JP2011025610A - Embossed decorative sheet for skin material, laminate of embossed decorative sheet and adhesive layer, and integral molding of embossed decorative sheet using embossed decorative sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an embossed decorative sheet capable of simultaneously solving both collapse of embossing in injection molding and whitening of the sheet, and to provide a laminate in which the embossed decorative sheet and an adhesive layer are laminated so that a core material may fully stick to the embossed decorative sheet. <P>SOLUTION: The embossed decorative sheet which acts as a skin material in an injection molding process, wherein the embossed decorative sheet does not whiten in bending test, is 70% or more in embossing residual factor after injection molding as measured by 60° reflectance and is 20% or less in the rate of gate damage area of the embossing decorative surface. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

The present invention relates to an embossed decorative sheet used as a skin material in a molding method by injection molding, a laminate of the embossed decorative sheet and an adhesive layer, and an embossed decorative integrally molded product using the embossed decorative sheet About.

The main production methods for the skin and core material are the skin insert integrated molding method in which the core material is injection-molded onto the skin material, and the two-stage molding method in which the skin is pasted after the core material is molded. However, the two-stage molding method is difficult to mold curved surfaces, and it takes time to manufacture and is inferior in productivity. In recent years, water-based and solvent-based adhesives have been applied as the skin material. A method (Patent Documents 1 and 2) in which a decorative sheet is integrally formed with an insert is mainly used.

In skin insert molding, high heat and pressure are applied to the skin material during injection molding, and the skin material may be deformed or damaged. Especially, a sheet with embossed decoration is used as the skin material. If so, the embossed decoration is crushed, and there is a tendency that only an object with a tactile sensation without unevenness can be obtained. In addition, it is known that by using a foam composite sheet with a foam layer formed on the back surface of the skin material, it is possible to produce a skin integrated molded product while retaining the embossed decoration to some extent. However, there is a problem that the followability with respect to the curved surface portion of the end surface of the molded product is lost.

In recent years, skin-integrated molded products such as various electronic equipment casings are becoming thinner and lighter, and the thickness of the skin material is also required to be thinner. In order to reduce the thickness, a skin integrated molded product using a skin material without a foam layer is being studied. For example, as an ingenuity from the mold surface, use a mold that has been embossed on the inner surface of the mold cavity, set a non-decorated sheet, inject the core material, and heat the core material to emboss the sheet It has been proposed to obtain a skin integrated molded product that is processed simultaneously and embossed on the sheet surface. Although this method can provide a skin-integrated molded product with sufficient unevenness on the surface and a high appearance design and touch, it is necessary to prepare an expensive injection mold for each embossing design, so it can be used for various embossing decoration variations. It is impossible to cope with this, and it is expensive to obtain a variety of integrally molded products.

Also, in recent years, there has been a rapid diversification of design variations in fields such as various electronic equipment casings, and in order to respond to this, integrated skin molded products using transfer foil and insert film are used. ing. However, the integrated skin molded product using transfer foil and insert film can realize abundant design variations, but there is a problem that excellent appearance design and tactile sensation cannot be obtained because there are few irregularities on the surface. There is a need for a skin integral molded product (embossed decorative integral molded product) using a decorative sheet.

Another means for suppressing the collapse of the embossed decorative sheet is to devise the composition of the decorative sheet and balance with other physical properties required for the sheet. Here, in order to improve the emboss crush caused by the injection pressure and shearing heat generation at the time of injection molding, when the high heat resistant resin is simply used, the sheet itself becomes fragile, and the curved surface portion of the end face of the molded product is whitened, There arises a problem that the sheet is whitened due to rough handling of the sheet or dropping during transportation, resulting in material loss. Moreover, when a soft resin is added to avoid whitening, the heat resistance is lowered and it is difficult to avoid emboss crushing. Further, there is a problem that gloss and resin flow traces appear in the vicinity of the gate portion, which is a resin injection port, and in the vicinity of the gate, which is called gate damage, and the appearance on the decoration side is impaired. Thus, it was very difficult to solve the problems of emboss crushing and whitening at the same time by the conventional method.

Japanese Patent No. 3314271 JP-A-9-183163

An object of the present invention is to provide an embossed decorative sheet capable of simultaneously solving both embossing crushing and whitening of a sheet during injection molding, and a method for producing the same. Another object of the present invention is to provide a laminate in which the embossed decorative sheet and an adhesive layer are laminated so that the core material is sufficiently adhered to the embossed decorative sheet, and a method for producing the same. is there.

As a result of intensive studies to solve the above problems, the present inventors have found that a sheet having specific physical properties has no embossed crushing at the time of injection molding, and has a characteristic that it is difficult to whiten. In order to express the physical properties, it has been found that it is most suitable to use a thermoplastic resin sheet having a specific composition, and the present invention has been completed.

That is, the present invention
(1) An embossed decorative sheet used as a skin material in a molding method by injection molding,
It is characterized by not being whitened in a bending test and having an embossing residual ratio after injection molding measured by using a 60 ° reflectance of 70% or more and a gate damage area ratio of an embossed decorative surface of 20% or less. Embossed decorative sheet.
(2) The composition according to (1), comprising (A) 20 to 70% by weight of a styrenic resin, (B) 5 to 40% by weight of a polyolefin, and (C) 5 to 40% by weight of a thermoplastic elastomer. Embossed decorative sheet.
(3) The composition further comprises (D) 1 to 30 parts by weight of a modified polyolefin, with respect to 100 parts by weight of the total amount of the component (A), the component (B), and the component (C). (2) The embossed decorative sheet as described.
(4) The styrene resin of component (A) is acrylonitrile / conjugated diene rubber / styrene copolymer, acrylonitrile / olefin rubber / styrene copolymer, acrylonitrile / acrylic rubber / styrene copolymer, methyl methacrylate / conjugated diene rubber, The embossed decorative sheet according to (2) or (3), comprising at least one selected from a styrene copolymer and high impact polystyrene.
(5) The component (B) polyolefin is a polypropylene having a melt flow rate of 0.1 to 20 g / 10 min and a load deflection temperature of 70 to 160 ° C. The embossed decorative sheet described.
(6) The embossed decorative sheet according to any one of (2) to (5), wherein the thermoplastic elastomer of component (C) has a Shore A hardness of 20 to 80 in JIS K 6253.
(7) The modified polyolefin of component (D) is a polyolefin modified with a polar group, has a melt flow rate of 0.1 to 100 g / 10 min, and a Vicat softening point in JIS K 7206 of 40 to 100 ° C. The embossed decorative sheet according to any one of (3) to (6).
(8) The embossed decorative sheet according to any one of (1) to (7) and an adhesive layer, wherein the adhesive layer is laminated on a surface opposite to the embossed decorative surface of the embossed decorative sheet. A laminated body.
(9) The laminate according to (8), wherein the adhesive layer is composed of at least one selected from a solvent-based adhesive, a water-based adhesive, and a hot-melt adhesive.
(10) The laminate according to (9), wherein the hot melt adhesive mainly comprises an olefin elastomer and / or a styrene elastomer.
(11) The laminate according to (9), wherein the hot-melt adhesive has a modified polyolefin as a main component.
(12) The laminate according to any one of (9) to (11), wherein the hot-melt adhesive is an adhesive resin composition further containing a tackifier.
(13) The laminate according to any one of (10) to (12), wherein the hot melt adhesive is in a film form.
(14) After kneading the raw material components, the obtained raw material composition is molded to produce a sheet, and the sheet is laminated with an adhesive layer and embossed. (10) to (13) The manufacturing method of the laminated body in any one.
(15) An embossed decorative integrally formed product comprising the embossed decorative sheet according to any one of (1) to (7) and a core material.
(16) An embossed decorative integrally formed product comprising the laminate according to any one of (8) to (13) and a core material.
(17) The emboss residual rate measured using 60 ° reflectance is 70% or more, and the gate damage area rate of the embossed decorative surface is 20% or less (15) or (16) The embossed decorative integrated molded product described.
(18) A thermoplastic resin is injected onto the embossed decorative sheet according to any one of (1) to (7) or the embossed decorative surface of the laminate according to any one of (8) to (13). (15) to (17), characterized in that the temperature of the thermoplastic resin at the time of injection molding is 160 to 300 ° C., and the injection pressure at this time is 50 to 500 MPa. The manufacturing method of the embossed decorative integral molded article in any one.
I will provide a.

