JPH02223447A - Thermosetting sheet for covering - Google Patents

Abstract

PURPOSE:To cover easily the surface of the article having some unevenness or curved surface by a method in which the transparent resin layer in uncured state is laminated on the colored resin layer in uncured state containing reactive resin, colorant, etc., whereby the thermosetting sheet for covering is formed. CONSTITUTION:The film mold release-treated with silicone mold release agent is coated with the composition of transparent thermosetting resin and is dried, whereby the transparent resin layer 2 in uncured state is formed. Next, the surface of the transparent resin layer 2 is coated with the composition containing, as its main components, the reactive acryl resin having the weight- average molecular weight of 100000-1000000 and being solid at room temperature, block is isocyanate and colorant and is dried, and then the colored resin layer 1 in uncured state is laminated thereon. Then, the transparent resin layer and the colored resin layer are separated from said film, whereby the thermosetting sheet for covering is formed. This sheet can cover the surface of the article having some unevenness or curved surface without the occurrence of wrinkles.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a coating that is applied to the surface of furniture, steel plates, etc. and used for protection, decoration, or display of the surface of such articles by being heat-cured. This relates to sheets for use.

(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 water-based paints, it does not harm the working environment, but there are problems such as the drying time of the paint being longer or the need for a large amount of energy to dry the paint.Therefore, recently, Materials based on polyvinyl chloride have been proposed for sheet attachment. The material for this pasting is
It is attached to the surface of objects such as furniture and steel plates, and when using materials, it does not have any negative impact on the working environment.
And since it is in sheet form, there is no need for drying. but,
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.

Furthermore, JP-A-62-169630 proposes a colored film with excellent appearance and weather resistance, which is made by laminating two types of unsaturated polyester polyol layers with different molecular weights and a transparent resin layer made of a crosslinkable resin composition. ing.

JP-A No. 62-271735 discloses a cross-linked type comprising a surface layer of a thermoplastic resin composition having excellent durability and a metal powder and/or a coloring pigment on a substrate having good mold releasability and surface smoothness. A colored sheet with excellent appearance and durability has been proposed, which is made of a resin composition.

(Problems to be Solved by the Invention) The composite sheet disclosed in Japanese Patent Publication No. 57-13425 has a radical reaction: ゛ A layer having a non-active side compound and a layer having a radical reaction initiator are laminated. Because of its structure, it allows a uniform curing reaction to occur when heated and pressurized (
In this case, it is necessary to bring both layers into uniform contact for reaction, and it is difficult to control heating and pressurization. In addition, since paper, woven fabric, and nonwoven fabric are used as the sheet-like base material impregnated with the radical reaction initiator, the composite sheet is difficult to stretch when coating the surface of an article with uneven or curved surfaces. It has the disadvantage that "wrinkles" are easily formed 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,
After the transparent resin layer is cured, a colored resin layer is provided on the transparent resin layer, so the colored film obtained does not have ductility due to the effect of the cured transparent resin layer, and there is no possibility of uneven or curved surfaces. It is difficult to form a good coating because it does not have the ability to follow the surface of an article.

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 capable of forming a cured film having a 2m structure and 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 transparent resin layer is laminated on an uncured colored resin layer. The colored resin layer is a thermosetting resin whose main components are a reactive acrylic resin having a weight average molecular weight of 100,000 to 1.000,000 and solid at room temperature, a blocked isocyanate, and a coloring agent. The transparent resin layer is made of a transparent thermosetting resin composition, thereby achieving the above object.

The thermosetting resin composition forming the coating layer may further contain a reactive acrylic oligomer having a weight average molecular weight of 1,000 to 10,000. The transparent resin layer can be formed from a thermosetting resin composition whose main components are a reactive acrylic resin that is solid at room temperature and a blocked isocyanate. Further, the transparent resin layer may be formed from a thermosetting resin composition containing a thermoplastic acrylic resin, a reactive vinyl monomer, a peroxide and/or a photosensitizer as main components.

The present invention will be explained in detail below.

The thermosetting coating sheet of the present invention is formed by laminating an uncured transparent resin layer on an uncured colored resin layer.

The colored resin layer of the first invention has a weight average molecular weight of 1oo, o
It is formed from a thermosetting resin composition whose main components are a reactive acrylic resin that is solid at room temperature, a blocked isocyanate, and a coloring agent, and the transparent resin layer is a transparent thermosetting resin. It is formed from a resin composition.

Further, the colored resin layer of the second invention has a weight average molecular weight of 10
A reactive acrylic resin having a weight average molecular weight of 0.000 to 1.000.000 and solid at room temperature, and a weight average molecular weight of 1.000 to 1.000.000.
10.000, a block isocyanate, and a colorant as main components, and the transparent resin layer is made of a transparent thermosetting resin composition as in the first invention. formed from things. That is, the colored resin layer of the second invention has a weight average molecular weight of 1.000 to 10,000 in addition to the colored resin layer of the first invention.
It contains a reactive acrylic oligomer.

The reactive acrylic resin contained in the colored resin layer of the first invention and the second invention is an acrylic polymer having a plurality of hydroxyl groups, amino groups and/or carboxyl groups,
It 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-hydroxyethyl (meth)acrylate 2-aminoethyl. It is obtained by copolymerizing a (meth)acrylic acid ester monomer having an amino group such as (meth)acrylate or/and a monomer having a carboxyl group such as (meth)acrylic acid.

The weight average molecular weight (Mw) of the acrylic polyol can be changed depending on the conditions when performing a polymerization reaction using an initiator, and the reactive acrylic resin used in the first invention has a weight average molecular weight of 100. .000~1.
000.000 is selected. When the weight average molecular weight is less than 100.000, it becomes difficult for the obtained thermosetting coating sheet to maintain its sheet shape.

Therefore, for example, when pasting, sufficient elongation is obtained for stretching during work, but cracks or cracks may occur in some cases.

