JPH02223445A - Thermosetting resin for covering - Google Patents

Abstract

PURPOSE:To enable the surface of the article with unevenness or curved surface to be covered easily and uniformly by a method in which an uncured colored resin layer is laminated on the transparent resin layer with a specified composition in uncured state, whereby the thermosetting sheet for covering is formed. CONSTITUTION:The transparent resin layer 2 composed of the reactive acryl resin having the weight-average molecular weight of 1000-1000000 and being solid at room temperature, and the thermosetting resin composition containing block isocyanate as its main component is laminated on the surface of the colored resin layer 1 composed of colored thermosetting resin composition, whereby the thermosetting sheet for covering is formed. The obtained sheet is in uncured state before heating and is excellent in extensibility and flexibility, whereby it can cover sufficiently the surface of the article with unevenness or curved surface. The thickness of the transparent resin layer 2 is 10-50mum preferably, and the thickness of the colored resin layer 1 is preferably 50-150mum.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to coatings that are applied to the surfaces of furniture, steel plates, etc. and used for heat curing to protect, decorate, display, etc. It concerns the seat.

(Prior Art) Paint is generally used to decorate or display the surfaces of furniture, steel plates, etc.

However, when a solvent-based paint is used, the organic solvent evaporates during work, resulting in a poor work environment and an environmental health problem. When using a water-based paint, the work environment is not affected, but there are problems such as the drying time of the paint being longer or the fact that a large amount of energy is required to dry the paint.

Therefore, recently, sheet-like adhesive materials based on polyvinyl chloride have been proposed. In this pasting, the material is pasted on the surface of an article such as furniture or a steel plate, and when the material is used in this pasting, there is no adverse effect on the working environment, and since it is in sheet form, there is no need for drying. However, the material of this sheet-like adhesive is mainly made of soft polyvinyl chloride, which has the drawback of poor hardness and abrasion resistance.

As a method for improving this, a technique has been proposed in which a film with high surface hardness is obtained by curing the sheet material after application. For example, Japanese Patent Publication No. 57-13425 discloses that a porous sheet-like base material is impregnated with a radical reaction initiator, and a layer containing a polymer, a radically reactive monomer, etc. is laminated on one or both sides of the base material. Thermosetting composite sheets have been proposed.

In addition, JP-A-62-169630 discloses a colored film with excellent appearance and weather resistance, which is made of 81 transparent layers of two types of unsaturated polyester polyols having different molecular weights and a crosslinkable resin composition. is proposed.

Furthermore, JP-A No. 62-271735 discloses that a surface layer of a thermoplastic resin composition having excellent durability and a metal powder and/or a coloring pigment is formed on a substrate having good mold releasability and surface smoothness. A colored sheet with excellent appearance and durability, which is formed by laminating crosslinked resin In, has been proposed.

(Problems to be Solved by the Invention) The composite sheet disclosed in Japanese Patent Publication No. 13425/1987 has a structure in which a layer containing a radically reactive unsaturated compound and a layer containing a radical reaction initiator are laminated. Therefore, in order to achieve a uniform curing reaction when heated and pressurized,
Both layers must be brought into uniform contact, making it difficult to control heating and pressure, and also difficult to form a uniform cured film. In addition, since paper, woven fabric, non-woven fabric, etc. are used as the sheet-like base material to be impregnated with the radical reaction initiator, when coating the surface of an article with uneven or curved surfaces with Composite No. 1-1, the composite sheet It has the disadvantage that it is difficult to stretch and it is difficult to form a good film on the surface of the article.

The colored film disclosed in JP-A-62-169630 has a two-layer structure, and has good color depth and appearance. However, in manufacturing this colored film, a method is used in which a colored resin layer is provided on this transparent resin layer after the transparent resin layer is cured, so that Colored films do not have ductility and do not follow the surface of articles having unevenness or curved surfaces, making it difficult to form a good film.

The colored sheet disclosed in JP-A No. 62-271735 has the transparent resin layer and colored resin layer of the colored film disclosed in JP-A-62-169630 reversed, and is cured. Due to the influence of the colored resin layer, the sheet has no spreadability, and it is difficult to form a good film on the surface of an article having an uneven or curved surface.

The present invention is intended to solve the above-mentioned drawbacks, and its purpose is to provide good spreadability and flexibility before curing, and to coat surfaces of articles with unevenness and curved surfaces well. The object of the present invention is to provide a thermosetting coating sheet which can form a uniform and highly hard coating after curing.

Another object of the present invention is to provide a thermosetting coating sheet that has a two-layer structure and can form a cured film with a deep color and good appearance.

(Means for Solving the Problems) The thermosetting coating sheet of the present invention is a thermosetting coating sheet in which an uncured colored resin layer is laminated on an uncured transparent resin layer. The transparent resin layer is
The weight average molecular weight is o, o o o ~ 1. OO0,
000 and is solid at room temperature, and a thermosetting resin composition whose main components are a blocked isocyanate, and the colored resin layer is composed of a colored thermosetting resin composition. This achieves the above objectives.

The thermosetting resin composition forming the transparent resin layer further has a weight average molecular weight of 1.000 to lo, o o o
The reactive acrylic oligomer may be contained. The one-color resin j~ is a thermoplastic acrylic resin,
It may be formed from a thermosetting resin composition containing a reactive vinyl monomer, a colorant, a peroxide and/or a photosensitizer as main components.

The present invention will be explained in detail below.

The thermosetting liquid EL sheet of the present invention has an L-shape in which an uncured colored resin layer is laminated on an uncured transparent resin yr.

The transparent resin layer of the first invention has a weight average molecular weight of 10.00.
0 to 1.000.000 and is solid at room temperature (25°C), a blocked isocyanate,
The colored resin is formed from a thermosetting resin composition whose main component is a colored thermosetting resin. It is formed from a 11-layer composition.

In addition, the transparent resin layer of the second invention is manufactured by Jugo Keizai Bunkensha Co., Ltd.
, o o o~1.000. OOO and room temperature (2
5'C) and a solid reactive acrylic resin with a weight average molecular weight of 1. The colored resin layer is formed from a thermosetting resin composition mainly composed of a reactive acrylic oligomer having a molecular weight of OOO to 10.000 and a blocked isocyanate, and the colored resin layer is a thermosetting resin composition colored in the same manner as in the first invention. formed from things.

