JP2000141549A - Decorative sheet and decorative molded product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To eliminate the effect of the color of an adhered such as a resin molded article or the like and to improve color development in a decorative sheet and a decorative molded product. SOLUTION: A decorative sheet S is constituted by laminating a first layer 1 comprising a base material sheet, a second layer 2 containing an org. pigment as a colorant and having a pattern layer formed by printing and a third layer 3 having a whole solid layer containing an inorg. pigment as a main component of a colorant formed to the entire surface thereof by printing or coating. In the case of a transfer type, the second layer 2 and the third layer 3 become a transfer layer 5. Further, an adhesive layer may be laminated as a fourth layer 4. A decorative molded product is obtained if a resin molded article colored by a colorant is decorated by this decorative sheet S by an injection molding simultaneous decoration method due to lamination or transfer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a decorative sheet which can be used as a decorative sheet to be used in a simultaneous decorating method for injection molding, for example, a decorative sheet which is hardly influenced by the color tone of an adherend such as a resin molded product. The present invention relates to a decorative molded product decorated with the sheet.

[0002]

2. Description of the Related Art Conventionally, decorative molded products obtained by decorating the surface of a resin molded product have been used for various purposes. For example, in the simultaneous injection molding decorating method disclosed in Japanese Patent Publication No. 50-19132, etc., a molded article having a decorated surface is formed by laminating and integrating a decorative sheet on the surface of the resin molded article at the same time. Is obtained. The decorative sheets include a laminate type and a transfer type. In the former, the entire decorative sheet is laminated on a resin molded article to decorate, and in the latter, after the entire decorative sheet is laminated, only the base sheet is used. Decorating is performed by transferring the resin sheet after peeling it off and leaving only the transfer layer on the base material sheet on the resin molded product side.

[0003] Usually, a decorative sheet for decorating the surface of an adherend such as a resin molded product or the like includes, in order from the surface, a first layer 1 composed of a base material sheet and a printed ink. A sheet having a layered structure in which a second layer 2 having a pattern layer and a third layer 3 of an all solid layer formed of a colored ink (or a colored coating liquid) printed (or coated) on the entire surface are laminated. Are often used (see FIG. 1). Then, for example, in the case of a laminate type decorative sheet, for example, a transparent resin sheet is used for the first layer 1 made of the base material sheet, and the second layer 2 is used for the third layer 3. To be on the front side,
The first layer 1 is laminated on the surface of an adherend made of a resin molded product 6 or the like colored with a coloring agent by a simultaneous injection molding decoration method or the like, and the first layer 1 is a decorative molded product used for surface protection or imparting a feeling of painting. P (see FIG. 2A).

[0004]

Heretofore, conventionally, as the colorant used in the picture layer and all solid layers, either all organic pigments or all inorganic pigments were used. . For this reason, when the pattern layer and all the solid layers were all printed and coated using an ink or a coating liquid using an inorganic pigment, the coloring of the colorant was poor, and only the so-called sinking decoration could be performed. This is because a high chroma color was not produced with the inorganic pigment. On the other hand, if all organic pigments are used for the picture layer and all solid layers, the above-mentioned problem of coloring is solved,
Due to poor concealing properties, when the adherend is colored by laminating or transferring the decorative sheet, if the adherend is colored, the color of the adherend may be affected. . Therefore, it is necessary to form a picture layer and a solid layer in consideration of the color of the adherend such as a resin molded product. This was especially true when the color of the adherend was dark, such as black. In addition, when the decorative surface of the adherend is not a flat surface but a three-dimensional uneven surface, it is possible to decorate by a simultaneous injection molding decoration method or the like, but such a decorative sheet has a decorative surface uneven shape. When stretched and formed, it was susceptible to the color of the adherend. This is because, in the stretched decorative sheet portion, the thickness of the pattern layer and all solid layers is reduced, and the concealing property is reduced. Therefore, it was also attempted to use a mixture of both an organic pigment and an inorganic pigment as the colorant for the above-mentioned pattern layer and all solid layers, but the coloring and concealment were halfway, and a good one was not obtained. .

SUMMARY OF THE INVENTION It is an object of the present invention to provide a decorative sheet which can be decorated with a desired color tone unique to the decorative sheet with good coloring without being affected by the color tone of the adherend due to concealment. Another object of the present invention is to provide a decorative molded product which is not affected by the color tone of the adherend by using the decorative sheet.

[0006]

Therefore, in order to solve the above-mentioned problems, in the case of the back printing specification in the decorative sheet of the present invention, the first layer composed of the base material sheet and the organic pigment are colored in order from the surface. A second layer having a picture layer containing the agent and a third layer consisting of a solid layer containing an inorganic pigment as a main component of a coloring agent formed on the entire surface are laminated.
The above configuration is a case of so-called back printing specification, but in the front printing specification, in order from the surface, a second layer having a picture layer containing an organic pigment as a coloring agent and an inorganic pigment formed on the entire surface are mainly composed of a coloring agent. The structure was such that a third layer composed of all solid layers contained as components and a first layer composed of a base sheet were laminated. In this way, the kind of the coloring agent to be contained in the pattern layer and the whole solid layer below is changed, and the third layer composed of the whole solid layer is concealed by using the coloring agent as an inorganic pigment as a main component. It has excellent properties and can eliminate the influence of the color tone of the adherend such as a resin molded product. In addition, since the picture layer contains an organic pigment, the coloring is good, and both the coloring and the concealing property are achieved.