A decorative sheet with significantly improved emboss residual rate and gate damage resistance can be obtained.

It is a figure which shows the 60 degree reflectivity measurement position, gate damage area, and adhesiveness evaluation method in the embossed decorating sheet which concerns on this invention.

In the present invention, it is an embossed decorative sheet used as a skin material in a molding method by injection molding, and does not whiten in a bending test, and an embossing residual rate after injection molding measured by using a 60 ° reflectance is 70. An embossed decorative sheet is provided in which the gate damage area ratio of the embossed decorative surface is 20% or less.

The bending test is to test the degree of whitening of the sheet when the sheet is held by hand and bent by 90 degrees, and the presence or absence of whitening when the sheet is returned to its original state. The degree of whitening is determined visually. In the bending test, even if the sheet is not whitened or is whitened when bent, it is recovered to the extent that whitening is not noticeable when the sheet is returned to the original position. It is possible to avoid the problem that the sheet is whitened due to whitening or rough handling after sheet forming or dropping during transportation, resulting in material loss.
“No whitening in the bending test” means that the sheet does not whiten in the bending test, or even if the sheet is whitened when folded, the whitening is restored to an inconspicuous state when returned to the original position. To do.

Emboss residual ratio (%) after injection molding measured using 60 ° reflectivity is 60 ° reflectivity of embossed decorative surface before injection molding / injection molding for embossed decorative sheet subjected to injection molding. It is a numerical value calculated | required by the type | formula of the 60 degree reflectance x100 of a back embossing decoration surface.
More specifically, an embossed decorative sheet is set (inserted) in an injection mold, and thermoplastic resin is injected (injected) on the opposite side of the embossed decorative surface (the back side of the embossed decorative sheet). As shown in FIG. 1, on the embossed decorative surface of the test piece (120 mm square), before injection molding and after injection molding, the gate of the injection mold (open port to the mold cavity; high (2 mm in width × 5 mm in width) The 60 ° reflectance at a portion of 30 mm to 50 mm from the side in contact with the forming surface is measured using a gloss meter, and the emboss residual rate is calculated based on the above formula.
The emboss residual rate is 70% or more, preferably 80% or more, and more preferably 85% or more. A numerical value lower than 70% is not preferable in appearance because gloss appears in the molded product.

Gate damage refers to a phenomenon in which the embossing of the embossed decorative sheet is crushed by the resin pressure and shearing heat generation during injection molding, and gloss and resin flow traces appear, impairing the appearance of the embossed decorative surface. In order to quantify the gate damage, a gate damage area ratio (%) given by the formula: gate damage area of injection molded product ÷ embossed decorative area of injection molded product × 100 is introduced. Specifically, for the embossed decorative sheet subjected to injection molding as described above, as shown in FIG. 1, on the embossed decorative surface of a test piece (120 mm square), an injection mold gate ( The gate damage generated in the vicinity of the height (2 mm × width 5 mm) is visually confirmed, and the ratio of the area to the embossed decoration area (that is, 120 mm × 120 mm) of the injection molded product is calculated.
The gate damage area ratio is 20% or less, preferably 15% or less, and more preferably 10% or less. By suppressing the content to 20% or less, a molded product excellent in the appearance of the embossed decorative surface can be obtained. When the gate damage area ratio is larger than 20%, the glossy part is more conspicuous, and the embossed crushing spreads over the entire molded product, which is not preferable in appearance.

It is not whitened in the bending test of the present invention, the emboss residual ratio after injection molding measured using 60 ° reflectance is 70% or more and the gate damage area ratio of the embossed decorative surface is 20% or less. The composition constituting the resin sheet for producing the embossed decorative sheet is characterized by (A) 20 to 70% by weight of styrene resin, (B) 5 to 40% by weight of polyolefin, and (C) heat. It is preferable to use a composition comprising 5 to 40% by weight of a plastic elastomer (however, the total amount of the component (A), the component (B) and the component (C) is 100% by weight).

The (A) component styrenic resin has features such as heat resistance, flexibility, weather resistance (light) resistance, chemical resistance, and moldability, and the embossed decorative sheet as a skin material. Suitable as the main raw material. Various types of styrenic resins can be used without particular limitation. For example, ABS (acrylonitrile / conjugated diene rubber / styrene copolymer), AES (acrylonitrile / olefin rubber / styrene copolymer), AAS (acrylonitrile / acrylic rubber / styrene copolymer), MBS (methyl methacrylate / methyl methacrylate / Conjugated diene rubber / styrene copolymer), HIPS (high impact polystyrene), and the like.
Among these, ABS, AES, and MBS are more preferable from the viewpoint of heat resistance and flexibility.

The amount of component (A) is preferably 20 to 70% by weight, more preferably 30 to 70% by weight, and still more preferably 40 to 70% by weight. If it is less than 20% by weight, the shrinkage of the sheet increases, and if it exceeds 70% by weight, whitening tends to occur, which is not preferable.

Various types of polyolefin can be used as the component (B) polyolefin. For example, polyethylene such as low density polyethylene, high density polyethylene, linear low density polyethylene, homopolypropylene, random polypropylene, block polypropylene, etc. Polypropylene, polybutene-1, poly-4-methylpentene-1, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, ethylene-butene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid Examples thereof include copolymers having ethylene as a main component, such as ester copolymers.
Among polyolefins, it has high heat resistance and is particularly effective in suppressing emboss crushing due to heating during injection molding. Various types are easily available, are inexpensive, and are lightweight materials. Polypropylene is preferable in that it has characteristics such as properties, chemical resistance, waterproofness and heat sealability.