Conversely, if the weight average molecular weight exceeds 1.000.000, the mixture described below will have poor moldability, making it difficult to prepare a thermosetting coating sheet. In addition, these acrylic polyols have a Tg (glass transition point) in the range of θ to 80"C and a functional group value of 20 to 80"C in terms of hardness after curing.
A range of 200 is preferred. Furthermore, acrylic polyols can be combined with different types of materials as long as they are within these molecular weight ranges.

The blocked isocyanate contained in the colored resin layer is a reactive acrylic resin in the first invention, and a heat reaction type curing for curing a reactive acrylic resin and a reactive acrylic oligomer during heating in the second invention. used as an agent.

Here, the term "blocked isocyanate" refers to a compound obtained by blocking incyanate 1L, an incyanate compound having two or more incyanate groups in the molecule, with a blocking agent such as phenol, oxime, ε-caprolactam, or malonic acid ester. 1. As the incyanate compound, for example, monomers such as tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, inphorone diisocyanate,
trimethylolpropane adducts, incyanurate modified products, carbodiimide modified products, etc. In blocked isocyanate, the blocking agent is removed by heating, and the resulting isocyanate group is the sum of the functional groups (hydroxyl group, amino group, and carboxyl group) of the acrylic polyol (and acrylic polyol oligomer).The functional group value is the hydroxyl value and the amino group. The amine value is the sum of the value and the acid value, and the amine value is the 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 , the amount of carboxyl groups added during polymerization is calculated in the same way as the amount of hydroxyl groups, or the amount of carboxyl groups is determined using KOH, etc.) to cause a crosslinking reaction. 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 0.
,5 to 2.0, more preferably 0.8 to 1.2. Second
In the invention, the content of the blocked isocyanate is such that the ratio of the functional groups contained in the reactive acrylic resin and the reactive acrylic oligomer to the incyanate groups contained in the blocked isocyanate is in the range of 0.5 to 2.0. It is preferably adjusted so that it becomes, more preferably 0.8 to 1.
The range is 2.

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

When using a colorant having high hiding power, the amount of the entanglement colorant is preferably in the range of 2 to 100 parts per 100 parts by weight (hereinafter referred to as parts) of the solid content of the resin.

The reactive acrylic oligomer contained in the colored resin layer of the second invention is mainly used to obtain flexibility and elongation of the cured coating film. This reactive acrylic oligomer has multiple hydroxyl groups, amino groups, or
It is an acrylic polymer having a carboxyl group, and is a solid or solid solution polymer at room temperature. Such reactive acrylic oligomers are, for example, (meth)
Acrylic acid ester monomer, styrene 18 conductor monomer, (meth)acrylic acid ester monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate, and (meth)acrylic acid ester monomer having an amino group such as 2-aminoethyl (meth)acrylate. ) It is obtained by copolymerizing an acrylic acid ester monomer and/or a heptamer having a carboxyl group such as (meth)acrylic acid.

The reactive acrylic oligomer has a weight average molecular weight of 1
．． 000 to I 0.000 is selected.

The weight average molecular weight of the reactive acrylic oligomer is 1,00
If it is less than 0, the resulting resin will have poor moldability, making it difficult to prepare a covering sheet. Weight average molecular weight is 10.00
When it exceeds 0, the resulting sheet loses flexibility and has poor moldability. Additionally, these reactive acrylic oligomers are
From the relationship between sheet formability and hardness after curing, the glass transition point is within the range of 50°C to 40°C and the functional group value is 80 to 250.
Preferably, the range is . Furthermore, reactive acrylic oligomers can be combined with different types of materials as long as they have molecular weights within these ranges.

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

In this way, the colored resin layer of the first invention is formed of the solid reactive acrylic resin, the thermosetting resin composition containing the blocked isocyanate and the colorant as main components, and the solid reactive acrylic resin The colored resin layer of the second invention is formed from a thermosetting W resin composition containing a reactive acrylic oligomer, a blocked isocyanate, and a colorant as main components. Further, fillers, anti-aging agents, rust preventives, etc. may be added to the colored resin layers of the first and second inventions, if necessary. The obtained colored resin layer is in an uncured state before heating, and by heating it at a temperature higher than a predetermined temperature,
A hard film is formed.

Examples of the composition of the transparent thermosetting resin composition forming the transparent resin layer include the following four.

■Main components are reactive acrylic resin and blocked isocyanate, which are solid at room temperature.

■Thermoplastic acrylic resin and reactive vinyl monomer,
The main component is peroxide.

■Thermoplastic acrylic resin and reactive vinyl monomer,
The main ingredient is a photosensitizer.

■Thermoplastic acrylic resin and reactive vinyl monomer,
The main ingredients are peroxide and photosensitizer.

The blocked isocyanate contained in the transparent resin layer is used to cure the reactive acrylic resin contained in the transparent resin layer during heating.

As this blocked isocyanate and reactive acrylic resin, the same materials as those used for the colored resin layer can be used. The weight average molecular weight of the reactive acrylic resin is not limited like the reactive acrylic resin used for the colored resin layer, but is 100,000 to 1. o o o, o
oo is preferred, and those with a glass transition point of 0 to 80°C and an OH value of 20 to 200 are preferred. In addition, the blending amount of the block isocyanate and the reactive acrylic resin is such that the ratio of the functional groups contained in the acrylic polyol to the incyanate groups contained in the block isocyanate is 0.5.
It is preferably adjusted to fall within the range of ~2.0, more preferably within the range of 0.8 to 1.2.

The thermoplastic acrylic resin is a polyacrylic ester, and usually polymethyl methacrylate or polymethyl methacrylate copolymer can be used. Other acrylic ester polymers and blends may also be used.

As the above-mentioned reactive vinyl material, (meth)acrylic and styrene-based materials are suitable as materials having good compatibility with the above-mentioned thermoplastic acrylic resin. Examples of acrylic reactive vinyl monomers include methyl (meth)acrylate, ethyl (meth)acrylate, benzyl (meth)acrylate, and 2-ethoxyethyl (meth)acrylate.
Acrylate, monofunctional types such as phenoxydiethylene glycol (meth)acrylate, 1,6-hexadiol 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, and other multifunctional types can be applied.

