JPH07119096B2 - Thermosetting coating sheet - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial field of application) The present invention relates to a coating such as furniture, steel plate, etc., which is attached to the surface of an article by thermosetting for protection, decoration, or display of the article surface. 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 polyvinyl chloride has been proposed. This sticking material is stuck on the surface of articles such as furniture and steel plates. When this sticking material is used, it does not have an adverse effect on the working environment, and since it is a sheet, it does not need to be dried. However, 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 Japanese Examined Patent Publication No. 57-13425,
A thermosetting composite sheet has been proposed in which a porous sheet-shaped substrate is impregnated with a radical reaction initiator, and a layer containing a polymer and a radical-reactive monomer or the like is laminated on one or both sides of the substrate.

Further, JP-A-62-169630 discloses that different molecular weights are different from each other.
A colored film having excellent appearance and weather resistance, which is obtained by laminating different types of unsaturated polyester polyol layers and a transparent resin layer of a crosslinkable resin composition, has been proposed.

JP-A-62-271735 discloses a cross-linking type containing a surface layer of a thermoplastic resin composition having excellent durability, a metal powder and / or a coloring pigment on a substrate having good releasability and surface smoothness. There has been proposed a colored sheet comprising the above resin composition and having excellent appearance and durability.

(Problems to be Solved by the Invention) A composite sheet disclosed in JP-B-57-13425 has a structure in which a layer having a radical reactive unsaturated compound and a layer having a radical reaction initiator are laminated. Because
In order to carry out a uniform curing reaction at the time of heating and pressurizing, it is necessary to bring both layers into uniform contact to cause a reaction, and it is difficult to control heating and pressurizing. Further, since paper, woven cloth, and non-woven cloth are used as the sheet-shaped base material impregnated with the radical reaction initiator, when the composite sheet is coated on the surface of an article having irregularities or curved surfaces, the composite sheet is difficult to stretch. As a result, "wrinkles" are easily formed, and it is difficult to form a good film on the article surface.

The colored film disclosed in JP-A-62-169630 is
It has a two-layer structure and has good color depth and good appearance. However, in the production of this colored film, since a method of providing a colored resin layer on the transparent resin layer after curing the transparent resin layer is used, it is possible to obtain it by the effect of the cured transparent resin layer. The colored film obtained does not have spreadability and does not follow the surface of an article having irregularities or curved surfaces, making it difficult to form a good coating film.

The colored sheet disclosed in Japanese Patent Laid-Open No. 62-271735 has a transparent resin layer and a colored resin layer of the colored film disclosed in Japanese Laid-Open Patent Publication No. 62-169630, which are reversed, and is cured. Due to the influence of the 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 curtain having a two-layer structure and having a deep color and a good appearance.

(Means for Solving the Problems) The thermosetting covering sheet of the present invention is a thermosetting covering sheet in which an uncured colored resin layer is laminated with an uncured transparent resin layer. The colored resin layer, the weight-average molecular weight is 100,000 to 1,000,000, a solid reactive acrylic resin at room temperature, a block isocyanate, and a colorant, consisting of a thermosetting resin composition containing as a main component, The transparent resin layer is characterized by being composed of a transparent thermosetting resin composition, whereby the above object is achieved.

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 containing a reactive acrylic resin and a block isocyanate that are solid at room temperature as main components. 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.

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 on an uncured colored resin layer.

The colored resin layer of the first invention has a weight average molecular weight of 100,000-
1,000,000 is a solid-state reactive acrylic resin at room temperature, a block isocyanate, and a colorant, formed from a thermosetting resin composition containing as a main component, the transparent resin layer from a transparent thermosetting resin composition Has been formed.

The colored resin layer of the second invention has a weight average molecular weight of 100,
From a thermosetting resin composition containing 000 to 1,000,000 and a solid reactive acrylic resin at room temperature, a reactive acrylic oligomer having a weight average molecular weight of 1,000 to 10,000, a block isocyanate, and a colorant as main components Formed,
The transparent resin layer is formed of a transparent thermosetting resin composition as in the first invention. That is, the colored resin layer of the second aspect of the invention has a weight average molecular weight of the colored resin layer of the first aspect of the invention.
It contains a reactive acrylic oligomer of 1,000 to 10,000.

