifier, a chain transfer agent (molecular weight regulator), an electrolyte, water, and the like are used. In addition, although an emulsifier and a chain transfer agent may not be used depending on the situation, they are usually 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 amount of the polymerization initiator used is usually 0.1 to 5 parts by mass, preferably 0.5 to 2 parts by mass, when the total amount of the vinyl monomer (b1) is 100 parts by mass. In addition, when using the said polymerization initiator, it can add to a reaction system collectively or continuously.

  As emulsifiers, alkyl sulfonates such as alkane sulfonate, alkylbenzene sulfonate, and alkyl naphthalene sulfonate; gum rosin, wood rosin, tall oil rosin, disproportionated rosin obtained by disproportionating these, and purified rosin Rosinates such as alkali metal salts (sodium salt or potassium salt) of rosin acid (usually mainly abietic acid) such as sulfates of higher alcohols, higher aliphatic carboxylates, phosphates, etc. Anionic surfactants; nonionic surfactants and the like.

  The usage-amount of the said emulsifier is 0.1-5 mass parts normally, when the whole quantity of the said vinylic monomer (b1) is 100 mass parts, Preferably it is 0.1-3 mass parts.

  Examples of chain transfer agents include mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan; tetraethylthiuram sulfide, acrolein, methacrolein, allyl alcohol, 2-ethylhexylthioglycol, terpinolene, etc. Is mentioned. These compounds may be used alone or in combination of two or more.

  The amount of the chain transfer agent used is usually 0.01 to 5 parts by mass, preferably 0.05 to 3 parts by mass, when the total amount of the vinyl monomer (b1) is 100 parts by mass.

  When manufacturing the said graft copolymer (A1) by emulsion polymerization, superposition | polymerization temperature is 30 to 95 degreeC normally, Preferably it is 40 to 90 degreeC. In order to recover the graft copolymer (A1) from the latex obtained by emulsion polymerization, usually an inorganic salt such as calcium chloride, magnesium sulfate or magnesium chloride; an acid such as sulfuric acid, hydrochloric acid, acetic acid, citric acid or malic acid The graft copolymer (A1) is coagulated by adding a coagulant such as, and then a method of washing, filtering, drying and the like is applied as necessary. The obtained graft copolymer (A1) is usually a powder.

  When the graft copolymer (A1) is produced by solution polymerization, usually the rubbery polymer (a) and the vinyl monomer (b1) are aromatic hydrocarbons such as toluene and ethylbenzene; methyl ethyl ketone and the like. Ketones; a method in which a vinyl monomer (b1) is polymerized in the presence of a polymerization initiator after being dissolved in an inert polymerization solvent such as acetonitrile, dimethylformamide, N-methylpyrrolidone, or the initiation of polymerization A method of thermal polymerization in the absence of an agent is applied.

The graft copolymer (A1) obtained as described above usually includes a graft copolymer in which a copolymer of the vinyl monomer (b1) is grafted to the rubber polymer (a), and And a copolymer of the vinyl monomer (b1) which is not grafted to the rubber polymer (a). The weight average molecular weight of this copolymer is usually less than 500,000.
The graft copolymer (A1) obtained as described above contains a rubbery polymer (a) to which a copolymer of the vinyl monomer (b1) is not grafted. There is.

The graft ratio of the graft copolymer (A1) is preferably 20 to 170%, more preferably 20 to 150%, and still more preferably 30 to 150%. If the graft ratio is too low, when a sheet is formed using the thermoplastic resin composition, a flow mark may be generated on the surface, and the mechanical strength may not be sufficient. Moreover, when the graft ratio is too high, sheet formation may be difficult.
For the graft ratio of the graft copolymer (A1), the type and amount of the polymerization initiator used at the time of production, the addition method and addition time of the vinyl monomer (b1) at the time of polymerization, and a chain transfer agent are used. It is possible to adjust the case by appropriately selecting the type and amount of use.

The graft ratio can be determined by the following formula.
Graft ratio (mass%) = {(S−T) / T} × 100
In the above formula, S represents 1 g of the graft copolymer (A1) in 20 ml of acetone (acetonitrile when the rubbery polymer (a) is an acrylic rubber) and shaken under a temperature condition of 25 ° C. After incubating for 2 hours, the mixture is centrifuged for 60 minutes in a centrifuge (rotation speed: 23,000 rpm) under a temperature condition of 5 ° C., and the insoluble matter obtained by separating the insoluble matter from the soluble matter is obtained. The mass (g), and T is the mass (g) of the rubber-like polymer (a) contained in 1 g of the graft copolymer (A1). The mass of the rubbery polymer (a) is 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 intrinsic viscosity [η] (measured at 30 ° C. using methyl ethyl ketone as the solvent) of the graft copolymer (A1) soluble in acetone (acetonitrile when the rubbery polymer (a) is an acrylic rubber) is , Preferably 0.15 to 1.5 dl / g, more preferably 0.2 to 1.2 dl / g, still more preferably 0.2 to 0.8 dl / g. If the intrinsic viscosity [η] is too low, heat resistance and mechanical strength may not be sufficient when a sheet is formed using the thermoplastic resin composition. On the other hand, if the intrinsic viscosity [η] is too high, sheet formation may be difficult.

  The vinyl-based (co) polymer (A2) can be produced in the same manner as the method for producing the graft copolymer (A1) except that the rubbery polymer (a) is not used. That is, it can be obtained by bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization or the like. In the production of the vinyl (co) polymer (A2), the polymerization initiator, the emulsifier and the chain transfer agent (molecular weight regulator) are used in the same amount as the vinyl monomer in the method for producing the graft copolymer (A1). The body (b1) can be replaced with the vinyl monomer (b2) to obtain the same ratio.