Examples of styrene-based reactive vinyl styrene include styrene, α-methylstyrene, α-ethylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-ethoxystyrene, p-chlorostyrene,
-Various styrene derivatives such as chlorostyrene and 0-chlorostyrene can be applied. The amount of these reactive vinyl monomers added is preferably adjusted to be in the range of 20 to 200 parts, more preferably in the range of 40 to 150 parts, per 100 parts of the thermoplastic acrylic resin.

In addition, the reactive vinyl hexafluoride is not limited to the above-mentioned reactive vinyl species, and two or more species can be used in combination.

As the above-mentioned photosensitizer, commonly used photosensitizers can be used, and photosensitizers such as benzoin alkyl ether type, acetophenone type, benzophenone type, and thioxanthone type are preferably used. For example, benzoin ethers include benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, etc., and acetophenones include 2,2'-jetoxyacetophenone and 7% 2,2'-dibutoxyacetophenone. , 2-hydroxy-2-methylpropiophenone, P-ter-butyltrichloroacetophenone, etc.; benzophenone-based compounds include benzophenone, 4-chlorobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-4-methoxy; benzophenone,
Among dibenzosuberonato and thioquintone, there are thioxanthone, 2-chlorothioxanthone, 2-methylthioquintone, 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 it is preferably in the range of 0.5 to 3.0 parts per 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.

The above-mentioned peroxide is preferably a commonly used organic peroxide, and more preferably, from the viewpoint of storage stability at room temperature, for example, 2,2-bis(ter-butylperoxy)butane, The decomposition temperature is about 160°C, such as ter-butyl peroxybenzoate, di-ter-flupaoxyisophthalate, methyl ethyl ketone peroxide, dicumyl peroxide, and ter-butyl peroxy acetate. The amount of peroxide added is
Although the appropriate amount varies depending on the composition of the transparent resin layer described above, it is 0.5 to 2.0 parts per 100 parts of the reactive vinyl monomer.
A range of 0 parts is preferred. Moreover, the peroxide is not limited to one type, and two or more types can be used in combination.

The transparent resin layer obtained by mixing the above components is in an uncured state before heating and adheres well to the colored resin layer. A transparent resin layer forms a hard film by heating it at a temperature above a predetermined temperature, and in particular, a transparent resin layer containing a photosensitizer can also be cured by irradiation with light to form a hard film. is formed.

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, and the thickness of the colored resin layer 1 is preferably 50 to 150 μm.

In addition, if the colored resin layer 1 of the thermosetting coating sheet does not have sufficient adhesion to the article to be coated, as shown in FIG. By providing an adhesive layer 3 on the article and attaching the sheet to the surface of the article via this adhesive layer 3, it is possible to improve the adhesion between the hard coating and the article after hardening. 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, and blends or laminates of these may also be used.

When the resin composition constituting the thermosetting coating sheet has a low viscosity at room temperature, it becomes difficult for the sheet to maintain 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, with the support 84 being a thermosetting coating sheet. It is used to maintain the shape of the entire sheet, but when attaching the sheet to the surface of an article having a three-dimensional curved surface with this support layer 4, it is necessary to impart flexibility to this support layer 4. Heating is performed as necessary to ensure the desired ductility. 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 homogeneously mixed, 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 material in which the above-mentioned colored resin layer components are uniformly mixed is coated on the surface of this transparent resin layer,
It is obtained by forming a colored resin layer by drying, and then peeling off the transparent resin layer and the colored resin layer from the film. The temperature in each of the above drying steps is below the decomposition temperature of protsquison anate, the reactive vinyl monomer, and the peroxide.

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

Example 1 Acrylic polyol (Nippon Shokubai Kogyo (Yokozaki, Arotan 2)
040-145, weight average molecular weight 339.000, Tg
40°C, OHHBO2 solid content to 100 parts, block isocyanate) (gEB Yakuhin Kogyo ■, Takene) B8
15N, oxime block form of hydrogenated diphenylmethane diisocyanate, NC0% 7.3) 49 parts (this block isocyanate has 1.0 equivalent of incyanate group with respect to the hydroxyl group of the above-mentioned acrylic polyol) were mixed with thorough stirring. did.

This mixture was applied to a silicone release-treated polyethylene terephthalate film (manufactured by Soken Kako ■, film thickness 40 μm,
Coated on the release surface of the PET film (hereinafter referred to as PET film) and heated to 80°C.
was dried for 5 minutes to form a transparent resin layer.

On the other hand, acrylic polyol (manufactured by Nippon Shokubai Kogyo ■, Alotane 2040-145) solid content is 100 parts, blocked isocyanate (manufactured by Narita Pharmaceutical Co., Ltd., Takenate B815N)
) and 15 parts of titanium oxide were mixed with good stirring (this is referred to as coating material A). The mixture was coated on the transparent resin layer described above, and dried at 80 ° C. for 5 minutes. By forming a colored resin layer and peeling off the PET film, an uncured thermosetting coating sheet was obtained.The film thickness of this sheet was 30 μm for the transparent resin layer and 70 μm for the colored resin layer.
It was μm.

Example 2 Acrylic polyol (manufactured by Nippon Shokubai Kogyo ■, Arotan 20
40-139. Weight average molecular weight 320,000, Tg
20°C, OH value 100) to 100 parts solids, block isocyanate (Narita Pharmaceutical Co., Ltd., Takene) B81
5N) 62 parts (1 part per hydroxyl group of acrylic polyol)
．． 0 equivalents of isocyanate groups) were mixed with good stirring. This mixture was applied to the release surface of a PET film subjected to release treatment in the same manner as in Example 1, and dried at 80° C. for 5 minutes to form a transparent resin layer.

Next, the above coating film material A is coated on this transparent resin layer, 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 30 μm for the transparent resin layer and 70 μm for the colored resin layer.