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 ℃). Such a reactive acrylic resin includes, for example, a (meth) acrylic acid ester monomer, a styrene derivative monomer, a hydroxyl group-containing (meth) acrylic acid ester monomer such as 2-hydroxyethyl (meth) acrylate, and 2-amino. It is obtained by copolymerizing a (meth) acrylic acid ester monomer having an amino group such as ethyl (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 the polymerization reaction is performed using an initiator, and the reactive acrylic resin used in the first invention has a weight average molecular weight of 100,000. A range of ~ 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 the sheet shape. Therefore, for example, sufficient elongation cannot be obtained by stretching during the sticking operation, and in some cases, cracking or cracking occurs. Conversely, if the weight average molecular weight exceeds 1,000,000,
The mixture described below has poor moldability, making it difficult to prepare a thermosetting coating sheet. Further, these acrylic polyols preferably have a Tg (glass transition point) in the range of 0 to 80 ° C. and a functional group value in the range of 20 to 200 in view of the hardness after curing. Further, the acrylic polyol can be combined with different material types within the above molecular weight range.

The block isocyanate contained in the colored resin layer is a heat-reactive type curing agent 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. Here, the block isocyanate means an isocyanate group of an isocyanate compound having two or more isocyanate groups in the molecule, a phenol,
It means a compound which is blocked with a blocking agent such as oxime, ε-caprolactam, malonic acid ester and the like. 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. In the block isocyanate, the above-mentioned blocking agent is desorbed by heating, and the resulting isocyanate group is a functional group (a total of a hydroxyl group, an amino group and a carboxyl group) of the acrylic polyol (and the acrylic polyol oligomer). The functional group value is a hydroxyl value and an amino group. Value is the sum of the acid value and the acid value, and the amino group value is the value calculated by calculating the amount of amino groups added at the time of polymerization in the same manner as the hydroxyl value or by reacting the amino groups with nitrous acid and converting them into hydroxyl groups. , The amount of carboxyl groups added at the time of polymerization is calculated in the same manner as the amount of hydroxyl groups, or a cross-linking reaction occurs with a value obtained by quantifying carboxyl groups with KOH, etc.). 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 functional 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 range is 0.8 to 1.2.

As the colorant contained in the colored resin layer, pigments, dyes and the like used in ordinary coating can be used. For example, pigments include titanium oxide, iron oxide, carbon black, cyanine pigments, quinacridone pigments, and dyes include azo dyes, anthraquinone dyes, indigoid dyes, stilbene dyes, and aluminum flakes and nickel powder. Metal powders such as gold powder and silver powder may be added.
When a colorant having a high hiding power is used, the amount of the total colorant is preferably in the range of 2 to 100 parts based on 100 parts by weight of the resin solid content (hereinafter referred to as “parts”).

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

The reactive acrylic oligomer has a weight average molecular weight of 1,
Those in the range of 000 to 10,000 are selected. When the weight average molecular weight of the reactive acrylic oligomer is less than 1,000, the resin obtained is inferior in moldability and it becomes difficult to prepare a coating sheet. If the weight average molecular weight exceeds 10,000, the resulting sheet lacks flexibility and is inferior in moldability. Further, these reactive acrylic oligomers preferably have 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 from the relationship between the moldability of the sheet and the hardness after curing. . Further, the reactive acrylic oligomer can be combined with different material types within the above molecular weight range. In addition, isocyanate, epoxy, or melamine cross-linking agent may be added to these resin layers depending on the case.

Thus, the colored resin layer of the first invention is formed by the solid reactive acrylic resin and the thermosetting resin composition containing the block isocyanate and the colorant as the main components, and the solid reactive acrylic resin and The colored resin layer of the second invention is formed by the thermosetting resin composition containing the reactive acrylic oligomer, the block isocyanate and the colorant as the main components. Further, a filler, an antiaging agent, a rust preventive agent, 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 in a state before heating, and by heating at a predetermined temperature or higher,
A hard coating is formed.

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

Mainly composed of solid reactive acrylic resin and block isocyanate at room temperature.

Thermoplastic acrylic resin, reactive vinyl monomer,
Mainly composed of peroxide.

Thermoplastic acrylic resin, reactive vinyl monomer,
The main component is a photosensitizer.

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

The block isocyanate contained in the transparent resin layer is used to cure the reactive acrylic resin contained in the transparent resin layer when heated. As the block isocyanate and the 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 as the reactive acrylic resin used for the colored resin layer, but is 100,000.
The glass transition point is preferably in the range of 0 to 80 ° C, and the OH number is preferably 20 to 200. The blending amount of block isocyanate and reactive acrylic resin is
The ratio of the functional groups contained in the acrylic polyol and the isocyanate groups contained in the block isocyanate is 0.5 to 2.0.
Is preferably adjusted to fall within the range of 0.8 to 1.2, more preferably 0.8 to 1.2.