[0007] The decorative sheet having the above-described structure may further have a configuration in which an adhesive layer is laminated as a fourth layer on the rearmost surface. When the adhesion between the third layer and the adherend is insufficient, the adhesion can be improved.

Further, in the decorative molded article of the present invention, the surface of the resin molded article colored with a coloring agent is formed by laminating or transferring any of the decorative sheets described above so that the third layer of the decorative sheet becomes the third layer. A decorated molded article was formed on the resin molded article side of the two layers. With such a configuration, the color tone expressed by the decorative molded product is not affected by the color tone of the resin molded product as the adherend, and the molded product has good color development.

[0009]

Embodiments of the present invention will be described below with reference to the drawings. FIG. 1 is a cross-sectional view illustrating a typical example of a decorative sheet of the present invention (however, it is also used as a cross-sectional view of a conventional decorative sheet), and FIGS. 2 and 3. It is sectional drawing which illustrates a molded article. Also,
FIG. 4 is a conceptual diagram illustrating an injection molding simultaneous decorating method in a certain form as a method of obtaining a decorated molded product. FIG. 5 is a cross-sectional view illustrating another embodiment of the decorative sheet and the decorative molded product of the present invention.

Decorative sheet As shown in FIG. 1A, a decorative sheet S of the present invention has a first layer 1 composed of a base sheet and a pattern containing an organic pigment as a coloring agent. This is a sheet in which a second layer 2 having a layer and a third layer 3 of a solid layer containing an inorganic pigment as a main component of a colorant formed on the entire surface are laminated in this order. Then, the space between the first layer 1 and the second layer 2 is made to be releasable, and the second layer 2 and the third layer 3 are used as the transfer layer 5.
If the base sheet is peeled off after the decorative sheet is laminated on the adherend, it becomes a transfer type decorative sheet. Also,
If all of these sheets having interlayer adhesion are used in a form in which all layers of the decorative sheet are permanently laminated on the adherend, a laminate type decorative sheet is obtained. The upper side in FIG. 1 is the outermost layer when decorated on the surface side, that is, on an adherend such as a resin molded product. In the figure, the lower side is the back side, that is, the side that adheres to the adherend. In the decorative sheet S of FIG. 1A and the following FIG. 1B, for the sake of simplicity, the decorative sheets of the laminate type and the transfer type are simultaneously shown. The decorative sheet of the present invention is shown in FIG.
As illustrated in FIG. 1B, a configuration in which an adhesive layer is further laminated as a fourth layer 4 next to the third layer 3 (on the back side) in addition to the configuration in FIG. This is preferable as a configuration for improving the adhesion to the adherend.

[First Layer: Substrate Sheet] As the substrate sheet to be the first layer 1, a resin sheet having moldability is typically used. In addition, moldability is not necessarily essential, but is necessary when decorating the uneven surface by extending the decorating sheet by a simultaneous decorating method of injection molding or the like. Examples of the resin sheet include olefin resins such as polyethylene, polypropylene, polybutene, polymethylpentene, ethylene-propylene copolymer, ethylene-propylene-butene copolymer, olefin-based thermoplastic elastomer, polyethylene terephthalate, and polybutylene. Polyester resins such as terephthalate, ethylene terephthalate isophthalate copolymer, polyamide resins such as nylon, polymethyl (meth) acrylate, polybutyl (meth) acrylate, methyl (meth) acrylate
Butyl (meth) acrylate copolymer, methyl (meth)
Acrylic resins such as acrylate-styrene copolymers (however, (meth) acrylate means acrylate or methacrylate), vinyl chloride resins, ABS (acrylonitrile-butadiene-styrene copolymer) resins,
A single layer of a thermoplastic resin sheet such as an AS (acrylonitrile-styrene copolymer) resin, another thermoplastic elastomer such as a urethane-based resin, or a laminate of two or more layers of different materials is used. The thickness of the substrate sheet is not particularly limited, but is generally 30 to 20 for a laminate type.
It is about 0 μm, and about 20 to 100 μm for the transfer type.

