WO2017073077A1

WO2017073077A1 - Injection-molded complex and decorative sheet, and methods for producing same

Info

Publication number: WO2017073077A1
Application number: PCT/JP2016/004755
Authority: WO
Inventors: 侑史大澤; 利之井口
Original assignee: 株式会社クラレ
Priority date: 2015-10-30
Filing date: 2016-10-28
Publication date: 2017-05-04
Also published as: JPWO2017073077A1; JP6836511B2; TW201728452A; KR20180077186A; CN108349130A; CN108349130B

Abstract

The present invention provides: an injection-molded complex having excellent productivity and excellent adhesion between a decorative sheet and an injection-molded body; a decorative sheet thereof; and methods for producing the same. The injection-molded complex according to the present invention is provided with an injection-molded body, and a decorative sheet that coats at least a part of a surface of the injection-molded body, wherein the decorative sheet is a sheet formed through co-extrusion molding of a surface protective layer containing a transparent resin and having visible light transmissivity, a decorative layer containing a colorant, and a binding layer containing a binder resin as the main ingredient, in the layer order of the surface protective layer, the decorative layer, and the binding layer. At least a part of a surface of the injection-molded body is bound to the binding layer of the decorative sheet, and at least the portion, of the injection-molded body, bound to the decorative sheet contains, as the main ingredient, an injection-molded resin having not less than 60 mass% of a structural unit which is derived from a monomer and which is the same as a structural unit derived from a monomer of the binder resin.

Description

INJECTION MOLDED COMPOSITE AND DECORATION SHEET

The present invention relates to an injection molded composite and a decorative sheet suitable for three-dimensional thermoforming. Moreover, it is related with these manufacturing methods.

In recent years, for the purpose of improving design and reducing the weight of parts, the demand for three-dimensional molded products mainly made of plastic that can form complex shapes has increased for exterior parts and interior parts such as automobiles, household appliances, and interior furniture. ing.

From the viewpoint of providing a design with no joints and a high designability in the three-dimensional molded body, and from the viewpoint of simplifying the processing and assembly process of the molded body, for example, the main resin has a design such as a pattern in advance. An integral molding method is used in which the applied resin decorative sheets are stacked and molded at once with a press molding machine or the like. In addition, insert molding in which a thermoplastic resin is injection-molded on one surface of the injection-molding simultaneous decorating sheet is used (Patent Document 1).

In this situation, the decorative sheet is required to have performances such as easy moldability, good surface properties, and high designability. In particular, in terms of design, there is an increasing demand for decorative sheets for thermoforming that have excellent surface gloss, such as a piano black design, and have a design with a deep color.

As the decorative sheet used for the above purpose, a method of laminating a transparent resin layer serving as a protective layer on the outermost surface layer by any method is used. For example, a design such as coating is imparted to the resin sheet as a base material, and a primer layer and a methacrylic transparent resin layer are laminated thereon, or a colored base resin and a methacrylic transparent resin are coextruded. A method of forming a two-layer sheet is disclosed (Patent Documents 2 to 5).

Here, in the integral molding method and insert molding, the adhesion between the resin used for molding and the decorative sheet may be insufficient. In insert molding, the adhesiveness tends to improve if the temperature of the resin is increased during molding, but there is a problem that the resin deteriorates if the temperature of the resin is increased.

Patent Document 1 discloses a technique in which a base material sheet for improving adhesion is laminated on a laminate of a surface sheet and a pattern ink layer via an adhesive layer. However, the lamination process of an adhesive bond layer and a base material sheet was complicated, and productivity was bad. In addition, when a decorative sheet is used as a product, delamination may occur between the adhesive layer and the substrate layer due to exposure to various environments such as high temperature and high humidity.

JP 2003-170546 A JP 2011-200804 A JP 2012-76348 A JP 2012-116200 A JP 2012-213911 A

The present invention has been made in view of the above background, and the object of the present invention is an injection-molded composite and a decorative sheet thereof that are excellent in productivity and excellent in adhesion between the decorative sheet and the injection-molded product. As well as providing these manufacturing methods.

As a result of intensive studies by the present inventors, it has been found that the above problems can be solved in the following aspects, and the present invention has been completed.
[1]: An injection-molded composite comprising an injection-molded body and a decorative sheet covering at least a part of the surface of the injection-molded body, wherein the decorative sheet contains a transparent resin and is visible A sheet obtained by coextruding a surface protective layer having light permeability, a decorative layer containing a coloring material, and a bonding layer mainly composed of a binder resin in the order of lamination of the surface protective layer / decorative layer / bonding layer And at least a part of the surface of the injection molded body is bonded to the bonding layer of the decorative sheet, and at least a bonded portion of the injection molded body to the decorative sheet is a single piece of the binder resin. An injection-molded composite whose main component is an injection-molded resin containing 60% by mass or more of a monomer-derived structural unit in common with a monomer-derived structural unit.
[2]: The injection molded composite according to [1], wherein the binder resin uses at least one of acrylonitrile-butadiene-styrene copolymer and polycarbonate resin.
[3] The injection molded composite according to [1] or [2], wherein the transparent resin is a (meth) acrylic resin.
[4]: A methacrylic resin (A) having a structural unit derived from methyl methacrylate of 80% by mass or more and a methacrylic acid ester polymer block (b1) of 10 to 80% by mass with respect to the total amount of the (meth) acrylic resin. And a block copolymer (B) having an acrylic acid ester polymer block (b2) of 90 to 20% by mass in an amount of 1% by mass or more based on the total amount of the resin, [3].
[5] The injection-molded composite according to any one of [1] to [4], wherein the decorative layer contains at least one of a polycarbonate resin and a (meth) acrylic resin containing rubber particles.
[6]: The surface protective layer has a thickness of 0.01 to 0.25 mm, the decorative layer has a thickness of 0.05 to 0.5 mm, and the bonding layer has a thickness of 0.01 to 0.4 mm. [1] The injection-molded composite according to any one of [5].
[7] The injection-molded composite according to any one of [1] to [6], wherein the colorant is an organic dye.
[8] The injection-molded composite according to any one of [1] to [7], which does not have an adhesive layer between the injection-molded product and the decorative sheet.
[9]: A decorative sheet that is joined to the surface of an injection-molded body and used to form an injection-molded composite, and is used for the injection-molded composite used in any one of [1] to [8] Decorated sheet.
[10] A method for producing an injection-molded composite, comprising a transparent resin, a surface protective layer having visible light permeability, a decorative layer containing a coloring material, and a bonding layer mainly composed of a binder resin. A step of obtaining a decorative sheet formed in the order of surface protective layer / decorative layer / joining layer by coextrusion, and a step of forming an injection-molded body by injection molding so as to contact the joining layer, At least a joint portion with the decorative sheet in the injection-molded body is mainly composed of an injection-molded resin containing 60% by mass or more of a monomer-derived structural unit in common with the binder resin monomer-derived structural unit. A method for producing an injection-molded composite.
[11]: A method for producing a decorative sheet used for an injection-molded composite, a surface protective layer containing a transparent resin as a main component, a decorative layer containing a coloring material, and a bonding layer containing a binder resin as a main component A step of obtaining a decorative sheet by coextrusion so as to be a laminate of a surface protective layer / decorative layer / joining layer, wherein the binder resin is at least in an injection molded body constituting the injection molded composite The manufacturing method of the decorating sheet made into resin which contains 60 mass% or more of structural units derived from the monomer in common with the structural unit derived from the monomer of the main component resin which comprises a junction part with the said decorating sheet.

