JPH0584772A - Coating molding sheet, coated molded product and production thereof - Google Patents

Abstract

PURPOSE:To form a film excellent in decoration to the surface of an article haying unevenness or a curved surface, for example, a car body. CONSTITUTION:A clear layer 34 composed of a photosetting or electron beam curable resin composition in an uncured or semicured state, a light-colored layer 33, a dark-colored layer 32 and a base material layer 31 are laminated in this order to form a coating sheet 3. This sheet 3 is laminated to a molded product and the clear layer 34 of the sheet 3 is irradiated with light and electron beam to be cured.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is to decorate the outer surface of vehicle bodies such as automobiles and motorcycles, housings such as office automation equipment and home appliances, and molded products such as sanitary products. The present invention relates to a coated molding sheet for forming a coating having excellent scratch resistance, chemical resistance, etc., a coated molded article using the coated molding sheet, and a method for producing the coated molded article.

[0002]

2. Description of the Related Art Conventionally, paint is generally used to decorate the surface of an article or to give an indication to the surface of the article. Usually, the paint uses an organic solvent, so that the influence on the working environment (contamination, harmful to hygiene) is a problem. Further, in the water-based paint, the work ring does not pose a problem, but there is a problem that the drying time becomes long or a large amount of energy for drying is required.

Recently, sheet-like adhesive materials mainly composed of polyvinyl chloride have been proposed. When this sheet is used, there is no effect on the work environment, and because it is in sheet form, there is no need to dry it. However, this sheet-shaped patch material mainly uses a soft polyvinyl chloride sheet, and has a drawback that it is inferior in hardness and scratch resistance.

As a method for improving this, there has been proposed a method in which a sheet material is cured after being attached. For example, in JP-B-57-13425, a porous sheet-shaped substrate is impregnated with a radical initiator, and a layer containing a polymer and a radical-reactive monomer is laminated on one or both sides of the substrate. Thermosetting composite sheets have been proposed.

Further, Japanese Patent Publication No. 60-21630 discloses a powder containing a radical reactive unsaturated compound which is solid at room temperature and a room temperature in a self-supporting continuous layer made of a thermoplastic and / or rubber material. A heat-curable sheet material prepared by mixing powder containing a solid radical reaction initiator has been proposed.

[0006]

[Problems to be Solved by the Invention] Japanese Patent Publication No. 57-1342
The sheet disclosed in Japanese Patent Publication No. 5 has a structure in which a layer having a radical-reactive unsaturated compound and a layer having a radical reaction initiator are laminated, so that the sheet should be made uniform in order to carry out a uniform curing reaction. There is a drawback that it is difficult to control these because it is necessary to pressurize and heat. In addition, since paper, woven fabric, and non-woven fabric are used as the sheet-shaped base material impregnated with the radical reaction initiator, when coating the surface of an article having irregularities or curved surfaces, it is difficult to obtain sheet elongation and a good film is formed. Difficult to do.

The sheet disclosed in Japanese Examined Patent Publication No. 60-21630 has spreadability and is considered to be able to be attached to irregularities or curved surfaces. However, in order to manufacture a sheet, since operations such as freeze pulverization and powder mixing are required, a non-uniform coating film is likely to be formed, and there is a problem not only in surface performance of the sheet but also in appearance such as pigment dispersibility. ..

The present invention solves the above problems and makes it easy to provide gloss, depth, weather resistance, scratch resistance and chemical resistance on the outer surface of a molded product having irregularities and curved surfaces even in the unstretched state. It is an object of the present invention to provide a coated molding sheet which is excellently decorated, a coated molded article coated with the coated molding sheet, and a method for producing the coated molded article.

[0009]

The invention according to claim 1 of the present invention comprises an uncured or semi-cured clear layer comprising a photocurable or electron beam curable composition, a light colored layer, and a dark colored layer. A coated molding sheet in which a colored layer and a base material layer are laminated in this order.

The invention according to claim 2 of the present invention is the uncured or semi-cured composition comprising the photocurable or electron beam curable composition, wherein the coated molding sheet according to claim 1 is coated on the outer surface of the molded article body. A coated molded article in which a clear layer in a state, a light colored layer, a dark colored layer, and a base material layer are laminated in this order on the outer surface of the molded article body, and the clear layer is cured.

According to a third aspect of the present invention, a cavity having an inner surface shape corresponding to the outer surface shape of a molded product to be molded is formed in a mold including a female mold and a male mold, and the cavity is formed in the cavity. 1. A method for producing a coated molded article by supplying the coated molding sheet and the main body molding resin of 1, wherein the coated molding sheet is placed in the cavity after the clear layer is directed toward the mold surface. Supplying the main body molding resin, an uncured or semi-cured clear layer made of a photocurable or electron beam curable composition, a light colored layer, a dark colored layer, and a substrate layer. In this order, laminate molding is performed on the outer surface of the molded product body, then the mold is opened, the molded product is taken out, and the clear layer is cured by irradiating the clear layer with light or an electron beam. is there.

The present invention will be described in detail below. Examples of the photocurable composition for forming the clear layer include:
Compounds that have reactive double bonds such as vinyl groups in the molecule (not only low molecular weight compounds, but also polymers)
An initiator necessary for photocuring, a base (coloring layer, and optionally a base material layer) protective material, for example, an ultraviolet absorber, and, if necessary, a high molecular weight substance for improving sheet retention,
For example, those containing a resin as a main component may be mentioned.

The electron beam curable composition for forming the clear layer is, for example, a compound having a reactive double bond such as a vinyl group in the molecule, a base protective material (ultraviolet absorber), and if necessary. Those containing a resin as a main component are mentioned.

The compound having a reactive double bond in the molecule has a (meth) acryloyl group, for example, methyl (meth) acrylate, ethyl (meth) acrylate, benzyl (meth) acrylate, 2-ethoxyethyl. Monofunctional types such as (meth) acrylate and phenoxydiethylene glycol (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate,
Polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. There are multifunctional types.