The reactive acrylic resin contained in the transparent resin layer of the first invention and the second invention is an acrylic polymer having a plurality of hydroxyl groups, and is a solid polymer at room temperature (25° C.). Such reactive acrylic resins include, for example, a (meth)acrylic acid ester monomer, a styrene derivative monomer, and a (meth)acrylic acid ester monomer having a hydroxyl group such as 2-hydroquinethyl (meth)acrylate, 2-aminoether. It is obtained by copolymerizing a (meth)acrylic acid ester monomer having an amine group such as (meth)acrylate or a monomer having a carboxyl group such as (meth)acrylic acid. The weight average molecular weight pm (Mw) of the reactive acrylic resin can be changed depending on the conditions when performing a polymerization reaction using an initiator, and the weight average molecular weight of the reactive acrylic resin is 90.000. -1.00o, o o o range is selected. If the weight average molecular weight is less than go or ooo, the obtained thermosetting coating sheet will have cracks after molding, resulting in an unfavorable appearance. Conversely, if the weight average molecular weight is 1. If it exceeds Oo o, o o o, the resulting resin composition will have poor moldability and it will be difficult to prepare a thermosetting coating sheet. In addition, these reactive acrylic resins have a Tg (glass transition point) in the range of 0 to 80°C due to the hardness after curing, and have functional groups (the sum of hydroxyl groups, amino groups, and carboxyl groups).

Functional group value is the sum of hydroxyl value, amino group value and acid value,
The amine value is a value determined by calculating the amount of amino groups added during polymerization in the same way as the hydroxyl value, or by reacting the amino groups with nitrous acid and converting them into hydroxyl groups. The acid value is calculated by calculating the amount of carboxyl groups added during polymerization in the same way as the amount of hydroxyl groups, or by quantifying one carboxyl group using KOH, etc.) is 20 to 20.
A value in the range of 0 is preferred. In addition, different reactive acrylic resins may be used in combination as long as they have molecular weights within these ranges.

The blocked isocyanate contained in the above-mentioned transparent resin J- is a reactive acrylic resin in the first invention, and a reactive acrylic resin and a reactive acrylic oligomer in the second invention by a heating reaction for curing the reactive acrylic resin and the reactive acrylic oligomer during heating. Used as a mold hardening agent. What is blocked isocyanate?
It refers to a compound in which the isocyanate group of an isonanate compound having two or more isocyanate groups in the molecule is blocked with a blocking agent such as phenol, oxime, ε-caprolactam, or malonic acid ester. Examples of the isonanate compound include monomers such as tolylene diisocyanate, diphenylmethane diisonanate, hexamethylene diisocyanate, and isophorone diisonanate, or trino-10-thyrolpropane adducts, isocyanurate-modified products, and carbodiimide-modified products thereof. There are bodies, etc. In blocked isocyanate, the blocking agent is removed by heating, and the resulting isocyanate group causes a crosslinking reaction with the functional group of the reactive acrylic resin (reactive acrylic resin and reactive acrylic oligomer if it contains a reactive acrylic oligomer). . In the first invention, the content of the blocked isocyanate is such that the ratio of the functional groups contained in the reactive acrylic resin to the isocyanate groups contained in the blocked isocyanate is α5 to 2.
．． It is preferably adjusted to be in the range of 0, more preferably in the range of 0.8 to L2. In the second invention,
The content of blocked isocyanate is the hydroxyl group contained in the reactive acrylic resin and reactive acrylic oligomer,
The ratio to the isocyanate group contained in the blocked isocyanate is preferably adjusted to be in the range of 0.5 to 2.0, more preferably in the range of 0.8 to L2.

The transparent resin layer of the second invention (the reactive acrylic oligomer contained in this layer is mainly used to obtain flexibility and elongation of the cured coating film. Like the above-mentioned reactive acrylic resin, this reactive acrylic oligomer is It is an acrylic polymer having a hydroxyl group, an amino group, or/and a carboxyl group, and is preferably a polymer that is solid or a solid solution at room temperature.Such reactive acrylic oligomers are, for example, (
meth)acrylic acid ester monomers, styrene derivative monomers, and (meth)acrylic acid ester monomers having hydroxyl groups such as 2-hydroxyethyl (meth)acrylate (meth)acrylic acid ester monomers having more amino groups such as 2-aminoethyl (meth)acrylate. It can be obtained by copolymerizing a meth)acrylic acid ester monomer and/or a monomer having a carboxyl group such as (meth)acrylic acid.

The reactive acrylic oligomer has a weight average molecular weight of 1
．． 000 to 10.000 is selected. The weight average molecular weight of the reactive acrylic oligomer is 1.000
If it is less than 20%, the moldability of the obtained thermosetting resin composition will be poor and it will be difficult to prepare a thermosetting coating sheet. When the weight average molecular weight exceeds 10,000, the resulting sheet lacks flexibility and has poor moldability. In addition, these reactive acrylic oligomers have glass transition points within the range of 150°C to 40°C due to the relationship between sheet formability and hardness after curing.
It is preferable to use one having a functional group value of 80 to 250. As long as the reactive acrylic oligomer falls within these molecular weight ranges, a combination of multiple types of reactive acrylic oligomers may be used.

Further, an isocyanate, epoxy, or melamine crosslinking agent may be added to these resin layers depending on the case.

In this way, the transparent resin layer of the first invention is formed from the thermosetting resin composition containing the solid reactive acrylic resin and the blocked isocyanate as main components, and also the solid reactive acrylic resin and the reactive The transparent resin layer of the second invention is formed from a thermosetting resin composition containing an acrylic oligomer and a blocked isocyanate as main components. If necessary, fillers, anti-aging agents, etc. may be added to the transparent resin layers of the first and second inventions within a range that does not impair transparency. The obtained transparent resin layer is in an uncured state before heating, and a hard transparent film is formed by heating at a predetermined temperature or higher.

Examples of the composition of the thermosetting resin composition forming the colored resin layer include the following three.

■ Main ingredients are thermoplastic acrylic resin, reactive vinyl monomer, peroxide and colorant.

■ Main ingredients are thermoplastic acrylic resin, reactive vinyl monomer, photosensitizer, and colorant.

■ Main ingredients include thermoplastic acrylic resin, reactive vinyl monomer, peroxide, photosensitizer, and colorant.

The thermoplastic acrylic resin contained in the colored resin Ji is a polyacrylic ester, and usually polymethyl methacrylate or polymethyl methacrylate copolymer can be used. Other acrylic ester polymers and blends thereof can also be used.

As the coloring agent, pigments, dyes, etc. used in ordinary painting can be used. For example, pigments include titanium oxide, iron oxide, carbon black, anine pigments, and quinacridone pigments; dyes include azo dyes, anthraquinone dyes, indigoid dyes, and stilbene dyes; and aluminum flakes, Metal powder such as nickel powder, gold powder, silver powder, etc. may be added.