  Moreover, the intrinsic viscosity [η] (measured at 30 ° C. using methyl ethyl ketone as a solvent) of the vinyl (co) polymer (A2) is preferably 0.15 to 1.5 dl / g, more preferably 0. .2 to 1.2 dl / g, more preferably 0.2 to 0.9 dl / g. If the intrinsic viscosity [η] is too low, heat resistance and mechanical strength may not be sufficient when a sheet is formed using the thermoplastic resin composition. On the other hand, if the intrinsic viscosity [η] is too high, sheet formation may be difficult.

The intrinsic viscosity [η] can be determined in the following manner.
A polymer for measurement is dissolved in methyl ethyl ketone, five different concentrations are prepared, and the reduced viscosity of the solution at each concentration is measured at 30 ° C. with an Ubbelohde viscosity tube to determine the intrinsic viscosity [η].

As described above, the rubber-modified aromatic vinyl resin (A) according to the present invention is a graft copolymer (A1) or a mixture of a graft copolymer (A1) and a vinyl-based (co) polymer (A2). However, at least one of the graft copolymer (A1) and the vinyl (co) polymer (A2) contains a structural unit derived from a functional group-containing vinyl monomer.
In the present invention, the content of the structural unit derived from the functional group-containing vinyl monomer is 0.1 to 1.2% by mass with respect to the rubber-modified aromatic vinyl resin (A), preferably It is 0.1-1.1 mass%, More preferably, it is 0.2-1.0 mass%, Most preferably, it is 0.2-0.9 mass%. When the content of the structural unit derived from the functional group-containing vinyl monomer is in the above range, when producing an embossed decorative integral molded product by injection molding, the convex portion or concave portion ( Embossing with excellent appearance characteristics with excellent followability (vacuum formability) to the surface of the groove part, excellent shape stability without deformation or disappearance of the convex part, and the desired uneven pattern is clear A decorative integrated molded product can be manufactured.

  In the present invention, the content of the rubbery polymer (a) used for the formation of the graft copolymer (A1) is preferably 5 to 80% by mass with respect to the rubber-modified aromatic vinyl resin (A). Preferably it is 5-70 mass%, More preferably, it is 10-65 mass%.

The polyamide resin (B) is not particularly limited as long as it has an acid amide bond (—CO—NH—) in the main chain. In the present invention, homopolyamide, copolyamide and the like obtained by polymerization of lactam or amino acid having a ring structure or polycondensation of dicarboxylic acid and diamine can be used.
Specifically, a polymer obtained by polymerizing ε-caprolactam, aminocaproic acid, enanthractam, 7-aminoheptanoic acid, 11-aminoundecanoic acid, 9-aminononanoic acid, α-pyrrolidone, α-piperidone, etc .; Hexamethylene diamine, nonamethylene diamine, undecamethylene diamine, dodecamethylene diamine, metaxylylene diamine and other diamines and terephthalic acid, isophthalic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, glutaric acid and other dicarboxylic acids Polymers obtained by polycondensation; these copolymers, for example, nylon 4, 6, 7, 8, 11, 12, 6.6, 6.9, 6.10, 6.11, 6.12 , 6T, 6 / 6.6, 6/12, 6 / 6T, 6T / 6I, MXD6 and the like.
In addition, the terminal of the polyamide resin may be sealed with carboxylic acid or amine. Examples of the carboxylic acid used for sealing include aliphatic monocarboxylic acids such as caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, and behenic acid. Examples of the amine used for sealing include aliphatic primary amines such as hexylamine, octylamine, decylamine, laurylamine, myristylamine, palmitylamine, stearylamine, and behenylamine. The amount of carboxylic acid or amine used is preferably about 30 μeq / g. In the present invention, when a polyamide resin sealed with a carboxylic acid or an amine is used, a polyamide resin sealed with a carboxylic acid or an amine having a hydrocarbon group having 6 to 22 carbon atoms is preferable.

The relative viscosity of the polyamide resin (B) is preferably 2.0 to 4.0 when measured at a temperature of 25 ° C. with a concentration of 1% by mass in 98% sulfuric acid in accordance with JIS-K6810. When this relative viscosity is in the above range, a sheet having excellent mechanical strength can be obtained using the thermoplastic resin composition.
In this invention, a polyamide resin may be used independently and may be used in combination of 2 or more.
In the present invention, nylon 6, copolymer nylon 6/66, nylon 66, and the like are preferable from the viewpoint of heat resistance and mechanical strength.

The embossed decorative sheet of the present invention may contain other resins. Examples of other resins include vinyl (co) polymers excluding the vinyl (co) polymer (A2), polyolefin resins, polyvinyl chloride resins, polyvinylidene chloride resins, saturated polyester resins, fluororesins, and the like. .
The upper limit in the case of containing other resins is preferably 10 parts by mass, more preferably 5 parts by mass with respect to a total of 100 parts by mass of the rubber-modified aromatic vinyl resin (A) and the polyamide resin (B). It is.

In the present invention, the other resin is preferably a vinyl (co) polymer having a weight average molecular weight of 1,500,000 to 5,000,000 from the viewpoint of vacuum moldability. This vinyl (co) polymer is a (co) polymer obtained by using a vinyl monomer, and examples of the vinyl monomer include aromatic vinyl compounds, vinyl cyanide compounds, (meth) Acrylic acid alkyl ester, maleimide compound, hydroxyl group-containing unsaturated compound, epoxy group-containing unsaturated compound, substituted or unsubstituted amino group-containing unsaturated compound, carboxyl group-containing unsaturated compound, acid anhydride group-containing unsaturated compound And oxazoline group-containing unsaturated compounds. These compounds may be used alone or in combination of two or more.
The other resin according to the present invention is particularly preferably a vinyl (co) polymer containing at least one of a structural unit derived from an aromatic vinyl compound and a structural unit derived from a (meth) acrylic acid alkyl ester compound ( C).

As said vinyl type (co) polymer (C), the structure derived from the (co) polymer (C1) and the (meth) acrylic-acid alkylester compound containing 1 or more types of the structural unit derived from an aromatic vinyl compound. From (co) polymer (C2) composed of one or more units, and one or more structural units derived from an aromatic vinyl compound and one or more structural units derived from a (meth) acrylic acid alkyl ester compound And a copolymer (C3).
These (co) polymers (C1) to (C3) may be used alone or in combination of two or more.