Polypropylene preferably has a melt flow rate of 0.1 to 20 g / 10 min and a load deflection temperature of 70 to 160 ° C., and can be used without limitation of random, homo, and block.
Here, the melt flow rate is MFR in JIS K 7210. The melt flow rate is more preferably from 0.1 to 15 g / 10 minutes, and further preferably from 0.1 to 10 g / 10 minutes. If the melt flow rate is less than 0.1 g / 10 min, surface properties are reduced during sheet molding. If it is greater than 20 g / 10 min, compatibility with the component (A) is improved due to an extreme improvement in fluidity. Is not preferable.
The load deflection temperature is based on JIS K 7191. The load deflection temperature is more preferably 70 to 140 ° C, and further preferably 70 to 120 ° C. When the load deflection temperature is lower than 70 ° C., sufficient heat resistance is not exhibited and the gate damage area ratio increases, and when it is higher than 160 ° C., it becomes difficult to balance heat resistance and flexibility.

(B) As a compounding quantity of a component, 5 to 40 weight% is preferable, 5-35 weight% is more preferable, and 10 to 30 weight% is further more preferable. If it is less than 5% by weight, sufficient heat resistance cannot be imparted, and there is a great possibility that the residual embossing rate and the gate damage property are deteriorated. When the amount is more than 40% by weight, the balance between flexibility and heat resistance cannot be achieved, and the shrinkage rate is increased, which is not preferable.

The thermoplastic elastomer of component (C) preferably has a Shore A hardness of 20 to 80 in JIS K 6253, more preferably a soft type with a Shore A hardness of 20 to 60, and a Shore A hardness of 30 to 30. More preferably, it is 50. If the Shore A hardness is less than 20, the adhesiveness becomes strong, and in the sheeting and embossing steps, a problem of sticking to the roll occurs or it becomes difficult to balance physical properties. On the other hand, if it is greater than 80, the sheet becomes too hard and it is difficult to prevent whitening.

Examples of such thermoplastic elastomers include polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, diene rubber such as polyisoprene, ethylene-α-olefin copolymer, ethylene-α-olefin. -Non-diene rubber such as polyene copolymer, styrene-butadiene diblock copolymer, hydrogenated styrene-butadiene diblock copolymer, styrene-isoprene block copolymer, hydrogenated styrene-isoprene block copolymer Polymer, styrene-isobutylene diblock copolymer, styrene-butadiene-styrene triblock copolymer, hydrogenated styrene-butadiene-styrene triblock copolymer, styrene-isoprene-styrene triblock copolymer, hydrogenated styrene- Isoprene Examples include a ethylene triblock copolymer, a styrene-isobutylene-styrene triblock copolymer, an ethylene-propylene elastomer, a styrene-grafted ethylene-propylene elastomer, and an ethylene ionomer resin.
Among these, since the compatibility with the styrene resin of the component (A) and the polyolefin resin of the component (B) is good and flexibility can be imparted without lowering the heat resistance, styrene Butadiene diblock copolymer, hydrogenated styrene-butadiene diblock copolymer, styrene-isobutylene diblock copolymer, styrene-isoprene diblock copolymer, hydrogenated styrene-isoprene diblock copolymer, styrene-isobutylene Diblock copolymer, styrene-butadiene-styrene triblock copolymer, hydrogenated styrene-butadiene-styrene triblock copolymer, styrene-isoprene-styrene triblock copolymer, hydrogenated styrene-isoprene-styrene triblock Copolymer, styrene-isobutylene-styrene Styrenic thermoplastic elastomers and dynamically crosslinked olefin elastomer emissions triblock copolymer are preferable.

(C) As a compounding quantity of a component, 5 to 40 weight% is preferable, 5 to 30 weight% is more preferable, and 5 to 20 weight% is further more preferable. If it is less than 5% by weight, the flexibility is inferior and whitening tends to occur. If it is more than 40% by weight, the gate damage area ratio increases due to a decrease in heat resistance, and the cost increases, which is not preferable.

In the present invention, there is no whitening by using a composition containing the (A) component styrene resin, the (B) component polyolefin, and the (C) component thermoplastic elastomer in an appropriate blending ratio. An embossed decorative sheet with improved emboss crushing and gate damage during injection molding can be obtained, but for the purpose of further improving the compatibilization of these three components, a modified polyolefin of component (D) is further blended. May be.

The (D) modified polyolefin is not particularly limited, and various types can be used, but a polyolefin modified with a polar group is preferred. For example, a polymer obtained by oxidizing or copolymerizing an α-olefin such as ethylene, propylene, butene-1, 4-methylpentene-1 or octene-1 and introducing a carboxyl group; Random copolymer of ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-glycidyl acrylate copolymer, ethylene-glycidyl methacrylate and the above α-olefin and ethylenically unsaturated carboxylic acid or its derivative And the like.

It is also possible to use a modified polyolefin obtained by graft polymerization of an ethylenically unsaturated carboxylic acid or a derivative thereof to a polyolefin. There is no restriction | limiting in particular as polyolefin, What was shown by the specific example of (B) component can be used. The ethylenically unsaturated carboxylic acid or derivative thereof is a compound having an ethylenic double bond and at least one carboxylic acid or derivative part thereof in the molecule. Specifically, acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, norbornene dicarboxylic acid, bicyclo [2,2,1] hept-2-ene-5 , 6-dicarboxylic acid and the like, or acid anhydrides or derivatives thereof (for example, acid halides, amides, imides, esters, etc.). Specific examples of the compound include maleenyl chloride, maleenylimide, maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylic acid. Acid anhydride, dimethyl maleate, monomethyl maleate, diethyl maleate, diethyl fumarate, dimethyl itaconate, diethyl citraconic acid, dimethyl tetrahydrophthalate, bicyclo [2,2,1] hept-2-ene-5,6- Examples thereof include dimethyl dicarboxylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, aminoethyl methacrylate and aminopropyl methacrylate. Among these, acrylic acid, methacrylic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylic anhydride, Hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, and aminopropyl methacrylate are preferred.

The amount of the ethylenically unsaturated carboxylic acid or derivative thereof used is not particularly limited, but is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the main chain polyolefin. When the amount is less than 0.1 parts by weight, the effect of compatibilization is small. When the amount is more than 20 parts by weight, a large amount of residual monomer is generated, which adversely affects physical properties.

When graft-polymerizing an ethylenically unsaturated carboxylic acid or a derivative thereof to polyolefin, other monomers may be used within a range not impairing the object of the present invention. Other monomers include hydroxyl group-containing ethylenically unsaturated compounds, amino group-containing ethylenically unsaturated compounds, epoxy group-containing ethylenically unsaturated compounds, aromatic vinyl compounds, conjugated diene compounds, vinyl ester compounds, vinyl chloride. And oxazoline group-containing unsaturated monomers.
Among these, aromatic vinyl compounds and conjugated diene compounds are suppressed in molecular chain scission during grafting to molecular chain-cleavable polyolefins such as polypropylene, and the ethylenically unsaturated carboxylic acid is maintained while maintaining a high molecular weight. Since an acid or its derivative can be introduce | transduced in a high ratio, it is preferable.

