JPH04201216A - Manufacture of injection-molded product - Google Patents

Abstract

PURPOSE:To form a film having soft touch feeling on a surface by sticking a photo-setting sheet under an uncured or half-cured state on the inner surface of a mold, injection-molding a molding resin and irradiating a coated substance with light. CONSTITUTION:A photo-setting sheet is formed of a photo-setting resin composition mainly comprising an acrylic resin having weight average molecular weight of 50000-1000000 and being solid at normal temperature, a low molecular weight substance having a (meth)acryloyl group in a molecule, an optical initiator and elastic beads. A coated substance obtained through a method, in which the sheet is molded and fast stuck to the inside of a mold by a vacuum or pressure forming and the resin is injected, etc., or sheet insert injection molding is irradiated with light, thus curing the sheet. The photo-setting sheet under an uncured or half-cured state has excellent stretchability, flexibility, extensibility, etc., the sheet can be stuck superiorly along the inner surface of the mold even in deep draw forming, and a film having soft touch feeling can be formed by light irradiation because the sheet is shaped of the photo-setting resin composition containing elastic beads.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a method for manufacturing molded products formed by injection molding, such as housings for office automation equipment, home appliances, stationery, etc.
In particular, the present invention relates to a method for manufacturing molded products in a field where painting or the like is conventionally performed in a post-process to improve appearance and tactility.

(Conventional technology) In order to give a soft touch feel (suede-like) to injection molded products such as housings for office equipment, home appliances, stationery, etc.
Paints that have a soft touch feel (suede-like) have generally been used. However, when applying a soft touch feeling to the surface of an article using a paint, it is necessary to adjust the viscosity and concentration of the paint, which makes the work complicated. especially,
Paints using organic solvents contaminate the working environment and pose health and safety problems.

In order to solve these problems, a sheet-like suede-like coating material has been proposed as an alternative to paint.

For example, Japanese Patent Application Laid-Open No. 2-41243 discloses a suede fabric in which a coating film of a matte paint prepared by adding bead pigments to an ionizing radiation-curable resin is provided on a base film made of ABS resin, polypropylene, etc. A standard sheet has been proposed.

(Problems to be Solved by the Invention) However, in such a sheet, since the coating film is made of a resin crosslinked by electron beams, the spreadability of the entire sheet is poor. Therefore, for example, when injection molding a deep-drawn molded product, the sheet cannot be stretched sufficiently and the sheet cannot be formed into a female shape, and there is a risk that the sheet will break when the resin is injected. there were.

The present invention improves the above-mentioned problems and provides a method for manufacturing injection molded products that can form a coating with a soft touch feeling on the surface of deep drawn products without any problems. .

(Means for Solving the Problems) The method for producing an injection molded article of the present invention is to vacuum and/or remove an uncured or semi-cured photocurable sheet formed from a photocurable resin composition containing elastic beads. Alternatively, a process of attaching it to the inner surface of a mold by air pressure molding, a process of injection molding a molding resin into the mold to form a covering body covered with a photocurable sheet, and a process of irradiating the covering body with light. curing the photocurable sheet, thereby achieving the above object.

The details are as follows.

Photocurable sheets used in the present invention include the following.

■ (a) Weight average molecular weight is so, ooo ~ 1,00
0.000 and is solid at room temperature, (b
) A curable sheet formed from a photocurable resin composition containing as main components a low molecular weight material having a (meth)acryloyl group in the molecule, (C) a photoinitiator, and (d) elastic beads.

(e) Has multiple functional groups such as hydroxyl, amino, and carboxyl groups in the molecule, and has a weight average molecular weight of 50.0
00 to 1.000.000 and is solid at room temperature, (b) a low molecular weight substance having a (meth)acryloyl group in the molecule, (c) a photoinitiator, and (d) elastic beads. , (f) formed from a photocurable resin composition containing as a main component one or more crosslinking agents selected from the group consisting of incyanate crosslinking agents, melamine crosslinking agents, and epoxy crosslinking agents. hardenable sheet.

(g) It has multiple (meth)acryloyl groups in the molecule and has a weight average molecular weight of so, ooo to 1.000.00.
0 and is solid at room temperature; (b) a low molecular weight substance having a (meth)acryloyl group in the molecule;
) A photocurable sheet formed from a photocurable resin composition containing as main components a photoinitiator and (d) elastic beads.

(h) It has multiple functional groups such as hydroxyl groups, amino groups, and carboxyl groups and (meth)acryloyl groups in the molecule,
Weight average molecular weight is so, ooo~i, ooo, o
(b) a low-molecular compound having a (meth)acryloyl group in the molecule;
C) The main components are a photoinitiator, (d) elastic beads, and (f) at least one crosslinking agent selected from the group consisting of an isocyanate crosslinking agent, a melamine crosslinking agent, and an epoxy crosslinking agent. A curable sheet made of a photocurable resin composition.

(a) The acrylic resin that is solid at room temperature and has a weight average molecular weight of so, ooo to 1.000.000÷ contained in the photocurable sheet is, for example, methyl (meth)acrylate, ethyl (meth)acrylate, butyl Obtained by copolymerizing a (meth)acrylic acid ester such as (meth)acrylate with a styrene derivative monomer or a maleic acid monomer in the presence of a reaction initiator (such as various peroxides or chain transfer agents). I can do it.

The (e) molecule contained in the photocurable sheet has a plurality of functional groups such as a hydroxyl group, an amide group, and a carboxyl group, and has a weight average molecular weight of so, ooo, 00o, o.
oo and is solid at room temperature, for example, (
(meth) having a carboxyl group such as acrylic acid
Acrylic acid ester monomer, 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)
Among (meth)acrylic acid ester monomers having a hydroxyl group such as acrylate, and (meth)acrylic acid ester monomers having ami7 groups such as 2-aminoethyl (meth)acrylate and 3-aminopropyl (meth)acrylate, a monomer having at least one functional group;
It can be obtained by copolymerizing other (meth)acrylic acid esters, styrene derivative monomers, maleic acid monomers, etc. in the presence of a reaction initiator (such as various peroxides and chain transfer agents).

The (g) molecule contained in the photocurable sheet has a plurality of (meth)acryloyl groups, the weight average molecular weight is so,
ooo to 1,000,000 and is solid at room temperature; (h) has a plurality of functional groups such as hydroxyl, amino, and carboxyl groups and (meth)acryloyl groups in the molecule, and has a weight average molecular weight of so , oo.

