JPH04201217A - Manufacture of injection-molded product - Google Patents

Abstract

PURPOSE:To form a film having soft touch feeling even to the surface of an article having irregularities and a curved surface by sticking a thermo-setting sheet under an uncured or half-cured state onto the inner surface of the recessed section of a mold, injection-molding the sheet and heating the sheet. CONSTITUTION:A thermo-setting sheet under an uncured or half-cured state mainly comprises a reactive acrylic resin having weight average molecular weight of 20000-1000000, block isocyanate and elastic beads as a composition. The sheet of at least the sticking section of an article, on which the sheet is stuck through a method, in which the sheet is fast stuck on the inner surface of the recessed section of a mold by a vacuum or pressure forming and a resin for injection molding is injected into the recessed section, etc., or sheet insert injection molding, is heated, thus curing the sheet. The thermo-setting sheet under the uncured or half-cured state can be stuck easily even in deep draw forming because it has excellent stretchability before curing, the sheet is rigid and has superior solvent resistance, durability, etc., because elastic beads are included, and a film having soft touch feeling can be formed.

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 soft-touch (suede-like) coating with excellent scratch resistance and the like.

(Prior art) Paints with a soft touch feel (suede look) are generally used to add a soft touch feel (suede look) to injection molded products such as housings for OA equipment, home appliances, stationery, etc. and increase added value. has been used. 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, if you try to attach the sheet to the surface of an article that has unevenness or a curved surface, the sheet cannot be stretched sufficiently, so it is impossible to easily impart a suede feel, especially to deep-drawn molded products. there were.

The present invention is intended to solve the above-mentioned drawbacks, and its purpose is to form a film that can be applied without any problem even to the surface of an article having an uneven or curved surface, and that has a soft touch feeling. An object of the present invention is to provide a method for manufacturing injection molded products. (Means for Solving the Problems) The method for producing an injection molded article of the present invention is to place an uncured or semi-cured thermosetting sheet made of a thermosetting resin composition containing elastic beads into a mold. A step of attaching the molding resin to the inner surface of the recess by vacuum and/or pressure forming, a step of tightening the mold and injection molding the molding resin into the recess of the mold, and a step of curing the resin by heating during and/or after molding. The method includes a step of curing the adhesive sheet, thereby achieving the above object.

The thermosetting sheet of the present invention is formed from an uncured or semi-cured thermosetting resin composition containing elastic beads, and the composition of the thermosetting sheet is as follows.

(2) A thermosetting sheet in an uncured or semi-cured state whose main components are a reactive acrylic resin with a weight average molecular weight of 20,000 to 1,000.000, blocked isocyanate, and elastic beads.

■The main components are a reactive acrylic resin with a weight average molecular weight of 20.000 to 1.000.000, blocked isocyanate, at least one crosslinking agent consisting of unblocked incyanate, melamine, and epoxy, and elastic beads. A thermosetting sheet in a semi-cured state.

The above-mentioned reactive acrylic resin is an acrylic resin having functional groups such as a hydroxyl group, an amino group, and a carboxyl group. For example, (meth)acrylic acid ester monomers having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate; 2-aminoethyl (meth)acrylate and 3-aminopropyl ( (meth)acrylic acid ester monomers having 7 amino groups such as meth)acrylate;
A monomer material selected from (meth)acrylic acid having a carboxyl group such as acrylic acid; generally, other (meth)acrylic acid esters, styrene derivative monomers, maleic acid monomers, etc. are combined with various peroxides or It is obtained by polymerization using a chain transfer agent or the like as a catalyst.

The reactive acrylic resin preferably has a weight average molecular weight (Mw) of 20.000 to L, 000,000, more preferably 100.000 to aoo, o.
It is oo.

If the weight average molecular weight is less than 20,000, the thermosetting sheet will not have sufficient elongation when applied to, for example, a molded article, and cracks may occur. If the weight average molecular weight of the reactive acrylic resin exceeds 1,00o or ooo, it becomes difficult to dissolve in a solvent (and the viscosity of the solution when dissolved is too high, making it difficult to create a sheet from a thermosetting 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 reactive acrylic resins preferably have a Tg (glass transition point) within the range of -20 to 80°C, in view of the relationship between the hardness after sheet curing and the soft touch feel (suede feel).

If the Tg is below 120'C, the coating film obtained after curing will have poor scratch resistance and will be easily scratched.

Different types of reactive acrylic resins may be combined as long as they fall within these molecular weight ranges. In addition, the functional group values of these reactive acrylic resins (usually OH group value and NH2
Base value (the amount of NH2 group added during NH2 polymerization
Calculation similar to the value, or quantitatively determined by reacting NH2 group with nitrous acid and converting it to OH group) and C0OH group value (COO
H value: The amount of C0OH groups added during polymerization is calculated in the same way as the OH value, or the value obtained by titrating the C0OH groups with KOH)) The total value is preferably in the range of 20 to 200. If the functional group value is below the above range, excellent solvent resistance and scratch resistance cannot be obtained. However, if there is no need for moderate solvent resistance or scratch resistance, it can be applied even outside these ranges.

These reactive 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, materials that can be used as blocks with these reactive acrylic resins include not only acrylic-based materials but also materials that are compatible with styrene-based, maleic acid-based, and imide-based acrylic resins, as well as silicone-based and fluorine-based materials. You can combine it with any material that can be made into blocks. In this case, there are 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 above-mentioned blocked isocyanate blocks (masks) the isocyanate groups of monomers or modified products such as isocyanates having two or more incyanate groups in the molecule, such as tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and inphorone diisocyanate. ). In addition to phenols, block components include oximes, lactams, malonic acid esters, and the like.

This blocked isocyanate is one in which the block is removed by heating and the isocyanate group becomes active, and acts as a curing agent for the above-mentioned reactive acrylic resin. The blending ratio of blocked isocyanate and reactive acrylic resin is usually determined by the total number of functional groups in the reactive acrylic resin (
Total functional group value)/Number of isocyanate groups (NC0 value) =
0.5-2.0, preferably 0.8-1.
Make it 2.

The unblocked isocyanate is an isocyanate compound having two or more incyanate groups in the molecule. For example, tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, toridine diisocyanate, triphenylmethane triisocyanate, tris(isocyanate phenyl) thiophosphite, p-phenyl diisocyanate, xylylene diisocyanate, bis(incyanate methyl)cyclo Monomers such as beef san, dicyclohexylmethane diisocyanate, hexyl methylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, or trimethylolpropane adducts of these monomers, incyanurate modification There are various types of polyamides, such as biuret modified products, carbodiimide modified products, urethane modified products, allophanate modified products, etc. The amount of incyanate added varies depending on the sheet molding method, but the NCO is the functional value of the reactive acrylic resin, and the functional value: NC0 = 1: 0.0
It is about 1 to 0.3.

In the thermosetting sheet mentioned above, the melamine crosslinking agent includes melamine, urea, thiourea, guanidine, guanamine, acetoguanamine, benzoguanamine,
Trimethylolmelamine, hexamethylolmelamine, which is obtained by reacting formaldehyde with a material having polyfunctional amino groups such as dicyandiamide and guanamine;
There are etherified melamine resins reacted with alcohols such as phthyl alcohol and propyl alcohol, such as dimethylol urea, dimethylol guanidine, dimethylol acetoguanamine, and dimethylol benzoguanamine. The amount of these melamine-based crosslinking agents to be added is difficult to determine based on the functional group value of the reactive acrylic resin, such as incyanate. It is preferable to decide. The amount of the melamine crosslinking agent added is determined based on the functional value of the reactive acrylic resin: 0R (z-thyl value) = l: 0.1 to 0.
About 3 is preferable.

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.

This Lewis acid is preferably one that is microencapsulated in order to delay the reaction. For example, butadiene dioxide, hexazine dioxide, diglycidyl ester of phthalic acid, diglycidyl ether of bisphenol-A, diglycidyl ether of bisphenol-F, triglycidyl ether amine of paraaminophenol, diglycidyl ether of aniline, phenylene Glycidyl compounds such as tetraglycidyl ether of diamine, diglycidyl ether of sulfonamide, triglycidyl ether of glycerin, polyether-modified diglycidyl, polyester-modified diglycidyl, urethane-modified diglycidyl compound (polymer), vinylcyclohexene dioxide, dicyclopentadiene Dioxide etc. The amount of this epoxy crosslinking agent added is based on the functional group value of the reactive acrylic resin: CH2CH2O(
Epoxy group) =l: preferably about 0.01 to 0.2. In addition, since this epoxy crosslinking agent reacts with functional groups to generate OH groups, the amount of pro-tsukiisocyanate added at the same time is between 3 to 30% of the remaining functional groups of the reactive acrylic resin and the generated OH groups. It is preferable to add about 80%.