When using a colorant with high hiding power, the total amount of colorant is 100 parts by weight of the solid content of the resin (hereinafter simply referred to as parts).
The range of 2 to 100 parts is preferable.

As the reactive hynyl monomer, (meth)acrylic and styrene materials are suitable as materials having good compatibility with the thermoplastic acrylic resin. Examples of acrylic reactive vinyl monomers include methyl (meth)acrylate, ethyl (meth)acrylate, benzyl (meth)acrylate, and 2-ethynethyl (meth)acrylate.
Acrylate, monofunctional types such as phenoxydiethylene glycol (meth)acrylate, 1,6-hexanethiol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polybropylene glycol di( meth)acrylate, trimethylpropane tri(meth)acrylate, pentaerythritol tri(meth)
Multifunctional types such as acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate are applicable.

Styrene-based reactive vinyl monomers include styrene, α-methylstyrene, α-ethylstyrene, p-methylstyrene, p-methkinstyrene, p-phenylstyrene, p-ethoxystyrene, p-chlorostyrene, m
-Various styrene derivatives such as chlorostyrene and 0-chlorostyrene can be applied. The amount of these reactive vinyl monomers added is 100 parts of thermoplastic acrylic resin + r
On the other hand, it is preferably adjusted to be in the range of 20 to 200 parts, more preferably in the range of 40 to 150 parts. Moreover, the above-mentioned reactive vinyl monomers are not limited to one type, and two or more types can be used in combination.

The above-mentioned peroxide is preferably a commonly used organic peroxide type, and more preferably, from the viewpoint of storage stability at room temperature, for example, 2,2-bis(ter-butylperoquine)butane, ter= Peroxides such as butyl peroxybenzoate, di-ter-butyl peroquine isophthalate, methyl ethyl ketone peroxide, dicumyl peroxide, and ter-butyl peroquine acetate have a decomposition temperature of about 160"C. The appropriate amount of addition differs depending on the composition of the above-mentioned color resin layer, but α5 to
A range of 2.0 parts is suitable. Moreover, the peroxide is not limited to one type, and two or more types can be used in combination.

As the above-mentioned photosensitizer, commonly used photosensitizers can be applied, and for example, photosensitizers of benzoin alkyl ether type, acetophenone type, benzophenone type, thioxanthone type and the like are preferably used. Benzoin ethers include benzyl, benzoin, benzoin methyl ether,
Among the acetophenone series, such as benzoin ethyl ether and benzoin isopropyl ether, 2°2'-jethoxyacetophenone, 2. z-dibutoxyacetophenone, 2-hydroquine-2-methylpropiophenone, p
-ter-butyltrichloroacetophenone, etc., benzophenone, 4-chlorobenzophenone, 4,4'-dichlorobenzophenone, 3゜3'-dimethyl-4-methoxybenzophenone, dibenzosuberone, etc., thioxanthone, thioxanthone, etc.
2-chlorothioxanthone, 2-methylthioquinthone,
Examples include 2-isopropylthioxanthone and 2-ethylanthraquinone.

The appropriate amount of the photosensitizer added varies depending on the type of pigment used in the thermosetting coating sheet, but is preferably in the range of 0.5 to 3.0 parts based on 31,100 parts of the reactive vinyl monomer. Moreover, the photosensitizer is not limited to one type, and two or more types can be used in combination.

A colored thermosetting resin composition is obtained by mixing the above components, and a colored resin layer is formed with this thermosetting resin composition. The colored resin layer is in an uncured state before heating, and adheres well to the transparent resin layer. A hard coating is formed by heating the colored resin layer at a temperature above a predetermined temperature, and in particular, a colored resin layer containing a photosensitizer is cured by being irradiated with light to form a hard coating.

The thermosetting coating sheet of the present invention thus obtained is formed by laminating a transparent resin layer 2 on the surface of a colored resin layer 1, as shown in FIG. It is in an uncured state, has excellent spreadability and flexibility, and can be well coated along the surface of an article having an uneven or curved surface.

The thickness of the transparent resin layer 2 is preferably 10 to 50 μm,
The thickness of the colored resin layer 1 is preferably 50 to 150 μm. However, when the colored &l fat/lll11 is an ultraviolet curing type, the thickness of the colored resin layer 1 is preferably 50 to 80 μm.

In addition, if the colored resin layer 1 of the thermosetting coating sheet does not have sufficient adhesive strength to the article to be coated, as shown in FIG. By providing the adhesive layer 3 and attaching the sheet to the surface of the article via the adhesive layer 3, it is possible to improve the adhesiveness between the hard coating and the article after curing. Examples of the adhesive layer 3 include EvA hot melt adhesive, SIS hot melt film adhesive, acrylic hot melt film adhesive, uncrosslinked unsaturated polyester, acrylic adhesive, and post-cured acrylic. Examples include adhesives,
A blend or a laminate of these may be used.

When the viscosity of the resin composition constituting the primary thermosetting coating sheet at room temperature is low, it becomes difficult to shape the sheet into its shape. In such a case, by providing a support layer on the surface of the transparent resin layer 2 of the thermosetting coating sheet, the shape retention of the thermosetting coating sheet can be improved. Furthermore, as shown in FIG. 3, an adhesive layer 3 may be provided on the back surface of the colored resin layer 1, and a support layer 4 may be provided on the surface of the transparent resin layer 2. The support layer 4 is used to maintain the shape of the entire thermosetting coating sheet, but when the sheet is attached to the surface of an article having a three-dimensional curved surface with this support jI14, this support layer 4 is used to maintain the shape of the entire thermosetting coating sheet. Heating is performed as necessary to impart flexibility to layer 4 and ensure desired malleability. After the thermosetting coating sheet is applied to an article and cured, the support layer 4 may be peeled off and removed.

The thermosetting coating sheet constructed in this manner may be manufactured by any method. For example, the components of the transparent resin layer described above are mixed uniformly, this mixture is applied onto a film that has been subjected to a release treatment with a silicone release agent, and is dried to form a transparent resin layer. Next, a colored resin layer is formed by coating the surface of this transparent resin 1- with a colored material in which the above-mentioned colored resin layer components are uniformly mixed and drying, and then the transparent resin layer and the colored resin layer are separated from the film by #J. # Then you can get it from t. Alternatively, a thermosetting coating sheet can be obtained by forming a transparent resin layer and a colored resin layer on a film, and then loosening both layers using a roll press or the like to make them piezoelectric, and then removing the film. The temperature in each of the above drying steps is below the decomposition temperature of proccison anate and peroxide.

(Example) The present invention will be explained in detail below based on examples.

