JPH04201218A - Manufacture of injection-molded product - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention is used to manufacture products such as housings for office automation equipment, home appliances, stationery, etc. by injection molding. For more details on the method of manufacturing molded products in the field where painting, etc.
The present invention relates to a method for producing an injection molded product that can form a coating having a soft touch feel (suede feel) with excellent scratch resistance and the like.

(Prior Art) Suede-like paints have generally been used to impart a suede feel to injection molded products such as office automation equipment, household appliances, and stationery to increase added value. However, when painting with a paint, it is necessary to adjust the viscosity and concentration of the paint, which makes the work complicated. In particular, paints using organic solvents cause pollution of the working environment and 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. Further, an apparatus for decorating during injection molding using these sheets has been proposed, for example, in Japanese Patent Application Laid-Open No. 59-202830.

(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 trying to attach the sheet to the surface of an article that has unevenness or a curved surface, the sheet may be torn because the sheet cannot be stretched sufficiently, and especially in deep drawing, it is difficult to easily impart a suede feel. was impossible.

The present invention is intended to solve the above-mentioned drawbacks, and its purpose is to provide a product that can be affixed without any problem even to the surface of an article having an uneven or curved surface, and has a soft touch feeling (suede R). An object of the present invention is to provide a method for manufacturing an injection molded product that can form a coating.

(Means for Solving the Problems) The method for producing an injection molded article of the present invention uses a photocurable sheet in an uncured or semi-cured state formed of a photocurable resin composition containing a porous inorganic material. , a step of pasting the inner surface of the recess of the mold by vacuum and/or pressure molding, a step of tightening the mold and injection molding a molding resin into the recess of the mold to produce a covering, and a step of exposing the covering to light. curing the photocurable sheet by irradiation, thereby achieving the above object.

An uncured or semi-cured photocurable sheet (hereinafter referred to as a curable sheet) formed from a photocurable resin composition containing a porous inorganic material used in the present invention is expandable at room temperature and under heating. Ductile, visible and ultraviolet light (200-500nm
), the photoinitiator dissociates or extracts hydrogen to generate radicals, which polymerize and harden the double bonds of the (meth)acryloyl group, resulting in a soft touch feel (suede feel) with excellent abrasion and scratch resistance. ), examples of which 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 containing as main components:) a low molecular weight substance having a (meth)acryloyl group in the molecule; (C) a photoinitiator; and (d) a porous inorganic material.

(e) It has a plurality of at least one functional group selected from the group consisting of hydroxyl group, amine group and carboxyl group in the molecule, and has a weight average molecular weight of so, ooo to 1.00.
0,000 and is solid at room temperature, (b
) a low molecular weight substance having a (meth)acryloyl group in the molecule; (C) a photoinitiator; (d) a porous inorganic material;
f) At least one selected from the group consisting of incyanate crosslinking agents, melamine crosslinking agents, and epoxy crosslinking agents.
A curable sheet whose main component is a crosslinking agent.

(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; (1)) a low molecular weight substance having a (meth)acryloyl group in the molecule;
A curable sheet containing (C) a photoinitiator and (d) a porous inorganic material as main components.

(h) It has a plurality of (meth)acryloyl groups and at least one functional group selected from the group consisting of hydroxyl group, amine group, and carboxyl group in the molecule, and has a weight average molecular weight of so, ooo 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;
(d) A curable sheet whose main components are a porous inorganic material and Cf') at least one crosslinking agent selected from the group consisting of incyanate crosslinking agents, melamine crosslinking agents, and epoxy crosslinking agents. .

(a) The weight average molecular weight contained in the sheet is so,
Acrylic resins that are ooo~i, ooo, ooo and are solid at room temperature include (meth)acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, styrene derivative monomers, etc. or a maleic acid monomer with a reaction initiator (
It can be obtained by copolymerization in the presence of various peroxides, chain transfer agents, etc.).

(e) molecules contained in the sheet have a plurality of at least one functional group selected from the group consisting of hydroxyl group, amine group, and carboxyl group, and have a weight average molecular weight of so,
ooo~1,000,000 and is solid at room temperature, for example, a (meth)acrylic acid ester monomer having a carboxyl group such as (meth)acrylic acid, 2-hydroxyethyl (meth)acrylate, 4
- (meth)acrylic acid ester monomers having hydroxyl groups such as hydroxybutyl (meth)acrylate, and (meth)acrylic acid esters having amine groups such as 2-aminoethyl (meth)acrylate and 3-aminopropyl (meth)acrylate. Among the monomers, a monomer having at least one kind of functional group and other (meth)acrylic acid esters, styrene derivative monomers, maleic acid monomers, etc. are reacted with a reaction initiator (such as various peroxides and chain transfer agents). It can be obtained by copolymerization in the presence of.

The (g) molecule contained in the sheet has a plurality of (meth)acryloyl groups, and has a weight average molecular weight of 50.000 to 50.000.
1, 000.000 and is solid at room temperature; (h) the molecule contains a small number of functional groups selected from the group consisting of hydroxyl groups, amino groups and carboxyl groups (both one type of functional group and a (meth)acryloyl group); Acrylic resins that have a plurality of acrylic resins, have a weight average molecular weight of 50.000 to 1,000.000, and are solid at room temperature include, for example, (meth)acrylic acid having a carboxyl group such as (meth)acrylic acid, and 2- A (meth)acrylic acid ester monomer having a hydroxyl group such as hydroxyethyl (meth)acrylate or 4-hydroxybutyl (meth)acrylate, and 2-aminoethyl (
A (meth)acrylic acid ester monomer having an amine group such as meth)acrylate or 3-aminopropyl(meth)acrylate, and 2-(1-aziridinyl)ethyl(
(meth)acrylic acid ester monomers having aziridinyl such as meth)acrylate, 2-(1-aziridinyl)butyl (meth)acrylate, and (meth)acrylic acid ester monomers having epoxy groups such as glycidyl (meth)acrylate. At least 1fiii of them
A monomer having a functional group is copolymerized with 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). It can be obtained by adding a monomer having the above functional group to an acrylic copolymer having a functional group.

