JP7172365B2 - Decorative sheet, decorative resin molded product, and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a decorative sheet, a decorative resin molded product, and methods for producing these.

BACKGROUND ART Decorated resin molded products obtained by laminating a decorative sheet on the surface of a resin molded product are used for vehicle interior parts, building interior materials, home appliance housings, and the like. As a method for molding such a decorative resin molded product, a decorative sheet is formed into a three-dimensional shape in advance using a vacuum forming mold, the molded sheet is inserted into an injection mold, and a resin in a fluid state is injected into the mold. An insert molding method that integrates resin and a molded sheet by injection (see, for example, Patent Document 1), a decorative sheet inserted into a mold during injection molding, and a molten resin that is injected into a cavity. An injection-molding simultaneous decoration method (see, for example, Patent Documents 2 and 3) is known, in which the resin molding is integrated and the surface of the resin molded body is decorated.

When producing a decorated resin molded product using such a decorative sheet, the decorative sheet is heated to a high temperature (e.g., 140° C. or higher) when subjected to injection molding or prior preforming (vacuum molding). .

Japanese Patent Application Laid-Open No. 2004-322501 Japanese Patent Publication No. 50-19132 Japanese Patent Publication No. 61-17255

The inventors of the present invention have studied the production of decorative resin molded products using decorative sheets, and found that air bubbles may be generated in the decorative sheet during injection molding and preforming of the decorative sheet. Found

Further, the inventors of the present invention have further studied the problem of air bubbles. It was confirmed that during the injection molding or preforming of the decorative sheet, the solvent vaporized while trapped between the base material layer and the surface layer, causing air bubbles.

Under such circumstances, the main object of the present invention is to provide a decorative sheet in which the generation of air bubbles during the molding process is effectively suppressed. Another object of the present invention is to provide a method for manufacturing the decorative sheet, a decorative resin molded product using the decorative sheet, and a method for manufacturing the same.

The inventors of the present invention have made intensive studies to solve the above problems. As a result, at least in the production of the decorative sheet having a base layer and a surface layer, the use of a solvent having a predetermined boiling point effectively suppresses the generation of air bubbles during the molding process of the decorative sheet. I found The present invention has been completed through further studies based on such findings.

That is, the present invention provides inventions in the following aspects.
Section 1. having at least a substrate layer and a surface layer,
A decorative sheet containing a solvent having a boiling point of 140°C or higher.
Section 2. Item 2. The decorative sheet according to Item 1, wherein the surface layer is formed of a cured resin composition containing an ionizing radiation-curable resin.
Item 3. Item 3. The decorative sheet according to Item 2, wherein the resin composition further contains a thermoplastic resin.
Section 4. Item 4. The decorative sheet according to any one of Items 1 to 3, further comprising a solvent having a boiling point of less than 90°C.
Item 5. Item 5. The decorative sheet according to any one of Items 1 to 4, wherein the surface layer has a multilayer structure.
Item 6. Item 6. The decorative sheet according to any one of Items 1 to 5, comprising at least one of a primer layer and a pattern layer between the base layer and the surface layer.
Item 7. A decorative sheet obtained by laminating a surface layer containing a solvent having a boiling point of 140° C. or higher on a base material layer.
Item 8. A method for producing a decorative sheet, comprising the step of laminating a surface layer containing a solvent having a boiling point of 140° C. or higher on a base material layer.
Item 9. It has at least a molding resin layer, a substrate layer, and a surface layer,
A decorative resin molded product containing a solvent having a boiling point of 140°C or higher.
Item 10. Item 8. A method for producing a decorated resin molded product, comprising a step of laminating a molded resin layer on the base layer side of the decorative sheet according to any one of Items 1 to 7 by injecting a resin.

According to the present invention, it is possible to provide a decorative sheet in which air bubbles are effectively suppressed during the molding process. Further, according to the present invention, it is possible to provide a method for manufacturing the decorative sheet, a decorative resin molded product using the decorative sheet, and a method for manufacturing the same.

It is a schematic diagram of the cross-sectional structure of one form of the decorative sheet of this invention. It is a schematic diagram of the cross-sectional structure of one form of the decorative sheet of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram of the cross-sectional structure of one form of the decorative resin molding of this invention.

1. Decorative Sheet The decorative sheet of the present invention has at least a substrate layer and a surface layer, and is characterized by containing a solvent having a boiling point of 140° C. or higher. By containing such a specific solvent, the decorative sheet of the present invention effectively suppresses the generation of air bubbles during the molding process.

The decorative sheet of the present invention will be described in detail below. In this specification, the numerical range indicated by "-" means "above" and "below", except where "above" and "below" are specified. For example, the notation of 2 to 15 mm means 2 mm or more and 15 mm or less. Further, in this specification, "(meth)acrylate" means "acrylate or methacrylate", and other similar terms have the same meaning. Moreover, the decorative sheet of the present invention may not have a pattern layer or the like, and may be transparent, for example.

Laminated Structure of Decorative Sheet The decorative sheet of the present invention has a laminated structure in which at least a substrate layer 1 and a surface layer 2 are laminated.

In the decorative sheet of the present invention, between the base material layer 1 and the surface layer 2, in order to improve the adhesion between the surface layer 2 and the underlying layer (for example, the pattern layer 4), A primer layer 3 may be provided as necessary.

Further, under the surface layer 2, a pattern layer 4 may be provided as necessary for the purpose of imparting decorativeness. For example, when the primer layer 3 is provided, the design layer 4 may be provided between the base material layer 1 and the primer layer 3 .

In addition, a masking layer (not shown) may be provided between the base layer 1 and the surface layer 2 as necessary for the purpose of suppressing color change and unevenness of the base layer 1 . For example, when the primer layer 3 is provided, the concealing layer may be provided between the base material layer 1 and the primer layer 3, and when the pattern layer 4 is provided, the concealing layer may be It may be provided between the material layer 1 and the pattern layer 4 .

Furthermore, under the surface layer 2, a transparent resin layer (not shown) may be provided as necessary for the purpose of improving abrasion resistance (scratch resistance). For example, when the primer layer 3 and the pattern layer 4 are provided, the transparent resin layer may be provided between the pattern layer 4 and the primer layer 3 .

Furthermore, in the decorative sheet of the present invention, the back surface of the decorative sheet (the surface opposite to the surface layer 2) for the purpose of increasing the adhesion to the molding resin when the decorative sheet is molded, A back adhesive layer (not shown) may be provided if desired.