Regarding the amount of these crosslinking agents added, the amounts described above are preferred, but in reality, depending on the reactivity with the reactive acrylic resin used, the functional groups of the reactive acrylic resin and the crosslinking agent may interact with each other, for example, melamine-based crosslinking agents may interact with each other. Since a reaction occurs between the crosslinking agent and the epoxy crosslinking agent, it is preferable to conduct a preliminary experiment before making a decision.

Furthermore, when adding an unblocked incyanate, melamine, or epoxy crosslinking agent, it is necessary to reduce the amount of the blocked isocyanate added so that the amount of crosslinking agent in the entire resin sheet does not increase. The ratio is calculated from the above-mentioned functional group value: the functional group of the crosslinking agent.

The above-mentioned 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, polystyrene, styrene-isoprene copolymers, polyvinylidene chloride, and copolymers of vinylidene chloride and other monomers. It is preferable to add 20 to 400 parts by weight of elastic beads having a particle size distribution maximum of 1 to 50 .mu.m to 100 parts by weight of the resin. The particle size of elastic beads is 1μm
below, the resulting sheet has a sufficient soft touch feel (
If the particle size exceeds 50 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, and if the amount added is too large,
Cracks tend to occur on the surface of the sheet when it is stretched. The number of elastic beads is not limited to one type, and two or more types may be used in combination.

For example, the following methods can be used to produce the thermosetting sheets of (1) and (2) above. The above-mentioned materials of the thermosetting resin composition are thoroughly dissolved and stirred in an organic solvent, etc., and the resulting solution is cast using a casting method such as a knife coater, a comma footer, or a bar coater to coat process paper (usually PET treated with silicone release treatment). : Polyethylene terephthalate, paper, etc.) is coated and dried to remove the solvent to form a base layer (resin layer). A sheet is then obtained by peeling the process paper from the base layer.

Further examples of thermosetting sheets used in the present invention include those shown in the following (1) to (0).

■Reactive vinyl materials such as reactive vinyl monomers and/or oligomers having functional groups, a photopolymerization initiator, at least one endogenous crosslinking agent consisting of (block) incyanate, melamine, and epoxy, and elastic beads. A thermosetting sheet in an uncured or semi-cured state. Such a sheet can be obtained by casting the above material and then irradiating it with light.

■In addition to the resin composition of ■ above, thermoplastic resin and/or
Or a thermosetting sheet obtained by containing a reactive resin.

Examples of this reactive vinyl material include (meth)acrylic materials, styrene materials, and materials having vinyl groups such as vinyl acetate. For example, (meth)acrylics include methyl (meth)acrylate, ethyl (meth)acrylate,
Benzyl (meth)acrylate, 2-ethoxyethyl (
meth)acrylate, phenoxydielene glycol (
From monofunctional types such as meth)acrylate to 1,6-hexadiol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glyfur di(meth)acrylate, polybrobylene glycol di(meth)acrylate, and trimethylpropane. bird
Multifunctional types such as (meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate are applicable. In the styrene series, styrene, α-methylstyrene, α-ethylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-ethoxystyrene, p-
Various styrene derivatives such as -chlorostyrene, -chlorostyrene, and 0-chlorostyrene can be used.

As the photopolymerization initiator, commonly used ones can be used.
For example, photopolymerization initiators such as benzoin alkyl ether, acetophenone, benzophenone, thioxanthone, and acylphosphine oxide are preferably used. Benzoin ethers include Ha, Hensyl, benzoin, benzine methyl ether, benzoin ethyl ether, and benzoin propyl ether. Acetophenone series include 2.2-jetoxyacetophenone, 2-
Hydroxy-2-methylpropiophenone, p-ter
-butyltrichloroacetophenone, etc. Examples of benzphenones include benzophenone, 4-chlorobenzophenone, 4,4-dichlorobenzophenone, 3,3°-dimethyl-4-methoxybenzophenone, and dibenzosuberenone. Among the thioxanthone types, thioxanthone,
Examples include 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, and 2-ethylanthraquinone. Examples of acylphosphine oxides include jetoxyphosphine oxide and 2.4.6
-) Limethylbenzoyldiphenylphosphine oxide, etc.

Although the appropriate amount of the photopolymerization initiator to be added differs depending on each material, it is preferably within the range of 0.5 to 5.0 parts by weight per 100 parts by weight of the reactive vinyl monomer.

Further, the number of photopolymerization initiators is not limited to one type, and two or more types may be used in combination.

The materials mentioned above are used as the isocyanate, melamine, and epoxy crosslinking agents, and the amount of the crosslinking agent is determined based on the amount of functional groups (functional group value).
and OR (ether value) and CHCHO (epoxy group) = 1: preferably about 0.8 to 1.5.

Moreover, the thermoplastic resin added to these is a material that dissolves in a part of the reactive vinyl monomer and has good compatibility with other reactive vinyl monomers. For example, polyacrylic acid ester, polystyrene-based materials, etc. are usually used, such as polymethyl methacrylate, polymethyl methacrylate copolymer, polystyrene, polyvinyl acetate, polyvinyl chloride, and the like. The amount of the thermoplastic resin added is preferably about 5 to 2 l:o with respect to the reactive vinyl monomer.

The curable sheets described in (1) and (2) above are created by coating these materials on processing paper (usually PET (polyethylene terephthalate, paper, etc. that has been released with silicone) using a casting method such as a knife coater, comma coater, or reverse coater. The coating is applied using a footing, and then irradiated with light using a high-pressure mercury lamp, metal halide lamp, or xenon lamp.

A thermosetting sheet in an uncured or semi-cured state, the main components of which are a zero-reactive vinyl monomer and/or oligomer, a thermoplastic resin and/or a vinyl group-containing polymer, a peroxide, and elastic beads.

As the reactive vinyl monomer used here, the same reactive monomers as those described above can be used.

The same applies to thermoplastic resins.

Any known organic peroxide type peroxide can be used. Preferably, from the viewpoint of storage stability at room temperature, for example, 2,2-bis(ter-butylperoxy)phthane, ter-phthyl peroxybenzoate, di-ter
-Butyl peroxyisophthalate, methyl ethyl ketone peroxide, dicumyl peroxide, dite
r-Butyl peroxide, cyclohexane peroxide, cumene I\idoronomer oxide, benzoyl peroxide, 1<-hexaperoxide, ter
-butyl/<-oxyacetate, ter-butylperoxyisobutyrate, ter-butylperoxyisobutyrate, 3.5.5-trimethylhexanoate, and various other compounds can be used. The appropriate amount of peroxide to be added varies depending on the materials used, but it is preferably within the range of 0.5 to 4.0 parts by weight based on 100 parts of the reactive vinyl monomer. Moreover, the peroxide is not limited to one type, but can be used in combination of two or three types.

In order to manufacture this thermosetting sheet, each of the above materials is thoroughly dissolved and stirred in an organic solvent etc. in the same way as in the above
It is produced by coating on processing paper (usually PET (polyethylene terephthalate, paper, etc. that has been released with silicone) using a casting method such as a knife coater, commafuta, or reverse coater, and then drying it to remove the solvent.

■ A thermosetting sheet in a semi-cured state whose main components are a reactive silicone resin having a weight average molecular weight of 20.000 to 3,000.000 and having multiple hydroxyl groups, 7 amino groups, and carboxyl groups, blocked isocyanate, and elastic beads. .

■Weight average molecule 1) At least one of a reactive silicone resin having a plurality of hydroxyl groups, amine groups, and carboxyl groups of O, ooo to 3.000.000, a block isocyanate, and a crosslinking agent consisting of incyanate, melamine, and epoxy. A semi-cured thermosetting sheet whose main components are seeds and elastic beads.

■Thermosetting in an uncured or semi-cured state mainly consisting of a reactive fluororesin having multiple hydroxyl groups, amino groups, and carboxyl groups with a weight average molecular weight of 20.000 to 1,000.000, blocked isocyanate, and elastic beads. sex sheet.

■At least one type of crosslinking agent consisting of a reactive fluororesin having a weight average molecular weight of 20.000 to 1.000.000 and a plurality of hydroxyl groups, amine 7 groups, and carboxyl groups, blocked isocyanate, incyanate, melamine, and epoxy. A thermosetting sheet in a semi-cured state whose main components are: and elastic beads.

0 Reactive polyester resin having a plurality of hydroxyl groups, amine 7 groups, and carboxyl groups with a weight average molecular weight of 10.000 to 2.000.000, blocked isocyanate, and elasticity □
A thermosetting sheet in an uncured or semi-cured state whose main component is beads.