The weight average molecular weight (Mw) of these acrylic resins (a), (e), (g), and (h) can be changed depending on the conditions when performing a 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 100%, it will be difficult for the obtained sheet to maintain its shape, and sufficient elongation will not be obtained during stretching during the pasting operation, and there is a risk that cracks will 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 creating a sheet 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 thicken the sheet. Tg (glass transition point) is -2 due to the relationship between hardness and soft touch feel (suede feel).
A temperature range of 0°C to 80°C is preferable. Different types of acrylic resins may be used in combination as long as they have molecular weights within these ranges. Above acrylic resin (e) (h)
Because it has functional groups such as hydroxyl group, amide group, and carboxyl group, it is crosslinked by the above-mentioned crosslinking agent, thereby making it possible to improve the flexibility of the sheet. The functional group values (OH group value and NH2 group value (NH
Divalent: NH2 group added during polymerization is calculated in the same manner as the OH value, or NH2 group is reacted with nitrous acid and determined by converting it into an OH group) and C0OH group value (COOH value C0OH added during polymerization) Calculate the amount of groups in the same way as the OH value, or titrate the C0OH group with KOH).
A value in the range of 0 is preferred. 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 the surface hardness is not very high, for example, 2B or less (23°C) by the pencil hardness method, or if the sheet does not require much elongation, it may be applicable even outside these ranges.

Furthermore, these acrylic resin materials can also be used as pro-copolymers in which the reactive portions of the acrylic resin are shaped into blocks or combs. In this case, materials that can be used as blocks 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 and fluorine-based materials. It does not matter if it is combined with any material that can be made into blocks. 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.

The (b) low molecular weight substance having a (meth)acryloyl group in the molecule contained in the above sheet is, for example, methyl (meth)acrylate, ethyl (meth)acrylate, benzyl (meth)acrylate, 2-ethynethyl (meth)acrylate, etc.
Acrylate, monofunctional types such as phenoxydiethylene glycol (meth)acrylate, 1,6-hexanethiol di(meth)acrylate, neobentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, etc. ) acrylate, trimethylpropane tri(
meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)
Acrylate, dipentaerythritol hexa(meth)
There are multifunctional types such as acrylate. Further, there are oligomers such as polyester acrylate, polyurethane acrylate, epoxy acrylate, polyether acrylate, oligoacrylate, alkyd acrylate, and polyol acrylate.

The amount of the low molecular weight substance added is approximately related to the Tg of the acrylic resin and the viscosity of the low molecular weight substance added (plasticizing effect on the reactive acrylic resin). For example, Tg=60~
When using acrylic resin at 80°C, the viscosity is 500c.
Acrylic resin 10 for low molecular weight substances below ps (25℃)
10 to 150 parts by weight relative to 0 parts by weight, viscosity 500 cp
It is preferable to add 30 to 300 parts by weight of the low molecular weight substance having a molecular weight of s (25° C.) or more. If the amount added is small, sufficient chemical resistance, scratch resistance, etc. cannot be obtained after curing. 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.

As the photoinitiator (C), any commonly used photoinitiator can be used, and photoinitiators such as benzoin alkyl ether, acetophenone, benzophenone, and thioxanthone are preferably used. Examples of benzoin ethers include benzyl, benzine, benzoin methyl ether, benzine ethyl ether, and benzoin propyl ether. Examples of acetophenone include 2.2-jethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, p-ter-butyltrichloroacetophenone, and 2.4.61-lymethylbenzoyldiphenylphosphine oxide. In the benzphenone series, benzophenone, 4-chlorobenzophenone, 4.4'-
Examples include dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, and dibenzosuberenone. Thioxanthone types include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, and 2-ethylanthraquinone. The photoinitiator is 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 above (d) porous inorganic material is, for example, hydrated silicic acid (Si02.xH2O) or hydrated aluminum silicate (A
1203.9Si02.xH2O) and natural diatomaceous earth. -For boat fishing, there is something called white carbon, silica gel, etc. These inorganic materials vary depending on the thickness of the sheet to be obtained, but for example, when obtaining a sheet with a thickness of 100 μm or less, the average particle diameter is preferably 30 μm or less, more preferably 1 to 20 μm. It is. If the grain size is larger than 30 μm, the surface of the resulting coating will have large irregularities, making it impossible to obtain an excellent soft feel, and cracks are likely to occur on the surface when the sheet is stretched. Furthermore, porous materials generally have an oil absorption amount that indicates the degree of their porosity. This varies depending on the properties of the binder used (acrylic resin, low molecular weight material), but for example, if the binder used has good compatibility with the above-mentioned inorganic material, a large amount of the binder will be retained in the inorganic material, so the inorganic material The oil absorption amount is preferably 50 m 1 / 100 g or more, more preferably 100 to 300 m 1 / 100
It is g.