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

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 reactive vinyl monomer include 1 such as methyl (meth) acrylate, ethyl (meth) acrylate, benzyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, and phenoxydiethylene glycol (meth) acrylate. Functional type, 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, penta A polyfunctional type such as erythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) 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. Further, the reactive vinyl monomer is not limited to one type, and two or more types can be used in combination.

As the photosensitizer, a commonly used photosensitizer can be applied, and benzoin alkyl ether-based, acetophenone-based, benzophenone-based, thioxanthone-based photosensitizers and the like are preferably used. For example, in benzoin ether type, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, etc., in acetophenone type, 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone,
Examples of benzophenone-based compounds such as P-ter-butyltrichloroacetophenone include benzophenone, 4-chlorobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-4-methoxybenzophenone, and dibenzophenone. 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 0.3 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.

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-butylperoxybenzoate, di-ter
-Butyl peroxyisophthalate, methyl ethyl ketone peroxide, dicumyl peroxide, and ter-butyl peroxyacetate having a decomposition temperature of about 160 ° C. The appropriate amount of the peroxide added varies depending on the composition of the transparent 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.

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. The transparent resin layer forms a film of hardness by heating at a predetermined temperature or higher. Particularly, the transparent resin layer containing the photosensitizer is hardened by being hardened by being irradiated with light. Is formed.

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 thickness of the transparent resin layer 2 is preferably 10 to 50 μm,
The thickness of the colored resin layer 1 is preferably 50 to 150 μm.

When the colored resin layer 1 of the thermosetting coating sheet does not have a sufficient adhesive force to the article to be coated, as shown in FIG. By providing the adhesive layer 3 on the sheet and attaching the sheet to the surface of the article via the adhesive layer 3, the adhesiveness between the hard coating after curing and the article can be improved. Examples of the adhesive layer 3 include EVA hot melt adhesive, SIS hot melt film adhesive, acrylic hot melt film adhesive, unsaturated polyester uncrosslinked material, acrylic adhesive, and post-curing acrylic adhesive. 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, an adhesive layer 3 may be provided on the back surface of the colored resin layer 1 and a support layer 4 may be provided on the surface of the transparent resin layer 2. The support layer 4 is for thermosetting coating. It is used to retain the shape of the entire sheet, but when the sheet is attached to the surface of an article having a three-dimensional curved surface with the support layer 4, the support layer 4 is given flexibility. And heating is performed as necessary to ensure the 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 coloring material obtained by uniformly mixing the colored resin layer components is applied to the surface of the transparent resin layer and dried to form a colored resin layer, and then the transparent resin layer and the colored resin layer are peeled from the film. It is obtained by The temperature of each of the above drying steps is lower than the decomposition temperature of the block isocyanate, the reactive vinyl monomer and the 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, weight average molecular weight 339,000, Tg40 ° C, OH number 80)
Block isocyanate (Takeda Yakuhin Co., Ltd., Takenate B815N, hydrogenated diphenylmethane diisocyanate oxime block, NCO% 7.3) in 100 parts of solid content
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 (Souken Kako Co., Ltd., film thickness 40 μm) treated with silicone release
m, hereinafter referred to as PET film), and coated on the release surface, 80 ℃
And dried for 5 minutes to form a transparent resin layer.

On the other hand, 100 parts of acrylic polyol (Nippon Shokubai Kogyo Co., Ltd., Arotane 2040-145) solid content, 49 parts of block isocyanate (Takeda Pharmaceutical Co., Ltd., Takenate B815N) and 15 parts of titanium oxide are well stirred. By mixing the mixture (referred to as coating material A) on the transparent resin layer described above and drying at 80 ° C. for 5 minutes to form a colored resin layer, the PET film is peeled off. Thus, an uncured thermosetting coating sheet was obtained. The thickness of this sheet was 30 μm for the transparent resin layer and 70 μm for the colored resin layer.

Example 2 Acrylic polyol (manufactured by Nippon Shokubai Kogyo Co., Ltd., Arotane)
2040-139; weight average molecular weight 320,000, Tg 20 ° C, OH number 100)
To 100 parts of solid content, 62 parts of block isocyanate (Takenate B815N, manufactured by Takeda Pharmaceutical Co., Ltd.) (having 1.0 equivalent of isocyanate groups based on the hydroxyl groups of the acrylic polyol) was mixed with good stirring. This mixture was applied to the release surface of a PET film which had been subjected to a 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 material A is coated on the transparent resin layer,
A colored resin layer was formed by drying at 5 ° C. for 5 minutes, and the PET film was peeled off to obtain an uncured thermosetting coating sheet. The thickness of this sheet is 30μ for the transparent resin layer.
m, and the color resin layer was 70 μm.

