JP2001018251A - Sheet for injection molding in-mold decoration and in- mold decorated molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make transparency and surface physical properties excellent and to make lamination with good adhesiveness possible even for inexpensive polyolefin resin and to decrease curling after molding. SOLUTION: A sheet S for injection molding in-mold decoration has a constitution wherein e.g. a decorative layer 2 whose binder resin is a mixture of a vinyl chloride-vinyl acetate copolymer and an acrylic resin or an acryl-urethane resin, a primer layer 3 of a urethane resin, an adhesive layer 4 of a chlorinated polypropylene and an olefinic thermoplastic elastomer sheet 5 are laminated on a transparent acryl resin sheet 1 to be the outermost layer. An in-mold decorated article is prepd. by laminating this injection molding in-mold decorating sheet on the surface of a resin molded article by means of injection molding in-mold decoration.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sheet for simultaneous painting with injection molding which can be laminated with good adhesion to a resin molded product made of a polyolefin resin. The present invention also relates to a painted molded product obtained by laminating the sheet on the surface of a resin molded product.

[0002]

2. Description of the Related Art Conventionally, painted molded products obtained by painting the surface of a resin molded product have been used for various purposes. For example, Japanese Patent Publication No. 50-19132, Japanese Patent Publication No. 43-27488
In the simultaneous injection molding simultaneous painting method disclosed in Japanese Patent Application Publication No. H10-103, the injection molding simultaneous painting sheet is placed between the male and female molds of the injection molding, and then the molten resin is injected and filled into the cavity to form a resin molded product. At the same time, a method is disclosed in which a sheet for simultaneous painting with injection molding is adhered and laminated on the surface to obtain a painted molded article painted with the sheet.

[0003] Conventionally, the injection molding resin used for the resin molding by the simultaneous injection molding painting method is AB
There were many S resins (acrylonitrile-butadiene-styrene copolymer), acrylic resins, polycarbonate resins, and the like. For this reason, a laminated type injection molding simultaneous painting sheet used for laminating on the surface of the resin molded product by the injection molding simultaneous painting method is also generally of a specification having good adhesion to these injection molding resins. .

[0004] In order to give the resulting painted molded product a design feeling such as a painting feeling and a surface gloss to give a high-grade feeling and to obtain sufficient surface physical properties such as abrasion resistance and weather resistance, (1) )
A transparent acrylic resin sheet such as polymethyl methacrylate (PMMA), which has excellent transparency, is used as the resin sheet as the outermost surface layer, and a decorative layer etc. is formed by printing on the back side (the side to be the resin molded product side). (See Japanese Patent Publication No. 50-19132). (2) Further, in this state, in order to prevent the color of the resin molded product from being easily seen through, and to adjust the moldability in vacuum molding with an injection molding die, etc. In addition, a sheet for simultaneous painting with injection molding having a structure in which a colored ABS resin sheet is laminated as a colored concealing layer has been used. (3) In addition, in view of the fact that it is an inexpensive resin sheet, a sheet for simultaneous painting with injection molding having a configuration in which a decorative layer is formed by printing or the like on the back side of a polyolefin resin sheet such as polypropylene or polyethylene has been used. (See Japanese Patent Publication No. 50-19132).

[0005]

Recently, however, it has often been desired to use an inexpensive polyolefin resin such as polypropylene as the injection molding resin. However, none of the sheets for simultaneous painting with injection molding having the constitutions as described in (1) to (3) above can be laminated with a satisfactory adhesion to a resin molded product made of a polyolefin resin. In addition, in the sheet for simultaneous painting with injection molding having the constitution (1), the acrylic resin sheet itself is harder at room temperature than the polyolefin-based resin sheet and the plasticized vinyl chloride resin sheet, and has a thickness of 0.1 mm. 1
Since the thickness is 0.2 mm, the resin sheet does not have stiffness (shape retention) and is easily broken at the same time, and there is a problem that it is difficult to handle the sheet at the time of printing a decorative layer or at the same time as painting with injection molding. Was. In addition, in the sheet for simultaneous painting with injection molding having the configuration of (2), the suitability of the sheet for handling is improved as compared with the configuration of (1).
The S resin sheet was difficult to adhere to a resin molded product made of a polyolefin resin such as polypropylene. Also, (3)
In the sheet for simultaneous painting with injection molding having the structure of the above, both the suitability of the sheet for handling and the adhesion to the polyolefin-based resin molded product are improved as compared with the acrylic resin sheet, but the polyolefin-based resin sheet serving as the outermost surface layer is improved. However, it was inferior in weather resistance, scratch resistance and transparency.

Accordingly, an object of the present invention is to provide a laminate type injection-molded simultaneous painting sheet which can impart sufficient transparency and surface physical properties to the resulting painted article.
The purpose of the present invention is to provide a sheet which can be laminated on a resin molded product with good adhesion even when a polyolefin resin such as polypropylene is used as the injection molding resin. It is still another object of the present invention to provide a painted product having transparency and surface properties imparted by laminating such a sheet for simultaneous injection-molded painting.

[0007]

Therefore, in order to solve the above-mentioned problems, in a first invention of a sheet for simultaneous painting with injection molding of the present invention, the sheet for simultaneous painting with injection molding S illustrated in FIG. As described above, in the laminate type sheet for simultaneous painting with injection molding, at least the binder resin is formed of vinyl chloride resin on the transparent acrylic resin sheet 1 serving as the outermost surface layer.
A decorative layer 2 mainly composed of a mixture of a vinyl acetate copolymer and an acrylic resin or an acrylic urethane resin, a primer layer 3 mainly composed of a urethane resin, and an olefin-based thermoplastic elastomer sheet 5 are laminated in this order. The configuration was made.

In a second aspect of the present invention, a sheet for simultaneous simultaneous painting with injection molding, such as a sheet for simultaneous simultaneous painting with injection molding S shown in FIG. A transparent acrylic resin sheet 1 serving as the outermost surface layer has at least a decorative layer 2 whose binder resin is a mixture of a vinyl chloride-vinyl acetate copolymer and an acrylic resin or an acrylic urethane resin as a main component.
And a primer layer 3 containing a urethane resin as a main component, an adhesive layer 4 containing a chlorinated polypropylene as a main component, and an olefin-based thermoplastic elastomer sheet 5 laminated in this order.

In a third aspect of the present invention, a sheet for simultaneous simultaneous painting with injection molding, such as a sheet for simultaneous simultaneous painting with injection molding S shown in FIG. A transparent acrylic resin sheet 1 serving as the outermost surface layer has at least a decorative layer 2A whose binder resin is mainly a mixture of a vinyl chloride-vinyl acetate copolymer and an acrylic resin, and a vinyl chloride-vinyl acetate copolymer. A configuration in which a primer layer 3A mainly composed of a united body and an olefin-based thermoplastic elastomer sheet 5A having a polar functional group in a molecule are laminated in this order.

According to a fourth aspect of the present invention, a sheet for simultaneous simultaneous painting with injection molding, such as a sheet for simultaneous simultaneous painting with injection molding S shown in FIG. A transparent acrylic resin sheet 1 serving as the outermost surface layer has at least a decorative layer 2 whose binder resin is a mixture of a vinyl chloride-vinyl acetate copolymer and an acrylic resin or an acrylic urethane resin as a main component.
And a primer layer 3 mainly composed of a urethane resin, a second primer layer 3B mainly composed of a vinyl chloride-vinyl acetate copolymer, and an olefin-based thermoplastic elastomer sheet 5A having a polar functional group in the molecule. Are stacked in this order.

In the fifth invention of the sheet for simultaneous painting with injection molding of the present invention, as in the sheet for simultaneous painting with injection molding S illustrated in FIGS. 2A and 2B, FIG. 1
The olefin having no polar functional group in the molecule on the back surface of the olefin-based thermoplastic elastomer sheet 5A having a polar functional group in the molecule of the sheet S for simultaneous painting with injection molding of the third or fourth invention of (D). The structure was such that the thermoplastic thermoplastic elastomer sheets 5B were laminated. Note that FIG. 2A shows a case where both the 5A and 5B layers are directly heat-sealed without an adhesive layer therebetween, and FIG. The drawing shows a case where the layers are laminated via the primer layer 3C. In these, the two layers of the laminated olefin-based thermoplastic elastomer sheets 5A and 5B can be regarded as the two-layered olefin-based thermoplastic elastomer sheet 5.

In the case of the olefin-based thermoplastic elastomer sheet 5 according to the first and second aspects of the present invention, the olefin-based thermoplastic elastomer sheet 5A having a polar functional group in the molecule and the polar olefin-based thermoplastic elastomer sheet 5 in the molecule are used. It may be constituted by any of an olefin-based thermoplastic elastomer sheet 5B having no functional group, or a laminate including these 5A and 5B.