~1.000.000 and is solid at room temperature, for example, (meth)acrylic acid having a carboxyl group such as (meth)acrylic acid, 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meta)
(meth)acrylic acid ester monomers having a hydroxyl group such as acrylate; (meth)acrylic acid ester monomers having ami7 groups such as 2-aminoethyl (meth)acrylate and 3-aminopropyl (meth)acrylate; (meth)acrylic acid ester monomers having aziridinyl such as (1-aziridinyl)ethyl (meth)acrylate and 2-(1-aziridinyl)butyl (meth)acrylate; and (meth)acrylic acid ester monomers having epoxy groups such as glycidyl (meth)acrylate. ) Among the acrylic acid ester monomers, monomers having at least one kind of functional group are reacted with other (meth)acrylic acid esters, styrene derivative monomers, maleic acid monomers, etc. using a reaction initiator (various peroxides and chain It can be obtained by adding a monomer having the above functional group to an acrylic copolymer having a functional group, which can be obtained by copolymerizing in the presence of a transfer agent (transfer agent, etc.).

These acrylic resins (a), (e), (g) and (
The weight average molecular weight (M w ) of h) can be changed depending on the conditions when carrying out the polymerization reaction using a reaction initiator. The acrylic resin used in the present invention is selected from those having a weight average molecular weight in the range of so, ooo to 1.000,000. Weight average molecular weight is so, oo
If it is less than o, it becomes difficult for the obtained sheet to maintain its shape, and sufficient elongation is not obtained for stretching during the pasting operation, and cracks may occur. When the weight average molecular weight exceeds 1,000°000, it becomes difficult to dissolve in a solvent and it becomes difficult to prepare a sheet from the photocurable resin composition. For example, when a sheet is created by solvent casting, the viscosity of the solvent increases, so the resin can only be cast at a low concentration, which makes it difficult to increase the thickness of the sheet.

These acrylic resins have hardness and softness after hardening. : In view of the relationship with A (suede feel), it is preferable to have a Tg (glass transition point) in the range of -20'C to 100C. Different types of acrylic resins may be used in combination as long as they have molecular weights within these ranges.

Since the acrylic resins (e) and (h) have functional groups such as hydroxyl groups, amine groups, and carboxyl groups, they are crosslinked by the crosslinking agent, thereby improving the flexibility of the sheet. The functional group values of the above-mentioned reactive acrylic resin (usually OH group value and NH2 group value (NH2 value: Calculate the amount of NH2 groups added during polymerization in the same way as the OH value, or react the NH2 group with nitrous acid to form an OH group) ) and C0OH group value CC0OH value added during polymerization
Calculate the amount of 0OH group in the same way as the OH value or use CoOH
It is preferable that the sum of the values (values obtained by titrating the groups with KOH) is in the range of 2 to 50. If the functional group value is 2 or less, no improvement in flexibility can be expected. Further, if the functional group value is 50 or more, sufficient elongation of the sheet cannot be obtained. However, if little elongation of the sheet is required, values outside these ranges can be applied.

Further, these acrylic resins can also be used as block copolymers in which the reactive portions of the acrylic resin are shaped into blocks or combs. In this case, the materials to be blocked with these reactive acrylic resin materials include not only acrylic-based materials but also styrene-based, maleic acid-based, and imide-based materials that are compatible with acrylic, as well as silicone-based,
It may be combined with any material that can be made into blocks, such as fluorine-based materials. In this case, there is a method in which the weight average molecular weight of this material is within the above range, and a method in which these block polymers are blended with the above-mentioned reactive acrylic resin.

Examples of the low molecular weight substances having (meth)acryloyl groups in the molecule (b) contained in the above sheet include methyl (meth)acrylate, ethyl (meth)acrylate, benzyl (meth)acrylate, 2-ethoxyethyl (meth) )
Monofunctional types such as acrylate, phenolic ethylene glycol (meth)acrylate, 1,6-hexanethiol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polybrobylene glycol Di(meth)acrylate, trimethylpropane tri(meth)acrylate, pentaerythritol tri(meth)
There are multifunctional types such as acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate. Further, there are oligomers such as polyester acrylate, polyurethane acrylate, epoxy acrylate, polyether acrylate, oligoacrylate, alkyd acrylate, and polyol acrylate.

The above (d) elastic beads have the property of elastically recovering when the beads are pressurized until their shape is deformed and then released. Examples of materials for forming the elastic beads include polyurethane, acrylic-urethane copolymers, polyvinylidene chloride, copolymers of vinylidene chloride and other monomers, polystyrene, and styrene-isoprene copolymers. The maximum particle size distribution of elastic beads is between 1 and 50.
It is preferable to add 20 to 400 parts by weight of a material having a diameter in the range of .mu.m to 100 parts by weight of the solid content of the resin. If the particle size of the elastic beads is less than 1 μm, it will not be possible to impart a sufficient soft touch feel (suede feel) to the resulting sheet, and the particle size will be less than 50 μm.
If it exceeds μm, cracks are likely to occur on the surface of the sheet when it is stretched. If the amount of elastic beads added is less than 20 parts by weight, a sufficient soft touch feeling (suede feeling) cannot be obtained,
If the amount added is more than 400 parts by weight, cracks are likely to occur on the surface of the sheet during stretching. Moreover, the number of elastic beads is not limited to one type, and two or more types may be used in combination.

Since the above-mentioned low molecular weight substance has the effect of plasticizing the reactive acrylic resin, the amount added is approximately related to the Tg of the acrylic resin and the viscosity of the low molecular weight substance to be added. for example,
When using acrylic resin with Tg = 60 to 80°C, low molecular weight materials with a viscosity of 500 cps (25°C) or less should be
It is preferable to add 0 to 150 parts by weight and 50 to 300 parts by weight of low molecular weight substances having a viscosity of 500 cps (25°C) or more. If the amount added is small, sufficient wear resistance and chemical resistance cannot be obtained after the sheet is cured. If the amount added is large, the handling properties of the sheet will deteriorate. The above-mentioned low molecular weight substances may be used in combination of different types.

The incyanate crosslinking agent mentioned above is an incyanate compound having two or more incyanate groups in the molecule, such as tolylene diisocyanate, diphenylmethane isocyanate, naphthalene diisocyanate, toridine diisocyanate, triphenylmethane triisocyanate, tris(incyanate), etc. cyanate phenyl) thiophosphite, P-7 22 diisocyanate, xylylene diisocyanate, bis(incyanate methyl) cyclohexane, dicyclohexylmethane diisocyanate,
Monomers such as hexamethylene diisocyanate, lysine diisocyanate, hexamethylene diisocyanate, inphorone diisocyanate, or trimethylolpropane adducts and incyanurate modified products of these monomers,
There are biuret modified products, carbodiimide modified products, urethane modified products, allophanate modified products, etc.