Example 1 Acrylic polyol (manufactured by Nippon Shokubai Kogyo ■, Arotan 20
40-145, Tg40'C1 weight average molecule ffi 3
39.000, OHHBO2 solid content 100 parts, blocked isocyanate (manufactured by Shikinichi Yakuhin Kogyo ■, Takenate B-
815N, hydrogenated tuphenylmethane diisonanate ocime block, NC0% 7.3) 49 parts (this block isocyanate has to equivalent isocyanate groups to the hydroxyl groups of the acrylic polyol)
were mixed with thorough stirring. This mixture is mixed into polyethylene terephthalate film (
A transparent resin layer (hereinafter referred to as transparent resin layer A) was formed by coating the mold release surface of a PET film manufactured by Soken Kako ■ with a film thickness of 40 μm or less and drying at 80° C. for 5 minutes.

On the other hand, 300 parts of ethyl acetate, 100 parts of thermoplastic acrylic resin (manufactured by Asahi Kasei Corporation, Delpera l-8500), 40 parts of methyl methacrylate, 0 parts of ter-butyl peroxide.
．． 6 parts and 50 parts of titanium oxide were mixed with thorough stirring. The mixture was coated on the transparent resin layer A described above, and
A colored resin layer was formed by drying at .degree. C. for 5 minutes, and the PET film was peeled off to obtain an uncured thermosetting coating sheet. The film thickness of this sheet is 20 mm for the transparent resin layer.
The μm1 colored resin layer was 100 μm.

Example 2 Acrylic polyol (manufactured by Nippon Shokubai Kogyo ■, 70 tan 20
40-139, weight average molecule 1132o, o o o
, Tg 20°C, OH value 100) as a solid content, and 62 parts of blocked isocyanate (manufactured by Shikinichi Yakuhin Kogyo ■, Takenate B-815N) (having 10 equivalents of isocyanate groups with respect to the hydroxyl groups of the acrylic polyol). Mixed with stirring.

This mixture was applied to the release surface of the PET film that had been subjected to release treatment, and dried at 80°C for 5 minutes to form a transparent resin layer (hereinafter referred to as
A transparent resin layer B) was formed.

Next, 300 parts of ethyl acetate, 100 parts of thermoplastic acrylic resin (manufactured by Asahi Kasei Kogyo ■, Delpet 85oo), 50 parts of neopentyl glycol dimethacrylate, 0.8 part of dibutylperoxyisophthalate, and 50 parts of titanium oxide.
The parts were mixed with thorough stirring. The mixture is coated on the above-mentioned transparent resin layer B, dried at 80°C for 5 minutes to form a colored resin layer, and the PET film is peeled off to form an uncured thermosetting coating sheet. Obtained. The film thickness of this sheet is 15 μm for the transparent resin layer and 70 μm for the colored resin layer.
It was m.

Example 3 300 parts of ethyl acetate, 100 parts of thermoplastic acrylic resin (manufactured by Asahi Kasei Kogyo ■, Delpet 8500), 40 parts of tripropylene glycol dimethacrylate, LO part of ter-butyl peroquine penzoate and 50 parts of titanium oxide. Mixed with stirring. This mixture was added to the above transparent resin layer A.
A colored resin layer was formed by coating on top and drying at 70° C. for 30 minutes, and the PET film was peeled off to obtain an uncured thermosetting coating sheet. The film thickness of this sheet was 30 μm for the transparent resin layer and 80 μm for the colored resin layer.

Example 4 300 parts of ethyl acetate, 100 parts of thermoplastic acrylic resin (manufactured by Asahi Kasei Kogyo ■, Delpet 8500), 60 parts of hexamethylene glycol dimethacrylate, LO part of ter-butyl peroquine benzoate, and 50 parts of titanium oxide. were mixed with stirring. This mixture is coated on the transparent resin layer B, dried at 70°C for 30 minutes to form a colored resin layer, and the PET film is peeled off to obtain an uncured thermosetting coating sheet. Ta. The film thickness of this sheet is 15 μm for the transparent resin layer and 100 μm for the colored resin layer.
Met.

Example 5 300 parts of ethyl acetate, 100 parts of thermoplastic acrylic resin (manufactured by Asahi Kasei Tamagogyo ■, Chilpet 8500), 40 parts of dipropylene glycol dimethacrylate, 1.40 parts of methyl methacrylate, terbutyl peroxypenzo 10 parts of ester, 6 parts of 4-chlorobenzofene α, and 50 parts of titanium oxide were mixed with stirring. This mixture is coated on the transparent resin MA, dried at 70°C for 30 minutes to form a colored resin layer, and the PET film is peeled off to form an uncured heat- and photo-curable coating sheet. Obtained. The film thickness of this sheet was 30 μm for the transparent resin layer and 60 μm for the colored resin layer.

Example 6 300 parts of ethyl acetate, 100 parts of thermoplastic acrylic resin (manufactured by Asahi Kasei Kogyo ■, Delpera 1-8500), 40 parts of dipropylene glycol dimethacrylate, 40 parts of methyl methacrylate, 10 parts of ter-butyl peroxobenzoate, benzyl 0.6 parts and 50 parts of titanium oxide were mixed with stirring. This mixture was added to the above transparent resin IS.
It was coated on B and dried at 70° C. for 30 minutes to form a colored resin layer, and the PET film was peeled off to obtain an uncured heat- and photo-curable coating sheet. The film thickness of this sheet was 15 μm for the transparent resin layer and 55 μm for the colored resin j-.

Example 7 300 parts of ethyl acetate, 100 parts of thermoplastic acrylic resin (Delpet 8500 manufactured by Asahi Kasei Gyokugyo ■), 40 parts of fenoquine diethylene glycol nucacrylate, 40 parts of 0-chlorostyrene, 8 parts of benzoin α, and 5 parts of titanium oxide.
0 parts were mixed with stirring. By coating this mixture on the transparent resin layer A, drying at 80°C for 10 minutes to form a colored resin layer, and peeling off the PET film,
A heat- and photo-curable coating sheet was obtained in an uncured state. The film thickness of this sheet was 30 μm for the transparent resin layer and 55 μm for the colored resin layer.

Example 8 300 parts of ethyl acetate, 100 parts of thermoplastic acrylic resin (manufactured by Asahi Kasei Kogyo ■, Delpet 8500), 40 parts of fenoquine dipropylene glycol methacrylate, 40 parts of p-chlorostyrene, 8 parts of benzoin α, and 50 parts of titanium oxide. Mixed with stirring. This mixture is coated on the transparent resin layer B, dried at 80° C. for 10 minutes to form a colored resin layer, and the PET film is peeled off to form an uncured heat- and photo-curable coating sheet. I got it. The film thickness of this sheet was 15 μm for the transparent resin layer and 60 μm for the colored resin layer.