Example 3 100 parts of a thermoplastic acrylic resin (Hi-Pellet HBS, manufactured by Mitsubishi Rayon), 40 parts of diethylene glycol dimethacrylate, and 1.0 part of ter-butyl peroxybenzoate were mixed with 300 parts of ethyl acetate with stirring. This mixture was peeled off in the same manner as in Example 1.
It was applied to the release surface of the film and dried at 70° C. for 15 minutes to form a transparent resin layer.

Next, the above coating film material A is coated on this transparent resin layer, and 7
Dry at 0°C for 30 minutes to form a colored resin layer, and PET
By peeling off the film, a =25- uncured thermosetting coating sheet was obtained. The film thickness of this sheet is 20 μm for the transparent resin layer and 80 μm for the colored resin layer.
It was m.

Example 4 100 parts of a thermoplastic acrylic resin (Hi-Pellet HBS, manufactured by Mitsubishi Rayon), 60 parts of methyl methacrylate, and 1.0 part of ter-butyl peroxybenzoate were mixed with 300 parts of ethyl acetate with stirring. This mixture was applied to the release surface of a PET film subjected to release treatment in the same manner as in Example 1, and dried at 70° C. for 15 minutes to form a transparent resin layer.

Next, the above coating material AK is coated on this transparent resin layer, and 7
Dry at 0°C for 30 minutes to form a colored resin layer, and PET
By peeling off the film, an uncured thermosetting coating sheet was obtained. The film thickness of this sheet was 20 μm for the transparent resin layer and 80 μm for the colored resin layer.

Example 5 To 300 parts of ethyl acetate, 1006 parts of thermoplastic acrylic resin (manufactured by Mitsubishi Rayon, Hi-Pellet HBS), 30 parts of methyl methacrylate, 20 parts of diethylene glycol dimethacrylate, 0.8 parts of methyl ethyl ketone peroxide, and 0.4 parts of benzophenone. were mixed with stirring. This mixture was applied to the release surface of a PET film that had been subjected to release treatment in the same manner as in Example 1, and
It was dried for a minute to form a transparent resin layer.

Next, the above coating film material A is coated on this transparent resin layer, and 7
Dry at 0°C for 30 minutes to form a colored resin layer, and PET
By peeling off the film, an uncured heat- and photo-curable coating sheet was obtained.

The film thickness of this sheet was 20 μm for the transparent 11N resin layer and 60 μm for the colored resin layer.

Example 6 To 300 parts of ethyl acetate, 100 parts of a thermoplastic acrylic resin (Mitsubishi Rayon, Hibelet HBS), 30 parts of p-methoxystyrene, 10 parts of pentaerythritol trimethacrylate, and 0.0 parts of methyl ethyl ketone peroxide were added.
8 parts and 0.5 parts of benzophenone were mixed with stirring. This mixture was peeled off in the same manner as in Example 1.
It was applied to the release surface of the film and dried at 70° C. for 15 minutes to form a transparent resin layer.

Next, the above coating film material A is coated on this transparent resin layer, and 7
Dry at 0°C for 30 minutes to form a colored resin layer, and PET
By peeling off the film, an uncured heat- and photo-curable coating sheet was obtained.

The film thickness of this sheet was 30 μm for the transparent resin layer and 60 μm for the colored resin layer.

Example 7 To 300 parts of ethyl acetate, 100 parts of a thermoplastic acrylic resin (Hykuret HBS, manufactured by Mitsubishi Rayon), 30 parts of methyl methacrylate, 20 parts of diethylene glycol dimethacrylate, and 1.0 part of thioxanthone were mixed with stirring. This mixture was applied to the release surface of a PET film subjected to release treatment in the same manner as in Example 1, and dried at 80° C. for 5 minutes to form a transparent resin layer.

Next, the above coating film material A is coated on this transparent resin layer, and 8
Dry at 0°C for 10 minutes to form a colored resin layer, and PET
By peeling off the film, an uncured heat- and photo-curable coating sheet was obtained.

The film thickness of this sheet was 40 μm for the transparent resin layer and 60 μm for the colored resin layer.

Example 8 30 parts of p-methoxystyrene in 300 parts of ethyl acetate,
10 parts of pentaerythritol trimethacrylate and 1.0 part of thioxanthone were mixed with stirring. This mixture was treated with PI! in the same manner as in Example 1. It was coated on the m* side of the T film and dried at 80° C. for 5 minutes to form one transparent Ifll layer.

Next, the above coating material A was coated on this transparent resin layer, and 80%
A colored resin layer was formed by drying at ℃ for 10 minutes, and the PET film was peeled off to obtain an uncured heat- and photo-curable coating sheet.

The film thickness of this sheet was 407' m s for the transparent resin layer and 60 µm for the colored resin layer.

Example 9 Acrylic polyol (manufactured by Nippon Shokubai Kogyo ■, Arotan 20
40-145, weight average molecular weight 339.000) solid content, and 49 parts of blocked isocyanate (manufactured by Shikinichi Yakuhin Kogyo ■, Takene) B815N) (this block isocyanate has 1. 0 equivalents of incyanate groups) were mixed with good stirring. This mixture was coated on the release surface of a silicone release-treated polyethylene terephthalate film (manufactured by Soken Kako, PET film with a film thickness of 40 μm or less), dried at 80°C for 5 minutes, and a transparent resin was applied.
formed a layer.

On the other hand, acrylic polyol (manufactured by Nippon Shokubai I■, Arotan 2040-14') solid content: 100 parts, manufactured by acrylic polyol oligomer, dicaride H-870, weight average molecular weight II 2,
200~2,500, Tg-20℃, OH
30 parts of titanium oxide (200), 86 parts of blocked isocyanate (Takene 1-B815N, manufactured by Shikinichi Yakuhin Kogyo ■), and 15 parts of titanium oxide were mixed with thorough stirring (this is referred to as coating film material B). The mixture is coated on the transparent resin layer described above, dried at 80°C for 5 minutes to form a colored resin layer, and the polyethylene terephthalate film is peeled off to form an uncured thermosetting coating. I got a sheet for use. The film thickness of this sheet was 30 μm for the transparent resin layer and 70 μm for the colored resin layer.