According to the present invention, it has an excellent effect of being able to provide an injection molded composite that is excellent in productivity and also excellent in adhesion between a decorative sheet and an injection molded body, and a decorative sheet thereof, and a production method thereof. .

Explanatory drawing of the peeling strength test of the test piece which concerns on an Example and a comparative example. Explanatory drawing of the peeling strength test of the test piece which concerns on an Example and a comparative example.

Hereinafter, an example of an embodiment to which the present invention is applied will be described. It should be noted that various design changes are possible as long as they meet the spirit of the present invention, and it goes without saying that other embodiments may also belong to the category of the present invention. Moreover, the numerical value specified by this specification shows the value obtained when it measures by the method described in the Example mentioned later. Further, the numerical values “A to B” specified in the present specification indicate ranges that are larger than the numerical values A and A and satisfy the values smaller than the numerical values B and B.

<Injection molded composite>
The injection molded composite of the present invention has a three-dimensional molded body in which at least a part of the surface of the injection molded body is covered with a decorative sheet. In the injection molded composite, another three-dimensional molded body, a sheet, or the like may be laminated on the injection molded body. The decorative sheet contains a transparent resin and has a surface protective layer having visible light permeability, a decorative layer containing a coloring material, and a bonding layer mainly composed of a binder resin. It is a sheet formed by coextrusion molding in the layer stacking order. A bonding layer of a decorative sheet is coated on at least a part of the surface of the injection molded body. That is, at least a part of the surface of the injection molded body is bonded to the bonding layer in the decorative sheet.

Here, in this specification, the “main component” refers to a component that occupies 60% by mass or more with respect to each total amount of layers or injection-molded parts composed of the same composition. Further, “visible light transmission” means a layer having transparency when visually observed. That is, it means a layer in which luminous transmittance is recognized in the visible light wavelength region. “Transparent resin” refers to a transparent resin having a high light transmittance in a band of 400 to 800 nm.

In the injection-molded body, at least the joint with the decorative sheet is made of a composition mainly composed of the same type of injection-molded resin as the binder resin that is the main component of the decorative sheet bonding layer (layer directly in contact with the injection-molded body). It is an injection-molded product. Here, the same type refers to an injection molding resin containing 60% by mass or more of a monomer-derived structural unit in common with the binder resin monomer-derived structural unit. Adhesiveness between the decorative sheet and the injection-molded product can be kept good by making the monomer-derived structural unit common to 60 mass% or more of all the structural units. More preferably, the above conditions are satisfied and the types of resins are the same. “The same type of resin” means a resin having the same type of resin, such as a methacrylic resin, an acrylic resin, an ABS resin, or a polycarbonate resin. The binder resin and the injection molding resin constituting the main component may be independently one kind of resin or two or more kinds of mixed resins. Also in the case of a mixed resin, the structural unit derived from a common monomer may be 60% by mass or more in the total structural unit of each of the binder resin and the injection molding resin, and it is more preferable that the types of the resins are the same. . The binder resin and the injection molding resin may satisfy the above conditions, and the number average molecular weight, weight average molecular weight, dispersity, MVR, and the like may be different. Moreover, what changed the kind and quantity of an additive is also contained. Moreover, as long as the said conditions are satisfy | filled, other resin may be included.

The injection-molded body may be a molded body made of a plurality of injection-molded resins, in addition to the molded body mainly composed of the injection-molded resin. For example, after forming a molded body from a composition mainly composed of the same type of injection molding resin as the binder resin of the decorative sheet, further molding the injection molding composite using another injection molding resin. The body can be formed.

According to the injection molded composite of the present invention, the binder resin that is the main component of the bonding layer of the decorative sheet and the injection molding resin that is the main component of the bonded portion of at least the decorative sheet in the injection molded body are as described above. Since the same kind of resin is used, an injection-molded composite excellent in design and adhesion can be provided without impairing the advantages of the co-extrusion method that can be produced with high productivity and low cost. Moreover, when it does not have an adhesive bond layer, it is not necessary to laminate | stack the layer from which a viscosity differs, and it is preferable at the point from which the handleability and productivity are excellent.

<Decoration sheet>
The decorative sheet is composed of a surface protective layer having visible light permeability, a decorative layer containing a coloring material, and a bonding layer mainly composed of a binder resin in the order of lamination of the surface protective layer / decorative layer / bonding layer. This is an extruded sheet. The decorative sheet is preferably formed of these three layers, but may be provided with other layers such as an adhesive layer and a base material layer as necessary. Manufacturing cost can be reduced by setting it as a three-layer structure of a surface protective layer / decorative layer / joining layer. If the number of layers is 2 or less, the function of each layer described later cannot be satisfied. When the number of layers is four or more, the equipment for coextrusion molding becomes large, which tends to increase the cost of products. In addition, the increase in the number of interfaces of each layer may increase the resin retention in the T-die and cause gel defects, resulting in a defect, or the appearance quality of the product may be reduced due to the sharkskin flow. Although the aspect which interposed an adhesive bond layer in a part of an injection molded body and a decoration sheet is not excluded, the aspect joined by the joining layer of a decoration sheet contacting an injection molded body directly is preferable. The aspect which does not have an adhesive bond layer between an injection molded object and a decorating sheet especially is preferable.

The bonding layer constituting the decorative sheet is a layer in contact with the injection molded body, and plays a role as a binder layer that maintains good adhesion to the injection molded body. The bonding layer contains a binder resin as a main component. As described above, the binder resin is composed of a structural unit derived from a monomer common to the injection molding resin whose main component is 60% by mass or more. The structural unit derived from a common monomer of the binder resin and the injection molding resin is more preferably 70% by mass or more, further preferably 80% by mass or more, and more preferably 90% by mass or more in each resin. It is particularly preferred.

The binder resin and the injection molded resin are not particularly limited as long as they satisfy the above conditions and do not depart from the spirit of the present invention. Suitable resins include polycarbonate resin; polystyrene, acrylonitrile-butadiene-styrene copolymer (ABS resin), styrene-maleimide copolymer, styrene-N-phenylmaleimide copolymer, styrene-N-phenylmaleimide-acrylonitrile. Copolymer, styrene-N-phenylmaleimide-methyl methacrylate copolymer, styrene-N-phenylmaleimide-butyl acrylate copolymer, rubber-reinforced impact-resistant polystyrene, styrene-acrylonitrile copolymer (AS resin), Ethylene-propylene rubber reinforced styrene-acrylonitrile copolymer (AES resin), polyacrylate rubber reinforced styrene-acrylonitrile copolymer (AAS resin), styrene-methyl methacrylate copolymer (MS resin), styrene - methyl methacrylate - butadiene copolymer (MBS resin) Styrene-based resin, etc., or a mixture thereof can be exemplified. Of these, polycarbonate resins and acrylonitrile-butadiene-styrene copolymers are preferred.