Examples of the laminated structure of the decorative sheet of the present invention include a laminated structure in which base layer 1/surface layer 2 is laminated; a laminated structure in which base layer 1/primer layer 3/surface layer 2 are laminated in order; Laminated structure in which layer 1/picture layer 4/surface layer 2 are laminated in order; laminated structure in which substrate layer 1/picture layer 4/primer layer 3/surface layer 2 are laminated in order; base layer 1/pattern layer 4 A laminated structure in which /transparent resin layer/primer layer 3/surface layer 2 are laminated in this order may be used.

FIG. 1 shows a cross-sectional view of a decorative sheet in which base layer 1/surface layer 2 are laminated as one embodiment of the laminated structure of the decorative sheet of the present invention. FIG. 2 shows a cross-sectional view of a decorative sheet in which base layer 1/pattern layer 4/primer layer 3/surface layer 2 are laminated in this order, as one embodiment of the laminated structure of the decorative sheet of the present invention.

The decorative sheet of the present invention contains a solvent with a boiling point of 140° C. or higher (hereinafter sometimes referred to as a “high-boiling solvent”). The high boiling point solvent is included in the production process of the decorative sheet. That is, when forming the surface layer, the primer layer, and the printing layer located on the base material layer by printing, by blending the high boiling point solvent in the composition used for printing, the solvent is added to the decorative sheet. can be included.

In addition, conventionally, in the process of manufacturing a decorative sheet, in the formation of a layer laminated on a substrate layer such as a surface layer, a primer layer, and a printing layer, the composition used for printing generally contains methyl ethyl ketone. , ethyl acetate, etc., are widely used. When a layer above the base material layer is formed using a composition containing such a low boiling point solvent, the low boiling point solvent remains in the decorative sheet, and injection molding or preforming of the decorative sheet occurs. In this case, the solvent may evaporate while trapped between the base material layer and the surface layer, resulting in air bubbles. On the other hand, the decorative sheet of the present invention contains a solvent having a boiling point of 140° C. or higher (that is, when forming the surface layer, primer layer, pattern layer, etc. located on the base material layer by printing, By adding the high boiling point solvent to the composition used for printing), the high boiling point solvent can be used even when the decorative sheet is heated to a high temperature (for example, 140 ° C. or higher) during injection molding or preforming. Furthermore, even when a low boiling point solvent is contained together with a high boiling point solvent, vaporization of the low boiling point solvent can be suppressed, and as a result, the generation of air bubbles during the molding process can be effectively suppressed.

In addition, in the decorative sheet of the present invention, the layer containing the high boiling point solvent and/or the low boiling point solvent is not particularly limited. When a solvent is used in the manufacturing process of the decorative sheet, the solvent usually migrates across the layers and evaporates within the existing layers during the molding process to generate air bubbles. In the decorative sheet, generation of air bubbles is effectively suppressed regardless of the position of the solvent in any layer.

The high boiling point solvent is not particularly limited as long as it has a boiling point of 140° C. or higher and can be used for forming a layer by printing or the like. The boiling point of the high boiling point solvent is preferably about 140 to 300°C. Specific examples of high-boiling solvents include diethylene glycol monobutyl ether acetate (boiling point of 247°C at 1 atmosphere), isophorone (boiling point of 215°C at 1 atmosphere), diethyl succinate (boiling point of 218°C at 1 atmosphere), Ethyl lactate (boiling point under 1 atmosphere is 154°C), propylene glycol monomethyl ether acetate (boiling point under 1 atmosphere is 145.8°C), and the like. Only one type of high boiling point solvent may be used, or two or more types may be mixed and used.

In this specification, the boiling point of a solvent means the boiling point (°C) under 1 atmosphere.

In the decorative sheet of the present invention, the content of the high boiling point solvent is not particularly limited, but from the viewpoint of effectively suppressing the generation of air bubbles during the molding process, it is preferably about 10 to 200 mg/m ² , more preferably about 10 to 200 mg/m 2 . About 50 to 180 mg/m ² , more preferably about 80 to 150 mg/m ² can be mentioned.

In addition, when the decorative sheet of the present invention contains a low boiling point solvent, the low boiling point solvent has a boiling point of less than 90° C. and can be used for forming layers by printing or the like. Specific examples of low boiling point solvents include methyl ethyl ketone (boiling point: 79.5°C), ethyl acetate (boiling point: 77.1°C), and isopropyl alcohol (boiling point: 89.5°C). Only one type of low boiling point solvent may be contained, or two or more types may be contained.

When the decorative sheet of the present invention contains a low boiling point solvent, the content of the low boiling point solvent is not particularly limited, but from the viewpoint of effectively suppressing the generation of air bubbles during the molding process, it is preferably 1 to 300 mg/ about m ² , more preferably about 1 to 100 mg/m ² , more preferably about 1 to 60 mg/m ² .

When the decorative sheet of the present invention contains a low boiling point solvent, the content ratio of the high boiling point solvent and the low boiling point solvent is not particularly limited. The high boiling point solvent is more preferably contained in an amount of 50 to 300 parts by mass, more preferably 70 to 200 parts by mass, and even more preferably 80 to 150 parts by mass with respect to 100 parts by mass of the solvent.

Composition of each layer of the decorative sheet [base layer 1]
The base material layer 1 is a resin sheet (resin film) that serves as a support in the decorative sheet of the present invention. The resin component used in the base material layer 1 is not particularly limited, and may be appropriately selected according to moldability, compatibility with the molding resin, etc., but a resin film made of a thermoplastic resin is preferable. . Specific examples of the thermoplastic resin include acrylonitrile-butadiene-styrene resin (hereinafter sometimes referred to as "ABS resin") and acrylonitrile-styrene-acrylic acid ester resin (hereinafter referred to as "ASA resin"). polyolefin resins such as acrylic resins, polypropylene and polyethylene, polycarbonate resins, vinyl chloride resins, and polyethylene terephthalate (PET). Among these, ABS resin and acrylic resin are preferable from the viewpoint of moldability. Further, the substrate layer 1 may be formed of a single-layer sheet of these resins, or may be formed of a multi-layer sheet of the same or different resins.

As described above, in the decorative sheet of the present invention, the layer containing a high boiling point solvent and/or a low boiling point solvent is not particularly limited, and the base material layer 1 contains a high boiling point solvent and/or a low boiling point solvent. may be included.

In addition, among the resins constituting the base layer 1, if the ABS resin is used, the solvent easily permeates the ABS resin. In particular, it can be said that air bubbles caused by a low boiling point solvent are likely to occur. is suitably suppressed, and ABS resin can be suitably used as the resin constituting the base material layer 1 .