There are also oligomers such as polyester acrylate, polyurethane acrylate, epoxy acrylate, polyether acrylate, oligo acrylate, alkyd acrylate and polyol acrylate. Further, examples thereof include a styrene monomer having a vinyl group or an allyl group, α-methylstyrene, divinylbenzene, vinyl acetate, pentene, hexene, and an unsaturated compound. These compounds further introduce polar groups such as a hydroxyl group, an amino group, a carboxyl group, a carbonyl group, and an epoxy group in order to improve the adhesion with the printing layer (described later) and the compatibility with the undercoat protection material. Sometimes.

The photo-curing polymerization initiator is added especially when it is cured by ultraviolet rays. This polymerization initiator is usually called a photoinitiator, and for example, a benzoin alkyl ether-based, acetophenone-based, benzophenone-based, thioxanthone-based photoinitiator is preferably used.

Examples of the benzoin ether type include benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether and benzoin propyl ether. For acetophenone type, 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, p
-Ter-butyltrichloroacetophenone, 2,4
6-trimethylbenzoyldiphenylphosphine oxide and the like.

In the benzophenone series, benzophenone,
There are 4-chlorobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-4-methoxybenzophenone, dibenzosuberenone and the like.

In the thioxanthone system, thioxanthone, 2
-Chlorothioxanthone, 2-methylthioxanthone,
2-isopropyl thioxanthone, 2-ethyl anthraquinone and the like.

The photoinitiator is added in an amount of 0.05 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the compound having a reactive double bond. Further, the photoinitiator is not limited to one type, and two or more types may be used in combination.

As the material for protecting the underlayer, a commercially available ultraviolet absorber or the like can be used. The material to be added is selected from those having good dispersion stability in the composition and not being modified by light irradiation. For example, phenyl salicylate, p-tert-butylphenyl salicylate,
salicylic acid compounds such as p-octylphenyl salicylate,
2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, and other benzophenone-based compounds, 2-
(2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-tert)
-Butylphenyl) benzotriazole,-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotrizole, and other benzotriazole compounds, 2-ethylhexyl-2-cyano-3,3 3 '
-Diphenyl acrylate, ethyl-2-cyano-3,
There are cyanoacrylate materials such as 3'-diphenyl acrylate.

The UV absorber is added in an amount of 0.01 to 3 parts by weight, preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the compound having a reactive double bond. Also,
The ultraviolet absorber is not limited to one type in order to improve the underlayer protection, and it is preferable to use two or more types in combination. Further, a hindered amine light stabilizer or an antioxidant may be added.

The high molecular weight material as a sheet retainability improving material does not have a reactive double bond added for improving the handleability (flexibility) of the sheet and the tack of the sheet surface. A material having good compatibility with the compound having is selected. For example, when the compound having a double bond has a urethane skeleton and a (meth) acryloyl group, an acrylic resin or polyester resin made of methyl methacrylate, a urethane resin, or the like can be used.

At this time, there is SP (solvability parameter) as a standard, and a combination of materials having similar values is preferable. In addition to this, a fluororesin, a silicone resin, etc. are used for this high molecular weight substance. Further, in order to improve the adhesion with the printing layer (described later) and the compatibility with the undercoat protection material, these high molecular weight substances may further contain a hydroxyl group, an amino group,
A polar group such as a carboxyl group, a carbonyl group or an epoxy group may be introduced.

A peroxide may be added to the clear layer, if desired. As the peroxide, a usual organic peroxide can be used. More preferably, in view of storage stability at room temperature, an organic peroxide having a decomposition temperature of 100 ° C or higher. For example, 2,2-bis (tert-butylperoxy) butane, tert-butylperoxybenzoate, di-tert-butylperoxyisophthalate, methylethylketone peroxide, dicumylperoxide, tert-butylperoxy. There is acetate.

The amount of the peroxide added is 100 parts by weight of the low molecular weight product having the (meth) acryloyl group.
The range of 0.5 to 5.0 parts by weight is preferable. Further, the peroxide is not limited to one type, and two or more types may be used in combination. By adding these peroxides, it is possible to further heat-cure the portion that is hard to be cured by irradiation with light.

If necessary, a small amount of a coloring agent such as a pigment or a dye and a high hardness fine particle material for increasing hardness are added to the clear layer. As the colorant, pigments and dyes used in paints can be used. Examples of pigments include titanium oxide, iron oxide, carbon black, cyanine pigments, and quinacridone pigments. Examples of dyes include azo dyes, anthraquinone dyes, indigoid dyes, and stilbenzene dyes. Also, aluminum flakes, nickel powder,
You may use metal powders, such as gold powder and silver powder, as a coloring agent. It is preferable that these materials are fine particles. Further, as a material for increasing the hardness, fine particles (average particle diameter: 20 nm or less) of titanium oxide, silica, diamond or the like is used if necessary.

When these coloring materials are added, it is preferable that the photoinitiator undergoes an initiation reaction with light having a wavelength with which the colorant does not absorb much. Below, the combination of materials centering on acrylic is shown. The materials can be similarly combined in other systems. (A) Weight average molecular weight of 20,000 to 1,000
(B) Acrylic fat that is solid at room temperature
A photocurable clear layer comprising a low molecular weight compound having a double bond in the molecule and (c) a photoinitiator as main components. (D) having a plurality of at least one functional group selected from the group consisting of a hydroxyl group, an amino group and a carboxyl group in the molecule, and having a weight average molecular weight of 20,000 to 1.00
Acrylic resin that is solid at room temperature
(B) a low molecular weight product having a double bond in the molecule, (c)
A photocurable clear layer containing a photoinitiator and (e) at least one crosslinking agent selected from the group consisting of an isocyanate crosslinking agent, a melamine crosslinking agent and an epoxy crosslinking agent as main components. (F) an acrylic resin having a plurality of reactive double bonds in the molecule and having a weight average molecular weight of 20,000 to 1,000,000 and being solid at room temperature; and (b) a double bond in the molecule. A photocurable clear layer containing the low molecular weight compound and the photoinitiator as main components. (G) having at least one functional group selected from the group consisting of hydroxyl group, amino group and carboxyl group in the molecule and a plurality of reactive double bonds, and having a weight average molecular weight of 20,0.
An acrylic resin having a solid content of 0 to 1,000,000 at room temperature, (b) a low molecular weight compound having a double bond in the molecule, (c) a photoinitiator, and (e) an isocyanate-based crosslinking agent, A photocurable clear layer containing, as a main component, at least one crosslinking agent selected from the group consisting of a melamine crosslinking agent and an epoxy crosslinking agent.