  The vinyl (co) polymer (C) is preferably the (co) polymer (C1). In the present invention, a copolymer comprising one or more structural units derived from an aromatic vinyl compound and one or more structural units derived from a vinyl cyanide compound, the structural unit derived from an aromatic vinyl compound Is preferably 65 to 80% by mass, more preferably 68 to 77% by mass.

  The weight-average molecular weight of the vinyl (co) polymer (C) is preferably 1.7 million to 4.5 million, more preferably 2 million to 4 million.

  The method for producing the vinyl (co) polymer (C) is the same as the method for producing the vinyl (co) polymer (A2).

  When the embossed decorative sheet of the present invention contains the vinyl (co) polymer (C), the content thereof is a total of 100 of the rubber-modified aromatic vinyl resin (A) and the polyamide resin (B). Preferably it is 0.1-5 mass parts with respect to a mass part, More preferably, it is 0.2-4 mass parts, More preferably, it is 0.5-3 mass parts. When the content of the vinyl (co) polymer (C) is in the above range, the above effects are sufficiently exhibited.

The embossed decorative sheet of the present invention includes additives such as inorganic fillers, lubricants, heat stabilizers, antioxidants, ultraviolet absorbers, anti-aging agents, plasticizers, flame retardants, antistatic agents, antibacterial agents, and coloring agents. May be included.
In the present invention, by making an embossed decorative sheet containing an inorganic filler, when manufacturing an embossed decorative integrated product by injection molding, it is possible to suppress damage to the sheet, deformation of the convex portion, etc. It is possible to produce an embossed decorative integrally molded product having a clear concavo-convex pattern and excellent appearance.

Examples of the inorganic filler include glass fiber, carbon fiber, talc, mica, glass flake, wollastonite, potassium titanate, magnesium sulfate, sepiolite, zonolite, aluminum borate, glass beads, balloon, calcium carbonate, silica, and kaolin. , Clay, carbon black, titanium oxide, barium sulfate, zinc oxide, magnesium hydroxide and the like. These may be used alone or in combination of two or more.
In the present invention, talc is preferred because of the excellent effects described above.

Talc is a kind of clay mineral of hydrous magnesium silicate, and its composition is (MgO) _x (SiO ₂ ) _y · zH ₂ O (x, y and z are positive numbers). (MgO) ₃ (SiO ₂ ) ₄ .H ₂ O]. Moreover, a part of Mg atoms in this composition may be substituted with Ca atoms.
The size of the talc is appropriately selected as long as the appearance of the uneven pattern is not impaired. In the present invention, the volume-based average particle diameter D ₅₀ by the laser scattering method is preferably 0.5 to 50 μm, more preferably 1.0 to 25 μm, still more preferably 1.5 to 20 μm.

  The content of the inorganic filler is preferably 1 to 10 parts by mass, more preferably 1.5 to 100 parts by mass with respect to a total of 100 parts by mass of the rubber-modified aromatic vinyl resin (A) and the polyamide resin (B). 8 parts by mass, more preferably 2 to 7 parts by mass.

  Examples of the lubricant include wax, silicone, and lipid. These can be used alone or in combination of two or more.

  Examples of the heat stabilizer include phenol-based heat stabilizers, phosphorus-based heat stabilizers, amine-based heat stabilizers, Group Ib, Group IIb, Group IIIa, Group IIIb, Group IVa, and Group IVa of the periodic table. Examples thereof include metal salts of group IVb elements, alkali metal halides, alkaline earth metal halides, and the like. These compounds 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 compounds 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 compounds 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 compounds 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 compounds 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 Examples thereof include phosphorus flame retardants such as phosphazene derivatives containing elements and nitrogen elements; guanidine salts; silicone compounds.

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.

The thermoplastic resin composition constituting the embossed decorative sheet of the present invention is a composition obtained by melting and kneading raw materials containing a rubber-modified aromatic vinyl resin (A) and a polyamide resin (B). As described above, since the rubber-modified aromatic vinyl resin (A) includes a structural unit derived from the functional group-containing vinyl monomer, the rubber-modified aromatic vinyl resin (A) and the polyamide resin (B) are melted. When kneaded, the reaction product of both formed through the functional group may be contained in the thermoplastic resin composition.
The proportions of the rubber-modified aromatic vinyl resin (A) and the polyamide resin (B) used are 35 to 75% by mass and 25 to 65% by mass, respectively, when the total of both is 100% by mass. , Preferably 40 to 70 mass% and 30 to 60 mass%, more preferably 45 to 65 mass% and 35 to 55 mass%. By using the rubber-modified aromatic vinyl resin (A) and the polyamide resin (B) in the above proportions, heat resistance, chemical resistance, vacuum moldability when producing an embossed decorative integrally molded product, and convex portions Excellent shape stability.
In addition, content of the rubber-like polymer (a) derived from the graft copolymer (A1) contained in the embossed decorative sheet of the present invention is the rubber-modified aromatic vinyl resin (A) and the polyamide resin. When the sum total of (B) is 100 mass%, it is 5-30 mass%, Preferably it is 5.5-27 mass%, More preferably, it is 6-25 mass%.

  In the thermoplastic resin composition, for example, each component is mixed at a predetermined mixing ratio by a tumbler mixer, a Hensell mixer, etc., and then a single screw extruder, a twin screw extruder, a Banbury mixer, a kneader, a roll, a feeder ruder. Etc., and can be produced by melt-kneading under suitable conditions. In addition, the usage method of each component is not specifically limited, All the components may be knead | mixed collectively, and you may knead | mix and knead | mix in multiple steps. The temperature at the time of melt-kneading is preferably 240 ° C to 280 ° C, more preferably 250 ° C to 270 ° C.