As described above, a transparent acrylic resin sheet is used as the outermost layer after lamination, while an olefin-based thermoplastic elastomer sheet is used as the outermost layer in contact with the resin molded product. The layer is provided between them, and a primer layer is provided between the decorative layer and the olefin-based thermoplastic elastomer sheet in order to laminate the decorative layer with good adhesion. Further, in the second invention, an adhesive layer is provided.
In the fourth invention, the second primer layer has a layer structure provided between the (first) primer layer and the olefin-based thermoplastic elastomer sheet, and the decorative layer, the primer layer, or the adhesive layer is further provided. By adopting and combining specific materials for each, it is possible to impart excellent transparency and surface properties to the resulting painted molded product, and it can be laminated to a resin molded product of polyolefin resin with good adhesion, and simultaneously painting with injection molding The adhesion in the layer of the sheet for use can also be improved.
In addition, since the olefin-based thermoplastic elastomer is used for the rearmost layer, curling after sheet molding which occurs when polypropylene is used for the rearmost layer can also be prevented.

In the third aspect of the present invention, since the olefin-based thermoplastic elastomer sheet 5A has a polar functional group in the molecule, it has an easy adhesive property, and has an excellent adhesive property.
A relatively versatile and inexpensive vinyl acetate copolymer, unlike the two-component curable urethane resin, which does not undergo a curing reaction with time, can be used for the primer layer in contact with the olefin-based thermoplastic elastomer sheet.

As in the fourth invention, the olefin-based thermoplastic elastomer sheet 5A has a polar functional group in the molecule, but the main component of the binder resin of the decoration layer 2 is vinyl chloride-acetic acid. In addition to the case of the mixture of the vinyl copolymer and the acrylic resin, in a form including the case where the main component is an acrylic urethane resin, the second primer is a primer layer mainly including a vinyl chloride-vinyl acetate copolymer. By providing the primer layer 3 made of urethane resin as the (first) primer layer between the second primer layer and the decorative layer as the layer 3B, the interlayer adhesion is further improved. In such a configuration including two primer layers, the intermediate product (3B / 5A) in which the second primer layer 3B is formed on the olefin-based thermoplastic elastomer sheet 5A in advance and the acrylic resin sheet 1 are decorated. The intermediate product (1/2) on which the layer 2 has been printed is separately prepared and stored in stock, and when necessary, both intermediate products are laminated in a dry lamination process using the first primer layer 3 in a necessary amount. Sheet for simultaneous painting with injection molding (1/2/3/3
B / 5A) can be manufactured, and inventory management of intermediate products becomes easy. The first primer layer 3 is made of dry
Since it is only necessary to be in an uncured state during the printing process, there is no problem in using a two-component curable urethane resin having a long-term curability but a strong adhesive force.

Further, as in the fifth invention, an olefin-based thermoplastic elastomer sheet 5A having a polar functional group in the molecule and an olefin-based thermoplastic elastomer sheet 5B having no polar functional group in the molecule is provided. By using the thermoplastic elastomer sheet 5, the back side of the sheet for simultaneous painting with injection molding is thermally fused with a resin molded product of a polyolefin resin, so even an inexpensive olefin-based thermoplastic elastomer sheet 5 B having no polar functional groups can be used. In the case where the adhesive performance is sufficiently exhibited and all the layers of the olefin-based thermoplastic elastomer sheet 5 have a polar functional group in the molecule, it is possible to prevent the cost from becoming too high and causing inconvenience.

Further, the painted molded article of the present invention has a configuration in which any one of the above-mentioned sheets for simultaneous painting with injection molding is laminated on the surface of a resin molded article made of a polyolefin resin. By doing so, a molded article having excellent transparency, surface properties, and adhesion can be obtained even with respect to a resin molded article of a polyolefin resin.

[0018]

Embodiments of the present invention will be described below. 1 and 2 are cross-sectional views illustrating various examples of the sheet for simultaneous painting with injection molding of the present invention, and FIG. 3 is a diagram illustrating a method for simultaneous painting with injection molding which is an application of the sheet for simultaneous painting with injection molding of the present invention. FIG. 4 is a conceptual diagram for explaining the present invention, and FIG. 4 is a cross-sectional view illustrating a painted molded product of the present invention obtained by using the sheet for simultaneous painting with injection molding of the present invention.

[Sheet for simultaneous painting with injection molding] First, FIG.
In (A), the sheet for simultaneous painting with injection molding of the present invention will be described by way of an example. In the sheet for simultaneous painting with injection molding S of the present invention, the outermost surface layer is made of a transparent acrylic resin sheet 1, The back layer is composed of an olefin-based thermoplastic elastomer sheet 5 and has a decorative layer 2 between these layers, and further has a primer layer 3 between the decorative layer 2 and the olefin-based thermoplastic elastomer sheet 5. And For such a layer configuration, in the embodiment of FIG. 1A, the constituent materials of the respective layers are the decorative layer 2 and the primer layer (after adopting the specific material for the outermost layer and the lowermost layer). Third, the following specific materials are used to improve the adhesion between the layers. That is, the decoration layer 2 is a layer whose binder resin is a mixture of a vinyl chloride-vinyl acetate copolymer and an acrylic resin or an acrylic urethane resin as a main component,
The primer layer 3 is a layer containing a urethane resin as a main component.

In addition to the form shown in FIG. 1A, the sheet for simultaneous painting with injection molding according to the present invention has a structure shown in FIGS.
(D) and a configuration as shown in FIG.

Hereinafter, each layer will be described in detail.

(Acrylic Resin Sheet) The acrylic resin sheet 1 is a transparent resin sheet made of acrylic resin.
Examples of the acrylic resin include acrylic resins such as polymethyl (meth) acrylate, polybutyl (meth) acrylate, methyl (meth) acrylate-butyl (meth) acrylate copolymer, and methyl (meth) acrylate-styrene copolymer [ , (Meth) acrylate means acrylate or methacrylate] alone or as a mixture of two or more. In order to impart good scratch resistance to the acrylic resin sheet, it is preferable to add a lubricant such as a hydrocarbon lubricant or a fatty acid lubricant as a lubricant.
However, if the lubricant is added too much, the sheet slips in the mold at the time of simultaneous painting with injection molding, and wrinkles, distortions, and the like are likely to occur. Therefore, the lubricant has a dynamic friction coefficient of 0. 0 on the surface of the acrylic resin sheet.
It is good to add so that it may be set to 2-0.9. The amount of addition is about 0.1 to 0.5% by weight. The acrylic resin sheet may be used as a resin sheet of a laminate of two or more layers in addition to a single layer. Further, the term “transparent” generally means non-colored and transparent, but it may be colored and transparent by adding a known coloring agent as needed. By using an acrylic resin sheet as the outermost layer and using the decorative layer as a lower layer, it is possible to impart a high-quality design such as a painted feeling and a surface gloss due to the excellent transparency of the acrylic resin sheet. In addition, surface properties such as weather resistance and scratch resistance can be improved as compared with a polyolefin resin sheet or the like. The thickness of the acrylic resin sheet is not particularly limited, but it is not necessary for the acrylic resin sheet to have the strength as the whole sheet for simultaneous painting with injection molding. Since it becomes too strong and the handling becomes poor, it is usually about 20 to 200 μm depending on the surface characteristics such as transparency and coating feeling to be imparted.

(Decoration Layer) The decoration layers 2 and 2A are layers expressing a pattern or the like by printing or the like. The decorative layers 2 and 2A use a specific resin as a main component of the binder resin.
That is, the decorative layer 2 in each of the first, second and fourth inventions and the fifth invention with respect to the fourth invention [FIG.
(A), (B), (D) and FIG. 2 (B)] show a mixture of a vinyl chloride-vinyl acetate copolymer and an acrylic resin or an acrylic urethane resin as a main component of a binder resin. I do. The decorative layer 2A according to the fifth invention with respect to the third and third inventions (see FIGS. 1C and 2A) is a mixture of a vinyl chloride-vinyl acetate copolymer and an acrylic resin. Constitutes the main component of the binder resin. By using such a specific resin, in the sheet for simultaneous painting with injection molding of each invention, the acrylic resin sheet in contact with the decorative layer and the specific resin corresponding to the binder resin of the decorative layer are used. Good adhesion to the primer layer. In addition, in the combination of the mixture of the vinyl chloride-vinyl acetate copolymer and the acrylic resin, the acrylic resin contributes to the improvement of the adhesion to the acrylic resin sheet, and the vinyl chloride-vinyl acetate copolymer improves the printability and moldability. To contribute. Acrylic urethane resin alone can satisfy these suitability.

The vinyl chloride-vinyl acetate copolymer generally has a vinyl acetate content of about 5 to 20% by weight,
Those having an average degree of polymerization of about 350 to 900 are used. Further, the vinyl chloride-vinyl acetate copolymer, if necessary,
Further, those obtained by copolymerizing a carboxylic acid such as maleic acid or fumaric acid may be used.