The bending elastic modulus of the base material layer 1 is not particularly limited. For example, when the decorative sheet of the present invention is integrated with a molding resin by an insert molding method, the bending elastic modulus at 25° C. of the substrate layer 1 in the decorative sheet of the present invention is 500 to 4,000 MPa, preferably 750 to 3,000 MPa can be mentioned. Here, the flexural modulus at 25°C is a value measured according to JIS K7171. If the flexural modulus at 25° C. is 500 MPa or more, the decorative sheet will have sufficient rigidity, and even if it is subjected to the insert molding method, the surface properties and moldability will be much better. In addition, when the flexural modulus at 25° C. is 3,000 MPa or less, sufficient tension can be applied in the case of roll-to-roll production, and slack is less likely to occur, so the pattern is printed over and over again without shifting. The so-called pattern registration becomes good.

In order to improve the adhesion with the layer provided thereon, the substrate layer 1 is subjected to a physical or chemical surface treatment such as an oxidation method or roughening method on one side or both sides, if necessary. may Examples of the oxidation method for the surface treatment of the substrate layer 1 include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone ultraviolet treatment, and the like. Further, examples of the roughening method performed as the surface treatment of the base material layer 1 include a sandblasting method, a solvent treatment method, and the like. These surface treatments are appropriately selected according to the type of the resin component that constitutes the substrate layer 1, but from the viewpoint of effects, operability, and the like, a corona discharge treatment method is preferred.

Further, the substrate layer 1 may be subjected to a treatment such as forming a known adhesive layer.

Furthermore, the base material layer 1 may be colored using a coloring agent, or may be uncolored. Moreover, the base material layer 1 may be in any mode of opaque, colorless and transparent, colored and transparent, and translucent. The coloring agent used for the substrate layer 1 is not particularly limited, but preferably includes a coloring agent that does not change color even under temperature conditions of 150° C. or higher. Specifically, existing dry colors, paste colors, and masterbatch resins. composition and the like.

The thickness of the base material layer 1 is appropriately set according to the application of the decorative sheet, the molding method for integration with the molding resin, and the like, and is usually about 25 to 1000 μm and about 50 to 700 μm. More specifically, when the decorative sheet of the present invention is subjected to insert molding, the thickness of the substrate layer 1 is usually about 50 to 1000 μm, preferably about 100 to 700 μm, more preferably 100 to 500 μm. degree. Further, when the decorative sheet of the present invention is subjected to the simultaneous injection molding decoration method, the thickness of the base material layer 1 is usually about 25 to 200 μm, preferably about 50 to 200 μm, more preferably about 70 to 200 μm. is mentioned.

[Surface layer 2]
The surface layer 2 is a layer provided on the outermost surface of the decorative sheet for the purpose of improving the scratch resistance and weather resistance of the decorative sheet. The material forming the surface layer 2 is not particularly limited, but resins such as thermoplastic resins, thermosetting resins, and ionizing radiation-curable resins are usually used, and ionizing radiation-curable resins are preferably used.

The surface layer 2 may have a single layer structure or a multilayer structure. Moreover, when the surface layer 2 has a multilayer structure, the materials constituting each layer may be the same or different. Even when the surface layer 2 has a multilayer structure, each layer is preferably formed of a cured resin composition containing an ionizing radiation-curable resin. In addition, the surface layer 2 may have an uneven surface for the purpose of imparting a three-dimensional tactile sensation and a sense of design to the decorative sheet.

When the surface layer 2 is formed of a cured product of a resin composition containing an ionizing radiation-curable resin, the surface layer 2 is less permeable to the solvent. Therefore, in the manufacturing process of the decorative sheet, the solvent is difficult to evaporate through the surface layer 2, and in particular, bubbles due to the low boiling point solvent are likely to occur. On the other hand, in the decorative sheet of the present invention, since the predetermined high boiling point solvent is contained, the generation of air bubbles due to the vaporization of the solvent is suitably suppressed. Ionizing radiation curable resins can be preferably used. The ionizing radiation-curable resin suitably used for forming the surface layer 2 will be described in detail below.

(Ionizing radiation curable resin)
The ionizing radiation-curable resin used for forming the surface layer 2 is a resin that crosslinks and cures when irradiated with ionizing radiation. A suitable mixture of at least one of prepolymers, oligomers, monomers, and the like. Here, the ionizing radiation means, among electromagnetic waves or charged particle beams, those having energy quanta capable of polymerizing or cross-linking molecules, and usually ultraviolet rays (UV) or electron beams (EB) are used. ray, electromagnetic waves such as γ-rays, charged particle beams such as α-rays and ion beams. Among ionizing radiation curable resins, electron beam curable resins can be solvent-free, do not require a photopolymerization initiator, and provide stable curing characteristics, and are therefore suitable for forming the surface layer 2. used.

As the monomer used as the ionizing radiation-curable resin, a (meth)acrylate monomer having a radically polymerizable unsaturated group in the molecule is suitable, and a polyfunctional (meth)acrylate monomer is particularly preferable. The polyfunctional (meth)acrylate monomer may be a (meth)acrylate monomer having two or more (difunctional or more), preferably three or more (trifunctional or more) polymerizable unsaturated bonds in the molecule. Specific examples of polyfunctional (meth)acrylates include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di( meth) acrylate, neopentyl glycol di(meth) acrylate, polyethylene glycol di(meth) acrylate, neopentyl glycol hydroxypivalate di(meth) acrylate, dicyclopentanyl di(meth) acrylate, caprolactone-modified dicyclopentenyl di( meth)acrylate, ethylene oxide-modified phosphate di(meth)acrylate, allylated cyclohexyl di(meth)acrylate, isocyanurate di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate , dipentaerythritol tri(meth)acrylate, propionic acid-modified dipentaerythritol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, propylene oxide-modified trimethylolpropane tri(meth)acrylate, tris(acryloxyethyl) isocyanurate , propionic acid-modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene oxide-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, and the like. These monomers may be used singly or in combination of two or more.