■At least one cross-linking agent consisting of a reactive polyester resin having a plurality of hydroxyl groups, amino groups, and carboxyl groups with a weight average molecular weight of 10,000 to 2.000.000, blocked isocyanate, incyanate, melamine, and epoxy. A thermosetting sheet in a semi-cured state whose main components are: and elastic beads.

For these materials ① to 0, the main chain is silicone-based, for example, siloxane polymer, etc., and fluorine-based, for example, alternating polyethylene and trifluoroethylene, polyethylene and difluoroethylene, etc. Copolymers, etc.; polyester-based materials, such as saturated ether type of terephthalic acid and ethylene glycol-based materials, unsaturated type of terephthalic acid and butadiene, etc., with hydroxyl groups, amino groups, and carboxyl groups in the side chains of various materials. This has been introduced.

The relationship between each functional group value and the crosslinking agent is the same as in the above items ① and ②.

Further, the thermosetting sheet obtained in steps 1 to 0 above may contain colorants such as pigments and dyes. As the coloring agent, pigments, dyes, etc. used in ordinary painting can be used. for example,
Examples of pigments include titanium oxide, iron oxide, carbon black, and cyanine pigments; examples of dyes include azo dyes, anthraquinone dyes, indigoid dyes, and stilbene dyes.

Metal powders such as aluminum flakes, nickel powder, gold powder, and silver powder may also be used. Regarding the amount of colorant, when obtaining a thermosetting sheet with high hiding properties, the total amount of colorant is 2 to 40 parts per 100 parts of solid content of the sheet material.
A range of 0 parts is preferred. Furthermore, the thermosetting sheet has
A reaction control catalyst, an inorganic filler, a metal material, an anti-aging agent, a rust preventive agent, etc. may be included for surface control, high functionality, etc.

[Form of thermosetting sheet]

A thermosetting resin composition is obtained by kneading the above-mentioned materials.

A base layer (resin layer) is created from the resin composition, and when the thermosetting sheet is a single layer, this base layer becomes the thermosetting 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, for example, there are 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 (and 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),
Examples include modified bophenylene oxide, polyphenylene sulfide, polyetherimide, polyether ether ketone, and polyethylene sulfide.

(2) A sheet comprising 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, inbrene 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 adherend immediately after the sheet is attached to the adherend, and then the sheet may be cured, and the sheet may be attached to the adherend and then cured before using these adherends. It may also be used as a protective layer in between. By adding embossing or patterns to the surface of the protective layer, the surface shape (appearance) of the sheet can be changed.

■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 thermosetting resin composition used for the base layer. In this case, the colored layer may not contain elastic beads.

■A sheet in which printing is applied to the front or back surface of the base layer of the thermosetting 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 thermosetting sheet obtained in steps ① to ① above is 20 to 00 L when it is applied to an uneven adherend surface.
Approximately 0μ is preferable, and when pasting on a flat surface, it is 10~
It may be about 500 μm. Further, the thickness of 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.

[Adjustment of thermosetting sheet]

The thermosetting sheet used in the present invention may be prepared in any manner. When the sheet is a single layer, the following casting method is preferred.

The thermosetting resin composition is sufficiently dissolved or dispersed in an organic solvent. The resulting solution is coated onto processing paper (usually a polyethylene terephthalate film or paper paper whose surface has been treated with silicone) using equipment such as a knife coater, humma coater or reverse footer, and then dried to remove the solvent. to form a 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 processing 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, by heating at least the part of the article to which the sheet is attached (by irradiating light if necessary), the sheet is cured to obtain an injection molded article. To heat the sheet, the sheet may be cured by heat molding and/or the heat of the injected resin during the above-mentioned molding, or the sheet may be cured by heating after molding. Good too.

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) The uncured or semi-cured thermosetting sheet used in the present invention has excellent stretchability before curing, so it can be easily applied during deep drawing by stretching the sheet. can. Since this sheet is thermosetting and contains elastic beads, by heating an article coated with the sheet, it becomes hard, has excellent solvent resistance, durability, etc., and has a soft touch feeling ( It is possible to form a coating having a suede-like appearance.

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

(A) Preparation of thermosetting sheet 1. Reactive acrylic resin (copolymer of methyl methacrylate and butyl methacrylate, copolymer of methacrylic acid and 2-aminoethyl acrylate, Mw=
55,000.7g 35℃, CooH value 20 and NH2H
Solid content of 2O4 is 100 parts ζ, blocked isocyanate (manufactured by Takeda Pharmaceutical Co., Ltd., Takenate (This crosslinking agent has 1.0 equivalent of isocyanate groups with respect to the functional groups of the above-mentioned reactive acrylic resin)
, elastic beads (manufactured by Nippon Shokubai Chemical Co., Ltd., EBSlo
o, acrylic-urethane beads, average particle size 13μ■)2
00 parts were mixed with thorough stirring. This mixture was applied with an applicator to the release surface of a silicone release-treated polyethylene terephthalate film (hereinafter referred to as PET film) and dried at 70° C. for 10 minutes to form a thermosetting resin layer.

The thickness of the sheet was 50 μm.

2. To 300 parts of ethyl acetate, add reactive acrylic resin (copolymer of methyl methacrylate and butyl acrylate, 2-hydroxyethyl methacrylate and ethyl acrylate,
Mw=250,000.7g15℃, OH number 40 and Co
OH value 40) to 100 parts solid content, blocked isocyanate (Takenate B-815N, hydrogenated bulk phenylene diisocyanate ketoxime block NGO = 7.3%, solid content 60%) solid content 59
1 part (this crosslinking agent has 1.2 equivalents of incyanate groups with respect to the functional group of the above-mentioned reactive acrylic resin), 2 parts of dibutyltintaurylate, elastic beads (manufactured by Nippon Shokubai Chemical Co., Ltd., EBSloo) 200 parts were mixed with thorough stirring. This mixture was applied to an ABS sheet (manufactured by Royal Resin Industry ■, A205, film thickness 500 μm) using an applicator and dried at 70° C. for 30 minutes to form a thermosetting resin layer.

The thickness of the sheet was 600 μm (including ABS).

3. To 300 parts of ethyl acetate, add reactive acrylic resin (copolymer of methyl methacrylate and butyl acrylate, 2-hydroxyethyl methacrylate and 4-aminobutyl methacrylate, Mw = 368°000.7g 10°C , O
Block acrylic polycarboxylic acid (copolymer of stearyl methacrylate and methacrylic acid, Mw = 55,000, T
g20°C1 acid value 20) 10 parts solids, blocked isocyanate (manufactured by Nippon Polyurethane Industries ■, Coronate 2)
513, ethyl acetoacetate block of isocyanurate of hexamethylene diisocyanate, NC0 = 10.2
%, solid content 80%) 47 parts (this crosslinking agent has 1.0 equivalent of isocyanate groups with respect to the functional group of the above-mentioned reactive acrylic resin), elastic beads (Nippon Shokubai Chemical Co., Ltd.)
100 parts of EBS300, acrylic-urethane beads, average particle size: 28 μm (manufactured by M. Co., Ltd.) were mixed with thorough stirring. This mixture was made of ABS sheet (manufactured by Royal Resin Industry, A205).
, film thickness 500 μm) using an applicator and heated at 70°C.
The mixture was dried for 15 minutes to form a thermosetting resin layer.

The thickness of the sheet was 600 μm (including the ABS sheet).

4. Add reactive acrylic resins (methyl methacrylate, butyl acrylate, 2-hydroxyethyl methacrylate, acrylic acid, and 4 methacrylic acid to 300 parts of ethyl acetate).
- Copolymer with aminoethyl, Mw=360,000.
7g35℃, OHH2O2CoOH value 20 and NH2H2
O4 to 100 parts of solid content, 59 parts of blocked isocyanate (Takenate B-815N, manufactured by Takeda Pharmaceutical Co., Ltd.) (this crosslinking agent has a
゜2 equivalents of incyanate groups), elastic beads (
250 parts of EBS300 (manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd.) were mixed with thorough stirring. This mixture was applied to the release surface of the PET film using an applicator and heated to 80℃ for 5 minutes.
After drying for 1 minute, an initial curing treatment was performed at 160° C. for 2 minutes to prepare a thermosetting sheet.

The initial curing of this thermosetting sheet was determined by infrared absorption analysis (I
From the quantitative determination of R), etc., 10% of the total functional groups were initially cured. The thickness of the sheet was 50 μm.

