JPH085166B2 - Thermosetting coating sheet - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial field of application) The present invention is for coating a surface of an article such as furniture, a steel plate, etc., which is heat-cured by being attached to the surface of the article, for decoration, display, etc. It is about the seat.

(Prior Art) When a surface of furniture, a steel plate or the like is decorated or displayed, a paint is generally used. However, when a solvent-based paint is used, the organic solvent is volatilized during the work, which deteriorates the working environment, which is a problem in terms of environmental hygiene. When a water-based paint is used, it does not impair the working environment, but there is a problem that it takes a long time to dry the paint or a large amount of energy is required to dry the paint.

Therefore, recently, a sheet-shaped patch material mainly composed of lipovinyl chloride has been proposed. This patch material is
It is to be attached to the surface of articles such as furniture and steel plates.When using this attachment material, there is no adverse effect on the work environment,
Moreover, since it is a sheet, it does not need to be dried. But,
This sheet-shaped patch material is mainly formed of soft polyvinyl chloride, and has a drawback that it is inferior in hardness and abrasion resistance.

As a method for improving this, there has been proposed a technique in which a sheet material having a high surface hardness is obtained by curing a sheet material after attachment. For example, in JP-B-57-13425, a porous sheet-shaped substrate is impregnated with a radical reaction initiator, and a layer containing a polymer and a radical-reactive monomer is laminated on one or both surfaces thereof. Thermosetting composite sheets have been proposed.

Further, JP-A-62-169630 proposes a colored film having excellent appearance and weather resistance, which is formed by laminating two types of unsaturated polyester polyol layers having different molecular weights and a transparent layer of a crosslinkable resin composition. Has been done.

Further, in JP-A-62-271735, a surface layer of a thermoplastic resin composition having excellent durability and a metal powder and / or a coloring pigment are contained on a substrate having good physical properties and surface smoothness. A colored sheet having excellent appearance and durability, which is formed by laminating cross-linking resin layers, has been proposed.

(Problems to be Solved by the Invention) The composite sheet disclosed in JP-B-57-13425 is
Since it has a structure in which a layer having a radical-reactive unsaturated compound and a layer having a radical reaction initiator are laminated, both layers should be uniform in order to carry out a uniform curing reaction during heating and pressurization. Since it is necessary to bring them into contact with each other, it is difficult to control heating and pressurization, and it is difficult to form a uniform cured film. Further, since paper, woven cloth, non-woven cloth, etc. are used as the sheet-like base material impregnated with the radical reaction initiator, when the composite sheet is coated on the surface of an article having unevenness or a curved surface, the composite sheet is stretched. It is difficult to form a good coating on the surface of the article.

The colored film disclosed in Japanese Patent Laid-Open No. 169630/1987 has a two-layer structure, and has good color depth and appearance.
However, in the production of this colored film, since the transparent resin layer is cured and then the transparent resin layer is provided with the colored resin layer, the transparent resin layer is softened. The produced colored film has no spreadability, does not follow the surface of an article having irregularities or curved surfaces, and it is difficult to form a good film.

The colored sheet disclosed in JP-A-62-271735,
The transparent resin layer and the colored resin layer of the colored film disclosed in JP-A-62-169630 are reversed.
Due to the effect of the cured colored resin layer, the sheet has no malleability and it is difficult to form a good coating on the surface of an article having irregularities or curved surfaces.

The present invention solves the above-mentioned drawbacks, and an object of the present invention is to coat well the surface of an article having good spreadability and flexibility before curing, and having irregularities or curved surfaces. Another object of the present invention is to provide a thermosetting coating sheet which is capable of forming 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 coating film having a two-layer structure and having a deep color and good appearance.

(Means for Solving the Problem) The thermosetting coating sheet of the present invention is a thermosetting coating sheet in which an uncured transparent resin layer is laminated with an uncured colored resin layer. The transparent resin layer comprises a thermosetting resin composition containing a reactive acrylic resin having a weight average molecular weight of 10,000 to 1,000,000 and solid at room temperature and a block isocyanate as a main component, and the colored resin. The layer is characterized by being composed of a colored thermosetting resin composition, whereby the above object is achieved.

The thermosetting resin composition forming the transparent resin layer,
Further, a reactive acrylic oligomer having a weight average molecular weight of 1,000 to 10,000 may be contained. The colored resin layer may be formed of a thermosetting resin composition containing a thermoplastic acrylic resin, a reactive vinyl monomer, a colorant, a peroxide and / or a photosensitizer as main components. good.

 Hereinafter, the present invention will be described in detail.

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

The transparent resin layer of the first invention has a weight average molecular weight of 10,000 to
A thermosetting resin composition that is formed from a thermosetting resin composition containing 1,000,000 and a solid reactive acrylic resin at room temperature (25 ° C.) as a main component and block isocyanate, and the colored resin layer is colored. Are formed from.

The transparent resin layer of the second invention has a weight average molecular weight of 1
Thermosetting resin composition mainly composed of 000 to 1,000,000 and solid reactive acrylic resin at room temperature (25 ° C), reactive acrylic oligomer having a weight average molecular weight of 1,000 to 10,000, and block isocyanate And the colored resin layer is formed from the thermosetting resin composition colored as in the first invention.

