JP7210981B2 - Laminates and decorative articles - Google Patents

Description

TECHNICAL FIELD The present invention relates to laminates and decorative articles.

2. Description of the Related Art Conventionally, decorative resin molded products obtained by laminating a decorative sheet on the surface of a resin molded product have been used for interior and exterior parts of vehicles, interior materials for building materials, housings of home electric appliances, and the like. In the production of such a decorative resin molded product, a molding method is used in which a decorative sheet having a design provided in advance is integrated with a resin by injection molding. As a representative example of the molding method of a decorative resin molded product, a decorative sheet is previously molded into a three-dimensional shape using a vacuum molding die, the molded sheet is inserted into an injection molding die, and a resin in a fluid state is molded. The insert molding method, which integrates the resin and the molding sheet by injecting it into An injection-molding simultaneous decoration method for decorating the surface of a molded product can be mentioned.

The decorative resin molded products obtained by these molding methods are used in various applications such as vehicle interior and exterior parts as described above. In addition to surface properties such as the above, various designs are required in line with the diversification of consumer tastes in recent years. For example, developments have been made to impart a texture to a resin molded product by imparting a matte finish or irregularities to a specific patterned portion (for example, Patent Document 1). In addition, a synthetic resin molded part having a changing design surface has been proposed as one having a variety of design impressions (for example, Patent Document 2).

Furthermore, a decorative sheet has been proposed in which a light source is arranged on the opposite side of the decorative sheet from the viewer's side, and a different design is exhibited when the light source is turned on and when it is turned off (for example, Patent Document 3).

JP 2009-132145 A JP 2010-125817 A JP 2013-14051 A

As described above, there are known decorative sheets that exhibit different designs when the light source is turned on and when the light source is turned off. In such a decorative sheet, it is desirable that the design that appears when the light source is turned on is not visible, and that the design is visible only when the light source is turned on.

However, in the conventional decorative sheet, even when the light source is turned off, the design that appears when the light source is turned on may be visible. For example, in a decorative sheet provided with a light-shielding part and a light-transmitting part, by laminating a design layer and a concealing layer in order from the observer side, the light-transmitting property of the light-transmitting part is ensured when the light source is turned on. On the other hand, it is required that the light shielding part has a sufficient light shielding property and that the shielding layer is hardly visible when the light source is turned off. However, in the conventional decorative sheet, the concealing layer may be visible from the observer side even when the light source is turned off. It can be said that such a problem is likely to occur particularly when a monochromatic design layer is provided on the entire surface on the observer's side.

Under such circumstances, the present invention provides a laminate in which a light shielding portion and a light transmitting portion are provided by laminating a design layer and a concealing layer, in which the light transmittance of the light transmitting portion is ensured when the light source is turned on. A main object of the present invention is to provide a laminate in which the light shielding part has sufficient light shielding properties and in which the shielding layer is hardly visible when the light source is turned off. Another object of the present invention is to provide a decorative article using the laminate.

The present inventors have made extensive studies to solve the above problems. As a result, it is composed of a laminate including at least a design layer and a concealing layer on one side of the base material layer, and when viewed from above, the laminate has a light shielding portion that shields light and a light shielding portion that transmits light. and a light-transmitting portion that allows the light-shielding portion to have an optical density of 4.3 or more and the light-transmitting portion to have an optical density of 1.0 or more and 3.0 or less. It has been found that the light-shielding part has a sufficient light-shielding property while ensuring the light transmittance of the light-transmitting part when lit, and that the masking layer is hardly visible when the light source is turned off. 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. A laminate comprising at least a design layer and a concealing layer on one side of a base material layer,
The laminate has a light shielding portion that shields light and a light transmitting portion that transmits light when viewed from above,
The laminated body, wherein the optical density of the light-shielding portion is 4.3 or more, and the optical density of the light-transmitting portion is 1.0 or more and 3.0 or less.
Section 2. Item 2. The laminate according to Item 1, wherein the design layer contains 30 parts by mass or more of the pigment with respect to 100 parts by mass of the binder resin.
Item 3. Item 3. The laminate according to Item 1 or 2, wherein the design layer and the concealing layer have the same color.
Section 4. 4. The laminate according to any one of Items 1 to 3, wherein the pigment contained in the design layer is black.
Item 5. 5. The laminate according to any one of Items 1 to 4, further comprising a color adjusting layer between the design layer and the concealing layer.
Item 6. Item 6. The laminate according to any one of Items 1 to 5, comprising the substrate layer, the design layer, and the concealing layer in this order.
Item 7. Item 6. The laminate according to any one of Items 1 to 5, comprising the base layer, the concealing layer, and the design layer in this order.
Item 8. Item 8. The laminate according to any one of Items 1 to 7, wherein the laminate is in the form of a sheet.
Item 9. Item 9. The laminate according to any one of Items 1 to 8, further comprising a molded resin layer on the side of the concealing layer opposite to the design layer.
Item 10. A laminate according to any one of Items 1 to 9,
a light source disposed on the side of the concealing layer of the laminate;
A decorative article.

According to the present invention, when the light source is turned on, the light-transmitting part has sufficient light-transmitting properties, while the light-shielding part has sufficient light-shielding properties. body can be provided. Further, according to the present invention, it is possible to provide a decorative article using the laminate.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram of the cross-sectional structure of an example (1st aspect) of the laminated body of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is schematic-drawing sectional drawing of an example (1st aspect) of the laminated body of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is schematic-drawing sectional drawing of an example (1st aspect) of the laminated body of this invention. FIG. 4 is a schematic cross-sectional view of a decorative article using the laminate shown in FIG. 3; BRIEF DESCRIPTION OF THE DRAWINGS It is the schematic diagram which planarly viewed the laminated body of this invention. It is a schematic diagram of the cross-sectional structure of an example (2nd aspect) of the laminated body of this invention. It is a schematic-drawing sectional drawing of an example (2nd aspect) of the laminated body of this invention. It is a schematic-drawing sectional drawing of an example (2nd aspect) of the laminated body of this invention. FIG. 9 is a schematic cross-sectional view of a decorative article using the laminate shown in FIG. 8;

1. Laminate The laminate of the present invention is a laminate comprising at least a design layer and a concealing layer on one side of a substrate layer, and the laminate comprises a light shielding portion that shields light when viewed from above. and a light-transmitting portion for transmitting light, wherein the optical density of the light-shielding portion is 4.3 or more, and the optical density of the light-transmitting portion is 1.0 or more and 3.0 or less. and By having such a configuration, the laminate of the present invention has a sufficient light shielding property in the light shielding portion while ensuring the light transmittance of the light transmitting portion when the light source is turned on. When the light is turned off, it is possible to exhibit the property that the concealing layer is difficult to be visually recognized. The laminate of the present invention will be described in detail below.

The laminate of the present invention can be suitably used for decorating the surface of resin molded products such as vehicle interior and exterior parts, building interior materials, home appliance housings, and the like. Therefore, the laminate of the present invention can be suitably used as a decorative sheet for three-dimensional molding. In particular, when the laminate of the present invention is in the form of a sheet, it can be molded as a decorative sheet for three-dimensional molding, and laminated with a molded resin layer 9 described later to form a suitably decorated resin molded product.

In this specification, the numerical range indicated by "-" means "more than" and "less than". For example, the notation of 2 to 15 mm means 2 mm or more and 15 mm or less. Further, as will be described later, the laminate of the present invention may not have a design layer or the like, and may be transparent, for example. In addition, "(meth)acrylate" means "acrylate or methacrylate", and other similar terms have the same meaning.

