JP2001030294A - Injection molding simultaneous decorative sheet and decorative molded product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide good solvent resistance, plasticizer transfer durability, and good handling, and to adhere to a styrene resin molded product such as ABS resin, AS resin, PS resin, etc. with good adhesion. SOLUTION: The sheet S for simultaneous painting with injection molding has a structure in which a thermoplastic polyester resin sheet 1, an adhesive layer 2 made of a two-component curable urethane resin, and an ABS resin sheet 3 are laminated. Between the thermoplastic polyester resin sheet 1 and the adhesive layer 2, a picture layer 4 formed of ink using a two-component curable urethane resin as a binder resin may be provided. In the decorative molded product, the sheet for simultaneous injection molding and decorating is made of ABS resin, acrylonitrile-styrene copolymer, polystyrene, or ABS resin.
The resin sheet side faces the resin molded product side and is bonded and integrated.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate type sheet for simultaneous injection molding decoration and a decorative molded product.

[0002]

2. Description of the Related Art Conventionally, decorative molded products having the surface of a resin molded product painted thereon have been used for various purposes. For example, Japanese Patent Publication No. 50-19132, Japanese Patent Publication No. 43-27488 discloses an injection molding simultaneous decorating method disclosed in Japanese Patent Publication No. Sho 43-27488, etc. By injecting and filling the molten resin into the cavity, a sheet for simultaneous injection molding and decorating is laminated and integrated with the surface of the resin molded article at the same time as molding the resin molded article, and a decorative molded article decorated with the sheet is obtained. A method is disclosed.

Conventionally, ABS resins (acrylonitrile-butadiene-styrene copolymer) and AS (acrylonitrile-
As a sheet for simultaneous decorating by injection molding applied when a styrene copolymer) resin, a PS (polystyrene) resin, or the like is used, a sheet using the following base sheet is generally used.

For example, a sheet for simultaneous decorating by injection molding of a specification in which a pattern layer is printed and formed on an acrylic resin sheet such as PMMA (polymethyl methacrylate) as a base sheet,
As a base sheet, a sheet for simultaneous injection molding decoration with a design layer in which a pattern layer is printed and formed between an acrylic resin sheet such as PMMA (polymethyl methacrylate) and an ABS resin sheet, and a PET (polyethylene terephthalate) sheet as a base sheet And a sheet for decorating simultaneously with injection molding having a specification in which a picture layer is formed by printing.

[0005]

However, in the sheet for simultaneous decorating by injection molding of the above specifications, the thickness of the base sheet is usually 0.1 to 0.2 mm, so that the sheet as a sheet at room temperature is required. There was no (shape retention), and it was difficult to handle at the time of decorating simultaneously with injection molding. In addition, since the sheet was hard, cracks and breaks were likely to occur when deformation was applied. In addition, the solvent resistance is poor, and attention must be paid to the formation of the picture layer by printing. The obtained decorative molded article is inferior in solvent resistance due to the acrylic resin base sheet as the outermost layer. Further, the plasticizer transfer durability was poor. For this reason, when the base material sheet that has become the outermost layer in the decorative molded product comes into contact with, for example, a vinyl chloride resin product containing a plasticizer, the plasticizer moves to the decorative molded product side, and the physical properties deteriorate. There was a thing.

Further, in the sheet for simultaneous decorating with injection molding of the above specifications, since the outermost surface layer of the decorative molded article is an acrylic resin sheet, the solvent resistance is poor and the plasticizer transfer durability is also poor. Was.

Further, in the sheet for simultaneous decorating with injection molding of the above specification, since the outermost layer of the decorative molded article is a polyethylene terephthalate sheet, the problem of solvent resistance and plasticizer transfer durability is solved. However, when the polyethylene terephthalate sheet is thin, there is no stiffness (shape retention), and it is difficult to handle at the time of decorating simultaneously with injection molding.
Conversely, when the thickness is large, there is a problem that there is stiffness (shape retention) but rigidity, lack of printing suitability (mechanical transport suitability) on a continuous belt-like sheet, and insufficient moldability. Was. In the polyethylene terephthalate sheet, the adhesiveness of the injection molded resin to the ABS resin was low.