Polycarbonate resin is a polymer obtained by reaction of a polyfunctional hydroxy compound and a carbonate ester-forming compound. Examples of the polyfunctional hydroxy compound include 4,4′-dihydroxybiphenyls which may have a substituent; bis (hydroxyphenyl) alkanes which may have a substituent; and the like. Of these polyfunctional hydroxy compounds, 2,2-bis (4-hydroxyphenyl) propane is preferred. Examples of the carbonate ester-forming compound include various dihalogenated carbonyls such as phosgene, haloformates such as chloroformate, and carbonate ester compounds such as bisaryl carbonate. The amount of the carbonate ester-forming compound may be appropriately adjusted in consideration of the stoichiometric ratio (equivalent) of the reaction.

The polycarbonate-based resin may contain a unit having a polyester, polyurethane, polyether, or polysiloxane structure in addition to the polycarbonate unit. The polycarbonate-based resin suitably used in the present invention is not particularly limited by its molecular weight, but from the viewpoint of ease of production by extrusion, one having a viscosity average molecular weight of about 13,000 to 30,000, or at 250 ° C. and 100 sec ⁻¹ . A melt viscosity of about 13,000 to 60,000 poise is preferred. The molecular weight can be adjusted by adjusting the amount of the terminal terminator or branching agent.

In the ABS resin, the ratio of the diene rubber component in 100% by mass of the acrylonitrile-butadiene-styrene copolymer component is preferably 8 to 50% by mass, more preferably 10 to 35% by mass. The rubber particle diameter of the ABS resin is preferably 0.1 to 5.0 μm, more preferably 0.3 to 1.5 μm. The structure of the rubber particles may form a single phase or may have a salami structure.

When using a composition containing a polycarbonate-based resin and an ABS resin, each pellet is introduced into a single-screw or twin-screw extruder with separate feeders and melt-kneaded, or the pellets are blended in advance and then melted. It can be manufactured by kneading. The mixing ratio of the polycarbonate-based resin and the ABS resin is not particularly limited in a strict sense, but is usually preferably in the range of 20/80 to 90/10 by mass ratio. By using polycarbonate resin and ABS resin, fluidity and impact strength can be increased. For example, “Multilon TN7500” manufactured by Teijin Chemicals Ltd., “Cycoloy C6600” manufactured by Sabic Innovative Plastics, Inc. can be used.

The bonding layer may contain a resin other than the binder resin that satisfies the above conditions. In addition, the bonding layer includes various additives as necessary, for example, antioxidants, stabilizers, ultraviolet absorbers, lubricants, processing aids, antistatic agents, colorants, impact resistance aids, foaming agents, Fillers, matting agents and the like may be blended.

The thickness of the bonding layer is preferably 10 to 400 μm. If it is smaller than 10 μm, the layer thickness may be non-uniform in extrusion. Even if the thickness is larger than 400 μm, the adhesion is not remarkably improved, but rather the thickness of the entire sheet increases, which may cause problems in handling properties and cutting properties. Moreover, when the insert molding is performed by increasing the thickness of the entire sheet, the followability of the film at the end of the molded body may be reduced. Therefore, the lower limit of the thickness of the bonding layer is more preferably 30 μm, still more preferably 50 μm, and the upper limit of the thickness of the bonding layer is more preferably 350 μm, further preferably 300 μm or less.

The decoration layer which comprises a decoration sheet | seat is an intermediate | middle layer containing a coloring material, and functions as a decoration layer. A sheet having excellent design properties can be provided by the surface protective layer and the decorative layer. For example, a sheet having excellent surface gloss such as piano black tone and deep color can be provided.

The decorative layer can be formed using a composition containing a known resin, a dye (including an organic dye), and a colorant such as a pigment without departing from the spirit of the present invention. Suitable examples of the resin include (meth) acrylic resins, styrene resins, and polycarbonate resins. From the viewpoint of excellent weather resistance, transparency and surface hardness, a (meth) acrylic resin is preferred. From the viewpoint of excellent impact resistance, a polycarbonate resin and a (meth) acrylic resin containing rubber particles, or a mixture thereof are preferable. More preferably, the rubber particle is a multilayer structure rubber particle having a crosslinked polymer layer containing an alkyl acrylate unit having an alkyl group having 3 to 8 carbon atoms, and having a particle size of 0.05 to 0.3 μm. preferable. Such rubber particles may be, for example, the particles disclosed in JP-A-10-182755.

Examples of the polycarbonate-based resin include the resins exemplified in the bonding layer. Moreover, as (meth) acrylic resin, resin illustrated as transparent resin mentioned later can be illustrated. A known resin can be used as the styrene resin.

The proportion of rubber particles in the total amount of the decorative layer is preferably 10 to 50% by mass. By setting it within this range, it is possible to effectively pull out the cracking resistance at the time of cutting and increase the bending flexibility. The particle size of the rubber particles is preferably 0.07 to 0.2 μm. By making it in this range, it is possible to maintain good crack resistance and bending flexibility during cutting.

From the viewpoint of drawing out the jetness of the decorative layer more effectively, it is particularly preferable to use a dye. The dye is selected according to the purpose and needs. Suitable dyes include anthraquinones, anthrapyridones, perylenes, anthracenes, perinones, indanthrones, quinacridones, xanthenes, thioxanthenes, oxazines, oxazolines, indigoids, thioindigoides, quinophthalones. , Naphthalimides, cyanines, methines, pyrazolones, lactones, coumarins, bis-benzoxazolylthiophenes, naphthalenetetracarboxylic acids, phthalocyanines, triarylmethanes, aminoketones, bis (styryl) Biphenyls, azines, rhodamines, derivatives of the aforementioned compounds, and mixtures thereof. Anthraquinones are preferred from the viewpoint of availability.

It is possible to add additives to the decorative layer without departing from the spirit of the present invention. For example, antioxidants, stabilizers, ultraviolet absorbers, lubricants, processing aids, antistatic agents, colorants, impact resistance aids, foaming agents, fillers, matting agents, and the like may be blended.

The thickness of the decoration layer may vary depending on the application and needs, but is preferably 50 to 500 μm. If it is smaller than 50 μm, the color density of the colored layer may be insufficient. Even if the thickness is larger than 500 μm, the above-mentioned effect is not remarkably improved, but rather the thickness of the entire sheet increases, which may cause problems in handling property, cutting property, punching property, and the like. Moreover, when the insert molding is performed by increasing the thickness of the entire sheet, the followability of the film at the end of the molded body may be reduced. Therefore, the lower limit of the thickness of the decorative layer is more preferably 100 μm, further preferably 150 μm, and the upper limit of the thickness of the decorative layer is more preferably 350 μm, and further preferably 250 μm.