Laminate Structure and Physical Properties of Laminate As shown in FIGS. and As will be described later, when the molded resin layer 9 is provided on the laminate 10 of the present invention, the substrate layer 1 of the laminate 10 is used for transfer as shown in FIGS. A transfer mold of the first mode in which the material layer 1 (hereinafter sometimes referred to as a transfer base layer) is peeled off and is not included in the decorative article 20, or a laminate as shown in FIGS. Any of the laminate types of the second aspect in which the base material layer 1 of the body 10 (hereinafter sometimes referred to as a base material layer for lamination) is included in the decorative article 20 can be employed.

As shown in FIGS. 2 to 4 and 7 to 9, the laminate 10 of the present invention is provided with at least one layer such as a surface protective layer 5, a primer layer 6, and a color adjustment layer 7, if necessary. may be provided. The surface protective layer 5 can be provided to improve surface properties such as scratch resistance of the surface of the laminate. In addition, the surface protective layer 5 is laminated so as to be the surface of the laminate 10 when the laminate 10 is used for the decorative article 20 . The primer layer 6 can be provided in at least one place between the layers such as the base layer 1, the design layer 3, the surface protective layer 5, etc. for the purpose of improving the adhesion between these layers. The color adjustment layer 7 can be provided, for example, between the masking layer 2 and the design layer 3 for the purpose of adjusting the color of light emitted from the light source 30 .

Further, in the transfer mold laminate 10 of the first aspect, a release layer 4 may be provided under the base layer 1 as necessary for the purpose of enhancing the releasability of the base layer 1 . In addition, the outermost surface on the side where the laminate 10 is laminated with the molded resin layer 9 (in the transfer mold laminate of the first aspect, the surface opposite to the base layer 1, and the surface of the second aspect) In a laminated body, an adhesive layer 8 or the like may be provided on the surface on the side of the substrate layer 1 .

As described above, in the case of laminating the molding resin layer 9 on the laminate 10 of the present invention, in the transfer mold laminate 10 of the first embodiment, as shown in FIGS. After lamination on the side opposite to the layer 1 to obtain a laminate 10 with a transfer substrate layer, for example, as shown in FIG. 3, the substrate layer 1 is peeled off. Therefore, as shown in FIG. 4, when the laminate 10 is used for the decorative article 20, the laminate 10 does not include the base material layer 1. As shown in FIG. In addition, the layers to be transferred using the transfer base layer (specifically, the surface protective layer 5, the primer layer 6, the design layer 3, the color adjustment layer 7, the concealing layer 2, the adhesive layer 8, etc.) It is called a transfer layer 11 (see FIGS. 1 to 4).

On the other hand, in the laminate 10 of the second aspect, the molded resin layer 9 is formed on the base material layer 1 side. Therefore, as shown in FIG. 9 , the base layer 1 is included in the laminate 10 even when the laminate 10 is used for the decorative article 20 .

As the laminated structure of the transfer type laminated body of the first aspect of the present invention, a laminated structure in which concealing layer/design layer/base layer are laminated in this order; concealing layer/design layer/releasing layer/base layer. Laminated structure in this order; Concealing layer/Design layer/Surface protective layer/Release layer/Base layer laminated in this order; Concealing layer/Design layer/Primer layer/Surface protective layer/Releasing layer / Laminated structure in which the base layer is laminated in this order; Laminated structure in which the concealing layer / color adjustment layer / design layer / primer layer / surface protective layer / release layer / base layer are laminated in this order; adhesive layer / concealment Layer/color adjustment layer/design layer/primer layer/surface protective layer/release layer/base layer laminated in this order; molding resin layer/adhesive layer/concealing layer/color adjustment layer/design layer/primer A laminate structure in which a layer/surface protective layer/release layer/base layer are laminated in this order may be used. FIG. 1 is a schematic cross-sectional view of an example of a laminate in which a concealing layer/design layer/base material layer (transfer base layer) are laminated in this order as one aspect of the laminate structure of the laminate of the first embodiment. indicates FIG. 2 shows, as one aspect of the laminate structure of the laminate of the first aspect, adhesive layer/concealing layer/color adjusting layer/design layer/primer layer/surface protective layer/release layer/base layer (transfer base). A schematic cross-sectional view of an example of a laminate in which material layers) are laminated in this order. In FIG. 3, as one aspect of the laminate structure of the laminate of the first aspect, molding resin layer/adhesive layer/concealing layer/color adjusting layer/design layer/primer layer/surface protective layer/release layer/base layer ( A schematic cross-sectional view of an example of a laminate in which transfer substrate layers) are laminated in this order is shown.

As the laminated structure of the laminated laminate according to the second aspect of the present invention, a laminated structure in which base layer/concealing layer/design layer are laminated in this order; base layer/concealing layer/design layer/surface protective layer. Laminated structure in this order: base layer/concealing layer/design layer/primer layer/surface protective layer laminated in this order; base layer/concealing layer/color adjusting layer/design layer/primer layer/ Laminated structure in which surface protective layer is laminated in this order; laminated structure in which adhesive layer/base layer/concealing layer/color adjusting layer/design layer/primer layer/surface protective layer are laminated in this order; molding resin layer/adhesive layer /base material layer/concealing layer/color adjusting layer/design layer/primer layer/surface protective layer in this order. FIG. 6 is a schematic cross-sectional view of an example of a laminate in which a substrate layer (laminating substrate layer)/concealing layer/design layer are laminated in this order as one aspect of the laminate structure of the laminate of the second aspect. indicates FIG. 7 shows, as one aspect of the laminate structure of the laminate of the second aspect, an adhesive layer/base material layer (laminating base material layer)/concealing layer/color adjusting layer/design layer/primer layer/surface protective layer. A schematic cross-sectional view of an example of a laminate laminated in this order is shown. FIG. 8 shows one aspect of the laminated structure of the laminate of the second aspect, which is formed of molding resin layer/adhesive layer/base layer (laminating base layer)/concealing layer/color adjusting layer/design layer/primer layer/surface. A schematic cross-sectional view of an example of a laminate in which protective layers are laminated in this order is shown.

As shown in the cross-sectional views of FIGS. 1 to 4 and FIGS. 6 to 9 and the plan view of FIG. and a translucent portion T for transmission. The light-shielding portion S corresponds to the position where the concealing layer 2 is laminated, and the position where the concealing layer 2 is not laminated (that is, the portion other than the light-shielding portion S) corresponds to the light-transmitting portion T. .

The laminate 10 of the present invention is characterized in that the optical density of the light shielding portion S is 4.3 or more and the optical density of the light transmitting portion T is 1.0 or more and 3.0 or less. In the laminate 10 of the present invention, since the light shielding portion S and the light transmitting portion T have such a specific optical density (OD), the design layer and the concealing layer are laminated to form a light shielding portion. In the laminated body provided with the light-transmitting part, when the light source is turned on, the light-transmitting part has sufficient light-transmitting properties while the light-shielding part has sufficient light-shielding properties, and when the light source is turned off, the concealing layer is hard to be visually recognized.

The optical density of the light shielding portion S is preferably 5.0 or higher.

Further, the optical density of the transparent portion T is preferably in the range of about 1.0 to 3.0, more preferably about 1.5 to 2.5.

In the present invention, in the case of the transfer type laminate of the first aspect, the base material layer 1 and the release layer 4 provided if necessary are finally used after being peeled off, so the laminate 10 is light-shielded. The optical densities of the portion S and the translucent portion T are the optical densities of the transfer layer 11 excluding the base layer 1 and the release layer 4 . The optical density of the transfer layer 11 can be measured in the state of a resin molded article obtained by transferring onto a highly transparent molding resin layer such as polycarbonate. On the other hand, in the case of the laminated body of the second embodiment, the optical density of the light-shielding portion S and the light-transmitting portion T of the laminated body 10 itself is used because the base layer 1 is also included in the laminated body.