Examples of the acrylic resin include polymethyl (meth) acrylate, polybutyl (meth) acrylate, methyl (meth) acrylate-butyl (meth) acrylate copolymer, and methyl (meth) acrylate-styrene copolymer. Acrylic resin or methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, cyclohexyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate, 2-
An acrylic resin such as an acrylic polyol obtained by copolymerizing a (meth) acrylate having a hydroxyl group in a molecule such as hydroxy-3-phenoxypropyl (meth) acrylate is used alone or as a mixture of two or more kinds. . In addition, (meth) acrylate means acrylate or methacrylate. The mixing ratio of the vinyl chloride-vinyl acetate copolymer and the acrylic resin is about 1/9 to 9/1 (weight ratio) of the vinyl chloride-vinyl acetate copolymer / acrylic resin.

As the acrylic urethane resin, a two-component curable acrylic urethane resin or a thermoplastic acrylic urethane resin may be used.

For example, a two-component curable acrylic urethane resin is a urethane resin containing acrylic polyol as a main component and isocyanate as a crosslinking agent (curing agent). Examples of the acrylic polyol include a methyl (meth) acrylate-2hydroxyethyl (meth) acrylate copolymer, an octyl (meth) acrylate-ethylhexyl (meth) acrylate-2 hydroxyethyl (meth) acrylate copolymer, and a methyl (meth) acrylate. ) Acrylate-butyl (meth) acrylate-2 hydroxyethyl (meth) acrylate-styrene copolymer or the like is used alone or as a mixture of two or more. As the isocyanate, a polyvalent isocyanate having two or more isocyanate groups in a molecule is used. For example, 2,4-tolylene diisocyanate, xylene diisocyanate, 4,
Aromatic isocyanates such as 4'-diphenylmethane diisocyanate, or aliphatic (or cycloaliphatic) isocyanates such as 1,6-hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, or Adducts of the above various isocyanates,
Alternatively, a multimer can be used. For example, there are an adduct of tolylene diisocyanate and a trimer of tolylene diisocyanate. The thermoplastic acrylic urethane resin is made of a linear polymer, for example, obtained by urethane bonding divalent acrylic polyol and divalent isocyanate.

As the resin of the binder of the decorative layer, as a sub-component resin, if necessary, other resins other than the resin as a main component, for example, a thermoplastic polyester resin, a thermoplastic resin or a two-component resin Curable urethane resin (other than acrylic urethane resin) (in the case of decorative layer 2A)
May be used in combination.

The decorative layers 2 and 2A are basically not particularly limited except that the binder resin is composed of the above-mentioned specific resin. The decorative layers 2, 2A are usually formed of a printing ink or paint by a known printing or coating method (when the coating method is a solid pattern). Usually, the decorations 2 and 2A are formed on the acrylic resin sheet 1. If the acrylic resin sheet on which the decorative layer is formed is laminated with a known laminating method such as a dry lamination method with an olefin-based thermoplastic elastomer sheet via a primer layer or an adhesive layer therebetween, the present invention Is obtained. The colorant used for the printing ink (or paint) may be a known dye or pigment, for example, titanium white,
Inorganic pigments such as carbon black, red iron oxide, graphite, and cobalt blue; organic pigments such as aniline black, phthalocyanine blue, isoindolinone, and quinacridone; metallic pigments such as aluminum foil powder; and pearl luster such as titanium dioxide-coated mica ) Pigments and other dyes are used. The pattern of the decorative layer is arbitrary, such as wood grain, stone grain, cloth grain, sand grain, squeezed pattern, geometric pattern, letters, symbols, and solid on the entire surface.

The decorative layer may be a functional layer such as a conductive layer in which a conductive powder such as silver powder is dispersed in a binder, in addition to a decorative layer having a wood grain pattern or the like.

(Primer Layer) The primer layers 3, 3A,
3B and 3C are interposed between layers to improve interlayer adhesion. The main components of the primer layers 3, 3A and 3B are made of a specific resin. The resin includes the first, second and fourth inventions, and the primer layer 3 of the fifth invention with respect to the fourth invention [FIGS. 1 (A), (B) and (D), and FIG. In the third invention and the third invention according to the third invention, the primer layer 3A (see FIGS. 1C and 2A) uses a urethane resin. Use a polymer. In addition, the primer layer 3C which is appropriately provided as necessary may be made of an appropriate resin as a main component resin, but a urethane resin is a preferable resin.

In the fourth invention and the sheet S for simultaneous painting with injection molding of the fifth invention with respect to the fourth invention, the primer layer 3 and the second layer between the decorative layer 2 and the olefin-based thermoplastic elastomer sheet 5 are provided. In the primer layer 3B, a urethane resin is used for the primer layer 3, and a vinyl chloride-vinyl acetate copolymer is used for the primer layer 3B.
And the olefin-based thermoplastic elastomer sheet 5
Uses an olefin-based thermoplastic elastomer sheet 5A having a polar functional group in the molecule on the side of the second primer layer 3B. In particular, in the case of the fifth invention with respect to the fourth invention, the olefin-based thermoplastic elastomer sheet has a polar functional group in the molecule on the resin molded product side in addition to the olefin-based thermoplastic elastomer sheet 5A. It has a two-layer structure in which no olefin-based thermoplastic elastomer sheets 5B are laminated. Further, in the case of the form of FIG.
A third primer layer 3C is provided between these layers, and the third primer layer 3C is preferably composed mainly of a urethane resin.

As described above, in each of the primer layers 3, 3A and 3B (or even 3C), the above-mentioned specific resin is employed as a main component of the respective layers, so that the interlayer adhesion can be increased in each of the layers. Can be improved.

That is, as a first invention, interlayer adhesion between a decorative layer 2 mainly composed of a mixture of a vinyl chloride-vinyl acetate copolymer and an acrylic resin or an acrylic urethane resin, and an olefin-based thermoplastic elastomer sheet 5 In order to improve the properties (FIG. 1A), the primer layer 3 containing a urethane resin as a main component gives preferable results.

As a second invention, the decorative layer 2 whose binder resin is mainly a mixture of a vinyl chloride-vinyl acetate copolymer and an acrylic resin or an acrylic urethane resin, and the chlorinated polypropylene is a main component In order to improve the interlayer adhesion between the adhesive layer 4 (particularly, the interlayer adhesion after a heat resistance test) (FIG. 1B), the primer layer 3 containing a urethane resin as a main component gives a preferable result.

According to a third aspect of the invention, or as a fifth aspect of the third aspect of the present invention, there is provided a decorative layer 2A whose binder resin is mainly composed of a mixture of a vinyl chloride-vinyl acetate copolymer and an acrylic resin. In order to improve the interlayer adhesion with the olefin-based thermoplastic elastomer sheet 5A having a polar functional group in the molecule [FIGS. 1 (C) and 2 (A)], a vinyl chloride-vinyl acetate copolymer is mainly used. The primer layer 3A as a component gives preferable results.

As a fourth invention and a fifth invention with respect to the fourth invention, the decorative layer 2 mainly composed of a mixture of a vinyl chloride-vinyl acetate copolymer and an acrylic resin or an acrylic urethane resin is used. In order to improve the interlayer adhesion with the olefin-based thermoplastic elastomer sheet 5A having a polar functional group in the molecule [FIGS. 1 (D) and 2 (B)],
In a two-layer configuration of the primer layers 3 and 3B made of different resin materials, the primer layer 3 on the decoration layer 2 side is mainly composed of urethane resin, and the primer layer 3B on the other side is a vinyl chloride-vinyl acetate copolymer. When used as a main component, favorable results are obtained.

In the olefin-based thermoplastic elastomer sheet 5 having a two-layer structure as in the fifth invention, the third primer layer 3C is provided between the layers as shown in FIG. May be interposed. In this case, when the third primer layer 3C is mainly composed of urethane resin,
Gives favorable results.

The vinyl chloride-vinyl acetate copolymer used in the primer layer usually has a vinyl acetate content of about 5 to 20% by weight and an average degree of polymerization of 350 to 900.
The degree is used. Further, the vinyl chloride-vinyl acetate copolymer may be one obtained by further copolymerizing a carboxylic acid such as maleic acid or fumaric acid, if necessary.

As the urethane resin used for the primer layer, a two-component curable urethane resin, a one-component moisture-curable urethane resin, a thermoplastic urethane resin, or the like may be used.

For example, a two-component curable urethane resin has a polyol as a main component and an isocyanate as a crosslinking agent (curing agent).
Urethane resin. The polyol has two or more hydroxyl groups in the molecule, and examples thereof include polyethylene glycol, polypropylene glycol, acrylic polyol, polyester polyol, polyether polyol, polycarbonate polyol, and polyurethane polyol. As the isocyanate, a polyvalent isocyanate having two or more isocyanate groups in a molecule is used. For example, 2,4-tolylene diisocyanate, xylene diisocyanate,
Aromatic isocyanates such as 4,4'-diphenylmethane diisocyanate, or aliphatic (or alicyclic) isocyanates such as 1,6-hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, or In addition, adducts or multimers of the above various isocyanates can also be used. For example, there are an adduct of tolylene diisocyanate and a trimer of tolylene diisocyanate.