The thickness of the entire decorative sheet is preferably 500 μm or less. When the thickness is 500 μm or less, secondary workability such as handling property, cutting property and punching property is improved, and handling as a sheet becomes easy. Moreover, when the insert molding is performed by increasing the thickness of the entire sheet, the followability of the film at the end of the molded body may be reduced. Moreover, the usage-amount of the raw material per unit area can be reduced by setting it as 500 micrometers or less. The upper limit of the thickness of the decorative sheet is more preferably 400 μm, further preferably 300 μm, and the lower limit is preferably 50 μm, more preferably 100 μm. When the thickness of the whole decorative sheet is less than 50 μm, there is a concern that the sheet is heated and stretched at the time of insert molding, so that the second layer becomes thin and affected by the color of the injection resin.

The surface protective layer constituting the decorative sheet is a layer containing a transparent resin and functions as a surface protective layer. By providing the surface protective layer, the effect of giving depth to the decorative layer containing the adjacent colorant can be obtained. Moreover, the generation of surface haze accompanying the three-dimensional molding can be suppressed, and the color depth can be maintained after the three-dimensional molding.

As the transparent resin, a known resin can be used without departing from the gist of the present invention. Preferred examples include (meth) acrylic resin, styrene resin, polycarbonate resin, polyolefin resin, norbornene resin, cyclohexane. Examples thereof include olefin resins and polyester resins. A (meth) acrylic resin is preferred from the viewpoint of excellent weather resistance, transparency, and surface hardness. The “(meth) acrylic resin” is a concept including both a methacrylic resin and an acrylic resin. (Meth) acrylic resins also include acrylate / methacrylate derivatives, particularly acrylate / methacrylate (co) polymers. The repeating structural unit of the (meth) acrylic resin is not particularly limited.

The type of (meth) acrylic resin is not particularly limited, but includes a structural unit derived from (meth) acrylic acid ester from the viewpoint of excellent impact resistance and whitening resistance of a portion where the sheet is bent during injection molding. The block copolymer is preferably contained in an amount of 1 to 95% by mass, more preferably 60 to 90% by mass, based on the total amount of the (meth) acrylic resin. By making a block copolymer into the said range, surface smoothness after insert molding can be more effectively drawn out, maintaining surface height.
Further, instead of the block copolymer or in addition to the block copolymer, the multilayer structure rubber particles are preferably 1 to 90% by mass, more preferably 5 to 40% by mass with respect to the total amount of the (meth) acrylic resin. % Content can also be used. The multilayer rubber particles are the same as those described above for the decorative layer.

Preferred examples of the block copolymer include a methacrylic acid ester polymer block (b1) containing a structural unit derived from a methacrylic acid ester and an acrylate polymer block (b2) containing a structural unit derived from an acrylate ester. Each independently contains one or more in a molecule, and contains 10 to 80% by weight of the methacrylic ester polymer block (b1) and 90 to 20% by weight of the acrylate polymer block (b2). A block copolymer (B) can be illustrated. By using such a block copolymer (B), the whitening resistance at the time of bending can be more effectively brought out. In addition, an acrylic resin composition (C) in which the block copolymer (B) further contains a methacrylic resin (A) having 80% by mass or more of a structural unit derived from methyl methacrylate is preferable. In this case, from the viewpoint of surface hardness, the methacrylic resin (A) is 10 to 99 parts by weight, preferably 60 to 60 parts by weight with respect to a total of 100 parts by weight of the methacrylic resin (A) and the block copolymer (B). 95 parts by mass, and the block copolymer (B) is 90 to 1 part by mass, preferably 40 to 5 parts by mass. The (meth) acrylic resin can contain other (meth) acrylic resins other than the methacrylic resin (A) and the block copolymer (B). In that case, it is preferable to contain 1% by mass or more of the methacrylic resin (A) and the block copolymer (B) with respect to the total amount of the (meth) acrylic resin. In order to effectively bring out other properties of the (meth) acrylic resin, 90% by mass or less is preferable. Moreover, as a preferable aspect, the aspect which consists only of methacrylic resin (A) and a block copolymer (B) with respect to (meth) acrylic-type resin whole quantity, and methacrylic resin (A) and a block copolymer (B) are included. There is an aspect of over 90% and less than 100%. By setting it as such a range, the characteristics of the methacrylic resin (A) and the block copolymer (B) can be effectively extracted.

The structural unit derived from methyl methacrylate of the methacrylic resin (A) is preferably 90% by mass or more, and more preferably 95% by mass or more. That is, the proportion of structural units derived from monomers other than methyl methacrylate is 20% by mass or less, preferably 10% by mass or less, more preferably 5% by mass or less.

Such monomers other than methyl methacrylate include acrylic acid esters such as methyl acrylate and ethyl acrylate; methacrylic acid esters other than methyl methacrylate; unsaturated carboxylic acids; olefins; conjugated dienes; Is mentioned. The stereoregularity of the methacrylic resin (A) is not particularly limited, and for example, those having stereoregularity such as isotactic, heterotactic and syndiotactic may be used.

The melt viscosity of the methacrylic resin (A) at 220 ° C. and a shear rate of 122 / sec is in the range of 1500 to 3500 Pa · s. The melt viscosity is more preferably 1800 Pa · s or more, and particularly preferably 2000 Pa · s or more. Further, it is more preferably 3300 Pa · s or less, and particularly preferably 3100 Pa · s or less. By setting the pressure within the range of 1500 to 3500 Pa · s, the impact resistance and toughness of the decorative sheet to be obtained and the injection-molded composite comprising the same can be kept good.

Commercial products may be used for the methacrylic resin (A). Examples of such commercially available methacrylic resins include “Parapet H1000B” (MFR: 22 g / 10 min (230 ° C., 37.3 N)) and “Parapet GF” (MFR: 15 g / 10 min (230 ° C., 37.3 N). )), “Parapet EH” (MFR: 1.3 g / 10 min (230 ° C., 37.3 N)), “Parapet HRL” (MFR: 2.0 g / 10 min (230 ° C., 37.3 N)), “ Parapet HRS ”(MFR: 2.4 g / 10 min (230 ° C., 37.3 N)) and“ Parapet G ”(MFR: 8.0 g / 10 min (230 ° C., 37.3 N))) Kuraray Co., Ltd.].

The block copolymer (B) is a diblock copolymer or a triblock copolymer in which the methacrylate polymer block (b1) is bonded to one or both ends of the acrylate polymer block (b2). Particularly preferred. The block copolymer (B) has 30 to 80% by mass of an acrylate polymer block (b2) and 20 to 70% by mass of a methacrylic acid ester polymer block (b1), and the block copolymer It is preferable that (B) has a melt viscosity of 75 to 1500 Pa · s at 220 ° C. and a shear rate of 122 / sec.