Example 9 Acrylic polyol (manufactured by Nippon Shokubai Co., Ltd., Arotan 20
40-145) 100 parts solids, acrylic polyol oligomer (Nippon Carbide, Nikalide H-870)
, weight average molecular weight 2, 200-2.500, OH number 20
0) 30 parts, Block Ison Anate (Narita Pharmaceutical Co., Ltd.)
86 parts of Takenate B815N (manufactured by Takenate B815N) (this procisoanate has LO equivalent of isocyanate groups to the hydroxyl groups of the acrylic polyol and acrylic polyol oligomer) were mixed with thorough stirring. This mixture was applied in the same manner as in Example 1 (on the release surface of a PET film that had been subjected to a silicone release treatment, and dried at 80°C for 5 minutes to form a transparent resin # (hereinafter referred to as transparent resin layer C). .

Separately, 300 parts of ethyl acetate, 100 parts of a thermoplastic acrylic resin (Delpet 8500, Asahi Kasei Gyokugyo), 40 parts of methyl methacrylate, 0.6 parts of ter-butyl peroxyacetate, and 50 parts of titanium oxide were mixed with stirring. . This mixture was coated on the transparent resin MC, and 8
A colored resin layer was formed by drying at 0° C. for 5 minutes, and the PET film was peeled off to obtain an uncured thermosetting coating sheet. The film thickness of this sheet was 20 μm for the transparent resin layer and 100 μm for the colored resin layer.

Example 10 Acrylic polyol (manufactured by Nippon Shokubai Kogyo ■, Arotan 20
40-139) Solid content: 100 parts, acrylic polyol oligomer (manufactured by Nippon Shokubai Kogyo ■, Alotane 2040-1)
34, weight average fractionation 19,000, Tg 20°C, OH value 120) 20 parts, Protsquison anate (manufactured by Shikinichi Yakuhin Kogyo ■, Takenate B815N) 78 parts (this block isocyanate is a combination of the above acrylic polyol and acrylic polyol) (having 10 equivalent isonanate groups per hydroxyl group of the oligomer) was mixed with thorough stirring.

This mixture was applied to the release surface of a PET film that had been subjected to silicone release treatment in the same manner as in Example 1, and
It was dried at 80° C. for 5 minutes to form a transparent resin layer (hereinafter referred to as transparent resin layer).

On the other hand, 300 parts of ethyl acetate, 100 parts of thermoplastic acrylic resin (Delpet 8500, manufactured by Asahi Kasei Tamogyo ■), 50 parts of neopentyl glycol dimethacrylate, 0.8 parts of dibutyl peroquine isophthalate, and 5 parts of titanium oxide.
0 parts were mixed with stirring. This mixture was coated on the transparent resin Id D, dried at 80°C for 5 minutes to form a colored resin layer, and the PET film was peeled off to obtain an uncured thermosetting coating sheet. Ta. The film thickness of this sheet is 15 μm for the transparent resin layer and 70 μm for the colored resin layer.
It was μm.

Example 11 300 parts of ethyl acetate, 100 parts of thermoplastic acrylic resin (manufactured by Asahi Kasei Corporation, Delpera 8500), 40 parts of tripropylene glycol dimethacrylic L/-), ter
-10 parts of butyl peroxybenzoate and 50 parts of titanium oxide were mixed with stirring. This mixture is coated on the transparent resin layer C, dried at 70°C for 30 minutes to form a colored resin layer, and the PET film is peeled off to obtain an uncured thermosetting coating sheet. Ta. The film thickness of this sheet is 30 μm for the transparent resin layer and 80 μm for the colored resin layer.
It was μm.

Example 12 300 parts of ethyl acetate, 100 parts of thermoplastic acrylic resin (Delpet 8500, manufactured by Asahi Kasei Gyokugyo), 60 parts of hexamethylene glycol dimethacrylate, 10 parts of ter-butyl peroxybenzoate, and 50 parts of titanium oxide were stirred. while mixing. This mixture is coated on the transparent resin layer, dried at 70'C for 30 minutes to form a colored resin layer, and the PET film is peeled off to form an uncured thermosetting coating sheet. Obtained. The film thickness of this sheet is 15 μm for the transparent resin layer, 100 μm for the colored resin layer.
It was m.

Example 13 300 parts of ethyl acetate, 100 parts of thermoplastic acrylic resin (Delpet 8500, manufactured by Asahi Kasei Tamagayi), 40 parts of dipropylene glycol dimethacrylate, 40 parts of methyl methacrylate, 10 parts of ter-butyl peroxybenzoate, 4 0.6 parts of chlorobenzophenone and 50 parts of titanium oxide were mixed with stirring. This mixture is coated on the above transparent resin Ill C, dried at 70°C for 30 minutes to form a colored resin, and the PET film is peeled off to form a heat and photocurable coating in an uncured state. Got a sheet. The film thickness of this sheet was 30 μm for the transparent resin layer and 60 μm for the colored resin layer.

31 Example 14 300 parts of ethyl acetate, 100 parts of thermoplastic acrylic resin (Delpet 8500, manufactured by Asahi Kasei Tamagayi), 40 parts of dipropylene glycol dimethacrylate, 40 parts of methyl methacrylate, ter-fu F-ruperoquine To parts of benzoate, 0.6 parts of benzyl and 50 parts of titanium oxide were mixed with stirring. This mixture was added to the above transparent resin Jl.
d By coating on D and drying at 70°C for 30 minutes to form a colored resin layer, and peeling off the PET film,
A heat- and photo-curable coating sheet was obtained in an uncured state. The film thickness of this sheet was 15 μm for the transparent resin layer and 55 μm for the colored resin layer.

Stir 300 parts of ethyl acetate, 100 parts of thermoplastic acrylic resin (Delpet 8500, manufactured by Asahi Kasei Gyokugyo), 40 parts of fenoquine diethylene glycol methacrylate, 40 parts of 0-chlorostyrene, 0.8 part of benzoin, and 50 parts of titanium oxide. while mixing. This mixture is coated on the above transparent resin, resin fIC, dried at 80°C for 10 minutes to form a colored resin layer, and the PET film is peeled off. Got a sheet. The film thickness of this sheet was 30 μm for the transparent resin l- and 55 μm for the colored resin layer.