The one-component moisture-curable urethane resin is a composition containing a prepolymer having an isocyanate group at a molecular terminal as an essential component. The prepolymer is usually a polyisocyanate prepolymer having one or more isocyanate groups at both molecular terminals, and is a solid thermoplastic resin at normal temperature. Isocyanate groups react with each other due to moisture in the air to cause a chain extension reaction, and as a result, a reactant having a urea bond in a molecular chain is generated,
The urea bond further reacts with the isocyanate group at the molecular terminal, causing a biuret bond and branching to cause a crosslinking reaction. The skeleton structure of the molecular chain of the prepolymer having an isocyanate group at the molecular terminal is arbitrary, and specific examples include a polyurethane skeleton having a urethane bond, a polyester skeleton having an ester bond, and a polybutadiene skeleton. One or more of these skeletal structures are appropriately employed. When a urethane bond is present in the molecular chain, the terminal isocyanate group is also opposite to the urethane bond, so that an allophanate bond is generated, and a cross-linking reaction is also caused by the allophanate bond.

The thermoplastic urethane resin comprises a linear polymer obtained by urethane-bonding a divalent polyol and a divalent isocyanate.

The primer layer may be formed by a known printing method or coating method using an ink or a coating liquid using the specific resin as described above.

(Adhesive Layer) The adhesive layer 4 (see FIG. 1B) is provided between the primer layer 3 containing urethane resin as a main component and the olefin-based thermoplastic elastomer sheet 5 to bond these layers. It is. This adhesive layer is composed mainly of chlorinated polypropylene. For improving the interlayer adhesion between the primer layer 3 made of the specific material and the olefin-based thermoplastic elastomer sheet 5, favorable results can be obtained by using chlorinated polypropylene as a main component. The adhesive layer may be formed by an ink or a coating liquid using the above-mentioned specific resin by a known printing method or coating method. The thickness of the adhesive layer is not particularly limited, but is, for example, about 5 to 20 μm.

There are two main reasons for adopting the two-layer structure of the primer layer 3 and the adhesive layer 4.

(1) For the purpose of easy adhesion treatment of the olefin-based thermoplastic elastomer sheet; that is, in this case, the adhesive layer 4 is composed of an olefin-based thermoplastic elastomer sheet 5 which will be described in detail later. From the viewpoint of cost and the like, when the polar functional group contributing to the improvement of the adhesiveness is not introduced, the primer layer 3 is used as a resin layer instead of the olefin-based thermoplastic elastomer sheet into which the polar functional group is introduced. And the olefin-based thermoplastic elastomer sheet 5 in adhesion. in this case,
It is preferable that the adhesive layer 4 is formed on the surface of the olefin-based thermoplastic elastomer sheet 5 side from the viewpoint of improving the adhesive strength. The adhesive layer 4 is formed by a known coating method such as a gravure roll coat or a melt extrusion coat. It is needless to say that an adhesive layer may be used even when an olefin-based thermoplastic elastomer in which a polar functional group is introduced is used for the olefin-based thermoplastic elastomer sheet 5.

(2) When the purpose is to make the printing / coating step on the acrylic resin sheet 1 and the laminating step of the olefin-based thermoplastic elastomer sheet 5 off-line; that is, in this case, on the acrylic resin sheet 1 2A decorative layer
Until the primer layer 3 is formed, processing is continuously completed in-line by a conventional printing / coating machine. On the other hand, the lamination of the olefin-based thermoplastic elastomer sheet 5 is performed by a laminating machine different from the printing and coating machine. In the case where it is more efficient to mass-produce a large number of products, it is better to carry out the process assigned to each machine when the machine is vacant without making the process of the laminating machine and the process of the laminating machine separately and independently. There are many. And in this case, the acrylic resin sheet 1
The time from when the decorative layer 2A and the primer layer 3 are formed thereon to when the olefin-based thermoplastic elastomer sheet 5 is laminated is the time required for completing the curing reaction of the one-component or two-component curable urethane resin used for the primer layer 3 ( Pot life) may be longer. If the pot life is exceeded, the primer layer no longer loses adhesion. Therefore, after the primer layer 3 is formed, the adhesive layer 4
By forming the adhesive layer, the adhesive strength of the chlorinated polypropylene adhesive layer 4 having an infinite pot life to the olefin-based thermoplastic elastomer sheet 5 is unlimited. In that case, it is possible to use chlorinated polypropylene for the primer layer 3 and omit the addition of the adhesive layer 4 for the time being, but it cannot be concluded. This is because the adhesiveness between the mixture of the acrylic resin and the vinyl chloride-vinyl acetate copolymer constituting the decorative layer 2A and the chlorinated polypropylene is very weak. Therefore, in order to make the printing / coating process and the laminating process offline, the acrylic resin sheet 1 in which the decorative layer 2A, the primer layer 3 and the adhesive layer 4 are formed in-line is appropriately subjected to olefin heat treatment. The method of laminating the thermoplastic elastomer sheet 5 with the chlorinated polypropylene melt-bonded by a hot press is optimal. In this case, the adhesive layer 4 is formed on the surface side of the primer layer 3 of the acrylic resin sheet 1 by a known printing method or a coating method such as gravure roll coating using an ink or a coating liquid using the specific resin. , The decorative layer 2 </ b> A and the primer layer 3.

(Olefin-Based Thermoplastic Elastomer Sheet) As the olefin-based thermoplastic elastomer sheet 5, the olefin-based thermoplastic elastomer sheet having a polar functional group in the molecule is provided on the primer layer side in the third, fourth, and fifth inventions. A plastic elastomer sheet 5A is used. In the case of the fifth invention, in addition to the olefin-based thermoplastic elastomer sheet 5A, an olefin-based thermoplastic elastomer sheet 5B having no polar functional group in the molecule is used on the resin molded product side. In the first and second inventions, the olefin-based thermoplastic elastomer sheet 5 may or may not have a polar functional group. By using an olefin-based thermoplastic elastomer sheet as the outermost layer of the sheet for simultaneous painting with injection molding, the sheet for simultaneous painting with injection molding can be laminated with good adhesion to a resin molded product made of a polyolefin resin. . In addition, the required thickness of the entire sheet for simultaneous painting with injection molding is greater than that of an expensive acrylic resin sheet.
The use of this olefin-based thermoplastic elastomer sheet is low in cost, easy to bend, and easy to handle. In addition, since the olefin-based thermoplastic elastomer is composed of a hard segment made of a crystalline polyolefin resin and a soft segment made of a rubber (elastomer) component, as described later, the crystalline polyolefin resin (high-density polyethylene, isotactic polypropylene, etc.) ), Which is likely to occur in the case of the sheet, is unlikely to cause necking (concentration of the sheet elongation locally and unevenly), and is preferable in terms of moldability.

As the olefin-based thermoplastic elastomer used for the olefin-based thermoplastic elastomer sheet 5, for example, the following can be used.

(1) The soft segment described in JP-B-6-23278 (A) has a number average molecular weight Mn of 25,000 or more, and a ratio Mw / Mn of the weight average molecular weight Mw to the number average molecular weight Mn. 10 to 90% by weight of atactic polypropylene soluble in boiling heptane of ≦ 7,
(B) Soft polypropylene comprising, as a hard segment, a mixture of 90 to 10% by weight of a heptane-insoluble isotactic polypropylene having a melt index of 0.1 to 4 g / 10 min.

Among the olefinic thermoplastic elastomers of this type, those which are less likely to cause necking and have good suitability for molding processing include a mixture ratio of isotactic polypropylene and atactic polypropylene which is determined by the weight ratio of atactic polypropylene. 5% by weight or more and 50% by weight or less. The polypropylene-based olefin-based thermoplastic elastomer itself is already known, but when used in a conventionally known application such as a packaging container, the weight ratio of the soft segment atactic polypropylene is 5 to emphasize strength. Less than% by weight was exclusively used. However, when this is applied to a novel use of molding, necking occurs and good molding cannot be performed. Therefore, contrary to the design of the conventional composition, the weight ratio of the atactic polypropylene is set to 5% by weight or more in the polypropylene-based olefin-based thermoplastic elastomer, so that necking when forming into a three-dimensional shape is performed. Defects such as non-uniform sheet deformation and consequent wrinkles and pattern distortion can be eliminated. Particularly, the case where the weight ratio of the atactic polypropylene is 20% by weight or more is preferable. On the other hand, if the weight ratio of atactic polypropylene increases too much,
The sheet itself is easily deformed, the sheet is deformed when the sheet is passed through a processing machine such as a coating machine or a printing machine, the pattern is distorted at the time of printing, and the register is misaligned in multicolor printing. Is more likely to occur. Further, it is not preferable because it is easily broken during molding. For this reason, the upper limit of the weight ratio of the atactic polypropylene is 50% by weight or less, more preferably 40% by weight or less.