Melamine-based crosslinking agents include melamine, urea, thiourea, guanidine, guanamine, acetoguanamine,
Trimethylol melamine, hexamethylol melamine, dimethylol urea dimethylol guanidine, dimethylol acetoguanamine, dimethylol benzoguanamine, etc., which are made by reacting formaldehyde with a material having a polyfunctional amino group such as benzoguanamine, dicyandiamide, and guanamine, and phthyl alcohol and propyl alcohol. There are etherified melamine resins that are reacted with alcohols such as

Examples of the epoxy crosslinking agent include glycidyl compounds of polyhydric alcohols containing a plurality of epoxy groups, which are usually used together with a Lewis acid catalyst. The Lewis acid is preferably microencapsulated in order to delay the reaction. For example, butadiene cidoxide, hexacine dioxide, diglycidyl ester of phthalic acid, diglycidyl ether of bisphenol-A, diglycidyl ether of bisphenol-F, triglycidyl ether amine of para-aminophenol, diglycidyl ether of aniline, and diglycidyl ether of phenylene diamine. Tetraglycidyl ether, diglycidyl ether of sulfonamide,
These include glycidyl compounds such as triglycidyl ether of glycerin, polyether-modified diglycidyl, polyester-modified diglycidyl, urethane-modified diglycidyl compounds (polymers), vinylcyclohexene dioxide, dicyclopentadiene dioxide, and the like.

The amount of these crosslinking agents added is preferably about 1+0.7 to 1.3 (functional group value of acrylic resin:functional group value of crosslinking agent).

However, in reality, depending on the reactivity with the acrylic resin used, reactions occur not only with the functional groups of the acrylic resin, but also between crosslinking agents, such as between melamine crosslinking agents and between melamine crosslinking agents and epoxy crosslinking agents. It is preferable to conduct preliminary experiments before making a decision.

As the photoinitiator (C), commonly used photoinitiators can be used, and photoinitiators such as benzoin alkyl ether, acetophenone, benzophenone, thioxanthone, and acylphosphine oxide are preferably used. Examples of benzoin ethers include benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin propyl ether. In the acetophenone series, 2,2-jetoxyacetophenone,
2-hydroxy-2-methylpropiophenone, p-t
Examples include er-butyltrichloroacetophenone. In the benzphenone series, benzophenone, 4-chlorobenzophenone, 4.4-dichlorobenzophenone, 3.3-
Examples include dimethyl-4-methoxybenzophenone and dibenzosuberenone. Examples of the thioxanthone type include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, and 2-ethylanthraquinone, and examples of the acylphosphine oxide type include Shed beef diphosphine oxide.

The photoinitiator is usually 0.0 parts by weight per 100 parts by weight of the above-mentioned (meth)acryloyl group-containing acrylic resin and low molecular weight substance.
It is added in an amount of 5 to 20 parts by weight, preferably 0.5 to 10 parts by weight. Moreover, the number of photoinitiators is not limited to one type, and two or more types may be used in combination.

The photocurable sheet used in the present invention may include (
Peroxide may be added (for cases such as when a molded article with a complex shape is coated with a sheet and there are areas that are not exposed to light).

As the above-mentioned peroxide, a common organic peroxide can be used. More preferably, it is an organic peroxide having a decomposition temperature of 100° C. or higher in terms of storage stability at room temperature.

These include, for example, 2,2-bis(tert-butylperoxy)butane, tert-butylperoxybenzoate, di-tert-butylperoxyisophthalate,
Examples include methyl ethyl ketone peroxide, dicumyl peroxide, and ter-butyl peroxy acetate.

The amount of peroxide added is 0.5 to 5.0 parts by weight per 100 parts by weight of the above-mentioned low molecular weight substance having a (meth)acryloyl group.
Parts by weight ranges are preferred. Moreover, the number of peroxides is not limited to one type, and two or more types may be used in combination. By adding these peroxides, parts that are difficult to harden by light irradiation can be hardened by heating the sheet when molding the sheet in vacuum and/or pressure, or by heat during injection molding.

The photocurable resin composition used in the present invention may further contain materials such as colorants such as pigments and dyes, and antioxidants, if necessary.

As the colorant, pigments and dyes used in paints can be used. Pigments include titanium oxide, iron oxide, carbon black,
These include cyanine pigments and quinacridone pigments. Dyes include azo dyes, anthraquinone dyes, indigoid dyes, and stilbenzene dyes. Further, metal powders such as aluminum flakes, nickel powders, gold powders, and silver powders may be used as the coloring agent. It is preferable that these materials have as fine particles as possible. When using a highly opaque colorant, the amount of these additives should be 10% of the solid content of the resin.
The range of 2 to 400 parts by weight is preferable relative to 0 parts by weight. In addition, when these materials are added, it is preferable that the photoinitiator performs the initiation reaction with light having a wavelength that is less absorbed by the colorant.

Various functional agents may be added to impart various functions to the photocurable sheet of the present invention. The various functional agents mentioned above include conductive materials, anti-condensation agents, photochromic compounds, and rust preventive agents. When these materials are added, it is preferable that the photoinitiator performs the initiation reaction with light of a wavelength that is less absorbed by the functionality-imparting agent.

[Form of photocurable sheet]

A photocurable resin composition is obtained by kneading the above materials.

A base layer is created from the photocurable resin composition, and when the photocurable sheet is a single layer, this base layer becomes the photocurable sheet as it is. The sheet used in the present invention may consist of a single layer including only the base layer, or may consist of multiple layers. When the sheet is composed of multiple layers, there are, for example, the following forms.

■A sheet consisting of a transparent base layer (surface layer) and a colored layer containing a colorant.

The colored layer can be formed from the photocurable resin composition used for the base layer. In this case, the colored layer may not contain elastic beads.

■ A sort that has a base layer or sheet (■) and a back layer laminated on the back side of the sheet.

This back layer is used to improve the adhesion between the base layer and the injection resin.
This is provided to withstand the shear stress of the injected resin or to further improve the handling properties of the sheet.

In order to improve the adhesion between the base layer and the resin, it is preferable that the back layer and the injection resin are made of the same type of material or have excellent compatibility. If the adhesion between the base layer and the back layer is poor, a brimer layer may be provided between the two layers, or a plurality of back layers may be provided.

Since the sheet is stretched and attached to an adherend as necessary, these back layers (and the brimer layer) are preferably composed of a film that is malleable at least under heating.

Examples of the resin used for the back layer include polystyrene, acrylic polymer, polycarbonate, polyvinyl chloride, polyethylene, polypropylene, and ABS.
(acridonitrile-buta';

(2) A sheet having a base layer or the sheet obtained in (2) and (2) above, and an adhesive layer laminated on one side of the sheet (in the case of the sheet marked (2), the outer surface of the back layer).

As the adhesive used in the adhesive layer, pressure-sensitive adhesives, hot-melt adhesives, and post-curing adhesives are preferably used. Mixtures of these adhesives may also be used. A plurality of different types of adhesives may be sequentially laminated.