The above-mentioned 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 a reactive acrylic resin is, for example, a (meth) acrylic acid ester monomer, a styrene derivative monomer, and a (meth) acrylic acid ester monomer 2-aminoethyl having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate. It is obtained by copolymerizing a (meth) acrylic acid ester monomer having an amino group such as (meth) acrylate or a monomer having a carboxyl group such as (meth) acrylic acid. The weight average molecular weight (Mw) of the reactive acrylic resin can be changed depending on the conditions when the polymerization reaction is performed using an initiator, and the reactive acrylic resin has a weight average molecular weight of 1
Those in the range of 0,000 to 1,000,000 are selected. If the weight average molecular weight is less than 10,000, the resulting thermosetting coating sheet will be cracked after molding and the appearance will be unfavorable. On the other hand, when the weight average molecular weight exceeds 1,000,000, the resin composition obtained has poor moldability, and it becomes difficult to prepare a thermosetting coating sheet. In addition, these reactive acrylic resins have a Tg (glass transition point) due to their hardness after curing.
Is in the range of 0 to 80 ° C., the functional groups (sum of hydroxyl group, amino group and arboxyl group. Functional group value is the sum of hydroxyl group value, amino group value and acid value, and amino group value is added at the time of polymerization. The amount of amino groups is calculated in the same way as the hydroxyl value, or the value is determined by reacting amino groups with nitrous acid and converted into hydroxyl groups.The acid value is calculated by calculating the amount of carboxyl groups added during polymerization in the same manner as the amount of hydroxyl groups or The value of the carboxyl group quantified with KOH or the like) is preferably in the range of 20 to 200. Further, the reactive acrylic resin may be used in combination with different reactive resins as long as they have these molecular weight ranges.

The block isocyanate contained in the transparent resin layer is a heat-reactive curing for curing the reactive acrylic resin in the first invention and the reactive acrylic resin and the reactive acrylic oligomer in the second invention during heating. Used as an agent. The block isocyanate means a compound obtained by blocking the isocyanate group of an isocyanate compound having two or more isocyanate groups in the molecule with a blocking agent such as phenol, oxime, ε-caprolactam or malonic acid ester. Examples of the above-mentioned isocyanate compound include monomers such as tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate, or trimethylolpropane adducts thereof, isocyanurate modified products and carbodiimide modified products thereof. Blocking isocyanate causes elimination of the above-mentioned blocking agent, 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 when the reactive acrylic oligomer is included). . In the first invention, the content of the block isocyanate is preferably adjusted so that the ratio of the functional group contained in the reactive acrylic resin to the isocyanate group contained in the block isocyanate is in the range of 0.5 to 2.0. , And more preferably 0.8 to 1.2. In the second invention, the content of the block isocyanate is adjusted so that the ratio of the hydroxyl group contained in the reactive acrylic resin and the reactive acrylic oligomer to the isocyanate group contained in the block isocyanate is in the range of 0.5 to 2.0. It is preferable that the
It is in the range of 8 to 1.2.

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

The above-mentioned reactive acrylic oligomer has a weight average molecular weight of
Those in the range of 1,000 to 10,000 are selected. When the weight average molecular weight of the reactive acrylic oligomer is less than 1,000,
The obtained thermosetting resin composition is poor in moldability, and it becomes difficult to prepare a thermosetting coating sheet. Weight average molecular weight is 1
If it exceeds 000, the resulting sheet lacks flexibility and is inferior in moldability. Further, as these reactive acrylic oligomers, those having a glass transition point in the range of −50 ° C. to 40 ° C. and a functional group value in the range of 80 to 250 are used from the relationship between the moldability of the sheet and the hardness after curing. Is preferred. The reactive acrylic oligomer may be a combination of a plurality of types of reactive acrylic oligomers as long as they are within these molecular weight ranges.

In addition, isocyanate, epoxy, or melamine cross-linking 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 by the thermosetting resin composition containing the solid reactive acrylic resin and the block isocyanate as the main components, and the transparent reactive acrylic resin and the solid reactive acrylic resin react with each other. The transparent resin layer of the second invention is formed of the thermosetting resin composition containing the acrylic oligomer and the block isocyanate as the main components. If necessary, a filler, an antioxidant, etc. may be added to the transparent resin layer of the first and second inventions within a range not impairing transparency.
The obtained transparent resin layer is in an uncured state before heating, and a hard transparent coating film is formed by heating at a temperature of a predetermined temperature or higher.

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

Thermoplastic acrylic resin, reactive vinyl monomer, peroxide and colorant as main components.

The main component is a thermoplastic acrylic resin, a reactive vinyl monomer, a photosensitizer and a colorant.

Thermoplastic acrylic resin, reactive vinyl monomer, peroxide, photosensitizer and colorant as main components.

The thermoplastic acrylic resin contained in the colored resin layer is a polyacrylic acid ester, and usually polymethylmethacrylate or polymethylmethacrylate copolymer can be used. Polymers of other acrylic acid esters and blends thereof can also be used.

As the colorant, a pigment used in ordinary decoration,
Paint etc. can be used. For example, for pigments, titanium oxide,
There are iron oxide, carbon black, cyanine pigments, quinacridone pigments, and dyes such as azo dyes, anthraquinone dyes, indigoid dyes, stilbene dyes, aluminum flakes, nickel powder, gold powder,
Metal powder such as silver powder may be added. When using a colorant having a high hiding property, the amount of the total colorant is 2 to 100 parts by weight relative to 100 parts by weight of the solid content of the resin (hereinafter, simply referred to as “parts”).
A range of parts is preferred.