(2) A thermoplastic elastomer comprising an ethylene-propylene-butene copolymer resin. Here, as the butene, any of the three structural isomers of 1-butene, 2-butene and isobutylene can be used. Preferred specific examples of the ethylene-propylene-butene copolymer, which is a random copolymer and partially includes an amorphous portion, include the following (i) to (iii). (i) Those described in JP-A-9-111055. It is a random copolymer of a terpolymer of ethylene, propylene and butene. The weight ratio of the monomer components is 90% by weight or more of propylene. The melt flow rate is preferably 1 to 50 g / 10 minutes at 230 ° C. and 2.16 kg. And, for 100 parts by weight of such a ternary random copolymer, 0.01 to 50 parts by weight of a transparent nucleating agent containing a phosphate aryl ester compound as a main component,
It is obtained by melting and kneading 0.003 to 0.3 parts by weight of a fatty acid amide having 12 to 22 carbon atoms. (ii) Those described in JP-A-5-77371. this is,
80 to 0% by weight of crystalline polypropylene is added to 20 to 100% by weight of an amorphous polymer having a propylene content of 50% by weight or more, which is a terpolymer of ethylene, propylene and 1-butene. It is. (iii) Those described in JP-A-7-316358. This is a terpolymer of ethylene, propylene, and 1-butene, and the content of propylene and / or 1-butene is 50% by weight or more and 20 to 100% by weight of the low crystalline polymer. 0.5% by weight of an oil gelling agent such as N-acylamino acid amine salt or N-acylamino acid ester is added to a composition containing 80 to 0% by weight of a crystalline polyolefin such as isotactic polypropylene. It becomes.

The ethylene-propylene-butene copolymer resin may be used alone, or may be used in any of the above (i) to (iii).
If necessary, a polyolefin resin such as polyethylene (low density, high density, etc.), polypropylene, polymethylpentene, polybutene, etc. may be mixed and used.

(3) As described in JP-B-53-21021, (A) an olefin polymer (crystalline polymer) such as polyethylene, polypropylene or polymethylpentene is used as a hard segment, and (B) a partial cross-linking Monoolefin copolymer rubbers such as ethylene-propylene copolymer rubber and unsaturated ethylene-propylene-non-conjugated diene terpolymer rubber are used as soft segments, and these are uniformly blended and mixed. . In addition,
Monoolefin rubber / olefin polymer = 50 / 50-
Mix at a ratio of 90/10 (weight ratio).

(4) As described in JP-B-53-34210, etc., (B) an uncrosslinked monoolefin copolymer rubber (soft segment) and (A) an olefin copolymer (crystalline, hard segment) ) And a cross-linking agent, and is heated to apply shear stress to dynamically partially cross-link an olefin-based elastomer. (B) monoolefin rubber / (A) olefin copolymer = 60/40 to 80/20
(Weight ratio).

(5) As described in JP-B-56-15741, (A) isotactic polypropylene, propylene-ethylene copolymer, propylene-butene-1
A peroxide-decomposable olefin polymer (hard segment), which decreases its molecular weight when mixed and heated with a peroxide such as a copolymer to increase fluidity, and (B) ethylene-propylene copolymer rubber, ethylene-propylene-nonconjugated diene Peroxide-crosslinked monoolefin copolymer rubber (soft segment), which crosslinks and reduces fluidity by mixing and heating with a peroxide such as an original copolymer rubber, (C)
Peroxide non-crosslinked hydrocarbon rubber (soft segment / fluidity-modifying component) that does not crosslink even when mixed and heated with peroxides such as polyisobutylene and butyl rubber and has constant fluidity, and (D) paraffinic and naphthene An olefin-based elastomer obtained by mixing a mineral oil-based softener such as an oil-based or aromatic oil-based softener and dynamically heat-treating the mixture in the presence of an organic peroxide. (A) is 90 to 40 parts by weight, (B) is 10 to 60 parts by weight.
(A) + (B) = 100 parts by weight,
(C) and / or (D) have a compounding ratio of 5 to 100 parts by weight.

(6) An olefin-based thermoplastic elastomer comprising an ethylene-styrene-butylene copolymer as described in JP-A-2-139232.

As the olefin-based thermoplastic elastomer having a polar functional group in the molecule, the olefin-based thermoplastic elastomer (1) to (6) having a hydroxyl group and / or a carboxyl group as the polar functional group. Elastomers can be used. For example, an olefin-based thermoplastic elastomer having a hydroxyl group introduced by graft polymerization of an ethylene-vinyl alcohol copolymer or the like and a carboxyl group introduced by a copolymer of maleic acid, fumaric acid, itaconic acid or the like is used. Either one or both of these hydroxyl groups and carboxyl groups may be used in combination.

The olefin-based thermoplastic elastomer sheet may be added with an extender, a flame retardant, an ultraviolet absorber, a light stabilizer and the like, as necessary, in order to make the moldability and the like appropriate. As the extender pigment, particles having a particle size of about 0.1 to 10 μm such as calcium carbonate, barium sulfate, silica, alumina, kaolinite and the like are used. Aluminum hydroxide, magnesium hydroxide, or the like is used as the flame retardant. Benzotriazole-based, benzophenone-based and the like are used as the ultraviolet absorber. As the light stabilizer, a hindered amine radical scavenger or the like is used.

The olefin-based thermoplastic elastomer sheet may be a stretched sheet or an unstretched sheet, but is laminated so that the sheet is stretched at the time of simultaneous painting with injection molding.
When moldability is desired, unstretched sheets are preferred. The olefin-based thermoplastic elastomer sheet may be a sheet already formed by a known film forming method such as a T-die extrusion method, but may be used for a laminated sheet in which a decorative layer, a primer layer, and the like are formed on an acrylic resin sheet. The sheet may be laminated simultaneously with the film formation by a T-die extrusion method or the like. In the case of the former, lamination may be performed by a known lamination method such as dry lamination. The thickness of the olefin-based thermoplastic elastomer sheet depends on the application and the like.
It is about 0 to 500 μm. The thickness is preferably such that the total thickness of the entire sheet for simultaneous painting with injection molding is 300 μm or more from the viewpoint of easy handling and the like. For these reasons, the thickness is usually made larger than the thickness of the acrylic resin sheet.

Further, a coloring agent may be appropriately added to the olefin-based thermoplastic elastomer sheet as needed. By adding a coloring agent to impart a color concealing property, it is possible to conceal the color of the resin for laminating the sheet for simultaneous painting with injection molding and to adjust the base color of the decorative layer. As the coloring agent, a known coloring agent may be used as described above for the decorative layer.

The olefin-based thermoplastic elastomer sheet may have a multilayer structure such as two layers. FIGS. 2A and 2B, which are examples of the fifth embodiment, or FIGS.
The sheet S for simultaneous painting with injection molding shown in FIG. In the case of two layers, two layers may be directly laminated by heat fusion as shown in FIG. 2A, but a primer layer (third primer layer 3C in FIG. 2B) between the layers as shown in FIG. 2B. May be laminated via a thin film. In addition, the sheet S for simultaneous painting with injection molding illustrated in the cross-sectional view of FIG. 2C differs from the structure shown in FIG. This is a two-layer structure of the thermoplastic elastomer sheets 5A and 5B. That is, a transparent acrylic resin sheet 1 serving as the outermost surface layer includes a decorative layer 2 whose binder resin is a mixture of a vinyl chloride-vinyl acetate copolymer and an acrylic resin or an acrylic urethane resin as a main component, and a urethane resin. A primer layer 3 as a main component and an olefin-based thermoplastic elastomer sheet 5 are laminated in this order, and the olefin-based thermoplastic elastomer sheet 5 has a molecule on the side in contact with the primer layer 3 containing a urethane resin as a main component. Olefinic thermoplastic elastomer sheet 5 having polar functional groups
A to secure the adhesion to the primer layer 3 and the olefin thermoplastic elastomer sheet 5B having no polar functional group in the molecule on the side in contact with the resin molded product to provide the olefin necessary for simultaneous injection molding. The configuration is such that the total thickness of the thermoplastic elastomer sheet 5 is ensured and the price increase is minimized.

As described above, when the olefin-based thermoplastic elastomer sheet 5 has a two-layer structure, even when the primer layer is the primer layer 3 containing a urethane resin as a main component,
An olefin-based thermoplastic elastomer sheet 5A having a polar functional group in the molecule is disposed on the primer layer 3 side.
The olefin-based thermoplastic elastomer sheet 5 having a layer structure may be used.

It should be noted that, without interposing a primer layer therebetween,
In order to form a multi-layer structure with the layers and the like, for example, the layers may be laminated simultaneously with film formation by a co-extrusion method using a T-die.

As described above, by forming the olefin-based thermoplastic elastomer sheet 5 into a two-layer structure, for example, the olefin-based thermoplastic elastomer sheet 5B on the resin molded product side can be formed.
Is used exclusively as a color concealing layer as a layer that secures the color concealment imparting property, moldability, and the thickness necessary for simultaneous painting with injection molding, and the olefin-based thermoplastic elastomer sheet 5A on the primer layer side (front side) is Without adding a coloring agent or the like, the layer can be used exclusively as a layer ensuring the close contact with the primer layer, thereby minimizing cost and satisfying a plurality of required physical properties. The hiding power makes it possible to stabilize the color tone expression by painting without being influenced by the color of the injection molding resin.