The acrylic ester polymer block (b2) is mainly composed of a structural unit derived from an acrylic ester. The proportion of structural units derived from the acrylate ester in the acrylate polymer block (b2) is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and particularly preferably 90% by mass. %, And a composition of 100% by mass is also included.

Examples of the acrylate ester include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, acrylic Amyl acid, Isoamyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, pentadecyl acrylate, dodecyl acrylate, isobornyl acrylate, phenyl acrylate, benzyl acrylate, phenoxyethyl acrylate, acrylic acid Examples include 2-hydroxyethyl, 2-methoxyethyl acrylate, glycidyl acrylate, and allyl acrylate. An acrylic acid ester polymer block (b2) can be formed by polymerizing these acrylic acid esters alone or in combination of two or more. Among these, those obtained by (co) polymerizing n-butyl acrylate and / or benzyl acrylate are preferable from the viewpoints of cost, low temperature characteristics, transparency and the like.

The methacrylic acid ester polymer block (b1) is mainly composed of structural units derived from methacrylic acid esters. The proportion of structural units derived from the methacrylic acid ester in the methacrylic acid ester polymer block (b1) is preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, and particularly preferably 98% by mass. %, And all structural units are monomers derived from methacrylic acid esters. As such a methacrylic acid ester, methyl methacrylate is preferable from the viewpoint of improving transparency and heat resistance. As for the stereoregularity of the methacrylic acid ester polymer block (b1), it is preferable that the syndiotacticity (rr) of triplet display is 60% or more from the viewpoint of improving heat resistance. By setting the syndiotacticity to 60% or more, the glass transition temperature is increased and excellent heat resistance is exhibited in the resin composition of the present invention. More preferably, it is 65% or more, more preferably 70% or more, and most preferably 75% or more.

The block copolymer (B) may have a functional group such as a hydroxyl group, a carboxyl group, an acid anhydride, or an amino group in the molecular chain or at the molecular chain end as necessary.

The method for producing the block copolymer (B) is not particularly limited, and a method according to a known method can be employed. For example, a method of living polymerizing monomers constituting each polymer block is generally used. Examples of such living polymerization methods include a method of anionic polymerization using an organic alkali metal compound as a polymerization initiator in the presence of a mineral acid salt such as an alkali metal or an alkaline earth metal salt, and an organic alkali metal compound. A method of anionic polymerization in the presence of an organoaluminum compound as a polymerization initiator, a method of polymerization using an organic rare earth metal complex as a polymerization initiator, a copper compound using an α-halogenated ester compound as an initiator Examples thereof include a radical polymerization method. In addition, a method of producing a mixture containing the block copolymer (B) used in the present invention by polymerizing monomers constituting each block using a polyvalent radical polymerization initiator or a polyvalent radical chain transfer agent, etc. Also mentioned. Among these methods, in particular, the block copolymer (B) can be obtained with high purity, the molecular weight and the composition ratio can be easily controlled, and it is economical. A method in which anionic polymerization is used in the presence of an organoaluminum compound is preferred.

The transparent resin is preferably 90% by mass or more, more preferably 98% by mass or more, and still more preferably 99% by mass or more with respect to the total amount of the surface protective layer, from the viewpoint of enhancing visible light transmittance. Transparent resin is used individually by 1 type or in combination of 2 or more types.

In the surface protective layer, additives (for example, an antioxidant, a stabilizer, an ultraviolet absorber, a lubricant, a processing aid, an antistatic agent, a colorant, an impact resistance aid, and foaming are used without departing from the spirit of the present invention. Agents, fillers, matting agents) can be added. From the viewpoint of imparting weather resistance to the surface protective layer and the decorative layer, an ultraviolet absorber may be added. The ultraviolet absorber is a compound having an ability to absorb ultraviolet rays, and is a compound mainly having a function of converting light energy into heat energy. Examples of the ultraviolet absorber include benzophenones, benzotriazoles, triazines, benzoates, salicylates, cyanoacrylates, succinic anilides, malonic esters, formamidines, and the like. Among these, benzotriazoles and triazines are preferable. An ultraviolet absorber can be used individually by 1 type or in combination of 2 or more types.

Examples of the benzotriazoles include 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) 6- (2H-benzotriazol-yl) phenol] (manufactured by Asahi Denka Kogyo Co., Ltd .; trade name ADK STAB LA-31), 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol (manufactured by Ciba Specialty Chemicals; trade name TINUVIN329), 2 -(2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol (manufactured by Ciba Specialty Chemicals; trade name TINUVIN234). Examples of the triazines include Toyotsu Chemiplus; trade name TINUVIN479. Of these ultraviolet absorbers, triazines are preferably used from the viewpoint that resin deterioration due to ultraviolet irradiation can be suppressed.

The thickness of the surface protective layer may vary depending on applications and needs, but is preferably 10 to 250 μm. If it is smaller than 10 μm, the weather resistance, transparency and surface hardness may be insufficient. Moreover, from the point which improves a weather resistance, the addition effect of a ultraviolet absorber falls because the thickness of a surface protective layer becomes thin. Although a method of increasing the concentration of the ultraviolet absorber can be considered for this problem, since the ultraviolet absorber is generally a low molecule, the compatibility with the resin is low and the sheet surface tends to bleed during long-term use. . Since bleed appears more conspicuously as the concentration of the ultraviolet absorber is higher, the concentration of the ultraviolet absorber is limited. Further, even if the thickness of the surface protective layer is larger than 250 μm, the above function is not remarkably improved. Rather, the increase in the thickness of the entire sheet causes problems in handling properties, cutting properties, punching properties, crack resistance, and the like. There is a case. The lower limit of the thickness of the surface protective layer is more preferably 30 μm, still more preferably 40 μm, and the upper limit of the thickness of the surface protective layer is more preferably 150 μm, still more preferably 100 μm.

<Method for producing injection molded composite>
As a manufacturing method of an injection-molded composite, a decorative sheet can be manufactured by coextrusion molding, and the injection-molded body can be insert-molded, that is, injection-molded into the decorative sheet. The decorative sheet can prepare a composition of each of the surface protective layer, the decorative layer, and the bonding layer, and can produce a multilayer laminate by a coextrusion method using these compositions. By performing coextrusion molding, excellent interlayer adhesion can be obtained while increasing productivity.

The composition of the surface protective layer, the decorative layer, and the bonding layer is heated and melted, supplied to the extrusion die through different flow paths from different extruders and pumps, etc., and laminated after being extruded into multiple layers from the extrusion die. By bonding, a multilayer laminate is formed. Examples of the extrusion die include a coextrusion molding method using a film forming apparatus such as a T-die extrusion molding machine such as a multi-manifold die and a field block.