5. Reactive acrylic resin (copolymer of methyl methacrylate and butyl acrylate, methacrylic acid and 3-aminopropyl acrylate, Mw=
621,000.7g10℃, CoOH value 40 and NH2
40) to 100 parts of solid content, 59 parts of blocked isocyanate (Takenate B-815N, manufactured by Takeda Pharmaceutical Co., Ltd.) (
This cross-linking agent is used for the functional groups of the above-mentioned reactive acrylic resin.
1.2 equivalents of incyanate groups), 100 parts of titanium oxide, elastic beads (manufactured by Nippon Shokubai Chemical Co., Ltd., E
BS300) 100 parts were mixed with thorough stirring.

This mixture was applied to the release surface of the PET film using an applicator and dried at 80° C. for 5 minutes to form a thermosetting resin layer. The thickness of the sheet was 100 μm.

6. To 300 parts of ethyl acetate, add reactive acrylic resin (copolymer of methyl methacrylate and butyl methacrylate, methacrylic acid and 2-aminoethyl acrylate, Mw=
492,000.7g 35℃, C00H value 40 and NH2
Value 40) Solid content 100 parts D.

Blocked isocyanate (manufactured by Takeda Pharmaceutical Co., Ltd., Takenate B-87ON, oxime block of isophorone diisocyanate keto, NC0 = 12.6%, solid content 60%
) 23 parts (this crosslinking agent has 0.8 equivalents of incyanate groups with respect to the functional groups of the above-mentioned reactive acrylic resin)
, epoxy crosslinking agent (manufactured by Chiha Kaigy, Araldite C
Y175, z poxy equivalent 160, epoxy value corresponding to functional group value 220) 4.9 parts (10% of the functional groups of the reactive acrylic resin are initially cured), elastic beads (manufactured by Nippon Shokubai Chemical Co., Ltd.) , EBS300) were mixed with thorough stirring. This mixture was applied to an ABS sheet (manufactured by Royal Resin Industry ■, A205, film thickness 500 μm) using an applicator and dried at 80° C. for 5 minutes to form a thermosetting resin layer. The thickness of the sheet was 580 μm (including ABS).

7. To 300 parts of ethyl acetate, add a reactive acrylic resin (copolymer of methyl methacrylate and butyl acrylate, 2-hydroxyethyl methacrylate and acrylic acid, Mw 90,000, Tg 15°C, OH value 40, CoOH value 4
0) To 100 parts of solid content, 59 parts of blocked isocyanate (Takenate B-815N, manufactured by Takeda Pharmaceutical Co., Ltd.) (this crosslinking agent has 1.
2 equivalents of isocyanate groups) and isocyanate (manufactured by Nippon Polyurethane Industry ■, Coronate L, NC0
= 12.0) in solid content (30% of the functional groups of the reactive acrylic resin are initially cured) and 100 parts of elastic beads (manufactured by Nippon Shokubai Chemical Co., Ltd., EBS300) were mixed with thorough stirring. . This mixture was applied to an ABS sheet (manufactured by Royal Resin Industry ■, A205, film thickness 500 μm) using an applicator and dried at 80° C. for 5 minutes to form a thermosetting resin layer. The thickness of the sheet was 600 μm (including ABS).

8. To 300 parts of ethyl acetate, add reactive acrylic resin (copolymerization of methyl methacrylate and butyl acrylate, 2-hydroxyethyl methacrylate and 4-aminobutyl methacrylate L Mw = 368°000.7g at 10°C,
OH value 40 and NH2 value 40) to 100 parts solid content, block copolymer reactive acrylic resin (copolymer of methyl methacrylate and 2-hydro half diethyl methacrylate,
Mw = 36.000, Tg 40°C, OH number 40) 10 parts solid content, 40 parts blocked isocyanate (Coronate 2513, manufactured by Nippon Polyurethane Industries) (this crosslinking agent combines the above reactive acrylic resin and block reactive acrylic resin). (having 1.0 equivalent of incyanate group with respect to the functional group of
polyisocyanate (NC0 = 12.0%, solid content 75%), which was prepared by coronating and reacting 3 mol of tolylene diisocyanate and 1 mol of trimethylolpropane.
Solid content: 2.4 parts (10% of the total functional groups of the above reactive acrylic resin and block reactive acrylic resin are initially cured), elastic beads (manufactured by Nippon Shokubai Chemical Co., Ltd., EBS)
loo) 200 parts were mixed with thorough stirring. This mixture was applied to the release surface of the PET film using an applicator and dried at 70° C. for 10 minutes to form a thermosetting resin layer. The thickness of the sort was 60 μm.

9. Add reactive acrylic resins (methyl methacrylate, butyl acrylate, 2-hydroxyethyl methacrylate, acrylic acid, and 4 methacrylic acids to 300 parts of ethyl acetate).
-copolymer with aminoethyl, Mw=480,000,
7g35℃, OHH2O2C00H value 20 and NH2H2
To 100 parts of O4 solid content, 39 parts of blocked isocyanate (Takenate B-815N, manufactured by Takeda Pharmaceutical Co., Ltd.) (this crosslinking agent has a 0.
8 equivalents of incyanate groups) and a melamine crosslinking agent (Dainippon Ink Chemical Co., Ltd., Super Beckamin (Bulrinated Melamine Resin) J-820-60) solids content of 4.6 parts (functionality of reactive acrylic resin). 5% of the group is initially cured
l), elastic beads (manufactured by Nippon Shokubai Chemical Co., Ltd., EBS
loo) 200 parts were mixed with thorough stirring. This mixture was applied to the release surface of the PET film using an applicator and dried at 80° C. for 5 minutes to form a thermosetting resin layer. Thereafter, a polyethylene sheet (50 μm) was heat laminated. The thickness of the thermosetting sheet was 60 μm.

10. Reactive acrylic resin (copolymer of methyl methacrylate and butyl acrylate, methacrylic acid and 3-aminopropyl acrylate, Mw
=621,000S 7g10℃, CoOH value 40 and N
Acrylic polycarboxylic acid oligomer (copolymer of ethyl acrylate and acrylic acid, Mw = 25.000, Tg-30°C, CoO
H number 100) solid content 20 parts, block isocyanate (Nippon Polyurethane Kogyo ■, Coronae) 2513) solid content 58 parts (this crosslinking agent is a carboxyl compound of the functional group of the above-mentioned reactive acrylic resin and the acrylic polycarboxylic acid oligomer) 1.0 equivalent of isocyanate group) and incyanate (manufactured by Nippon Polyurethane Industry ■,
Coronate L) Solid content: 4.4 parts (10% of the functional groups of the reactive acrylic resin and the carboxyl groups of the acrylic polycarboxylic acid oligomer are initially cured) 50 parts of phthalocyanine blue, elastic beads (Nippon Shokubai Chemical Co., Ltd. ) made,
EBSloo) 200 parts were mixed with three rolls while thoroughly kneading. This mixture was applied to the release surface of the PET film and dried at 70° C. for 10 minutes to form a thermosetting resin layer. The thickness of the sheet was 80 μmt'.

11. 70 parts of methyl methacrylate and 15 parts of balanonylphenoxydiethylene glycol acrylate, 2
-Hydroxyethyl acrylate 15 parts, 2, 4.
6-) 2.8 parts of limethylbenzoyl diphenylphosphine oxide and 34 parts of blocked isocyanate (manufactured by Nippon Polyurethane Kogyo Co., Ltd., Coronate 2513, solid content 100%, NGO = 12.8%) (total functional groups) 1 equivalent of incyanate), elastic beads (manufactured by Nippon Shokubai Chemical Co., Ltd., EBSloo) 20
0 parts was stirred well. This mixture was coated on an ABS sheet (manufactured by Royal Resin Industry ■, A205, film thickness 500 μm),
A thermosetting resin layer was created by irradiating with a metal halide lamp (100 W/cm) for 20 seconds. The thickness of the sheet is 600
μm (including ABS sheets).

12. 70 parts of methyl methacrylate, 15 parts of paranonylphenoxydiethylene glycol acrylate, 15 parts of 2-hydroxyethyl acrylate, 2, 4. 6-
2.8 parts of dolimethylbenzoyldiphenylphosphinol and 31 parts of isocyanate (manufactured by Takeda Pharmaceutical Co., Ltd., Takenate D 170 N, incyanurate of hexamethylene diisocyanate = 20.8%) (total functional groups) 1.2 equivalents of incyanate), elastic beads (manufactured by Nippon Shokubai Chemical Co., Ltd., EBS
150 parts of the solution were stirred well. Add this mixture to ABS
Sheet (manufactured by Royal Resin Industry ■, A205, film thickness 500um
) and metal halide lamp (100W/(1)
) for 20 seconds to create a thermosetting resin layer. The thickness of the sheet was 600 μm (including the ABS sheet).