The olefin-based thermoplastic elastomer sheet is employed as a layer on the back side of the sheet for simultaneous painting with injection molding in order to improve the adhesion to a resin molded product made of a polyolefin-based resin. By using an olefin-based thermoplastic elastomer sheet among resins, curling after sheet molding, which occurs when polypropylene is used, can also be prevented. If curl occurs during sheet molding, during the simultaneous painting by injection molding, after the sheet for simultaneous painting with injection molding is molded as a vacuum mold, the curl force in the injection mold causes deflection floating etc. As a result, it is difficult to obtain a molded article with high accuracy. Further, advantages such as prevention of pattern distortion due to necking in a portion where the sheet is stretched at the time of molding, availability, versatility, and low cost can be obtained.

[Injection Simultaneous Painting Method] Here, the injection molding simultaneous painting method, which is an application of the above-described sheet for simultaneous injection molding painting of the present invention, will be briefly described. The simultaneous painting method for injection molding here is in the form of a laminate, and is disclosed in JP-B-50-19132, JP-B-43-19743.
As described in Japanese Patent No. 27488, etc., after a sheet for simultaneous painting with injection molding is disposed between a pair of molds, both molds are clamped, and a resin in a fluid state is poured into a cavity formed by both molds. Injecting, filling and solidifying, laminating a sheet for injection molding simultaneous painting on the surface at the same time as molding of the resin molded product,
This is a method of painting a resin molded product.

Incidentally, the injection molding simultaneous painting method can take various conventionally known forms. For example, a form in which preliminary molding of the sheet for simultaneous painting with injection molding is performed, or a form in which preforming is not performed. In addition, a mode for preheating the sheet for simultaneous painting with injection molding and a mode for not preheating. In addition, the sheet for simultaneous painting with injection molding is usually preheated at the time of preforming.

Of course, when the drawing of the sheet for simultaneous painting with injection molding is large, it is preferable to carry out preliminary molding. On the other hand, if the drawing of the sheet for simultaneous painting with injection molding is small, the sheet may be formed by the resin pressure of the resin in the flowing state to be injected. At this time, if the drawing is shallow, the sheet for simultaneous injection molding and painting may be formed by the resin pressure of the resin in the flowing state filled into the mold simultaneously with the resin injection without preforming. Further, even when the sheet for simultaneous painting with injection molding is formed by resin pressure, the sheet may use the heat of the injection resin without preheating. In addition, the preliminary molding of the sheet for simultaneous painting with injection molding is usually performed using the injection mold as a vacuum mold, but before supplying the sheet between the molds, a separate vacuum mold is used outside the mold. Preforming such as vacuum forming the sheet may be used. In addition, the preforming is preferably performed in such a manner that the injection molding die is also used as a vacuum molding die in that the lamination can be performed efficiently and accurately. In the present invention, the vacuum forming includes vacuum pressure forming.

FIG. 3 is a conceptual diagram for explaining the injection molding simultaneous painting method in one embodiment. In the embodiment shown in FIG. 3, before clamping, the sheet for simultaneous painting with injection molding is heated and softened between the molds, preformed by vacuum molding with an injection mold, and then clamped to inject the resin. is there. Next, the injection molding simultaneous painting method will be further described with reference to FIG.

First, as shown in FIG. 3 (A), 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.
1 and a pair of molds of a mold Mb which also serves as a preforming mold for the transfer foil. These molds are made of metal such as iron or ceramics. Both molds Ma and Mb in the mold open state
In the meantime, the sheet S for simultaneous painting with injection molding is supplied, and the sheet S for simultaneous painting with injection molding is mounted on the mold Mb in the form of a frame-shaped sheet clamp 42.
Press to fix. At this time, the olefin-based thermoplastic elastomer sheet side of the sheet for simultaneous painting with injection molding should be the injection resin side on the right side of the drawing. Next, the sheet for simultaneous painting with injection molding is heated and softened by a heater (not shown) inserted between both molds as appropriate. The heating is, for example, non-contact radiation heating, but may be conduction heating by contact. Then, the sheet is drawn through the suction hole and vacuum formed, and the injection molding simultaneous painting 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. 2B, and a cavity formed by the two dies is filled with a resin in a flowing state such as a heated and molten state. When there is an unnecessary portion of the sheet for simultaneous painting with injection molding, the trimming is appropriately trimmed to obtain the painted molded product P of the present invention as conceptually shown in the sectional view of FIG.

[Injection Molding Resin] In the simultaneous injection molding painting method, the resin that is injection-molded into a resin molded product is basically a resin that is conventionally known in the injection molding simultaneous painting method. It can be used without any particular limitation, and is selected according to the required physical properties and cost of the product. However, since the sheet for simultaneous painting with injection molding of the present invention is configured to have good adhesion to the polyolefin resin, the polyolefin resin is preferable. Examples of polyolefin resins include, for example, highly crystalline non-elastomeric polyolefin resins such as polyethylene, polypropylene, polybutene, polymethylpentene, ethylene-propylene copolymer, propylene-butene copolymer, or various olefin-based thermoplastics. An elastomer is used.

The sheet for simultaneous painting with injection molding of the present invention is constituted so as to have good adhesion to these polyolefin resins, but if it is necessary to further improve the adhesion, these polyolefin resins may be used. It is advisable to add ethylene propylene rubber. Ethylene propylene rubber is a rubber made of an ethylene-propylene copolymer (EP
R), which is an amorphous random copolymer. Also,
As the ethylene propylene rubber, an ethylene-propylene-diene terpolymer (EPDM) can be used in addition to a pure ethylene-propylene copolymer. Ethylene propylene rubber is 1 per 100 parts by weight of polyolefin resin.
The addition in the range of from 40 to 40 parts by weight is preferable from the viewpoint of improving adhesion and maintaining rigidity.

As the injection molding resin, a resin colored by adding a coloring agent may be used as appropriate according to the application.
As the colorant, a known colorant as described in the decorative layer can be used. In addition, the injection molding resin may contain, as necessary, various known additives such as silica, alumina, calcium carbonate, inorganic powders such as aluminum hydroxide, fillers such as glass fibers, stabilizers, and lubricants. .

[Picture Molded Article] A painted molded article of the present invention is a polyolefin-based sheet S for simultaneous painting with injection molding of the present invention, like a painted molded article P conceptually shown in the sectional view of FIG. This is a molded product having a configuration laminated on the surface of a resin molded product 6 made of resin. Of course, the sheet S for simultaneous painting with injection molding is laminated such that the olefin-based thermoplastic elastomer sheet is in contact with the resin molded product. The resin molding 6 is a polyolefin resin. The polyolefin-based resin is a resin as described in the injection molding resin. Injection molding simultaneous painting sheet S on the surface of resin molding 6
Can be laminated according to the injection molding simultaneous painting method described above. INDUSTRIAL APPLICABILITY The painted product of the present invention has excellent adhesion between the sheet for simultaneous painting with injection molding and the resin molded product, and also has good surface transparency.

[0077]

The present invention will be described in more detail with reference to the following examples.

Example 1 Second Invention A sheet S for simultaneous painting with injection molding having a structure as shown in FIG. 1B was produced as follows. Uncolored polymethyl methacrylate (PMM
A) A sheet (thickness 0.125 mm) was used as a transparent acrylic resin sheet 1, and on one surface thereof, a binder resin was a mixture of vinyl chloride-vinyl acetate copolymer and acrylic resin in a ratio of 1: 1 by weight. Is formed by printing a coloring ink using a coloring agent containing as a main component a wood-grain decorative layer 2, and further containing a two-pack curable urethane resin composed of acrylic polyol and 1,6-hexamethylene diisocyanate as a main component. The primer ink was printed on the entire surface to form a primer layer 3 having a thickness of 5 μm, thereby obtaining a printed sheet. Next, an opaque olefin-based thermoplastic elastomer sheet 5 (80 parts by weight of isotactic polypropylene and atactic elastomer) which is colored yellow-brown by adding a coloring agent mainly composed of red iron oxide, titanium white, graphite, and carbon black. 100 parts by weight of a mixture of 20 parts by weight of tic polypropylene, 10 parts by weight of a calcium carbonate powder, and a 0.3 mm-thick sheet of a resin obtained by adding a total of 5 parts by weight of the above-mentioned colorant) to one side of which chlorinated polypropylene is the main component Apply an adhesive to make the thickness 4
After the adhesive layer 4 having a thickness of μm is formed, the olefin-based thermoplastic elastomer sheet 5 is dry-laminated to the printed sheet so that the adhesive layer 4 is in contact with the uncured primer layer 3 of the printed sheet. The sheet S for simultaneous painting with injection molding of the present invention was obtained by laminating by the method.