Example 3 300 parts of ethyl acetate were mixed with 100 parts of a thermoplastic acrylic resin (manufactured by Mitsubishi Rayon, Hyperet HBS), 40 parts of diethylene glycol methacrylate and 1.0 part of ter-butyl peroxybenzoate while stirring. This mixture was applied to the release surface of a PET film which had been subjected to a 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 coating material A is coated on the transparent resin layer,
A colored resin layer was formed by drying at 30 ° C. for 30 minutes, and the PET film was peeled off to obtain a thermosetting coating sheet in an uncured state. The film thickness of this sheet is 20μ for the transparent resin layer.
m, and the color resin layer was 80 μm.

Example 4 To 300 parts of ethyl acetate, 100 parts of a thermoplastic acrylic resin (manufactured by Mitsubishi Rayon, Hyperet HBS), 60 parts of methyl methacrylate and 1.0 part of ter-butyl peroxybenzoate were mixed with stirring. This mixture was applied to the release surface of a PET film which had been subjected to a release treatment in the same manner as in Example 1, and the mixture was applied at 70 ° C for 1
It was dried for 5 minutes to form a transparent resin layer.

Next, the coating material A is coated on the transparent resin layer,
A colored resin layer was formed by drying at 30 ° C. for 30 minutes, and the PET film was peeled off to obtain a thermosetting coating sheet in an uncured state. The film thickness of this sheet is 20μ for the transparent resin layer.
m, and the color resin layer was 80 μm.

Example 5 300 parts of ethyl acetate, 100 parts of a thermoplastic acrylic resin (manufactured by Mitsubishi Rayon, Hyperet 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 which had been subjected to a 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 coating material A is coated on the transparent resin layer,
A colored resin layer was formed by drying at 30 ° C. for 30 minutes, and the PET film was peeled off to obtain an uncured heat and light curable coating sheet. The film thickness of this sheet was 20 μm for the transparent resin layer and 60 μm for the colored resin layer.

Example 6 300 parts of ethyl acetate, 100 parts of a thermoplastic acrylic resin (manufactured by Mitsubishi Rayon, Hyperet HBS), 30 parts of p-methoxystyrene, 10 parts of pentaerythritol trimethacrylate.
Parts, 0.8 parts of methyl ethyl ketone peroxide and 0.5 parts of benzophenone were mixed with stirring. This mixture was applied to the release surface of a PET film which had been subjected to a 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 coating material A is coated on the transparent resin layer,
A colored resin layer was formed by drying at 30 ° C. for 30 minutes, and the PET film was peeled off to obtain an uncured heat and light curable coating sheet. The 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 (manufactured by Mitsubishi Rayon, Hyperet HBS), 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 which had been subjected to a 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 material A is coated on the transparent resin layer,
A colored resin layer was formed by drying at 10 ° C. for 10 minutes, 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 40 μm for the transparent resin layer and 60 μm for the colored resin layer.

Example 8 To 300 parts of ethyl acetate, 30 parts of p-methoxystyrene, 10 parts of pentaerythritol trimethacrylate and 1.0 part of thioxanthone were mixed with stirring. This mixture was applied to the release surface of a PET film which had been subjected to a 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 material A is coated on this transparent resin layer, and the temperature is 80 ° C.
Was dried for 10 minutes to form a colored resin layer, and the PET film was peeled off to obtain a heat- and photo-curable coating sheet in an uncured state. The film thickness of this sheet is
The thickness was 40 μm and the color resin layer was 60 μm.

Example 9 Acrylic Polyol (Nippon Shokubai Kogyo KK, Arotane)
2040-145, weight average molecular weight 339,000) 100 parts by solid content, block isocyanate (manufactured by Takeda Pharmaceutical Co., Ltd.,
Takenate B815N) 49 parts (this block isocyanate has 1.0 equivalent of isocyanate groups with respect to the hydroxyl groups of the above-mentioned acrylic polyol) were mixed with good stirring. Polyethylene terephthalate film (Siken Kako Co., Ltd., film thickness) obtained by subjecting this mixture to silicone release treatment
40 μm, hereafter referred to as PET film)
It was dried at 0 ° C. for 5 minutes to form a transparent resin layer.