Example 10 A transparent resin layer formed in the same manner as in Example 2 was coated with the above coating material B, dried at 80°C for 5 minutes to form a colored resin layer, and the PET film was peeled off. A thermosetting coating sheet in an uncured state was obtained. The film thickness of this sheet is 30ttm for the transparent resin layer and 70μm for the colored resin N.
Met.

Example 11 300 parts of ethyl acetate, 10 parts of thermoplastic acrylic resin (manufactured by Asahi Kasei Kogyo, Delpera I-7500) (1, 40 parts of dipropylene glycol dimecrylate and 1.0 parts of ter-butyl peroxybenzoate were stirred) This mixture was coated on the release surface of the PET film,
A transparent resin layer was formed by drying at 70° C. for 15 minutes.

Next, the above coating film material B is applied to this transparent resin layer T, and 7
Dry at 0°C for 30 minutes to form a colored resin layer, and PET
By peeling off the film, an uncured thermosetting coating sheet was obtained. The film thickness of this sheet was 20 μm for the transparent resin layer and 80 μm for the colored resin layer.

Example 12 The above coating material B was applied to a transparent resin layer formed in the same manner as in Example 4, except that Delpetsu l-7500 manufactured by Asahi Kasei Kogyo ■ was used as the thermoplastic acrylic resin, and the coating material B was coated at 70°C. A colored resin layer was formed by drying for 30 minutes, and the PET film was peeled off to obtain an uncured thermosetting mW receipt.

The film thickness of this sheet was 20 μm for the transparent resin layer and 80 μm for the colored resin layer.

Example 13 The above &11 film material B was coated on a transparent resin layer formed in the same manner as in Example 5, except that Delpetsu 7500 (manufactured by Asahi Kasei Kogyo ■) was used as the thermoplastic acrylic resin, and the film material B was heated at 70°C.
A colored resin layer was formed by drying for 30 minutes, 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 70 μm for the colored resin layer.

Example 14 The above coating material B was applied to a transparent resin layer formed in the same manner as in Example 6, except that Delpetsu 7500 (manufactured by Asahi Kasei Corporation) was used as the thermoplastic acrylic resin, and the coating material B was coated with a trowel at 70°C. A colored am layer was formed by drying for 30 minutes, 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 70 μm for the colored resin layer.

Example 15 300 parts of ethyl acetate, 100 parts of thermoplastic acrylic resin (Asahi Kasei Kogyo, Delpera l-7500), p-10
30 parts of styrene, 20 parts of dipropylene glycol dimethacrylate, and 1.0 part of thioxanthone were mixed with stirring. This mixture was applied to the release surface of a PET film subjected to release treatment in the same manner as in Example 1, and dried at 80° C. for 5 minutes to form a transparent resin layer.

Next, the above-mentioned coating film material B is coated on this transparent resin layer, and 8
Dry at 0°C for 10 minutes to form a colored resin layer, and PET
By peeling off the film, an uncured heat- and photo-curable coating sheet was obtained.

The film thickness of this sheet was 30 μm for the transparent resin layer and 70 μm for the colored resin layer.

Example 16 300 parts of ethyl acetate was added with thermoplastic resin (Asahi Kasei #@
100 parts of Delpet 7500, manufactured by Co., Ltd., 30 parts of p-methoxystyrene, 10 parts of pentaerythritol trimethacrylate, and 1.0 part of thioxanthone were mixed with stirring. This mixture was peeled off in the same manner as in Example 1.
It was applied to the release surface of the ET film and dried at 80° C. for 5 minutes to form a transparent resin layer.

Next, the above-mentioned coating film material B is coated on this transparent resin layer, and 8
Dry at 0°C for 10 minutes to form a colored resin layer, and PET
By peeling off the film, an uncured heat- and photo-curable coating sheet was obtained.

The film thickness of this sheet was 30 μm for the transparent resin layer and 60 parts for the colored resin layer and 1 m.

Example 17 Acrylic polyol (manufactured by Nippon Shokubai Kogyo ■, Arotan 20
40-145, weight average molecular weight 339,000) solid content, and 49 parts of blocked isocyanate (Takenate B815N, manufactured by Shikinichi Yakuhin Kogyo ■) (this block inocyanate has a weight average molecular weight of 1. 0 equivalents of incyanate groups) were mixed with good stirring. This mixture was applied to the release surface of a PET film subjected to silicone release treatment and dried at 80° C. for 5 minutes to form a transparent resin layer.

On the other hand, acrylic polyol (manufactured by Nippon Shokubai Kogyo ■, Arotan 2040-145) solid content was 100 parts, acrylic polyol oligomer (manufactured by Nippon Carbide, dicalide H-
270, weight average molecular weight 2.200-2.500, Tg
-19°C, oxidation 200) 40 parts, blocked isocyanate (manufactured by Shikinichi Yakuhin Kogyo @ J, Takenate B815N) 9
8 parts and 15 parts of titanium oxide were mixed with thorough stirring (this is referred to as coating film material C). The mixture was coated on the transparent resin layer described above, 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 was 30 μm for the transparent resin layer and 70 μm for the colored resin layer.

Example 18 The above coating film material C was applied to the transparent resin layer formed in the same manner as in Example 2, and dried at 80 ° C. for 5 minutes to form a colored resin layer, and the PET film was peeled off. An uncured thermosetting coating sheet was obtained. The film thickness of this sheet is 30 μm for the transparent resin layer and 70 μm for the colored resin layer.
It was m.

Example 19 The above coating film material C was applied to a transparent resin layer formed in the same manner as in Example 3, except that Delpet 7500 manufactured by Asahi Kasei Kogyo ■ was used as the thermoplastic acrylic resin, and the coating material C was heated at 70°C for 30 minutes. It was dried for minutes at °C to form a colored resin layer and the PET film was peeled off.

Example 20 The above coating film material C was applied to a transparent resin layer formed in the same manner as in Example 4, except that Delpet 7500 manufactured by Asahi Kasei Kogyo ■ was used as the thermoplastic acrylic resin. A colored resin layer was formed by drying for a minute, and the PET film was peeled off to obtain an uncured thermosetting coating sheet.