In the case of the feed block method, the resin layered in the feed block is guided to a sheet forming die such as a T-die and formed into a sheet shape, and then flows into the gap between a pair of pressure rolls to form a bank. To do. And it passes through the gap | interval of a pressurization roll, is cooled, and a decorating sheet is obtained. On the other hand, in the case of the multi-manifold system, the resin layered in the multi-manifold die is similarly formed into a sheet inside the die. Then, it may flow into a pair of pressure rolls to form a bank. And it passes through the gap | interval of a pressurization roll, is cooled, and a decorating sheet is obtained. A multi-manifold die is preferable from the viewpoint of keeping the thickness uniformity of each layer good.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. In addition, this invention is not restrict | limited by a following example. In addition, the present invention includes all aspects that are obtained by arbitrarily combining the above-described items representing technical characteristics such as characteristic values, forms, manufacturing methods, and uses.

The measurement of physical property values in Examples and Comparative Examples was performed by the following method.
[Weight average molecular weight (Mw) and molecular weight distribution]
The weight average molecular weight (Mw) and molecular weight distribution during and after the polymerization of each resin were determined by polystyrene-equivalent molecular weight by GPC (gel permeation chromatography).
・ Equipment: Tosoh GPC equipment “HLC-8320”
・ Separation column: “TSKguardcolum SuperHZ-H”, “TSKgel HZM-M” and “TSKgel SuperHZ4000” manufactured by Tosoh Corporation are connected in series. ・ Eluent: Tetrahydrofuran ・ Eluent flow rate: 0.35 mL / min
-Column temperature: 40 ° C
・ Detection method: Differential refractive index (RI)

[Composition ratio of each polymer block]
The composition ratio of each polymer block was determined by ¹ H-NMR ( ¹ H-nuclear magnetic resonance) measurement.
・ Equipment: JEOL Nuclear Magnetic Resonance Device “JNM-LA400”
・ Deuterated solvent: Deuterated chloroform

[Peel strength]
FIG. 1 shows an explanatory diagram of a sample used in the peel strength test. Test pieces of the decorative sheet 1 and the injection molded body 2 were produced. Under the present circumstances, the peelable polyimide film 3 was interposed in the decorative sheet 1 and a part of the injection molded body 2, and the non-joining part 4 with the injection molded body 2 was provided in the edge part of the decorative sheet 1. FIG. Then, the peel strength was measured according to JIS K 6854-1. Specifically, as shown in FIG. 2, the non-bonded portion 4 of the decorative sheet 1 is pulled vertically with respect to the surface of the injection molded body 2 (see FIG. 2), and the decorative sheet peeled from the injection molded body. The peel strength of was measured. Specific measurement conditions are as follows. Some of them had high peel strength and material destruction.
・ Width: 25mm
・ Minimum length: 50mm
・ Grasp movement speed: 50mm / min
・ Measuring device: EZ-XS manufactured by Shimadzu Corporation

[Formability evaluation method for molded products]
The decorative sheet was cut into a test piece of 300 mm (MD) × 210 mm (TD), attached and fixed using the vacuum pressure forming machine NGF manufactured by Fuse Vacuum Co., Ltd., and the followability was evaluated.
Using a far-infrared heater, when the surface temperature of the decorative sheet reaches 130 ° C., the mold (the bottom is 10 cm long and 10 cm wide, the top is 9 cm wide 9 cm wide, 3.5 cm high) The bonding layer side was brought into close contact with the upper surface, and preforming was performed by vacuum forming. In the case where the moldability is good, the sheet part which hits the four corners of the mold follows the mold cleanly, but in the case where the moldability is bad, wrinkles and cracks occur in the four corners. The quality of the moldability was judged visually and evaluated according to the following criteria.
A: Good without wrinkles or cracks.
B: Wrinkles and cracks were observed in a very small part, but there was no practical problem.
C: Wrinkles or cracks that have practical problems.

[Evaluation of crack resistance]
A pre-formed sheet was used during the follow-up evaluation. Adhering the sheet to the mold for insert molding (bottom size is 9cm in width 9cm in width, 3.5cm in depth), and the surface protection layer side of the sheet trimmed with a cutter in advance according to the mold Fixed. An injection molding composite was obtained by performing insert molding using an injection molding resin using an injection molding machine M-100C manufactured by Meiki Seisakusho. Thereafter, unnecessary portions of the sheet were trimmed with a cutter as necessary. Those with good crack resistance can be trimmed without cracking the sheet, but those with poor cracking cause cracking of the sheet during trimming. Evaluation was made according to the following criteria.
A: No cracks or cracks are observed (visual observation).
B: Some cracks were observed (visual observation).
C: A crack occurred (visual observation).
D: The whole surface was cracked and clouded (visually).

[Decoration sheet surface hardness measurement method]
The decorative sheet prepared under the above-described film forming conditions and the stretched molded body were cut out into 30 mm × 30 mm, respectively, and used as test pieces. Set a test piece on a pencil hardness tester (manufactured by Toyo Seiki Seisakusho Co., Ltd .: pencil scratch coating film hardness tester), measure the pencil hardness on the surface protective layer side in accordance with JIS-K5600-5-4, The pencil hardness before and after stretching was compared.

[Surface haze]
The molded product used for the evaluation of the crack resistance was visually evaluated from the surface protective layer side. The evaluation method was evaluated by looking at the light from the indoor fluorescent lamp at an incident angle of 45 ° and a reflection angle of 45 °, and observing the surface haze at the boundary between the fluorescent lamp reflected on the film and the ceiling. Evaluation was made according to the following criteria.
A: A test piece having no haze on the surface.
C: A test piece in which haze is generated on the surface.

<Production Example 1> [Synthesis of Block Copolymer (A-1)]
A glass-lined 3 m ³ reaction vessel equipped with a brine-cooled jacket and a stirrer that was degassed and purged with nitrogen, was charged with 735 kg of dry toluene, 0.4 kg of hexamethyltriethylenetetramine, and isobutyl bis (2,6 at room temperature). -Di-t-butyl-4-methylphenoxy) 39.4 kg of a toluene solution containing 20 mol of aluminum was added, and 1.17 mol of sec-butyllithium was further added. To this, 35.0 kg of methyl methacrylate was added and reacted at room temperature for 1 hour. The polymer contained in the reaction solution was sampled and the weight average molecular weight (hereinafter referred to as Mw (a1-1)) was measured, and it was 40,000. The methyl methacrylate polymer is further block copolymerized with an acrylate ester, whereby the methyl methacrylate polymer is converted into a methacrylate ester polymer block (b1) (hereinafter referred to as “methyl methacrylate polymer block (b1-1)”). ").

Next, the reaction solution was brought to −25 ° C., and a mixed solution of 24.5 kg of n-butyl acrylate and 10.5 kg of benzyl acrylate was added dropwise over 0.5 hours. Immediately after the dropping, the polymer contained in the reaction solution was sampled and the weight average molecular weight was measured, and it was 80,000. Since the weight average molecular weight of the methyl methacrylate polymer block (b1-1) was 40,000, the weight of the acrylate polymer block (b2) composed of a copolymer of n-butyl acrylate and benzyl acrylate. The average molecular weight (Mw (b2)) was determined to be 40,000.