Examples of aromatic vinyl compounds include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-chlorostyrene, m-chlorostyrene, p-chloromethylstyrene, 4- Vinylpyridine, 2-vinylpyridine, 5-ethyl-2-vinylpyridine, 2-methyl-5-vinylpyridine, 2-isopropenylpyridine, 2-vinylquinoline, 3-vinylisoquinoline, N-vinylcarbazole, N-vinylpyrrolidone And so on.
Examples of the conjugated diene compound include 1,3-butadiene, isoprene, and piperylene.

A modified polyolefin is obtained by reacting the above polyolefin with an ethylenically unsaturated carboxylic acid or derivative thereof and, if necessary, other monomers by heating in the presence or absence of a radical polymerization initiator. be able to.
Examples of radical polymerization initiators include organic peroxides and azo compounds. Illustrative examples include ketone peroxides such as methyl ethyl ketone peroxide and methyl acetoacetate peroxide; 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t- Peroxyketals such as butylperoxy) cyclohexane, n-butyl-4,4-bis (t-butylperoxy) valerate, 2,2-bis (t-butylperoxy) butane; permethane hydroperoxide, 1 , 1,3,3-tetramethylbutyl hydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, etc .; dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butyl Peroxy) hexane, α, α′-bis ( -Butylperoxy-m-isopropyl) benzene, t-butylcumyl peroxide, di-t-butyl peroxide, dialkyl such as 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3 Peroxides; diacyl peroxides such as benzoyl peroxide; peroxydicarbonates such as di (3-methyl-3-methoxybutyl) peroxydicarbonate and di-2-methoxybutylperoxydicarbonate; t-butylperoxy Octate, t-butyl peroxyisobutyrate, t-butyl peroxylaurate, t-butyl peroxy-3,5,5-trimethylhexanoate, t-butyl peroxyisopropyl carbonate, 2,5-dimethyl -2,5-di (benzoylperoxy) hexa , T- butyl peroxy acetate, t- butyl peroxybenzoate, one or more organic peroxides such as peroxy esters such as di -t- butyl peroxy isophthalate and the like.

Of these, those having a particularly high hydrogen abstraction ability are preferred. Examples of such radical polymerization initiators include 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1. Peroxyketals such as bis (t-butylperoxy) cyclohexane, n-butyl-4,4-bis (t-butylperoxy) valerate, 2,2-bis (t-butylperoxy) butane; dicumyl Peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, α, α'-bis (t-butylperoxy-m-isopropyl) benzene, t-butylcumyl peroxide, di Dialkyl peroxides such as t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3; Diacyl peroxides such as benzoyl peroxide; t-butyl peroxyoctate, t-butyl peroxyisobutyrate, t-butyl peroxylaurate, t-butyl peroxy-3,5,5-trimethylhexanoate , T-butylperoxyisopropyl carbonate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate, t-butylperoxybenzoate, di-t-butylperoxyisophthalate 1 type, or 2 or more types, such as peroxyesters.

The addition amount of the radical polymerization initiator is preferably in the range of 0.01 to 10 parts by weight and in the range of 0.2 to 5 parts by weight with respect to 100 parts by weight of the polyolefin resin. Further preferred. If it is less than 0.01 part by weight, the modification does not proceed sufficiently, and if it exceeds 10 parts by weight, fluidity and mechanical properties may be lowered.
Graft modification of a polyolefin-based polymer can be performed by a conventionally known method. For example, a polyolefin-based polymer is dissolved in an organic solvent, and then an ethylenically unsaturated carboxylic acid or a derivative thereof, and if necessary, other graft units. A monomer and a radical initiator are added to the solution and reacted at a temperature of 70 to 200 ° C., preferably 80 to 190 ° C., for 0.5 to 15 hours, preferably 1 to 10 hours.

It can also be obtained by heating, kneading, and reacting the polyolefin polymer, the graft monomer, and the radical polymerization initiator in the absence of solvent using an extruder or the like. The reaction temperature is equal to or higher than the melting point of the polyolefin polymer, specifically in the range of 120 to 250 ° C. The reaction time under such temperature conditions is usually 0.5 to 10 minutes.

The blending amount of the component (D) is preferably 1 to 30 parts by weight, preferably 1 to 20 parts by weight when the total blending amount of the components (A), (B), and (C) is 100 parts by weight. Part is more preferable, and 3 to 15 parts by weight is still more preferable. If it is less than 1 part by weight, the compatibilizing effect of the (A) component styrene resin, the (B) component polyolefin and the (C) component thermoplastic elastomer is poor, and the embossing residual rate is deteriorated and whitening occurs. If the amount is more than 30 parts by weight, it is not preferable because the gate damage is deteriorated and a problem of sticking to the roll surface during sheet molding may occur.

As the physical properties of the component (D), it is preferable that the melt flow rate is 0.1 to 100 g / 10 min, and the Vicat softening point in JIS K 7206 is in the range of 40 to 100 ° C., more preferably, the melt flow rate is 0 0.1 to 50 g / 10 min, and Vicat softening point in JIS K 7206 is 50 to 80 ° C. The melt flow rate is more preferably 0.1 to 20 g / 10 min. When the melt flow rate is less than 0.1 g / 10 min, unevenness tends to appear in the sheet before embossing, and when it is greater than 100 g / 10 min, there is a tendency that tackiness appears in the sheet itself. The Vicat softening point is more preferably 55 to 80 ° C. When the Vicat softening point is lower than 40 ° C., the heat resistance of the sheet tends to be lowered, and when higher than 100 ° C., the flexibility of the sheet tends to be impaired.

Furthermore, the resin composition for embossed decorative sheets of the present invention is generally well known for the purpose of imparting moldability, such as antioxidants, metal deactivators, phosphorus processing stabilizers, ultraviolet absorbers, ultraviolet rays. Stabilizers, optical brighteners, metal soaps, antacid adsorbents, or crosslinking agents, chain transfer agents, nucleating agents, lubricants, plasticizers, fillers, reinforcing materials, pigments, dyes, flame retardants, electrification You may add additives, such as an inhibitor, in the range which does not impair the effect of this invention.

A resin sheet used for manufacturing the embossed decorative sheet of the present invention can be obtained by kneading each of the above components to prepare a raw material composition, molding and forming a sheet. The kneading of each component can be performed by using, for example, an extruder, a Banbury mixer, a mill, a kneader, a heating roll, or the like. The sheet can be formed by a conventionally used molding method such as calendar molding, T-die extrusion molding or press molding.