As the reactive vinyl monomer, a (meth) acrylic or styrene-based material is suitable as a material having good compatibility with the thermoplastic acrylic resin. Examples of the acrylic-based reactive vinyl monomer include 1 such as methyl (meth) acrylate, emethyl (meth) acrylate, benzyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, and phenoxydiethylene glycol (meth) acrylate. Functional type, 1,6-hexanediol (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylpropane tri (meth) acrylate, pentaerythritol A polyfunctional type such as tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol hexa (mer) acrylate can be applied.

Examples of the styrene-based reactive vinyl monomer include styrene, α-methylstyrene, α-ethylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-ethoxystyrene, p-chlorostyrene,
Various styrene derivatives such as m-chlorostyrene and o-chlorostyrene can be applied. The amount of the reactive vinyl monomer added is preferably adjusted to be in the range of 20 to 200 parts, more preferably 40 to 150 parts, relative to 100 parts of the thermoplastic acrylic resin. In addition, the reactive vinyl monomer is not limited to one type, and two or more types can be used in combination.

As the above-mentioned peroxide, a commonly used organic peroxide type is preferably used, and more preferably from the viewpoint of storage stability at room temperature, for example, 2,2-bis (ter-butylperoxy) butane, ter-butyl peroxybenzoate, di-ter-butyl peroxyisophthalate, methyl ethyl ketone peroxide, dicumyl peroxide, te
The decomposition temperature of r-butylperoxyacetate is 160
It is about ℃. The appropriate amount of the peroxide added varies depending on the composition of the colored resin layer described above, but is preferably in the range of 0.5 to 2.0 parts with respect to 100 parts of the reactive vinyl monomer. Further, the peroxide is not limited to one kind, and two or more kinds can be used in combination.

As the photosensitizer, a commonly used photosensitizer can be applied, and for example, a benzoin alkyl ether-based, acetophenone-based, benzophenone-based, thioxanthone-based photosensitizer is preferably used. For benzoin ether type, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, etc .; for acetophenone type, 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2- Hydroxy-2-methylpropiophenone,
Among benzophenone-based compounds such as p-ter-butyltrichloroacetophenone, benzophenone, 4-chlorobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-4-methoxybenzophenone, dibenzosu Examples of thioquinton-based compounds such as beron include thioxanthone, 2-chlorothioxanthone, 2-methylthioquinton, 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 per 100 parts of the reactive vinyl monomer. Further, the photosensitizer is not limited to one type, and two or more types can be used in combination.

The above components are mixed to obtain a colored thermosetting resin composition, and the thermosetting resin composition forms a colored resin layer. The colored resin layer is in an uncured state before heating and adheres well to the transparent resin layer. The colored resin layer is heated at a predetermined temperature or higher to form a hard coating, and in particular, the colored resin layer containing the photosensitizer is cured by irradiation with light to form a hard coating. It

The thermosetting coating sheet of the present invention thus obtained is, as shown in FIG. 1, formed by laminating the transparent resin layer 2 on the surface of the colored resin layer 1, and before heating. It is in an uncured state, has excellent spreadability and flexibility, and can be satisfactorily coated along the surface of an article having irregularities or curved surfaces. The transparent resin layer 2 preferably has a thickness of 10 to 50 μm, and the colored resin layer 1 preferably has a thickness of 50 to 150 μm. However, when the colored resin layer 1 is an ultraviolet curable type, the thickness of the colored resin layer 1 is preferably 50 to 80 μm.

In addition, the colored resin layer 1 of the thermosetting coating sheet,
If the article to be coated does not have a sufficient adhesive force, an adhesive layer 3 is provided on the back surface of the colored resin layer 1 as shown in FIG. By sticking the sheet on the surface, the adhesion between the hard coating after curing and the article can be improved. Examples of the adhesive layer 3 include EVA-based hot melt adhesives, SIS-based hot melt film adhesives, acrylic resin hot melt film adhesives, unsaturated polyester-based uncrosslinked materials, acrylic adhesives, and post-cured acrylic adhesives. Examples of the agent include blends or laminates of these.

When the viscosity of the resin composition constituting the thermosetting coating sheet at room temperature is low, 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. Further, as shown in FIG. 3, the adhesive layer 3 may be provided on the back surface of the colored resin layer 1 and the support layer 4 may be provided on the surface of the transparent resin layer 2. The support layer 4 is used for retaining the shape of the entire thermosetting coating sheet, and when the sheet is attached to the surface of an article having a three-dimensional curved surface with the support layer 4, Heating is performed as necessary in order to impart flexibility to the support layer 4 and ensure desired spreadability. After the thermosetting coating sheet is attached to the article and cured, the support layer 4 may be peeled off and removed.

The thermosetting coating sheet thus configured may be manufactured by any method. For example, the components of the transparent resin layer described above are uniformly mixed, and this mixture is applied onto a film release-treated with a silicone release agent and dried to form a transparent resin layer. Then, a colored resin layer is formed by applying a coloring material obtained by uniformly mixing the above-mentioned colored resin layer components onto the surface of this transparent resin layer and drying, and then peeling the transparent resin layer and the colored resin layer from the film. Is obtained by A thermosetting coating sheet is obtained by forming a transparent resin layer and a colored resin layer on a film respectively, then laminating both layers by a roll press or the like and pressing them together, and then removing the film. The temperature of each of the above drying steps is carried out at a temperature not higher than the decomposition temperature of block isocyanate and peroxide.