The base sheet is transparent or translucent in the case of a laminate type in which the picture layer and all solid layers are located on the back side of the base sheet, as shown in FIG. 1, but as shown in FIG. Layer and all solid layers are located on the surface side of the base sheet.
In the case of the transfer type and the transfer type, it may be opaque. In the state of the laminate type, the decorative sheet as shown in FIG. 5 is laminated on the adherend, and the decorative sheet used so that the base sheet is closer to the adherend than the pattern layer and all solid layers (so-called decorative sheet). In the case of front printing, the transparency of the substrate sheet does not matter, but in this case, the substrate sheet cannot be used as a protective layer such as a picture layer. On the other hand, in the decorative sheet as shown in FIG. 1, the base sheet can be used as a pattern layer and a protective layer for all solid layers in a state of being laminated on an adherend.

In the decorative sheet of the laminate type as shown in FIG. 1, a coloring agent such as a pigment may be kneaded into the resin of the base sheet so that the base sheet may be subjected to a decoration process for making the base sheet colored and transparent. In the decorative sheet of the laminate type as shown in FIG. 1, in the resin of the base sheet, if necessary, a lubricant such as wax, a lubricating agent composed of particles such as silica and spherical α-alumina, Various additives such as benzotriazole-based, benzophenone-based, fine particle cerium oxide-based ultraviolet absorbers, light stabilizers such as hindered amine-based radical scavengers, plasticizers, stabilizers, etc. may be added for physical property adjustment. good.

In the transfer type decorative sheet, a sheet having releasability from the transfer layer is used as the base sheet. For this reason, if necessary, the base sheet is provided with a release layer on the transfer layer side in order to improve releasability from the transfer layer. The release layer separates from the transfer layer and is removed as a part of the base sheet when the base sheet is separated. For the release layer, for example, silicone resin,
A single substance or a mixture of two or more of melamine resin, polyamide resin, urethane resin, polyolefin resin, wax and the like are used. The release layer may be formed on the substrate by a known printing method (or coating method) such as gravure printing (or roll coating) using an ink (or coating liquid) containing the above resin. In addition, since the base sheet of the transfer type decorative sheet may be opaque, depending on the formability, paper, metal,
A sheet other than the resin sheet such as a nonwoven fabric or a woven fabric, or a laminate in which a release layer or a layer made of the above-described resin is provided thereon may be used.

[Second Layer: Picture Layer] The picture layer serving as the second layer 2 is usually a layer which expresses a pattern picture with a pattern or character, but may be a solid layer. The design of the design layer is arbitrary, but the design is, for example, a design made of wood grain, stone grain, cloth grain, sand grain, geometric pattern, characters and the like. The pattern layer is basically not particularly limited except that an organic pigment is used as at least a part of the colorant. The picture layer is usually formed by a known printing method such as gravure printing with a printing ink. Known resins may be used as the binder resin for the printing ink.

As the organic pigment, known organic pigments may be appropriately selected and used according to the color tone to be expressed, and there is basically no particular limitation. For example, for example, in red, quinacridone, perylene, or various azo pigments such as monoazo, disazo, and polyazo, and in yellow, isoindolinone,
Alternatively, various azo pigments such as monoazo, disazo and polyazo, etc., such as phthalocyanine blue and indaslen blue RS for blue and aniline black for black. By including these organic pigments in the picture layer, color saturation can be improved and coloring can be improved. The content of the organic pigment is usually about 15% by weight or more based on the total amount of the pattern layer (including the binder resin and the like), but is not particularly limited. What is necessary is just to make it correspond to the tone to be expressed. In addition, the coloring agent to be contained in the pattern layer uses at least an organic pigment,
If necessary, an inorganic pigment may be used in combination as a colorant. As the inorganic pigment, those described in the description of all solid layers described later can be used.

The resin of the binder of the printing ink is not particularly limited, and the adhesiveness to the base sheet, the printing suitability,
It may be selected according to the required physical properties such as weather resistance, etc., for example, acrylic resin, thermoplastic or two-part curable urethane resin, nitrified cotton, cellulose acetate, cellulose resin such as cellulose acetate propionate, polyester resin , Chlorinated polyolefin resins such as chlorinated polypropylene, polyamide resins and the like may be used alone or in combination of two or more. As a specific example of a laminate type decorative sheet using an acrylic resin or a vinyl chloride resin as a base material sheet, as a binder resin, a mixture of an acrylic resin and a vinyl chloride-vinyl acetate copolymer as a main component When used, the adhesiveness to the base sheet, printability, and moldability are excellent. Here, as the acrylic resin used for the picture layer, besides appropriately selecting from the same ones listed for the base sheet, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) ) Acrylate, 2-ethylhexyl (meth)
(Meth) acrylic acid alkyl esters such as acrylate and octyl (meth) acrylate; and 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate and 2-hydroxy-3-phenoxypropyl (meth) acrylate An acrylic polyol obtained by copolymerizing a (meth) acrylate having a hydroxyl group in the molecule can also be used. The acrylic polyol may be an acrylic polyol obtained by further copolymerizing styrene, if necessary. The vinyl chloride-vinyl acetate copolymer usually has a vinyl acetate content of about 5 to 20% by weight and an average degree of polymerization of 350 to 9%.
About 00 is used. If necessary, a carboxylic acid such as maleic acid or fumaric acid may be further copolymerized with the vinyl chloride-vinyl acetate copolymer. The mixing ratio of the acrylic resin and the vinyl chloride-vinyl acetate copolymer is as follows: acrylic resin / vinyl chloride-vinyl acetate copolymer = 1/9 to 9/1
(Weight ratio).