Example 16 300 parts of ethyl acetate, 100 parts of thermoplastic acrylic resin (manufactured by Asahi Kasei Corporation, Delpera l-8500), 40 parts of phenoquine dipropylene glycol methacrylate, p-
40 parts of chlorostyrene, 0.8 parts of benzoin, and 50 parts of titanium oxide were mixed with stirring. This mixture is coated on the transparent resin ll1ilD, dried at 80°C for 10 minutes to form a colored resin layer, and the PET film is peeled off to form an uncured heat- and photo-curable coating sheet. Obtained. The film thickness of this sheet is 15 μm for the transparent resin layer.
One colored resin layer was 60 μm.<Performance of thermosetting coating sheet> The performance of the sheet was tested for elongation, vacuum formability, adhesion, and hardness.

The elongation property was evaluated by elongating the sheet 100% under 30° C. atmospheric conditions and determining whether or not the sheet was torn. The moldability was evaluated based on the ease of coating and the appearance of the sheet when the sheet was attached to a base material and the laminate was vacuum-formed at 60°C.

The adhesion of the sheet was as described above (
After heating the R layer body at 160°C for 30 minutes or heating it at 160°C for 30 minutes and irradiating it with a high-pressure mercury lamp (160W/σ, height 15a) for 2 minutes, the surface of the cured coating was coated with 1 part at 1 interval. 100 cuts were made in the shape of a base plate, a commercially available adhesive tape was pasted thereon, and the tape was then applied to indicate the percentage of remaining base pieces.

Hardness was evaluated by a pencil hardness test according to JIS K5400. Table 1 shows the test results when a steel plate was used as the base material, and Table 2 shows the test results when a painted steel plate was used as the base material. When a painted steel plate is used as the base material, in order to maintain the adhesion of the sheet to the painted steel plate during vacuum forming, adhesive M (acrylic adhesive, seed Vacuum forming was carried out using a 18-dyne WHD from Suikagaku Kogyo (thickness: 10 μm).

(Left below) Comparative Example 1 Acrylic polyol (manufactured by Nippon Shokubai Kogyo ■, Arotan 20)
40-136, weight average molecular weight 29゜000) solid content: 100 parts, blocked isocyanate (Shikinichi Pharmaceutical Co., Ltd.
49 parts of Takenate B-815N (manufactured by Takenate B-815N) (containing 10 parts per hydroxyl group of the acrylic polyol) were mixed with good stirring. This mixture was coated on the release surface of a PET film subjected to release treatment, and dried at 80° C. for 5 minutes to form a transparent resin layer. Next, 300 parts of ethyl acetate was added with a thermoplastic acrylic resin (manufactured by Asahi Kasei Corporation, Delpet 85).
00), 40 parts of methyl methacrylate, 20 parts of diethylene glycol dimethacrylate, 10 parts of thioxanthone, and 40 parts of titanium oxide were mixed with stirring. This mixture is coated on the transparent resin layer, dried at 80°C for 5 minutes to form a colored resin layer, and the PET film is peeled off to form an uncured heat- and photo-curable coating sheet. Obtained. The film thickness of this sheet was 15 μm for the transparent resin layer and 70 μm for the colored resin layer.

Comparative Example 2 Acrylic polyol (manufactured by Nippon Shokubai Kogyo ■, Arotan 20
40-134, weight average molecular weight 9.000) Solid content: 1
00 parts and 49 parts of blocked isocyanate (Takenate B-815N, manufactured by Shikinichi Yakuhin Kogyo ■) (having 10 parts per hydroxyl group of the acrylic polyol) were mixed with thorough stirring. This mixture was coated on the release surface of a PET film subjected to release treatment, and dried at 80° C. for 5 minutes to form a transparent resin layer. Next, thermoplastic acrylic resin (manufactured by Asahi Kasei Kogyo ■, Delpet 850) was added to 300 parts of ethyl acetate.
0), 30 parts of methyl methacrylate, 20 parts of diethylene glycol dimethacrylate, 210 parts of thioxant and 40 parts of titanium oxide were mixed with stirring. This mixture is coated on the transparent resin layer, dried at 80°C for 5 minutes to form a colored resin layer, and the PET film is peeled off to form an uncured heat- and photo-curable coating sheet. Obtained. The film thickness of this sheet is 1
The thickness of one colored resin layer was 70 μm.

Comparative Example 3 Acrylic polyol (manufactured by Nippon Shokubai Kogyo, Arotan 20
40-136, weight average molecular weight 2,900, OHHBO
2 solid content is 100 parts, and 30 parts of acrylic polyol oligomer (Nippon Carbide, Nikalide H-870, weight average molecular weight 2,200-2.500) (The solid content of Nikalide is 30 parts with respect to the solid content of Arothane. ), blocked isocyanate (manufactured by Shikinichi Yakuhin Kogyo ■, Takenate B-
815N) (10 equivalents based on the hydroxyl groups of the acrylic polyol and acrylic polyol oligomer) were mixed with thorough stirring. This mixture was coated on the release surface of a PET film subjected to release treatment, and dried at 80° C. for 5 minutes to form a transparent resin layer. Next, thermoplastic acrylic resin (manufactured by Asahi Kasei Kogyo ■,
Chilpet 8500) 100 parts, methyl methacrylate 30 parts, diethylene glycol dimethacrylate 20 parts
210 parts of thioxant and 40 parts of titanium oxide were mixed with stirring. This mixture is coated on the above transparent resin J-, dried at 80°C for 5 minutes to form a colored resin layer, and the PET film is peeled off to form an uncured heat and photocurable coating sheet. I got it. The film thickness of this sheet was 15 μm for the transparent resin layer and 70 μm for the colored resin layer.

Comparative Example 4 Acrylic polyol (manufactured by Nippon Shokubai Kogyo Co., Ltd., Alotane 2040-141, heavy electric average molecular weight 10°000, Tg
100 parts of O'C, OHHBO2 solid content, 50 parts of acrylic polyol oligomer (manufactured by Nippon Carbide Kogyo ■, Nikalide H-870), and 111 parts of block isonanate (manufactured by Shikinichi Yakuhin Kogyo ■, Takenate B-815N) (
The acrylic polyol (having 10 equivalent isocyanate groups per hydroxyl group) was mixed with thorough stirring. This mixture was coated on the release surface of a PET film subjected to release treatment, and dried at 80° C. for 5 minutes to form a transparent resin layer. Next, 100 parts of thermoplastic acrylic resin (manufactured by Asahi Kasei Tamagogyo ■, Delpet 8500), 30 parts of methyl methacrylate, 20 parts of tripropylene glycol dimethacrylate, 210 parts of thioxant and 40 parts of titanium oxide were added to 300 parts of ethyl acetate. Mixed with stirring. This mixture is coated on the transparent resin layer, dried at 80°C for 5 minutes to form a colored resin layer, and the PET film is peeled off to form an uncured heat- and photo-curable coating sheet. Obtained. The film thickness of this sheet was 20 μm for the transparent resin layer and 70 μm for the colored resin layer.