On the other hand, acrylic polyol (Nippon Shokubai Kogyo KK, Arotane 2040-145) solid content 100 parts, acrylic polyol oligomer (Nippon Carbide, Nikalite H-870,
Weight average molecular weight 2,200-2,500, Tg-20 ° C, OH number 200) 30
Block, block isocyanate (manufactured by Takeda Pharmaceutical Co., Ltd.,
86 parts of Takenate B815N) and 15 parts of titanium oxide were mixed with good stirring (this is referred to as coating material B). The mixture is applied onto 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 obtain an uncured thermosetting coating sheet. Obtained. The thickness of this sheet was 30 μm for the transparent resin layer and 70 μm for the colored resin layer.

Example 10 The 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. An uncured thermosetting 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 70 μm.

Example 11 300 parts of ethyl acetate, 100 parts of a thermoplastic acrylic resin (Delpett 7500 manufactured by Asahi Chemical Industry Co., Ltd.), 40 parts of dipropylene glycol dimethacrylate and 1.0 part of ter-butylperoxybenzoate were mixed with stirring. This mixture was applied to the release surface of PET film and dried at 70 ° C. for 15 minutes to form a transparent resin layer.

Next, the coating material B is coated on the transparent resin layer,
By drying at 30 ° C. for 30 minutes to form a colored resin layer, the PET film was peeled off to obtain an uncured thermosetting coating sheet. The film thickness of this sheet is 20μ for the transparent resin layer.
m, and the color resin layer was 80 μm.

Example 12 The transparent resin layer formed in the same manner as in Example 4 was coated with the above coating material B at 70 ° C., except that Delpett 7500 manufactured by Asahi Kasei Kogyo Co., Ltd. was used as the thermoplastic acrylic resin. 30
After drying for a minute to form a colored resin layer, the PET film was peeled off to obtain an uncured thermosetting coating sheet. The thickness of this sheet was 20 μm for the transparent resin layer and 80 μm for the colored resin layer.

Example 13 A transparent resin layer formed in the same manner as in Example 5 was coated with the above coating material B at 70 ° C., except that Delpett 7500 manufactured by Asahi Kasei Corporation was used as the thermoplastic acrylic resin. 30
After drying for a minute to form a colored resin layer, the PET film was peeled off to obtain a heat- and photocurable coating sheet in an uncured state. The thickness of this sheet is 15μ for the transparent resin layer.
m, and the color resin layer was 70 μm.

Example 14 The transparent resin layer was formed in the same manner as in Example 6 except that Asahi Kasei Kogyo Co., Ltd. Delpett 7500 was used as the thermoplastic acrylic resin. A colored resin layer was formed by drying for 30 minutes, and the PET film was peeled off to obtain an uncured heat and light curable coating sheet. The thickness of this sheet is 15 μm for the transparent resin layer,
The colored resin layer had a thickness of 70 μm.

Example 15 300 parts of ethyl acetate, 100 parts of thermoplastic acrylic resin (Delpett 7500 manufactured by Asahi Kasei Kogyo Co., Ltd.), 30 parts of p-chlorostyrene, dipropylene glycol dimethacrylate
20 parts and 1.0 part of thioxanthone were mixed with stirring. This mixture was applied to the release surface of a PET film which had been subjected to a 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 material B is coated on the transparent resin layer,
A colored resin layer was formed by drying at 10 ° C. for 10 minutes, and the PET film was peeled off to obtain a heat- and photocurable coating sheet in an uncured state. 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 and thermoplastic resin (Asahi Kasei Co., Ltd.)
Made, Delpett 7500) 100 parts, p-methoxystyrene 30
Parts, pentaerythritol trimethacrylate 10 parts and thioxanthone 1.0 parts were mixed with stirring. This mixture was applied to the release surface of a PET film which had been subjected to a 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 material B is coated on the transparent resin layer,
A colored resin layer was formed by drying at 10 ° C. for 10 minutes, 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 30 μm for the transparent resin layer and 60 μm for the colored resin layer.

Example 17 Acrylic polyol (Nippon Shokubai Kogyo KK, Arotane
2040-145, weight average molecular weight 339,000) 100 parts by solid content, block isocyanate (manufactured by Takeda Pharmaceutical Co., Ltd.,
Takenate B815N) 49 parts (this block isocyanate has 1.0 equivalent of isocyanate groups with respect to the hydroxyl groups of the above-mentioned acrylic polyol) were mixed with good stirring. This mixture was applied to the release surface of a PET film that had been subjected to a silicone release treatment, and dried at 80 ° C. for 5 minutes to form a transparent resin layer.