The embossed decorative sheet of the present invention is a sheet that has a convex portion on the surface on at least one surface side, and reveals a concavo-convex pattern such as a dot tone, a satin texture, a line texture, a leather texture, a hairline texture, a woodgrain texture, Since an embossed and decorative integrally molded product excellent in the shape stability of the convex portion and the appearance of the concavo-convex pattern is obtained, the upper limit of the height of the convex portion is preferably 200 μm, more preferably 100 μm. In addition, in this invention, it is preferable that the height of the convex part of an embossed decorating sheet has a length of 20 to 60% with respect to the thickness of an embossed decorating sheet.
In addition, the thickness of the embossed decorative sheet of the present invention is preferably 50 to 600 μm, more preferably, since an embossed decorative integrally molded product having excellent shape stability of the convex portion and the appearance of the uneven pattern can be obtained. It is 70-400 micrometers.

The embossed decorative sheet of the present invention is, for example, embossed with the obtained smooth resin sheet after subjecting it to calender molding, inflation molding, T-die extrusion molding, etc., using the thermoplastic resin composition as a molding material. It can manufacture by using for.
Embossing is, for example, a method in which a convex portion (uneven pattern) is formed by applying pressure to a smooth resin sheet heated to an appropriate temperature with an emboss roll (shrink roll). Although the heating temperature of a smooth resin sheet should just be more than the softening point of a sheet | seat (thermoplastic resin composition), it is not specifically limited, Preferably it is 150 to 200 degreeC.
Prior to embossing, the surface of the smooth resin sheet may be subjected to surface treatment, printing, painting, hard coat treatment, or the like, if necessary.

2. Embossed decorative integrated product The embossed decorative integrated product of the present invention is a core obtained by using the skin portion obtained by using the embossed decorative sheet of the present invention and the thermoplastic resin composition (Z). It is a composite having a convex portion on the surface of the skin portion.

The thermoplastic resin composition (Z) is not particularly limited as long as it has adhesiveness with the thermoplastic resin composition constituting the embossed decorative sheet. The thermoplastic resin (hereinafter referred to as “thermoplastic resin (T)”) contained in the thermoplastic resin composition (Z) includes an aromatic vinyl resin containing a structural unit derived from an aromatic vinyl compound, (meth) An acrylic resin, a polycarbonate resin, a polyolefin resin, a saturated polyester resin, a polyamide resin, a fluororesin and the like containing a structural unit derived from an acrylic acid alkyl ester can be given. These thermoplastic resins may be used alone or in combination of two or more.
In the present invention, the thermoplastic resin (T) is preferably an aromatic vinyl resin containing a structural unit derived from an aromatic vinyl compound, a polycarbonate resin, and an alloy resin using these in combination.

  As said aromatic vinyl resin, what contains 50 mass% or more of structural units derived from an aromatic vinyl compound is preferable, High impact polystyrene (HIPS) formed by dispersing rubber particles made of polybutadiene or the like in a continuous layer of polystyrene, Examples include ethylene / styrene random copolymer resins, styrene / olefin alloys, ABS resins, that is, graft copolymers obtained by polymerizing aromatic vinyl compounds, vinyl cyanide compounds, etc. in the presence of diene rubber. It is done. These resins may be used alone or in combination of two or more. In the present invention, an ABS resin is preferred.

  The polycarbonate resin is not particularly limited as long as it has a carbonate bond in the main chain, and may be an aromatic polycarbonate or an aliphatic polycarbonate. Moreover, you may use combining these. In the present invention, an aromatic polycarbonate is preferable from the viewpoint of heat resistance. The polycarbonate resin may have a terminal modified with an R—CO— group or an R′—O—CO— group (R and R ′ each represents an organic group). Polycarbonate resin may be used independently and may be used in combination of 2 or more.

  When the aromatic vinyl resin and the polycarbonate resin are used in combination as the thermoplastic resin (T), it is preferable to use both at a ratio of 10 to 90% by mass and 10 to 90% by mass.

  The thermoplastic resin composition (Z) may be composed only of the thermoplastic resin (T), and further includes an inorganic filler, a lubricant, a heat stabilizer, an antioxidant, an ultraviolet absorber, and an anti-aging agent. In addition, additives such as plasticizers, flame retardants, antistatic agents, antibacterial agents, and coloring agents may be included.

  The thickness of the core portion containing the thermoplastic resin composition (Z) is appropriately selected depending on the use, etc., but from the viewpoint of mechanical strength and design properties, the thickness of the embossed decorative integrally formed product, that is, It is preferable to have a length of 60 to 98% with respect to the total thickness of the skin portion and the core portion made of the embossed decorative sheet.

The embossed decorative integral molded product of the present invention is a thermoplastic resin composition (Z) on the embossed decorative sheet or the surface of the processed molded product that does not have a convex portion that gives a three-dimensional design feeling. Can be manufactured by injection molding. Specific examples are shown below.
(1) The embossed decorative sheet is pre-shaped by vacuum forming, pressure forming, press forming or the like to obtain a processed molded product. Next, this processed molded product is mounted on an injection mold so that the thermoplastic resin composition (Z) that becomes the core portion is injection-molded on a surface that does not have a convex portion that gives a three-dimensional design feeling. Thereafter, the thermoplastic resin composition (Z) is injection-molded into the cavity, and the processed molded product and the cavity-shaped thermoplastic resin composition (Z) are integrated to obtain an embossed decorative integrally molded product.
(2) The embossed decorative sheet is intermittently or continuously so that the thermoplastic resin composition (Z) that becomes the core portion is injection-molded on the surface that does not have a convex portion that gives a three-dimensional design feeling. After supplying to the core part side of the injection mold and fixing with the sheet pressing frame, the thermoplastic resin composition (Z) is injection molded into the cavity, embossed decorative sheet, and cavity-shaped thermoplastic resin composition The product (Z) is integrated to obtain an embossed decorative integrated molded product.

  The injection molding uses an injection molding machine, sets the embossed decorative sheet on the female mold side, closes the male mold and the female mold, and inserts the thermoplastic resin composition (Z in the cavity formed between the molds. ) To fill.