When the oil absorption amount is less than 50 m I 7100 g, it is necessary to add a large amount of inorganic material to make the sheet surface rough (uneven surface), and as a result, the formed film becomes hard and does not have excellent properties. It becomes impossible to obtain a soft feeling. The amount of the inorganic material added varies depending on the thickness of the sheet to be obtained and the compatibility of the inorganic material and binder used. 100 parts by weight (hereinafter referred to as parts)
It is preferable to add 10 to 40 parts to the total amount. If the amount added is less than 10 parts, the surface of the coating cannot be sufficiently roughened, and an excellent soft feel (slip feeling...lower coefficient of friction) cannot be obtained. If the amount added is large, cracks are likely to occur on the surface of the notebook during stretching. These inorganic materials are not limited to one type, and two or more types may be used in combination.

The above-mentioned isocyanate-based crosslinking agent is an isocyanate compound having two or more isocyanate groups in the molecule, such as tolylene diisocyanate, diphenylmethane isocyanate, naphthalene diisocyanate, tolydine diisocyanate, triphenylmethane diisocyanate, etc. Isocyanate, tris (isocyanate phenyl) thiophosphite, P-phenylene diisonanate, xylylene diisocyanate, bis (isocyanate 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,
Examples include Hilaret modified products, carbodiimide modified products, urethane modified products, and allophanate modified products.

Melamine-based crosslinking agents are trimethylol melamine, hexamethylol melamine, which is produced by reacting formaldehyde with materials having polyfunctional amino groups such as melamine, urea, thiourea, guanidine, guanamine, acetoguanamine, benzoguanamine, dicyandiamide, and guanamine. It is an etherified melamine resin made by reacting dimethylol urea, dimethylol guanidine, dimethylol acetoguanamine, dimethylol benzoguanamine, etc. with an alcohol such as butyl alcohol or propyl alcohol.

The epoxy crosslinking agent is a glycidyl compound of polyhydric alcohol containing a plurality of epoxy groups, and is used together with a Lewis acid catalyst. The Lewis acid is preferably microencapsulated in order to delay the reaction. For example, butadiene cidoxide, hexacin dioxide, diglycidyl ester of phthalic acid, diglycidyl ether of bisphenol-A, bisphenol-F
Grindyl compounds such as diglycidyl ether of para-aminophenol, triglycidyl etheramine of para-aminophenol, diglycidyl ether of aniline, tetragrindyl ether of phenylenediamine, diglycidyl ether of sulfonamide, triglycidyl ether of glycerin, polyether-modified diglycidyl, and polyester. These include modified diglycidyl, urethane-modified diglycidyl compounds (polymers), vinylcyclohexene dioxide, dicyclopentadiene dioxide, and the like.

The amount of these crosslinking agents added is preferably such that the functional group value of the acrylic resin: the functional group value of the crosslinking agent=1: about 0.7 to 1.3.

However, in reality, due to the reactivity with the acrylic resin used, reactions may occur between the functional groups of the acrylic resin and the crosslinking agent, such as between melamine crosslinking agents and between melamine crosslinking agents and epoxy crosslinking agents, so it is necessary to conduct preliminary experiments beforehand. It is preferable to decide.

The curable sheet of the present invention may further contain pigments, if necessary.
Colorants such as dyes and materials such as antioxidants are added.

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 ab 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 is preferable relative to 0 parts. Also,
When these materials are added, the photoinitiator is preferably one that initiates the reaction with light of a wavelength that is less absorbed by the colorant.

Peroxide may be added to the curable sheet of the present invention as necessary (for example, when the sheet is attached to an adherend with a complex shape, and there are areas that are not exposed to light). As the above-mentioned peroxide, a common organic peroxide can be used. From the viewpoint of storage stability at room temperature, organic peroxides with a decomposition temperature of 100"C or higher are more preferable. Examples include 2,2-bis(ter-butylperoxy)butane, Examples include luperoquine benzoate, di-ter-butyl peroxyisophthalate, methyl ethyl ketone peroxide, dicumyl peroxide, and ter-butyl peroxy acetate. The amount is preferably in the range of 0.5 to 5.0 parts by weight per 100 parts by weight of the peroxide.Also, 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 cure by light irradiation can be cured by heat generation during light irradiation or by further heating.

Various functional agents may be added to impart various functions to the curable 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 curable 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 curable sheet is a single layer, this base layer becomes the curable sheet as it is. The sheet of 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.

(2) A sheet having a base layer and a back layer laminated on the back side of the base layer.

This back layer is provided to further improve the handling properties of the sheet, to improve adhesion to the injection resin when the sheet is used for sheet insert injection molding, or to withstand the shear stress of the injection resin. It will be done. If the adhesion between the base layer and the back layer is poor, a primer layer may be provided between the two layers, or a plurality of back layers may be provided.

Since the sheet of the present invention is stretched as necessary and attached to an adherend, these back layers (and primer 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-butadiene-styrene copolymer)
, modified polyphenylene oxide, polyphenylene sulfide, polyetherimide, polyether ether ketone, polyethylene sulfide, and the like.

(2) A sheet having a base layer or the sheet obtained in (1) above, and an adhesive layer laminated on one side of the sheet (in the case of the sheet (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) and (2) 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, isoprene rubber, butadiene rubber, chloroprene rubber, urethane rubber, silicone rubber, and acrylic rubber. Mixtures of these thermoplastic resins and combs can also be used. Alternatively, both films may be laminated.

The protective layer may be peeled off from the adherend after pasting the sheet to the adherend, and then the sheet may be cured. It can be used as a protective layer (X may also be used) until the surface of the protective layer is embossed or patterned to change the surface shape (appearance) of the sheet.