13. 70 parts of methyl methacrylate and 15 parts of lanonyl phenoxydiethylene glycol acrylate, 2-
15 parts of hydroquine ethyl acrylate, 2, 4. 6
-2.8 parts of dolimethylbenzoyldiphenylphosphine oxide and 26 parts (total) of incyanate (manufactured by Takeda Pharmaceutical Company Ltd., Takenate D 170 N, incyanurate NGO of hexamethylene diisocyanate = 20.8%) (total) 1 equivalent of incyanate)
, 0.01 part of dibutyltinwaurilate, elastic beads (
200 parts of EBSLOO (manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd.) were thoroughly stirred. This mixture was applied to an ABS sheet (manufactured by Royal Resin Industry ■, A205, film thickness 500 μm) using an applicator and irradiated with a metal halide lamp (100 W/cm) for 20 seconds to create a thermosetting resin layer.

The thickness of the sheet was 600 μm (including the ABS sheet).

14. 70 parts of methyl acrylate, 15 parts of lanonylphenoquine diethylene glycol acrylate, 2-hydroxyethyl acrylate is iL 2°4.6
- 2.8 parts of dolimethylbenzoyl diphenylphosphine oxide and melamine crosslinking agent (Dainippon Ink Chemical Co., Ltd., Super Beckamine (butylated, melamine resin) J-8
20-60 (100% solids)) (150 parts of J-shaped elastic beads (manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd., EBSLOO) that will eventually fully react and harden) were thoroughly stirred. This mixture was mixed with an ABS sheet (Royal Resin Coated on a metal halide lamp (100 μm) manufactured by Kogyo ■, A205, film thickness 500 μm.
W/cm) for 20 seconds to create a thermosetting resin layer.

The thickness of the sheet was 600 μm (including the ABS sheet).

15. 70 parts of methyl acrylate, 15 parts of balanonylphenoxydiethylene glycol acrylate, 2.8 parts of 2-hydroxyethyl acrylate 15L2゜4.6-)limethylbenzoyl diphenylphosphine oxide, and an epoxy crosslinking agent (manufactured by Civer Geigy, Araldite CY)
175. Epoxy equivalent: 160, epoxy value corresponding to functional group value: 220) Based on 52 parts of total functional groups,
1 equivalent of epoxy) and 200 parts of elastic beads (manufactured by Nippon Shokubai Chemical Co., Ltd., EBSloo) were thoroughly stirred.

This mixture was applied to the release surface of the PET film and irradiated with a metal halide lamp (100W/c+n) for 20 seconds to create a thermosetting resin layer. The thickness of the sheet was 80 μm.

16. 60 parts of methyl acrylate, 20 parts of phenoxyethyl acrylate, 20 parts of acrylic acid, 2.8 parts of 2゜4-diethylthioxanthone, and isoaminoester of valadimethylaminobenzoic acid 5. 6 parts, blocked isocyanate (manufactured by Nippon Polyurethane Industry ■, 100% solid content of Furonate 2513, NC0 = 12.8%) 90
part (1 equivalent amount of incyanate to total functional groups) Elastic beads (manufactured by Nippon Shokubai Chemical Co., Ltd., EBS
300 parts of the solution were stirred well. Add this mixture to PET
Coat it on the release surface of the film and use a metal halide lamp (1
00 W/am) for 20 seconds to create a thermosetting resin layer. The thickness of the sheet was 80 μm.

17. 60 parts of methyl acrylate, 20 parts of phenoxyethyl acrylate, 10 parts of acrylic acid, 10 parts of 2-hydroxyethyl acrylate, 2.8 parts of 2.4-diethylthioxanthone, and 5.6 parts of isoaminoester of valadimethylaminobenzoic acid. and isocyanate (manufactured by Takeda Pharmaceutical Co., Ltd., Takenate D170 N, incyanurate of hexamethylene diisocyanate NC0 = 20.8%) 4
6 parts (1 equivalent of isocyanate to total functional groups), elastic beads (manufactured by Nippon Shokubai Chemical Co., Ltd., E
BS300) 200 parts were stirred well. This mixture was applied to the release surface of the PET film, and a high-pressure mercury lamp (1
00 W/cm) for 25 seconds to create a thermosetting resin layer. The thickness of the sheet was 100 μm.

18. 60 parts of methyl methacrylate, 20 parts of balanonylphenoxydiethylene glycol acrylate, 20 parts of acrylic acid, 2 parts of 2,4-diethylthioxanthone, 4 parts of paradimethylaminobenzoic acid inoamino ester, and isocyanate (manufactured by Takeda Pharmaceutical Company Ltd., Takenate D 17
0 N, isocyanurate of hexamethylene diisocyanate NC0 = 20.8%) 55 parts (1 equivalent of isocyanate to the total functional group), 0.01 part of dibutyltinwaurilate Elastic beads (Nippon Shokubai Chemical Co., Ltd. 150 parts of EBS300 (manufactured by Co., Ltd.) were thoroughly stirred.

This mixture was applied to the release surface of the PET film and irradiated with a metal halide lamp (100W/c+n) for 20 seconds to create a thermosetting resin layer. The thickness of the sheet was 80 μm.

19. 60 parts of methyl methacrylate, 20 parts of phenoxyethyl acrylate, 20 parts of acrylic acid, 2 parts of 2,4-diethylthio beef santhone, 4 parts of neuradimethylamine benzoic acid isoamino ester, and a melamine crosslinking agent (manufactured by Dainippon Ink Chemical Co., Ltd.) , Super Beckamine (100% solid content of butylated melamine resin J-820-60) 20 parts (the amount that will finally react and harden sufficiently), Elastic beads (manufactured by Nippon Shokubai Chemical Co., Ltd., EBS300) 200 parts was stirred well. This mixture was applied to the release surface of a PET film, and irradiated with a high-pressure mercury lamp (100 W/cm) for 20 seconds to create a thermosetting resin layer. After that, HMA sheet (70 μm
) were heat laminated. The thickness of the thermosetting sheet is 1
It was 00 μm.

20. 60 parts of methyl acrylate, 20 parts of phenoxyethyl acrylate, 20 parts of methacrylic acid, 2, 4.
2.8 parts of 6-drimethylbenzoyldiphenylphosphine oxide and 59 parts of epoxy crosslinking agent (manufactured by Civer Geigy, Araldite CY175, epoxy equivalent 160, epoxy value 220 corresponding to the functional group value) (based on the total functional group) , 1 equivalent of epoxy) elastic beads (manufactured by Nippon Shokubai Chemical Co., Ltd., EBS300) were mixed (stirred). ) was irradiated for 20 seconds to create a thermosetting resin layer.The thickness of the sheet was 6.
It was 0 μm.

21. 70 parts of methyl methacrylate, 10 parts of balanonylphenoxydiethylene glycol acrylate, 5 parts of 2-hydroquine ethyl acrylate, reactive acrylic resin (methyl methacrylate, 2-hydroxyethyl methacrylate, acrylic acid, and methacrylic acid) Copolymer with 4-aminoethyl, Mw = 480,000, Tg 35°C,
oHH2O2C00H value 20 and NH2H2O4 solid content 1
00%) 15 copies, 2,4.6-t! 2.8 parts of J methylbenzoyl diphenylphosphine oxide and blocked isocyanate (manufactured by Nippon Polyurethane Kogyo ■, Coronate 2513 with a solid content of 100%, NGO=12.
8%) (1 equivalent amount of incyanate based on the total functional groups) and 250 parts of elastic beads (manufactured by Nippon Shokubai Chemical Co., Ltd., EBS300) were mixed (stirred).This mixture was placed on an ABS sheet ( Made by Royal Resin Industry ■, A205,
Coated with a film thickness of 500 μm) and heated with a metal halide lamp (1
00 W/cm) for 20 seconds to create a thermosetting resin layer. The thickness of the sheet was 560 μm (including the ABS sheet).

22. 40 parts of methyl methacrylate, 15 parts of balanonylphenoxydiethylene glycol acrylate, 15 parts of 2-hydroboxydiethyl acrylate, and a reactive acrylic resin (methyl methacrylate, methacrylic acid, and 2-aminoethyl acrylate). Copolymer, Mw=492,000
, Tg 35°C, C00H number 40 and NH2H2O4 solid content 100%) 30L 2.8 parts of 2,4.6-drimethylbenzoyldiphenylphosphine oxide and incyanate (manufactured by Takeda Pharmaceutical Company, Takenate D 170N)
.