The embossed decorative sheet used as the skin material is embossed on one side, and an embossed pattern such as irregularities is given, and the embossed surface is the surface side of the skin material in the embossed decorative integrated molded product (Hereinafter also referred to as the surface side of the embossed decorative sheet). The embossing is not particularly limited. For example, the embossing is performed by a method of applying an embossing pattern such as an uneven relief pattern on the surface by applying pressure to the resin sheet heated to an appropriate temperature with an embossing roll (for example, embossing roll). be able to. Moreover, the heating temperature of a sheet | seat should just be more than the softening temperature of a sheet | seat, Although it does not specifically limit, It is preferable that it is 160-220 degreeC. In addition, the surface side of the embossed decorative sheet may be further subjected to surface treatment, printing, painting, hard coat treatment, and the like, as long as the object and effect of the present invention are not impaired. Printing and painting are not particularly limited, and can be performed by conventional methods such as gravure printing, silk screen printing, and offset printing.

The thickness of the embossed decorative sheet is preferably in the range of 200 μm to 1500 μm. If it is thinner than 200 μm, the gate damage is remarkable, the design of the embossed decorative integrated product is deteriorated, and the emboss may be lost. Also, if the thickness of the embossed decorative sheet is greater than 1500 μm, the core cavity thickness becomes extremely thin at the time of injection molding, resulting in an extremely thin core material, resulting in an incomplete molded product (short shot). Is not preferable.

An embossed decorative integrated molded product can be obtained by injecting a resin as a core material into the embossed decorative sheet obtained as described above.

Moreover, the embossed decorative integral molded product according to the present invention can also be obtained by injecting a resin serving as a core material into a laminate in which an adhesive layer is laminated on the back side of the embossed decorative sheet. The embossed decorative sheet and the core material can be welded by heat during injection molding, but sufficient adhesion can be imparted by interposing an adhesive layer.
The adhesive used in the adhesive layer is not particularly limited, and various types such as water-based, solvent-based, and hot-melt type can be used. Based on the composition of the skin material and the core material to be used What is necessary is just to select suitably.

Examples of water-based adhesives include vinyl acetate resin emulsion type, vinyl acetate copolymer resin emulsion type, EVA resin emulsion type, acrylic resin emulsion type, phenol resin emulsion type, urea resin emulsion type, melamine resin type An emulsion type, a synthetic rubber latex type, etc. are mentioned.
Examples of the solvent-based adhesive include a vinyl acetate resin solvent type, an acrylic resin solvent type, a chloroprene solvent type, and a rubber solvent type.

Examples of hot melt adhesives include ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer, ethylene-methacrylic acid copolymer. Copolymer, ethylene-maleic anhydride copolymer, ethylene-ethyl acrylate-maleic anhydride copolymer, ethylene-glycidyl methacrylate copolymer, ethylene-glycidyl methacrylate-vinyl acetate copolymer, ethylene-glycidyl methacrylate-methyl acrylate copolymer Polymer, ethylene-methacrylic acid-maleic anhydride copolymer, ethylene-glycidyl methacrylate-vinyl acetate copolymer, maleic anhydride grafted polypropylene, maleic anhydride grafted ethylene-vinyl acetate copolymer, Polyolefin hot melt adhesives such as water maleic acid grafted polyethylene, urethane adhesives, synthetic rubber hot melt adhesives, polyester hot melt adhesives, polyamide hot melt adhesives, olefin thermoplastics Elastomer resins, styrene thermoplastic elastomer resins, urethane thermoplastic elastomer resins, ester thermoplastic elastomer resins, amide thermoplastic elastomer resins, and the like can be used.
In addition, it is possible to use reactive adhesives such as epoxy resin adhesives, cyanoacrylate adhesives, polyurethane adhesives, acrylic resin adhesives, and pressure sensitive adhesives such as natural rubbers and acrylics. It is.

Since the hot melt adhesive does not contain a solvent, it can be applied relatively thickly to the skin material (embossed decorative sheet). When the adhesive layer is thick, it acts as a cushion layer against heat and pressure during injection molding, which can advantageously improve gate damage and emboss crushing.
Examples of hot melt adhesives include ethylene-propylene copolymers that are olefin elastomers and their elastomers, ethylene-α-olefin copolymers, and styrene-butadiene copolymers (SBR) that are styrene elastomers and their hydrogen. Chemical compound, styrene-isobutylene-styrene (SIBS), and styrene-ethylene-propylene-styrene (SEPS) are preferable in terms of tackiness and adhesiveness.
In addition, when bonding an embossed decorative sheet for skin material having a relatively low polarity and a core material made of engineering resin having a relatively high polarity, polyolefins modified with polar groups are particularly used as hot melt adhesives. preferable. The modified polyolefin is not particularly limited, and all those exemplified in the description of the component (D) can be suitably used.

A tackifier resin may be added to the hot melt adhesive in order to adjust the adhesion to the embossed decorative sheet and the core material, which are adherends. Conventionally known tackifying resins can be used without limitation, and specific examples thereof include rosin resins, terpene resins, terpene-phenol resins, coumarone-indene resins, dammar rubber, aromatic petroleum Examples thereof include resins, aliphatic petroleum resins, alkylphenol formaldehyde resins, urea resins and the like.
The amount of the tackifying resin used is preferably 1 to 50 parts with respect to 100 parts by weight of the main resin constituting the hot melt adhesive. If it is less than 1 part, the tackifying effect is small, and if it is more than 50 parts, the tackiness becomes too high. For example, when a release film is laminated, it becomes difficult to peel off.

Hot-melt adhesive can be applied to a resin sheet as a skin material by melting pellets or powder, or the resin sheet and hot-melt adhesive can be laminated by coextrusion. It is also possible to form the film in advance and laminate it with the resin sheet. By forming a film, there is an advantage that a uniform adhesive layer can be easily formed without the coating unevenness seen when using a water-based adhesive or a solvent-based adhesive. The adhesive formed into a film and the resin sheet can be laminated by a conventionally known method such as a laminator or a press molding machine.

When the hot melt adhesive is previously formed into a film, the thickness is preferably in the range of 30 μm to 1300 μm. If it is thinner than 30 μm, the hot melt adhesive is broken and cannot be produced in the lamination process with the decorative sheet. If the thickness is larger than 1000 μm, the thickness of the laminate increases, and therefore, the thickness of the core material becomes extremely thin, which causes an incomplete molded product (short shot), which is not preferable.

The total thickness of the embossed decorative sheet and the adhesive layer in the present invention is preferably 200 to 1500 μm, and is characterized in that no whitening remains when folded by hand and after being folded back. When the thickness is 200 μm or less, the decorative sheet strength is inferior to the flowing resin pressure during injection molding, and there is a possibility of breakage. The total thickness is preferably 300 to 800 μm, and more preferably 300 to 600 μm for injection molding.