The optical densities of the light-shielding portion S and the light-transmitting portion T of the laminate 10 of the present invention are each measured using a microscopic spectrophotometer.

As described later, the optical densities of the light-shielding portion S and the light-transmitting portion T are determined by the color and content of the pigment contained in the design layer 3, the color and content of the coloring agent contained in the concealing layer 2, and the It is adjusted by the components, thickness, etc. contained in (including layers other than the design layer 3 and the concealing layer 2).

Composition of each layer forming the laminate [design layer 3]
The design layer 3 is a layer provided on the viewer's side (the side opposite to the light source where the concealing layer 2 is positioned) for the purpose of imparting decorativeness to the laminate. The design of the design layer 3 is a design that is visible from the observer side when the light source is turned off.

The design layer 3 can be a layer in which a desired pattern is formed using an ink composition, for example. For example, when the concealing layer 2, which will be described later, is formed in a pattern and the design layer 3 has a monochromatic design on the entire surface, when the light source is turned off, the monochromatic design on the entire surface of the design layer 3 is visually recognized. The design of 2 is not visually recognized, and when the light source is turned on, the pattern-shaped design (for example, the pattern described later such as symbols and character information) of the part where the concealing layer 2 is not formed (that is, the translucent part T) is visible. It can be configured to be visible.

In the laminate 10, the design layer 3 may be provided partially or over the entire surface, preferably over the entire surface.

The design layer 3 can be formed, for example, by printing ink for forming the design layer by a conventionally known printing method such as gravure printing, silk screen printing, or offset printing. As the ink composition used for forming the design layer 3, 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.

A pigment is used as a colorant used in the ink composition. Examples of pigments include, but are not limited to, carbon black (ink), iron black, titanium white, antimony white, yellow lead, titanium yellow, red iron oxide, cadmium red, ultramarine blue, inorganic pigments such as cobalt blue; quinacridone red, Organic pigments or dyes such as isoindolinone yellow and phthalocyanine blue; metal pigments consisting of scale-like foils such as aluminum and brass; pearl luster (pearl) consisting of scale-like foils such as titanium dioxide-coated mica and basic lead carbonate A pigment etc. are mentioned.

The optical densities of the light-shielding portion S and the light-transmitting portion T of the laminate 10 of the present invention are set to the predetermined values, and when the light source is turned on, the light-shielding portion sufficiently shields light while ensuring the light transmittance of the light-transmitting portion. In addition, when the light source is turned off, the concentration of the pigment contained in the design layer 3 is The lower limit is preferably 30 parts by mass or more, more preferably 50 parts by mass or more, and the upper limit is preferably 95 parts by mass or less, more preferably 80 parts by mass or less. 95 parts by mass, 30 to 80 parts by mass, 50 to 95 parts by mass, and 50 to 80 parts by mass.

The pattern formed by the design layer 3 is not particularly limited. Patterns imitating fabric patterns, tiled patterns, brickwork patterns, etc., may be mentioned, and patterns such as marquetry and patchwork that combine these may be used, or monochromatic solid colors (so-called all-over solid) may be used. 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.

Moreover, the design layer 3 may include a portion composed of a metal thin film. Examples of metals forming the metal thin film include tin, indium, chromium, aluminum, nickel, copper, silver, gold, platinum, zinc, and alloys containing at least one of these. The method for forming the metal thin film 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. 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.

As described above, the design layer 3 preferably has a monochromatic design on the entire surface, and particularly preferably has a black design on the entire surface.

The thickness of the design layer 3 is not particularly limited as long as the optical densities of the light-shielding portions S and the light-transmitting portions T are set to the predetermined values, but the lower limit is preferably 0.5 μm or more, more preferably 1 μm or more. The upper limit is preferably 30 μm or less, more preferably 20 μm or less, and preferable ranges are about 0.5 to 30 μm, about 0.5 to 20 μm, about 1 to 30 μm, and about 1 to 20 μm. is mentioned.

[Concealing layer 2]
As described above, in the laminate 10 of the present invention, the light shielding portion S corresponds to the position where the concealing layer 2 is laminated, and the position where the concealing layer 2 is not laminated (the portion other than the light shielding portion S) is , corresponding to the translucent portion T. The shielding layer 2 is a layer provided on the light source side and provided to block transmission of light from the light source to the viewer side.

Since the masking layer 2 is provided to block light, it is generally formed as an opaque layer.

The concealing layer 2 is formed using an ink composition in which a coloring agent such as a pigment or 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 masking layer is appropriately selected from those used for the design layer 3 and used.

It is preferable that the design layer 3 and the concealing layer 2 have the same color (for example, black).

As described above, when the concealing layer 2 is formed in a pattern and the design layer 3 has a monochromatic design on the entire surface, when the light source is turned off, the monochromatic design on the entire surface of the design layer 3 is visually recognized. The design of 2 is not visually recognized, and when the light source is turned on, the pattern-shaped design (for example, the pattern described later such as symbols and character information) of the part where the concealing layer 2 is not formed (that is, the translucent part T) is visible. It can be configured to be visible.

The thickness of the masking layer 2 is not particularly limited as long as the optical densities of the light-shielding portion S and the light-transmitting portion T are set to the predetermined values, but the lower limit is preferably 0.5 μm or more, more preferably 1 μm or more. The upper limit is preferably 30 μm or less, more preferably 20 μm or less, and preferable ranges are about 0.5 to 30 μm, about 0.5 to 20 μm, about 1 to 30 μm, and about 1 to 20 μm. is mentioned.

[Base material layer 1]
The base material layer 1 is formed of a resin sheet (resin film) serving as a support in the laminate 10 of the present invention.

In the laminate 10 of the first aspect, the base layer 1 (transfer base layer) is a layer provided for transferring the transfer layer 11 to the molded resin layer 9, and is a resin that also serves as a support. It is formed of a sheet (resin film).

The resin component used in the transfer substrate layer is not particularly limited, and may be appropriately selected according to the releasability from the transfer layer 11, etc., but thermoplastic resins are preferred. Specific examples of the thermoplastic resin include the same as those exemplified in the later-described lamination substrate layer of the first aspect. Among these, polyethylene terephthalate (PET) resin is preferable as the transfer substrate layer. As the resin component forming the base material layer for transfer, only one type may be used, or two or more types may be mixed and used. Further, the transfer substrate layer 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.

The thickness of the transfer substrate layer is not particularly limited, and is appropriately set according to the use of the laminate, and is usually about 10 to 150 μm, preferably about 10 to 125 μm, more preferably about 10 to 80 μm. be done.

In addition, in the laminate 10 of the second aspect, the resin component used in the base material layer 1 (laminating base material layer) is not particularly limited. It may be selected as appropriate, but thermoplastic resins are preferred. Specific examples of thermoplastic resins include acrylonitrile-butadiene-styrene resin (hereinafter sometimes referred to as "ABS resin"); acrylonitrile-styrene-acrylic acid ester resin; acrylic resin; polyolefins such as polypropylene and polyethylene Resin; polycarbonate resin; vinyl chloride resin; polyethylene terephthalate (PET) resin and the like. Among these, ABS resin is preferable from the viewpoint of three-dimensional moldability. As the resin component forming the base material layer for lamination, only one kind may be used, or two or more kinds may be mixed and used. Moreover, the base material layer for lamination 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.

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

In addition, the base material layer for lamination may be colored by blending a coloring agent or the like, painted for adjusting the color, formed with a pattern for imparting design, etc., but may be partially transparent or semi-transparent. It is preferably transparent.

The thickness of the base material layer for lamination is not particularly limited, and is appropriately set according to the use of the laminate. be done. When the thickness of the base material layer for lamination is within the above range, the laminate can be provided with even more excellent three-dimensional formability.