Accordingly, an object of the present invention is to provide a laminate-type sheet for simultaneous injection molding decoration, which can impart solvent resistance and plasticizer transfer durability to the obtained decorative molded product, and has good handling and ABS. Resin, AS resin, PS
It is an object of the present invention to provide a sheet for decorating simultaneously with injection molding, which has high adhesiveness to a resin molded product of a styrene resin such as a resin and has good moldability, and a decorative molded product in which the decorative sheet is laminated on the surface.

[0009]

Therefore, in order to solve the above-mentioned problems, in a first aspect of the present invention, a sheet for simultaneous simultaneous injection molding and decorating is shown in FIG. 1 (A). As in S, a thermoplastic polyester resin sheet 1, an adhesive layer 2 made of a two-component curable urethane resin, and an ABS resin sheet 3 were laminated in this order. As a result, the thermoplastic polyester resin sheet provides solvent resistance and plasticizer transfer durability, and furthermore, ABS
Since the resin sheet is also laminated, handling is not hindered, and the adhesiveness to a resin molded product of a styrene resin such as an ABS resin, an AS resin, and a PS resin is also excellent.

In the second aspect of the present invention, the sheet for simultaneous simultaneous injection molding and decorating, as shown in the sheet S for simultaneous simultaneous injection molding and decorating illustrated in FIG. In particular, a structure having a pattern layer 4 formed of an ink using a two-component curable urethane resin as a binder resin between a transparent thermoplastic polyester resin sheet 1A and an adhesive layer 2 formed of a two-component curable urethane resin. And As a result,
The decorating effect can be imparted by the picture layer, and the picture layer is formed of the ink of the specific binder resin, so that the picture layer has good adhesion.

In the third aspect of the present invention, the sheet for simultaneous decorating with injection molding is provided with a transparent thermoplastic polyester resin sheet 1A, such as the sheet for simultaneous decorating with injection molding S illustrated in FIG. A primer layer 5 made of a polyester resin, a pattern layer 4A formed of an ink using a mixture of a vinyl chloride-vinyl acetate copolymer and an acrylic resin as a binder resin, an acrylic resin, a vinyl chloride-vinyl acetate copolymer, or An adhesive layer 2A made of these mixtures and an ABS resin sheet 3 were laminated in this order. As described above, the primer layer is provided between the transparent thermoplastic polyester resin sheet 1A and the picture layer 2A, and each layer is made of a specific resin, whereby each layer can be laminated with good adhesion.
And, the solvent resistance and the plasticizer transfer durability are obtained by the transparent thermoplastic polyester resin sheet.
Since the resin sheet is also laminated, handling is not hindered, and the adhesiveness with a resin molded product of a styrene resin such as an ABS resin, an AS resin, and a PS resin is excellent, and a decorative effect can be imparted by the picture layer.

As shown in FIG. 3, the decorative molded article of the present invention is provided on a resin molded article 6 of any one of ABS resin, acrylonitrile-styrene copolymer and polystyrene. The sheet S for simultaneous decorating by injection molding according to the invention of the invention is configured such that the ABS resin sheet 3 side faces the resin molded product 6 side and is bonded and integrated. FIG. 1 shows an embodiment in which a sheet having the configuration illustrated in FIG. With such a configuration, a decorative molded article having excellent solvent resistance and plasticizer transfer durability can be obtained. In addition, since the used injection molding simultaneous decorating sheet is well handled, it is easy to manufacture a decorated molded product.

[0013]

Embodiments of the present invention will be described below.

FIG. 1 is a cross-sectional view illustrating various embodiments of the sheet for simultaneous injection molding and decorating according to the present invention, and FIG. 2 is the simultaneous decoration for injection molding which is an application of the sheet for simultaneous decorating with injection molding according to the present invention. FIG. 3 is a conceptual diagram illustrating the method, and FIG. 3 is a cross-sectional view illustrating one embodiment of the decorative molded product of the present invention.