On the other hand, acrylic polyol (Nippon Shokubai Kogyo KK, Arotane 2040-145) solid content 100 parts, acrylic polyol oligomer (Nippon Carbide, Nikalite H-270,
Weight average molecular weight 2,200-2,500, Tg-19 ° C, oxidation 200) 40
Block, block isocyanate (manufactured by Takeda Pharmaceutical Co., Ltd.,
98 parts of Takenate B815N) and 15 parts of titanium oxide were mixed with good stirring (this is referred to as coating material C). 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 PET film is peeled off to obtain an uncured thermosetting coating sheet. It was
The thickness of this sheet is 30 μm for the transparent resin layer and for the colored resin layer.
It was 70 μm.

Example 18 The transparent resin layer formed in the same manner as in Example 2 was coated with the above coating material C, 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 thickness of this sheet is
The transparent resin layer had a thickness of 30 μm and the colored resin layer had a thickness of 70 μm.

Example 19 The transparent resin layer formed in the same manner as in Example 3 was coated with the above coating material C at 70 ° C., except that Delpett 7500 manufactured by Asahi Kasei Corporation was used as the thermoplastic acrylic resin. 30
After drying for a minute to form a colored resin layer, the PET film was peeled off to obtain an uncured thermosetting coating sheet. The thickness of this sheet was 40 μm for the transparent resin layer and 100 μm for the colored resin layer.

Example 20 The transparent resin layer formed in the same manner as in Example 4 was coated with the above coating material C at 70 ° C., except that Delpett 7500 manufactured by Asahi Kasei Corporation was used as the thermoplastic acrylic resin. 30
After drying for a minute to form a colored resin layer, the PET film was peeled off to obtain an uncured thermosetting coating sheet. The 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 sheet performance was tested for extensibility, moldability, adhesion and hardness.

Regarding the extensibility, the sheet was stretched 100% under an atmosphere condition of 30 ° C., and it was examined whether or not the sheet was torn. The formability was evaluated by the formability when the sheet was attached to a base material and this laminate was vacuum-formed at 60 ° C. The adhesion of the sheet is determined by heating the laminate formed as described above at 160 ° C. for 30 minutes or
Heating at 60 ℃ for 30 minutes and high pressure mercury lamp (160W / cm, height 15c
After irradiating for 2 minutes at m), put 100 cuts at 1 mm intervals on the surface of the cured coating in a grid pattern, attach a commercially available adhesive tape to this, and then peel off the tape to determine the residual% of the grid pattern. displayed. The hardness was evaluated by a pencil hardness test according to JIS K5400. Examples 1 to 16 show 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, in order to improve the adhesion of the sheet to the coated steel sheet during vacuum forming, an adhesive layer (acrylic adhesive, Sekisui Vacuum molding was carried out using a product provided by Chemical Industry Co., Ltd., S-Dyne WHD, thickness 10 μm). In addition, Examples 17 to 20 are shown in Table 3.

Example 21 300 parts of ethyl acetate was added to a reactive acrylic resin (a copolymer of methyl methacrylate and methacrylic acid and 2-aminoethyl acrylate, Mw = 50,000, Tg 35 ° C., COOH value 40 and NH ₂
Value 40) 100 parts of solid content, 34 parts of block isocyanate (Takenate Yakuhin Kogyo Co., Takenate B-870N, isophorone diisocyanate oxime block NCO = 12.6%) 34 parts (this cross-linking agent is based on the functional group of the reactive acrylic resin, 0.9
Equivalent isocyanate groups) were added and mixed with stirring. This mixture was coated on the release surface of a polyethylene release-treated polyethylene terephthalate (PET) film with an applicator and dried at 80 ° C. for 5 minutes to form a transparent resin layer. The thickness of the sheet was 30 μm.

On the other hand, to 300 parts of ethyl acetate, a reactive acrylic resin (copolymer of methyl methacrylate and 2-hydroxyethyl methacrylate, methacrylic acid and ethyl acrylate, Mw
= 550,000, Tg15 ° C, OH value 40 and COOH value 20) in 100 parts of solid content, reactive acrylic oligomer (methyl acrylate, 2-hydroxyethyl methacrylate, butyl acrylate, copolymer of 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 groups to the functional groups of the reactive acrylic resin and reactive acrylic oligomer). And 120 parts of titanium oxide were mixed with good stirring (this is referred to as coating material G). This mixture was applied onto the transparent resin layer so that the film thickness of the sheet would be 100 μm, dried at 80 ° C. for 20 minutes and laminated.