[Release layer 4]
The release layer 4 is provided between the transfer substrate layer and the transfer layer 11 as necessary in the laminate of the first embodiment. The release layer 4 is a layer having a role of enhancing the releasability of the transfer substrate layer from the transfer layer 11 .

The release layer 4 may be a solid release layer that covers the entire surface of the transfer substrate layer (the entire surface is solid), or may be provided partially. In general, a solid release layer is preferred in consideration of releasability.

The release layer 4 is made of silicone resin, fluorine resin, acrylic resin (including acrylic-melamine resin), polyester resin, polyolefin resin, polystyrene resin, polyurethane resin, cellulose resin. , vinyl chloride-vinyl acetate copolymer resins, thermoplastic resins such as nitrocellulose, copolymers of monomers forming the thermoplastic resins, or those resins modified with (meth)acrylic acid or urethane , can be formed using a single resin composition or a mixture of a plurality of resin compositions. Among them, acrylic resins, polyester resins, polyolefin resins, polystyrene resins, copolymers of monomers forming these resins, and urethane-modified ones thereof are preferable, and more specifically, acrylic-melamine. resin alone, acrylic-melamine resin-containing composition, resin composition obtained by mixing polyester resin with urethane-modified copolymer of ethylene and acrylic acid, copolymer of acrylic resin with styrene and acrylic and a resin composition mixed with an emulsion of Among these, it is particularly preferable to configure the release layer 4 with an acrylic-melamine resin alone or a composition containing 50% by mass or more of an acrylic-melamine resin.

Moreover, as a material for forming the release layer 4, an ionizing radiation-curable resin, which will be exemplified for the surface protective layer 5 described later, can also be used. When the release layer 4 is formed of an ionizing radiation-curable resin, among the ionizing radiation-curable resins, polycarbonate (meth)acrylate (polycarbonate-based urethane (meth)acrylate, etc.) or acrylic (meth)acrylate, which will be described later, can be used. preferable.

The thickness of the release layer 4 is, for example, approximately 0.01 to 10 μm, preferably approximately 0.05 to 5 μm.

[Surface protective layer 5]
The surface protective layer 5 is a layer provided on the surface of the laminate as necessary in order to enhance the scratch resistance, chemical resistance, etc. of the laminate 10 . The resin forming the surface protective layer 5 is not particularly limited, and examples thereof include thermosetting resins, thermoplastic resins, and ionizing radiation-curable resins. Among these, ionizing radiation-curable resins are preferable from the viewpoint of achieving both excellent scratch resistance and excellent three-dimensional moldability.

The thermosetting resin forming the surface protective layer 5 is not particularly limited, and examples thereof include acrylic polyol; polyester polyol; urethane polyol such as polyester urethane polyol and acrylic-urethane polyol; polyethylene polyol, polypropylene polyol, polybutadiene polyol, poly polyolefin polyols such as isoprene polyol; and resins containing polyol resins and curing agents. A thermosetting resin may be used individually by 1 type, and may be used in combination of 2 or more types.

The thermoplastic resin forming the surface protective layer 5 is not particularly limited, and examples thereof include acrylic resins such as polymethyl (meth)acrylate and polyethyl (meth)acrylate; polyolefin resins such as polypropylene and polyethylene; polycarbonate resin; vinyl chloride. system resin; polyethylene terephthalate (PET); acrylonitrile-butadiene-styrene resin (ABS resin); acrylonitrile-styrene-acrylate resin; The thermoplastic resin may be used singly or in combination of two or more.

(Ionizing radiation curable resin)
The ionizing radiation-curable resin used for forming the surface protective layer 5 is a resin that crosslinks and cures when irradiated with ionizing radiation. A suitable mixture of at least one of prepolymers, oligomers, and monomers having 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 are suitable for forming the surface protective layer 5 because they can be solvent-free, do not require a photopolymerization initiator, and provide stable curing properties. used for

In the laminate of the present invention, when an ionizing radiation-curable resin is used to form the surface protective layer 5, the surface protective layer 5 in the state of the laminate may be cured, uncured or semi-cured. It may be cured. When the surface protective layer 5 in the laminate state is uncured or semi-cured, the surface protective layer 5 is cured after forming the laminate.

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. The polycarbonate (meth)acrylate may be, for example, a polycarbonate-based urethane (meth)acrylate, which is a 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, polyester polyol, or caprolactone-based 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. Among these, as polyfunctional (meth)acrylate oligomers, polycarbonate (meth)acrylates (polycarbonate-based urethane (meth)acrylates, etc.), urethane (meth)acrylates, and the like are particularly preferable. These oligomers may be used singly or in combination of two or more.

Among the ionizing radiation-curable resins described above, from the viewpoint of achieving both excellent scratch resistance and excellent three-dimensional moldability, it is preferable to use polycarbonate (meth)acrylate (polycarbonate-based urethane (meth)acrylate, etc.). It is particularly preferable to use a combination of polycarbonate (meth)acrylate (polycarbonate-based urethane (meth)acrylate, etc.) and polyfunctional (meth)acrylate.

Polycarbonate (meth)acrylate is obtained, for example, by converting some or all of the hydroxyl groups of polycarbonate polyol into (meth)acrylate (acrylic acid ester or methacrylic acid ester). This esterification reaction can be carried out by a normal esterification reaction. For example, 1) a method of condensing a polycarbonate polyol and an acrylic acid halide or a methacrylic acid halide in the presence of a base, 2) a method of condensing a polycarbonate polyol and an acrylic anhydride or a methacrylic acid anhydride in the presence of a catalyst, Alternatively, 3) a method of condensing a polycarbonate polyol and acrylic acid or methacrylic acid in the presence of an acid catalyst can be used.

The above polycarbonate polyol is a polymer having a carbonate bond in the polymer main chain and 2 or more, preferably 2 to 50, more preferably 3 to 50 hydroxyl groups in the terminal or side chain. A representative method for producing this polycarbonate polyol is a method by a polycondensation reaction from a diol compound (A), a polyhydric alcohol (B) having a valence of 3 or more, and a compound (C) serving as a carbonyl component. The diol compound (A) used as a raw material is represented by the general formula HO--R ¹ --OH. Here, R ¹ is a divalent hydrocarbon group having 2 to 20 carbon atoms and may contain an ether bond in the group. For example, it is a linear or branched alkylene group, cyclohexylene group, or phenylene group.

Specific examples of the diol compound (A) include ethylene glycol, 1,2-propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, polyethylene glycol, neopentyl glycol, 1,3-propanediol and 1,4-butane. diol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,3-bis(2-hydroxyethoxy)benzene, 1,4- bis(2-hydroxyethoxy)benzene, neopentyl glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and the like. These diols may be used alone or in combination of two or more.

Examples of trihydric or higher polyhydric alcohol (B) include alcohols such as trimethylolpurpan, trimethylolethane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, glycerin and sorbitol. Furthermore, alcohols having hydroxyl groups obtained by adding 1 to 5 equivalents of ethylene oxide, propylene oxide, or other alkylene oxides to the hydroxyl groups of these polyhydric alcohols may also be used. These polyhydric alcohols may be used alone or in combination of two or more.

The compound (C) to be the carbonyl component is any compound selected from diester carbonate, phosgene, and equivalents thereof. Specific examples thereof include carbonic acid diesters such as dimethyl carbonate, diethyl carbonate, diisopropyl carbonate, diphenyl carbonate, ethylene carbonate and propylene carbonate; phosgene; and halogenated formic acid esters such as methyl chloroformate, ethyl chloroformate and phenyl chloroformate. etc. These may be used alone or in combination of two or more.