[Third Layer: All Solid Layer] The all solid layer to be the third layer 3 is a colored layer colored with an inorganic pigment, and is a color concealment for concealing the base color of the adherend by a resin molding or the like. Layer. When the decorative sheet is laminated on an adherend such as a resin molded product, or when only a transfer layer such as a pattern layer and an all solid layer is laminated on the adherend by transfer, In addition, the color tone of the decorative surface of the decorative article such as the obtained decorative molded article can be expressed by the decorative sheet independently without being affected by the color tone of the adherend such as the resin molded article. For this reason, as a coloring agent to be contained in all the solid layers, an inorganic pigment having excellent concealing properties is used as a main component. The entire solid layer is basically not particularly limited except that an inorganic pigment is used as a main component of the colorant. The entire solid layer is formed by a known printing method such as gravure printing using ink, or a known coating method such as roll coating using a coating solution. Known resins may be used as the binder resin for the ink or the coating liquid.

The inorganic pigment may be appropriately selected from known inorganic pigments according to the color tone to be expressed, and is not particularly limited. For example, in red, red, red,
In yellow, such as cadmium red and chrome vermillion,
For example, graphite, yellow iron oxide, cadmium yellow, titanium yellow, antimony yellow, blue, navy blue, ultramarine, cobalt blue, etc .; black, carbon black; white, titanium dioxide, zinc white, antimony trioxide, etc. The glitter pigments include pearl pigments composed of scale-like foil pieces such as titanium dioxide-coated mica, bismuth oxychloride, and basic lead carbonate. As the colorant, it is preferable to use only an inorganic pigment from the viewpoint of concealing properties. However, if a desired color tone cannot be obtained, an organic pigment may be used in combination within the range of an auxiliary component. In this case, the organic pigment to be used may be appropriately selected and used from known organic pigments according to the color tone to be expressed, and there is basically no particular limitation. For example, an organic pigment as described in the picture layer is used. In addition, all solid layers have a two-layer configuration, and the solid layer closer to the picture layer is:
The ratio of the organic pigment, which is an auxiliary component, may be increased with respect to all the solid layers far away. In addition, the content of the inorganic pigment is the total solid layer total amount (all including the binder resin and the like).
On the other hand, it is usually preferable that the content be about 50% by weight or more. If the addition amount is less than this, the concealing property decreases,
On the other hand, if the addition amount is larger than this, printability and the like will be reduced.

The resin of the binder of the ink or the coating liquid used for forming the entire solid layer is not particularly limited, and a resin suitable for the intended use may be used. For example, one kind or a mixture of two or more kinds of resins such as those listed in the picture layer may be used. For example, a mixed resin of an acrylic resin and a vinyl chloride-vinyl acetate copolymer, a single resin of a vinyl chloride-vinyl acetate copolymer, or the like is used. In addition, the thickness of all solid layers is usually about 3 to 5 g / m ^{2 in} terms of coating amount to provide concealing properties, but is not limited thereto. If the coating amount is too small, sufficient concealing properties cannot be obtained, and if it is too large, the cost will simply increase.

[Transfer Layer] When the decorative sheet is of a transfer type, at least the transfer layer 5 is composed of the second layer 2 composed of the picture layer and the third layer 3 composed of all solid layers. I do. However, as the transfer layer 5, in addition to the adhesive layer described later, although not shown, in order to adjust the releasability between the base sheet and the picture layer to an appropriate degree, a release layer is formed on the base sheet. It may be provided as a layer in contact. This release layer can be regarded as a layer belonging to the second layer having the picture layer. Of course, since the release layer is a transfer layer, after the substrate sheet is released,
This layer is left on the adherend side. The resin or the like listed in the picture layer is used for the release layer, and is formed by a known printing or coating method.