Isocyanurate of hexamethylene diisocyanate
NC0=20. 8%) 35 parts (1 equivalent of incyanate to 9k(1) functional group), elastic beads (
200 parts of EBSloo (manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd.) were thoroughly stirred. This mixture was applied to an ABS sheet (manufactured by Royal Resin Industry ■, A205, film thickness 500 μm) and irradiated with a metal halide lamp (100 W/C1l+) for 20 seconds to create a thermosetting resin layer. The thickness of the sheet is 620
μm (including ABS sheets).

23. 40 parts of methyl methacrylate, 15 parts of balanonylphenoxydiethylene glycol acrylate, 15 parts of 2-hydroxyethyl acrylate, reactive acrylic resin (methyl methacrylate, 2-hydroxyethyl methacrylate, acrylic acid, and 4 parts of methacrylic acid) -Copolymer with aminoethyl, Mw=480,000.7g35℃
, OHH2O2C00H value 20 and NH2H2O4 solid content 100%) 30 parts, 2. 4. 6-Dolimethylbenzoyldiphenylphosphine oxide2. 8 parts and isocyanate (manufactured by Takeda Pharmaceutical Co., Ltd., Takene) D17ON
1 Isocyanurate of hexamethylene diisocyanate NC0=20. 8%) 35 parts (1 equivalent of isocyanate based on the total functional groups), 0.01 part of dibutyltinlauryl), and 300 parts of elastic beads (manufactured by Nippon Shokubai Chemical Co., Ltd., EBSIOQ) were thoroughly stirred. did. This mixture was applied to an ABS sheet (manufactured by Royal Resin Industries, A2).
05, film thickness 500 μm) and irradiated with a metal halide lamp (100 W/em) for 20 seconds to create a thermosetting resin layer. The thickness of the sheet was 580 μm (including the ABS sheet).

24, 40 parts of methyl acrylate, 10 parts of balanonylphenoxydiethylene glycol acrylate), 15 parts of 2-hydroxyethyl acrylate, reactive acrylic resin (
Copolymer of methyl methacrylate, 2-hydroxyethyl methacrylate and 4-aminobutyl methacrylate,
Mw=368,000, Tg 10℃, OH value 40 and NH
2H2O4 solid content 100%) 35 parts, 2. 4. 6-
2.8 parts of dolimethylbenzoyl diphenylphosphine oxide and melamine crosslinking agent (Dainippon Ink Chemical Co., Ltd., Super Beckamine (bullated melamine resin) J-820-
60 parts (100% solids content of 60) (the amount that will finally fully react and cure), elastic beads (manufactured by Nippon Shokubai Chemical Co., Ltd., E
BSloo) 200 parts were thoroughly stirred.

This mixture was applied to the release surface of a PET film, and irradiated with a metal halide lamp (100 W/cm) for 20 seconds to create a thermosetting resin layer. The thickness of the sheet was 100 μm.

25, 40 parts of methyl acrylate, 15 parts of paranonylphenoquine diethylene glycol acrylate, 15 parts of 2-hydroxyethyl acrylate, reactive acrylic resin (
Copolymer of methyl methacrylate, 2-hydroxyethyl methacrylate and 4-aminobutyl methacrylate,
Mw=368,000, Tgl 0℃, OH value 40 and N
H2H2O4 solid content 100%) 35 parts2. 4. 6-
2.8 parts of dolimethylbenzoyl diphenylphosphine oxide and 45 parts of epoxy crosslinking agent (manufactured by Civer Geigy, Araldite CY175, epoxy equivalent weight 160, epoxy value 220 corresponding to the functional group value) (1 Equivalent amount of epoxy) and 200 parts of elastic beads (Nippon Shokubai Kagaku Kogyo Co., Ltd. &!, EBSloo) were thoroughly stirred. This mixture was coated on the release surface of the PET film, and a metal halide lamp (I00W/c+n) was applied for 20 minutes.
A thermosetting resin layer was created by irradiation for seconds. The thickness of the sheet is
It was 80 μm.

26, 60 parts of methyl acrylate, 20 parts of acrylic acid,
Thermoplastic acrylic resin (manufactured by Asahi Kasei Corporation, Delpet 5)
R8500) 20 parts, 2,4-diethylthioxanthone 2.8 parts and valadimethylaminobenzoic acid isoamino ester 5.6 parts, blocked isocyanate (manufactured by Nippon Polyurethane Kogyo ■, 100% solid content of Coronate 2513, NGO = 12.8%) 90 parts, elasticity lx'-
(manufactured by Nippon Shokubai Chemical Co., Ltd., EBS300) 10
0 part was stirred well. This mixture was applied to the release surface of the PET film, and a metal halide lamp (100W/cm) was applied.
) A thermosetting resin layer was created by irradiating for 720 seconds. The thickness of the sheet was 80 μm.

27, 60 parts of methyl acrylate, 10 parts of acrylic acid,
2-Hydrobovine diethyl acrylate 109, thermoplastic acrylic resin (manufactured by Asahi Kasei Corporation, Delpet 5R8200)
) 20 parts, 2.8 parts of 2,4-diethylthio beef santhone and 5.6 parts of paradimethylaminobenzoic acid isoamino ester
part and incyanate (Takeda Pharmaceutical special product, Takenate D
17ON, incyanurate of hesyl methylene diisocyanate NC0 = 20.8%) 46 parts, elastic beads (
150 parts of EBS300 (manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd.) were thoroughly stirred. This mixture was applied to the release surface of a PET film and irradiated with a high-pressure mercury lamp (100 W/cm) for 25 seconds to create a thermosetting resin layer. The thickness of the sheet is 1
It was 00 μm.

28, 60 parts of methyl methacrylate, 20 parts of paranonylphenoxydiethylene glycol acrylate, 20 parts of methacrylic acid, thermoplastic acrylic resin (Asahi Kasei Kogyo ■
20 parts of 2,4-diethylthioxanthone, 4 parts of paradimethylaminobenzoic acid isoamino ester, and incyanate (manufactured by Takeda Pharmaceutical Co., Ltd., Delpet 5R8200) D17ON, incyanurate of hexamethylene diisocyanate NC0 =20.8%)4
6 parts, dibutyltin laurylate o, oIN, elastic beads (manufactured by Nippon Shokubai Chemical Co., Ltd., EBS300) 200
The mixture was stirred well. This mixture was applied to the release surface of the PET film, and a metal halide lamp (100W/crn) was applied.
) for 20 seconds to create a thermosetting resin layer. The thickness of the sheet was 80 μm.

298 60 parts of methyl acrylate, 5 parts of phenoxy-7 dithyl acrylate, 20 parts of acrylic acid, thermoplastic acrylic resin (manufactured by Asahi Kasei Corporation, Delvet 5R8200) 15
1 part, 2 parts of 2,4-diethylthioxanthone, 4 parts of paradimethylaminobenzoic acid isoamino ester, and a melamine crosslinking agent (Dainippon Ink Chemical Co., Ltd., Super Beckamine (butylated melamine resin) J-820-60, 100% solids) ) 20 parts, elastic beads (manufactured by Nippon Shokubai Chemical Co., Ltd., E
BS300) 100 parts were thoroughly stirred. This mixture was applied to the release surface of the PET film, and a high-pressure mercury lamp (1
00 W/crn) for 20 seconds to create a thermosetting resin layer. The thickness of the thermosetting sheet was 100 μm.

30. 60 parts of methyl acrylate, 20 parts of methacrylic acid, 20 parts of polystyrene (HI Styron 403R, manufactured by Asahi Kasei Corporation), 2. 4. 2.8 parts of 6-trimethylbenzoyldiphenylphosphine oxide and Epoquin crosslinking agent (manufactured by Civer Geigy, Araldite CYI)
75, epoxy equivalent: 160, epoxy value corresponding to the functional group value: 220), and 100 parts of elastic beads (manufactured by Nippon Shokubai Chemical Co., Ltd., EBS300) were thoroughly stirred. This mixture was applied to the release surface of the PET film and irradiated for 20 seconds with a high-pressure mercury lamp (100 W/cm ) to create a thermosetting resin layer.

The thickness of the sheet was 300 μm.

31. In 500 parts of ethyl acetate, thermoplastic acrylic resin (manufactured by Asahi Kasei Kogyo ■, Delpet 5R8200) ioo
parts, 1,6-hexadiol di(meth)acrylate 4
0 parts, neopentyl glycol di(meth)acrylate 40 parts, ter-butyl peroxyisobutyrate 2.
5 parts, elastic beads (manufactured by Nippon Shokubai Chemical Co., Ltd., EBS
300) 300 parts were mixed with thorough stirring. This mixture was applied to the release surface of the PET film using an applicator and dried at 60° C. for 30 minutes to form a thermosetting resin layer. The thickness of the sheet was 60 μm.