The laminate according to the present invention can be obtained by applying an adhesive to the back side of the embossed decorative sheet to form an adhesive layer. Moreover, while laminating | stacking the resin sheet obtained from said embossing decorating sheet raw material composition with an adhesive bond layer, it can also obtain by embossing the surface on the opposite side to an adhesive bond layer. In the latter case, embossing can be performed by the same method as embossing in the production of the embossed decorative sheet.

Moreover, it is preferable that the embossed decorative sheet and the laminate have a high temperature tensile elastic modulus (high temperature 50% modulus) at 140 ° C. of 0.15 to 1.5 MPa. When the high-temperature tensile elastic modulus is less than 0.15 MPa, the skin material is difficult to flow during injection molding, and there is a possibility that gate damage occurs where the core material floats on the surface. On the other hand, if the high-temperature tensile elastic modulus exceeds 1.5 MPa, it tends to be difficult to perform predetermined embossing at the time of embossing or to form a corner shape in injection molding.

The embossed decorative integrally formed product of the present invention comprises the above-mentioned skin material (embossed decorative sheet) or laminate and a core material integrally molded with the above-mentioned skin material or laminated body by injection molding. As described above, the embossed decorative integrally molded product of the present invention can be reduced in weight, thinned, and diversified in design by using a thin non-foamed embossed decorative sheet as a skin material.

The core material is not particularly limited, and various resins can be used. For example, general-purpose resins such as polyolefin resins, styrene resins, rubber-reinforced polystyrene resins, vinyl chloride resins, and polyacetal resins. Engineering resins such as polyester resins, polyamide resins, polycarbonate resins, modified polyphenylene ether resins, polyphenylene sulfide resins, and the like.
Among these, at least one kind of resin selected from the group consisting of styrene-based resins and polycarbonate-based resins is used as a main component for electrical and electronic equipment casings for which the embossed decorative sheet of the present invention is assumed to be used. Often used. Here, the “main component” refers to a resin component that is contained in an amount of 50% by mass or more based on the entire resin component of the core material.

The styrene resin is not particularly limited, and a conventional styrene resin can be used. For example, ABS resin, MBS resin, methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS resin) obtained by graft copolymerization of monomers such as acrylonitrile, styrene, methyl methacrylate (MMA) to butadiene rubber latex Etc. can be used alone or in combination of two or more. Further, high impact polystyrene (HIPS) obtained by dispersing rubber particles in a continuous layer of polystyrene (PS), ethylene-styrene random copolymer resin, styrene-olefin alloy, or the like can also be used.

The polycarbonate resin (PC resin) is not particularly limited. For example, a resin obtained by polymerization by bisphenol A and diphenyl carbonate transesterification, and polymerization between two phases of methylene chloride and an aqueous alkali solution of bisphenol A are performed. A polycarbonate resin such as a resin obtained by forming an adduct of pyridine and phosgene and polymerizing it by reaction with bisphenol A can be used. Further, these PC resins may be mixed with a small amount of a PBT (polybutylene terephthalate) resin, a PET (polyethylene terephthalate) resin, a PA (polyamide) resin, a PO (polyolefin) resin, or the like. .

The styrenic resin and PC resin used for the core material may be used alone or in combination. An embossed decorative integrated product having excellent heat distortion resistance is obtained. Moreover, when using the embossed decorative integrally molded product of the present invention as an electronic device casing, it is particularly preferable to use a resin mixture of a PC resin and an ABS resin as a material for the core material. This is because the performance such as heat deformation required for an electronic device casing is extremely excellent. The mixing ratio of the polycarbonate resin and the ABS resin is not particularly limited, but is preferably PC resin / ABS resin = 90/10 to 10/90 in terms of weight ratio. From the balance, it is particularly preferable that PC resin / ABS resin = 80/20 to 20/80.

The resin used for the core material is a known additive generally added to a thermoplastic resin, for example, a stabilizer, an antioxidant, an ultraviolet absorber, a plasticizer, an antistatic agent, a surfactant, Fillers, colorants, and the like may be arbitrarily blended depending on the purpose, but in blending additives, the type and blending amount of additives are considered so as not to impair the purpose and effect of the present invention. There is a need.

The MFR of the core material is preferably 50 to 200 (measurement temperature 260 ° C., load 10 kg), and more preferably 50 to 100. If the MFR of the core material is less than 50, molding defects such as short shots, appearance defects such as weld lines, and residual distortion tend to increase, and molding defects such as warp tend to occur. On the other hand, when the MFR of the core material exceeds 200, the impact strength of the molded product and the like are liable to be reduced, and there is a tendency that defects such as heat resistance are reduced. In addition, when using the resin mixture of ABS resin and PC resin as a material of the said core material, it is preferable that MFR of these resin mixtures is 50-200 (measurement temperature 260 degreeC, load 10kg).

The thickness of the core material is preferably 40 to 80% of the thickness of the integrally molded product (the total thickness of the embossed decorative sheet, the adhesive layer, and the core material). If it is less than 40%, the core material may have insufficient strength or poor filling, and if it exceeds 80%, it is difficult to reduce the weight of the integrally molded product.

The embossed decorative integrated molded product preferably has a maximum major axis of 200 mm or more, and more preferably 200 to 500 mm. This is because it is effective for molding a large-sized skin integral molded product such as a large electronic device casing. In the present invention, the “maximum long diameter” is a parameter for expressing the size of the embossed decorative integrated molded product, and means the maximum length when the length of the molded product is measured linearly. For example, when the embossed decorative integrated product is substantially square, the diagonal length is the maximum major axis. Here, “substantially square” means a shape having straight portions with two sides facing each other that are parallel to each other, and includes a shape with rounded corners. Examples include a substantially square shape, a substantially rectangular shape, a diamond shape, and a trapezoidal shape.

The embossed decorative integrally molded product has an embossing residual rate measured using a 60 ° reflectance of 70% or more and a gate damage area rate of the embossed decorative surface of 20% or less.

Hereinafter, the manufacturing method of the embossed decorative integrated product of the present invention will be described.
The manufacturing method of the embossed decorative integrally molded product of the present invention is not particularly limited as long as it is a manufacturing method in which the core material is integrally formed by injection molding with respect to the skin material. For example, (I) First, an embossed decorative sheet or laminate is pre-shaped by conventional vacuum forming, pressure forming, press forming or the like. Next, the embossed decorative sheet or laminate is mounted on an injection mold in the direction in which the thermoplastic resin that is the core material is injection-molded on the opposite side of the embossed decorative surface, and the core material is formed in the cavity space. A thermoplastic resin is injection-molded, and the embossed decorative sheet or laminate and the core material are integrated to form an embossed decorative integrated molded product. Or (II) intermittently / continuously supplying embossed decorative sheets or laminates to the core side of the injection mold in the direction in which the thermoplastic resin as the core material is injection-molded on the opposite side of the embossed decorative surface Then, after fixing with the sheet pressing frame, the thermoplastic resin to be the core material is injection-molded in the mold cavity space, and the embossed decorative sheet or laminate and the core material are integrated to emboss the decorative integral It may be a molded product. At that time, the sheet near the gate may be sucked and brought into contact with the core side of the mold.