The film thickness of this sheet was 40 μm for the transparent resin layer and 80 μm for the colored resin layer.

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

The elongation property was determined by elongating the sheet 100% under 30° C. atmospheric conditions and examining whether or not the sheet was torn. The moldability was evaluated by attaching the sheet to a base material and vacuum forming the laminate at 60°C. The adhesion of the sheet is
The laminate formed as described above was heated at 160°C for 30 minutes, or heated at 160°C for 30 minutes and then heated with a high-pressure mercury lamp (160°C).
0W/dll.

After irradiating for 2 minutes at a height of 15 am), 100 cuts with IW intervals were made on the surface of the cured film in the form 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. In Examples 1 to 16, 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.

In addition, when a painted steel plate is used as the base material, an adhesive layer (acrylic adhesive, seed Manufactured by Suikagaku Kogyo ■, S Dyne WHD1 thickness 10 μm)
Vacuum forming was carried out using a device equipped with Also, Example 17~
20 are shown in Table 3.

(Left below) Comparative Example 1 In 300 parts of ethyl acetate, 100 parts of a thermoplastic acrylic resin (Hi-Pellet HBS manufactured by Mitsubishi Rayon), 30 parts of methyl methacrylate, 20 parts of diethylene glycol dimethacrylate, and 1.0 part of thioxanthone were stirred. while mixing. This mixture was applied to the release surface of the PET film and dried at 80° C. for 5 minutes to form a transparent resin layer.

Next, acrylic polyol (manufactured by Nippon Shokubai Kogyo ■, Alotane 2040-144, weight average molecular weight 104°000,
Blocked isocyanate (manufactured by Shikinichi Yakuhin Kogyo ■, Takenate B-815) was added to 100 parts of OHHBO2 solid content.
N) 49 parts (1.
0) and titanium oxide 1
5 parts were mixed with thorough stirring (this was used as the coating material).

The coating material was applied on the transparent resin layer and heated at 80°C for 5 minutes.
A colored resin layer was formed by drying for a minute, and the PET film was peeled off to obtain an uncured heat- and photo-curable coating sheet. The film thickness of this sheet is 30 mm for the transparent resin layer.
The μm1 colored resin layer was 70 μm.

Comparative Example 2 300 parts of ethyl acetate was mixed with a thermoplastic acrylic resin (Hi-Pellet HBS manufactured by El Rayon) Zo.

30 parts of p-methoxystyrene, 10 parts of pentaerythritol trimethacrylate, and 0.8 parts of methyl ethyl ketone peroxide were mixed with stirring. This mixture was applied to the release surface of the PET film and dried at 70° C. for 15 minutes to form a transparent resin layer.

Next, the above coating film material is coated on this transparent resin layer, and 7
Dry at 0°C for 30 minutes to form a colored resin layer, and PET
By peeling off the film, an uncured thermosetting coating sheet was obtained. The film thickness of this sheet was 30 μm for the transparent resin layer and 70 μm for the colored resin layer.

Comparative Example 3 Thermoplastic Acrylic IJ) and resin (
100 parts of Delpera 7500 (manufactured by Asahi Kasei Industries, Ltd.), 30 parts of methyl methacrylate, 20 parts of diethylene glycol dimethacrylate, and 1.0 part of thioxanthone were mixed with stirring. This mixture was applied to the release surface of the PET film and dried at 80° C. for 5 minutes to form a transparent resin layer.

Next, acrylic polyol (manufactured by Nippon Shokubai Kogyo ■, Alotane 2040-144, weight average molecular weight 104°000)
Solid content: 100 parts, acrylic polyol oligomer (Nippon Carbide, Nicalite H-870, weight average molecular weight 2,200-2.500, OH value 200) 30 parts, blocked isocyanate (Shikiyaku Kogyo ■Shi, Takenate B815N) 86 parts (having 1.0 incyanate groups of our company with respect to the hydroxyl groups of the acrylic polyol) and 15 parts of titanium oxide were mixed with thorough stirring (this is referred to as coating material E).

Coating film material E was coated on the transparent resin layer and heated at 80°C for 5 minutes.
A colored resin layer was formed by drying for a minute, and the PET film was peeled off to obtain an uncured sheet for thermosetting and corrosion-resistant coating. The thickness of this sheet is
The transparent resin layer had a thickness of 20 μm, and the colored resin layer had a thickness of 70 μm.

Comparative Example 4 300 parts of ethyl acetate, 100 parts of thermoplastic acrylic resin (manufactured by Asahi Kasei Kogyo, Delpet 7500), 30 parts of p-methoxystyrene, 10 parts of pentaerythritol trimethacrylate), and 0 parts of methyl ethyl ketone peroxide.
．． 8 parts were mixed with stirring. This mixture was applied to the release surface of the PET film and dried at 70° C. for 15 minutes to form a transparent resin layer.

Next, the coating film material E is coated on this transparent resin layer, and 7
Dry at 0°C for 30 minutes to form a colored resin layer, and PET
By peeling off the film, an uncured thermosetting coating sheet was obtained. The film thickness of this sheet was 30 μm for the transparent resin layer and 80 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 not obtained, and it did not adhere to the steel plate after vacuum forming at 80°C and 100°C.