■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 does not need to contain any inorganic material.

■A sheet in which printing is applied to the front or back side of the base layer of the curable sheet obtained in steps (■) to (■) above.

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 curable sheet obtained in steps ① to ① above is 20 to 1,000 μm when pasted to an uneven adherend surface.
m is preferable, and when pasting on a flat surface, it is 10 to 50 m.
It may be about 0 μm. Further, the thickness of other layers laminated on the sheet is usually 10 to 500 μm, and in particular,
The thickness of the adhesive layer is preferably 10 to 100 μm.

[Preparation of curable sheet]

The curable 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 on process paper (usually polyethylene terephthalate film or paper paper whose surface has been treated with silicone) using equipment such as a knife coater, a coater, or a bar 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 processing paper, dried to remove the solvent to form a resin layer, and then another resin is coated on top of this resin layer. A solution containing the layer composition is coated and dried to remove the solvent to form another resin layer. According to the lamination method, each layer is formed by separately applying a solution containing the resin composition of each resin layer onto process paper and drying to volatilize the solvent, and then both layers are laminated. (Heat) Press with a roll press.

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

[Manufacturing method for injection molded products]

In injection molding, the above-mentioned sheet is molded and adhered to the inner surface of the recessed part of the mold at room temperature or by heating, by vacuum and/or pressure forming, and after the mold is closed, the resin for injection molding is injected and filled into the recessed part. The method is the commonly used sheet insert injection molding. Thereafter, the sheet is cured by irradiating light onto at least the portion of the covering body to which the sheet is pasted (heating may be performed if necessary) to obtain an injection molded product.

As the injection molding resin, any conventionally used injection molding resin can be used. for example,
Polystyrene, acrylic polymer, polycarbonate, polyvinyl chloride, polyethylene, polypropylene, A
BS (acrylonitrile-butadiene-styrene copolymer), modified polyphenylene oxide, polyphenylene sulfide, polyetherimide, whethyl ether ketone, polyethylene sulfide, liquid crystal polymer,
Examples include glass fiber reinforced polyester, glass fiber reinforced epoxy, and glass fiber reinforced acrylic resin.

(Function) Since the photocurable sheet used in the present invention has excellent stretchability before curing, it can be easily applied even in deep drawing by stretching the sheet. Since this sheet is photocurable and contains elastic beads, by irradiating the sheet with light, it becomes hard, solvent resistant, durable, and has a soft touch. It is possible to form a coating that has a suede feel.

(Margin below) (Example) The present invention will be described in detail below based on Examples.

(A) Creation of curable sheet Example 1 Acrylic resin (copolymer of methyl methacrylate, ethyl methacrylate, and butyl acrylate, weight average molecular weight 58,000. Tg = 40'C) 10
0 parts acrylate monomer (manufactured by S Honkayaku Co., Ltd., KAYAR
AD MANDA) 80 parts Photoinitiator (Nippon Kayaku Co., Ltd., Kayacure-DETX)
1-part photopolymerization accelerator (Kayacure EPA manufactured by Nippon Kayaku Co., Ltd.)
) 2-part silica gel (manufactured by Fuji Davison Chemical Co., Ltd., Thyroid 244, average particle size 1.11 μm, oil absorption j1310+al
/100g) 30 parts or more of ethyl acetate was 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 a curable sheet in an uncured state. The thickness of the obtained curable sheet (thickness of the sheet other than ABS) was 100 μm.

Example 2 Acrylic resin (copolymer of methyl methacrylate, ethyl methacrylate, and butyl acrylate, weight average molecular weight 1t754.000.Tg=20″C) 1
00 parts acrylate monomer (manufactured by Nippon Kayaku Co., Ltd., KAYAR
AD MANDA) 20 parts Actulate Motsuma (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 Silica gel (manufactured by Fuji Davison Chemical Co., Ltd., Cyroid 65, average particle size 3.5 μm, oil absorption j195n+l) /lo
og) 70 parts At least 300 parts 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 curable sheet. The thickness of the obtained curable sheet (thickness of the sheet other than ABS) was 10
The amount was 0 μl.

Example 3 Acrylic resin (copolymer of methyl methacrylate, ethyl methacrylate, and butyl acrylate, weight average molecular weight 387,000, Tg・20°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 Silica gel (manufactured by Fuji Davison Chemical Co., Ltd., Cyroid 72, Average particle size z, sμm, oil absorption 1t220ml/l
o○g) 20 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 Kaisho Kako Co., Ltd., film thickness 50 μm).
m, hereinafter referred to as PET film) on the mold release surface, and
After drying at 0°C for 5 minutes, the PET film was peeled off to obtain a curable sheet in an uncured state. The thickness of the obtained curable sheet was 80 μm.

Example 4 Acrylic resin (copolymer of methyl methacrylate, ethyl methacrylate, and butyl acrylate, weight average molecular weight 257,000, Tg = 10 ° C) 100
Acrylate monomer (manufactured by Nippon Kayaku Co., Ltd., KAYAR)
AD R551) 80 parts Photoinitiator (2,4,6,-)limethyl benzoyl diphenylphosphine oxide) 4 parts N-methyljetanolamine 2 parts Iron oxide 100 parts Silica gel (manufactured by Fuji Davison Chemical Co., Ltd., Thyroid 620, average Particle size 12μm, oil absorption 1t180i1/1
00g) 50 parts 300 parts or more of ethyl acetate were mixed with stirring.