Example 22 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 ₂ value 4) in 300 parts of ethyl acetate
0) to 100 parts of solid content, reactive acrylic oligomer (methyl acrylate, 2-hydroxyethyl methacrylate,
Butyl acrylate, methacrylic acid copolymer, Mw = 4,
000, Tg-10 ° C, OH value 100, COOH value 40), solid content 30 parts, block isocyanate (manufactured by Takeda Pharmaceutical Co., Takenate B)
-815N, hydrogenated diphenylmethane diisocyanate ketoxime block NCO 7.3%) 75 parts (This crosslinking agent has 1.0 equivalent of isocyanate groups based on the functional groups of the above-mentioned reactive acrylic resin and reactive acrylic oligomer) Were mixed with good stirring. This mixture was coated on the release surface of a polyethylene release-treated polyethylene terephthalate (PET) film with an applicator and dried at 80 ° C. for 5 minutes to form a transparent resin layer. Sheet thickness is 20 μm
It was.

Next, coating material G was laminated on the above coating so that the sheet thickness was 80 μm, and dried at 80 ° C. for 20 minutes.

Example 23 To 300 parts of ethyl acetate, a reactive acrylic resin (a copolymer of methyl methacrylate, 2-hydroxyethyl methacrylate and ethyl acrylate, Mw = 250,000, Tg 15 ° C., OH
Value 40 and COOH value 20) in solid content 100 parts, reactive acrylic oligomer (same as above) 20 parts solid content, block isocyanate (same as 2) 54 parts (this crosslinker is reactive acrylic resin and reactive acrylic resin). For functional groups with oligomers, 1.
(With 0 equivalents of isocyanate groups) were mixed with good stirring. PET obtained by silicone-releasing this mixture
The release surface of the film was coated with an applicator and dried at 80 ° C for 5 minutes to prepare a thermosetting sheet. The thickness of the sheet was 100 μm.

Next, coating material G was laminated on the above coating so that the sheet thickness was 80 μm, and dried at 80 ° C. for 20 minutes.

Example 24 300 parts of ethyl acetate was added to a reactive acrylic resin (a copolymer of methyl methacrylate, 2-hydroxyethyl methacrylate and ethyl acrylate, Mw = 250,000, Tg15 ° C., OH).
A valency of 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 ℃, NH ₂ value 60, COOH value 30) solids 10 parts, block isocyanate (same as 1) 35 parts (this cross-linking agent is 1.0 equivalent to the functional groups of the reactive acrylic resin and the reactive acrylic oligomer) Of polyisocyanate obtained by reacting 3 moles of tolylene diisocyanate with 1 mole of trimethylol propane, NCO = 13.0%, manufactured by Nippon Polyurethane Industry Co. 30% of the functional groups of the reactive acrylic resin were initially cured) and mixed with good stirring. Apply this mixture to the release surface of PET film with silicone release treatment with an applicator, and apply
A thermosetting sheet was prepared by drying at 5 ° C for 5 minutes. The thickness of the sheet was 15 μm.

Next, coating material G was laminated on the above coating so that the sheet thickness was 100 μm, and dried at 80 ° C. for 20 minutes.

Example 25 To 300 parts of ethyl acetate, a reactive acrylic resin (copolymer of methyl methacrylate and methacrylic acid and 2-aminoethyl acrylate, Mw = 492,000, Tg 35 ° C., COOH value 40 and NH ₂
Value 40) 100 parts solid content, reactive acrylic oligomer (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 with respect to the functional groups of the above-mentioned reactive acrylic resin and reactive acrylic oligomer), epoxy cross-linking agent (Ciba Geigy, Araldide CY175, Epoxy equivalent 160, epoxy value 220 corresponding to the functional group value) 7.5 parts (10% of the functional group of the reactive acrylic resin)
Is initially cured) was mixed with good stirring. This mixture was applied to the release surface of a polyethylene terephthalate (PET) film that had been subjected to silicone release treatment with an applicator and dried at 80 ° C. for 5 minutes to prepare a thermosetting sheet.
The thickness of the sheet was 80 μm.

On the other hand, in 300 parts of ethyl acetate, a reactive acrylic resin (a copolymer of methyl methacrylate, 2-aminoethyl methacrylate, ethyl methacrylate and methacrylic acid,
Mw = 360,000, Tg25 ℃, NH ₂ value 40 and COOH value 40) solid content 10
In 0 parts, 54 parts of block isocyanate (same as 2) (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 120 parts of titanium oxide are often used. It mixed, stirring (this is set to the coating material H). Apply this mixture onto the transparent resin layer so that the film thickness of the sheet will be 100 μm, and
It was dried at 0 ° C. for 20 minutes and laminated.