Example 21 A reactive acrylic resin (a copolymer of methyl methacrylate, methacrylic acid, and 2-aminoethyl acrylate, Mw = 50,000, Tg 3) was added to 300 parts of ethyl acetate.
5°C, C001 value 40 and NH2 value 40) 100 parts of solid content, 34 parts of blocked isocyanate (manufactured by Shikinichi Yakuhin Kogyo, Takeho 1-B-8 FON, oxime block NGO of inphoron diisocyanate = 12° 6%) (This crosslinking agent has an incyanate group equivalent to 0.2 g relative to the functional group of the reactive acrylic resin) was added and mixed with stirring. This mixture was applied with an applicator to the release surface of a silicone release-treated polyethylene terephthalate (PET) film, 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 (methyl methacrylate, 2-hydroxyethyl methacrylate, copolymer of methacrylic acid and ethyl acrylate,
Mw = 550.000, Tg 15℃, 06 valence 40
and C0OH value 20) to 100 parts solid content, reactive acrylic oligomers (methyl acrylate, methacrylic acid 2-
Copolymer of hydroxyethyl, butyl acrylate, methacrylic acid, MY=4.000, Tg -10℃, 0
H (ililoo, cOOH value 40), solid content 20 parts,
While stirring well, 31 parts of blocked isocyanate (same as above) (this crosslinking agent has 1.0 equivalent of incyanate group with respect to the functional groups of the reactive acrylic resin and reactive acrylic oligomer) and 120 parts of titanium oxide are added. (This is referred to as coating film material G). This mixture was coated on the transparent resin layer so that the film thickness of the sheet was 1100p, and
The layers were dried and laminated at ℃ for 20 minutes.

Example 22 A reactive acrylic resin (copolymer of methyl methacrylate, methacrylic acid, and 2-aminoethyl acrylate, Mw = 25,000) was added to 300 parts of ethyl acetate.

Tg 35°C, CoOH value 40 and NH2 value 40) to 100 parts solid content, reactive acrylic oligomer (copolymer of methyl acrylate, 2-hydroxyethyl methacrylate, butyl acrylate, methacrylic acid, Mvr =
4.000, Tg-10°C, O1'11 parts 00, C0
0H value: 40), solid content: 30 parts, blocked isocyanate (Takenate B-815N, manufactured by Shikinichi Yakuhin Kogyo Co., Ltd.).

Ketoxime block of hydrogenated diphenylmethane diisocyanate (NCO7.3%) 75 parts (this crosslinking agent has 1.0 equivalent of incyanate groups with respect to the functional groups of the above-mentioned reactive acrylic resin and reactive acrylic oligomer) Mixed with thorough stirring.

This mixture was applied with an applicator to the release surface of a silicone release-treated polyethylene terephthalate (PET) film, and dried at 80° C. for 5 minutes to form a transparent resin layer. The thickness of the sheet was 20 μm.

Next, coating film material G was applied onto the above coating film to form a sheet film J of 180 μm.
They were laminated so as to have the following properties and dried at 80°C for 20 minutes.

Example 23 A reactive acrylic resin (a copolymer of methyl methacrylate, 2-hydroxyethyl methacrylate, and ethyl acrylate, My=250.000) was added to 300 parts of ethyl acetate.
, Tg 15°C, solid content of 06 value 40 and COOH value 20), 20 parts of reactive acrylic oligomer (same as above) solid content, blocked isocyanate (same as 2) 54
(this crosslinking agent has 1.0 equivalent of incyanate groups with respect to the functional groups of the reactive acrylic resin and reactive acrylic oligomer) were mixed with thorough stirring. This mixture was applied with an applicator to the release surface of a PICT film subjected to silicone release treatment, and dried at 80'C for 5 minutes to produce a thermosetting sheet. The thickness of the sheet is 1
It was 00 μm.

Next, coating film material G was laminated on the above coating film to a sheet thickness of 8 μm, and dried at 80° C. for 20 minutes.

Example 24 To 300 parts of ethyl acetate, a reactive acrylic resin (copolymer of methyl methacrylate, 2-hydroxyethyl methacrylate, and acrylic acid, My = 25o, o o
o, Tg 15°C, OH number 4o and CoOH number 40), a reactive acrylic oligomer (copolymer of methyl acrylate, 2-aminoethyl methacrylate, acrylic acid and methyl methacrylate, Mw = 8.0
00, Tg-10'C1NH2 value 60°CoOH value 30
) with solid content of 10 parts, blocked isocyanate (same as 1) and 35 parts (this crosslinking agent has 1.0 equivalent of incyanate groups with respect to the functional groups of the above-mentioned reactive acrylic resin and reactive acrylic oligomer). , Incyanate (manufactured by Nippon Polyurethane Industries, polyisocyanate coronated and reacted with 13 mol of tolylene diisocyanate and 1 mol of trimethylolpropane, NC0 = 13° 0%)
12 parts solids (30 parts of the functional group of the reactive acrylic resin)
% of initial hardening) were mixed with thorough stirring. This mixture was applied with an applicator to the release surface of a PET film subjected to silicone release treatment, and dried at 80° C. for 5 minutes to produce a thermosetting sheet. The thickness of the sheet was 15 μm.

Next, coat film material G is applied to the above coating film with a film thickness of 100 μm.
They were laminated so as to have the following properties and dried at 80°C for 20 minutes.

Example 25 A reactive acrylic resin (a copolymer of methyl methacrylate, methacrylic acid, and 2-aminoethyl acrylate, Mw = 492,000, Tg) was added to 300 parts of ethyl acetate.
35℃, coo'u value 40 and NH2 value 40) solid content 1
00 parts, reactive acrylic oligomer (copolymer of methyl acrylate, 2-aminoethyl methacrylate, acrylic acid and methyl methacrylate, Mw = 8.00
0, Tg-10℃, NH2 value 60, C00H value 30) in solid content 20 parts, blocked isocyanate (same as 1)
35 parts (this crosslinking agent has 1.0 parts of incyanate group with respect to the functional groups of the above-mentioned reactive acrylic resin and reactive acrylic oligomer), epoxy crosslinking agent (manufactured by Civer Geigy, Araldite CY175, epoxy part ff1)
Epoxy value corresponding to 160° functional group value 220) 7.
5 parts (10% of the functional groups of the reactive acrylic resin are initially cured) were mixed with good stirring. This mixture was made from polyethylene terephthalate (PE) treated with silicone mold release.
T) Coat on the release surface of the film with an applicator,
It was dried at ℃ for 5 minutes to create a thermosetting sheet. The thickness of the sheet was 80 μm.