(Example) Hereinafter, the present invention will be described in detail based on examples.

Example 1 Acrylic polyol (manufactured by Nippon Shokubai Kogyo Co., Ltd., Arotane 2040-145, Tg 40 ° C., weight average molecular weight 339,000, OH value 8)
0) 100 parts by solids, block isocyanate (Takeda Yakuhin Kogyo KK, Takenate B-815N, hydrogenated phenyl methane diisocyanate oxime block, NCO% 7.
3) 49 parts (this block isocyanate has 1.0 equivalent of isocyanate groups with respect to the hydroxyl groups of the acrylic polyol) were mixed with good stirring. A polyethylene terephthalate film (Siken Kako Co., Ltd., film thickness 40 μm, PE hereinafter
T film) was applied to the release surface and dried at 80 ° C. for 5 minutes to form a transparent resin layer (hereinafter referred to as transparent resin layer A).

On the other hand, 300 parts of ethyl acetate, 100 parts of a thermoplastic acrylic resin (Asahi Kasei Kogyo KK, Delpett 8500), 40 parts of methyl methacrylate, 0.6 part of ter-butylperoxide and 50 parts of titanium oxide were mixed with good stirring. The mixture is applied to the transparent resin layer A described above, dried at 80 ° C. for 5 minutes to form a colored resin layer, and the PET film is peeled off to obtain an uncured thermosetting coating sheet. Obtained.
The film thickness of this sheet is 20 μm for the transparent resin layer and for the colored resin layer.
It was 100 μm.

Example 2 Acrylic polyol (Nippon Shokubai Kogyo KK, Arotane 2040-139, weight average molecular weight 320,000, Tg 20 ° C., OH value 10
100 parts by weight of solids) and 62 parts of block isocyanate (Takenate B-815N, manufactured by Takeda Pharmaceutical Co., Ltd.) (having 1.0 equivalent of isocyanate groups with respect to the hydroxyl groups of the acrylic polyol) were mixed with good stirring. .

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

Next, 300 parts of ethyl acetate, 100 parts of thermoplastic acrylic resin (Delpett 8500 manufactured by Asahi Kasei Kogyo Co., Ltd.), 50 parts of neopentyl glycol dimethacrylate, 0.8 parts of dibutyl peroxyisophthalate and 50 parts of titanium oxide are well stirred. While mixing. The mixture is applied onto the 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 obtain an uncured thermosetting coating sheet. Obtained. The thickness of this sheet was 15 μm for the transparent resin layer and 70 μm for the colored resin layer.

Example 3 300 parts of ethyl acetate, 100 parts of a thermoplastic acrylic resin (Delpett 8500 manufactured by Asahi Kasei Kogyo Co., Ltd.), 40 parts of tripropylene glycol dimethacrylate, 1.0 part of ter-butyl peroxybenzoate and 50 parts of titanium oxide were stirred. While mixing. This mixture is coated on the transparent resin layer A and dried at 70 ° C. for 30 minutes to form a colored resin layer, and PET is used.
By peeling off the film, an uncured thermosetting coating sheet was obtained. The 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 a thermoplastic acrylic resin (Delpett 8500 manufactured by Asahi Chemical Industry Co., Ltd.), 60 parts of hexamethylene glycol dimethacrylate, 1.0 part of ter-butyl peroxybenzoate and 50 parts of titanium oxide were stirred. While mixing. This mixture was coated on the transparent resin layer B and dried at 70 ° C. for 30 minutes to form a colored resin layer.
By peeling off the T film, a thermosetting coating sheet in an uncured state was obtained. The film thickness of this sheet was 15 μm for the transparent resin layer and 100 μm for the colored resin layer.

Example 5 300 parts of ethyl acetate, 100 parts of thermoplastic acrylic resin (Asahi Kasei Kogyo KK, Delpett 8500), 40 parts of dipropylene glycol dimethacrylate, 40 parts of methyl methacrylate, 1.0 part of ter-butyl peroxybenzoate, 4
-0.6 parts of chlorobenzophenone and 50 parts of titanium oxide were mixed with stirring. This transparent resin layer A is coated with this mixture, 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 photocurable coating sheet. Got The thickness of this sheet was 30 μm for the transparent resin layer and 60 μm for the colored resin layer.

Example 6 Ethyl acetate 300 parts, thermoplastic acrylic resin (Asahi Kasei Kogyo KK, Delpett 8500) 100 parts, dipropylene glycol dimethacrylate 40 parts, methyl methacrylate 40 parts, ter-butyl peroxybenzoate 1.0 part, benzyl 0.6 parts and titanium oxide 50 parts were mixed with stirring. This mixture is applied 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 form an uncured heat- and light-curable coating sheet. Got The thickness of this sheet is 15 for the transparent resin layer.
μm, and the colored resin layer was 55 μm.

Example 7 300 parts of ethyl acetate, 100 parts of thermoplastic acrylic resin (Asahi Kasei Kogyo KK, Delpett 8500), 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 A, 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 light curable coating sheet. Got The film thickness of this sheet was 30 μm for the transparent resin layer and 55 μm for the colored resin layer.