In addition, as the oligomer used as the ionizing radiation-curable resin, a (meth)acrylate oligomer having a radically polymerizable unsaturated group in the molecule is suitable, and among them, two or more polymerizable unsaturated bonds in the molecule. A polyfunctional (meth)acrylate oligomer having (2 or more functionalities) is preferred. Examples of polyfunctional (meth)acrylate oligomers include polycarbonate (meth)acrylate, acrylic silicone (meth)acrylate, urethane (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate, and polyether (meth)acrylate. , polybutadiene (meth)acrylate, silicone (meth)acrylate, oligomers having a cationic polymerizable functional group in the molecule (e.g., novolak type epoxy resin, bisphenol type epoxy resin, aliphatic vinyl ether, aromatic vinyl ether, etc.). . Here, the polycarbonate (meth)acrylate is not particularly limited as long as it has a carbonate bond in the polymer main chain and a (meth)acrylate group in the terminal or side chain. It can be obtained by esterification with acrylic acid. Polycarbonate (meth)acrylate may be, for example, urethane (meth)acrylate having a polycarbonate skeleton. A urethane (meth)acrylate having a polycarbonate skeleton can be obtained, for example, by reacting a polycarbonate polyol, a polyvalent isocyanate compound, and a hydroxy (meth)acrylate. Acrylic silicone (meth)acrylates can be obtained by radically copolymerizing silicone macromonomers with (meth)acrylate monomers. Urethane (meth)acrylate can be obtained, for example, by esterifying a polyurethane oligomer obtained by reacting a polyether polyol or polyester polyol with a polyisocyanate compound with (meth)acrylic acid. Epoxy (meth)acrylate can be obtained, for example, by reacting (meth)acrylic acid with an oxirane ring of a relatively low-molecular-weight bisphenol-type epoxy resin or novolac-type epoxy resin for esterification. A carboxyl-modified epoxy (meth)acrylate obtained by partially modifying this epoxy (meth)acrylate with a dibasic carboxylic acid anhydride can also be used. Polyester (meth)acrylate is obtained, for example, by esterifying the hydroxyl groups of a polyester oligomer having hydroxyl groups at both ends obtained by condensation of polyhydric carboxylic acid and polyhydric alcohol with (meth)acrylic acid, or to polyhydric carboxylic acid. It can be obtained by esterifying the terminal hydroxyl group of the oligomer obtained by adding alkylene oxide with (meth)acrylic acid. Polyether (meth)acrylate can be obtained by esterifying the hydroxyl groups of polyether polyol with (meth)acrylic acid. Polybutadiene (meth)acrylate can be obtained by adding (meth)acrylic acid to the side chain of polybutadiene oligomer. A silicone (meth)acrylate can be obtained by adding (meth)acrylic acid to the terminal or side chain of a silicone having a polysiloxane bond in its main chain. These oligomers may be used singly or in combination of two or more.

Among the ionizing radiation-curable resins described above, it is preferable to use polycarbonate (meth)acrylate from the viewpoint of obtaining excellent moldability. Moreover, from the viewpoint of achieving both moldability and scratch resistance, it is more preferable to use a combination of polycarbonate (meth)acrylate and urethane (meth)acrylate.

More preferably, the surface layer 2 is made of a cured resin composition containing an ionizing radiation-curable resin and a thermoplastic resin. The ratio of the ionizing radiation curable resin and the thermoplastic resin in the surface layer 2 is preferably ionizing radiation curable resin:thermoplastic resin=10:90 to 25:75, preferably 15:85 to 15:85. About 25:75 is more preferable, and about 20:80 to 25:75 is even more preferable.

The thermoplastic resin is not particularly limited, but preferably acrylic resin, acrylic-modified polyolefin resin, chlorinated polyolefin resin, vinyl chloride-vinyl acetate copolymer, thermoplastic urethane resin, thermoplastic polyester resin, polyamide resin, rubber system resins, and the like. Among these, acrylic resins are particularly preferable from the viewpoint of obtaining excellent chemical resistance. When the ionizing radiation curable resin and the acrylic resin are used together, the chemical resistance is improved, but the solvent hardly permeates the surface layer 2. Therefore, it can be said that bubbles due to the low boiling point solvent are particularly likely to occur. As described above, in the decorative sheet of the present invention, since the predetermined high boiling point solvent is contained, the generation of air bubbles due to the vaporization of the solvent is suitably suppressed. Chemical resistance can be favorably enhanced while suppressing air bubbles by using a combination of a curable resin and an acrylic resin.

Acrylic resins include homopolymers of (meth)acrylic acid esters, copolymers of two or more different (meth)acrylic acid ester monomers, and copolymers of (meth)acrylic acid esters and other monomers. Specific examples include polymethyl (meth)acrylate, polyethyl (meth)acrylate, polypropyl (meth)acrylate, polybutyl (meth)acrylate, methyl (meth)acrylate-(meth) ( A (meth)acrylic resin composed of a homopolymer or a copolymer containing a meth)acrylic acid ester is preferably used.

The weight average molecular weight of the thermoplastic resin is not particularly limited, but from the viewpoint of obtaining excellent chemical resistance, it is preferably about 90,000 to 150,000, more preferably about 100,000 to 140,000, further preferably about 110,000. Up to about 130,000 can be mentioned.

The weight average molecular weight of the thermoplastic resin in this specification is a value measured by gel permeation chromatography using polystyrene as a standard substance.

(other additive ingredients)
Various additives can be added to the surface layer 2 according to the desired physical properties of the surface layer 2 . Examples of such additives include weather resistance improvers such as ultraviolet absorbers and light stabilizers, abrasion resistance improvers, polymerization inhibitors, cross-linking agents, infrared absorbers, antistatic agents, adhesion improvers, leveling agents, Examples include thixotropic agents, coupling agents, plasticizers, antifoaming agents, fillers, solvents, colorants and the like. These additives can be appropriately selected and used from commonly used ones. As the ultraviolet absorber or light stabilizer, a reactive ultraviolet absorber or light stabilizer having a polymerizable group such as a (meth)acryloyl group in the molecule can also be used.

(Thickness of surface layer 2)
The thickness of the surface layer 2 after curing is not particularly limited, but is, for example, 1 to 100 μm, preferably 1 to 50 μm, more preferably 1 to 30 μm. When the thickness in such a range is satisfied, sufficient physical properties as a surface protective layer such as scratch resistance and weather resistance can be obtained. Since it is possible to irradiate radiation uniformly, it is possible to cure uniformly, which is economically advantageous.

(Formation of surface layer 2 when ionizing radiation curable resin is used)
The surface layer 2 is formed by, for example, preparing an ionizing radiation-curable resin composition containing an ionizing radiation-curable resin, applying the composition, and cross-linking and curing the composition. The viscosity of the ionizing radiation-curable resin composition may be any viscosity that allows the formation of an uncured resin layer on the surface of the layer adjacent to the surface layer 2 by the application method described below.