[Thermoplastic Polyester Resin Sheet] As the thermoplastic polyester resin used for the thermoplastic polyester resin sheet 1 or the transparent thermoplastic polyester resin sheet 1A limited to a transparent one, polyethylene terephthalate, polybutylene terephthalate, ethylene- Terephthalate-isophthalate copolymer, polyethylene naphthalate, polyester-based thermoplastic elastomer and the like can be used. In addition, the polyester-based thermoplastic elastomer used a high crystalline, high melting point aromatic polyester for the hard segment, and an amorphous polyether having a glass transition temperature of -70 ° C or less for the soft segment.
It is a block polymer. For example, polybutylene terephthalate is used for the highly crystalline, high melting point aromatic polyester, and polytetramethylene ether glycol is used for the amorphous polyether, for example.

Thermoplastic polyester resin sheets 1 and 1
A may be colored with a coloring agent such as a dye or a pigment, if necessary. However, the coloring of the thermoplastic polyester resin sheet 1 is colored and transparent when a picture layer is provided between the thermoplastic polyester resin sheet 1 and the ABS resin sheet 3 or when the ABS resin sheet is used as a colored sheet to make use of its color. The coloring of the transparent thermoplastic polyester resin sheet 1A is, of course, only colored and transparent. The reason why the transparent thermoplastic polyester resin sheet 1A is specified as a transparent (colorless or colored) transparent object is to make the pattern layer observable through the sheet 1A.

Known coloring agents can be used as the coloring agent. For example, coloring agents include inorganic pigments such as titanium white, carbon black, red iron oxide, cobalt blue, and graphite; organic pigments such as phthalocyanine blue, isoindolinone, and quinacridone; metal pigments such as aluminum powder; and mica coated with titanium dioxide. A pearlescent (pearl) pigment such as a powder or a dye is used.

Preferably, the thermoplastic polyester resin sheet 1 and the transparent thermoplastic polyester resin sheet 1A have a surface on the side of the adhesive layer 2 which has a carboxyl surface treated by an easy adhesion treatment such as a corona discharge treatment or a plasma treatment. It is preferable to generate active hydrogen-containing polar functional groups such as groups and hydroxyl groups. As a result, the polyester resin sheet 1 or 1
A layer (adhesive layer 2, pattern layer 4, primer layer 5)
Etc.) are improved.

The thickness of the thermoplastic polyester resin sheet 1 and the transparent thermoplastic polyester resin sheet 1A depends on the application, but is usually 20 depending on the surface characteristics such as transparency and painting as the design expression to be employed. ~ 70μ
m. Further, the thermoplastic polyester resin sheet 1 and the transparent thermoplastic polyester resin sheet 1A are used after stretching without stretching, uniaxially stretching, or biaxially stretching as necessary.

[Adhesive Layer] The adhesive layer 2 in the first and second aspects of the present invention is preferably made of a two-component curable urethane resin. As a result,. The adhesive layer 2 is interposed between the thermoplastic polyester resin sheet 1 or the picture layer 4 formed on the resin sheet and the ABS resin sheet 3 so that they can be adhered to each other with good adhesion. Further, the adhesive layer 2A in the third invention is preferably made of an acrylic resin, a vinyl chloride-vinyl acetate copolymer, or a mixture thereof. As a result, the adhesive layer 2A is interposed between the picture resin layer 4A formed on the transparent thermoplastic polyester resin sheet 1A via the primer layer 5 and the ABS resin sheet 3 and can be laminated with good adhesion.