Meanwhile, 300 parts of ethyl acetate, reactive acrylic resin (
Copolymer of methyl methacrylate, diaminoethyl methacrylate, ethyl methacrylate, and methacrylic acid, Mw = 360,000, Tg 25°C, NH2 value 40
and C001 value 40) to 100 parts of solid content, and 54 parts of blocked isocyanate (same as 2) (this crosslinking agent is 1.0 equivalent of incyanate to the functional groups of the above-mentioned reactive acrylic resin and reactive acrylic oligomer). 120 parts of titanium oxide were mixed with sufficient stirring (this was referred to as coating material H). Apply this mixture to a sheet thickness of 100
It was coated on a transparent resin layer so that the thickness of
The layers were dried for 0 minutes and laminated.

Example 26 A reactive acrylic resin (a copolymer of methyl methacrylate, 2-hydroxyethyl methacrylate, acrylic acid, and butyl methacrylate, MY) was added to 300 parts of ethyl acetate.
= 50. OOOlTg 35℃, OH number 40 and C
oOH value 40) Solid content: 100 parts, reactive acrylic oligomer (methyl acrylate, 2-aminoethyl methacrylate, copolymer of acrylic acid and methyl methacrylate, Mw = 8,000, Tg-10 °C, NH2 value 6
0, CoOH value 30), solid content: 10 parts, blocked isocyanate (same as 2), 55 parts (this crosslinking agent is 1.0 equivalent of incyanate, based on the functional groups of the above-mentioned reactive acrylic resin and reactive acrylic oligomer). group) and incyanate (Coronate L manufactured by Nippon Polyurethane Industries)
.

Polyinsyanate, N
GO=13.0%) in solid content (30% of the functional groups of the reactive acrylic resin were initially cured) were mixed with good stirring. PET treated with silicone mold release from this mixture
It was applied to the release surface of the film using an applicator and dried at 80° C. for 5 minutes to create a thermosetting sheet. The thickness of the sheet was 20 μm.

Next, coat film material G is applied to the above coating film with a film thickness of 100 μm.
They were laminated so as to have the following properties and dried at 80°C for 20 minutes.

Example 27 300 parts of ethyl acetate, 100 parts of thermoplastic acrylic resin (manufactured by Asahi Kasei Corporation, Delpet 7500), 40 parts of dipropylene glycol dimecrylate, and 1.0 part of ter-butylperoxybenzoate were stirred. while mixing. Coat this mixture on the release surface of the PET film, and
A transparent resin layer was formed by drying at 0° C. for 15 minutes.

Next, the above-mentioned coating film material H is coated on this transparent resin layer, and 7
Dry at 0°C for 30 minutes to form a colored resin layer, and PET
By peeling off the film, an uncured thermosetting coating sheet was obtained. The film thickness of this sheet was 20 μm for the transparent resin layer and 80 μm for the colored resin layer.

Example 28 In 300 parts of ethyl acetate, 100 parts of thermoplastic acrylic resin (manufactured by Asahi Kasei Kogyo ■, Delpet 7500), 30 parts of p-chlorostyrene, 20 parts of dipropylene glycol dimethacrylate, and 1.0 part of thioxanthone were stirred. while mixing. This mixture was applied to the release surface of a PET film subjected to release treatment in the same manner as in Example 1, and dried at 80° C. for 5 minutes to form a transparent resin layer.

Next, the coating film material H was coated on this transparent resin layer, and 8
Dry at 0°C for 10 minutes to form a colored resin layer, and PET
By peeling off the film, an uncured thermosetting coating sheet was obtained. The film thickness of this sheet was 30 μm for the transparent resin layer and 70 μm for the colored resin layer.

<Performance of thermosetting coating sheet> The performance of the sheet was tested in terms of elongation, moldability, adhesion, and hardness.

The elongation property was determined by elongating the sheet 100% under 30° C. atmospheric conditions and examining whether or not the sheet was torn. Formability was determined by pasting the sheet onto a base material and heating the 'viS body at 60°C.
The moldability was evaluated by vacuum forming. The adhesion of the sheet was determined by heating the laminate formed as described above at 160°C and 30°C.
Only in Example 8, after heating at 160°C for 30 minutes and irradiating with a high-pressure mercury lamp (160W/z1 height 15α) for 2 minutes, cuts were made at 1-frame intervals on the surface of the cured coating film. A commercially available adhesive tape was attached to the sample, and then the tape was peeled off and the remaining percentage of the base piece was expressed. Hardness was evaluated using a pencil hardness test according to JIS K5400.

(Margins below) (Effects of the Invention) The structure of the thermosetting coating sheet of the present invention is as described above, and when the temperature is below the curing temperature, it has excellent ductility and flexibility, and is flat and flat. It is possible to satisfactorily coat surfaces of articles with uneven or curved surfaces without causing wrinkles. In addition, the thermosetting coating sheet forms 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 or heating and irradiating with ultraviolet rays. Can be done.

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, and improve gloss, sharpness, etc. A film with good appearance can be formed.

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.

DESCRIPTION OF SYMBOLS 1... Colored resin layer, 2... Transparent resin layer, 3... Adhesive layer,... Support layer.

Below Up

Claims (1)

[Scope of Claims] 1. A thermosetting coating sheet in which an uncured transparent resin layer is laminated on an uncured colored resin layer,
The colored resin layer has a weight average molecular weight of 100,000 to 1
, 000,000 and is solid at room temperature, a thermosetting resin composition containing as main components a blocked isocyanate, and a colorant, and the transparent resin layer is a transparent thermosetting resin. A thermosetting coating sheet comprising a composition. 2. The thermosetting coating according to claim 1, wherein the thermosetting resin composition forming the colored resin layer further contains a reactive acrylic oligomer having a weight average molecular weight of 1,000 to 10,000. Sheet for use. 3. The thermosetting coating sheet according to claim 1 or 2, wherein the transparent resin layer is made of a thermosetting resin composition whose main components are a reactive acrylic resin that is solid at room temperature and a blocked isocyanate. 4. Claim 1 or 2, wherein the transparent resin layer is composed of a thermosetting resin composition whose main components are a thermoplastic acrylic resin, a reactive vinyl monomer, and a peroxide and/or a photosensitizer.
The thermosetting coating sheet described above.