Examples of the pressure-sensitive adhesive include rubber-based, acrylic-based, urethane-based, and silicone-based adhesives. Examples of hot melt adhesives include ethylene-vinyl acetate copolymer (EVA), styrene-isoprene-styrene block copolymer (SIS), and the like. Post-curing adhesives include, for example, microcapsule-curing adhesives.

Examples of the material include uncrosslinked unsaturated polyester adhesives, uncrosslinked acrylic adhesives, and the like.

(2) A sheet comprising the sheet obtained in (1) to (3) above and a protective layer laminated on one side of the sheet.

The protective layer is laminated to provide shape retention during storage and use of the sheet and surface protection after application.

Since the sheet of the present invention is stretched as necessary and attached to an adherend, it is preferable that the protective layer is made of at least a film that is malleable under heating (for example, a thermoplastic resin film or a rubber film).

Examples of the thermoplastic resin include polyvinyl chloride, polyurethane, acrylic resin, polyester, ethylene-vinyl acetate copolymer, polyethylene, and polypropylene. Examples of the rubber film include natural rubber, styrene-butadiene rubber, nitrile-butadiene rubber, imprene rubber, butadiene rubber, chloroprene rubber, urethane rubber, silicone rubber, and acrylic rubber. Mixtures of these thermoplastic resins and rubbers can also be used. Alternatively, both films may be laminated.

The protective layer may be peeled off from the coating before photocuring the sheet, or may be used as an open protective layer until the injection molded article is used. By adding embossing or patterns to the surface of the protective layer, the surface shape (appearance) of the sheet can be changed.

■A sheet in which the front or back surface of the base layer of the photocurable sheet obtained in steps (■) to (■) above is printed.

When printing is performed on the back side of the base layer, the printed surface can be protected by the base layer.

The thickness of the photocurable sheet obtained in steps ① to ② above is 20 to 1,000 when it is applied to an uneven adherend surface.
It is preferable to have about 10 to 5 μm when pasting on a flat surface.
It may be about 00 μm. Further, the thickness of the other layers laminated on the sheet is usually 10 to 500 μm, and the thickness of the adhesive layer is particularly preferably 10 to 100 μm.

[Preparation of photocurable sheet]

The photocurable sheet of the present invention may be prepared by any method. When the sheet is a single layer, the following casting method is preferred.

The photocurable resin composition is sufficiently dissolved or dispersed in an organic solvent. The resulting solution is coated onto processing paper (usually polyethylene terephthalate film or paper with a silicone-treated surface) using equipment such as a knife coater, comma coater or reverse coater, and then dried to remove the solvent. Form the base layer. A sheet is obtained by peeling the processing paper from the base layer.

When the sheet is formed of multiple layers, it can be obtained by a casting method or a lamination method. According to the casting method, a solution containing the resin composition of one of the layers is coated onto process paper and dried to remove the solvent to form a base layer, and then the composition of the other base layer is coated on this base layer. A solution containing the substance is coated and dried to remove the solvent to form another base layer. According to the lamination method, each layer is formed by separately applying a solution containing the resin composition of each base layer onto process paper, drying and volatilizing the solvent, and then laminating both layers ( Heating) Press with a roll press.

The process paper used during manufacturing can be used as a protective sheet.

[Manufacturing method for injection molded products]

Injection molding is sheet insert injection molding, which is usually performed by heating a sheet at room temperature or heating it, molding it closely to the inside of a mold using vacuum and/or pressure forming, and then injecting resin after closing the mold. It will be held in Next, the obtained coating (in which the outside of the solidified injection resin is coated with a sheet) is irradiated with light and heated as necessary) to cure the sheet and obtain a molded product. The resin to be injected can be any material that can be injection molded. For example, polystyrene, acrylic polymer,
Polycarbonate, polyvinyl chloride, polyethylene, polypropylene, ABs (acrylonitrile-butadiene-styrene copolymer), modified polyphenylene oxide,
Polyphenylene sulfide, polyetherimide, whethyl ether ketone, polyethylene sulfide,
Examples include liquid crystal polymer, glass fiber reinforced polyester, glass fiber reinforced epoxy, and glass fiber reinforced acrylic resin.

(Function) The above-mentioned uncured or semi-cured photocurable sheet has excellent spreadability, flexibility, elongation, etc., so it can be attached well along the inner surface of the mold even during deep drawing. can do. Moreover, since this sheet is formed from a photocurable resin composition containing elastic beads, it is possible to form a film having a soft touch feeling (suede H) by light irradiation.

(The following is a blank space) (Examples) The present invention will be described in detail below based on Examples. In addition, "part" means "part by weight."

(A) Creation of curable sheet Example 1 Acrylic resin (copolymer of methyl methacrylate, ethyl methacrylate, and butyl acrylate, weight average molecule j 158,000.Tg・20°C) 1
00 parts acrylate monomer (manufactured by Nippon Kayaku Co., Ltd., KAYAR
AD R604) 80 parts photoinitiator (Nippon Kayaku Co., Ltd., Kayakinia-DETX
) 1 part photopolymerization accelerator (Kayakinia-EPA manufactured by Nippon Kayaku Co., Ltd.)
) 2-part elastic beads (manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd., acrylic urethane copolymer elastic beads EBS100, particle size 8-15
μ1) 50 parts and 300 parts or more of ethyl acetate were mixed with stirring.

This mixture was made of ABS sheet (manufactured by Royal Resin Industry Co., Ltd., A
205, film thickness 500 μm, hereinafter referred to as ABS sheet) and dried at 80° C. for 5 minutes to obtain an uncured coating sheet. The thickness of the obtained covering sheet (thickness of sheets other than the ABS sheet) was 100 μ■
Met.

Example 2 Acrylic resin (copolymer of methyl methacrylate, ethyl methacrylate, and butyl acrylate, weight average molecular weight 754.000, Tg・20°C) 100
Acrylate monomer (manufactured by Nippon Kayaku Co., Ltd., KAYAR)
AD MANDA) 20 parts acrylate monomer (manufactured by Nippon Kayaku Co., Ltd., KAYAR
AD DPCA20) 80 parts Photoinitiator (manufactured by Nippon Ciba Geigy Co., Ltd., Irgacure 184) 2 parts N-methyljetanolamine 2 parts Elastic beads (manufactured by Nippon Shokubai Chemical Co., Ltd., EBSIoo)
) 200 parts of ethyl acetate and 300 parts or more were mixed without stirring.

This mixture was applied to an ABS sheet and dried at 80° C. for 5 minutes to obtain an uncured coating sheet. The thickness of the obtained covering sheet (thickness of sheets other than the ABS sheet) was IOQμl.