Example 8 Ethyl acetate 300 parts, thermoplastic acrylic resin (Asahi Kasei Kogyo KK, Delpett 8500) 100 parts, phenoxydipropylene glycol methacrylate 40 parts, p-chlorostyrene 40 parts, benzoin 0.8 parts and titanium oxide 50. The parts were mixed with stirring. This mixture is mixed with the transparent resin layer B
It was coated on the above, dried at 80 ° C. for 10 minutes to form a colored resin layer, and the PET film was peeled off to obtain a heat and photocurable coating sheet in an uncured state. The thickness of this sheet was 15 μm for the transparent resin layer and 60 μm for the colored resin layer.

Example 9 100 parts by weight of acrylic polyol (Nippon Shokubai Kogyo KK, Arotane 2040-145) solid content, acrylic polyol oligomer (Nippon Carbide, Nicalite H-870, weight average molecular weight 2,200-2,500, OH value 200) 30 Block, Block isocyanate (Takeda Pharmaceutical Co., Ltd., Takenate B815)
N) 86 parts (this block isocyanate has 1.0 equivalent of isocyanate groups with respect to the hydroxyl groups of the above acrylic polyol and acrylic polyol oligomer) were mixed with good stirring. This mixture was applied to the release surface of a PET film subjected to silicone release treatment in the same manner as in Example 1 and dried at 80 ° C. for 5 minutes to form a transparent resin layer (hereinafter referred to as transparent resin layer C).

On the other hand, ethyl acetate 300 parts, thermoplastic acrylic resin (Asahi Kasei Co., Ltd., Delpett 8500) 100 parts, methyl methacrylate 40 parts, ter-butyl peroxyacetate 0.6
And 50 parts of titanium oxide were mixed with stirring. This mixture is applied onto the transparent resin layer C, dried at 80 ° C. for 5 minutes to form a colored resin layer, and the PET film is peeled off to obtain an uncured thermosetting coating sheet. It was
The thickness of this sheet was 20 μm for the transparent resin layer and 100 μm for the colored resin layer.

Example 10 Acrylic polyol (Nippon Shokubai Kogyo Co., Ltd., Arotane 2040-139) 100 parts by solid content, acrylic polyol oligomer (Nippon Shokubai Kogyo KK, Arotane 2040-134,
Weight average molecular weight 9,000, Tg20 ° C, OH value 120) 20 parts, block isocyanate (Takeda Pharmaceutical Co., Ltd., Takenate)
b815N) 78 parts (this block isocyanate has 1.0 equivalent of isocyanate groups with respect to the hydroxyl groups of the above-mentioned acrylic polyol and acrylic polyol oligomer) were mixed with good stirring. As in Example 1, this mixture was applied to the release surface of the PET film treated with silicone release in the same manner as in Example 1 and dried at 80 ° C. for 5 minutes to form a transparent resin layer (hereinafter referred to as transparent resin layer D). Formed).

On the other hand, while stirring 300 parts of ethyl acetate, 100 parts of thermoplastic acrylic resin (Asahi Kasei Kogyo KK, Delpett 8500), 50 parts of neopentyl glycol dimethacrylate, 0.8 parts of dibutyl peroxyisophthalate and 50 parts of titanium oxide. Mixed. This mixture is coated on the transparent resin layer D and dried at 80 ° C. for 5 minutes to form a colored resin layer,
By peeling off the PET film, an uncured thermosetting coating sheet was obtained. The thickness of this sheet was 15 μm for the transparent resin layer and 70 μm for the colored resin layer.

Example 11 300 parts of ethyl acetate, 100 parts of a thermoplastic acrylic resin (Asahi Kasei Kogyo KK, Delpett 8500), 40 parts of tripropylene glycol dimethacrylate, 1.0 part of ter-butyl peroxybenzoate and 50 parts of titanium oxide were stirred. While mixing. This mixture is coated on the transparent resin layer C and dried at 70 ° C. for 30 minutes to form a colored resin layer,
By peeling off the T film, a thermosetting coating sheet in an uncured state was obtained. The thickness of this sheet was 30 μm for the transparent resin layer and 80 μm for the colored resin layer.

Example 12 300 parts of ethyl acetate, 100 parts of thermoplastic acrylic resin (Asahi Kasei Co., Ltd., Delpett 8500), 60 parts of hexamethylene glycol dimethacrylate, 1.0 part of ter-butyl peroxybenzoate and 50 parts of titanium oxide were stirred. While mixing. This mixture is coated on the transparent resin layer D and dried at 70 ° C. for 30 minutes to form a colored resin layer, and PET is used.
By peeling off the film, an uncured thermosetting coating sheet was obtained. The film thickness of this sheet was 15 μm for the transparent resin layer and 100 μm for the colored resin layer.

Example 13 Ethyl acetate 300 parts, thermoplastic acrylic resin (Asahi Kasei Kogyo KK, Delpett 8500) 100 parts, dipropylene glycol dimethacrylate 40 parts, methyl methacrylate 40 parts, ter-butyl peroxybenzoate 1.0 part, 4
-Chlorobenzophenone 0.6 and 50 parts titanium oxide were mixed with stirring. This mixture is coated on the transparent resin layer C and dried at 70 ° C. for 30 minutes to form a colored resin layer,
By peeling off the PET film, an uncured heat and light curable coating sheet was obtained. The thickness of this sheet is
The transparent resin layer had a thickness of 30 μm and the colored resin layer had a thickness of 60 μm.