The polycarbonate polyol is synthesized by subjecting the diol compound (A), the trihydric or higher polyhydric alcohol (B), and the carbonyl component compound (C) to a polycondensation reaction under general conditions. . For example, the charged molar ratio of the diol compound (A) and the polyhydric alcohol (B) is preferably in the range of 50:50 to 99:1. The molar ratio of A) to the polyhydric alcohol (B) charged is preferably 0.2 to 2 equivalents with respect to the hydroxyl groups of the diol compound and the polyhydric alcohol.

The number of equivalents (eq./mol) of hydroxyl groups present in the polycarbonate polyol after the polycondensation reaction at the charging ratio is, on average, 3 or more, preferably 3 to 50, more preferably 3 to 50 per molecule. is 20. Within this range, a necessary amount of (meth)acrylate groups are formed by the esterification reaction described below, and appropriate flexibility is imparted to the polycarbonate (meth)acrylate resin. The terminal functional groups of this polycarbonate polyol are usually OH groups, but part of them may be carbonate groups.

The method for producing the polycarbonate polyol described above is described, for example, in JP-A-64-1726. This polycarbonate polyol can also be produced by transesterification reaction between a polycarbonate diol and a polyhydric alcohol having a valence of 3 or more, as described in JP-A-3-181517.

The molecular weight of the polycarbonate (meth)acrylate used in the present invention is preferably 500 or more, more preferably 1,000 or more, as measured by GPC analysis and converted to standard polystyrene. , 2,000 or more. Although the upper limit of the weight average molecular weight of the polycarbonate (meth)acrylate is not particularly limited, it is preferably 100,000 or less, more preferably 50,000 or less, from the viewpoint of controlling the viscosity so as not to become too high. It is more preferably 2,000 or more and 50,000 or less, and particularly preferably 5,000 to 20,000.

Polycarbonate (meth)acrylate is preferably used together with polyfunctional (meth)acrylate in the ionizing radiation-curable resin composition. The mass ratio of polycarbonate (meth)acrylate and polyfunctional (meth)acrylate is more preferably polycarbonate (meth)acrylate:polyfunctional (meth)acrylate=98:2 to 50:50. When the mass ratio of polycarbonate (meth)acrylate and polyfunctional (meth)acrylate is less than 98:2 (that is, the amount of polycarbonate (meth)acrylate is 98% by mass or less with respect to the total amount of the two components) , the aforementioned durability and chemical resistance are further improved. On the other hand, when the mass ratio of polycarbonate (meth)acrylate and polyfunctional (meth)acrylate is greater than 50:50 (that is, the amount of polycarbonate (meth)acrylate is 50% by mass or more with respect to the total amount of the two components) ), further improving the three-dimensional formability. Preferably, the weight ratio of polycarbonate (meth)acrylate to polyfunctional (meth)acrylate is 95:5 to 60:40.

The polyfunctional (meth)acrylate used in the present invention is not particularly limited as long as it is a (meth)acrylate having a functionality of two or more. Here, bifunctional refers to having two ethylenically unsaturated bonds {(meth)acryloyl groups} in the molecule. The number of functional groups is preferably about 2 to 6.

Polyfunctional (meth)acrylates may be either oligomers or monomers, but polyfunctional (meth)acrylate oligomers are preferred from the viewpoint of achieving both excellent scratch resistance and excellent three-dimensional moldability.

Examples of the polyfunctional (meth)acrylate oligomers include urethane (meth)acrylate oligomers, epoxy (meth)acrylate oligomers, polyester (meth)acrylate oligomers, and polyether (meth)acrylate oligomers. Here, the urethane (meth)acrylate oligomer can be obtained, for example, by esterifying a polyurethane oligomer obtained by reacting a polyether polyol or polyester polyol with a polyisocyanate with (meth)acrylic acid. Epoxy (meth)acrylate oligomers can be obtained, for example, by reacting (meth)acrylic acid with the oxirane ring of a relatively low-molecular-weight bisphenol-type epoxy resin or novolac-type epoxy resin to esterify it. A carboxyl-modified epoxy (meth)acrylate oligomer obtained by partially modifying this epoxy (meth)acrylate oligomer with a dibasic carboxylic acid anhydride can also be used. The polyester (meth)acrylate oligomer is obtained, for example, by esterifying the hydroxyl groups of a polyester oligomer having hydroxyl groups at both ends with (meth)acrylic acid, obtained by condensation of a polyhydric carboxylic acid and a polyhydric alcohol. It can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding an alkylene oxide to a carboxylic acid with (meth)acrylic acid. A polyether (meth)acrylate oligomer can be obtained by esterifying the hydroxyl groups of a polyether polyol with (meth)acrylic acid.

Furthermore, other polyfunctional (meth)acrylate oligomers include highly hydrophobic polybutadiene (meth)acrylate oligomers having (meth)acrylate groups in the side chains of polybutadiene oligomers, and silicone (meth)acrylate oligomers having polysiloxane bonds in the main chain. ) acrylate-based oligomers, aminoplast resins (meth)acrylate-based oligomers obtained by modifying aminoplast resins having many reactive groups in small molecules, and the like.

Further, as the polyfunctional (meth)acrylate monomer, specifically, 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, neopentylglycol hydroxypivalate di(meth)acrylate, dicyclopentanyl di(meth)acrylate, caprolactone modified di(meth)acrylate Cyclopentenyl 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(acryloxy) ethyl)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, etc. be done. One of the polyfunctional (meth)acrylate oligomers and polyfunctional (meth)acrylate monomers described above may be used alone, or two or more thereof may be used in combination.

In the present invention, a monofunctional (meth)acrylate can be appropriately used in combination with the polyfunctional (meth)acrylate for the purpose of reducing the viscosity, etc., as long as the object of the present invention is not impaired. Examples of monofunctional (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl ( meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isobornyl (meth)acrylate and the like. One of these monofunctional (meth)acrylates may be used alone, or two or more thereof may be used in combination.

The content of polycarbonate (meth)acrylate in the ionizing radiation curable resin composition forming the surface protective layer 5 is not particularly limited, but from the viewpoint of achieving both excellent scratch resistance and excellent three-dimensional moldability. , preferably about 98 to 50% by mass, more preferably about 90 to 65% by mass.

When the surface protective layer 5 is formed using an ionizing radiation-curable resin, the surface protective layer 5 is formed by, for example, preparing an ionizing radiation-curable resin composition, applying it, and cross-linking and curing it. . The viscosity of the ionizing radiation-curable resin composition may be any viscosity that allows the formation of an uncured resin layer by the application method described below.

In the present invention, the prepared coating solution is applied to a desired thickness by a known method such as gravure coating, bar coating, roll coating, reverse roll coating, comma coating, preferably gravure coating. A cured resin layer is formed.

The surface protective layer 5 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 chosen so that the thickness of layer 5 is substantially equal. In addition, when the release layer 4 formed on the transfer substrate layer and the surface protective layer 5 are cured together with the electron beam, the total penetration depth of the electron beam, the release layer 4 and the surface protective layer 5 The acceleration voltage is chosen so that the thicknesses are substantially equal. As a result, it is possible to suppress the irradiation of excess electron beams to the transfer substrate layer located under the release layer 4, and to minimize the deterioration of the transfer substrate layer due to excess electron beams. can.

The irradiation dose is an amount that provides a sufficient value for the crosslink density of the surface protective layer 5, preferably 30 to 300 kGy (3 to 30 Mrad), more preferably 30 to 100 kGy (3 to 10 Mrad). By setting the irradiation dose within this range, it is possible to suppress the deterioration of the layers located under the surface protective layer 5 due to the ionizing radiation that has passed through the surface protective layer 5 . In the above example, the number of functional groups of the polyfunctional (meth)acrylate is 2, and an appropriate irradiation dose is required according to the number of functional groups.