In the above, the gate shape at the time of injection molding is not particularly limited, but from the viewpoint of preventing warpage of thin products and improving the fluidity of the core material, a point gate, a film gate, a fan gate, etc. It is preferable to use it. Among them, from the viewpoint of filling properties of the core material into the mold cavity, etc., a film gate in which the opening to the mold cavity has a rectangular shape with a minor axis of 0.5 to 2.5 mm and a major axis of 20 to 100 mm or A fan gate is particularly preferred. Furthermore, for molding of a large embossed decorative integrated product used as a large electronic device casing having a maximum major axis of 200 mm or more, etc., the major axis is 1.0 to 2.5 mm and the major axis is 30 to 100 mm. It is preferable to use a fan gate.

Injection molding uses an injection molding machine, sets the embossed decorative sheet in a female mold, closes the male and female molds, and forms a thermoplastic resin as a core material in the mold cavity formed between the molds. Is injected and filled. The cylinder temperature and nozzle temperature during the injection molding depend on the type of thermoplastic resin used as the core material to be used. For example, the cylinder temperature is 160 to 300 ° C. so that the temperature of the thermoplastic resin is 160 to 300 ° C. The nozzle temperature is preferably 180 to 280 ° C. The temperature of the thermoplastic resin is more preferably 200 to 260 ° C. If the temperature of the thermoplastic resin is less than 160 ° C, short shots may occur or the embossed decorative sheet may be torn, and if it exceeds 300 ° C, the core material may be thermally decomposed.

The injection speed during injection molding is preferably in the range of 70 to 200 mm / second. When the injection speed is less than 70 mm / second, there is a tendency that the emboss is crushed, and when it exceeds 200 mm / second, burrs tend to occur and trimming tends to be difficult. In particular, the range of 100 to 130 mm / second is more preferable from the viewpoint of leaving the emboss of the embossed decorative sheet as a skin material.

Moreover, the injection pressure in the case of injection molding has the preferable range of 50-500 MPa, and 70-250 MPa is more preferable from a viewpoint that the embossing of the embossing decoration sheet used as a skin material remains. If the injection pressure is less than 50 MPa, a short shot tends to occur, and if it exceeds 500 MPa, the gate damage area ratio tends to increase.
As described above, according to the manufacturing method of the present invention, by combining a specific gate shape, cylinder temperature, nozzle temperature, injection speed, injection pressure, etc., it is possible to improve the persistence of embossed patterns such as irregularities, and Large-size skin integral molded products can be molded.

Moreover, according to the manufacturing method of this invention, it is not necessary to use what was uneven | corrugated as an injection mold by using an embossed decorating sheet as a skin material. That is, it is efficient because it is not necessary to provide unevenness to the injection mold that matches the shape and size of the skin integral molded product, and the manufacturing cost of the mold can also be reduced.
Further, according to the production method of the present invention, the embossed decorative sheet has a thickness of 0.2 to 1.5 mm and a high temperature tensile elastic modulus (high temperature 50% modulus) at 140 ° C. of 0.15 to 1.5 MPa. Or by using a laminated body, a large-sized embossed decorative integrated molded product can be obtained with a thin skin without damaging the skin during injection molding.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in full detail, this invention is not limited to these.

[Raw materials]
(A) Component: Styrene resin ABS: Asahi Kasei Co., Ltd. Stylack 321
AES: Mitsubishi Rayon Co., Ltd. dial rack SE60
MBS: Telalloy A-10 manufactured by Kaneka Corporation
(B) Component: Polyolefin PP-1: Prime Polymer Co., Ltd. Prime Polypro B221WB (Load deflection temperature 90 ° C., MFR 0.5)
PP-2: Prime Polypro E111G manufactured by Prime Polymer Co., Ltd. (load deflection temperature 115 ° C., MFR 0.5)
(C) Component: Thermoplastic elastomer SEPS: Kuraray Co., Ltd. Septon 2063 (Shore A hardness 36)
TPV (dynamically cross-linked olefin elastomer): Suntoprene 211-55 (Shore A hardness 55) manufactured by ExxonMobil
Component (D): Modified polyolefin-modified PO: NOF Corporation Modiper A8200 (MFR0.3, Vicat 68 ° C.)

[Evaluation methods]
(Whitening)
The embossed decorative sheet before injection molding was bent by 90 degrees by hand, and whitening was evaluated by visual observation based on the following criteria.
◎: No whitening ○: Whitening occurs slightly when folded, but whitening disappears when restored. Δ: Slightly whitened when folded, and slightly whitened when restored. ×: Completely whitened when folded, restored to original Also whitened (embossing residual rate)
Before and after injection molding, the 60 ° reflectance of embossed decorative sheet (120 mm square) was measured using gloss meter VG-2000 (manufactured by Nippon Denshoku Industries Co., Ltd.). The residual rate was calculated. About the reflectance, the site | part 30-30 mm away from the edge | side which was in contact with the gate formation surface of an injection mold was measured.
(Gate damage area rate)
It calculated from the area of the gate damage generated near the gate of the injection mold on the embossed decorative surface of the injection molded product (120 mm square) and the embossed decorative area of the injection molded product (that is, 120 mm × 120 mm).
(Adhesiveness)
As shown in FIG. 1, on the skin side of the center part of the injection molded product (120 mm square), two cuts with a depth reaching the core material in the resin flow direction (100 mm length from the outer periphery of the molded product, The skin material between the two cuts was peeled by hand from the cut end (outer peripheral part of the molded product), and the adhesion of the skin material to the core material was evaluated based on the following criteria.
◎: Not peeled at all ○: Slightly peeled off at the end (the length of the peeled skin material is within 5 mm)
Δ: Peeled to the center (the length of the peeled skin material is 30 to 60 mm)
X: All peeled off (the length of the peeled skin material is 100 mm)

(Production Example 1)
Production of Adhesive Layer A 100 parts by weight of ethylene-propylene copolymer (ethylene content 15% by weight, MFR = 8), 1,3-di (t-butylperoxyisopropyl) benzene (Perbutyl P manufactured by NOF Corporation, Twin screw extruder (44 mmφ, L / D = 38.5, manufactured by Nippon Steel Co., Ltd., product name) with 0.5 parts by weight set to a cylinder temperature of 200 ° C. and a screw rotation speed of 150 rpm. Then, 5 parts by weight of glycidyl methacrylate and 5 parts by weight of styrene were added and melt-kneaded from the middle of the cylinder to obtain modified polyolefin resin pellets. The obtained pellets were formed with a T-die extruder to obtain a film having a width of 400 mm and a thickness of about 100 μm.