Subsequently, 35.0 kg of methyl methacrylate was added, the reaction solution was returned to room temperature, and stirred for 8 hours, whereby the second methacrylate polymer block (b1) (hereinafter, “methyl methacrylate polymer block ( b1-2) ”). Thereafter, 4 kg of methanol was added to the reaction solution to stop the polymerization, and then the reaction solution was poured into a large amount of methanol to obtain a block copolymer (B) (hereinafter referred to as “block copolymer”) which is a triblock copolymer. A-1) ”) was precipitated, filtered, and isolated by drying at 80 ° C. and 1 torr (about 133 Pa) for 12 hours. The weight average molecular weight Mw (A) of the obtained block copolymer (A-1) was 120,000. Since the weight average molecular weight of the diblock copolymer was 80,000, the weight average molecular weight (referred to as Mw (a1-2)) of the methyl methacrylate polymer block (b1-2) was 40,000. Were determined. Since the weight average molecular weight Mw (b1-1) of the methyl methacrylate polymer block (b1-1) and the weight average molecular weight Mw (b1-2) of the methyl methacrylate polymer block (b1-2) are both 40,000. , Mw (b1) is 40,000, and Mw (b1-total) is 80,000.

20 parts by mass of a block copolymer (A-1), 80 parts by mass of a methacrylic resin (HR-S manufactured by Kuraray Co., Ltd.), and TINUVIN479 (manufactured by Toyotsu Chemiplus Co., Ltd.) were melt-kneaded at 250 ° C. with a twin screw extruder. . Thereafter, the pellets of the acrylic resin composition (A-2) were produced by extrusion and cutting.

<Production Example 2> [Synthesis of dye-containing resin (B-1)]
70 parts by mass of impact-resistant acrylic resin containing rubber fine particles (“GR-10000” manufactured by Kuraray Co., Ltd.), 30 parts by mass of acrylic resin (“EH” manufactured by Kuraray Co., Ltd.), and 1.7 masses of anthraquinone dye (manufactured by LANXESS) The part was melt-kneaded to obtain a black acrylic resin.

<Production Example 3> [Synthesis of dye-containing resin (B-2)]
1.7 parts by mass of an anthraquinone dye (manufactured by LANXESS) was melt-kneaded with 100 parts by mass of a polycarbonate resin (“300 series” MFR = 10 manufactured by Sumika Stylon Polycarbonate) to obtain a black polycarbonate resin.

Example 1
Using the acrylic resin composition (A-2) of Production Example 1 as a transparent resin to be a surface protective layer, it was extruded at a discharge rate of 5 kg / hr using a 30 mmΦ vent type single screw extruder, and at the same time as a decorative layer Using the black acrylic resin of Production Example 2, extruded at 15 kg / hr using a 50 mmΦ vent type single screw extruder, and simultaneously using an ABS resin (MFR = 11, uncolored) as a binder resin to be a bonding layer, Extrusion was performed at 5 kg / hr using a 30 mmΦ vent type single screw extruder.
And each is laminated using a multi-manifold die with a width of 300 mm, extruded at a temperature of 240 ° C., nipped with a metal mirror roll at 100 ° C. and 105 ° C., and taken at a speed of 5.6 m / min, A decorative sheet having a surface protective layer thickness of 50 μm, a decorative layer thickness of 150 μm, a bonding layer thickness of 50 μm, and a total thickness of 250 μm was formed.
Next, an injection molded composite having a total thickness of 3.0 mm was formed by injection molding ABS resin (MFR = 11, uncolored) on the bonding layer side of the decorative sheet by the method described in [Evaluation of crack resistance]. Manufactured. The resin temperature at the time of injection molding was 220 ° C.

(Example 2)
A decorative sheet was formed in the same manner as in Example 1 except that the discharge amount of the extruder was changed to set the bonding layer thickness to 100 μm and the total thickness to 300 μm. Next, an injection molded composite was produced in the same manner as in Example 1.

(Example 3)
A decorative sheet was formed in the same manner as in Example 1 except that the discharge amount of the extruder was changed to make the surface protective layer thickness 25 μm and the total thickness 225 μm. Next, an injection molded composite was produced in the same manner as in Example 1.

Example 4
A decorative sheet was formed in the same manner as in Example 1 except that the discharge amount of the extruder was changed so that the thickness of the surface protective layer was 100 μm and the total thickness was 300 μm. Next, an injection molded composite was produced in the same manner as in Example 1.

(Example 5)
A decorative sheet was formed in the same manner as in Example 1 except that the resin of the decorative layer was changed to the black polycarbonate of Production Example 3. Next, an injection molded composite was produced in the same manner as in Example 1.

(Example 6)
A decorative sheet was formed in the same manner as in Example 1 except that the resin of the bonding layer was polycarbonate (“301-4” manufactured by Sumika Stylon Polycarbonate).
Next, an injection-molded composite was produced in the same manner as in Example 1 except that the resin for injection molding was polycarbonate (“301-22” manufactured by Sumika Stylon Polycarbonate) and the resin temperature was 280 ° C.

(Example 7)
A decorative sheet was formed in the same manner as in Example 1 except that the resin for the surface protective layer was an acrylic resin (Parapet “HR-S” manufactured by Kuraray Co., Ltd.). Next, an injection molded composite was produced in the same manner as in Example 1.

(Production Example 4)
In Production Example 1, up to an acrylate polymer block was synthesized in the same manner, and a diblock copolymer consisting of a methyl methacrylate polymer block (Mw: 45,000) and an acrylate polymer block (Mw: 45,000) was prepared. A polymer (A-3) was obtained. Using the diblock copolymer (A-3) instead of the block copolymer (A-1), similarly to Production Example 1, pellets of the acrylic resin composition (A-4) were produced.

(Example 8)
Using the acrylic resin composition (A-4) of Production Example 4 as a transparent resin to be a surface protective layer and using “Multilon TN7500” manufactured by Teijin Chemicals Ltd. as a bonding layer, a decorative sheet is produced under the conditions shown in Table 1. Filmed. Next, using “Multilon TN7500” manufactured by Teijin Chemicals Ltd. as the injection resin, a decorative sheet was formed in the same manner as in Example 1 under the conditions shown in Table 1. Next, an injection molded composite was produced in the same manner as in Example 1.

(Comparative Example 1)
A decorative sheet was formed in the same manner as in Example 1 except that the resin of the bonding layer was polycarbonate (“300 series” MFR = 10 manufactured by Sumika Stylon Polycarbonate). Next, an injection molded composite was produced in the same manner as in Example 1.

(Comparative Example 2)
A decorative sheet was formed in the same manner as in Comparative Example 1. Subsequently, an injection-molded composite was produced in the same manner as in Comparative Example 1 except that the resin temperature was changed to 240 ° C.

(Comparative Example 3)
A decorative sheet was formed in the same manner as in Example 1 except that the resin used as the bonding layer was not formed and only the surface protective layer and the decorative layer were molded, and the total thickness was 200 μm. Next, an injection molded composite was produced in the same manner as in Example 1.

(Comparative Example 4)
A decorative sheet was formed in the same manner as in Comparative Example 3. Next, an injection-molded composite was produced in the same manner as in Comparative Example 3 except that the resin temperature was changed to 240 ° C.

(Comparative Example 5)
A decorative sheet was formed in the same manner as in Example 1 except that the resin for forming the surface protective layer was not used and only the decorative layer and the bonding layer were formed, and the total thickness was 200 μm. Next, an injection molded composite was produced in the same manner as in Example 1.

For Examples and Comparative Examples, peel strength, presence / absence of surface haze after insert molding, formability (followability, crack resistance), and surface hardness were evaluated. The results are shown in Table 1.

In Examples 1 to 8, in which the same resin as the resin for injection molding was used as the bonding layer, when the peel strength was measured, the material was destroyed and the adhesiveness was excellent. Furthermore, in these examples, surface haze after insert molding did not occur, and excellent results were obtained. Examples 1 to 6 and 8 using an acrylic resin composition containing the block copolymer (A-2) or (A-4) as the surface protective layer have excellent peel strength, moldability, and surface hardness. The balance of performance was good without surface haze. Although Example 7 which does not contain a block copolymer in a surface protective layer was inferior in crack resistance, other evaluations are favorable and can be used if it is an application which does not involve the shaping | molding process to a complicated shape.

Comparative Example 1 using a resin different from the resin for injection molding as the bonding layer was inferior in peel strength to the examples. And also in Comparative Example 2 in which the resin temperature was higher in injection molding, no improvement in peel strength was observed. Comparative Example 3 having no bonding layer was inferior in peeling strength to the examples. And also in the comparative example 4 which made the resin temperature higher in injection molding, the improvement of peeling strength was not seen. In Comparative Example 5 having no surface protective layer, surface haze after insert molding occurred, which was inferior to the examples.

This application claims priority based on Japanese Patent Application No. 2015-214726 filed on Oct. 30, 2015, the entire disclosure of which is incorporated herein.

The injection-molded composite and the decorative sheet of the present invention can be applied to all injection-molded composites that require design properties. For example, billboard parts such as advertising towers, stand signboards, sleeve signboards, billboard signs, rooftop signboards; display parts such as showcases, partition plates, store displays; fluorescent lamp covers, mood lighting covers, lamp shades, light ceilings, light walls Lighting parts such as chandeliers; Interior parts such as furniture, pendants, mirrors, etc .; Building parts such as doors, domes, safety window glass, partitions, staircases, balconies, roofs of leisure buildings; aircraft windshields, pilots Transport equipment related parts such as visor, motorcycle, motorboat windshield, bus shading plate, automotive side visor, rear visor, head wing, headlight cover, automotive interior parts, bumper and other automotive exterior parts; name plate for audio images, stereo cover , TV protection masks, vending machines, mobile phones, personal computers, etc. Child equipment parts; Medical equipment parts such as incubators and X-ray parts; Machine-related parts such as machine covers, instrument covers, experimental devices, rulers, dials, observation windows; road signs, guide plates, curved mirrors, sound barriers, etc. Transportation related parts: Others: Greenhouses, large aquariums, box aquariums, bathroom components, clock panels, bathtubs, sanitary, desk mats, game parts, toys, face decoration masks and protective films for welding, etc. Wallpaper: used for marking film and the like.

1: decorative sheet, 2: injection-molded body, 3: polyimide film, 4: non-joined part

Claims

An injection-molded composite comprising an injection-molded body and a decorative sheet that covers at least a part of the surface of the injection-molded body,
The decorative sheet contains a transparent resin and has a surface protective layer having visible light permeability, a decorative layer containing a coloring material, and a bonding layer mainly composed of a binder resin. It is a sheet that is co-extruded in the stacking order of the bonding layers,
At least a part of the surface of the injection-molded body is bonded to the bonding layer in the decorative sheet,
At least a portion of the injection-molded body joined to the decorative sheet is mainly composed of an injection-molded resin containing 60% by mass or more of a monomer-derived structural unit common to the binder resin monomer-derived structural unit. An injection molding composite.
2. The injection-molded composite according to claim 1, wherein the binder resin is at least one of acrylonitrile-butadiene-styrene copolymer and polycarbonate resin.
The injection-molded composite according to claim 1 or 2, wherein the transparent resin is a (meth) acrylic resin.
Methacrylic resin (A) having 80% by mass or more of structural units derived from methyl methacrylate, 10 to 80% by mass of methacrylic acid ester polymer block (b1), and acrylic acid with respect to the total amount of the (meth) acrylic resin The injection-molded composite according to claim 3, wherein the block copolymer (B) having 90 to 20% by mass of the ester polymer block (b2) is contained by 1% by mass or more based on the total amount of the resin.
The injection-molded composite according to any one of claims 1 to 4, wherein the decorative layer contains at least one of a polycarbonate resin and a (meth) acrylic resin containing rubber particles.
The thickness of the surface protective layer is 0.01 to 0.25 mm, the thickness of the decorative layer is 0.05 to 0.5 mm, and the thickness of the bonding layer is 0.01 to 0.4 mm. The injection-molded composite according to any one of the above.
The injection molded composite according to any one of claims 1 to 6, wherein the colorant is an organic dye.
The injection-molded composite according to any one of claims 1 to 7, which does not have an adhesive layer between the injection-molded product and the decorative sheet.
A decorative sheet that is bonded to the surface of an injection molded body and used to form an injection molded composite,
A decorative sheet used for the injection-molded composite used in any one of claims 1 to 8.
A method for producing an injection molded composite comprising:
A surface protective layer containing a transparent resin and having visible light permeability, a decorative layer containing a coloring material, and a bonding layer mainly composed of a binder resin are formed in the order of surface protective layer / decorative layer / bonding layer. Obtaining a decorative sheet by coextrusion;
A step of forming an injection molded body by injection molding so as to be in contact with the bonding layer,
At least the joint portion of the injection molded body with the decorative sheet is composed mainly of an injection molded resin containing 60% by mass or more of a monomer-derived structural unit in common with the binder resin monomer-derived structural unit. A method for producing an injection-molded composite.
A method for producing a decorative sheet used for an injection molded composite,
Co-extrusion of surface protective layer with transparent resin as main component, decorative layer with coloring material and bonding layer with binder resin as main component so as to form a laminate of surface protective layer / decorative layer / bonding layer Comprising the step of obtaining a decorative sheet by
The binder resin is a structural unit derived from a monomer in common with a structural unit derived from a monomer of a main component resin that constitutes at least a joint portion with the decorative sheet in the injection molded body constituting the injection molded composite. The manufacturing method of the decorating sheet made into resin which contains 60 mass% or more.