  Hereinafter, an example of a method for manufacturing the embossed decorative integrated product 1 will be described with reference to FIG. The form shown in FIG. 6 manufactures the embossed decorative integrated molded product 1 using an injection mold having a male mold 81 and a female mold 82.

  First, as shown in FIG. 6A, the embossed decorative sheet 20 is arranged so that the convex portions formed on the surface thereof face the mold 80 side. Thereafter, as shown in FIG. 6 (B), the embossed decorative sheet 20 is brought into close contact with the inner surface of the mold 80 by using suction means such as the suction holes 85 arranged in the mold 80, and the processed molded product. Get 70. Since the embossed decorative sheet 20 has flexibility, it can be easily brought into close contact with the inner surface of the mold 80.

  Next, as shown in FIG. 6C, the processed molded product 70 is disposed on the inner surface of the female mold 82 of the injection mold, and the male mold 81 and the female mold 82 are clamped. Then, the thermoplastic resin composition (Z) 10 in a heated and melted state, that is, in a fluid state, is supplied to the cavity formed by both molds. At this time, the processed molded product 70 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 embossed decorative sheet, it is appropriately trimmed. Through the above steps, an embossed decorative integrated product 1 shown in FIG. 6D is obtained.

  According to the present invention, by using an embossed decorative sheet as the skin material, it is necessary to use an inner mold whose surface is uneven according to the convex portion of the embossed decorative sheet. There is no. That is, it is efficient because it is not necessary to provide unevenness on the injection molding die that matches the shape, size, etc. of the embossed decorative integrated molded product, and the manufacturing cost of the mold can also be reduced.

  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. Measurement method GPC measurement conditions for a vinyl-based (co) polymer, which is a raw material for producing an embossed decorative sheet, and an evaluation method for the embossed decorative sheet are shown below.

1-1. Vacuum Formability The vacuum formability is determined by visual observation of a processed molded product 70 (see FIG. 3 (IV)) obtained using a small vacuum forming machine “300X” manufactured by Seiko Sangyo Co., Ltd. having the vacuum forming mold 80 shown in FIG. It was observed and evaluated by determining the followability of the embossed decorative sheet to the vacuum forming die 80. The vacuum forming die 80 shown in FIG. 2 has a height of 45 mm, a bottom surface size of 150 mm × 150 mm, a top surface size of 140 m × 140 mm, and a center of the top surface of 100 mm × 100 mm. A recess having a size of 20 mm in depth is formed and has fine through holes throughout.

First, the embossed decorative sheet was cut to prepare a test piece having a size of 500 mm (MD direction) × 350 mm (TD direction). Then, as shown in FIG. 3 (I), the test piece was placed in a state where the surface having the convex portion was directed toward the surface of the vacuum forming die 80, and the vacuum forming die 80. The upper surface was fixed at an interval of 40 mm from the upper surface. Thereafter, as shown in FIG. 3 (II), the test piece was heated from the peripheral side using a heater (not shown) heated to 450 ° C. in advance. Next, the vacuum forming die 80 at 23 ° C. was moved upward to bring the upper surface of the vacuum forming die 80 into contact with the convex surface of the test piece. Next, as shown in FIG. 3 (III), the pressure was reduced from the bottom surface side of the recess of the vacuum forming die 80, the test piece was brought into close contact with the inner surface of the recess of the vacuum forming die 80, and vacuum forming was performed. Thereafter, the vacuum forming die 80 was removed to obtain a processed product 70 shown in FIG. 3 (IV). The appearance of the processed molded product 70 was visually observed, and the vacuum moldability was evaluated according to the following criteria.
○: Wrinkles were not recognized.
X: Wrinkles were recognized.

1-2. Convex part survivability Convex part survivability is determined by preparing an embossed decorative sheet having a convex part by the following method, and then allowing to stand at a predetermined temperature, and the light reflectance (R1) on the convex part surface before this heat treatment. ) And the reflectance (R2) of the light on the convex surface after the heat treatment, the convex residual ratio (C) is calculated based on the following formula (1). Evaluation was performed.
C = (R2 / R1) × 100 (1)
○: C is 90 or more.
Δ: C is 80 or more and less than 90.
X: C is less than 80.

First, a smooth resin sheet (thickness: 100 μm) whose surface was not processed was cut to prepare a test piece having a size of 297 mm (MD direction) × 210 mm (TD direction). Then, this test piece was placed on the surface of a glass plate having a quadrangular pyramid shape, and convex portions having a height of 80 μm and having convex portions formed at intervals of 1 mm in the vertical and horizontal directions, and a laminator. Set. Then, preheating was performed at 170 ° C. for 3 minutes, and the shape was transferred at atmospheric pressure for 1 minute to produce an embossed decorative sheet. Subsequently, it left still for 30 minutes in the oven set to 150 degreeC, and heat processing was performed.
The light reflectance before and after the heat treatment was measured under the conditions of a temperature of 23 ° C. and a measurement angle of 60 degrees using “GH-26D” (model name) manufactured by Murakami Color Research Laboratory.

1-3. Heat Resistance A test piece was prepared from the embossed decorative sheet, and the dimensions in the extrusion direction of the thermoplastic resin composition as a raw material and the direction perpendicular thereto were measured before and after the heat treatment to examine the degree of change.
A square of 100 mm (MD) × 100 mm (TD) was drawn at the center of the surface of a test piece of 120 mm (MD: extrusion direction of resin from T die) × 120 mm (TD: method orthogonal to MD). This test piece was left still in a thermostat and heat-treated at 150 ° C. or 130 ° C. for 30 minutes in an air atmosphere. Thereafter, the test piece was taken out, the length of each side in the square MD and TD directions was measured at 25 ° C., and the shrinkage was calculated according to the following formula.
Shrinkage rate (%) = [{(length before heating) − (length after heating)} / (length before heating)] × 100
From the shrinkage rate obtained from the above formula, the heat resistance was evaluated according to the following criteria. In addition, the following shrinkage rate becomes a positive value when the test piece contracts after heating, and becomes a negative value when the test piece expands after heating.
○: Shrinkage rate (s) was −2.0% <s ≦ 0% or 0% ≦ s <2.0%.
Δ: Shrinkage rate (s) was −3.0% <s ≦ −2.0% or 2.0% ≦ s <3.0%.
X: Shrinkage rate (s) was s ≦ −3.0% or s ≧ 3.0%.