Example 14 300 parts of ethyl acetate, 100 parts of thermoplastic acrylic resin (Asahi Kasei Kogyo KK, Delpett 8500), 40 parts of dipropylene glycol dimethacrylate, 40 parts of methyl methacrylate, 1.0 part of ter-butyl peroxybenzoate, benzyl 0.6 parts and 50 parts of titanium oxide were mixed with stirring. This mixture is coated on the transparent resin layer D, and the temperature is 70 ° C.
Was dried for 30 minutes to form a colored resin layer, and the PET film was peeled off to obtain an uncured heat and light curable coating sheet. The film thickness of this sheet is
The thickness was 15 μm and the color resin layer was 55 μm.

Example 15 Ethyl acetate 300 parts, thermoplastic acrylic resin (Asahi Kasei Kogyo KK, Delpett 8500) 100 parts, phenoxydiethylene glycol methacrylate 40 parts, o-chlorostyrene 40 parts, benzoin 0.8 parts and titanium oxide 50 parts. Were mixed with stirring. The transparent resin layer C is coated with this mixture, 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 photocurable coating sheet. Got The film thickness of this sheet was 30 μm for the transparent resin layer and 55 μm for the colored resin layer.

Example 16 300 parts of ethyl acetate, 100 parts of thermoplastic acrylic resin (produced by Asahi Chemical Industry Co., Ltd., Delpett 8500), 40 parts of phenoxydipropylene glycol methacrylate, 40 parts of p-chlorostyrene, 0.8 part of benzoin and 50 parts of titanium oxide. The parts were mixed with stirring. This mixture is used as the transparent resin layer D
It was coated on the above, dried at 80 ° C. for 10 minutes to form a colored resin layer, and the PET film was peeled off to obtain a heat and photocurable coating sheet in an uncured state. The thickness of this sheet was 15 μm for the transparent resin layer and 60 μm for the colored resin layer.

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

The extensibility was evaluated based on whether the sheet was stretched 100% under an atmosphere condition of 30 ° C. and the sheet was torn. The moldability was evaluated by the ease of coating when the sheet was attached to a substrate and the laminate was vacuum formed at 60 ° C, and the appearance of the sheet.

The adhesion of the sheet is measured by heating the laminated body molded as described above at 160 ° C. for 30 minutes or at 160 ° C. for 30 minutes and irradiating with a high pressure mercury lamp (160 W / cm, height 15 cm) for 2 minutes, On the surface of the cured coating film, 100 cuts at 1 mm intervals were placed in a grid pattern, a commercially available adhesive tape was attached to this, and then the tape was peeled off, and the remaining% of the grid pattern pieces was displayed.

The 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 results when the coated steel plate was used as the base material. When using a coated steel sheet as the base material, in order to maintain the adhesion with the coated steel sheet of the sheet during vacuum forming,
Adhesive layer (acrylic adhesive, Sekisui Chemical Co., Ltd., Sdyne WHD, thickness 10μ on the back of the colored resin layer of the sheet
m) was provided, and vacuum forming was performed.

Comparative Example 1 Acrylic polyol (Nippon Shokubai Kogyo Co., Ltd., Arotane 2040-134, weight average molecular weight 9,000) 100 parts by solids, and block isocyanate (Takeda Yakuhin Kogyo Co., Ltd.),
49 parts of Takenate B-815N) (having 1.0 equivalent to the hydroxyl groups of the acrylic polyol) were mixed with good stirring. This mixture was applied to the release surface of a PET film which had been subjected to a release treatment, and dried at 80 ° C. for 5 minutes to form a transparent resin layer. Next, in 300 parts of ethyl acetate, 100 parts of a thermoplastic acrylic resin (Asahi Kasei Co., Ltd., Delpett 8500), 30 parts of methyl methacrylate, 20 parts of diethylene glycol dimethacrylate, 1.0 part of thioxanthone and 40 parts of titanium oxide were stirred. While mixing. 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 obtain an uncured heat and light curable coating sheet. Obtained. The thickness of this sheet was 15 μm for the transparent resin layer and 70 μm for the colored resin layer.

<Performance of Thermosetting Coating Sheet> The thermosetting coating sheet obtained in Comparative Example 1 was used in Example 1
Tested in the same manner as. As a result, 100% elongation at 30 ° C was obtained, but cracks were formed on the surface of the transparent resin layer.

Example 17 300 parts of ethyl acetate was added to a reactive acrylic resin (a copolymer of methyl methacrylate, butyl methacrylate, methacrylic acid and 2-aminoethyl acrylate, Mw = 30.00).
0, Tg 35 ° C, COOH value 40 and NH ₂ value 40) 100 parts of solid content, block isocyanate (Takeda B-Takenate B-
870N, oxime block of isophorone diisocyanate
NCO = 12.6%) 34 parts (this crosslinking agent has 0.9 equivalent of isocyanate groups based on the functional groups of the reactive acrylic resin) were added and mixed with stirring. This mixture was coated on the mold release surface of polyethylene phthalate (PET) film, which had been subjected to silicone mold release, with an applicator, and the mixture was heated at 80 ° C for 5 minutes.
After being dried for a minute, a transparent resin layer was formed (this is referred to as transparent resin layer G). The thickness of the sheet was 30 μm.