[Fourth Layer: Adhesive Layer] In the case where the adhesion between the decorative sheet and the adherend such as a resin molded product is insufficient, the surface of the decorative sheet in contact with the adherend (the back surface) In order to improve the adhesiveness, the back surface is subjected to an easy adhesion treatment such as corona discharge treatment or various known primer coatings, or the adhesive layer is subjected to a known printing or coating method such as gravure printing or roll coating. Thus, it may be provided as the fourth layer 4. Known resins such as a thermoplastic resin and a thermosetting resin are used for the adhesive layer.
For example, in a thermoplastic resin, polystyrene, a styrene resin such as poly α-methylstyrene or a styrene copolymer,
Acrylic resins such as poly (methyl) methacrylate, polyethyl (meth) acrylate, and poly (butyl methacrylate); chlorinated polyolefin resins such as chlorinated polypropylene; vinyl chloride resin; vinyl acetate resin;
One or two or more of vinyl acetate copolymers, vinyl polymers such as polyvinyl butyral, rubber resins such as polyisoprene rubber, polyisobutyl rubber, styrene butadiene rubber, butadiene acrylonitrile rubber, and thermoplastic resins such as polyamide resins. Is used. As the thermosetting resin, a urethane resin, an epoxy resin, or the like is used. For example, when the adherend is made of ABS resin, and when all solid layers are mainly composed of a mixture of acrylic resin and vinyl chloride-vinyl acetate copolymer, the adhesive layer is also made of acrylic resin and vinyl chloride-vinyl acetate. Mixtures with copolymers are preferred. Since no coloring agent is required in the adhesive layer, the adhesiveness is improved even with similar resin systems. When the adherend is made of a polyolefin resin, a two-component curable urethane resin using a chlorinated polyolefin such as chlorinated polypropylene or a blocked isocyanate as a curing agent is preferable.

The thickness of the adhesive layer may be appropriately set according to the required physical properties and the like, and is usually about 1 to 100 μm. The method for forming the adhesive layer is not particularly limited,
Usually, the resin is formed as an ink or coating liquid composed of a resin liquid obtained by diluting the resin with a diluting solvent, by a known printing or coating means such as gravure printing or roll coating. Further, in the adhesive layer, in order to adjust and improve various physical properties such as printing (or coating) suitability of the ink (or coating liquid), if necessary, other auxiliary materials, for example, Various additives such as pigments may be added.

Attached object of decorative sheet The decorative sheet of the present invention described above allows laminating
The adherend to be decorated by transfer or transfer is typically a resin molded product, and the resulting product is a decorative molded product of the present invention described below. However, as an adherend of the decorative sheet, an article made of a material other than a resin, for example, a wood-based material such as MDF (medium density fiberboard), a metal-based material such as iron, or a non-metallic inorganic-based material such as ceramics. Goods may be used.

Decorative Molded Article The decorative molded article of the present invention is obtained by laminating or transferring the decorative sheet S of the present invention as described above, as in the decorative molded article P illustrated in FIGS. This is a molded product in which the third layer 3 is positioned closer to the resin molded product 6 than the second layer 2 and the resin molded product colored with a coloring agent is decorated. The decorative molded product P in FIG. 2 is a molded product in which all layers of the decorative sheet S are laminated on the resin molded product 6 by laminating, and the decorative molded product P in FIG. This is a molded product having a configuration in which only the transfer layer 5 of the sheet S is laminated on the resin molded product 6.

By the way, the decorative molded product P in FIG.
In order from the front side, a first layer 1 made of a base sheet, a second layer 2 having a picture layer formed by printing or the like containing an organic pigment as a coloring agent, and an inorganic layer formed by printing, coating, etc. over the entire surface The third layer 3 made of a solid layer containing a pigment as a main component of a colorant is laminated on a resin molded product 6 colored with the colorant. On the other hand, the decorative molded product P in FIG.
An adhesive layer is interposed as a fourth layer 4 between the third layer 3 and the resin molding 6. This adhesive layer is shown in FIG.
Although illustrated as a component of the decorative sheet S, it may be supplied after being applied to the resin molded product 6 side. FIG. 2 (A)
The decorative sheet S used for the decorative molded product P of FIG.
The decorative sheet S used in the decorative molded product P in FIG. 2B corresponds to the decorative sheet S in FIG. 2A, and corresponds to the decorative sheet S in FIG.

Next, the decorative molded product P of FIG. 3A obtained by the transfer has, in order from the front side, a second layer 2 having a picture layer formed by printing or the like containing an organic pigment as a coloring agent. ,
This is a configuration in which a third layer 3 composed of an all-solid layer containing an inorganic pigment as a main component of a coloring agent formed by printing, coating, or the like on the entire surface is laminated on a resin molding 6 colored with a coloring agent. On the other hand, the decorative molded product P in FIG. 3B is similar to FIG.
An adhesive layer is interposed as a fourth layer 4 between the third layer 3 and the resin molding 6. This adhesive layer is also shown in FIG.
Similarly, in FIG. 3B, the decorative sheet S is illustrated as a constituent element, but may be supplied after being applied to the resin molded product 6 side.

The decorative molded product is usually a three-dimensional object whose decorative surface formed by laminating or transferring decorative sheets is non-planar with an uneven surface or the like. However, the decorative molded article of the present invention does not exclude a three-dimensional object whose decorative surface is flat but the other surface is non-planar and a plate-like object whose decorative surface is flat.