1-4. Film-forming property Using the apparatus shown in FIG. 4, the melted thermoplastic resin composition is supplied from the T-die 30 of the twin-screw T-die extruder to the transfer roll 40 (rotation speed 10 rpm) having a surface temperature of 95 ° C. And the position which leaves | separates from the transfer roll 40 before the soft film 50 moves to the cooling roll 45 was observed visually, and film forming property was evaluated (refer FIG. 5). FIG. 5A is a view of the transfer roll 40 and the soft film 50 as viewed from the lateral direction. The soft film 50 is separated from the position of the transfer roll 40 between 6 o'clock and 8 o'clock on the clock face. Indicates. FIG. 5 (a) is a view of the transfer roll 40 and the soft film 50 as viewed from the lateral direction. The soft film 50 is separated from the position of the transfer roll 40 between 5 o'clock and 6 o'clock on the clock face. Indicates. FIG. 5C is a view of the transfer roll 40 and the soft film 50 as viewed from the lateral direction. The soft film 50 is separated from the position of the transfer roll 40 before 5 o'clock on the dial of the watch. Show.
○: The soft film 50 is separated from the position shown in FIG.
(Triangle | delta): The soft film 50 left | separated from the position shown in FIG.
X: The soft film 50 has left | separated from the position shown in FIG.

1-5. Cracking property A smooth resin sheet (thickness: 100 μm) whose surface was not processed was bent in the MD direction, and the presence or absence of cracks was visually observed.
○: It was not cracked.
X: Cracking occurred.

1-6. Chemical resistance Chemical resistance was evaluated by using ethyl acetate soaked in a cotton swab using “Rubbing Tester” (trade name) manufactured by Ohira Rika Kogyo Co., Ltd.
A cotton swab soaked with ethyl acetate was rubbed on the surface of an unprocessed smooth resin sheet (thickness: 100 μm) at a load of 2 N for 10 reciprocations (10 seconds). Then, the part which contacted the cotton swab was visually observed.
○: There was no change.
Δ: Whitened.
X: Dissolved.

1-7. GPC
Using a high-speed GPC device “HLC-8220GPC” (model name) manufactured by Tosoh Corporation, tetrahydrofuran as a solvent and two “TSKgel Super Multipore HZ-H” (φ4.6 mm × 150 mm) as columns are connected to connect Mw and Mn. It was measured.

2. 2. Raw material for thermoplastic resin composition 2-1. Resin for rubber-modified aromatic vinyl resin (1) Graft copolymer (A1-1)
It is a graft copolymer obtained by emulsion polymerization of 43 parts of styrene and 17 parts of acrylonitrile in the presence of 40 parts of polybutadiene rubber. The graft ratio is 55%, and the intrinsic viscosity [η] of acetone-soluble matter (in methyl ethyl ketone, 30 ° C.) is 0.45 dl / g.
(2) Graft copolymer having a carboxyl group (A1-2)
It is a graft copolymer obtained by emulsion polymerization of 42.8 parts of styrene, 14.2 parts of acrylonitrile and 3 parts of methacrylic acid in the presence of 40 parts of polybutadiene rubber. The graft ratio is 61%, and the intrinsic viscosity [η] of acetone-soluble matter (in methyl ethyl ketone, 30 ° C.) is 0.51 dl / g.
(3) Graft copolymer (A1-3)
In the presence of 22 parts of an ethylene / propylene copolymer having a ratio of ethylene and propylene of 78:22 and a Mooney viscosity (ML _{1 + 4} , 100 ° C.) of 20, 54.6 parts of styrene and 23.4 parts of acrylonitrile. It is a graft copolymer obtained by solution polymerization. The graft ratio is 50%, and the intrinsic viscosity [η] of the acetone-soluble component is 0.47 dl / g.
(4) Vinyl copolymer (A2-1)
Styrene having a limiting viscosity [η] (in methyl ethyl ketone, 30 ° C.) of 0.75 dl / g obtained by solution polymerization of 70.5 parts of styrene and 29.5 parts of acrylonitrile, and having Mw of 170,000 and Mn of 76,000. -An acrylonitrile copolymer.

2-2. Polyamide resin (B-1)
Nylon 6 “Amilan CM1021T” (trade name) manufactured by Toray Industries, Inc. was used. The relative viscosity is 3.0, the melt viscosity by the Koka flow tester is 1200 Pa · s (230 ° C.), 740 Pa · s (250 ° C.), 90 Pa · s (270 ° C.), and the residual oligomer amount is 0.71. %.

2-3. Vinyl copolymer (C-1)
It is a styrene / acrylonitrile copolymer having Mw of 3.1 million and Mn of 550,000 obtained by emulsion polymerization of 72 parts of styrene and 28 parts of acrylonitrile.

2-4. Inorganic filler (D-1)
Talc “MW HS-T” (trade name) manufactured by Hayashi Kasei Co., Ltd. was used. The average particle diameter D50 based on the laser diffraction / scattering particle size distribution analyzer is 2.75 μm, and the apparent density based on JIS K5101 is 0.2 g / ml.

2-5. Hydrogenated styrene thermoplastic elastomer (E-1)
“Tuftec H1041” (trade name) manufactured by Asahi Kasei Chemicals Corporation was used. The ratio of styrene to ethylene butylene is 30:70, and the MFR (230 ° C., load 2.16 kg) based on ISO 1133 is 5.0 g / 10 min.

2-6. Polypropylene resin (F-1)
“NOVATEC PP FY6C” (trade name) manufactured by Nippon Polypro Co., Ltd. was used. The MFR (230 ° C., load 2.16 kg) based on JIS K7210 is 2.4 g / 10 minutes.