As the electron beam curable clear layer, for example, a composition obtained by removing the photoinitiator from the composition of the above photocurable clear layer is used. The acrylic resin (a) having a weight average molecular weight of 20,000 to 1,000,000 and solid at room temperature contained in the clear layer is, for example, methyl (meth) acrylate, ethyl (meth) acrylate or butyl (meth). ) It can be obtained by copolymerizing a (meth) acrylic acid ester such as acrylate with a styrene derivative monomer or a maleic acid type monomer in the presence of a reaction initiator (various peroxides, chain transfer agents, etc.).

The (d) molecule contained in the clear layer has a plurality of at least one functional group selected from the group consisting of a hydroxyl group, an amino group and a carboxyl group and has a weight average molecular weight of 20,000 to 1. The acrylic resin that is solid at room temperature is, for example, (meth) acrylic acid ester monomer having a carboxyl group such as (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, and 4-hydroxybutyl. A (meth) acrylic acid ester monomer having a hydroxyl group such as (meth) acrylate and a (meth) acrylic acid ester monomer having an amino group such as 2-aminoethyl (meth) acrylate and 3-aminopropyl (meth) acrylate Of these, at least one type of functional group-containing monomer and other (meth) acrylic acid It can be obtained by copolymerizing ether and styrene derivative monomers and maleic acid monomers in the presence of a reaction initiator (various peroxides and chain transfer agent).

An acrylic resin having a plurality of (meth) acryloyl groups in the molecule (f) contained in the clear layer and having a weight average molecular weight of 20,000 to 1,000,000 and solid at room temperature ( g) having a plurality of at least one functional group selected from the group consisting of a hydroxyl group, an amino group and a carboxyl group and a (meth) acryloyl group in the molecule, and having a weight average molecular weight of 20,000 to 1,000,000. The acrylic resin that is solid at room temperature includes, for example, (meth) acrylic acid having a carboxyl group such as (meth) acrylic acid; 2-hydroxyethyl (meth) acrylate;
A (meth) acrylic acid ester monomer having a hydroxyl group such as hydroxybutyl (meth) acrylate; and a (meth) acrylic acid ester having an amino group such as 2-aminoethyl (meth) acrylate and 3-aminopropyl (meth) acrylate Monomers and; 2- (1-aziridinyl) ethyl (meth) acrylate, 2- (2-aziridinyl) butyl (meth) acrylate and other (meth) acrylic acid ester monomers having aziridinyl; and epoxy groups such as glycidyl (meth) acrylate Among the (meth) acrylic acid ester monomers having the above, a monomer having at least one kind of functional group and another (meth) acrylic acid ester, a styrene derivative monomer, a maleic acid-based monomer, etc. In the presence of oxides, chain transfer agents, etc.) The acrylic copolymer having a functional group which can be obtained by polymerizing, can be obtained by adding a monomer having a functional group.

These acrylic resins (a), (d),
The weight average molecular weights (Mw) of (f) and (g) can be changed depending on the conditions when carrying out the polymerization reaction using a reaction initiator. The acrylic resin used in the present invention is
The weight average molecular weight is 20,000 to 1,000,000.
Those in the range of 0 are preferably used.

When the weight average molecular weight is less than 20,000, sufficient elongation cannot be obtained by stretching during the sheet sticking work, and cracks may occur. When the weight average molecular weight exceeds 1,000,000, it becomes difficult to dissolve in a solvent and it becomes difficult to prepare a coating sheet from the photocurable resin composition.

For example, when a sheet is prepared by solvent casting, the solvent viscosity increases, and therefore the resin can be cast only at a low concentration, which makes it difficult to increase the thickness of the sheet.

These acrylic resins have a Tg (glass transition point) of − because of the relationship between the hardness after sheet curing and scratch resistance.
It is preferably in the range of 20 ° C to 100 ° C. However, when the surface hardness is not too high, for example, 2B or less (23 ° C.) by the pencil hardness method, or when elongation of the sheet is almost unnecessary, the application is possible even if it is out of these ranges. Acrylic resins may be used in combination of different types as long as they have these molecular weight ranges.

Since the acrylic resins (d) and (g) have functional groups such as hydroxyl group, amino group and carboxyl group, they are cross-linked by the above-mentioned cross-linking agent, whereby the flexibility of the sheet can be improved. ..

Functional group value of the acrylic resins (d) and (g) {OH group value and NH ₂ group value (NH ₂ : NH added during polymerization)
The amount of ₂ groups is calculated in the same manner as the OH value, or the NH ₂ group is reacted with sodium nitrate to be quantified by changing it to an OH group) and COOH value (COOH value: the amount of COOH group added at the time of polymerization is OH
It is preferable that the calculation is the same as the valence or the sum of the values obtained by titrating COOH groups with KOH)} is in the range of 2 to 50. When the functional group value is less than 2, improvement in flexibility of the sheet cannot be expected. If the functional group value exceeds 50, sufficient elongation of the sheet cannot be obtained. However, if sheet elongation is rarely needed, and if sheet flexibility is sufficient,
It is applicable even if it is outside these ranges.

Further, these acrylic resin materials may be used as a block copolymer in which the reactive portion of the acrylic resin is block-shaped or comb-shaped. In this case, as the material that forms a block with these reactive acrylic resin materials, not only acrylic materials but also styrene-based materials, maleic acid-based materials, and imide-based materials having good compatibility with acrylics, silicone-based materials, and fluorine-based materials. Any combination of materials that can be blocked can be used. 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 the above-mentioned reactive acrylic resin is blended with these block polymers.

The low molecular weight compound having a double bond in the molecule (b) contained in the clear layer is, for example, methyl (meth) acrylate, ethyl (meth) acrylate, benzyl (meth) acrylate or 2-ethoxyethyl. Monofunctional types such as (meth) acrylate and phenoxydiethylene glycol (meth) acrylate, and 1,6-
Hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, penta There are polyfunctional types such as erythritol tetra (meth) acrylate and dipentaerythritol hexa (meth) acrylate.