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, carbon arc lamps, and ultraviolet light emitting diodes (LED-UV).

Although the thickness of the surface protective layer 5 is not particularly limited, it is preferably about 1 to 30 μm, more preferably about 2 to 20 μm, still more preferably about 3 to 15 μm. When the thickness falls within such a range, the laminate can effectively exhibit excellent scratch resistance and excellent three-dimensional formability. Further, when the surface protective layer 5 is formed from an ionizing radiation-curable resin, it is possible to uniformly irradiate the ionizing radiation-curable resin composition with ionizing radiation. It is economically advantageous.

[Primer layer 6]
The primer layer 6 is a layer that is optionally provided at least one place between these layers for the purpose of improving the adhesion between the layers such as the base material layer 1, the design layer 3, and the surface protective layer 5. . The primer layer 6 can be formed from a resin composition for forming a primer layer.

The resin used in the primer layer-forming resin composition is not particularly limited, but examples include polyol and/or cured products thereof, urethane resin, acrylic resin, (meth)acrylic-urethane copolymer resin, polyester resin, butyral resin. etc. Among these resins, polyols and/or cured products thereof, urethane resins, acrylic resins, and (meth)acrylic-urethane copolymer resins are preferred. These resins may be used singly or in combination of two or more.

In the present invention, the primer layer 6 is preferably made of a resin composition containing polyol and urethane resin. The polyol may be a compound having two or more hydroxyl groups in the molecule, and specific examples thereof include polyester polyol, polyethylene glycol, polypropylene glycol, acrylic polyol, polyether polyol, etc. Acrylic polyol is preferred. mentioned.

When polyol and urethane resin are used to form the primer layer 6, the mass ratio of these (polyol:urethane resin) is preferably about 5:5 to 9.5:0.5, more preferably 7:3. up to about 9:1.

Examples of cured polyols include urethane resins. 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.

Specific examples of isocyanates include polyvalent isocyanates having two or more isocyanate groups in the molecule; aromatic isocyanates such as 4,4-diphenylmethane diisocyanate; hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogen Aliphatic (or cycloaliphatic) isocyanates such as added diphenylmethane diisocyanate can be mentioned. When isocyanate is used as a curing agent, the content of isocyanate in the primer layer-forming resin composition is not particularly limited. It is preferably 3 to 45 parts by mass, more preferably 3 to 25 parts by mass, based on 100 parts by mass of the above polyol.

Among the above urethane resins, a combination of acrylic polyol or polyester polyol as a polyol and hexamethylene diisocyanate or 4,4-diphenylmethane diisocyanate as a cross-linking agent is preferable from the viewpoint of improving adhesion after cross-linking; includes a combination of acrylic polyol and hexamethylene diisocyanate.

The acrylic resin is not particularly limited. and a copolymer with a monomer of As the (meth)acrylic resin, more specifically, polymethyl (meth)acrylate, polyethyl (meth)acrylate, polypropyl (meth)acrylate, polybutyl (meth)acrylate, (meth)acrylic acid Methyl - butyl (meth) acrylate copolymer, ethyl (meth) acrylate - butyl (meth) acrylate copolymer, ethylene - methyl (meth) acrylate copolymer, styrene - methyl (meth) acrylate copolymer Examples thereof include (meth)acrylic acid esters such as polymers.

(Meth)acrylic-urethane copolymer resins are not particularly limited, but include, for example, acrylic-urethane (polyester urethane) block copolymer resins. Various isocyanates described above are used as the curing agent. The ratio of acrylic to urethane in the acrylic-urethane (polyester urethane) block copolymer resin is not particularly limited. For example, the acrylic/urethane ratio (mass ratio) is 9/1 to 1/9, preferably 8. /2 to 2/8.

The thickness of the primer layer 6 is not particularly limited, but is, for example, about 0.1 to 10 μm, preferably about 1 to 10 μm (that is, the coating amount is, for example, about 0.1 to 10 g/m ² , preferably 1 to 10 g/m). m ² ). By satisfying such a thickness of the primer layer 6, the adhesion between the layers such as the base layer 1, the design layer 3 and the surface protective layer 5 can be effectively enhanced.

Various additives can be added to the composition forming the primer layer 6 according to the desired physical properties. 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, coloring agents, and matting agents. These additives can be appropriately selected from those commonly used, and examples of matting agents include silica particles and aluminum hydroxide particles. 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.

The primer layer 6 is formed by using a resin composition for forming a primer layer, 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, It is formed by a normal coating method such as wire bar coating, flow coating, comma coating, flow coating, brush coating, spray coating, or a transfer coating method. Here, the transfer coating method is a method of forming a coating film of the primer layer 6 and the adhesive layer on a thin sheet (film base layer), and then coating the target layer surface in the laminate.

When the primer layer 6 is formed on the surface of the surface protective layer 5, it may be formed on the surface protective layer 5 after curing. Further, after forming the primer layer 6 by laminating a layer made of the composition for forming the primer layer on the layer of the ionizing radiation curable resin composition forming the surface protective layer 5, the layer made of the ionizing radiation curable resin is formed. The surface protective layer 5 may be formed by irradiating ionizing radiation to harden the layer made of the ionizing radiation-curable resin.

[Color adjustment layer 7]
In the laminate of the present invention, the color adjustment layer 7 is provided between the masking layer 2 and the design layer 3 as necessary for the purpose of adjusting the color of light emitted from the light source 30. layer.

The color adjustment layer 7 only needs to be able to adjust the color of the light emitted from the light source 30. For example, the color adjustment layer 7 is colored and transparent, but may be colorless, transparent, or translucent. Examples of the resin component forming the color adjustment layer 7 include the binder resins exemplified for the design layer 3 . Further, examples of the coloring agent blended in the color adjustment layer 7 include the pigments exemplified for the design layer 3 .

The color adjustment layer 7 can be formed by known printing methods such as gravure printing, flexographic printing, silk screen printing, and offset printing.

Although the thickness of the color adjustment layer 7 is not particularly limited, it is generally about 0.1 to 10 μm, preferably about 1 to 10 μm.

[Adhesion layer 8]
The adhesive layer 8 is formed on the outermost surface of the laminate 10 on the molding resin layer 9 side for the purpose of improving adhesion and adhesion with the molding resin layer 9 when the molding resin layer 9 is provided on the laminate 10 . It is a layer provided as needed. The resin forming the adhesive layer 8 is not particularly limited as long as it can improve the adhesiveness and adhesion of the molded resin layer 9, and for example, a thermoplastic resin or a thermosetting resin is used. Examples of thermoplastic resins include acrylic resins, acrylic-modified polyolefin resins, chlorinated polyolefin resins, vinyl chloride-vinyl acetate copolymers, thermoplastic urethane resins, thermoplastic polyester resins, polyamide resins, rubber resins, and the like. . The thermoplastic resin may be used singly or in combination of two or more. Further, examples of thermosetting resins include urethane resins and epoxy resins. A thermosetting resin may be used individually by 1 type, and may be used in combination of 2 or more types.

The adhesive layer 8 is not necessarily a necessary layer, but when it is assumed that the laminate of the present invention is applied to a decoration method by sticking it onto a resin molded body prepared in advance, such as a vacuum pressure bonding method described later, , is preferably provided. When the adhesive layer 8 is used for the vacuum pressure bonding method, it is preferable to form the adhesive layer 8 using, among the various resins described above, a commonly used resin that develops adhesiveness when pressurized or heated.

[Molding resin layer 9]
In the laminate 10 of the present invention, as shown in FIGS. 3 and 8, the molded resin layer 9 may be integrated with the concealing layer 2 side and molded.