32. Thermoplastic acrylic resin (
Manufactured by Asahi Kasei Kogyo ■, Delvera) SR8200) 100 copies,
Pentaerythritol tri(meth)acrylate 50
Part, neobentyl glycol di(meth)acrylate 4
0 parts, ter-butyl peroxyisobutyrate 3.5
Part, elastic beads (manufactured by Nippon Shokubai Chemical Co., Ltd., EBS3
00) 250 parts were mixed with thorough stirring. This mixture was applied to the release surface of the PET film using an applicator and dried at 60"C for 30 minutes to form a thermosetting resin layer. The thickness of the sheet was 80 μm.

33. Thermoplastic acrylic resin (
Manufactured by Asahi Kasei Kogyo ■, Delpera) SR8200) 100 copies,
40 parts p-methoxystyrene, 4 parts p-phenylstyrene
0 parts, neobentyl glycol di(meth)acrylate 20 parts, ter-butyl peroxyisobutyrate 3.
5 parts, elastic beads (manufactured by Nippon Shokubai Chemical Co., Ltd., EBS
loo) 200 parts were mixed with thorough stirring. This mixture was subjected to ABS sorting (manufactured by Royal Resin Industry ■, A205,
The thermosetting resin layer was coated with an applicator to a film thickness of 500 μm and dried at 60° C. for 30 minutes to form a thermosetting resin layer. The thickness of the sheet was 560 μm (including the ABS sheet).

34. Thermoplastic acrylic resin (
Manufactured by Asahi Kasei Kogyo ■, Delvet 5R8200) 100 copies,
Pentaerythritol tri(meth)acrylate 20
parts, dipentaerythritol hexa(meth)acrylate 30 parts, neopentyl glycol di(meth)acrylate 40 parts, ter-butylperoxyisobutyrate 4.0 parts, elastic beads (manufactured by Nippon Shokubai Chemical Co., Ltd., E
150 parts of BSIOQ) were mixed with thorough stirring. This mixture was made of ABS sheet (manufactured by Royal Resin Industry, A205).
, film thickness 500 μm) using an applicator and heated at 60°C.
This was dried for 30 minutes to form a thermosetting resin layer.

The thickness of the sheet was 580 μm (including the ABS sheet).

35. Thermoplastic acrylic resin (
Asahi Kasei Kogyo ■, Delvera l-5R8200) 100 parts, 1,6-hexadiol di(meth)acrylate 40
Part, neopentyl glycol di(meth)acrylate 4
0 parts, ter-butyl pero half sea 3. 5. 2.5 parts of 5-trimethylhexanoate, 60 parts of titanium oxide,
Elastic beads (manufactured by Nippon Shokubai Chemical Co., Ltd., EBSloo
) 200 parts were mixed with three rolls (mixed while kneading. This mixture was applied to the release surface of the PET film with an applicator and dried at 60°C for 30 minutes to create a thermosetting resin layer. Sort The thickness was 60 μm.

36. 500 parts of ethyl acetate, thermoplastic acrylic resin (
Manufactured by Asahi Kasei Corporation, Delbe Yto 5R8200) 100 parts, pentaerythritol tri(meth)acrylate 5
0 parts, neopentyl glycol di(meth)acrylate 40 parts, ter-butyloxyisobutyrate 3 parts
．． 5 parts of iron oxide, 40 parts of iron oxide, and 100 parts of elastic beads (manufactured by Nippon Shokubai Chemical Co., Ltd., EBSloo) were mixed while thoroughly kneading with a triple roll.

This mixture was applied to the release surface of the PET film using an applicator and dried at 60"C for 30 minutes to form a thermosetting resin layer. The thickness of the sheet was 80 μm.

37. Thermoplastic acrylic resin (
Manufactured by Asahi Kasei Kogyo ■, Delpera) SR8200) 100 copies,
40 parts p-methoxystyrene, 4 parts p-phenylstyrene
0 parts, neopentyl glycol di(meth)acrylate 20 parts, ter-butylperoxy-3,5,5-)limethylhexanoate 3. 5 parts, phthalocyanine blue 20 parts, elastic beads (manufactured by Nippon Shokubai Chemical Co., Ltd., E
BSloo) were mixed by thoroughly kneading with three rolls.

This mixture was applied to the release surface of the PET film using an applicator and dried at 60°C for 30 minutes to form a thermosetting resin layer. The thickness of the sheet was 60 μm.

38. Thermoplastic acrylic resin (
Manufactured by Asahi Kasei Kogyo ■, Delpet 5R8200) 100 copies,
Pentaerythritol tri(meth)acrylate 20
part, dipentaerythritol, 30 parts of bovine (meth)acrylate, 40 parts of neopentyl glycol di(meth)acrylate, 4.0 parts of ter-butylperoxyisobutyrate, 50 parts of titanium oxide, elastic beads (Nippon Shokubai Chemical) 250 parts of EBSloo (manufactured by Kogyo Co., Ltd.) were mixed while thoroughly kneading with three rolls. This mixture was applied to the release surface of the PET film using an applicator and dried at 60°C for 30 minutes to form a thermosetting resin layer. The thickness of the sheet was 80 μm.

39. To 300 parts of ethyl acetate, reactive acrylic resin (copolymer of methyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, acrylic acid, and 4-aminoethyl methacrylate, Mw = 480 ．．
000.7g35℃, OHH2O2CoOH value 20 and N
82 value 40) To 100 parts of solid content, block isocyanate (manufactured by Takeda Pharmaceutical Company Ltd., Takenate B-815N) 39
part (this crosslinking agent has 0.8 equivalent of incyanate group with respect to the functional group of the above-mentioned reactive acrylic resin), and a melamine crosslinking agent (manufactured by Dainippon Ink Chemical Co., Ltd., Super Beckamine (Bullated Melamine Resin) J) -820-60) solid content: 4.6 parts (amount for initial curing of 5% of the functional groups of the reactive acrylic resin), elastic beads (manufactured by Nippon Shokubai Chemical Co., Ltd.),
EBSloo) 200 parts were mixed with thorough stirring. This mixture was applied to the release surface of the PET film using an applicator and dried at 80° C. for 5 minutes to form a thermosetting resin layer.

The thickness of the sheet was 20 μm. This was used as a surface layer, and then 100 parts of a thermoplastic acrylic resin (manufactured by Asahi Kasei Kogyo ■, Delvet 5R8200) was added to 500 parts of ethyl acetate. 6-hexadiol di(meth)acrylate 4
0 parts, neopentyl glycol di(meth)acrylate 40 parts, ter-butyl peroxyisobutyrate 2.
5 parts were mixed with good stirring. This mixture was coated over the above-mentioned surface layer using an applicator and heated to 60°C.
This was dried for 30 minutes to form a thermosetting resin layer.

The thickness of the sheet was 60 μm, and the total thickness was 80 μm.

40, 300 parts of ethyl acetate, reactive acrylic resin (copolymer of methyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, acrylic acid, and 4-aminoethyl methacrylate, Mw = 360)
,000, Tg 35°C, OHH2O2CoOH value 20 and NH2H2O4 to 100 parts solid content, blocked isocyanate (Takenate B-815N, manufactured by Takeda Pharmaceutical Company Ltd.)
59 parts (this crosslinking agent has 1.2 equivalents of incyanate groups relative to the functional groups of the reactive acrylic resin), elastic beads (manufactured by Nippon Shokubai Chemical Co., Ltd., EBSloo)
200 parts were mixed with thorough stirring. This mixture is P
Coat it on the release surface of the ET film with an applicator,
It was dried at ℃ for 5 minutes to create a thermosetting resin layer. The thickness of the sheet was 20 μm. This was used as a surface layer, and then a reactive acrylic resin (a copolymer of methyl methacrylate and butyl acrylate, a copolymer of methacrylic acid and 3-aminopropyl acrylate, Mw=
621゜000.7g 10℃, CoOH value 40 and NH2
H2O4 to 100 parts of solid content, 59 parts of blocked isocyanate (Takenate B-815N, manufactured by Shikinichi Yakuhin Kogyo) (
This cross-linking agent is used for the functional groups of the above-mentioned reactive acrylic resin.
(having 1.2 equivalents of incyanate groups) and 100 parts of titanium oxide were mixed with thorough stirring. This mixture was coated over the above-mentioned surface layer using an applicator, and 7
It was dried at 0''C for 20 minutes to form a thermosetting resin layer.

The thickness of the sheet was 100 μm, and the total thickness was 120 μm.