The two-component curable urethane resin used for the adhesive layer 2 is a urethane resin containing polyol as a main component and isocyanate as a crosslinking agent (curing agent). As a polyol, those having two or more hydroxyl groups in the molecule,
For example, polyethylene glycol, polypropylene glycol, acrylic polyol, polyester polyol,
Polyether polyol, polycarbonate polyol, polyurethane polyol and the like are used. As the isocyanate, a polyvalent isocyanate having two or more isocyanate groups in a molecule is used. For example, aromatic isocyanates such as 2,4-tolylene diisocyanate, xylene diisocyanate, 4,4'-diphenylmethane diisocyanate, or 1,6-hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, etc. Aliphatic (or alicyclic) isocyanate, or an adduct or multimer 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 acrylic resin used for the adhesive layer 2A includes polymethyl (meth) acrylate, polybutyl (meth) acrylate, methyl (meth) acrylate
Butyl (meth) acrylate copolymer, methyl (meth)
Homo- or copolymers of alkyl (meth) acrylate monomers such as acrylate-styrene copolymer, methyl (meth) acrylate-butyl (meth) acrylate-2 hydroxyethyl (meth) acrylate copolymer, or It is a copolymer of an alkyl (meth) acrylate monomer and another monomer, or a mixture of two or more of these. In addition, (meth) acrylate means acrylate or methacrylate.

[ABS resin sheet] ABS resin sheet 3
A well-known resin sheet made of an ABS resin (acrylonitrile-butadiene-styrene copolymer) can be used. By adopting the ABS resin sheet 3 as a layer on the back side of the sheet for simultaneous injection molding decoration, the sheet for simultaneous injection molding decoration is made of a styrene-based resin such as ABS resin, acrylonitrile-styrene copolymer, and polystyrene. The lamination can be performed with good adhesion to the resin molded product. The ABS resin sheet has a thickness of 50 to 300.
Use a material of about μm. In addition, the ABS resin sheet is usually added with a coloring agent to cover the color of the resin molded product or to decorate the sheet for simultaneous injection molding decoration (and, by extension, the decorative molded product) by coloring. And As the coloring agent, for example, known coloring agents listed in the above-mentioned thermoplastic polyester resin sheet can be used.

[Pattern Layer] The pattern layers, such as the pattern layers 4 and 4A,
Although it is not essential in the sheet for simultaneous injection molding decoration of the first invention, it is an essential component in the sheet for simultaneous injection molding decoration of the second and third inventions. In the present invention, a picture layer 4 is provided, and in the third invention, a picture layer 4A is provided.

The picture layer 4 is formed with an ink using a two-component curable urethane resin as a binder resin, and the picture layer 4A is formed with an ink using a mixture of a vinyl chloride-vinyl acetate copolymer and an acrylic resin as a binder resin. Form. These inks, like ordinary inks, include a vehicle made of a binder resin and the like, a coloring agent such as a pigment and a dye, and various additives appropriately added thereto, and the coloring agent is added to the thermoplastic polyester resin sheet. Known coloring agents such as those listed above can be used. The pattern layers 4 and 4A may be formed using the above-mentioned specific ink by a printing method such as gravure printing, silk screen printing, offset printing, ink jet printing, or a known forming method such as hand-drawing.
The patterns of the pattern layers 4 and 4A include, for example, a wood pattern such as a plate grain or a straight grain, a stone pattern such as marble or granite, a tile pattern, a brick pattern, a cloth pattern, a character, a geometric pattern, and a solid pattern. Etc. are optional.

As the two-part curable urethane resin, for example, the resins listed in the above-mentioned adhesive layer can be used. Therefore, further description is omitted here.

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 described above, by using a specific resin as the binder resin, in the sheet for simultaneous decorating by injection molding of each invention, the pattern layer is in contact with the layer (the adhesive layer 2, the adhesive layer 2). It can be formed with good adhesion to the layer 2A and the primer layer 5).

As the binder resin for the picture layer,
If necessary, other resins such as thermoplastic polyester resin, thermoplastic resin,
A resin such as a liquid curing type urethane resin (in the case of the pattern layer 2A) or the like may be used in combination.

Basically, there is no particular limitation on the picture layers 4 and 4A, except that the binder resin is composed of the specific resin. The picture layers 4 and 4A are usually formed on the thermoplastic polyester resin sheet 1 or the transparent thermoplastic polyester resin sheet 1A. Then, if the polyester resin sheet on which the pattern layer is formed is laminated with an ABS resin sheet through a known laminating method such as a dry lamination method via an adhesive layer therebetween, the injection molding simultaneous decoration of the present invention is achieved. Sheet is obtained.