On the other hand, in 300 parts of ethyl acetate, a reactive acrylic resin (copolymer of methyl methacrylate and 2-hydroxyethyl methacrylate, methacrylic acid and ethyl acrylate,
Mw = 250,000, Tg20 ° C, OH number 40 and COOH number 20), solid content 100
Part, reactive acrylic oligomer (methyl acrylate,
Copolymer of 2-hydroxyethyl methacrylate, butyl acrylate, methacrylic acid, Mw = 4,000, Tg-10
℃, OH value 100, COOH value 40) solid content 20 parts, block isocyanate (same as above) 31 parts (this cross-linking agent is 1.0 equivalent of isocyanate group to the functional group of the reactive acrylic resin and reactive acrylic oligomer). And 150 parts of titanium oxide were mixed with good stirring. This mixture was applied onto the transparent resin layer G so that the film thickness of the sheet would be 100 μm, dried at 80 ° C. for 20 minutes and laminated.

Example 18 300 parts of ethyl acetate was added to a reactive acrylic resin (copolymer of methyl methacrylate and methacrylic acid and 2-aminoethyl acrylate, Mw = 25,000, Tg 35 ° C., COOH value 40 and NH.
_Divalent 40) to the solid content 100 parts reactive acrylic oligomer (methyl acrylate, 2-hydroxyethyl methacrylate, butyl acrylate, copolymers of methacrylic acid,
Mw = 4,000, Tg-10 ° C, OH value 100, COOH value 40), solid content 30
Part, block isocyanate (Takenate B-815N, hydrogenated diphenylmethane diisocyanate ketooxime block NCO 7.3%, manufactured by Takeda Pharmaceutical Co., Ltd.) 75 parts (this crosslinking agent is a functional mixture of the above-mentioned reactive acrylic resin and reactive acrylic oligomer). (With 1.0 equivalent of isocyanate groups to the groups) was mixed with good stirring. Polyethylene terephthalate (PET) obtained by subjecting this mixture to silicone release treatment
The release surface of the film was coated with an applicator and dried at 80 ° C. for 5 minutes to form a transparent resin layer (this is referred to as transparent resin layer H). The thickness of the sheet was 20 μm.

On the other hand, to 300 parts of ethyl acetate, a reactive acrylic resin (a copolymer of methyl methacrylate and 2-hydroxyethyl methacrylate and ethyl acrylate, Mw = 250,000, Tg1
5 ° C, OH value 40 and COOH value 20) in solid content 100 parts, reactive acrylic oligomer (same as above) solid content 20 parts, block isocyanate (same as 2) 54 parts (this crosslinking agent is the above reactive acrylic resin) And the reactive acrylic oligomer have 1.0 equivalent of isocyanate groups with respect to the functional groups of) and iron oxide 60
The parts were mixed with good stirring. This mixture is coated on the transparent resin layer H so that the film thickness of the sheet is 100 μm,
It was dried at 20 ° C. for 20 minutes and laminated.

Example 19 300 parts of methyl acetate was added to a reactive acrylic resin (copolymer of methyl methacrylate, 2-hydroxyethyl methacrylate and acrylic acid, Mw = 250,000, Tg15 ° C., OH value 40).
And a COOH value of 40), a solid content of 100 parts, a reactive acrylic oligomer (a copolymer of methyl acrylate and 2-aminoethyl methacrylate, acrylic acid and methyl methacrylate,
Mw = 8,000, Tg-10 ° C, NH ₂ value 60, COOH value 30), solid content 10
Parts, block isocyanate (same as 1) 35 parts (this cross-linking agent has 1.0 equivalent of isocyanate groups based on the functional groups of the above-mentioned reactive acrylic resin and reactive acrylic oligomer), and isocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate L, polyisocyanate obtained by reacting 3 mol of tolylene diisocyanate with 1 mol of trimethylolpropane, NCO = 13.0%) in a solid content of 12 parts (30% of functional groups of reactive acrylic resin is initially cured) Were mixed with good stirring. Apply this mixture to the release surface of PET film with silicone release treatment with an applicator, and apply
A transparent resin layer was prepared by drying at 5 ° C for 5 minutes (this is referred to as transparent resin I). The thickness of the sheet was 15 μm.

On the other hand, to 300 parts of ethyl acetate, a reactive acrylic resin (copolymer of methyl methacrylate and methacrylic acid and 2-aminoethyl acrylate, Mw = 492,000, Tg35 ° C, COOH value 4
0 and NH ₂ valency 40) to a solid content of 100 parts, a reactive acrylic oligomer (a copolymer of methyl acrylate and 2-aminoethyl methacrylate, acrylic acid and methyl methacrylate,
Mw = 8,000, Tg-10 ° C, NH ₂ value 60, COOH value 30) in solid content
20 parts, block isocyanate (same as 1) 35 parts (this cross-linking agent has 1.0 equivalent of isocyanate groups based on the functional groups of the above-mentioned reactive acrylic resin and reactive acrylic oligomer), epoxy cross-linking agent (manufactured by Ciba Geigy, Araldide CY175, an epoxy equivalent of 160, and an epoxy value of 220 corresponding to the functional group value of 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 good stirring. This mixture is applied to a sheet with a thickness of 100 μm
Was applied onto the transparent resin layer I, and dried at 80 ° C. for 20 minutes to be laminated.