Example 3 Acrylic resin (copolymer of methyl methacrylate, ethyl methacrylate, and butyl acrylate, weight average molecular weight 387,000.Tg・80°C) 100
Acrylate monomer (manufactured by Nippon Kayaku Co., Ltd., KAYAR)
AD R604) 40 parts Photoinitiator (2,4,6-trimethyl benzoyl diphenylphosphine oxide) 4 parts N-methyljetanolamine 2 parts Rutile titanium oxide 100 parts Elastic beads (manufactured by Nippon Shokubai Chemical Co., Ltd., acrylic) Urethane copolymer elastic beads EBS300, particle size 25-3
5 μm) 200 parts and 300 parts or more of ethyl acetate were mixed with stirring.

This mixture was applied to a silicone release-treated polyethylene terephthalate film (manufactured by Soken Kako Co., Ltd., film thickness 50 μm).
Coated on the release surface of PET film (hereinafter referred to as PET film),
After drying at 0°C for 5 minutes, the PET film was peeled off to obtain an uncured coating sheet. The thickness of the resulting coating sheet was 80 μm.

Example 4 Acrylic resin (copolymer of methyl methacrylate, ethyl methacrylate, and butyl acrylate, weight average molecular weight 257.Goo, Tg=10″C) 10
0 parts acrylate monomer (manufactured by Nippon Kayaku Co., Ltd., KAYAR
AD R55I) 80 parts Photoinitiator (2,4,6-trimethyl benzoyl diphenylphosphine oxide) 4 parts N-methyljetanolamine 2 parts Iron oxide 100 parts Elastic beads (manufactured by Nippon Shokubai Chemical Co., Ltd., EBS300
) 150 parts and 300 parts or more of ethyl acetate were mixed with stirring.

This mixture was applied to an ABS sheet and dried at 80°C for 5 minutes to obtain an uncured coating sheet. Thickness of the obtained covering sheet (thickness of sheets other than ABS sheets)
was 50 μl.

Example 5 Acrylic resin (copolymer of methyl methacrylate, ethyl methacrylate, and butyl acrylate, weight average molecular weight 183.000, Tg・40°C) 100
Acrylate monomer (manufactured by Nippon Kayaku Co., Ltd., KAYAR)
AD DPCA-20) 5 (1 part photoinitiator (2,4
,6,-Trimethyl benzoyl diphenylphosphine oxide) 2 parts N-methyljetanolamine 2 parts Elastic beads (manufactured by Nippon Shokubai Chemical Co., Ltd., EBS3Go
) 200 parts and 300 parts or more of ethyl acetate were mixed with stirring.

Coat this mixture on the release surface of the PET film and
It was dried at C for 5 minutes. The thickness of the obtained covering sheet (
The thickness of the sheet other than PET was 50μ.

(Clear layer) Acrylic resin (copolymer of methyl methacrylate, ethyl methacrylate, and butyl acrylate, weight average molecular weight 183,000. Tg = 40°C) 10
0 parts acrylate monomer (manufactured by Shin Nakamura Kogyo Co., Ltd., NPA-
LOG) 80 parts Photoinitiator (2,4,5-trimethyl benzoyl diphenylphosphine oxide) 4 parts N-methyljetanolamine 2 parts Rutile titanium oxide 100 parts Ethyl acetate or more 300 parts were mixed with stirring.

This mixture was coated on the above clear layer and heated at 80°C for 5 minutes.
After drying for a minute, the PET film was peeled off to obtain an uncured coating sheet. The thickness of the resulting coating sheet was 50 μm for the clear layer and 50 μm for the colored layer.

Example 6 Acrylic resin (copolymer of methyl methacrylate, ethyl methacrylate, and butyl acrylate, weight average molecular weight 188.000, Tg = lO ℃) 100 parts acrylate monomer (manufactured by Nippon Kayaku Co., Ltd., KAYAR
AD R604) 100 parts Photoinitiator (2,4,6,-)limethyl benzoyl diphenylphosphine oxide) 4 parts N-methyljetanolamine 2 parts Rutile type titanium oxide 100 parts Ethyl acetate 300 parts or more were mixed with stirring.

This mixture was made of ABS sheet (manufactured by Royal Resin Industry Co., Ltd.)
205, film thickness 500 μm) and dried at 80° C. for 5 minutes. The thickness of the obtained covering sheet (thickness of sheets other than the ABS sheet) was 50 μm (colored layer)
.

Acrylic resin (copolymer of methyl methacrylate, ethyl methacrylate, and butyl acrylate, weight average molecular weight 33,000, Tg=40°C) 100 parts acrylate monomer (manufactured by Nippon Kayaku Co., Ltd., KAYAR
AD DPCA-20) 50 parts photoinitiator (2,4,
6,-) Limethyl benzoyl diphenylphosphine oxide) 2 parts N-methyljetanolamine 2 parts Elastic beads (manufactured by Nippon Shokubai Chemical Co., Ltd., EBS300
) 200 parts and 300 parts or more of ethyl acetate were mixed with stirring.

This mixture was coated on the colored layer and dried at 8o''C for 5 minutes.The thickness of the obtained covering sheet (thickness of the sheet other than the ABS sheet) was 50 μm for the colored layer, 40 μm for the clear layer, and 40 μm for the colored layer. Met.

Example 7 Acrylic resin (copolymer of methyl methacrylate, ethyl methacrylate, and butyl acrylate, weight average molecular weight 387.000, Tg/30°C) 100 parts acrylate monomer (manufactured by Nipponka M Co., Ltd., IAY
ARAD R604) 40 parts Photoinitiator (2,4,6-trimethyl benzoyl diphenylphosphine oxide) 4 parts N-methyljetanolamine 2 parts Peroxide (manufactured by NOF Corporation, Perhexa 3M) 1 part Rutile 100 parts titanium oxide type elastic beads (manufactured by Nippon Shokubai Chemical Co., Ltd., EBS300
) 150 parts and 300 parts or more of ethyl acetate were mixed with stirring.

Coat this mixture on the release surface of the ABS sheet and
The coating sheet was dried for 30 minutes to obtain an uncured coating sheet.

The thickness of the obtained covering sheet (other than the ABS sheet) was 200 μm.

Example 8 Reactive acrylic resin (reactive acrylic resin obtained by adding 2-hydroxyethyl methacrylate to a copolymer of methyl methacrylate, butyl acrylate, and acrylic acid, weight average molecular weight = 175.000, Tg 20)
．． Average double bond per molecule = 58) ioo moiety acrylate monomer (manufactured by Shin Nakamura Chemical Co., Ltd., NP
A-10G) 50 parts Photoinitiator (2,4,6-trimethyl benzoyl diphenylphosphine oxide) 4 parts N-methyljetanolamine 2 parts Elastic beads (E1 manufactured by Hon Shokubai Kagaku Kogyo Co., Ltd., EBSlo
o) 200 parts and 300 parts or more of ethyl acetate were mixed with stirring.