In the case where a pattern layer is provided on the sheet for simultaneous decorating with injection molding of the first invention as required, the binder resin of the ink forming the pattern layer is not particularly limited.
A form in which a two-component curable urethane resin is used as the binder resin is the sheet for simultaneous decorating by injection molding of the second invention. Even when a binder resin other than the two-component curable urethane resin is used, the effects of the present invention such as solvent resistance, plasticizer transfer durability, and good handling suitability can be obtained. Among them, one of the structures capable of laminating each layer with good adhesion is the second invention or the third invention using a primer layer together. Instead of the pattern layer, a metal thin film layer or the like in which a metal such as aluminum or chromium is formed on a part or the entire surface by a known vapor deposition method or the like may be provided.

The sheets for simultaneous decorating by injection molding according to the second and third aspects of the present invention have a picture layer as an essential component for decorating. In addition to the pattern layer described above, a functional layer such as a conductive layer in which conductive powder such as silver powder is dispersed in a binder may be used. Such a functional layer is used in combination with the picture layer, or used alone in the first invention.

[Primer Layer] The primer layer 5 is interposed between layers to improve interlayer adhesion. This primer layer 5
Is preferably composed of a polyester resin. By using the polyester resin, good interlayer adhesion between the picture layer 2A and the transparent thermoplastic polyester resin sheet 1A can be obtained. In addition, the primer layer may be formed by a known printing method such as gravure printing or roll coating or a coating method using a primer agent using the above specific resin.

As the above polyester resin, for example,
Polycondensates obtained from dibasic acids such as phthalic anhydride and adipic acid and dihydric alcohols such as propylene glycol and ethylene glycol can be used. The polyester resin may be a curable polyester resin in addition to the thermoplastic polyester resin.

[Easy Adhesion Treatment on Back Side] The sheet for decorating simultaneously with injection molding of the present invention is an ABS resin sheet on the back side, and
It has good adhesion to styrene resins such as BS resin, acrylonitrile-styrene copolymer, and polystyrene, but the surface of the ABS resin sheet is subjected to corona discharge treatment as needed to obtain stronger adhesion. A known easy adhesion treatment such as a primer coating or an adhesive coating may be applied. Alternatively, when the sheet for simultaneous injection molding and decorating of the present invention is used to adhere to a resin other than the styrene-based resin, for example, a polyolefin-based resin such as polypropylene, an adhesive made of chlorinated polypropylene or the like is applied. You may. The solvent resistance, plasticizer transfer durability, and good handling suitability of the sheet for simultaneous decorating with injection molding of the present invention can be enjoyed.

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

As the simultaneous decoration method for injection molding, various conventionally known modes can be adopted. For example, a form in which the injection molding simultaneous decoration sheet is preformed or not. In addition, a mode in which the sheet for simultaneous decorating with injection molding is preheated is not performed. In addition, at the time of preliminary molding, the sheet for decorating simultaneously with injection molding is usually preheated.

Of course, when the sheet for simultaneous injection molding and decorating is large, it is preferable to perform preliminary molding. On the other hand, if the drawing of the sheet for simultaneous injection molding decoration 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 decorating may be formed by resin pressure of a resin in a flowing state to be filled in a mold simultaneously with resin injection without preforming. Further, even when the injection molding simultaneous decorating sheet is formed by the resin pressure, the sheet may use the heat of the injection resin without preheating. In addition, the pre-molding of the sheet for simultaneous decorating with injection molding is usually performed using the injection mold as a vacuum mold, but before supplying the sheet between the molds, another vacuum mold outside the mold is used. Pre-forming 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. 2 is a conceptual view for explaining the injection molding simultaneous decorating method in one embodiment. In the embodiment shown in FIG. 2, before the mold clamping, the sheet for simultaneous injection molding decoration is heated and softened between the molds, pre-molded by vacuum molding with an injection mold, and then the resin is injected by clamping. It is. Next, the injection molding simultaneous decorating method will be further described with reference to FIG.