The decorative molded article of the present invention can be easily obtained by using the above-described decorative sheet of the present invention, but if the structure is the same, the decorative sheet of the present invention can be used. It does not exclude products manufactured without. For example, it is a decorative molded product in which each layer on the resin molded product is formed by painting or hand-drawing. However, it is needless to say that the decorative sheet of the present invention is preferably used because of easy production. Further, as a method of manufacturing a decorative molded product by decorating a resin molded product with such a decorative sheet, a so-called simultaneous injection molding decoration method is suitable. However, the method for obtaining the decorative molded product of the present invention is not limited to this simultaneous injection molding decorative method. For example, it can be obtained by another decoration method as appropriate according to the resin molded article (the shape of the decoration surface with the decoration sheet in the adherend), the available manufacturing equipment, and the like. For example,
No. 45768 (overlay method), Japanese Patent Publication No. 60-
A so-called vacuum forming and laminating method described in JP-A-58014 (vacuum pressing method) or the like may be used. Of course, it is preferable to adopt the simultaneous injection molding decorating method in that molding and decorating can be performed simultaneously in one step, and the production efficiency is good.

[Resin Molded Product] In the case where a decorative molded product is obtained by the simultaneous injection molding and decorating method, the resin molded product 6 is a molded product that forms simultaneously with the molding of the decorative molded product. When a decorative molded product is obtained by a forming and laminating method or the like, the molded product has already formed before the production of the decorative molded product. As the resin forming the resin molded product, if the resin is colored with a coloring agent,
There is no particular limitation, and a known resin may be used. The resin may be selected according to the required physical properties and cost of the product. For example, in the case of a thermoplastic resin, ABS (acrylonitrile-butadiene-styrene copolymer) resin, styrene resin, acrylic resin, vinyl chloride resin, polycarbonate resin, or polyethylene, polypropylene, polybutene, polymethylpentene, ethylene-propylene copolymer Polyolefin resins such as polymers, ethylene-propylene-butene copolymers, and olefin-based thermoplastic elastomers. In the case of a curable resin, a two-component curable resin, for example,
Uncured resin liquids such as urethane resins, unsaturated polyester resins, and epoxy resins. In the simultaneous decorating method of injection molding, the thermoplastic resin is heated and melted, injected into the cavity in a fluid state, and cooled and solidified. In addition, the curable resin (the uncured product) is injected at room temperature or by appropriately heating and flowing, and is crosslinked and polymerized to be solidified. The colorant for coloring the resin is not particularly limited and may be a known colorant, and may be an inorganic pigment, an organic pigment, a dye, or the like. For example, as the inorganic pigment and the organic pigment, the pigments listed in the picture layer and the solid layer can be used.

Injection Simultaneous Decorating Method Next, a so-called simultaneous injection molding decorating method, which is one preferable method for obtaining the decorative molded article of the present invention, will be described here.

The method of simultaneous decoration by injection molding is roughly classified into lamination and transfer, as described in JP-B-50-19132 and JP-B-43-27488. A so-called injection molding simultaneous painting lamination method in which a decorative sheet is permanently laminated on the surface of a resin molded article at the same time as molding using a decorative sheet, or JP-A-6-315950, As described in JP-A-42080, etc., so-called injection molding simultaneous picture transfer, in which a transfer type decorative sheet is used, and at the same time, only a transfer layer is transferred from the decorative sheet to the surface of the resin molded product by transfer. There is a law. Laminate and transfer are selected according to the intended use of the decorative molded product, required specifications, and the like.

In the simultaneous decorating method by injection molding, various conventionally known modes can be adopted. For example, either a mode in which the decorative sheet is preformed or a mode in which the preforming is not performed may be used. Also,
Preheating of the decorative sheet may or may not be performed.
Note that the decorative sheet is usually preheated at the time of preforming. Of course, when the decorative sheet has a large drawing, it is preferable to perform preforming. On the other hand, when the decorative sheet has a small drawing, the decorative sheet can be formed only by the resin pressure of the injected resin in the fluid state. At this time, if the drawing is shallow, the decorative sheet may be formed by the resin pressure of the resin in the flowing state, which is filled into the mold at the same time as the resin injection without preforming. Further, even when the decorative sheet is formed by the resin pressure, the decorative sheet may utilize the heat of the injection resin without preheating. In addition, in the preforming of the decorative sheet, usually, the injection mold is also used as the vacuum forming die, but before supplying the decorative sheet between the molds, the decorative sheet is formed with another vacuum forming die outside the mold. Preforming such as vacuum forming may be used. In addition, the vacuum forming includes vacuum pressure forming.

The injection molding simultaneous decorating method will be described with reference to a conceptual diagram of FIG. In addition, the form described here is a form in which the decorative sheet is heated and softened between the molds, preliminarily molded by vacuum molding with an injection mold, and then resin is injected by clamping before the mold is clamped. . In addition, this form is, in the above-described various forms of preforming and preheating of the decorative sheet, when the drawing of the decorative sheet is deep,
This is a more preferred form.