There are also oligomers such as polyester acrylate, polyurethane acrylate, epoxy acrylate, polyether acrylate, oligo acrylate, alkyd acrylate and polyol acrylate. These low molecular weight substances may further have functional groups such as a hydroxyl group, an amino group and a carboxyl group.

The above-mentioned isocyanate-based cross-linking agent is an isocyanate compound having two or more isocyanate groups in the molecule, and examples thereof include tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, tolidine diisocyanate, triphenylmethane triisocyanate and tris (isocyanate. Phenyl)
Monomers of thiophosphite, P-phenylene diisocyanate, xylylene diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, etc. Examples include methylolpropane adduct, isocyanurate modified product, biuret modified product, carbodiimide modified product, urethane modified product, and allophanate modified product.

The melamine-based cross-linking agent is trimethylamine melamine obtained by reacting formaldehyde with a material having a polyfunctional amino group such as melamine, urea, thiourea, guanidine, guanamine, acetoguanamine, benzoguanamine, dicyandiamide and guanamine. Hexamethylol melamine, dimethylol urea dimethylol guanidine, dimethylol acetoguanamine, dimethylol benzoguanamine and the like are etherified melamine resins obtained by reacting with alcohols such as butyl alcohol and propyl alcohol.

The epoxy-based crosslinking agent is a glycidyl compound of a polyhydric alcohol containing a plurality of epoxy groups and is used together with a Lewis acid catalyst. The Lewis acid is preferably microencapsulated to delay the reaction.

For example, butadiene sidioxide, hexazine dioxide and diglycidyl ester of phthalic acid, bisphenol-A diglycidyl ether, bisphenol-F diglycidyl ether, para-aminophenol triglycidyl ether amine, aniline diglycidyl ether, Phenylenediamine tetraglycidyl ether, sulfonamide diglycidyl ether,
Examples thereof include glycidyl compounds such as triglycidyl ether of glycerin, polyether-modified diglycidyl, polyester-modified diglycidyl, urethane-modified diglycidyl compound (polymer), vinylcyclohexenedioxide, and dicyclopentadienedioxide.

The addition amount of these cross-linking agents is preferably about functional group value of acrylic resin: functional group value of cross-linking agent = 1: 0.7 to 1.3. However, in reality, due to the reactivity with the acrylic resin used, the functional groups of the acrylic resin and the cross-linking agents, for example, the melamine-based cross-linking agents, the reaction of the melamine-based cross-linking agent and the epoxy-based cross-linking agent, etc. occur. It is preferable to decide. The light colored layer and the dark colored layer are those in which a colorant such as a pigment is favorably dispersed in a binder material. As the binder material, an acrylic resin or urethane resin having a polar group such as a hydroxyl group or a carboxyl group, which has good pigment dispersibility, a polyester, or a vinyl chloride resin, an ABS resin, or PS, which similarly has good pigment dispersibility,
Resins and the like, and further modified materials and various copolymers and the like. For example, acrylic resin is an acrylic polyol that is solid at room temperature (containing only hydroxyl groups or carboxyl groups).
When the pigment is dispersed in a solvent system, the weight average molecular weight is 20,000 because the material needs to be soluble in the solvent.
The range of 1,000,000 is preferable.

When the pigment is dispersed by a kneader, it may be out of this range. However, in order to make the color of the colored layer as vivid as the paint, it is necessary to increase the pigment concentration of the colored layer material, and therefore it is preferable to use a solvent system.
Further, the urethane resin is classified into a linear type and a crosslinked type.

When a linear type urethane resin is used, there are a method of forming a colored layer by casting as it is and a method of forming a colored layer by polymerizing at the time of casting film formation.

When the cross-linking type is used, it is preferable to form a sheet by the latter method. These materials are, for example, tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, tolidine diisocyanate, P-phenylene diisocyanate, xylylene diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, lysine diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate,
Diisocyanates such as tetramethylxylylene diisocyanate and trimethylhexamethylene diisocyanate, polyester diols (condensed polyester diols, lactone polyester diols, polycarbonate diols, etc.), polyether diols and other diols, ethylene glycol, 1,4-butanediol , A chain extender such as hydroquinone diethylol ether.

When the casting film is formed as it is,
These materials can be previously polymerized in a solution (a catalyst such as dibutyltin dilaurate may be added in order to accelerate this reaction).

In this case, the urethane resin preferably has a weight average molecular weight in the range of 20,000 to 1,000,000. If the weight average molecular weight is less than 20,000, the sheet is likely to be cracked when the sheet is spread. When the weight average molecular weight exceeds 1,000,000, it becomes difficult to dissolve in a solvent. For example, when a sheet is prepared by solvent casting, the solvent viscosity becomes high, and therefore the resin can be cast only at a low concentration, and therefore the thickness is It would be very expensive to make the colored layers of the membrane.

Further, in the case of polymerizing at the time of casting, the above-mentioned low molecular weight materials or polymer materials obtained by polymerizing them are used, and bifunctional isocyanate is further added to polymerize by the heat at the time of film formation to form a colored layer. Is.

As for the cross-linking type, as in the case of polymerizing at the time of casting described above, a low molecular weight material or a polymer material obtained by polymerizing them is used, and at least trifunctional or higher functional isocyanate is further added to polymerize by heat during film formation. Then, the covering sheet is prepared.

These isocyanates are added within the range where the sheet can be spread (curved surface followability). For example, isocyanurate of hexamethylene diisocyanate and isocyanate such as trimethylolpropane adduct.
In addition to isocyanates, melamine crosslinkers may also be used. It is possible to further improve the solvent resistance of the covering sheet by using urethane partially cross-linked in this way.

The polyester resin used for the colored layer is
For example, there are a saturated type obtained from terephthalic acid and an ethylene glycol-based material, and an unsaturated type obtained from terephthalic acid and butadiene. The weight average molecular weight of the polyester resin is preferably in the range of 20,000 to 1,000,000.