First, as shown in FIG. 2A, as an injection mold, a mold Ma having a runner and a gate (gate) communicating with the injection nozzle, and a suction hole 4 in the cavity surface.
A pair of molds Mb having a number of 1 and also serving as a preliminary mold for the sheet for simultaneous decorating with injection molding is used. These molds are made of metal such as iron or ceramics. In the mold open state, the sheet S for simultaneous injection molding and decorating is supplied between the two molds Ma and Mb, and the sheet S for simultaneous injection molding and decorating is fixed to the mold Mb by pressing with a frame-shaped sheet clamp 42 or the like. I do. At this time, it goes without saying that the ABS resin sheet side of the sheet for simultaneous decorating with injection molding is the injection resin side on the right side in the drawing. Next, the sheet for simultaneous injection molding and decorating is heated and softened by a heater (not shown) inserted between the two molds as appropriate. The heating is, for example, non-contact radiation heating, but may be conduction heating by contact. Then, the sheet is vacuum-formed by suction through the suction hole, and the injection-decorative simultaneous decorating 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. Then, if there is an unnecessary portion of the sheet for simultaneous decorating with injection molding, if it is trimmed appropriately, the decorative molded product P of the present invention as conceptually shown in the sectional view of FIG. 3 is obtained.

[Injection Molded Resin] In the simultaneous injection molding decorating method, the resin to be formed into a resin molded product by injection molding is basically a conventionally known resin in the injection molding simultaneous decorating method. They can be used without any particular limitation, and are selected according to the required physical properties and cost of the product. However, the sheet for simultaneous decorating by injection molding of the present invention is preferably formed of a styrene-based resin because it is configured to have good adhesion to a sretin-based resin. As the styrene resin, for example, ABS resin,
An acrylonitrile-styrene copolymer, polystyrene, and the like are included.

As the injection molding resin, a resin colored by adding a coloring agent may be used according to the intended use.
As the colorant, a known colorant as described above for the thermoplastic polyester resin sheet can be used. In addition, the injection molding resin, if necessary, silica, alumina, calcium carbonate, inorganic powder such as aluminum hydroxide, wood powder,
Various known additives such as a filler such as glass fiber, a stabilizer, and a lubricant are contained.

[Decoration molded article] The decorative molded article of the present invention obtained by using the sheet for simultaneous injection molding decoration of the present invention is shown in FIG.
As shown in the decorative molded product P conceptually shown in the sectional view of FIG.
Is formed on the surface of a resin molded product 6 of any one of ABS resin, acrylonitrile-styrene copolymer, and polystyrene,
It is a molded product having a configuration formed by lamination. Of course, the sheet S for simultaneous decoration by injection molding is laminated such that the ABS resin sheet is in contact with the resin molded product. In order to laminate the sheet S for simultaneous injection molding and decorating on the surface of the resin molded product 6, the above-described simultaneous decoration method for injection molding may be used. Decorative molded products
It is excellent in adhesion between the sheet for simultaneous decoration during injection molding and the resin molded product, and also has solvent resistance and plasticizer transfer durability.

[0045]

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

Example 1 A sheet S for simultaneous decoration by injection molding having a structure as shown in FIG. 1B was produced as follows. After applying a corona discharge treatment to one surface of a colorless and transparent biaxially stretched polyethylene terephthalate film having a thickness of 50 μm as a thermoplastic polyester resin sheet 1, the treated surface is treated with a binder resin in an amount of 1 part by weight based on 100 parts by weight of an acrylic polyol base material. Printing using a two-pack curable urethane resin containing 5 parts by weight of a curing agent of 2,6-hexamethylene diisocyanate, and inks using red stalks, phthalocyanine blue, isoindolinone, and carbon black as coloring agents Then, a wood-grain pattern layer 4 was formed, and a printing sheet was first prepared.

Next, on the surface of the picture layer 4 of the printing sheet,
1,6 based on 100 parts by weight of the main component of the acrylic polyol
An adhesive consisting of a two-part curable urethane resin using 5 parts by weight of a hardening agent of hexamethylene diisocyanate is applied by a gravure roll coating method to form an adhesive layer 2 having a thickness of 10 μm;
Is formed on the whole surface of the adhesive layer 2 in an uncured state.
The printed sheet and the ABS resin sheet are laminated by a dry lamination method so that the 0 μm colored and concealable ABS resin sheet 3 is in contact with the resin sheet, and then the two-part curable urethane resin is cured in a 40 ° C. atmosphere for 3 days. Thus, the sheet S for simultaneous decoration by injection molding of the present invention was obtained.