Examples 1-10
After mixing the raw materials with a Henschel mixer at the blending ratio shown in Table 1, using a twin screw extruder “TEX44” (model name) manufactured by Nippon Steel Works, it is melt kneaded at a barrel set temperature of 250 ° C. to be a thermoplastic resin. A composition was prepared. And the obtained composition was pelletized. In Table 1, “raw material” and “configuration” of “thermoplastic resin composition” are shown. “Functional group structural unit amount” in the “Configuration” column is the content ratio of the structural unit derived from methacrylic acid used for forming the resin A1-2 to the entire rubber-modified aromatic vinyl resin (A) before melt-kneading. Yes, the “rubber polymer amount” is the content of the rubber polymer (total amount) used for forming the graft copolymer (A1) with respect to the entire rubber-modified aromatic vinyl resin (A) before melt-kneading. It is.
Next, this pellet was supplied to an extruder of a film forming machine equipped with a T-die (die width 1400 mm, lip interval 0.5 mm) and a twin-screw T-die extruder with a screw diameter of 65 mm. Resin was discharged at a melting temperature of 270 ° C. to obtain a soft film. Thereafter, the soft film was brought into surface contact with a cast roll having a surface temperature set to 90 ° C. with an air knife and cooled and solidified to obtain a smooth resin sheet having a thickness of 100 μm.
Then, using a plastic embosser manufactured by Kojima Seisakusho, the smooth resin sheet (sheet before embossing) was passed through a 190 ° C. shibo roll at a line speed of 10 m / min, and had a quadrangular pyramid shape. An embossed decorative sheet was obtained in which convex portions having a length of 80 μm were widely formed on one surface at intervals of 1 mm in the width direction (TD direction) and the length direction (MD direction). The thickness of the part not having the convex part is 100 μm.

  About thermoplastic resin composition, evaluation of film forming property, about smooth resin sheet, evaluation of cracking property and chemical resistance, and about embossed decorative sheet, evaluation of convex portion residual property, vacuum formability and heat resistance Respectively. Furthermore, based on the following manufacture 1 and manufacture 2, using an embossed decorative sheet, an embossed decorative integrated molded product is manufactured, and the appearance of the obtained embossed decorative integrated molded product is visually observed, and the uneven pattern is When it was clear, it was indicated by “◯”. These results are shown in Table 1.

(Manufacturing 1)
The embossed decorative sheet is inserted into a female-type sheet mounting frame for a housing having a maximum long diameter of 300 mm, closed with a male mold to form a cavity, and Techno Polymer's ABS resin “Techno ABS130” (product) Name, MFR = 18.0 g / 10 min (temperature 220 ° C., load 98 N) was injected and filled to obtain an embossed decorative integrally molded product having a box shape. This is an all-electric injection molding machine “J35AD” (model name) manufactured, and the molding conditions are a cylinder temperature of 210 ° C. to 230 ° C., a nozzle temperature of 230 ° C., an injection pressure of 100 MPa, an injection speed of 40 mm / second, and a mold temperature of 60 ° C. .
(Manufacturing 2)
As an injection resin, an ABS / PC alloy “Excelloy CK10” (trade name, MFR = 15.0 g / 10 minutes (temperature 240 ° C., load 98 N) manufactured by Technopolymer Co., Ltd.), which is an equal mixture of polycarbonate resin and ABS resin, Embossed decorative integrally molded product in the same manner as in Production 1 except that the molding conditions are cylinder temperature 250 ° C. to 270 ° C., nozzle temperature 270 ° C., injection pressure 120 MPa, injection speed 70 mm / sec, mold temperature 70 ° C. Got.

Comparative Examples 1-9
A thermoplastic resin composition was prepared in the same manner as in Example 1 except that the raw materials were used at the blending ratio shown in Table 2, and then the smooth resin sheet was processed to obtain an embossed decorative sheet.

  About thermoplastic resin composition, evaluation of film forming property, about smooth resin sheet, evaluation of cracking property and chemical resistance, and about embossed decorative sheet, evaluation of convex portion residual property, vacuum formability and heat resistance Respectively. These results are shown in Table 2.

Comparative Example 10
After mixing the raw materials with a Henschel mixer at the blending ratios shown in Table 2, using a twin-screw extruder “TEX44” (model name) manufactured by Nippon Steel Works, kneaded at a barrel set temperature of 230 ° C., and the heat obtained The plastic resin composition was pelletized.
Next, this pellet was supplied to an extruder of a film forming machine equipped with a T die (die width 1400 mm, lip interval 0.5 mm) and an extruder with a screw diameter of 65 mm, and the melting temperature was 220 ° C. from the T die. The resin was discharged with a soft film. Thereafter, the soft film was brought into surface contact with a cast roll having a surface temperature set to 90 ° C. with an air knife and cooled and solidified to obtain a smooth resin sheet having a thickness of 100 μm.
Then, using a plastic embosser manufactured by Kojima Seisakusho Co., Ltd., the smooth resin sheet is passed through a 190 ° C. shibo roll at a line speed of 10 m / min, and has a quadrangular pyramid shape with a height of 80 μm. However, the embossed decorative sheet formed at intervals of 1 mm in the width direction (TD direction) and the length direction (MD direction) was obtained. The thickness of the part not having the convex part is 100 μm.

  Next, various evaluations were performed in the same manner as in Comparative Example 1. The results are shown in Table 2.