This mixture was applied to an AB'S sheet and dried at 80° C. for 5 minutes to obtain an uncured curable sheet. The thickness of the obtained curable sheet (thickness of sheets other than ABS) was 50
It was μm.

Example 5 Acrylic resin (copolymer of methyl methacrylate, ethyl methacrylate, and butyl acrylate, weight average molecular weight 183,000, Tg・10°C) 100
Acrylate monomer (manufactured by Nippon Kayaku Co., Ltd., KAYAR)
AD DPCA-20) 80 parts photoinitiator (2,4,
6-dotrimethyl benzoyl diphenylphosphine oxide) 2 parts N-methyljetanolamine 2 parts Gel (manufactured by Fuji Davison Chemical Co., Ltd., Thyroid 72, average particle size 2.5 μm, oil absorption It 220Ill/
100 g) 50 parts and 300 parts or more of ethyl acetate were mixed with stirring.

This mixture was coated on the release surface of the PET film, and 80'
It was dried at C for 5 minutes. Thickness of the obtained curable sheet (
The thickness of the sheet other than PET was 50 μm.

(Clear layer) 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 Shin-Nakamura Kogyo Co., Ltd., NPA-
LOG) 80 parts Photoinitiator (2,4,6,-)limethyl benzoyl diphenylphosphine oxide) 4 parts N-methyljetanolamine 2 parts Rutile titanium oxide 100 parts At least 300 parts 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 curable sheet. The thickness of the obtained curable 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 = 10 ° C) 100
Acrylate monomer (manufactured by Nippon Kayaku Co., Ltd., KAYAR)
AD R604) 100 parts Photoinitiator (2,4,6-trimethyl benzoyl diphenylphosphine oxide) 4 parts N-methyljetanolamine 2 parts Rutile type titanium oxide 100 parts At least 300 parts of ethyl acetate were mixed with stirring.

This mixture was mixed with ABS No. 1- (manufactured by Royal Resin Industry Co., Ltd.),
A205. (film thickness: 500 μm) and heated at 80°C.
and dried for 5 minutes. Thickness of the obtained curable sheet (A
The thickness of the sheet other than BS was 50 μm (colored layer).

Acrylic resin (copolymer of methyl methacrylate, ethyl methacrylate, and butyl acrylate, weight average molecular weight 33,000, Tg・20°C) 100
Acrylate monomer (manufactured by Nippon Kayaku Co., Ltd., KAYAR)
AD DPCA-20) 50 parts photoinitiator (2,4,
5,-) Limethyl benzoyl diphenylphosphine oxide) 2 parts N-methyljetanolamine 2 parts Silica gel (manufactured by Fuji Davison Chemical Co., Ltd., Cyroid 244, average particle size 1.8 μm, oil absorption 310 m 1/1
00g) 35 parts 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 curable sheet (the thickness of the sheet other than ABS) was 50 Atm for the colored layer + 40 Atm for the clear layer.
It was a μm layer.

Example 7 Acrylic resin (copolymer of methyl methacrylate, ethyl methacrylate, and butyl acrylate, weight average molecular weight 3g 7.000.Tg・15°C) 100
Acrylate monomer (manufactured by Nippon Kayaku Co., Ltd., KAYAR)
AD R604) 70 parts Photoinitiator (2,4,6,-)limethyl benzoyl diphenylphosphine oxide) 4 parts N-methyljetanolamine 2 parts Peroxide (manufactured by NOF Corporation, Barhexa 3M) 1 part Rutile type titanium oxide 100 parts Silica gel (manufactured by Fuji Davison Chemical Co., Ltd., Thyroid 244, average particle size 1.8 μm, oil absorption 310 m1/1
00g) 25 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
This was dried for 30 minutes to obtain an uncured curable sheet.

The thickness of the obtained curable sheet (other than ABS) was 2.
It weighed 0.00 parts.

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 = 17s, ooo, 7μm0)
Average double bond per molecule = 58) 100 parts acrylate monomer (manufactured by Nippon Kayaku Co., Ltd., KAYAR
AD R2O3) 40 parts Photoinitiator (2,4,6-trimethyl benzoyl diphenylphosphine oxide) 4 parts N-methyljetanolamine 2 parts Silica gel (manufactured by Fuji Davison Chemical Co., Ltd., Cyroid 404, average particle size 5,2 μm % Oil absorption amount 200
++1/100g) 45 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 curable sheet. The thickness of the obtained curable sheet (thickness of the part other than ABS) was 150
It was μl.

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・01
Average double bond per molecule = 70) 100 parts acrylate monomer (manufactured by Nippon Kayaku Co., Ltd., KAYAR
AD DPCA-20) 50 parts photoinitiator (2,4,
6,-) 4 parts N-methyl benzoyl diphenylphosphine oxide) 2 parts N-methyljetanolamine 50 parts rutile titanium oxide
0 g) 20 parts and 300 parts or more of ethyl acetate were mixed with stirring.

This mixture was coated on an ABS sheet, dried at 80°C for 5 minutes, and then coated with an ethylene-methyl acrylate film (Chevron Chemical 1PE22s5, Membrane E!20μ).
(m) was laminated with the protective layer) to obtain a curable sheet in an uncured state. The thickness of the obtained curable sheet (the thickness of the portion other than the ABS) was 50 μm for the colored layer + 20 μm for the protective layer.