First, as shown in FIG. 4A, the injection mold includes a mold Ma having a runner (runner) and a gate (gate) communicating with the injection nozzle, and a suction hole 4 formed in the cavity surface.
A pair of molds Mb having the number 1 and also serving as a sheet preform is used. These molds are made of metal such as iron or ceramics. Both molds Ma and Mb in the mold open state
The decorative sheet S is supplied in between, and the decorative sheet S is fixed to the mold Mb by pressing it with a frame-shaped sheet clamp 42 or the like. In this case, it is a matter of course that the decorative sheet has the third layer closer to the injection resin side on the right side of the drawing than the second layer.
Next, the decorative sheet is appropriately heated and softened by a heater (not shown) inserted between both molds. The heating is, for example, non-contact radiation heating, but may be contact heating. Then, the decorative sheet is sucked through the suction hole and vacuum formed, and the decorative sheet is preformed along the cavity surface of the mold Mb. In addition, vacuum forming may be vacuum press forming using both pressure and air, and this is also included. Next, the heater is retracted from between the two dies, the two dies are clamped as shown in FIG. 4B, and a cavity formed by the two dies is filled with a resin in a flowing state such as a heated and molten state. After the resin is solidified by cooling or the like, the mold is opened and the molded product is taken out.
In the case where the decorative sheet is a laminate sheet, if there is an unnecessary portion of the decorative sheet, trimming is appropriately performed, and the decorative sheet S is laminated and decorated on the resin molded article 6 as shown in FIG. 2, for example. A molded product P is obtained. When the decorative sheet is a transfer sheet, the molded article is taken out with the base sheet left on the mold Mb side, or the molded article is taken out with the entire decorative sheet laminated, and then the base material is taken out. When the sheet is peeled, a decorative molded product P in which only the transfer layer is laminated and decorated as shown in FIG. 3 is obtained.

Other Embodiments The decorative sheet and the decorative molded article of the present invention have a configuration in which an all solid layer and a pattern layer are formed on the surface side of the base sheet (front printing specification). You can do it. A typical example is shown in FIG. The decorative sheet S of FIG. 5 (A) has, in order from the surface, a second layer 2 having a picture layer containing an organic pigment as a coloring agent, and an all-solid layer containing an inorganic pigment formed over the entire surface as a main component of the coloring agent. And a first layer 1 made of a base sheet are laminated in this order. FIG. 1 (A) shows the material and forming method of each layer.
Is the same as FIG. 5B shows a decorative molded product P obtained by laminating the decorative sheet S of FIG. 5A on the surface of the resin molded product 6. The resin molding 6 is the same as that in FIG.
Further, a fourth layer 4 composed of an adhesive layer may be formed on the back surface side of the third layer 3 composed of all solid layers in the configuration shown in FIGS. 5A and 5B (not shown). ). FIG.
When the decorative sheet S having the configuration of (A) is used as a transfer sheet, as shown in FIG. 5C, a sheet having releasability is temporarily laminated on the front side of the decorative sheet S as the support sheet 7. 5D, and laminated on a resin molded product 6 as shown in FIG. 5 (D).
Get. The second layer 2, the third layer 3, and the first layer 1 become the transfer layer 5 to which transfer is performed.

[0037]

The present invention will be described in more detail with reference to the following Examples and Comparative Examples.

Example A decorative sheet S of the present invention having the structure shown in FIG. 1B was obtained as follows. A transparent acrylic resin sheet (125 μm in thickness) made of a methyl methacrylate-butyl acrylate copolymer was prepared as the base sheet serving as the first layer. On one surface of the base sheet, as a second layer 2, a pattern layer of a wood grain pattern by three-color printing, as a third layer 3, an all-solid layer (consisting of one layer) of concealing properties, a fourth layer 4
An adhesive layer was formed by gravure printing in this order.
As a colorant for the picture layer, quinacridone and isoindolinone were used as organic pigments, and further, pearl pigments composed of carbon black as an inorganic pigment and titanium dioxide coated mica foil pieces were used in combination. The organic pigment ratio of the picture layer (the ratio of the organic pigment to the total colorant) was 35% by weight.
Iron oxide, titanium oxide and carbon black were used as inorganic pigments as the colorants for all solid layers. The organic pigment ratio of all solid layers was 0% by weight. For the pattern layer, all solid layer and adhesive layer, a mixed resin system of acrylic resin and vinyl chloride-vinyl acetate copolymer in a weight ratio of 1: 1 was used. The printed layer thickness is 10μ in total.
m.

The decorative sheet is laminated and integrated on the surface of an adherend made of a resin molded product simultaneously with the molding of the adherend made of a resin molded product by the simultaneous injection molding and decorating method as shown in the conceptual diagram of FIG. 2 (B), the decorative sheet S (all layers)
Was formed on the resin molded product 6 to obtain a decorative molded product P of the present invention. In addition, in the injection molding simultaneous decorating method, the decorating sheet was a form in which the injection mold was used as a vacuum mold, supplied between the molds, heated to a sheet temperature of 110 ° C., softened, and preformed by vacuum molding. In addition, the injection molding die has a panel for vehicle interior, which is 40 mm wide, 400 mm long, and 3 mm thick.
A mold having a suction hole for preforming a sheet was used on the female mold side. As the injection resin, a black ABS resin to which carbon black was added as a coloring agent was used. And the injection resin temperature 240
The resin was injected at a temperature of 70 ° C. and a mold temperature of 70 ° C.