Example 20 300 parts of ethyl acetate, 100 parts of a thermoplastic acrylic resin (Asahi Kasei Co., Ltd., Delpett 8500), 40 parts of tripropylene glycol dimethacrylate, 1.0 part of ter-butyl peroxybenzoate and 50 parts of titanium oxide while stirring Mixed. This mixture is coated on the transparent resin layer G and dried at 70 ° C. for 30 minutes to form a colored resin layer, and PET is used.
By peeling off the film, an uncured thermosetting coating sheet was obtained. The 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 a thermoplastic acrylic resin (Asahi Kasei Co., Ltd., Delpett 8500), 60 parts of hexamethylene glycol dimethacrylate, 1.0 part of ter-butyl peroxybenzoate and 50 parts of titanium oxide were stirred. While mixing. This mixture is applied on the transparent resin layer H and dried at 70 ° C. for 30 minutes to form a colored resin layer, and PET is used.
By peeling off the film, an uncured thermosetting coating sheet was obtained. The film thickness of this sheet was 15 μm for the transparent resin layer and 100 μm for the colored resin layer.

Example 22 300 parts ethyl acetate, 100 parts thermoplastic acrylic resin (Asahi Kasei Co., Ltd., Delpett 8500), 40 parts dipropylene glycol dimethacrylate, methyl methacrylate
40 parts, ter-butyl peroxybenzoate 1.0 part, 4-
0.6 parts of chlorobenzophenone and 50 parts of titanium oxide were mixed with stirring. This mixture is coated on the transparent resin layer I and dried at 70 ° C. for 30 minutes to form a colored resin layer,
By peeling off the PET film, an uncured thermosetting coating sheet was obtained. The thickness of this sheet was 30 μm for the transparent resin layer and 60 μm for the colored resin layer.

Example 23 300 parts ethyl acetate, 100 parts thermoplastic acrylic resin (Asahi Kasei Kogyo KK, Delpet 8500), 40 parts dipropylene glycol dimethacrylate, methyl methacrylate
40 parts, ter-butyl peroxybenzoate 1.0 part, benzyl 0.6 part and titanium oxide 50 parts were mixed with stirring. This mixture is applied onto 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. It was The thickness of this sheet is 15 μm for the transparent resin layer,
The colored resin layer had a thickness of 55 μm.

Example 24 300 parts ethyl acetate, 100 parts thermoplastic acrylic resin (Asahi Kasei Kogyo KK, Delpett 8500), 40 parts phenoxydiethylene glycol methacrylate, 40 parts o-chlorostyrene, 0.8 parts benzoin and 50 parts titanium oxide. Were mixed with stirring. This mixture is applied 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 obtain an uncured thermosetting coating sheet. It was The film thickness of this sheet was 30 μm for the transparent resin layer and 55 μm for the colored resin layer.

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

The extensibility was evaluated based on whether the sheet was stretched 100% under an atmosphere condition of 30 ° C. and the sheet was torn. The moldability was evaluated by the ease of coating when the sheet was attached to a substrate and the laminate was vacuum formed at 60 ° C, and the appearance of the sheet.

Adhesion of the sheet, the laminate molded as described above, 160 ℃, heating for 30 minutes, Examples 22,23,24 160 ℃, 30
After heating for 1 minute and irradiating for 2 minutes with a high pressure mercury lamp (160 W / cm, height 15 cm), put 100 cuts at 1 mm intervals on the surface of the cured coating in a grid pattern and attach a commercially available adhesive tape to it. Then, the tape was peeled off and the remaining percentage of the cross-cut pieces was indicated.

The 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 results when the coated steel plate was used as the base material. When a coated steel sheet is used as the base material, an adhesive layer (acrylic adhesive, Sekisui Chemical Co., Ltd.) is provided on the back surface of the colored resin layer of the sheet to maintain the adhesion of the sheet to the coated steel sheet during vacuum forming. Co., Ltd., S-Dyne WHD, thickness 10
(μm) was used for vacuum forming.

(Effect of the invention) The constitution of the thermosetting coated sheet of the present invention is as described above, and in the state of the curing temperature or lower, it has excellent malleability and flexibility, and not only a flat surface but also some irregularities and curved surfaces. It is possible to satisfactorily coat the surface of an article with "crease". In addition, the thermosetting coating sheet can form a strong and uniform coating excellent in hardness and abrasion resistance by heating and curing the colored resin layer and the transparent resin layer together.

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 as seen in metalic coating and is excellent in performance.
Moreover, it is possible to form a film having a good appearance such as gloss and sharpness.

[Brief description of drawings]

FIG. 1 is a schematic sectional view of an embodiment of the present invention, FIG. 2 is a schematic sectional view of another embodiment of the above, and FIG. 3 is a schematic sectional view of yet another embodiment of the same. 1 ... Colored resin layer, 2 ... Transparent resin layer, 3 ... Adhesive layer, 4 ... Support layer.

Claims (3)

[Claims] 1. A thermosetting coating sheet in which an uncured transparent resin layer is laminated with an uncured colored resin layer, wherein the transparent resin layer has a weight average molecular weight of 10 , 0
A reactive acrylic resin that is 00 to 1,000,000 and is solid at room temperature, and a thermosetting resin composition having a block isocyanate as a main component, and the colored resin layer is a colored thermosetting resin composition. A thermosetting coating sheet characterized by: 2. The thermosetting coating sheet 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. . 3. The colored resin layer comprises a thermoplastic acrylic resin,
The thermosetting coating sheet according to claim 1 or 2, comprising a thermosetting resin composition containing a reactive vinyl monomer, a colorant, and a peroxide and / or a photosensitizer as main components.