Further, the decorative molded article P of the present invention as shown in FIG.
It was produced by the injection molding simultaneous decoration method as shown in the conceptual diagram of FIG. Injection molding simultaneous decoration is performed by inserting the injection molding simultaneous decoration sheet into both male and female molds Ma and Mb (mold temperature is 50 ° C.) so that the ABS resin sheet side is the male mold side, On the parting surface of the female mold Mb, the sheet for injection-molding simultaneous decorating was fixedly pressed by a sheet clamp 42 at the outer peripheral edge of the cavity. Then, in order to pre-mold the sheet for simultaneous decorating by injection molding, non-contact heating with an infrared radiation type hot plate,
The surface of the BS resin sheet was heated to 120 ° C., sucked through a suction hole 41 provided in the female mold for evacuation, and the injection molding simultaneous decoration sheet was brought into close contact with the female mold cavity surface. Next, both molds were clamped, and ABS resin (KU, manufactured by Sumitomo Nogutaku Co., Ltd.) was placed in the cavity formed between the molds.
-600) is injected from a male gate at a nozzle temperature of 240 ° C., cooled and solidified, and then a sheet for simultaneous injection molding and decoration is laminated and integrated on the surface of a resin molded product made of ABS resin. And a surplus sheet on the periphery of the molded product is cut out, and as shown in FIG.
Was obtained by laminating on the surface of the resin molded product 6 and bonding and integrating the same.

Example 2 A sheet S for simultaneous decoration by injection molding having the structure shown in FIG. 1C was produced as follows. First, as a transparent thermoplastic polyester resin sheet 1A,
Using a colorless and transparent polyester resin film made of a biaxially stretched polybutylene terephthalate film having a thickness of 50 μm, a primer agent made of a polyester resin is applied to one surface thereof by a gravure roll coating method, and a primer layer 5 having a thickness of 2 μm is entirely coated. After that, a mixture of vinyl chloride-vinyl acetate copolymer and acrylic resin in a ratio of 1: 1 by weight is used as a binder resin on the primer layer 5, and red pigment, phthalocyanine blue, and Gravure printing is performed using an ink using indolinone and carbon black to form a woodgrain pattern layer 4A, and then a vinyl chloride-vinyl acetate copolymer and acrylic are formed on the surface of the pattern layer 4A. An adhesive using a 1: 1 weight ratio mixture with a resin is applied by a gravure roll coating method to form an adhesive layer 2A having a thickness of 2 μm. Formed on the entire surface was first prepared print sheet.

Next, the printed sheet and the ABS resin sheet 3 are dried and laminated by a dry lamination method so that the separately prepared 200 μm-thick colored and concealable ABS resin sheet 3 is in contact with the adhesive layer 2A of the printed sheet. The sheets were laminated to obtain a sheet S for simultaneous decoration by injection molding of the present invention. Next, in the same manner as in Example 1, the simultaneous decoration by injection molding was performed.

[Performance Evaluation] The following items were evaluated.

Solvent resistance : Toern and methyl ethyl ketone were separately dropped onto the surface of the sheet for simultaneous decorative molding by injection molding on the decorative molded product, the surface was covered with a watch glass, left for 24 hours, and wiped off with a cloth. The surface appearance was visually observed. As a result, in both of the decorative molded products of Example 1 and Example 2, there was no change in the surface appearance, and the solvent resistance was good.

[0053] soluble plasticizer migration resistance: DOP a (dioctyl phthalate), after dropping to the injection-mold decorating sheet surface on the decorative molded article, 24 hours after standing over the surface with a watch glass, wiped with a cloth The surface appearance was visually observed. As a result, in both of the decorative molded products of Example 1 and Example 2, there was no change in the surface appearance, and the solvent resistance was good.