As described above, in the decorative sheet of the present invention, the layer containing a high boiling point solvent and/or a low boiling point solvent is not particularly limited, and the surface layer 2 contains a high boiling point solvent and/or a low boiling point solvent. It may be For example, the surface layer 2 can be formed by blending a high boiling point solvent and/or a low boiling point solvent in an ionizing radiation curable resin composition containing an ionizing radiation curable resin.

In the present invention, the prepared coating liquid is coated by a known method such as gravure coating, bar coating, roll coating, reverse roll coating, comma coating, preferably gravure coating, so as to have the above thickness, and is uncured. A resin layer is formed.

The surface layer 2 is formed by irradiating the uncured resin layer thus formed with ionizing radiation such as electron beams and ultraviolet rays to cure the uncured resin layer. Here, when an electron beam is used as the ionizing radiation, the acceleration voltage can be appropriately selected according to the thickness of the resin and the layer used, but the acceleration voltage is usually about 70 to 300 kV.

In electron beam irradiation, the higher the acceleration voltage, the higher the penetration ability. The acceleration voltage is selected so that the thicknesses of are substantially equal. As a result, it is possible to suppress the irradiation of excess electron beams to the layers located under the surface layer 2, and to minimize the deterioration of each layer due to the excess electron beams.

The irradiation dose is preferably an amount that saturates the crosslink density of the surface layer 2, and is usually selected in the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 50 kGy (1 to 5 Mrad).

Furthermore, the electron beam source is not particularly limited, and various electron beam accelerators such as Cockroft-Walton type, Vandegraft type, resonance transformer type, insulated core transformer type, linear type, dynamitron type, and high frequency type can be used. can be used.

When ultraviolet rays are used as the ionizing radiation, rays containing ultraviolet rays having a wavelength of 190 to 380 nm may be emitted. Examples of ultraviolet light sources include, but are not limited to, high-pressure mercury lamps, low-pressure mercury lamps, metal halide lamps, and carbon arc lamps.

By adding various additives to the surface layer 2 thus formed, the surface layer 2 has a hard coating function, an anti-fog coating function, an anti-fouling coating function, an anti-glare coating function, an anti-reflection coating function, an ultraviolet shielding coating function, an infrared ray A process of imparting a function such as a shielding coat function may be performed.

[Primer layer 3]
The primer layer 3 is provided under the surface layer 2 as necessary for the purpose of improving the adhesion of the surface layer 2 and the like. The primer layer 3 is provided between the base layer 1 and the surface layer 2, between the pattern layer 4 and the surface layer 2 when the pattern layer 4 is provided, and/or between the base layer 1 and the pattern layer 4. , are optional layers.

From the viewpoint of enhancing the adhesion between the surface layer 2 and the layers located therebelow, it is preferable that the primer layer 3 is provided immediately below the surface layer 2 .

The primer composition constituting the primer layer 3 includes urethane resin, (meth)acrylic resin, (meth)acrylic-urethane copolymer resin, vinyl chloride-vinyl acetate copolymer, polyester resin, butyral resin, and chlorinated polypropylene. , chlorinated polyethylene or the like as a binder resin is preferably used, and these resins can be used singly or in combination of two or more. Among these, urethane resins, (meth)acrylic resins, and (meth)acrylic-urethane copolymer resins are preferred.

As the urethane resin, a polyurethane containing polyol (polyhydric alcohol) as a main component and isocyanate as a cross-linking agent (curing agent) can be used. As the polyol, those having two or more hydroxyl groups in the molecule, for example, polyester polyol, polyethylene glycol, polypropylene glycol, acrylic polyol, polyether polyol and the like are used. Examples of the isocyanate include polyisocyanates having two or more isocyanate groups in the molecule, aromatic isocyanates such as 4,4-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, and hydrogenated diphenylmethane diisocyanate. Aliphatic (or alicyclic) isocyanates such as are used. It is also possible to mix urethane resin and butyral resin.

In terms of adhesion with the surface layer 2 after cross-linking, difficulty of causing interaction after lamination of the surface layer 2, physical properties, and moldability, acrylic polyol or polyester polyol as a polyol, hexamethylene diisocyanate as a cross-linking agent, A combination of 4,4-diphenylmethane diisocyanate is preferred, and a combination of acrylic polyol and hexamethylene diisocyanate is particularly preferred.

The (meth)acrylic resin may be a homopolymer of a (meth)acrylic acid ester, a copolymer of two or more different (meth)acrylic acid ester monomers, or a copolymer of a (meth)acrylic acid ester and another monomer. Polymers include, specifically, polymethyl (meth)acrylate, polyethyl (meth)acrylate, poly(meth)propyl acrylate, polybutyl (meth)acrylate, methyl (meth)acrylate- Butyl (meth)acrylate copolymer, ethyl (meth)acrylate-butyl (meth)acrylate copolymer, ethylene-methyl (meth)acrylate copolymer, styrene-methyl (meth)acrylate copolymer A (meth)acrylic resin comprising a homopolymer or a copolymer containing a (meth)acrylic acid ester such as is preferably used.

As the (meth)acrylic-urethane copolymer resin, for example, an acrylic-urethane (polyester urethane) block copolymer resin is preferable. As the curing agent, the various isocyanates described above are used. If desired, the acrylic/urethane ratio (mass ratio) of the acrylic-urethane (polyester urethane) block copolymer resin is preferably adjusted within the range of 9/1 to 1/9, more preferably 8/2 to 2/8. is preferred.

Although the thickness of the primer layer 3 is not particularly limited, it is, for example, about 0.5 to 20 μm, preferably 1 to 5 μm.

The primer layer 3 is formed using a primer composition by gravure coating, gravure reverse coating, gravure offset coating, spinner coating, roll coating, reverse roll coating, kiss coating, wheel coating, dip coating, solid coating by silk screen, wire bar coating, It is formed by a normal coating method such as flow coating, comma coating, flow coating, brush coating, spray coating, or a transfer coating method. Here, the transfer coating method is a method in which a coating film such as a primer layer or an adhesive layer is formed on a thin sheet (film substrate), and then the target layer surface in the decorative sheet is coated.

As described above, in the decorative sheet of the present invention, the layer containing a high boiling point solvent and/or a low boiling point solvent is not particularly limited, and the primer layer 3 contains a high boiling point solvent and/or a low boiling point solvent. It may be For example, the primer layer 3 can be formed by blending a high boiling point solvent and/or a low boiling point solvent in the primer composition.