This mixture was applied onto an ABS sheet and dried at 80° C. for 5 minutes to obtain an uncured coating sheet. The thickness of the obtained covering sheet (the thickness of the portion other than the ABS sheet) was recommended to be 150 μm.

Example 9 Reactive acrylic resin (reactive acrylic resin obtained by adding 2-hydroxyethyl methacrylate to a copolymer of methyl methacrylate, butyl acrylate, and acrylic acid, weight average molecular weight = 258, 300, Tg = 0 ．．
Average double bond per molecule = 70) 100 parts acrylate monomer (manufactured by Shin Nakamura Chemical Co., Ltd., NP
A-10G) 50 parts photoinitiator (2,4,li□-trimethyl benzoyl
Diphenylphosphine oxide) 4 parts N-methyljetanolamine 2 parts Rutile titanium oxide 50 parts Elastic beads (manufactured by Nippon Shokubai Chemical Co., Ltd., EBS300
) 200 parts and 300 parts or more of ethyl acetate were mixed with stirring.

After coating this mixture on an ABS sheet and drying it at 80°C for 5 minutes, an ethylene-methyl acrylate film (PE2255 manufactured by Chevron Chemical, H thickness 20 μm) was applied.
(protective layer) to obtain an uncured coating sheet. The thickness of the obtained covering sheet (the thickness of the portion other than the ABS sheet) was 50 μm for the colored layer±20 μl for the protective layer.

Example 10 Reactive acrylic resin (copolymer of methyl methacrylate, butyl acrylate, and 2-hydroxylethyl acrylate, Mw = 86.OOO, T g = 35°C, OH value =
5) 100 parts acrylate monomer (manufactured by Nippon Kayaku Co., Ltd., KAYAR
AD R604) 80 parts photoinitiator (manufactured by Nippon Kayaku Co., Ltd., Kayakinia = DETX
> 1 part photopolymerization accelerator (Nippon Kayaku Co., Ltd., Kaya Half Core EPA)
) Two-part elastic beads (manufactured by Nippon Shokubai Chemical Co., Ltd., EBSIoo)
) So part incyanate crosslinking agent (Japan Polyurethane Industry Co., Ltd.)
manufactured by Fronate L, NC0-13,0%, solid content 75%
) 2.2 parts by solid content (this crosslinking agent has incyanate groups equivalent to the functional groups of the above-mentioned reactive acrylic resin) 300 parts or more of ethyl acetate were mixed with stirring.

This mixture was applied to an ABS sheet and dried at 80° C. for 5 minutes to obtain an uncured coating sheet. The thickness of the obtained covering sheet (thickness other than the ABS sheet) was 100μ
It was bright.

Example 11 Reactive acrylic resin (copolymer of methyl methacrylate, butyl acrylate, and 2-aminoethyl acrylate,
Mw=143,000, Tg=25℃, NH2 value=10
) 100 parts acrylate monomer (manufactured by Nippon Kayaku Co., Ltd., KAYAR
AD MANDA) 20 parts acrylate monomer (manufactured by Nippon Kayaku Co., Ltd., KAYAR
AD DPCA20) 80 parts Photoinitiator (manufactured by Nippon Ciba Geigy Co., Ltd., Irgacure 184) 2 parts N-methyljetanolamine 2 parts Elastic beads (manufactured by Nippon Shokubai Chemical Co., Ltd., EBSIoo)
) Zoo part epoxy crosslinking agent (manufactured by Civer Geigy, Araldite CY
175, epoxy equivalent: 160, epoxy value corresponding to functional group value: 220) 3.6 parts (80% of the functional groups of the above-mentioned reactive acrylic resin reacts) 300 parts or more of ethyl acetate were mixed with stirring.

This mixture was applied to an ABS sheet and dried at 80°C for 5 minutes to obtain an uncured coating sheet. The thickness of the obtained covering sheet (thickness other than the ABS sheet) is ioo
It was a μ garden.

Example 12 Reactive acrylic resin (copolymer of methyl methacrylate, butyl acrylate, and acrylic acid, Mw = 243,0
00, Tg=O℃, CoOH value=lO) 100 parts acrylate monomer (Nippon Kayaku Co., Ltd. HlKAYARA
DR604) 40 parts Photoinitiator (2,4,6-trimethyl benzoyl diphenylphosphine oxide) 4 parts N-methyljetanolamine 2 parts Rutile titanium oxide 100 parts Elastic beads (manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd., EBS3Go)
) 100 parts incyanate crosslinking agent (Japan Polyurethane Industry Co., Ltd.)
manufactured by Coronate L, NGO = 13.0%, solid content 75%
) 5.2 parts by solid content (this crosslinking agent has 1.2 equivalents of incyanate groups with respect to the functional groups of the above-mentioned reactive acrylic resin) and 300 parts or more of ethyl acetate were mixed with stirring.

This mixture was applied to an ABS sheet and dried at 80° C. for 5 minutes to obtain an uncured coating sheet. The thickness of the obtained covering sheet (thickness other than the ABS sheet) is 80 μ■
Met.

Example 13 Reactive acrylic resin (copolymer of methyl methacrylate, butyl acrylate, 2-hydroxylethyl acrylate, and 3-aminopropyl acrylate, Mw 278.
000, Tg 65℃, OH value = 5, NH2 value 0)
Loo part acrylate monomer (manufactured by Nippon Kayaku Co., Ltd., KAYA
RAD R551) 50 parts Photoinitiator (2,4,6-trimethyl benzoyl diphenylphosphine oxide) 4 parts N-methyljetanolamine 2 parts Iron oxide 50 parts Elastic beads (manufactured by Nippon Shokubai Chemical Co., Ltd., EBS300
) 150 parts incyanate crosslinking agent (Japan Polyurethane Industry Co., Ltd.)
manufactured by Coronate L, NGO = 13.0%, solid content 75%
) 6.5 parts in solid content (this crosslinking agent has 1.0 equivalent of incyanate groups with respect to the functional groups of the above-mentioned reactive acrylic resin) and 300 parts or more of ethyl acetate were mixed with stirring.

This mixture was applied to the release surface of the PET film and heated to 80°C.
After drying for 5 minutes, the PET film was peeled off to obtain an uncured coating sheet.

The thickness of the obtained covering sheet was 50 μm.