[Comparative Example 1] In the example, the coloring agent for the picture layer was changed to an inorganic pigment such as red iron oxide, yellow iron oxide, pearl pigment composed of titanium dioxide coated mica foil pieces, and carbon black. A decorative sheet was produced in the same manner as in Example, except that the pigment ratio was 0% by weight. Using this decorative sheet, decoration was performed simultaneously with injection molding in the same manner as in the example to obtain a decorative molded product.

Comparative Example 2 In Examples, quinacridone, isoindolinone, and phthalocyanine blue organic pigments were used as colorants for all solid layers (organic pigment ratio was 10%).
0% by weight), except that the decorative sheet was produced in the same manner as in the example. Using this decorative sheet, decoration was performed simultaneously with injection molding in the same manner as in the example to obtain a decorative molded product.

[Comparison of Performance] The appearance of the decorative molded article was compared between the embodiment and each comparative example. As a result, in the example, as compared with the other comparative examples 1 and 2, the pattern was not darkened by the influence of the black color of the resin molded product, the concealing property (mainly due to all the solid layers) was good, and the pattern had high chroma. Was. A decorative molded product having an excellent design feeling was obtained. On the other hand, in Comparative Example 1, although there was no blackening of the pattern due to the black color of the resin molded product, the pattern itself was entirely sunken and had a low saturation.
Further, in Comparative Example 2, the black color of the underlying resin molded product was seen through, and the pattern became dark as a whole. In particular, the effect of the color of the adherend was significant in the portion where the decorative sheet was stretched, and the color of the pattern changed significantly from the decorative sheet alone (decorative sheet before being stretched).

[0043]

According to the decorative sheet of the present invention, the kind of the coloring agent to be contained in the picture layer and the entire solid layer under the pattern layer is changed, and the coloring agent is contained in the third layer composed of the entire solid layer. The use of inorganic pigments as the main component provides excellent concealment properties, eliminates the effects of the color tone of adherends such as resin moldings, and also allows the pattern layer to contain organic pigments, thus providing good color development and coloring. And concealment are compatible. Even if the adherend such as a resin molded product is black, for example, it is possible to express a design with high saturation without being affected by the color tone. If the adhesive layer is also provided as the fourth layer, the adhesiveness can be improved when the adhesiveness to the adherend is insufficient. ADVANTAGE OF THE INVENTION According to the decorative molded article of this invention, the color tone to express is a molded article with good coloring, without being influenced by the color tone of the resin molded article which is an adherend.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view showing a form example of a decorative sheet of the present invention.

FIG. 2 is a cross-sectional view illustrating an example of a decorative molded product (in the case of a laminate) of the present invention.

FIG. 3 is a cross-sectional view illustrating a form example of a decorative molded product (in the case of transfer) of the present invention.

FIG. 4 is a conceptual diagram illustrating an injection molding simultaneous decorating method as an example.

FIG. 5 is a sectional view illustrating another embodiment of the decorative sheet and the decorative molded product of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 1st layer (base sheet) 2 2nd layer (picture layer etc.) 3 3rd layer (all solid layers) 4 4th layer (adhesive layer) 5 transfer layer 6 resin molding 7 support sheet 41 suction hole 42 Sheet clamp Ma Injection mold (male) Mb Injection mold (female) P Molded product S Decorative sheet

 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) 4F100 AA21 AA37 AC05 AK15 AK22 AK25 AL01 AT00A AT00E BA04 BA05 BA07 BA10A BA10E CA13B CA13C CB00D CB03 EH36 GB15 GB71 HB00B HB01 HB31C HB31D JL01 JN21 A12 A12 A12 A12 CB01 CB19 CB22 CK41 CQ01 CQ06 4F206 AA13 AA21 AA36 AB12 AD09 AD10 AG03 JA07 JB19 JB22 JF05 JN43 JQ81

Claims (4)

[Claims] 1. In order from the surface, a first layer composed of a base sheet, a second layer having a picture layer containing an organic pigment as a colorant, and an inorganic pigment formed on the entire surface as a main component of the colorant. The third layer consisting of all solid layers is laminated,
Decorative sheet. 2. A second layer having a picture layer containing an organic pigment as a colorant in order from the surface, a third layer consisting of an all solid layer containing an inorganic pigment formed as a main component of the colorant formed on the entire surface, The first layer made of the base material sheet is laminated,
Decorative sheet. 3. The decorative sheet according to claim 1, wherein an adhesive layer is laminated as a fourth layer on the lowermost surface. 4. The surface of a resin molded product colored with a coloring agent, wherein the third layer of the decorative sheet is larger than the second layer by laminating or transferring the decorative sheet according to claim 1, 2 or 3. A decorative molded product that is decorated on the resin molded product side.