[Pattern layer 4]
The pattern layer 4 is a layer provided as necessary under the surface layer 2 for the purpose of imparting decorativeness to the decorative sheet. The pattern layer 4 is provided between the base layer 1 and the surface layer 2, between the base layer 1 and the primer layer 3 when the primer layer 3 is provided, or between the concealing layer and the surface layer 2 when the concealing layer is provided. etc., is a layer provided as necessary.

The pattern layer 4 can be a layer in which a desired pattern is formed using an ink composition, for example. As the ink composition used for forming the picture layer 4, a mixture of a binder, a coloring agent such as a pigment and a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, etc. is used. .

The binder used in the ink composition is not particularly limited, but examples include polyurethane resins, vinyl chloride/vinyl acetate copolymer resins, vinyl chloride/vinyl acetate/acrylic copolymer resins, chlorinated polypropylene resins, and acrylic resins. , polyester resins, polyamide resins, butyral resins, polystyrene resins, nitrocellulose resins, cellulose acetate resins, and the like. These binders may be used singly or in combination of two or more.

Colorants used in the ink composition are not particularly limited, but examples include carbon black (ink), iron black, titanium white, antimony white, yellow lead, titanium yellow, red iron oxide, cadmium red, ultramarine blue, and cobalt blue. organic pigments or dyes such as quinacridone red, isoindolinone yellow, and phthalocyanine blue; metal pigments consisting of scale-like foil pieces such as aluminum and brass; scale-like foils such as titanium dioxide-coated mica and basic lead carbonate A pearl luster (pearl) pigment consisting of flakes and the like can be mentioned.

The pattern formed by the pattern layer 4 is also not particularly limited, but may be, for example, a wood grain pattern, a marble pattern (e.g., travertine marble pattern), a stone grain pattern imitating the surface of a rock, or a texture or cloth-like pattern. Examples include a fabric pattern, a tiled pattern, and a brickwork pattern, and may be a pattern such as a parquet or patchwork that combines these, or may be a single-color solid pattern (so-called all-over solid pattern). These patterns are formed by multi-color printing using the usual process colors of yellow, red, blue, and black, but they can also be formed by special-color multi-color printing by preparing individual color plates that make up the pattern. can be formed.

As described above, in the decorative sheet of the present invention, the layer containing a high boiling point solvent and/or a low boiling point solvent is not particularly limited, and the pattern layer 4 contains a high boiling point solvent and/or a low boiling point solvent. It may be For example, the pattern layer 4 can be formed by blending a high boiling point solvent and/or a low boiling point solvent in the ink composition.

Although the thickness of the pattern layer 4 is not particularly limited, it is, for example, 1 to 30 μm, preferably 1 to 20 μm.

Also, the pattern layer 4 may be a metal thin film layer. Examples of metals forming the metal thin film layer include tin, indium, chromium, aluminum, nickel, copper, silver, gold, platinum, zinc, and alloys containing at least one of these. A method for forming the metal thin film layer is not particularly limited, and examples thereof include a vapor deposition method such as a vacuum vapor deposition method, a sputtering method, and an ion plating method using the above metals. The metal thin film layer may be provided on the entire surface or may be provided partially. Further, in order to improve adhesion with adjacent layers, a primer layer using a known resin may be provided on the front and rear surfaces of the metal thin film layer.

[Hiding layer]
The concealing layer is provided between the base layer 1 and the surface layer 2 for the purpose of suppressing color changes and variations in the base layer 1, and between the base layer 1 and the primer layer 3 if the primer layer 3 is provided. , or if the pattern layer 4 is provided, it is a layer provided between the base material layer 1 and the pattern layer 4 as necessary.

The concealing layer is provided to prevent the base layer from adversely affecting the color tone and pattern of the decorative sheet, and is generally formed as an opaque layer.

The concealing layer is formed using an ink composition in which a coloring agent such as a pigment or a dye, an extender, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, and the like are appropriately mixed with a binder. The ink composition for forming the concealing layer is appropriately selected from those used for the pattern layer described above.

The concealing layer is usually set to have a thickness of about 1 to 20 μm, and is desirably formed as a so-called solid printing layer.

The concealing layer can be formed by ordinary printing methods such as gravure printing, offset printing, silk screen printing, printing by transfer from a transfer sheet, inkjet printing; gravure coating, gravure reverse coating, gravure offset coating, spinner coating, roll coating, reverse roll. It is formed by a normal coating method such as coating.

As described above, in the decorative sheet of the present invention, the layer containing a high boiling point solvent and/or a low boiling point solvent is not particularly limited, and the concealing layer contains a high boiling point solvent and/or a low boiling point solvent. may be For example, the ink composition can be blended with a high boiling point solvent and/or a low boiling point solvent to form the hiding layer.

[Transparent resin layer]
For the purpose of improving chemical resistance and wear resistance, the transparent resin layer is provided between the base layer 1 and the surface layer 2, between the base layer 1 and the primer layer 3 when the primer layer 3 is provided, and the pattern layer 4 If provided, between the pattern layer 4 and the surface layer 2, or if the primer layer 3 and the pattern layer 4 are provided in this order on the base layer 1, between the primer layer 3 and the pattern layer 4, etc., as necessary. layer to be provided. The transparent resin layer is a layer preferably provided in the decorative sheet integrated with the molding resin by insert molding.

The resin component that forms the transparent resin layer is appropriately selected according to transparency, three-dimensional moldability, shape stability, chemical resistance, etc., but thermoplastic resins are usually used. The thermoplastic resin is not particularly limited, but examples include acrylic resins, polyolefin resins such as polypropylene and polyethylene, polycarbonate resins, ABS resins, polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), and vinyl chloride resins. etc. are used. Among these thermoplastic resins, from the viewpoint of chemical resistance, abrasion resistance, etc., acrylic resins, polyolefin resins, polycarbonate resins, and polyester resins are preferred; acrylic resins and polyester resins are more preferred; polyester resins are more preferred. resin.

In order to improve the adhesion with other layers in contact with the transparent resin layer, one side or both sides of the transparent resin layer may be subjected to physical or chemical surface treatment such as an oxidation method or a roughening method, if necessary. good too. These physical or chemical surface treatments are similar to the surface treatments applied to the substrate layer.

Although the thickness of the transparent resin layer is not particularly limited, it is, for example, 10 to 200 μm, preferably 15 to 150 μm.

The transparent resin layer may be laminated via an adhesive, or may be directly laminated without an adhesive. When laminating via an adhesive, examples of adhesives used include polyester resins, polyether resins, polyurethane resins, epoxy resins, phenol resins, polyamide resins, polyolefin resins, poly Examples include vinyl acetate resins, cellulose resins, (meth)acrylic resins, polyimide resins, amino resins, rubbers, and silicone resins. Moreover, when laminating|stacking without an adhesive agent, methods, such as an extrusion method, a sand lamination method, and a thermal lamination method, can be performed.