Example 14 Reactive acrylic resin (copolymer of methyl methacrylate, butyl acrylate, and 2-hydroxylethyl acrylate, Mw = 153.000, Tg = 45°C, OH
Value = lO) 100 parts acrylate monomer (Nippon KaM Co., Ltd. If!, K
AYARAD DPCA-20) 50 parts photoinitiator (
2,4,6,-1-limethyl benzoyl diphenylphosphine oxide) 2 parts N-methyljetanolamine 2 parts Elastic beads (manufactured by Nippon Shokubai Chemical Co., Ltd., EBS300
) 200 parts Isocyanate crosslinking agent (Japan Polyurethane Industries Co., Ltd.)
manufactured by Coronate L, NC0・13.0%, solid content 75%
) 5.2 parts by solid content (this crosslinking agent has 1.2 equivalents of incyanate groups with respect to the functional groups of the above-mentioned reactive acrylic resin) and 300 parts or more of ethyl acetate were mixed with stirring.

This mixture was applied to the release surface of the PET film and heated to 80°C.
and dried for 5 minutes. The thickness of the obtained covering sheet (P
The thickness of the sheets other than ET was 50 parts.

(Clear layer) Reactive acrylic resin (copolymer of methyl methacrylate, butyl acrylate, and 2-hydroxylethyl acrylate, M w = 653.000, Tg" 45°C, OH value = IO) 100 parts arc Relate monomer (manufactured by Shin-Nakamura Chemical Co., Ltd., N
PA-10G) 80 parts Photoinitiator (2,4,5,-trimethyl benzoyl diphenylphosphine oxide) 4 parts N-methyljetanolamine 2 parts Rutile titanium oxide 100 parts Incyanate crosslinking agent (Nippon Polyurethane Kogyo Co., Ltd.)
Manufactured by Coronate L, NGO rich 13.0%, solid content 75%
) 5.2 parts by solid content (this crosslinking agent has 1.2 equivalents of isocyanate groups with respect to the functional groups of the above-mentioned reactive acrylic resin) and 300 parts or more of ethyl acetate were mixed with stirring.

This mixture was coated on the above clear layer and heated at 80°C for 5 minutes.
After drying for a minute, the PET film was peeled off to obtain an uncured coating sheet. The thickness of the resulting coating sheet was 50 μm for the clear layer and 50 μm for the colored layer.

Example 15 Reactive acrylic resin (copolymer of methyl methacrylate, butyl acrylate, 2-hydroxylethyl acrylate, and 3-aminopropyl acrylate, Mw = 78
．． 000, T g = 30°C, OH value = 15, NH2 value = 1o) ioo moiety acrylate monomer (manufactured by Nippon Kayaku Co., Ltd., KAYAR
AD DPCA-20) 50 parts photoinitiator (2,4,
6,-Trimethyl benzoyl diphenylphosphine oxide) 4 parts N-methyljetanolamine 2 parts Elastic beads (manufactured by Nippon Shokubai Chemical Co., Ltd., EBS300
) 200 parts incyanate crosslinking agent (Japan Polyurethane Industry Co., Ltd.)
LSNCO = 13.0%, solid content 75%
) 10.8 parts by solid content (this crosslinking agent has incyanate groups equivalent to the functional groups of the above-mentioned reactive acrylic resin) and 300 parts or more of ethyl acetate were mixed with stirring.

This mixture was made of ABS sheet (manufactured by Royal Resin Industry Co., Ltd., A
205, film thickness so μm) and dried at 80° C. for 5 minutes. The thickness of the obtained covering sheet (thickness of sheets other than the ABS sheet) was 100 μm.

Example 16 Reactive acrylic resin (copolymer of methyl methacrylate, butyl acrylate, 2-hydroxylethyl acrylate, and 3-7 minobrovir acrylate, Mw = 78,0
00, T g = 30°C, OH value = 15, NH2 value = l
O) 100 parts acrylate monomer (manufactured by Nippon Kayaku Co., Ltd., AYAR)
AD R604) 1000 parts photoinitiator (2,4,6
,-) 4 parts N-methyl benzoyl diphenylphosphine oxide) 2 parts rutile titanium oxide 100 parts Incyanate crosslinking agent (Japan Polyurethane Industry Co., Ltd.)
manufactured by Coronate L, NGO = 13.0%, solid content 75%
) 10.8 parts in solid content (this crosslinking agent has an equivalent amount of incyanate groups to the functional groups of the above-mentioned reactive acrylic resin) and 300 parts or more of ethyl acetate were mixed with stirring.

This mixture was made of ABS sheet (manufactured by Royal Resin Industry Co., Ltd., A
205, film thickness 500 μm) and dried at 80°C for 5 minutes. The thickness of the obtained covering sheet (thickness of sheets other than the ABS sheet) was 50 μm (colored layer).

Reactive acrylic resin (copolymer of methyl methacrylate, butyl acrylate, 2-hydroxylethyl acrylate, and 3-aminopropyl acrylate, Mw = 71
1.000, Tg=30℃, OH value -15, NH2 value=
10) 100 parts acrylate monomer (manufactured by E1 Honkayaku Co., Ltd., KAYA
RAD DPCA-20) 50 parts photoinitiator (2,4
,6,-) 2 parts N-methyl benzoyl diphenylphosphine oxide) 2 parts Elastic beads (manufactured by Nippon Shokubai Chemical Co., Ltd., EBS3Do
) 200 parts incyanate crosslinking agent (Japan Polyurethane Industry Co., Ltd.)
manufactured by Coronate L, NC0=13.0%, solid content 75
%) solid content of 10.8 parts (this crosslinking agent has isocyanate groups equivalent to the functional groups of the above-mentioned reactive acrylic resin) and 300 parts or more of ethyl acetate were mixed with stirring.

This mixture was applied onto the colored layer and dried at 80°C for 5 minutes. The thickness of the obtained covering sheet (the thickness of the sheets other than the ABS sheet) was 50 μm for the colored layer, 40 μm for the clear layer.

Example 17 Reactive acrylic resin (copolymer of methyl methacrylate, butyl acrylate, 2-hydroxylethyl acrylate, acrylic acid, and 3-aminopropyl acrylate, M
w = 353.000, Tg = 45°C, OH value = 5
, C00H value = 5, NH2 value = 10) 100 parts acrylate monomer (manufactured by Nipponka M Co., Ltd., KAYARA
DR604) 40 parts photoinitiator (2,4,6,-1-limethyl benzoyl
Diphenylphosphine oxide) 4 parts N-methyljetanolamine 2 parts Peroxide (manufactured by Nippon Oil & Fats Co., Ltd., Perhexa 3M) 1 part Rutile type titanium oxide 100 parts Elastic beads (manufactured by Nippon Shokubai Chemical Co., Ltd., EBS300
) 150 parts melamine crosslinking agent (manufactured by Dainippon Ink Chemical Co., Ltd., Superbacamine J-820-60) 9.2 parts solids (40% of the functional groups of the above reactive acrylic resin react) incyanate System crosslinking agent (manufactured by Nippon Polyurethane Industry Co., Ltd.)
Fronate L, NGO=13. O%, solid content 75%) 5.2 parts solids (this crosslinking agent has 0.6 equivalents of incyanate groups with respect to the functional groups of the above-mentioned reactive acrylic resin) 300 parts or more of ethyl acetate were stirred. while mixing.