The molded resin layer 9 can be made of resin. The resin is preferably made of a thermoplastic resin, and is preferably transparent or translucent so that light can pass therethrough. The thermoplastic resin is not particularly limited, but acrylonitrile-butadiene-styrene resin (hereinafter sometimes referred to as "ABS resin"), acrylic resin; polyolefin resin such as polypropylene and polyethylene; polycarbonate resin; vinyl chloride resin polyethylene terephthalate (PET) resin, acrylonitrile-butadiene-styrene resin; acrylonitrile-styrene-acrylic acid ester resin, and the like. Among these materials, the molding resin layer 9 is preferably made of ABS resin. The resin forming the molded resin layer 9 may be of one type, or may be of two or more types. Moreover, as the shape of the molded resin layer 9, a plate-like body, a molded body, and the like are exemplified.

The laminate 10 including the molded resin layer 9 is formed by integrating the molded resin layer 9 with the concealing layer 2 side (light source 30 side). That is, the laminated body 10 including the molded resin layer 9 is characterized by further including the molded resin layer 9 on the opposite side of the concealing layer 2 from the design layer 3 side.

In the above-described first aspect, as shown in FIG. 3, the layered product 10 including the molded resin layer 9 may be provided with a transfer substrate layer (the layered product in such a state may be used as a transfer substrate). (also called laminate with layers). FIG. 3 is a cross-sectional view of a laminate 10 in which a molding resin layer 9 is laminated on the laminate shown in FIG. FIG. 4 shows a mode in which a laminate 10 obtained by peeling the transfer substrate layer from the laminate with the transfer substrate layer shown in FIG. 3 is used as a decorative article 20 . Moreover, in the above-described second embodiment as shown in FIGS. FIG. 8 is a cross-sectional view of a laminate 10 in which a molding resin layer 9 is laminated on the laminate shown in FIG.

The laminate 10 having the molded resin layer 9 is produced using the laminate of the present invention by various injection molding methods such as an insert molding method, a simultaneous injection molding decoration method, a blow molding method, and a gas injection molding method. be. Among these injection molding methods, the insert molding method and the simultaneous injection molding decoration method are preferred.

In the insert molding method, first, in the vacuum molding process, the laminate before the molded resin layer 9 is laminated is vacuum-molded (off-line pre-molding) in advance to the surface shape of the molded product with a vacuum molding die, and then, if necessary, an extra layer is formed. trimming to obtain a molded sheet. This molded sheet is inserted into an injection mold, the injection mold is clamped, and the resin in a fluid state is injected into the mold, solidified, and the laminate is integrated with the outer surface of the resin molding at the same time as the injection molding. Thus, the laminate 10 including the molded resin layer 9 is manufactured.

More specifically, the laminate 10 including the molded resin layer 9 is manufactured by an insert molding method including the following steps.
A vacuum forming step of forming a laminate into a three-dimensional shape in advance by a vacuum forming mold before laminating the molded resin layer 9, a trimming step of trimming an excess portion of the vacuum formed laminate to obtain a formed sheet, and a formed sheet. is inserted into the injection mold, the injection mold is closed, and the resin in a fluid state is injected into the injection mold to integrate the resin and the molded sheet.

In the vacuum forming step in the insert molding method, the laminated body may be heated and formed. The heating temperature at this time is not particularly limited, and may be appropriately selected depending on the type of resin constituting the laminate and the thickness of the laminate. For example, the temperature can be usually about 120 to 200°C. In addition, in the integration step, the temperature of the resin in a fluid state is not particularly limited, but it can usually be about 180 to 320°C.

In the simultaneous injection molding and decorating method, the laminate is placed in a female mold that also serves as a vacuum molding mold provided with injection molding suction holes, and after preforming (in-line preforming) in this female mold, The injection mold is clamped, and the resin in a fluid state is injected and filled into the mold, solidified, and at the same time as the injection molding, the laminate before being laminated with the molded resin layer 9 is integrated with the outer surface of the resin molded product. A laminate 10 having a molded resin layer 9 is manufactured by curing.

More specifically, the laminated body 10 including the molded resin layer 9 is manufactured by the simultaneous injection molding and decorating method including the following steps.
After setting the laminate before laminating the molding resin layer 9 so that the surface of the laminate faces the molding surface of a movable mold having a molding surface of a predetermined shape, the laminate is heated and softened. A preforming step of preforming a laminated body by applying vacuum suction from the movable mold side and adhering the softened laminated body along the molding surface of the movable mold,
After clamping a movable mold and a fixed mold that have a laminate that is in close contact along the molding surface, a resin in a fluid state is injected into the cavity formed by both molds, filled and solidified. A resin molded body is formed by forming a resin molded body by laminating and integrating the resin molded body and the laminate, and the movable mold is separated from the fixed mold to take out the resin molded body in which all the layers of the laminated body are laminated. extraction process.

In the preforming step of the injection molding simultaneous decoration method, the heating temperature of the laminate is not particularly limited, and may be appropriately selected depending on the type of resin constituting the laminate, the thickness of the laminate, etc. When a polyester resin film or an acrylic resin film is used as 1, 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 can usually be about 180 to 320.degree.

In addition, the laminate 10 including the molded resin layer 9 is obtained by forming a laminate before laminating the molded resin layer 9 on a three-dimensional resin molded body (molded resin layer 9) prepared in advance by a vacuum compression method or the like. It can also be produced by a decorating method of sticking.

In the vacuum compression bonding method, first, the laminated body before lamination of the molded resin layer 9 and the resin molded body are laminated in a vacuum compression bonding machine consisting of a first vacuum chamber located on the upper side and a second vacuum chamber located on the lower side. The laminate is placed in a vacuum crimping machine so that the body is on the first vacuum chamber side, the resin molded body is on the second vacuum chamber side, and the concealing layer 2 side of the laminate faces the resin molded body side, and the two vacuum chambers are vacuumed. state. 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 product is pressed against the laminate using a lifting table, and the pressure difference between the two vacuum chambers is used to stretch the laminate while stretching the surface of the resin molded product. affixed to Finally, the two vacuum chambers are opened to the atmospheric pressure, and the laminate 10 having the molded resin layer 9 can be obtained by trimming the excess portion of the laminate as necessary.

In the vacuum pressure bonding method, it is preferable to include a step of heating the laminate before the step of pressing the molded article against the laminate in order to soften the laminate and improve moldability. 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 laminate and the thickness of the laminate. Usually, it can be about 60 to 200°C.

In the laminate 10 including the molded resin layer 9, the molded resin layer 9 may be formed by selecting a resin according to the application. The molding resin that forms the molding resin layer 9 may be a thermoplastic resin or a thermosetting resin.

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

Further, examples of thermosetting resins include urethane resins and epoxy resins. These thermosetting resins may be used singly or in combination of two or more.

In the first aspect, the transfer substrate layer is peeled off from the transfer substrate layer-attached laminate obtained by integrating the laminate and the molding resin by the method described above. you get a body The step of peeling and removing the transfer substrate layer can be performed at any time. For example, the transfer substrate layer can be peeled off at the same time as the obtained laminate with the transfer substrate layer is removed from the molding apparatus. can. In addition, in the laminate with the transfer base layer, the transfer base layer serves as a protective sheet for the laminate 10 including the molded resin layer 9, so it is peeled off after the laminate with the transfer base layer is manufactured. The transfer substrate layer may be peeled off at the time of use after being stored as it is. By using it in such a manner, it is possible to prevent the laminated body from being scratched due to rubbing during transportation or the like.