[Back adhesive layer]
A back adhesive layer (not shown) is optionally provided on the side opposite to the outer surface of the decorative sheet for the purpose of enhancing adhesion to the molding resin when molding the decorative resin molded product. layer.

A thermoplastic resin or a curable resin is used for the back adhesive layer depending on the molding resin used for the decorative resin molded product.

Thermoplastic resins used for forming the back adhesive layer include, for example, acrylic resins, acrylic-modified polyolefin resins, chlorinated polyolefin resins, vinyl chloride/vinyl acetate copolymers, thermoplastic urethane resins, thermoplastic polyester resins, and polyamides. Resins, rubber-based resins, and the like can be mentioned. These thermoplastic resins may be used singly or in combination of two or more.

Thermosetting resins used for forming the back adhesive layer include, for example, urethane resins and epoxy resins. These thermosetting resins may be used singly or in combination of two or more.

(Manufacturing method of decorative sheet)
The decorative sheet of the present invention can be produced, for example, by a method comprising a step of laminating a surface layer 2 containing a solvent having a boiling point of 140° C. or higher on a substrate layer 1 . Further, when the decorative sheet of the present invention has the primer layer 3, the pattern layer 4, etc., for example, at least one of the surface layer 2, the primer layer 3, the pattern layer 4, etc. has a boiling point A decorative sheet can be produced by laminating on the substrate layer 1 while containing a solvent of 140° C. or higher. By such a production method, the decorative sheet of the present invention can contain a high-boiling solvent.

2. Decorative Resin Molded Product The decorative resin molded product of the present invention is formed by integrating a molding resin with the decorative sheet of the present invention. That is, the decorative resin molded product of the present invention has at least a molded resin layer, a substrate layer, and a surface layer, and is characterized by containing a solvent having a boiling point of 140° C. or higher.

FIG. 3 shows the cross-sectional structure of one embodiment of the decorative resin molded product of the present invention.

The decorative resin-molded product of the present invention can be produced by a method comprising the step of forming a molded resin layer by injecting a resin onto the substrate layer 1 side of the decorative sheet of the present invention. Specifically, using the decorative sheet of the present invention, various injection molding methods such as an insert molding method, an injection molding simultaneous decoration method, a blow molding method, and a gas injection molding method are produced.

In the insert molding method, first, in the vacuum forming process, the decorative sheet of the present invention is vacuum-formed (off-line preforming) in advance into the surface shape of the molded product using a vacuum forming mold, and then, if necessary, the excess portion is trimmed. Obtain a molded sheet. This molding sheet is inserted into an injection mold, the injection mold is clamped, and the resin in a fluid state is injected into the mold and solidified. A decorative resin molded product is manufactured by integrating the material layer 1 side.

More specifically, the decorated resin molded article (or the decorated resin molded article with a thermoplastic resin film layer) of the present invention is manufactured by an insert molding method including the following steps.

a vacuum forming step of forming the decorative sheet of the present invention into a three-dimensional shape in advance using a vacuum forming mold;
A step of trimming the excess portion of the vacuum-formed decorative sheet to obtain a molded sheet, and inserting the molded sheet obtained in the above step into an injection mold, closing the injection mold, and pouring the resin in a fluid state into the mold. The process of injecting the resin and molding sheet into one.

In the vacuum forming step in the insert molding method, the decorative sheet may be heated and formed. The heating temperature at this time is not particularly limited, and may be appropriately selected according to the type of resin forming the decorative sheet, the thickness of the decorative sheet, and the like. As described above, in the decorative sheet of the present invention, the inclusion of the high boiling point solvent effectively suppresses the generation of air bubbles even when heated to a high temperature of 140° C. or higher, for example. Therefore, in the method for manufacturing the decorative resin molded product of the present invention, when the molded resin layer is laminated by injecting the resin onto the base layer side of the decorative sheet of the present invention, the resin is heated to 140° C. or higher. good too. As a specific example of the heating temperature, when an ABS resin film is used as the substrate layer, it is usually about 140 to 250°C, preferably about 140 to 200°C. In addition, in the integration step, the temperature of the resin in a fluid state is not particularly limited, but it is usually about 180 to 320.degree. C., preferably about 220 to 280.degree.

In the simultaneous injection molding and decorating method, the decorative sheet of the present invention is arranged in a female mold that is also used as a vacuum molding mold provided with suction holes for injection molding, and preforming (in-line preforming) is performed in this female mold. After that, the injection mold is clamped, and the resin in a fluid state is injected and filled into the mold, solidified, and simultaneously with the injection molding, the base layer of the decorative sheet of the present invention is applied to the outer surface of the resin molded product. A decorative resin molded product is manufactured by integrating one side.

More specifically, the decorated resin molded article (or the decorated resin molded article with the thermoplastic resin film layer) of the present invention is manufactured by the simultaneous injection molding and decorating method including the following steps.

After the decorative sheet of the present invention is placed so that the base layer 1 side of the decorative sheet faces the molding surface of a movable mold having a molding surface of a predetermined shape, the decorative sheet is heated, A step of preforming a decorative sheet by softening and applying vacuum suction from the movable mold side to adhere the softened decorative sheet along the molding surface of the movable mold;
After the movable mold and fixed mold having the decorative sheet adhered along the molding surface are clamped, the resin molding material in a fluid state is injected and filled into the cavity formed by both molds. An injection molding process in which the formed resin molded body and the decorative sheet are laminated and integrated by solidification, and a resin molded body in which all layers of the decorative sheet are laminated by separating the movable mold from the fixed mold. The process of removing the

In the preforming step of the simultaneous injection molding and decorating method, the heating temperature of the decorative sheet is not particularly limited, and may be appropriately selected depending on the type of resin constituting the decorative sheet, the thickness of the decorative sheet, and the like. When a polyester resin film or an acrylic resin film is used as the base material layer, the temperature can be usually about 70 to 130°C. Also, in the injection molding process, the temperature of the resin in a fluid state is not particularly limited, but it is usually about 180 to 320.degree. C., preferably about 220 to 280.degree.

In addition, the decorative resin molded product (or the decorative resin molded product with a thermoplastic resin film layer) of the present invention is prepared by a vacuum pressure bonding method or the like on a three-dimensional resin molded product (molded resin layer) prepared in advance. It can also be produced by a decorating method of sticking the decorating sheet of the present invention.