Adhesion between the sheet and the resin molded product : 11 sheets (vertical) × 11 on the surface of the sheet for simultaneous decoration by injection molding on the decorative molded product in a grid pattern (line interval: 1 mm) with a cutter knife.
An incision was made to reach the book (horizontal) resin molded product. Next, a cellophane adhesive tape (manufactured by Nichiban Co., Ltd., “Cellotape” (registered trademark), 24 mm width, industrial use) was adhered to the cut, and the cross cut test of peeling by hand was repeated 10 times. As a result, neither the decorative molded products of Example 1 nor Example 2 had any cross-cuts (10 × 10).

Handling aptitude : In order to confirm the presence or absence of a handling problem at the time of decorating with injection molding, molding was continuously performed for 30 shots. As a result, in both Example 1 and Example 2, there was no problem in inserting the sheet for simultaneous decorating by injection molding between the male and female molds and in the preliminary molding, and the sheet was not broken or cracked, and the handling suitability was good. Was.

[0056]

According to the first aspect of the present simultaneous injection-molding decorative sheet, solvent resistance and plasticizer transfer durability can be obtained, handling is not hindered, and ABS resin, AS
It also has excellent adhesion to resin molded products of styrene resins such as resin and PS resin. According to the second aspect of the present injection molding simultaneous decorating sheet,
The decoration effect by the picture layer can be provided, and the adhesion of the picture layer is good. According to the third aspect of the present injection molding simultaneous decorating sheet,
The layers can be laminated with good adhesion, solvent resistance and plasticizer transfer durability can be obtained, and handling is not hindered.
It has excellent adhesiveness with resin molded products of styrene resins such as resin, AS resin and PS resin, and can provide a decorative effect by the picture layer. According to the decorative molded article of the present invention, solvent resistance and plasticizer transfer durability are excellent. Further, the sheet for simultaneous decorating with injection molding used is easy to manufacture because of good handling.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view illustrating an embodiment of a sheet for simultaneous decorating by injection molding according to the present invention.

FIG. 2 is a conceptual diagram illustrating an example of a simultaneous injection molding decoration method.

FIG. 3 is a cross-sectional view illustrating one embodiment of the decorative molded product of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Thermoplastic polyester resin sheet 1A Transparent thermoplastic polyester resin sheet 2, 2A Adhesive layer 3 ABS resin sheet 4, 4A Picture layer 5 Primer layer 6 Resin molding 41 Suction hole 42 Sheet clamp Ma Injection molding type (male type) Mb Injection mold (female mold) P Decorative molding S Sheet for simultaneous injection molding decoration

Continued on the front page F-term (reference) 4F100 AK12C AK12J AK13 AK15 AK15G AK15J AK16 AK22G AK22J AK25G AK27C AK27J AK41A AK41G AK42A AK51G JAKAB AK74A AA21E AA24 AA42E AF10 AG01 AG03 JA07 JB22 JB28 JF05 JL02

Claims (4)

[Claims] 1. A sheet for simultaneous injection-molding and decorating in which a thermoplastic polyester resin sheet, an adhesive layer made of a two-component curable urethane resin, and an ABS resin sheet are laminated in this order. 2. A pattern layer formed of an ink using a two-component curable urethane resin as a binder resin between a transparent thermoplastic polyester resin sheet and an adhesive layer formed of a two-component curable urethane resin. The sheet for simultaneous decoration by injection molding according to claim 1. 3. A transparent thermoplastic polyester resin sheet, a primer layer composed of a polyester resin, a pattern layer formed of an ink using a mixture of a vinyl chloride-vinyl acetate copolymer and an acrylic resin as a binder resin, an acrylic resin, An injection molding simultaneous decorating sheet obtained by laminating an adhesive layer made of a vinyl chloride-vinyl acetate copolymer or a mixture thereof, and an ABS resin sheet in this order. 4. The sheet for simultaneous injection-molding and decorating according to any one of claims 1 to 3, on a resin molded product of any one of ABS resin, acrylonitrile-styrene copolymer, and polystyrene, A decorative molded product in which the ABS resin sheet side is bonded to and integrated with the resin molded product side.