From Tables 1 and 2, the following is clear.
Comparative Example 1 is an example using only the polyamide resin (B-1), and the vacuum formability and film forming property were insufficient. Comparative Example 2 is an example in which only the graft copolymer (A1-1) having no functional group according to the present invention was used, and the convexity remaining property, heat resistance and chemical resistance were insufficient. . Comparative Examples 3 and 4 are examples in which the ratios of the rubber-modified aromatic vinyl resin (A) and the polyamide resin (B) according to the present invention are outside the scope of the present invention, both of which have insufficient vacuum formability. The convexity survivability was slightly inferior. In Comparative Example 4, the film forming property was further insufficient. Comparative Example 5 is an example in which neither the graft copolymer (A1-1) nor the vinyl copolymer (A2-1) has a functional group, and the vacuum formability and the convexity remaining property are not good. It was enough. Comparative Example 6 is an example in which the content of the structural unit derived from the functional group-containing vinyl monomer contained in the rubber-modified aromatic vinyl resin (A) is outside the scope of the present invention. The convexity survivability was insufficient. Comparative Example 7 was an example in which the content of the rubbery polymer contained in the modified aromatic vinyl resin (A) was small outside the scope of the present invention, and the vacuum moldability was insufficient. Comparative Examples 8 and 9 are examples in which the ratios of the rubber-modified aromatic vinyl resin (A) and the polyamide resin (B) according to the present invention are out of the scope of the present invention. The film forming property, cracking property and chemical resistance were insufficient. Comparative Example 10 is an example of the technique described in Japanese Patent Application Laid-Open No. 2011-25610, and the protrusion remaining property was insufficient.
On the other hand, Examples 1-10 are examples of the embossed decorative sheet and the embossed decorative integrated product of the present invention, and were excellent in various performances.

  The embossed decorative sheet of the present invention is used for interior materials for vehicles such as automobiles, construction materials such as baseboards and rims, interior materials such as window frames and door frames, interior materials for buildings such as walls, floors and ceilings, and games. Cases, surface materials and containers for home appliances such as machines, mobile phones, computers, washing machines, refrigerators, vacuum cleaners, rice cookers, microwave ovens, television receivers, air conditioners, audio equipment, video equipment, lighting equipment, musical instruments, etc. It is suitable as a skin material used for the formation of an embossed decorative integrated product such as an embossed decorative integrated product, and the resulting embossed decorative integrated product also has a clear concavo-convex pattern and an excellent appearance.

1: Embossed decorative integrated molded article 10: Molten thermoplastic resin composition (Z)
11: Core part 20: Embossed decorative sheet 21: Skin part 22: Embossed surface 30: T die 40: Transfer roll 45: Cooling roll 50: Soft film 60: Pre-embossed sheet 70: Processed molded product 80: Vacuum molding Mold 81: injection mold (male mold)
82: Injection mold (female)
85: Suction hole

Claims (7)

It is used as a skin material in a molding method by injection molding, an embossed decorative sheet having a convex portion on the surface on at least one surface side,
(A) A thermoplastic resin composition obtained by melt-kneading a raw material containing a rubber-modified aromatic vinyl resin and (B) a polyamide resin,
The rubber-modified aromatic vinyl resin (A) was obtained by polymerizing a vinyl monomer (b1) containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of the rubbery polymer (a). The graft copolymer (A1) or a mixture of the graft copolymer (A1) and a vinyl (co) polymer (A2) of a vinyl monomer (b2),
At least one of the vinyl monomer (b1) and the vinyl monomer (b2) is a hydroxyl group-containing unsaturated compound, an epoxy group-containing unsaturated compound, a substituted or unsubstituted amino group-containing unsaturated compound, Including at least one functional group-containing vinyl monomer selected from the group consisting of a carboxyl group-containing unsaturated compound, an acid anhydride group-containing unsaturated compound, and an oxazoline group-containing unsaturated compound,
The vinyl-based (co) polymer (A2) has a weight average molecular weight of less than 500,000,
The content of the structural unit derived from the functional group-containing vinyl monomer contained in the rubber-modified aromatic vinyl resin (A) is from 0.1 to the rubber-modified aromatic vinyl resin (A). 1.2% by weight,
The ratios of the rubber-modified aromatic vinyl resin (A) and the polyamide resin (B) are 35 to 75% by mass and 25 to 65% by mass, respectively, when the total of both is 100% by mass,
The content of the rubbery polymer (a) is 5 to 30% by mass when the total of the rubber-modified aromatic vinyl resin (A) and the polyamide resin (B) is 100% by mass. Characteristic embossed decorative sheet.   The rubber-modified aromatic vinyl resin (A) is a graft copolymer (A11) obtained by polymerizing a vinyl monomer composed of an aromatic vinyl compound and a vinyl cyanide compound in the presence of a rubbery polymer. And a graft copolymer (A12) obtained by polymerizing a vinyl monomer composed of an aromatic vinyl compound, a vinyl cyanide compound and a carboxyl group-containing unsaturated compound in the presence of a rubbery polymer. The embossed decorating sheet according to claim 1 comprising:   The thermoplastic resin composition further includes a vinyl (co) polymer (C) having a weight average molecular weight of 1,500,000 to 5,000,000, and the vinyl (co) polymer (C) is an aromatic vinyl compound. At least one of structural units derived from (meth) acrylic acid alkyl ester compounds, and the content ratio of the vinyl (co) polymer (C) is the rubber-modified aromatic vinyl resin ( The embossed decorative sheet according to claim 1 or 2, wherein the embossed decorative sheet is 0.1 to 5 parts by mass with respect to 100 parts by mass in total of A) and the polyamide resin (B).   The thermoplastic resin composition further includes an inorganic filler, and the content of the inorganic filler is 100 parts by mass in total of the rubber-modified aromatic vinyl resin (A) and the polyamide resin (B). It is 1-10 mass parts, The embossing decorating sheet as described in any one of Claims 1 thru | or 3.   The embossed decorative sheet according to claim 4, wherein the inorganic filler is talc. An embossed decorative integral molded product obtained using the embossed decorative sheet according to any one of claims 1 to 5 and a thermoplastic resin composition (Z),
An embossed decorative unit characterized in that a skin part made of the embossed decorative sheet and a core part made of the thermoplastic resin composition (Z) are joined, and has a convex part on the surface of the skin part. Molding.   The thermoplastic resin composition (Z) contains at least one resin selected from the group consisting of an aromatic vinyl resin containing a structural unit derived from an aromatic vinyl compound and a polycarbonate resin. Embossed decorative integrated molded product.

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