Example 26 300 parts of ethyl acetate was mixed with 300 parts of a reactive acrylic resin (a copolymer of methyl methacrylate, 2-hydroxyethyl methacrylate, acrylic acid and butyl methacrylate, Mw = 5).
000, Tg35 ℃, OH value 40 and COOH value 40) 100 parts solid content, reactive acrylic oligomer (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 (2
55 parts (this cross-linking agent has 1.0 equivalent of isocyanate groups with respect to the functional groups of the reactive acrylic resin and the reactive acrylic oligomer) and isocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., Cononate L, 3 mol). Mix 12 parts of solid content of polyisocyanate obtained by reacting tolylene diisocyanate with 1 mol of trimethylolpropane, NCO = 13.0% (30% of functional groups of reactive acrylic resin is initially cured) while stirring well. did. This mixture was applied to the release surface of a PET film that had been subjected to silicone release treatment with an applicator and dried at 80 ° C. for 5 minutes to prepare a thermosetting sheet. The thickness of the sheet was 20 μm.

Next, coating material G was laminated on the above coating so that the sheet thickness would be 100 μm, and dried at 80 ° C. for 20 minutes.

Example 27 300 parts of ethyl acetate, 100 parts of a thermoplastic acrylic resin (Delpett 7500 manufactured by Asahi Kasei Kogyo KK), 40 parts of dipropylene glycol dimethacrylate and 1.0 part of ter-butyl peroxybenzoate were mixed with stirring. This mixture was applied to the release surface of PET film and dried at 70 ° C. for 15 minutes to form a transparent resin layer.

Next, the above coating material H is coated on this transparent resin layer, and 70
A colored resin layer was formed by drying at 30 ° C. for 30 minutes, and the PET film was peeled off to obtain a thermosetting coating sheet in an uncured state. The film thickness of this sheet is 20μ for the transparent resin layer.
m, and the color resin layer was 80 μm.

Example 28 300 parts of ethyl acetate, 100 parts of thermoplastic acrylic resin (Delpett 7500 manufactured by Asahi Kasei Kogyo KK), 30 parts of p-chlorostyrene, dipropylene glycol dimethacrylate
20 parts and 1.0 part of thioxanthone were mixed with stirring. This mixture was applied to the release surface of a PET film which had been subjected to a 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 material H is coated on this transparent resin layer,
A colored resin layer was formed by drying at 0 ° C for 10 minutes, and the PET film was peeled off to obtain an uncured thermosetting coating sheet. The thickness of this sheet is 30μ for the transparent resin layer.
m, and the color resin layer was 70 μm.

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

Regarding the extensibility, the sheet was stretched 100% under an atmosphere condition of 30 ° C., and it was examined whether or not the sheet was torn. The formability was evaluated by the formability when the sheet was attached to a base material and this laminate was vacuum-formed at 60 ° C. The adhesion of the sheet was measured by heating the laminate formed as described above at 160 ° C. for 30 minutes, and in Example 8 only, heating at 160 ° C. for 30 minutes and a high pressure mercury lamp (160
After irradiating for 2 minutes at W / cm, height 15 cm), put 100 cuts at 1 mm intervals in a grid pattern on the surface of the cured coating film, attach a commercially available adhesive tape to this, and then peel off the tape and go It was expressed as the residual percentage of the eye piece. The hardness was evaluated by a pencil hardness test according to JIS K5400.

(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". Further, the thermosetting coating sheet forms a strong and uniform coating excellent in hardness and abrasion resistance by curing the colored resin layer and the transparent resin layer together by heating or heating and irradiation with ultraviolet rays. can do.

Further, 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 can provide gloss, sharpness and the like. It is possible to form a film having good appearance.

[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 (4)

[Claims] 1. A thermosetting coating sheet in which a transparent resin layer in an uncured state is laminated on a colored resin layer in an uncured state, the colored resin layer having a weight average molecular weight of 100,000 to 100.000.
1,000,000 and solid reactive acrylic resin at room temperature, a block isocyanate, and a colorant, consisting of a thermosetting resin composition containing as a main component, the transparent resin layer from a transparent thermosetting resin composition A thermosetting coating sheet, characterized in that 2. The thermosetting resin composition for forming the colored resin layer further contains a reactive acrylic oligomer having a weight average molecular weight of 1,000 to 10,000.
The thermosetting coating sheet described. 3. The thermosetting coating sheet according to claim 1, wherein the transparent resin layer comprises a thermosetting resin composition containing a reactive acrylic resin solid at room temperature and a block isocyanate as main components. . 4. The transparent resin layer comprises a thermosetting resin composition containing a thermoplastic acrylic resin, a reactive vinyl monomer, a peroxide and / or a photosensitizer as main components. 2. The thermosetting coating sheet according to 2.