Then, by the simultaneous injection molding method as shown in the conceptual diagram of FIG. 3, the above-mentioned injection molding was carried out using a polypropylene resin to which 10% by weight of ethylene-propylene copolymer rubber was added as the injection molding resin. The sheet for simultaneous painting is laminated on the surface of the resin molded product, and as shown in FIG.
A painted molded product P of the present invention in which the sheet S for simultaneous painting with injection molding was laminated on the resin molded product 6 was obtained. In addition, simultaneous injection molding painting, between the injection mold consisting of a pair of molds of a female mold having a vacuum suction hole and a male mold having a gate, with the olefin-based thermoplastic elastomer sheet side facing the male mold side. The sheet for simultaneous painting with injection molding is inserted, the sheet for simultaneous painting with injection molding is fixed to the parting surface of the female mold with a sheet clamp, and the sheet is heated and softened with a hot plate of an infrared radiation system to soften the sheet. The sheet is vacuum formed along the cavity surface of the female mold, and then the male and female molds are clamped.The molten resin of the polyolefin resin is injected into the cavity formed by both molds, and cooled and solidified. Was. Then, the mold was opened to obtain a painted molded product in which the sheet for simultaneous painting with injection molding was laminated on the surface of the resin molded product.

Example 2 First Invention A sheet S for simultaneous painting with injection molding having a structure as shown in FIG. 1A was produced as follows. A decorative layer 2 having the same contents as in Example 1 was formed on one side of the same acrylic resin sheet 1 (thickness: 0.125 mm) as in Example 1 to obtain a printed sheet. Next, the same olefin-based thermoplastic elastomer sheet 5 as in Example 1 was used.
A primer layer 3 is formed on one surface of a two-part curable type urethane resin composed of acrylic polyol and 1,6-hexamethylene diisocyanate as a main component, with a thickness of 5 μm. After printing, the primer layer 3 and the decorative layer 2 of the printed sheet
The olefin-based thermoplastic elastomer sheet 5 was laminated on the above-mentioned printed sheet by a dry lamination method in such a manner as to make contact with the above, to obtain a sheet for simultaneous painting with injection molding of the present invention. Further, a painted molded product of the present invention was obtained in the same manner as in Example 1.

Example 3 First Invention A sheet S for simultaneous painting with injection molding having a structure as shown in FIG. 1A was produced as follows. Example 2 was the same as Example 2 except that the binder resin of the decoration layer 2 was changed to acrylic urethane resin.
In the same manner as in the above, a sheet for simultaneous painting with injection molding of the present invention was obtained. Further, a painted molded product of the present invention was obtained in the same manner as in Example 1.

Example 4 Third Invention A sheet S for simultaneous painting with injection molding having the structure shown in FIG. 1C was produced as follows. A decorative layer 2 having the same contents as in Example 1 was formed as a decorative layer 2A on one surface of the same acrylic resin sheet 1 (thickness: 0.125 mm) as in Example 1 to obtain a printed sheet. Next, with respect to the olefin-based thermoplastic elastomer sheet 5 of Example 1, the thickness was changed to 0.2 mm, and the elastomer component was isotactic polypropylene having a carboxyl group introduced into the molecule by graft copolymerization of maleic acid. And an olefinic thermoplastic elastomer sheet 5A changed to atactic polypropylene, and a primer layer 3A was printed on one surface of the sheet with a primer ink composed of a vinyl chloride-vinyl acetate copolymer to a thickness of 4 μm over the entire surface. Then, the olefin-based thermoplastic elastomer sheet 5A is laminated on the printing sheet by a hot press method so that the primer layer 3A and the decorative layer 2A of the printing sheet are in contact with each other, and the sheet for simultaneous painting with injection molding of the present invention is provided. I got Further, a painted molded product of the present invention was obtained in the same manner as in Example 1.

Example 5 Third Invention A sheet S for simultaneous painting with injection molding having the structure shown in FIG. 1C was prepared as follows. In Example 4, a polypropylene-based olefin-based thermoplastic elastomer sheet 5A (in which a carboxyl group was introduced into the molecule by graft copolymerization of maleic acid) was used instead of the polypropylene-based olefin-based thermoplastic elastomer sheet 5A ( 10 parts by weight of casium carbonate powder was added to 90 parts by weight of a mixture of 60 parts by weight of polyethylene having a carboxyl group introduced into a molecule thereof by graft copolymerization of maleic acid into high-density polyethylene and 30 parts by weight of hydrogenated styrene-butadiene rubber. Of the present invention in the same manner as in Example 4 except that the colorant of the present invention is added with a total of 5 parts by weight of a coloring agent mainly composed of red iron oxide, titanium white, graphite, and carbon black. Was obtained. Further, a painted molded product of the present invention was obtained in the same manner as in Example 1.

Example 6: Fourth Invention A sheet S for simultaneous painting with injection molding having a structure as shown in FIG. 1D was produced as follows. A decorative layer 2 having the same contents as in Example 1 was formed on one surface of the same acrylic resin sheet (thickness: 0.125 mm) 1 as in Example 1 to obtain a printed sheet. On the other hand, a non-colored, transparent, 0.08 mm-thick polyethylene-based olefin-based thermoplastic elastomer sheet having a carboxyl group introduced into the molecule by graft copolymerization of maleic acid (the carboxyl group is grafted to male high-density polyethylene by maleic acid graft copolymerization (Composed of a mixture of 60 parts by weight of introduced polyethylene and 30 parts by weight of hydrogenated styrene-butadiene rubber). On the surface on the front side of 5A, a 2 .mu.m thick primer ink containing a vinyl chloride-vinyl acetate copolymer as a main component. Primer layer 3B, acrylic polyol and 1,
A primer layer 3 having a thickness of 5 μm made of a primer ink mainly composed of a two-component curable urethane resin composed of 6-hexamethylene diisocyanate is formed by printing over the entire surface in this order. The polyethylene sheet 5A was laminated on the above printed sheet by a dry lamination method so that the layer 2 was in contact with the layer 2 to obtain a sheet for simultaneous painting with injection molding of the present invention. Further, a painted molded product of the present invention was obtained in the same manner as in Example 1.

Example 7 Fourth Invention A sheet S for simultaneous painting with injection molding having the structure shown in FIG. 1D was produced as follows. Example 6 was the same as Example 6 except that the resin of the binder of the decoration layer 2 was changed to acrylic urethane resin.
In the same manner as in the above, a sheet for simultaneous painting with injection molding of the present invention was obtained. Further, a painted molded product of the present invention was obtained in the same manner as in Example 1.

Example 8 Fifth Invention A sheet S for simultaneous painting with injection molding having the structure shown in FIG. 2B was produced as follows. A decorative layer 2 having the same contents as in Example 1 was formed on one surface of the same acrylic resin sheet (thickness: 0.125 mm) 1 as in Example 1 to obtain a printed sheet. On the other hand, as the olefin-based thermoplastic elastomer sheet 5, a non-colored transparent polyethylene-based olefin-based thermoplastic elastomer sheet 5A having a carboxyl group introduced into the molecule by graft copolymerization of maleic acid and having a thickness of 0.08 mm is used.
(Same as in Example 6: a mixture of 60 parts by weight of polyethylene having a carboxyl group introduced by maleic acid graft copolymerization into high-density polyethylene and 30 parts by weight of hydrogenated styrene-butadiene rubber) and (Example 1) Opaque 0.12 mm thick polyethylene-based olefin-based thermoplastic elastomer sheet 5B colored with a coloring agent (same as described above) (a mixed system of 60 parts by weight of high-density polyethylene and 30 parts by weight of hydrogenated styrene-butadiene rubber). Acrylic polyol comprising 10 parts by weight of casium carbonate powder and 5 parts by weight of a total of coloring agents mainly composed of red iron oxide, titanium white, graphite and carbon black). Containing two-component curable urethane resin as a main component, comprising: and 1,6-hexamethylene diisocyanate Through between the primer layer 3C thick 10μm by Nki it was prepared which was laminated by dry lamination method. Then, on the surface of the thinner olefin-based thermoplastic elastomer sheet 5A of the two-layered olefin-based thermoplastic elastomer 5, a 2 μm-thick primer layer made of a primer ink containing a vinyl chloride-vinyl acetate copolymer as a main component. 3B, a 5 μm-thick primer layer 3 made of a primer ink mainly composed of a two-component curable urethane resin composed of an acrylic polyol and 1,6-hexamethylene diisocyanate was printed on the entire surface in this order, and then a primer layer was formed. An olefin-based thermoplastic elastomer sheet 5 was laminated on the print sheet by a dry lamination method such that the decorative layer 2 and the decorative layer 2 of the print sheet were in contact with each other, to obtain a sheet for simultaneous painting with injection molding of the present invention. Further, a painted molded product of the present invention was obtained in the same manner as in Example 1.

Embodiment 9: Fifth Invention A sheet S for simultaneous painting with injection molding having a structure as shown in FIG. 2B was produced as follows. Example 8 Example 8 was the same as Example 8 except that the binder resin of the decoration layer 2 was changed to acrylic urethane resin.
In the same manner as in the above, a sheet for simultaneous painting with injection molding of the present invention was obtained. Further, a painted molded product of the present invention was obtained in the same manner as in Example 1.