If the weight average molecular weight is less than 20,000, the sheet is likely to be cracked when the sheet is spread. When the weight average molecular weight exceeds 1,000,000, it becomes difficult to dissolve in a solvent. For example, when a colored layer is formed by solvent casting, the solvent viscosity becomes high, and therefore the resin can be cast only at a low concentration, and therefore, It would be very expensive to make thick film sheets.

As the colorant contained in the light colored layer and the dark colored layer, pigments and dyes used in paints can be used. Examples of pigments include titanium oxide, iron oxide, carbon black, cyanine pigments, and quinacridone pigments.

Examples of dyes include azo dyes, anthraquinone dyes, indigoid dyes and stilbenzene dyes. Further, aluminum flakes, metal powder such as nickel powder, gold powder, silver powder and the like may be used as the colorant. It is preferable that these materials are fine particles.

The amount of these colorants added is preferably 0.01 to 0.2 times the amount which hides the main body of the molded product in the light-colored colorant layer when it becomes a molded product, and is colored in dark color. The agent layer preferably has an amount of hiding when formed into a molded product, preferably not more than 0.1.
5-4 times added.

A light colorant layer and a dark colorant layer,
By providing in this order, the depth of the obtained molded product,
It is possible to improve gloss and the like. When these materials are added, it is preferable that the photoinitiator undergoes an initiation reaction with light having a wavelength at which the absorption of the colorant is small.

The base material layer is provided to further improve the handleability of the covering sheet. When the adhesion between the base material layer and the colored layer made of the resin composition is poor, it is preferable to provide a primer layer between the two layers. Since the sheet is stretched as necessary and attached to the adherend, it is preferable that the base material layer is composed of a film having a malleability at least under heating. This base material layer may optionally contain a colorant as described above.

Examples of the resin used for the base material layer include polystyrene, acrylic polymer, polycarbonate, polyvinyl chloride, polyethylene, polypropylene, ABS (acrylonitrile-butadiene-styrene copolymer) and the like.

In order to further improve the designability of the covering sheet used in the present invention, the sheet may be provided with a printing layer. In this case, the printed layer is between the clear layer and the colored layer,
Alternatively, it is preferably provided between the light colored layer and the dark colored layer or on the clear layer. The above-mentioned printing layer is provided by a method such as screen printing, offset printing, and gravure printing using ordinary printing ink.

The covering sheet of the present invention may be further provided with a protective layer. The protective layer is laminated to provide shape retention during sheet storage and use and surface protection after attachment. Since the sheet is stretched as necessary and attached to the adherend, the protective layer is preferably composed of a film (for example, a thermoplastic film or a rubber film) having a malleability at room temperature or under heating. [Preparation of photocurable or electron beam curable sheet] The sheet, a clear layer, a light colored layer, a dark colored layer,
Sheets that will form the respective layers with the base material layer are separately prepared by calender molding, extrusion molding, casting molding, etc. and laminated by lamination, or by casting the base material layer with a dark color. A colored layer, a light colored layer, and a light or electron beam-curable clear layer formed thereon by a casting method, or a method in which a clear layer is formed on a release polyethylene terephthalate sheet by casting. It can be prepared by, for example, a method of laminating a light colored layer and a dark colored layer and then laminating this sheet on a base material layer.

Casting is performed by using a coating machine having a comma roll, a knife coater or the like. The thickness of the light- or electron-beam curable sheet thus obtained is determined by the appearance of the molded product, performance such as scratch resistance and weather resistance. For example, when it is used as a molded product, that is, when the sheet is spread to reduce the sheet thickness, the initial film thickness is set so that the final thickness of the clear layer is at least 5 μm or more.

As the covering sheet, the above-mentioned minimum required film thickness of the clear layer, and further, the total thickness of the base material layer, the light-colored coloring layer and the dark-colored coloring layer is 200 to 1,000 μm.
It is preferable that the thickness is about the same.

The electron beam is emitted from an electron beam accelerator having various shapes and sizes, and the electron beam having a dose of usually 20 to 1,000 keV, preferably 100 to 500 keV is used. The ultraviolet ray used for light irradiation is irradiated from each direction by a high pressure mercury lamp or a metal halide lamp (particularly in the case of a three-dimensional shape), and the irradiation on the irradiation surface is 5 to 500 mW / cm ² , preferably 50 to 200 mW / It is assumed to be cm ² . [Use of coating sheet] For example, exterior materials such as automobile bumpers, spoilers, exterior plates, interior materials such as instrument panels, exterior materials such as motorcycle cowls, OA equipment, etc.
By covering the housing material of home electric appliances, etc., hardness, weather resistance,
Used to improve solvent resistance and aesthetics. [Production Method of Coated Product] The coating sheet of the present invention has various uses. In a method such as injection molding or stamping molding, in which a covering sheet is introduced into a mold in advance and attached to a molded product at the same time as molding, the sheet is vacuum or / and pressure-molded inside the mold at room temperature or heated. It is brought into close contact with the mold with, and then normal molding is performed.

In a method for continuously producing a molded product such as extrusion molding and pultrusion molding, a method of introducing a covering sheet into a mold and simultaneously molding the molded product and attaching it to the surface of the molded product, sizing, There is a method such as pasting after cooling.

The method of introducing the covering sheet into the mold is usually carried out by winding the covering sheet in front of and in the middle of the mold. In the method of sticking the covering sheet after molding (immediately), it is usually carried out by sticking with a pressure roller along the surface of the molded product.

In vacuum (pressure) molding, the coating sheet (base material layer) of the present invention is laminated on the sheet to be molded in advance,
It is done in the usual way. When the sheet is attached to a long member such as wood or aluminum sash, it can be performed using a commercially available profile laminator or the like. At this time, it is preferable to provide an adhesive layer on the sheet in order to improve the adhesiveness to the adherend. The coating sheet on which the pressure-sensitive adhesive is laminated is usually attached directly to the surface of the molded product by a hand or by using a double vacuum forming machine (sticking machine) or the like.

After the sheet is attached, the clear layer is cured by irradiating the clear layer with light or an electron beam and optionally further heating to cure the clear layer to finally obtain a coating.