Coat this mixture on the release surface of the ABS sheet and
The mixture was dried for 5 minutes to obtain an uncured sort for coating.

The thickness of the obtained covering sheet (thickness other than the ABS sheet) was 200 μm.

Example 18 Reactive acrylic resin (copolymer of methyl methacrylate, butyl acrylate, and acrylic acid with acrylic acid 2
- Reactive acrylic resin with added hydroxyethyl, weight average molecular weight = 175,000, Tg = 20. Average double bond per molecule = 18, CoOH value = 5) 100 parts acrylate monomer (Shin Nakamura Chemical Co., Ltd. ), NP
A-10G) 50 parts photoinitiator (,2,4,6,-)limethyl benzoyl
diphenylphosphine oxide) 4 parts N-methyljetanolamine 2 parts Elastic beads (manufactured by Nippon Shokubai Chemical Co., Ltd., EBSloo
) 200 parts Isocyanate crosslinking agent (Japan Polyurethane Industries Co., Ltd.)
manufactured by Fronate L, NC0=13.0%, solid content 75%
) 2.2 parts (solid content) (this crosslinking agent has an equivalent amount of incyanate groups to the functional groups of the above-mentioned reactive acrylic resin) and 300 parts or more of ethyl acetate were mixed with stirring.

This mixture was applied onto an ABS sheet and dried at 80° C. for 5 minutes to obtain an uncured coating sheet. The thickness of the obtained covering sheet (thickness other than the ABS sheet was 150 parts).

Example 19 Reactive acrylic resin (reactive acrylic resin obtained by adding 2-hydroxyethyl methacrylate to a copolymer of methyl methacrylate, butyl acrylate, and acrylic acid,
Weight average molecular weight = 258.300. Tg=0. Average double bond per molecule=40. C0OH value = 10) 10
0 parts acrylate monomer (manufactured by Shin Nakamura Chemical Co., Ltd., NP
A-10G) 50 parts Photoinitiator (2,4,6-trimethyl benzoyl diphenylphosphine oxide) 4 parts N-methyljetanolamine 2 parts Rutile type titanium oxide SO part Elastic beads (manufactured by Nippon Shokubai Chemical Co., Ltd., EBS300
) 200 parts Isocyanate crosslinking agent (Japan Polyurethane Industries Co., Ltd.)
manufactured by Coronate L, NC0 = 13.0%, solid content 75%
300 parts or more of ethyl acetate were mixed with stirring while stirring.

This mixture was coated on an ABS sheet and dried at 80'C for 5 minutes to laminate an ethylene-methyl acrylate film (PE2255 manufactured by Chevron Chemical, film thickness 20 μm) to obtain an uncured coating sheet. Ta. The thickness of the obtained covering sheet (thickness other than the ABS sheet) was 50 μm for the colored layer + 20 μm for the protective layer.

(B) Injection molding Injection molding was carried out as follows using the injection molding machine shown in FIG. This injection molding machine includes a movable mold 10 having a molding recess 10a and a vacuum hole, a fixed mold 12 having a convex part 12a, and disposed between both molds 10 and 12. It is equipped with a hot platen 14 having holes for vacuum and pressurized air and a resin injection machine 15, which can be moved outward from between the two molds 10 and 12.

First, as shown in FIG. 1 (1)), the movable mold 10
The sheet 13 was disposed between the heating plate 14 and the heating plate 14, and the sheet 13 was heated, and the sheet 13 was vacuum- and/or pressure-formed to be brought into close contact with the inner surface of the recess 10a of the mold 10. Next, as shown in FIG. 1(C), the hot platen 14 is taken out from between the molds 10 and 12, and then the movable mold 10 is moved from the fixed mold 10.
gII and close the mold. Next, ABS resin (manufactured by Denki Kagaku Kogyo ■, ABS-M) is injected from the resin injection machine 15.
E) was injected into the cavity formed by both molds 10 and 12. The injection molding conditions were such that the temperature at the nozzle tip of the resin injection machine was 230°C. After molding, take out the covering from the mold and heat it with Metal Para 4V571 under the conditions shown in the table below.
The curable sheet on the surface of the coating was cured with ' to obtain an injection molded product. Taper wear test on the surface of injection molded products after curing (
Taper IKg, C517, 1000 rotations), adhesion by base grain test (number of base grains remaining after tape removal),
The soft touch feeling (sensation) was evaluated. The test results are shown in Tables 1-4.

(Margin below) (Comparative example) ABS resin sheet (manufactured by Royal Resin Industry Co., Ltd., A205.
500 μm) with soft touch paint (manufactured by Cashew Co., Ltd.)
Nana Soft ■) was applied to a coating thickness of 50 μm and cured by heating at 80° C. for 30 minutes. Injection molding was performed using the obtained notebook in the same manner as in the example. When the ABS resin was injected after vacuum-pressure forming the sheet into a female mold at 160℃ and 180℃, the sheet could not be molded into the female mold shape due to insufficient elongation, and the sheet cracked at the same time as the resin was injected. Has entered.

(Effects of the Invention) The present invention covers the photocurable sheet by injection molding a molding resin with an uncured or semi-cured photocurable sheet affixed to the inner surface of a mold, and then coats the photocurable sheet with light irradiation. It forms a cured film of a photocurable sheet. For this reason, painting, which was previously done in the post-process, can be omitted.
This eliminates environmental problems such as the removal of painting space and the use of solvents, and also enables the manufacture of molded products without any problems even in deep drawing. Furthermore, since the photocurable sheet is formed from a photocurable resin composition containing elastic beads, it is possible to produce a molded article with a soft touch feel (suede-like).

Therefore, there is an advantage that decorating office equipment, home appliances, etc., and decorating stationery, etc. can be done easily and inexpensively.

4. No. 1 FIGS. 1(a) to 1(d) are explanatory diagrams showing the method for manufacturing an injection molded product of the present invention.

lO...Movable mold, 12...Fixed mold, 13...
Photocurable sheet, 14...heating plate, 15...resin injection machine.

that's all

Claims (1)

[Claims] 1. A step of attaching an uncured or semi-cured photocurable sheet made of a photocurable resin composition containing elastic beads to the inner surface of a mold by vacuum and/or pressure molding. , a step of injection molding a molding resin into a mold to form a covering covered with a photocurable sheet, and a step of curing the photocurable sheet by irradiating the covering with light. Method of manufacturing injection molded products.