<Performance of thermosetting coating sheet> The thermosetting coating sheets obtained in Comparative Examples 1 to 4 were tested in the same manner as in Example 1. As a result, 100 at 30℃
% elongation was obtained, but cracks appeared on the surface of the transparent resin layer.

Further, in vacuum forming at 80°C and 100°C, it did not stick to the steel plate.

Example 17 A reactive acrylic resin (a copolymer of methyl methacrylate, butyl methacrylate, methacrylic acid, and 2-aminoethyl acrylate, Mw = 30) was added to 300 parts of ethyl acetate.
,000, Tg 35℃, CoOH value 40 and NH, value 4
0) To 100 parts of solid content, block isonanate (manufactured by Shikinichi Yakuhin Kogyo, Takenate B-87ON, ochim block NGO of isophorone diisocyanate = 12.6%)
34 parts (this crosslinking agent has 01 g of O4 isocyanate groups relative to the functional groups of the reactive acrylic resin) were added and mixed with stirring. This mixture was coated with an applicator on the release surface of a polyethylene terephthalate (PET) film that had been subjected to release treatment using an applicator and dried at 80°C for 5 minutes to form a transparent resin layer.
). The thickness of the sheet was 30 μm.

On the other hand, in 300 parts of ethyl acetate, reactive acrylic resin (copolymer of methyl methacrylate, 2-hydroquinethyl methacrylate, methacrylic acid and ethyl acrylate,
M w = 250.000, Tg 20°C, OH value 40
and CoOH value 20) to 100 parts solid content, and reactive acrylic oligomers (methyl acrylate, methacrylic acid 2-
Copolymer of hydroquine ethyl, butyl acrylate, methacrylic acid, Mw = 4,000, Tg -10°C, OH value 100, CoOH value 40), solid content 20 parts, blocked isocyanate (same as above) 31 parts (this The crosslinking agent (having an isocyanate group in an amount of 10 equivalents to the functional groups of the reactive acrylic resin and reactive acrylic oligomer) and 150 parts of titanium oxide were mixed with thorough stirring.

This mixture was coated on the transparent resin layer G so that the sheet thickness was 100 μm, dried at 80° C. for 20 minutes, and laminated.

Example 18 300 parts of ethyl acetate [reactive acrylic resin (copolymer of methyl methacrylate, methacrylic acid, and 2-aminoethyl acrylate, Mw 46-25,000, Tg 35°C, CoOH value 40 and NH2 value 40) to 100 parts of solid content, reactive acrylic oligomer (copolymer of methyl acrylate, 2-hydroquinethyl methacrylate, butyl acrylate, methacrylic acid,
Mw=4,000°Tg-10°C, OH number 100, Co
Solid content: 30 parts of OH number 40), 75 parts of blocked isocyanate (Takene 1-B-815N, hydrogenated diphenylmethane diisonanate, Keto-Oquine Mubrosoku N G O 7,3%) (manufactured by Trial Yakuhin Kogyo Co., Ltd.) (this crosslinking agent The reactive acrylic resin and the reactive acrylic oligomer (having 10 equivalents of isone anate groups with respect to the functional groups) were mixed with thorough stirring. This mixture was applied with an applicator to the release surface of a polyethylene terephthalate (PET) film subjected to release treatment and dried at 80°C for 5 minutes to form a transparent resin layer (this will be referred to as transparent resin layer H). . The thickness of the sheet was 20 μm.

On the other hand, a reactive acrylic resin (a copolymer of methyl methacrylate, 2-hydroxyethyl methacrylate, and ethyl acrylate, M w = 250) was added to 300 parts of ethyl acetate.
．． 000%T g 15°C, 100 parts solid content of OH value 40 and CoOH value 20), 20 parts solid content of reactive acrylic oligomer (same as above), blocked isocyanate (2
54 parts (same as above) (this crosslinking agent has 10 equivalents of isone anate groups with respect to the functional groups of the above-mentioned reactive acrylic resin and reactive acrylic oligomer) and 60 parts of iron oxide were mixed with thorough stirring.

This mixture was coated on the transparent resin layer H so that the film thickness of the sheet was 100 μm, and dried at 80”C for 20 minutes to obtain a product tw L.

Example 19 A reactive acrylic resin (a copolymer of methyl methacrylate, 2-hydroxyethyl methacrylate, and acrylic acid, Mw = 250,000.T11) was added to 300 parts of ethyl acetate.
5°C, OH number 4o and CoOH number 40) 100 parts of solid content was added with a reactive acrylic oligomer (copolymer of methyl acrylate, 2-7minoethyl methacrylate, acrylic acid and methyl methacrylate, Mw = 8). ,000, Tg-1
0°C, NH2 function 60% COOH value 30) solid content 10 parts, blocked isocyanate (same as 1) 35 parts (this crosslinking agent has Lo equivalent to the functional group of the above reactive acrylic resin and reactive acrylic oligomer) isonanate group) and isocyanate (Coronate L, manufactured by Nippon Polyurethane Industries, polyisonanate made by reacting 3 mol of tolylene diisonanate and 1 mol of trimethylolpropane, NcO = 13.0%). 12 parts of the solid content (30% of the functional groups of the reactive acrylic resin were initially cured) were mixed with thorough stirring. This mixture was applied with an applicator to the release surface of a PET film that had been subjected to the release treatment using an applicator, and dried at 80° C. for 5 minutes to create a transparent resin layer (this will be referred to as Transparent Resin I). The thickness of the sheet is 15μ
It was m.

On the other hand, a reactive acrylic resin (
Methyl methacrylate, methacrylic acid and acrylic acid 2
-Aminoethyl copolymer, Mw==492,000.
Tg 35°C, CoOH value 40 and NH value 40) 100 parts of solids were added with reactive acrylic oligomer (copolymer of methyl acrylate, 2-7minoethyl methacrylate, acrylic acid and methyl methacrylate, Mw =8,000
, Tg-10'C1N H, value 60. C0OH value 30)
20 parts in solid content, 35 parts of blocked isocyanate (same as in 1) (this crosslinking agent has 10 equivalents of isone anate group with respect to the functional groups of the above reactive acrylic resin and reactive acrylic oligomer), epoxy crosslinking agent (Manufactured by Civer Geiki, Araldite CY175, Epoquin equivalent 16
7.5 parts (10% of the functional groups of the reactive acrylic resin are initially cured) and 130 parts of titanium oxide were mixed with thorough stirring.