It should be noted that, in the method for producing a coated article, in order to attach the coating sheet to the adherend as is clear from the above description, the visco-adhesive action is not an essential requirement. Lamination by is also preferably used.

[0072]

The coated molding sheet of the present invention comprises an uncured or semi-cured clear layer comprising a photocurable or electron beam curable composition, a light colored layer, a dark colored layer and a substrate. Since the layers are laminated in this order, they have excellent appearance such as luster and depth, and excellent stretchability. While stretching the sheet, it is a coating that gives excellent decoration to the outer surface of the molded product having irregularities and curved surfaces. It can be used as a forming sheet and can be applied to deep drawing.

In the coated molded article of the present invention, a clear layer, a light colored layer, a dark colored layer, and a base material layer are laminated on the outer surface of the molded article in this order. Since the clear layer is hardened, it has excellent gloss, depth, weather resistance, scratch resistance, chemical resistance and the like.

In the method for producing a coated molded article of the present invention, the above-mentioned coated molding sheet is laid along with the clear layer facing the mold surface, and then the resin for molding the main body is supplied into the cavity to carry out lamination molding. After that, the mold is opened, the molded product is taken out, and the clear layer is cured by irradiating the clear layer with light or an electron beam, so the outer surface of the molded product having irregularities or curved surfaces can be easily, deeply and weatherproofed. It is possible to manufacture a coated molded article in which a decoration having excellent properties, scratch resistance, chemical resistance, etc. is laminated. As a result, unlike the case where the conventional paint is used, the space for painting and painting is not required and the working environment is not affected by the solvent.

[0075]

EXAMPLES The present invention will be described in detail below based on examples. In addition, "part" means "part by weight".

Examples 1 to 10 (A) Materials used for each layer 1) Substrate layer (1) ABS sheet (thickness 500 μm) (2) PP sheet (thickness 300 μm) with chlorinated PP primer Laminated to a thickness of 10 μm (3) ABS sheet (thickness 300 μm) (4) PVC sheet (thickness 300 μm) 2) Dark colored resin layer resin composition A Acrylic resin (methyl methacrylate and methacrylic acid) And butyl methacrylate copolymer, Mw
= 158,000, Tg = 80 ° C.) 100 parts Quinacridone red 50 parts Ethyl acetate 300 parts Polymeric dispersant 10 parts A mixture obtained by mixing the above with stirring.

B acrylic polyol (a copolymer of methyl methacrylate and ethyl methacrylate, hydroxylethyl acrylate, butyl acrylate,
Mw = 754,000, Tg = 70 ° C.) 100 parts Rutile titanium oxide 200 parts Ethyl acetate 300 parts Polymeric dispersant 10 parts A mixture obtained by mixing the above with stirring.

C Vinyl chloride resin (degree of polymerization: 900) 10
0 parts Rutile titanium oxide 200 parts Ethyl acetate 300 parts A mixture obtained by mixing the above with stirring.

D Reactive Acrylic Resin (Copolymer of Methyl Methacrylate, Butyl Acrylate, and 2-Hydroxyl Acrylate, Mw = 653,000, T
g = 45 ° C., OH value = 10) 100 parts Isocyanate crosslinking agent (Nippon Polyurethane Industry Co., Ltd.)
Made, Coronate L, NCO = 13.0%, solid content 75
%) 5.2 parts by solid content (this cross-linking agent has 1.2 equivalents of isocyanate groups to the functional groups of the reactive allyl resin) Quinacridone red 50 parts Ethyl acetate 300 parts The above components were mixed with stirring. blend. 3) Light colored resin layer resin composition a Acrylic resin (copolymer of methyl methacrylate, ethyl methacrylate, butyl methacrylate, and methacrylic acid, Mw = 158,000, Tg = 8)
0 ° C. Aluminum flakes (average particle size 30 μm) 5 parts Ethyl acetate 300 parts A mixture obtained by mixing the above with stirring.

B Acrylic polyol (copolymer of methyl methacrylate, ethyl methacrylate, hydroxyethyl methacrylate and butyl acrylate, Mw = 754,000, Tg = 70 ° C.) 100 parts Aluminum flakes (average particle size) 20 μm) 2 parts Ethyl acetate 300 parts A mixture obtained by mixing the above with stirring.

C Vinyl chloride resin (degree of polymerization: 900) 10
0 parts Aluminum flakes (average particle size 20 μm) 2 parts Rutile titanium oxide 20 parts A mixture obtained by mixing the above with stirring.

D Reactive acrylic resin (copolymer of methyl methacrylate, butyl acrylate and -2-hydroxyethyl acrylate, Mw = 653,000, T
g = 45 ° C., OH value = 10) 100 parts Isocyanate cross-linking agent (manufactured by Nippon Polyurethane Industry Co., Ltd .: trade name “Coronate L”, NCO = 13, 0%, solid content 7)
5%) 5.2 parts by solid content (this cross-linking agent has 1.2 equivalents of isocyanate groups with respect to the functional groups of the reaction-produced acrylic resin) Mica 5 parts Kitecridone red 5 parts Ethyl acetate 300 parts A mixture of the above with stirring. 4) Printing layer resin composition Yellow (manufactured by Toyo Ink Mfg. Co., Ltd .: trade name “Screen Process Ink, SSNSA-214”) Indigo color (manufactured by Toyo Ink Mfg. Co .: trade name “Screen Process Ink, SSNSA-391) Black (Toyo Ink Ink Mfg. Co., Ltd .: trade name "Screen Process Ink, SSNSA-911) 5) Clear layer resin composition Acrylic resin (copolymer of methyl methacrylate, ethyl methacrylate and butyl acrylate, Mw = 183,000, Tg = 60 ° C. 100 parts Acrylate monomer (manufactured by Nippon Kayaku Co., Ltd .: trade name “KAY”)
ARADDPCA-20) 50 parts 2,4-dihydroxybenzophenone 0.4 parts Phenyl salicylate 0.3 parts Ethyl acetate 300 parts A mixture obtained by mixing the above with stirring.