In the laminate of the present invention, when the light source is turned on, the light-transmitting part has sufficient light-transmitting properties, while the light-shielding part has sufficient light-shielding properties. For example, interior or exterior materials 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 appliances such as television receivers and air conditioners can be used as a container or the like;

[Decorative goods]
A decorative article 20 of the present invention utilizes the laminate 10 of the present invention and includes the laminate 10 and a light source 30 . As shown in FIGS. 4 and 9, the light source 30 is arranged on the concealing layer 2 side. The details of the laminate 10 of the present invention are as described above.

The type of light source is not particularly limited, and includes, for example, light emitting diode (LED) light bulbs, incandescent light bulbs, fluorescent lights, and natural light.

In the decorative article 20 of the present invention, when the light source is turned on, the light-transmitting part has sufficient light-transmitting properties, while the light-shielding part has sufficient light-shielding properties. For example, interior or exterior materials for vehicles such as automobiles; fittings such as window frames and door frames; interior materials for buildings such as walls, floors, and ceilings; It can be used as a housing; a container or the like.

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.

[Production of laminate]
<Examples 1 to 5 and Comparative Examples 1 to 4>
A polyethylene terephthalate film (thickness: 75 μm) having an easy-adhesive layer formed on one surface was used as a transfer substrate. An electron radiation curable resin composition containing 100 parts by mass of acrylic acrylate and 1 part by mass of a reactive silicone resin is printed by gravure printing on the surface of the easy-adhesive layer of the polyethylene terephthalate film to form a coating film for forming a release layer ( 1.5 μm thick). Next, the coating film was irradiated with an electron beam at an acceleration voltage of 165 kV and an irradiation dose of 5 Mrad to cure the coating film for forming a release layer, thereby forming a release layer.

Next, an ionizing radiation-curable resin composition described later was applied onto the release layer using a bar coder to form an uncured coating film of the surface protective layer. Table 1 shows the content of pentaerythritol triacrylate (PETA) (the balance being polycarbonate acrylate and acrylic polymer) contained in the electron radiation curable resin composition used to form the protective layer. Next, the coating film is irradiated with an electron beam at an acceleration voltage of 165 kV and an irradiation dose (5 Mrad) shown in Table 1 to cure the uncured surface protective layer to form a surface protective layer (4 μm thick). bottom.

A primer layer-forming resin composition (acrylic polyol and hexamethylene diisocyanate) was applied onto the surface protective layer by gravure printing to form a primer layer (thickness: 1.5 μm). Furthermore, on the primer layer, a black type for forming a design layer containing a binder resin (50% by mass of acrylic resin, 50% by mass of vinyl chloride-vinyl acetate copolymer resin) and a black pigment (content shown in Table 1) Using the ink composition, a black design layer (thickness: 1.5 μm) was formed on the entire surface by gravure printing. Next, an ink composition containing a blue pigment was applied on the design layer to form a color adjustment layer (thickness: 1.5 μm). Furthermore, a concealing layer forming ink (ink composition containing a black pigment (in each example and comparative example, the content of the black pigment was adjusted)) was printed on the position to be the light shielding part, and the concealing layer (each (In the examples and comparative examples, the thickness was adjusted in the range of 4.5 μm to 6 μm) was formed.The position where the hiding layer was not formed became the transparent part.Next, on the hiding layer, Using a resin composition for forming an adhesive layer containing an acrylic resin (softening temperature: 125° C.), an adhesive layer (1.5 μm) is formed by gravure printing to form a base layer (transfer base layer). /Release layer/Surface protective layer/Primer layer/Design layer/Color adjustment layer/Hiding layer/Adhesive layer were laminated in order to obtain each transfer type laminate.In addition, one light shielding part is the laminate. When viewed from above, it was 10 mm long and 20 mm wide.

Each laminate obtained above is put into an injection mold and the mold is clamped, transparent polycarbonate as an injection resin is injected into the cavity of the mold, and the injection resin is laminated on the adhesive layer side of the laminate. Composed of surface protective layer/primer layer/design layer/color adjustment layer/concealing layer/adhesive layer/molding resin layer by integrally molding and peeling and removing the base material layer and release layer at the same time as removing from the mold. A resin molded product was obtained.

<Measurement of optical density>
The optical density of the translucent part (the part where the concealing layer is not formed) and the light shielding part (the part where the concealing layer is formed) of each resin molded product obtained above was measured with a microspectrophotometer (MSP manufactured by Photoscience). −1 V). OD values greater than 3.0 were measured using a GretagMacbeth D200-II transmission densitometer. Table 1 shows the results.

[Visibility of concealing layer when lights are off]
For each of the laminates obtained in Examples and Comparative Examples, after molding, the substrate layer and the release layer were separated from the interface between the release layer and the surface protective layer to obtain molded product samples for evaluation. Next, the evaluation sample was visually observed from the surface protective layer side, and the visibility of the masking layer when the light source was turned off was evaluated according to the following evaluation criteria. Table 1 shows the results.
A: The concealing layer cannot be seen even when viewed closely.
B: The concealing layer cannot be seen from a position 1 m away.
C: The concealing layer can be seen from a position 1 m away.

[Evaluation of light shielding property and light transmittance at the time of lighting]
A light source (LED light: illuminance of 130 lumens) was placed on the concealing layer side of each evaluation sample for which the visibility of the concealing layer when turned off was evaluated, and the evaluation sample was visually observed from the surface protective layer side. The light-shielding property of the light-shielding portion and the light-transmitting property of the light-transmitting portion were evaluated according to the evaluation criteria of . Table 1 shows the results.
A: The pattern is clearly visible.
B: The pattern can be seen from a position 1 m away.
C: The pattern cannot be seen from a position 1 m away.

REFERENCE SIGNS LIST 1 Base layer 2 Concealing layer 3 Design layer 4 Release layer 5 Surface protective layer 6 Primer layer 7 Color adjustment layer 8 Adhesive layer 9 Molded resin layer 10 Laminate 11 Transfer layer 20 Decorative article 30 Light source

Claims (10)

A laminate comprising at least a design layer and a concealing layer on one side of a base layer formed of a resin film ,
The laminate has a light shielding portion that shields light and a light transmitting portion that transmits light when viewed from above,
A decorative sheet for three-dimensional molding comprising a laminate, wherein the optical density of the light-shielding portion is 4.3 or more and the optical density of the light-transmitting portion is 1.0 or more and 3.0 or less. The decorative sheet for three-dimensional molding comprising the laminate according to claim 1, wherein the design layer contains 30 parts by mass or more of a pigment with respect to 100 parts by mass of the binder resin. 3. The decorative sheet for three-dimensional molding comprising the laminate according to claim 1 or 2, wherein the design layer and the concealing layer have similar colors. The decorative sheet for three-dimensional molding comprising the laminate according to any one of claims 1 to 3, wherein the pigment contained in the design layer is black. The decorative sheet for three-dimensional molding comprising the laminate according to any one of claims 1 to 4, further comprising a color adjusting layer between the design layer and the concealing layer. A decorative sheet for three-dimensional molding comprising the laminate according to any one of claims 1 to 5, comprising the substrate layer, the design layer, and the concealing layer in this order. The three-dimensional molding decorative sheet comprising the laminate according to any one of claims 1 to 5, comprising the base layer, the concealing layer, and the design layer in this order. A decorative sheet for three-dimensional molding comprising the laminate according to any one of claims 1 to 7, wherein the laminate is in the form of a sheet . The decorative sheet for three-dimensional molding comprising the laminate according to any one of claims 1 to 8, further comprising a molded resin layer on the side of the concealing layer opposite to the design layer. A decorative sheet for three-dimensional molding comprising the laminate according to any one of claims 1 to 9,
a light source disposed on the side of the concealing layer of the laminate;
A decorative article.

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