This mixture was coated on the transparent resin layer ■ to a film thickness of 100 μm, and dried at 80°C for 20 minutes to give a film thickness of 100 μm.
-Shit.

Example 20 300 parts of ethyl acetate, 100 parts of thermoplastic acrylic resin (manufactured by Asahi Kasei Tamagogyo, Delpera 8500), 40 parts of tripropylene glycol dimethacrylate, to parts of ter-butyl peroxybenzoate, and 50 parts of titanium oxide were stirred. while mixing. This mixture is added to the transparent resin layer G.
A colored resin layer was formed by coating on top and drying at 70° C. for 30 minutes, and the PET film was separated to obtain an uncured thermosetting coating sheet. The film thickness of this sheet was 30 μm for the transparent resin layer and 80 μm for the colored resin layer.

Example 21 300 parts of ethyl acetate, 100 parts of thermoplastic acrylic resin (Asahi Kasei Kogyo (altR1 Delpet 8500), 60 parts of hexamethylene glycol dimethacrylate, ter
-butylperoquinebenzoate-- and 50 parts of titanium oxide were mixed with stirring. Add this mixture to the above transparent 8" fat l! ! It was coated on IH and dried at 70°C for 30 minutes to form a colored resin layer, and the P E 1' film was peeled off to obtain an uncured thermosetting coating sheet. The film thickness of this sheet is 15 μm1 for transparent resin 1-
The colored resin layer was 100 μm.

Example 22 300 parts of ethyl acetate, 100 parts of thermoplastic acrylic resin (manufactured by Asahi Kasei Kogyo ■, Delpet 8500), 40 parts of dipropylene glycol dimethacrylate, 40 parts of methyl methacrylate, 10 parts of ter-butylveroxybenzoate, 4 0.61B of chlorobenzophenone and 50 parts of titanium arsenide were mixed with stirring. This mixture is coated on the transparent resin layer I, dried at 70°C for 30 minutes to form a colored resin layer, and the PET film is peeled off to obtain an uncured thermosetting coating sheet. Ta. The film thickness of this sheet was 30 μm for the transparent resin layer and 60 μm for the colored resin layer.

Example 23 300 parts of ethyl acetate, thermoplastic acrylic resin (Asahi Kasei r
:, manufactured by Awa ■, Delpet 8500), 100 parts of dipropylene glycol dimethacrylate, 40 parts of methyl methacrylate, to parts of terbutyl peroxybenzoate, 0.6 parts of benzyl and 50 parts of titanium oxide while stirring. Mixed. This mixture is coated on the transparent resin layer G, dried at 70°C for 30 minutes to form a colored resin layer, and the PET film is peeled off to obtain an uncured thermosetting coating sheet. Ta. The film thickness of this sheet was 15 μm for the transparent resin layer and 55 μm for the S colored resin layer.

Example 24 300 parts of ethyl acetate, 100 parts of thermoplastic acrylic resin (Delpera 8500 manufactured by Asahi Kasei Gyokugyo), 40 parts of phenoxydiethylene glycol methacrylate, 40 parts of 0-chlorostyrene, 0.8 part of benzoin, and 50 parts of titanium oxide. were mixed with stirring. This mixture is coated on the transparent resin layer H, dried at 80°C for 10 minutes to form a colored resin layer, and the PET film is peeled off to form an uncured thermosetting coating material. I got it. The film thickness of this sheet is 30 μm for the transparent resin layer and 55 μm for the colored resin layer.
It was μm.

<Performance of thermosetting coating sheet> The performance of the sheet was tested for elongation, vacuum formability, adhesion, and hardness.

The elongation property was evaluated by elongating the sheet 100% under 30° C. atmospheric conditions and determining whether or not the sheet was torn. The moldability was evaluated based on the ease of coating and the appearance of the sheet when the sheet was attached to a base material and the laminate was vacuum-formed at 60°C.

The adhesion of the sheet was determined by heating the laminate formed as described above at 160°C for 30 minutes.
Heating at 160℃ for 30 minutes and high pressure mercury lamp (160W/
am, height 15σ) for 2 minutes, then 100 cuts of 11 intervals were made on the surface of the cured coating in the shape of a base pattern.
A commercially available adhesive tape was attached to this, and then the tape was peeled off and the remaining percentage of the base piece was expressed.

Hardness was evaluated by a pencil hardness test according to JIS K5400. Table 1 shows the test results when a steel plate was used as the base material, and Table 2 shows the test results when a painted steel plate was used as the base material. When a painted copper plate is used as the base material, an adhesive layer (acrylic adhesive, dipping chemical, Vacuum forming was carried out using an S-dyne WHD (manufactured by Kogyo ■, 10 μm thick).

(Effects of the Invention) The structure of the thermosetting coating sheet of the present invention is as described above, and when it is below the curing temperature, it has excellent spreadability and flexibility, and it can be used not only on flat surfaces but also on slightly uneven and curved surfaces. The surface of the article can be coated well without causing wrinkles. Further, the thermosetting coating sheet can form a strong and uniform coating with excellent hardness and abrasion resistance by curing both the colored resin layer and the transparent resin layer by heating.

Furthermore, since the thermosetting coating sheet of the present invention has a two-layer structure of a colored resin layer and a transparent resin layer, it can express the depth of color seen in metallic coatings, has excellent performance, and has high gloss and It is possible to form a film with good appearance properties such as sharpness.

[Brief explanation of the drawing]

FIG. 1 is a schematic sectional view of one embodiment of the present invention, FIG. 2 is a schematic sectional view of another embodiment of the same, and FIG. 3 is a schematic sectional view of still another embodiment of the same. 1...Colored resin layer, 2...Transparent resin layer, 3...Adhesive layer, 4...Support layer. that's all

Claims (1)

[Claims] 1. A thermosetting coating sheet in which an uncured colored resin layer is laminated on an uncured transparent resin layer, the transparent resin layer having a weight average Molecular weight is 10,000
1,000,000 and is solid at room temperature, and a thermosetting resin composition whose main components are a blocked isocyanate, and the colored resin layer is colored. A thermosetting coating sheet characterized by comprising: 2. The thermosetting coating according to claim 1, wherein the thermosetting resin composition forming the transparent resin layer further contains a reactive acrylic oligomer having a weight average molecular weight of 1,000 to 10,000. sheet. 3. A claim in which the colored resin layer is made of a thermosetting resin composition whose main components are a thermoplastic acrylic resin, a reactive vinyl monomer, a colorant, and a peroxide and/or a photosensitizer. Thermosetting coating sheet according to 1 or 2.