Acrylic resin (copolymer of methyl methacrylate, ethyl methacrylate, and butyl acrylate, Mw = 387,000, Tg = 80 ° C.)
100 parts acrylate monomer (manufactured by Nippon Kayaku Co., Ltd .: trade name "KAY"
ARAD DPCA-20 ") 50 parts Photoinitiator (manufactured by Japan Ciba-Geigy: trade name" Irgacure 184 ") 2 parts 2-hydroxy-4-dodecyloxybenzophenone 0.7 parts 2- (2'-hydroxy-3 ', 5'-ditert-butylphenyl) benzotriazole 0.3 part Ethyl acetate 300 parts A mixture obtained by mixing the above with stirring.

Reactive acrylic resin (reactive acrylic resin obtained by adding 2-hydroxyethyl methacrylate to a copolymer of methyl methacrylate, butyl methacrylate, butyl acrylate and acrylic acid,
Mw = 175,000 Average double bond per molecule = 5
8) 100 parts acrylate monomer (manufactured by Nippon Kayaku Co., Ltd .: trade name "KA"
YARAD R604 ") 80 parts Photoinitiator (manufactured by Japan Ciba-Geigy: trade name" Irgacure 184 ") 2 parts 2-Ethylhexyl-2-cyano-3,3'-diphenyl acrylate 0.8 parts Ethyl acetate 300 parts Stirring above While mixing.

Reactive Acrylic Resin (Copolymer of Methyl Methacrylate, Butyl Acrylate, and 2-Hydroxyethyl Acrylate, Mw = 186,000, T
g = 65 ° C., OH value = 5) 100 parts Acrylate monomer (manufactured by Nippon Kayaku Co., Ltd .: trade name “KAY”)
ARAD DPCA-20 ") 100 parts Photoinitiator (manufactured by Nippon Kayaku Co., Ltd .: trade name" Kayakyu DET "
X) 1 part photopolymerization accelerator (manufactured by Nippon Kayaku Co., Ltd .: trade name "Kayacure EP
A ”) 2 parts Isocyanate cross-linking agent (manufactured by Nippon Polyurethane Industry Co., Ltd .: trade name“ Coronate L ”, NCO = 13.0%, solid content 7)
5%) 2.2 parts by solids (this crosslinker has an equivalent amount of isocyanate groups to the functional groups of the reactive allyl resin) 2-hydroxy-4-dodecyloxybenzophenone 1.0 part Ethyl acetate 300 parts A mixture of the above with stirring.

Reactive acrylic resin (reactive allyl resin obtained by adding -2-hydroxyethyl acrylate to a copolymer of methyl methacrylate, butyl acrylate and acrylic acid, weight average molecular weight = 175,000, Tg
= 80 ° C., average double bond per molecule = 18, COOH
Value = 5) 100 parts Acrylate monomer (manufactured by Shin-Nakamura Chemical Co., Ltd .: trade name "NPA-10G") 50 parts Photoinitiator (2,4,6-trimethylbenzoyldiphenylphosphine oxide) 1 part N-methyldiethanolamine 2 parts Isocyanate crosslinking Agent (Nippon Polyurethane Industry Co., Ltd .: trade name "Coronate L", NCO = 13.0%, solid content 7)
5% solids 2.2 parts (this crosslinker has an equivalent amount of isocyanate groups to the functional groups of the reactive allyl resin) 2- (2'-hydroxy-3 ', 5'-ditert-) Aminophenyl) benzotriazole 1.0 part Ethyl acetate 300 parts A mixture obtained by mixing the above with stirring. B) Preparation of coating sheet A dark colored resin composition is applied onto the base material layer, and the coating is applied at 80 ° C. for 1 hour.
Dry for 5 minutes, apply the resin composition for the light colored layer on the dark colored layer, dry for 15 minutes at 80 ° C., print some of the sheets by screen printing on the light colored layer, and Apply the clear layer resin composition on the colored layer (printing),
A clear layer was formed by drying at 80 ° C. for 15 minutes to obtain a coating sheet.

The base layer, the dark colored resin composition, the light colored resin composition and the clear resin composition used in each example are shown in Tables 1 and 2. In addition, in Table 1,
The thickness of the dark colored layer is 50 μm, the thickness of the light colored layer is 30 μm, and the thickness of the clear layer is 30 μm. In Table 2, the thickness of the dark colored layer is 70 μm, the thickness of the light colored layer is 50 μm, and the thickness of the clear layer is 50 μm. C) Method of Manufacturing Coated Product The method of manufacturing the coated molded article of the present invention will be described with reference to the drawings.

First, the mold used in the present invention will be described with reference to FIG. Reference numeral 1 denotes an injection molding die used in the present invention, which comprises a moving side female die 11 and a fixed side male die 12, with a U-shaped cross section between the female die 11 and the male die 12. A cavity 13 having an inner surface shape corresponding to the outer surface shape of a box-shaped molded product to be molded is provided.

That is, the female die 11 is provided with the concave portion 111 forming the outer surface of the molded product to be molded, and the male die 12 is provided with the convex portion 121 forming the inner surface of the molded product to be molded and the end surface. An end face forming part 122 to be formed is provided.

Then, when the mold 1 is closed, the concave portion 111 of the female mold 11 and the portion surrounded by the convex portion 121 of the male mold 12 and the end face forming portion 122 form a molded product.
It is set to 3.

The concave portion 111 of the female die 11 is provided with a large number of extremely small vent holes 112 so that suction of air and ejection of compressed air can be performed through the vent holes 112.

When the mold 1 is opened, the heating plate 4 is provided between the female mold 11 and the male mold 12 as shown in FIGS. 2 and 3.
Is provided so that it can move back and forth. The heating plate 4 is provided with a large number of extremely small ventilation holes 41, and it is possible to suck air and eject compressed air through the ventilation article 41.

Next, the manufacturing process of the coated molded article of the present invention will be described with reference to FIGS. First, as shown in FIG. 2, on the side surface where the concave portion 111 of the female die 11 is opened, a clear layer 34 having a size such that the peripheral portion protrudes from the opening,
The sheet 3 in which the light-colored coloring layer 33, the dark-colored coloring layer 32, and the base material layer 31 are laminated in this order, and the clear layer 34 is the female mold 1
1 is directed toward the concave portion 111 and is supplied together with the heating plate 4 in a state of being suction-fixed through the ventilation plate 41 in the heating plate 4.