Example 10 Reactive acrylic resin (copolymer of methyl methacrylate, butyl acrylate, and 2-hydroxylethyl acrylate, M w = 86.000, Tg = 25 °C1OH
Value = 5) 100 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 (Nippon Kayaku Co., Ltd., Kayagyu Ni-EPA)
) Part 2 7 Ricagel (manufactured by Fuji Davison Chemical Co., Ltd.), Thyroid 72, average particle size 25 μm, oil absorption 220a+l/lo.

g) 20 parts isocyanate crosslinking agent (manufactured by Nippon Polyurethane Kogyo Co., Ltd., Furonate L, NC0.13.0%, solid content 75%)
2.2 parts (solid content) (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 to an ABS sheet and dried at 80° C. for 5 minutes to obtain an uncured curable sheet. The thickness of the obtained curable sheet (thickness other than ABS) was 100 μm.

Example 11 Reactive acrylic resin (copolymer of methyl methacrylate, butyl acrylate, and 2-7 minoethyl 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 tomo/mer (manufactured by Nippon Kayaku Co., Ltd., KAYAl
? AD DPCA2'0) 80 parts Photoinitiator (manufactured by Nippon Ciba Geigy Co., Ltd., Irga Gyunia [14) 2 parts N-methyljetanolamine 2 parts Sysoka gel (manufactured by Fuji Wine Chemical Co., Ltd., Cyroid 244, average particle size 1 .8μm, oil absorption j1310ml/
I (10g) 50 parts Ebo beef crosslinking agent (manufactured by Civer Geigy, Araldite CY
175, Epo beef 11160. More than 300 parts of ethyl acetate (with which 80% of the functional groups of the above-mentioned reactive acrylic resin react) having an epoxy value corresponding to the functional group value (220) was mixed with stirring.

This mixture was applied to ABS/-T and dried at 80° C. for 5 minutes to obtain an uncured curable sheet. The thickness of the obtained curable sheet (thickness other than ABS) was 1o.

It was μmaro.

Example 12 Reactive acrylic resin (copolymer of methyl methacrylate, butyl acrylate, and acrylic acid, Mw = 243.0
00, Tg = 10°C, CoOH value = 10) too part agua acrylate monomer manufactured by Honkayaku Co., Ltd., KAYARA
DR604) 40 parts Photoinitiator (2,4,6-trimethyl benzoyl diphenylphosphine oxide) 4 parts N-methyljetanolamine 2 parts Rutile titanium oxide 100 parts Silica gel (manufactured by Fuji Devin Chemical Co., Ltd., Cyroid 244, Average particle size 1.8μm, oil absorption 310m1/10
0g) 4-part isocyanate crosslinking agent (manufactured by Nippon Polyurethane Industries Co., Ltd., Coronate L, NC0.13.0%, solid content 75%)
5.2 parts in 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 with ABS adhesive and dried at 80°C for 5 minutes to obtain an uncured curable sheet. The thickness of the obtained curable sheet (thickness other than ABS) was 80 μm.

Example 13 Reactive acrylic resin (copolymer of methyl methacrylate, butyl acrylate, 2-hydroxylethyl acrylate, and 3-aminopropyl acrylate, Mw = 278,
000. Tg=35℃, OH value=5, NH2 value: 1
0) 100 parts acrylate monomer (manufactured by Nippon Kayaku Co., Ltd., KAYAR
AD R55I) 50 parts Photoinitiator (2,4,6,-trimethyl benzoyl diphenylphosphine oxide) 4 parts N-methyljetanolamine 2 parts Iron oxide 50 parts Silica gel (manufactured by Fuji Davison Chemical Co., Ltd., Thyroid 65, average particle Diameter 3.5μm, oil absorption 95m1/100g
) 45 parts Isocyanate crosslinking agent (manufactured by Nippon Polyurethane Industries Co., Ltd.) Onate L, N CO = 13.0%, solid content 7
5%) solids content: 6.5 parts (this crosslinking agent has 1.0 equivalent I of incyanate groups with respect to the functional groups of the above-mentioned reactive acrylic resin) ethyl acetate 3f) 0 parts or more are mixed with stirring. did.

Coat this mixture on the release surface of the PET film and
After drying at C for 5 minutes, the PET film was peeled off to obtain a curable film in an uncured state.

The thickness of the obtained curable sheet was 50 μm.

Example 14 Reactive acrylic resin (copolymer of methyl methacrylate, butyl acrylate, and 2-hydroxylethyl acrylate, Mw=153,000STg=15°C.

H value = 10) 100 parts acrylate monomer (manufactured by Nippon Kayaku Co., Ltd., KAYAR
AD DPCA-20) 50 parts photoinitiator (2,4,
5,-) Limethyl benzoyl diphenylphosphine oxide) 2 parts N-methyljetanolamine 2 parts Silica gel (manufactured by Fuji Davison Chemical Co., Ltd., Thyroid 65, average particle size 3.5 μm, oil absorption 95 m 1/100
g) 45 parts isocyanate crosslinking agent (manufactured by Nippon Polyurethane Industries Co., Ltd., Coronate L, NC0 = 13.0%, solid content 75%)
5.2 parts (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 coated on the release surface of the P-edition film and 80'C
and dried for 5 minutes. Thickness of the obtained curable sheet (P
The thickness of the sheets other than ET) was 50 μm.

(Clear layer) Reactive acrylic resin (copolymer of methyl methacrylate, butyl acrylate, and 2-hydroxylethyl acrylate, Mw = 653,000. T g = 15°C,
OH value = 10) 100 parts acrylate monomer (manufactured by Shin Nakamura Chemical Co., Ltd., NP
A-10G) 80 parts Photoinitiator (2,4,6-trimethyl benzoyl diphenylphosphine oxide) 4 parts N-methyljetanolamine 2 parts Rutile titanium oxide 100 parts Incyanate crosslinking agent (manufactured by Nippon Polyurethane Kogyo Co., Ltd.) , Coronate L, NC0.13,0%, solid content 75%)
5.2 parts in terms of 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 clear layer, dried at 80'C for 5 minutes, and then the PET film was peeled off to obtain an uncured curable sheet. The thickness of the obtained curable sheet was 50 μm for the clear layer and 50 μm for the colored layer.
Met.