Embodiment 10: First Invention A decorative layer having the same contents as in Embodiment 1 was formed on one side of the same acrylic resin sheet (0.125 mm thick) as in Embodiment 1, and did. On the other hand, as a two-layer olefin-based thermoplastic elastomer sheet 5, a non-colored transparent polyethylene-based olefin-based thermoplastic elastomer sheet 5A having a carboxyl group introduced into the molecule by graft copolymerization of maleic acid and having a thickness of 0.08 mm is used. (60 parts by weight of polyethylene obtained by introducing a carboxyl group by maleic acid graft copolymerization into high-density polyethylene and hydrogenated styrene-
And a opaque thickness 0.1% colored with a colorant (same as in Example 1).
2 mm polyethylene-based olefin-based thermoplastic elastomer sheet 5B (60 parts by weight of high-density polyethylene;
For 90 parts by weight of a mixed system of 30 parts by weight of hydrogenated styrene-butadiene rubber, 10 parts by weight of casium carbonate powder, and a total of 5 parts by weight of a colorant mainly composed of red iron oxide, titanium white, graphite, and carbon black. And a two-part curable urethane resin composed of acrylic polyol and 1,6-hexamethylene diisocyanate. And those laminated by a dry lamination method. Then, on the surface of the thinner olefin-based thermoplastic elastomer sheet 5A of the two-layered olefin-based thermoplastic elastomer sheet 5, a two-part curable urethane resin composed of acrylic polyol and 1,6-hexamethylene diisocyanate is mainly used. A primer layer 3 made of a primer ink as a component is printed and formed on the entire surface, and then the primer layer and the decorative layer 2 of the printing sheet are brought into contact with each other so that the olefin-based thermoplastic elastomer sheet 5 is dry-laminated on the printing sheet. To obtain a sheet for simultaneous painting with injection molding of the present invention. Further, a painted molded product of the present invention was obtained in the same manner as in Example 1.

[Example 11: First invention] Injection molding of the present invention was performed in the same manner as in Example 10, except that the resin of the binder of the decorative layer 2 was changed to acrylic urethane resin. A sheet for simultaneous painting was obtained. Further, a painted molded product of the present invention was obtained in the same manner as in Example 1.

[Evaluation Results] In each of the above embodiments, the injection molding simultaneous painting sheet was inserted between the male and female molds.
Subsequent vacuum forming is also easy, and the sheet has curls,
Wrinkles and tears did not occur, and the following various performance evaluation results were all good. In addition, the painted molded article was painted with a wood grain pattern, had good transparency, and had a high-class design feeling.

[Performance Evaluation Test] Moldability: It is visually checked whether or not the sheet for simultaneous painting with injection molding is sufficiently formed to conform to the surface irregularities of the painted surface of the resin molded product. Those that followed the unevenness of the attachment surface were good, and those that were insufficient were poor. Adhesion: As a grid test, cuts were made in a grid pattern at 2 mm intervals on the surface of the painted molded product (sheet surface for simultaneous painting with injection molding), and 10 × 10 cells in the vertical and horizontal directions, for a total of 100 cells. After making the eyes, a cellophane adhesive tape (Nichiban Co., Ltd., “Cellotape” (registered trademark) 24 mm
(Width, industrial use) at 25 ° C., peeled off vigorously, and evaluated whether or not the sheet for simultaneous painting with injection molding peeled off together with the tape. A sample without any squares was evaluated as good, and a sample with squares was evaluated as poor. Heat resistance: 500 pieces of the painted product in an oven at 70 ° C.
After a period of time, the sample was taken out and cooled to room temperature, and the presence or absence of abnormalities was visually evaluated. Moisture resistance: After placing the painted product in a constant temperature / humidity bath at 50 ° C. and 95% RH for 500 hours, take it out, cool it down to room temperature, and visually evaluate the appearance for abnormalities. And those with abnormalities were regarded as defective. Warm water resistance: The painted product is placed in warm water of 40 ° C. for 24 hours, taken out, wiped off the surface moisture, cooled to room temperature, and visually evaluated for abnormalities in appearance. Some were considered bad.

[0092]

According to the sheet for simultaneous painting with injection molding of the present invention, excellent transparency can be imparted to the resulting painted molded article, and particularly, it can be laminated with good adhesion to a polyolefin resin, etc. Adhesion within the layer of the sheet can be improved. In addition, since the rearmost layer is made of an olefin-based thermoplastic elastomer, curling after sheet molding that occurs when polypropylene is used for the rearmost layer can be prevented, and stable simultaneous painting by injection molding can be achieved. As a result, conventionally, polyolefin-based resin molded products have been designed using raw materials as they were injection molded without surface cosmetics due to their difficulties. You can now plan. Also,
When the olefin-based thermoplastic elastomer sheet has a two-layer configuration, it secures the total thickness necessary for simultaneous painting on injection molding,
While keeping the overall price to a minimum, good adhesion to resin molded products made of polyolefin resin and vinyl chloride
Adhesion between the vinyl acetate copolymer and the primer layer can be ensured, and the processing of the olefin-based thermoplastic elastomer sheet and the processing of the acrylic resin sheet can be separately performed off-line. ADVANTAGE OF THE INVENTION According to the painting molded article of this invention, it can be set as the molded article which has excellent transparency and adhesiveness with respect to the resin molded article of a polyolefin resin.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view illustrating a form example of a sheet for simultaneous painting with injection molding of the present invention.

FIG. 2 is a cross-sectional view illustrating another example of the sheet for simultaneous painting with injection molding of the present invention.

FIG. 3 is a conceptual diagram illustrating an example of a simultaneous painting method for injection molding.

FIG. 4 is a cross-sectional view illustrating a painted product of the present invention.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 Acrylic resin sheet 2, 2A Decorative layer 3, 3A, 3B, 3C Primer layer 4 Adhesive layer 5, 5A, 5B Olefin-based thermoplastic elastomer sheet 6 Resin molding 41 Suction hole 42 Sheet clamp Ma Injection molding die (male type) ) Mb Injection mold (female mold) P Painting molding S Sheet for simultaneous injection molding painting

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) B29K 27:06 33:04 75:00 B29L 9:00 F term (Reference) 4F100 AA37H AK03D AK03E AK07 AK10G AK15E AK15G AK22E AK22G AK25A AK25B AK25J AK51B AK51C AK51J AK64 AL01B AL01E AL01G AL05B AL09D AL09E AN02 AT00E BA04 BA05 BA07 BA10A BA10D CA13 CB00 EJ65C EJ65E GB08 GB81 HB00B HB31 JB16D JB20D JB20E JK14 JL04 JL11 JN01 JN01A 4F206 AA03 AD05 AD09 AF10 AG03 JA07 JB13 JB19 JB28 JL02

Claims (6)

[Claims] 1. A laminate type sheet for simultaneous painting by injection molding, wherein a transparent acrylic resin sheet as an outermost surface layer has a binder resin at least containing a mixture of a vinyl chloride-vinyl acetate copolymer and an acrylic resin or an acrylic resin. A sheet for simultaneous painting with injection molding, comprising a decorative layer mainly composed of a urethane resin, a primer layer mainly composed of a urethane resin, and an olefin-based thermoplastic elastomer sheet laminated in this order. 2. A laminate type sheet for simultaneous painting by injection molding, wherein a transparent acrylic resin sheet as an outermost surface layer comprises a binder or a mixture of a vinyl chloride-vinyl acetate copolymer and an acrylic resin at least. A decorative layer mainly composed of urethane resin, a primer layer mainly composed of urethane resin, an adhesive layer mainly composed of chlorinated polypropylene, and an olefin-based thermoplastic elastomer sheet are laminated in this order. , Sheet for simultaneous painting with injection molding. 3. A laminate type sheet for simultaneous painting by injection molding, wherein a transparent acrylic resin sheet to be the outermost surface layer comprises at least a mixture of a vinyl chloride-vinyl acetate copolymer and an acrylic resin as a binder resin. A decorative layer as an ingredient,
A sheet for simultaneous painting by injection molding, comprising a primer layer containing a vinyl chloride-vinyl acetate copolymer as a main component, and an olefin-based thermoplastic elastomer sheet having a polar functional group in the molecule, laminated in this order. 4. A laminate type sheet for simultaneous painting by injection molding, wherein a transparent acrylic resin sheet as an outermost surface layer has a binder resin at least containing a mixture of a vinyl chloride-vinyl acetate copolymer and an acrylic resin or an acrylic resin. A decorative layer mainly composed of urethane resin, a primer layer mainly composed of urethane resin, a second primer layer mainly composed of vinyl chloride-vinyl acetate copolymer, and having a polar functional group in a molecule. A sheet for simultaneous painting with injection molding, wherein an olefin-based thermoplastic elastomer sheet is laminated in this order. 5. An olefin-based thermoplastic elastomer sheet having no polar functional group in the molecule is further laminated on the back surface of the olefin-based thermoplastic elastomer sheet having a polar functional group in the molecule. The sheet for simultaneous painting with injection molding described in the above. 6. A painted molded article, wherein the sheet for simultaneous painting at injection molding according to any one of claims 1 to 5 is laminated on a surface of a resin molded article made of a polyolefin-based resin.