41, 60 parts of methyl methacrylate, 20 parts of balanonylphenoxydiethylene glycol acrylate, 20 parts of acrylic acid, 2 parts of 2,4-jethylnao beef santhone, 4 parts of baladimethylaminobenzoic acid inamino ester, and incyanate (Takeda Pharmaceutical Co., Ltd.) Manufactured by Takenate D17O
N, isocyanurate of hexamethylene diisocyanate NC0 = 20.8%) 55 parts (1 equivalent of isocyanate to total functional groups), 0.01 part of dibutyl lamp urirate, elastic beads (Nippon Shokubai Chemical Co., Ltd. Co., Ltd.!l!, EBS300) 100 parts were thoroughly stirred. Coat this mixture on the release surface of the PET film,
A thermosetting resin layer was created by irradiating with a metal halide lamp (100 W/cm) for 5 seconds. The thickness of the sheet is 20μm
Met. Using this as a surface layer, next, 20 parts of phenoxyethyl acrylate was added to 60 parts of methyl methacrylate.
20 parts of acrylic acid, 2 parts of 2,4-diethylthioxanthone, 4 parts of valadimethylaminobenzoic acid isoamino ester, and melamine crosslinking agent (Dainippon Ink Chemical Co., Ltd., Super Beckamine (Bullated Melamine Resin') J- 820-6
20 parts (100% solids content of 100% solids) and 40 parts of titanium oxide were thoroughly kneaded with a triple roll. This mixture was coated over the above-mentioned surface layer using an applicator and irradiated for 20 seconds with a metal halide lamp (100 W/α) to form a thermosetting resin layer. The thickness of the sheet was 100 μm.

42. Toluene 3008R, reactive silicone resin (
Polymethyl polyol siloxane, weight average molecular weight 50
,000. 2100 parts of OHHBO, Pro-Tsukuisocyanate (manufactured by Shikinichi Yakuhin Kogyo, Takenate B-815N) 4
7 parts (this crosslinking agent is 1.0 parts per functional group of the resin)
equivalent amount of incyanate groups), titanium oxide 100
Part, elastic beads (manufactured by Nippon Shokubai Chemical Co., Ltd., EBS3
QO) 200 parts were mixed while thoroughly kneading with three rolls. This mixture was applied to the release surface of the PET film using an applicator and dried at 90° C. for 10 minutes to form a thermosetting resin layer. The thickness of the sheet was 100 μm.

43. To 300 parts of toluene, add reactive fluorine resin (alternating copolymer of ethylene and hydroxytrifluoroethylene, weight average molecular weight 100,000, OH value 455) 10
0 parts, 140 parts of Pro-Tsuki Isocyanate (Takenate B-815N, manufactured by Shikinichi Yakuhin Kogyo Co., Ltd.) (this crosslinking agent has 0.5 equivalents of isocyanate groups with respect to the functional groups of the above resin), elastic beads (Nippon Shokubai Co., Ltd.), Manufactured by Kagaku Kogyo Co., Ltd., EB
100 parts of S30(1) were mixed with thorough stirring.

This mixture was applied to the release surface of the PET film using an applicator and dried at 90° C. for 10 minutes to form a thermosetting resin layer. The thickness of the sheet was 100 μm 044
, 300 parts of toluene, 100 parts of a reactive fluorine resin (alternating copolymer of ethylene and hydroxytrifluoroethylene, weight average molecular weight 250,000, H value 455), blocked isocyanate (manufactured by Shikinichi Yakuhin Kogyo Co., Ltd.) , Takenate B-815N) 140 parts (this crosslinking agent has 0.5 equivalent of isocyanate groups with respect to the functional groups of the resin)
, isocyanate (manufactured by Nippon Polyurethane Industries, Ltd., Corone) L) 26 parts (this crosslinking agent has 0.1 equivalent of incyanate groups with respect to the functional group of the resin), elastic beads (Nippon Shokubai Chemical Co., Ltd.) manufactured by EBS300) 30
0 parts were mixed with thorough stirring. Add this mixture to PET
It was applied to the release surface of the film using an applicator and dried at 90° C. for 10 minutes to form a thermosetting resin layer. The thickness of the sheet was 100 μm.

45. The sheet of Example 43 was manufactured by applying it to the release surface of a PET film using an applicator so that the film thickness was 20 μm. Next, a reactive fluororesin (alternating copolymer of ethylene and hydroxytrifluoroethylene, weight average molecular weight Jlloo, 000, OH value 4) was added to 300 parts of toluene.
55) 100 parts, 140 parts of blocked isocyanate (Takenate B-815N, manufactured by Shikinichi Yakuhin Kogyo Co., Ltd.) (this crosslinking agent has 0.5 equivalents of incyanate groups with respect to the functional groups of the resin), 20 parts of phthalocyanine blue , elastic beads (manufactured by Nippon Shokubai Chemical Co., Ltd., EBS300) 20
0 parts were mixed while thoroughly kneading with three rolls.

Coat this mixture onto the above-mentioned sheet with an applicator,
It was dried at 90° C. for 10 minutes to form a thermosetting resin layer.

The thickness of the sheet was 100 μm, and the total thickness was 120 μm.

46. 300 parts of toluene, reactive fluororesin (alternating copolymer of ethylene and hydroxytrifluoroethylene,
Weight average molecular weight 250,000, OH number 455) 100
140 parts of blocked isocyanate (Takene B-815N, manufactured by Shikinichi Yakuhin Kogyo) (this crosslinking agent has 0.5 equivalent of isocyanate groups with respect to the functional group of the resin), isocyanate (manufactured by Nippon Polyurethane Industry) , Coronate L) 26 parts (this crosslinking agent has 0.1 equivalent of incyanate group with respect to the functional group of the resin), elastic beads (manufactured by Nippon Shokubai Chemical Co., Ltd., EBS300) 1
00 parts were mixed with thorough stirring. This mixture is PE
Apply to the release surface of T film with an applicator and heat to 90℃.
The mixture was dried for 10 minutes to form a thermosetting resin layer. Thereafter, 60 parts of HMA NC) was laminated and used as a support layer. The thickness of the thermosetting sheet was 100 μm.

47. 300 parts of xylene, reactive polyester resin (
Copolymer of 2-aminoterephthalic acid and hexamethylene glycol, weight average molecular weight 65°000, amide valence 2
26) 100 parts, blocked isocyanate (manufactured by Shikinichi Yakuhin Kogyo, Takenate B-815N) 111 parts (this crosslinking agent has an isocyanate group equivalent to 0.8 equivalent to the functional group of the resin) elastic beads (Nippon Shokubai Chemical Co., Ltd.) 200 parts of EBS300 (manufactured by Kogyo Co., Ltd.) were mixed with thorough stirring. This mixture was applied to the release surface of the PET film using an applicator and dried at 90° C. for 10 minutes to form a thermosetting resin layer. The thickness of the sheet was 80 μm.

(B) Injection molding Injection molding was performed as follows using the injection molding machine shown in Figure 1. 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 a movable mold 10 disposed between the two molds 10 and 12. It is equipped with a hot platen 14 having holes for vacuum and compressed air, which can be moved outward from between the two molds 10 and 12, and a resin injection machine 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 IO by vacuum and/or pressure forming. Next, as shown in East 1 diagram (C), heat plate 1
4 to the outside from between both molds 10 and 12, and then
The movable mold 10 is moved toward the fixed mold 12 and the molds are closed. Next, ABS resin (41;
Made by iKikagaku Kogyo ■, ABS-ME), both types 10.12
Injected into the semi-cavity formed by. 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 the thermosetting sheet was cured under the conditions shown in the table below to obtain an injection molded product.

Taper wear test after curing (Taper IKgS C5I
7.1000 rotations), adhesion (number of base lines remaining after tape peeling) and soft appearance (feel) were evaluated by a base line test.

The results are shown in Tables 1 to 10.

(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.)
Cenosoft II) was applied 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 problems, and when heated, the surface of the object has a soft touch feeling (suede) with excellent solvent resistance and scratch resistance. It is possible to form a film of The film is hard, has excellent scratch resistance and solvent resistance, and has a soft touch feeling (
Since it has a suede-like texture, it can be applied to decorating office equipment, household appliances, etc. and stationery, and has the advantage that these molded products can be decorated easily and at low cost.

Figures 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... Sheet, 14...
...Heating plate, 15...Resin injection machine.

that's all

Claims (1)

[Claims] 1. An uncured or semi-cured thermosetting sheet made of a thermosetting resin composition containing elastic beads is attached to the inner surface of the recess of a mold by vacuum and/or pressure forming. injection molding, which includes the steps of: tightening the mold and injecting a molding resin into the recesses of the mold; and curing the thermosetting sheet by heating during and/or after molding. method of manufacturing the product.