In the vacuum crimping method, first, the decorative sheet and the resin molding of the present invention are placed in a vacuum crimping machine consisting of a first vacuum chamber located on the upper side and a second vacuum chamber located on the lower side. It is placed in the vacuum pressure bonding machine so that the vacuum chamber side, the resin molded body is on the second vacuum chamber side, and the base layer 1 side of the decorative sheet faces the resin molded body side, and the two vacuum chambers are placed in a vacuum state. do. The resin molded body is placed on a vertically movable platform provided on the side of the second vacuum chamber. Next, while pressurizing the first vacuum chamber, the molded body is pressed against the decorative sheet using a lifting table, and the resin molded body is stretched while stretching the decorative sheet using the pressure difference between the two vacuum chambers. affixed to the surface of Finally, the two vacuum chambers are opened to the atmospheric pressure, and the excess portion of the decorative sheet is trimmed as required to obtain the decorated resin molded product of the present invention.

In the vacuum pressure bonding method, it is preferable to include a step of heating the decorative sheet in order to soften the decorative sheet and improve formability before the step of pressing the molding against the decorative sheet. A vacuum compression bonding method including the process is sometimes called a vacuum thermocompression bonding method. The heating temperature in this step may be appropriately selected depending on the type of resin constituting the decorative sheet and the thickness of the decorative sheet. , usually about 60 to 200°C.

In the decorative resin-molded product of the present invention, the molding resin layer may be formed by selecting a molding resin according to the application. The molding resin may be a thermoplastic resin or a thermosetting resin.

Examples of thermoplastic resins used as molding resins include polyolefin resins such as polyethylene and polypropylene, ABS resins, styrene resins, polycarbonate resins, acrylic resins, and vinyl chloride resins. These thermoplastic resins may be used singly or in combination of two or more.

Thermosetting resins used as molding resins include, for example, urethane resins and epoxy resins. These thermosetting resins may be used singly or in combination of two or more.

Since the decorative resin molded article of the present invention has excellent chemical resistance, wear resistance, etc., it can be used, for example, as an interior or exterior material for vehicles such as automobiles; Fittings such as window frames and door frames; interior materials for buildings such as walls, floors and ceilings; housings for home electric appliances such as television receivers and air conditioners;

EXAMPLES The present invention will be described in detail below with reference to examples and comparative examples. However, the present invention is not limited to the examples.

Examples 1-5
An ABS resin film (thickness: 475 μm) was used as the base layer. A resin composition in which 14 parts by mass of a thermoplastic resin (acrylic resin) and 5 parts by mass of an ionizing radiation-curable resin (EB resin A) are blended on the substrate layer (each of which is solvent A listed in Table 1 1.5% by mass of ~E, 79.5% by mass of ethyl acetate (boiling point of 77.1°C under 1 atmosphere), and 19.0% by mass of isopropyl alcohol (IPA, boiling point of 89.5°C under 1 atmosphere) %) was applied so that the thickness after curing was 10 μm to form an uncured resin layer. Next, these uncured resin layers were cured by irradiation with an acceleration voltage of 165 kV and an irradiation dose of 50 kGy (5 Mrad) to form a surface layer to produce each decorative sheet.

Details of the resins and solvents used in Examples and Comparative Examples are as follows.
EB resin A: bifunctional urethane acrylate monomer (molecular weight 500)
・Acrylic resin: Acrylic polymer (weight average molecular weight 120,000)
- Solvent A: diethylene glycol monobutyl ether acetate (boiling point under 1 atm is 247°C)
Solvent B: isophorone (boiling point under 1 atm is 215°C)
Solvent C: dibasic acid ester diethyl succinate (boiling point under 1 atm is 218°C)
Solvent D: ethyl lactate (boiling point under 1 atm is 154°C)
Solvent E: propylene glycol monomethyl ether acetate (boiling point under 1 atm is 145.8°C)

Comparative example 1
A decorative sheet was produced in the same manner as in Example 1-5, except that the resin composition forming the surface layer did not contain the solvents A to E listed in Table 1.

<Confirmation of bubble generation by heating>
Assuming preforming when producing a decorative resin molded product from the decorative sheet, each obtained decorative sheet is placed in a mold and heated from room temperature to 160°C with an infrared heater under vacuum forming conditions. Heated for 20 seconds. After the heating, the decorative sheet was removed from the mold, and the surface of the decorative sheet was visually observed to confirm the presence or absence of air bubbles. Table 1 shows the results.

In Table 1, EB resin means an ionizing radiation curable resin.

1 base material layer 2 surface layer 3 primer layer 4 design layer 5 molding resin layer

Claims (8)

having at least a substrate layer and a surface layer,
The base material layer is made of acrylonitrile-butadiene-styrene resin,
The surface layer is formed of a cured resin composition containing an ionizing radiation-curable resin,
The resin composition further contains a thermoplastic resin (excluding one containing a furyl group) ,
The mass ratio of the ionizing radiation curable resin and the thermoplastic resin in the surface layer is ionizing radiation curable resin:thermoplastic resin=10:90 to 25:75,
A decorative sheet containing a solvent having a boiling point of 140°C or higher. The decorative sheet according to claim 1, further comprising a solvent having a boiling point of less than 90°C. 3. The decorative sheet according to claim 1, wherein the surface layer has a multilayer structure. The decorative sheet according to any one of claims 1 to 3, comprising at least one of a primer layer and a pattern layer between the base layer and the surface layer. The decorative sheet according to any one of claims 1 to 4, which is obtained by laminating a surface layer containing a solvent having a boiling point of 140°C or higher on the base layer. The method for producing a decorative sheet according to any one of claims 1 to 4, comprising the step of laminating a surface layer containing a solvent having a boiling point of 140°C or higher on the base material layer. It has at least a molding resin layer, a substrate layer, and a surface layer,
The base material layer is made of acrylonitrile-butadiene-styrene resin,
The surface layer is formed of a cured resin composition containing an ionizing radiation-curable resin,
The resin composition further contains a thermoplastic resin (excluding one containing a furyl group) ,
The mass ratio of the ionizing radiation curable resin and the thermoplastic resin in the surface layer is ionizing radiation curable resin:thermoplastic resin=10:90 to 25:75,
A decorative resin molded product containing a solvent having a boiling point of 140°C or higher. A method for producing a decorated resin molded product, comprising a step of laminating a molded resin layer on the base layer side of the decorative sheet according to any one of claims 1 to 4 by injecting a resin.

Images