Example 15 Reactive acrylic resin (copolymer of methyl methacrylate, butyl acrylate, 2-hydroxylethyl acrylate, and 3-aminopropyl acrylate, Mw = 78
．． 000, Tg=30'C1OH value=15, N82 value;
10) 100 parts acrylate monomer (manufactured by Nippon Kayaku Co., Ltd., AYAR)
AD DPCA-20) 50 parts photoinitiator (2,4,
6,-Trimethyl benzoyl diphenylphosphine oxide) 4 parts N-methyljetanolamine 2 parts Silica gel (manufactured by Fuji Davison Chemical Co., Ltd., Cyroid 244, average particle size 1.8 μm, oil absorption J1310+II
l/100g) 35 parts isocyanate crosslinking agent (manufactured by Nippon Polyurethane Kogyo Co., Ltd., Coronate L, NC0 = 13.0%, solid content 75%)
28 parts of IO (this crosslinking agent has isocyanate groups equivalent to the functional groups of the above-mentioned reactive acrylic resin) in solid content 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 curable sheet (thickness of the sheet other than ABS) was 100 μm.

Example 16 Reactive acrylic resin (copolymer of methyl methacrylate, butyl acrylate, 2-hydroxylethyl acrylate, and 3-aminopropyl acrylate, Mw = 78,0
00, T g = 30°C, OH value = 15, NH2 value = 1
0>1 (10 parts acrylate monomer (manufactured by Nippon Kayaku Co., Ltd., KAYAR
AD R604) 100 parts Photoinitiator (2,4,6,-trimethyl benzoyl diphenylphosphine oxide) 4 parts N-methyljetanolamine 2 parts Rutile titanium oxide 100 parts Isocyanate crosslinking agent (manufactured by Nippon Polyurethane Kogyo Co., Ltd., Coronate) L, NC0・13.0%, solid content 75%)
10.8 parts in terms of 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 500 μm) and dried at 80″c for 5 minutes. The thickness of the obtained curable sheet (thickness of sheet other than ABS) was 50 μm (colored layer).

Reactive acrylic resin (copolymer of methyl methacrylate, butyl acrylate, 2-hydroxylethyl acrylate, and 3-aminopropyl acrylate, M W = 78
．． 000, Tg=30℃, OH value=15, NH2 value=1
0) 100 parts acrylate mo/mer (manufactured by Nippon Kayaku Co., Ltd., KAYAR
AD DPCA-20) 50 parts photoinitiator (2,4,
6,-)limethyl benzoyl diphenylphosphine oxide) 2m N-methyljetanolamine 2-part silica gel (manufactured by Fuji Johnson Chemical Co., Ltd., Thyroid 244, average particle size 1.8 μm, oil absorption 310 m 171
00g) 35 parts Isocyanate crosslinking agent (manufactured by Nippon Polyurethane Kogyo Co., Ltd.: IO-) L, NCO; 13.0%, solid content 75%) 10.8 parts solids (this crosslinking agent is At least 300 parts of ethyl acetate (having an equivalent amount of incyanate groups to the functional groups of the reactive acrylic resin) 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 curable sheet (the thickness of the sheet other than ABS) is 50 μm for the colored layer + 40 μm for the clear layer.
It was a layer.

Example 17 Reactive acrylic resin (copolymer of methyl methacrylate, butyl acrylate, 2-hydroxylethyl acrylate, acrylic acid, and 3-aminopropyl acrylate, M
w=353,000STg=20°C, OH number=5, C
0OH value: 5, NH2 value = 10) 100 parts acrylate monomer (manufactured by Nippon Kayaku Co., Ltd., KAYARAD R
604) 40 parts Photoinitiator (2,4,6,-)limethyl benzoyl diphenylphosphine oxide) 4 parts N-methyljetanolamine 2 parts Peroxide (manufactured by NOF Corporation, Perhexa 3M) 1 part Rutile Type titanium oxide 100 parts Silica gel (manufactured by Fuji Davison Chemical Co., Ltd., Thyroid 244, average particle size 1.8 μm, oil absorption 1310 m1/1
00g) 35 parts Melamine crosslinking agent (manufactured by Inu Nippon Ink Chemical Co., Ltd., Superbacamine J-820-60) 9.2 parts solids (40% of the functional groups of the above reactive acrylic resin react) Isocyanate Crosslinking agent (manufactured by Nippon Polyurethane Kogyo Co., Ltd., Furonate L, NC0.130%, solid content 75%) 5.2 parts solids (this crosslinking agent is 0.6 parts based on the functional group of the above-mentioned reactive acrylic resin) At least 300 parts of ethyl acetate (having an equivalent amount of isocyanate groups) were mixed with stirring.

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

The thickness of the obtained curable sheet was 200 μm.