(Production Example 2)
Production of Adhesive Layer B 10 parts by weight of a tackifier (YShara Chemical Co., Ltd., YS Polystar T130) was dry blended with respect to 100 parts by weight of the modified polyolefin resin obtained in the production of the adhesive layer A. A film having a width of 400 mm and a thickness of about 100 μm was obtained using a die extruder.

(Production Example 3)
Production of Adhesive Layer C 20 parts by weight of styrene elastomer (manufactured by Kaneka Co., Ltd., SIBSTAR 072T) is dry blended with respect to 100 parts by weight of the modified polyolefin resin obtained in the production of the adhesive layer A. A film having a width of 400 mm and a thickness of about 100 μm was obtained with an extruder.

Example 1
ABS: Asahi Kasei Co., Ltd. Stylack 321, Prime Polymer Co., Ltd. random polypropylene (Prime Polypro B221WB), and Kuraray Co., Ltd. styrene thermoplastic elastomer (Septon 2063) are mixed in the ratio shown in Table 1, Pre-kneading with a banbury mixer, and then put into a reverse L4 calender molding machine manufactured by Nippon Roll Manufacturing Co., Ltd., with a roll temperature of 180-200 ° C. and a take-up speed of 16-18 m / min, a thickness of about 300-400 μm Got the sheet. The obtained sheet was given a woodgrain pattern by gravure printing.
The printed sheet and the adhesive layer A obtained in Production Example 1 are heated to 180 to 200 ° C. with a plastic embosser manufactured by Kojima Seisakusho Co., Ltd., and the embossing step is performed at a line speed of 10 to 35 m / min. The laminating process was performed simultaneously to obtain an embossed decorative sheet. The total thickness of the obtained sheet was about 450 to 500 μm.
The whitening of the embossed decorative sheet was evaluated by the above method. The results are shown in Table 1.
Next, the obtained embossed decorative sheet was attached to the cavity side of a mold (gate diameter: thickness 2 mm × width 5 mm) from which a flat plate having a size of 120 mm × 120 mm × thickness 2 mm can be collected, and 80 tons made by Toshiba Corporation. Using injection molding machine, non-halogen flame retardant PC / ABS resin (Multilon TN-7000F) manufactured by Teijin Chemicals Ltd. as the core material, cylinder set temperature 260 ° C, mold temperature 60 ° C, injection speed about 100mm / sec Then, injection was performed at an injection pressure of 140 MPa to obtain an injection molded product.
The embossed residual rate, gate damage area rate, and adhesiveness of the molded product were evaluated according to the above methods. The results are shown in Table 1.

(Examples 2-8, Comparative Examples 1-3)
An embossed decorative sheet and an integrally molded product were obtained in the same manner as in Example 1, except that the composition of the skin material layer and the adhesive layer were changed as shown in Table 1. The results of various evaluations are shown in Table 1.

As is apparent from Table 1, the embossed decorative sheet of the present invention is not easily whitened, has a high emboss residual ratio when injection molded, and has a low gate damage area ratio. In Examples 1-7, since the adhesive layer is laminated on the embossed decorative sheet, the adhesiveness with the core material is also good. On the other hand, in the comparative examples 1 and 2 using only the component (A) as the component of the skin material, and in the comparative example 3 where the amounts of the components (B) and (C) are out of the scope of the present invention Also, whitening, emboss residual rate, and gate damage area rate are poor. In Comparative Examples 1 and 3 in which no adhesive layer was used, the adhesion was also poor.

Claims (18)

An embossed decorative sheet used as a skin material in a molding method by injection molding,
It is characterized by not being whitened in a bending test and having an embossing residual ratio after injection molding measured by using a 60 ° reflectance of 70% or more and a gate damage area ratio of an embossed decorative surface of 20% or less. Embossed decorative sheet. The emboss decoration of Claim 1 which consists of a composition which mix | blended (A) 20-70 weight% of styrene resin, (B) 5-40 weight% of polyolefin, and (C) thermoplastic elastomer 5-40 weight%. Sheet. The said composition contains 1-30 weight part of (D) modified polyolefin further with respect to a total of 100 weight part of the compounding quantity of (A) component, (B) component, and (C) component. The embossed decorative sheet described. The styrene resin of component (A) is acrylonitrile / conjugated diene rubber / styrene copolymer, acrylonitrile / olefin rubber / styrene copolymer, acrylonitrile / acrylic rubber / styrene copolymer, methyl methacrylate / conjugated diene rubber / styrene copolymer. The embossed decorative sheet according to claim 2 or 3, comprising at least one selected from coalescence and high impact polystyrene. The embossed decoration according to any one of claims 2 to 4, wherein the polyolefin as the component (B) is a polypropylene having a melt flow rate of 0.1 to 20 g / 10 min and a load deflection temperature of 70 to 160 ° C. Sheet. The embossed decorative sheet according to any one of claims 2 to 5, wherein the thermoplastic elastomer of component (C) has a Shore A hardness of 20 to 80 in JIS K 6253. The modified polyolefin of component (D) is a polyolefin modified with a polar group, having a melt flow rate of 0.1 to 100 g / 10 min and a Vicat softening point in JIS K 7206 of 40 to 100 ° C. The embossed decorative sheet according to any one of claims 3 to 6. The laminated body which consists of an embossed decorating sheet and adhesive layer in any one of Claims 1-7, and the said adhesive bond layer is laminated | stacked on the surface on the opposite side to the embossed decorating surface of an embossed decorating sheet. The laminate according to claim 8, wherein the adhesive layer is made of at least one selected from a solvent-based adhesive, a water-based adhesive, and a hot-melt adhesive. The laminate according to claim 9, wherein the hot-melt adhesive mainly comprises an olefin elastomer and / or a styrene elastomer. The laminate according to claim 9, wherein the hot-melt adhesive is mainly composed of a modified polyolefin. The laminate according to any one of claims 9 to 11, wherein the hot melt adhesive is an adhesive resin composition further containing a tackifier. The laminate according to any one of claims 10 to 12, wherein the hot-melt adhesive is in the form of a film. The raw material composition is kneaded, and then the obtained raw material composition is molded to produce a sheet, and the sheet is laminated with an adhesive layer, and embossed. A manufacturing method of a layered product. An embossed decorative integrated product comprising the embossed decorative sheet according to any one of claims 1 to 7 and a core material. An embossed decorative integrally formed product comprising the laminate according to any one of claims 8 to 13 and a core material. The emboss decoration according to claim 15 or 16, wherein an emboss residual ratio measured using a 60 ° reflectance is 70% or more and a gate damage area ratio of an embossed decorative surface is 20% or less. Integrated molded product. A thermoplastic resin is injection-molded on the side opposite to the embossed decorative surface of the embossed decorative sheet according to any one of claims 1 to 7 or the laminated body according to any one of claims 8 to 13, The temperature of the thermoplastic resin at the time of injection molding is 160-300 degreeC, and the injection pressure in this case is 50-500 Mpa, The embossing decoration integral in any one of Claims 15-17 characterized by the above-mentioned. Manufacturing method of molded products.

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