Next, as shown in FIG. 3, the sheet 3 is heated by the heating plate 4, vacuum suction is performed through the ventilation hole 112 of the concave view 111, and if necessary, the ventilation hole 41 of the heating plate 4 is used.
Compressed air is jetted through the sheet 3, and the sheet 3 is brought into close contact with the concave portion 111 with the clear layer 34 facing.

Then, as shown in FIG. 4, the heating plate 4 is removed and the mold 1 is closed. Then, in the mold 1, the sheet 3 is brought into close contact with the concave portion 111 of the female die 11, the peripheral portion of the sheet 3 is sandwiched between the female die 11 and the male die 12, and brought into close contact with the concave portion 111 of the female die 11. A closed cavity 13 surrounded by the sheet 3, the convex portion 121 of the male mold 12 and the end face forming portion 122 is formed.

In the cavity 13, the molten molding resin of the main body forming portion is injection molded by the injection molding machine through the sprue 123. Then, after a predetermined time has passed, the mold 1
After cooling inside, the mold 1 is opened, the molded product is taken out, the portion protruding from the outer peripheral surface of the molded product body 21 is removed, and the clear layer 34 is provided with the conditions shown in Tables 1 and 3,
By irradiating light or an electron beam to cure the clear layer 34, the clear layer 34 is formed on the outer surface of the molded article body 21.
Light colored layer 33, dark colored layer 32, and base material layer 31
A coated molded product 2 in which and were laminated in this order was obtained. D) Evaluation of Molded Article (Coating) As shown in Tables 1 and 2, the adhesion of the coating sheet obtained in each of the above Examples to an adherend, the hardness of the coating after curing the sheet, and the weather resistance were evaluated. evaluated.

The adhesiveness was determined by the adhesiveness test (the number of crosses remaining after the tape was peeled) by the cross-cut test, and the hardness was determined by the pencil hardness. The weather resistance was evaluated by the gloss retention and the color difference ΔE after 1,500 hours of sunshine weather meter. The results are shown in Tables 1 and 2.

[0098]

[Table 1]

[0099]

[Table 2]

Comparative Example 1 An ABS sheet (film thickness 500 μm was used as a coating molding sheet.
A coated molded product was produced and evaluated in the same manner as in Example 1 except that m) was used. As a result, the surface hardness of the obtained coated molded product was 6B or less.

Comparative Example 2 An ABS sheet (having a film thickness of 300 μm) was used as a coating molding sheet.
m, including 5 parts of aluminum flakes), a coated molded article was produced in the same manner as in Example 1. As a result, the sense of depth of the outer surface of the coated molded product was poor.

Comparative Example 3 An ABS sheet (film thickness 500 μm was used as a coating molding sheet.
A coated molded article was produced in the same manner as in Example 1 except that a sheet in which the dark colored layer A (film thickness 70 μm) used in Example 6 was laminated on m) was used. .. As a result, the sense of depth of the outer surface of the coated molded product was poor. The gloss was only 40. ) Method for manufacturing coated article

[0103]

EFFECTS OF THE INVENTION Since the covering molding sheet of the present invention has the above-mentioned constitution, it can be used as a covering molding sheet for excellently decorating the outer surface of a molded product having irregularities or curved surfaces. It can also be applied to deep drawing.

Since the coated molded article of the present invention has the above-mentioned constitution, it is a molded article excellent in gloss, depth, weather resistance, scratch resistance, chemical resistance and the like. Since the method for producing a coated molded article according to the present invention is configured as described above, a molded article obtained by simply laminating a coating film excellent in decoration as described above on the outer surface of the molded article having irregularities or curved surfaces. Can be manufactured. Further, in addition to being excellent in productivity, there is an advantage that the problem of the conventional painting space and the environmental problem such as the solvent are eliminated.

[Brief description of drawings]

FIG. 1 is a vertical sectional end view showing an example of a mold used in the present invention.

FIG. 2 is a vertical cross-sectional end view illustrating an example of a manufacturing process of a coated molded product of the present invention.

FIG. 3 is a vertical cross-sectional end view illustrating an example of a manufacturing process of a coated molded product of the present invention.

FIG. 4 is a vertical cross-sectional view illustrating an example of a manufacturing process of the coated molded product of the present invention.

FIG. 5 is a vertical cross-sectional perspective view showing an example of a coated molded article obtained by the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Mold 2 Molded product 3 Covering sheet 4 Heating plate 11 Female mold 12 Male mold 13 Cavity 21 Molded product body 31 Base material layer 32 Dark colored layer 33 Light colored colored layer 34 Clear layer 41 Vent hole 111 Recessed 112 through Porosity 121 Convex part 122 End face forming part

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Claims (3)

[Claims] 1. An uncured or semi-cured clear layer comprising a photocurable or electron beam curable composition, a light colored layer, a dark colored layer, and a substrate layer in this order. A coated molding sheet, which is laminated. 2. The coated molding sheet according to claim 1, which is coated on the outer surface of a molded article body, comprises an uncured or semi-cured clear layer comprising a photocurable or electron beam curable composition, and a light-colored composition. A coated molded article, wherein a colored layer, a dark colored layer, and a base material layer are laminated in this order on the outer surface of the molded article body, and the clear layer is cured. 3. A sheet for molding a cover and a body according to claim 1, wherein a cavity having an inner surface shape corresponding to an outer surface shape of a molded product to be molded is formed in a metal mold composed of a female mold and a male mold. A method for producing a coated molded product by supplying a molding resin, in which a sheet for molding a coating is placed with a clear layer facing the mold surface, and then a resin for molding a main body is supplied into a cavity. , An uncured or semi-cured clear layer composed of a photocurable or electron beam curable composition, a light colored layer, a dark colored layer, and a base material layer in this order on the molded article body. A method for producing a coated molded article, comprising laminating and molding the outer surface, opening the mold, taking out the molded article, and irradiating the clear layer with light or an electron beam to cure the clear layer.