Implementation fl118 Reactive acrylic resin (copolymer of methyl methacrylate, butyl acrylate, and acrylic acid, reactive acrylic resin with 2-hydroxyethyl acrylate added, weight average molecular weight = 175.OOO1Tg = 201 Average double bond per molecule = 18, CoOH value = 5) 10
0 parts acrylate monomer (manufactured by Shin Nakamura Chemical Co., Ltd., NP
A-100) 50 parts Photoinitiator (2,4,6,-)limethyl ben'/yl
Diphenylphosphine oxide) 4 parts N-methyljetanolamine 2 parts Silica gel (manufactured by Fuji Davison Chemical Co., Ltd., Thyroid 72, average particle size 2°5 μms, oil absorption 220 m 1710
0g) 30 parts Isocyanate crosslinking agent (manufactured by Nippon Polyurethane Kogyo Co., Ltd.: Io*-) L, N C043.0%,
2.2 parts (solid content 75%) of this crosslinking agent (having isocyanate groups equivalent to the functional groups of the 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 curable sheet. 7 The thickness of the curable sheet asked (thickness other than ABS) is 150 μm
Met.

Example 19 Reactive acrylic resin (reactive acrylic resin obtained by adding 2-hydroquinethyl methacrylate to a copolymer of methyl methacrylate, butyl acrylate, and acrylic acid,
Weight average molecular weight = 258.300, average double bond per molecule = 40, CoOH value = 10) 100
Acrylate monomer (manufactured by Shin-Nakamura Chemical Co., Ltd., NP)
A-10G) 50 parts Photoinitiator (2,4,L-)limethyl benzoyl diphenylphosphine oxide) 4 parts N-methyljetanolamine 2 parts Rutile titanium oxide 50 parts Silica gel (manufactured by Fuji Davison Chemical Co., Ltd., Cyroid 72) , average particle size 2.5μm, oil absorption 220m1/LO
Og) 30 parts Isocyanate crosslinking agent (manufactured by Nippon Polyurethane Kogyo Co., Ltd., Corofu-L, NC0.13.0%, solid content 75%)
5.2 parts in terms of 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 an ABS sheet and dried at 80°C for 5 minutes, and an ethylene-methyl acrylate film (PE2255 manufactured by Chevron Chemical, film thickness 20 μm) was laminated to obtain a curable sheet in an uncured state (protective layer). Ta. Thickness of the obtained curable sheet (thickness other than ABS)
The color layer was 50 μm+the protective layer was 20 μm.

(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. A heating plate 14 with holes for vacuum and compressed air, movable from between both molds 10.12 to the outside, and a resin injection I
! 15.

First, as shown in FIG. 1(b), a sheet 13 is placed between the movable mold 10 and the heating plate 14 (the sheet is made of PE).
For those provided on the T film, after the PET film was peeled off, the sheet 13 was heated, and the sheet 13 was brought into close contact with the inner surface of the recess 10a of the mold 10 by vacuum and/or pressure forming. Next, as shown in FIG. 1(C), the heating plate 1
4 from between the molds 10 and 12 to the outside, and then
The movable mold 10 is moved toward the fixed mold 12 and the molds are closed. Next, ABS resin (manufactured by Denki Kagaku Kogyo 1, ABS-ME) was injected from the resin injection machine 15 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, the molded product was removed from the mold and irradiated with a metal halide lamp under the conditions shown in the table below to cure the photocurable sheet and obtain an injection molded product. Taper abrasion test after curing (taper IKg, C517, 1000 rotations), adhesion by base grain test (number of base grains remaining after tape peeling), and Soft i! ! (sensation) was evaluated.

The results are shown in Tables 1 to 4.

(Comparative example) ABS resin sheet (manufactured by Royal Resin Industry Co., Ltd., AlO2,
500 μm) with soft touch paint (manufactured by Cashew Co., Ltd.)
Cenosoft II) It was coated to a coating thickness of 50 μm and cured by heating at 80″C for 30 minutes.

An injection molding test was conducted using the obtained sheet in the same manner as in the example. Move the sheet to mold 10 (female mold) 16
After vacuum-pressure forming at 0° C. and 180° C., ABS resin was injected, but due to insufficient elongation of the sheet, the sheet could not be molded into the shape of the recess 10a, and cracks appeared in the sheet when the resin was injected.

(Effects of the Invention) The present invention can form a coating on the surface of a molded product at the same time as manufacturing the molded product, so painting, which was conventionally done in a subsequent process, can be omitted, eliminating the need for painting space and eliminating the need for solvents, etc. This has the advantage of eliminating environmental problems. Furthermore, it is possible to form a film on the surface of not only flat objects but also objects with uneven or curved surfaces without any problem, and when irradiated with light, the surface of the object is coated with a suede-like (soft material) with excellent solvent resistance and scratch resistance. It is possible to form a film with a touch feeling). The coating is hard, has excellent scratch resistance and solvent resistance, and has a suede-like appearance, so it can be applied to the decoration of office equipment, home appliance housings, stationery, etc., and these molded products can be easily decorated. It also has the advantage of being inexpensive.

4. Removal of B FIGS. 1(a) to 1(d) are schematic explanatory diagrams showing the method for manufacturing an injection molded article of the present invention.

DESCRIPTION OF SYMBOLS 10... Moving mold, 10a... Recessed part, 12... Fixed mold, 12a... Convex part, 13.../-t, 14.
...Heating plate, 15...Resin injection machine.

that's all

Claims (1)

[Claims] 1. An uncured or semi-cured photocurable sheet formed from a photocurable resin composition containing a porous inorganic material,
A step of attaching the material to the inner surface of the recess of the mold by vacuum and/or pressure forming, a step of tightening the mold and injecting molding resin into the recess of the mold to create a covering, and irradiating the covering with light. A method for producing an injection molded article, comprising the step of curing the photocurable sheet by: