JPH07103250B2 - Thermosetting sheet - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Use) The present invention is capable of forming a uniform, suede-like cured coating having excellent solvent resistance on an article surface by coating the article surface and then curing the article. More particularly, it relates to a thermosetting sheet capable of forming a suede-like coating having excellent spreadability before curing and excellent solvent resistance and scratch resistance after curing.

(Prior Art) In order to give a suede feeling (soft touch feeling) to the surface of a plastic molded body, a metal molded body, or the like, a suede tone (soft touch feeling) paint has been generally used.

However, when a suede feeling is imparted to the surface of an article by using a paint, it is necessary to adjust the viscosity and the concentration of the paint, which makes the work complicated. In particular, coatings using organic solvents cause work environment pollution and safety and health problems.

In order to solve these problems, a sheet-like suede-like coating material has been proposed as an alternative to paint. For example, in Japanese Patent Application Laid-Open No. 41243/1990, a suede is formed by providing a coating film of a matting paint prepared by adding a bead pigment to an ionizing radiation curable resin on a base film made of ABS resin, polypropylene or the like. A toning sheet is proposed.

(Problems to be Solved by the Invention) However, in such a sheet, since the coating film is made of a resin crosslinked by an electron beam, the spreadability of the entire sheet is poor. Therefore, for example, when trying to attach the sheet to the surface of an article having unevenness or a curved surface, the sheet cannot be sufficiently stretched, so that the sheet cannot be attached exactly to the surface of the recess of the article, A gap may be formed between the surface of the article and the sheet.

The present invention is to solve the above-mentioned drawbacks, and an object of the present invention is to form a suede-like film on a surface of an article having irregularities or a curved surface, which can be exactly attached to the surface. It is to provide a thermosetting sheet that can be made.

(Means for Solving the Problems) The thermosetting sheets of the present invention each have a weight average molecular weight of
Formed with a thermosetting resin composition containing 20,000 to 1,000,000, one or more resins selected from reactive acrylic resin, reactive silicone resin, reactive fluororesin and reactive polyester resin, blocked isocyanate and elastic beads. An uncured or semi-cured state, or formed by a composition containing a reactive vinyl monomer and / or oligomer having a functional group, a photopolymerization initiator, viloc isocyanate and elastic beads. There, the above object is achieved thereby.

Examples of the composition of the thermosetting sheet are as follows.

An uncured or semi-cured thermosetting sheet mainly composed of a reactive acrylic resin having a weight average molecular weight of 20,000 to 1,000,000, a blocked isocyanate, and elastic beads.

An uncured or semi-cured state containing at least one reactive acrylic resin having a weight average molecular weight of 20,000 to 1,000,000, a blocked isocyanate, and a crosslinking agent composed of unblocked isocyanate, melamine and epoxy and elastic beads as main components. Thermosetting sheet.

The reactive acrylic resin is an acrylic resin having a functional group such as a hydroxyl group, an amino group and a carboxyl group. This is, for example, a (meth) acrylic acid ester monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate or 4-hydroxybutyl (meth) acrylate; 2-aminoethyl (meth) acrylate or 3-aminopropyl ( (Meth) acrylic acid ester monomer having an amino group such as (meth) acrylate; a monomer material selected from (meth) acrylic acid having a carboxyl group such as (meth) acrylic acid; and generally other (meth) It can be obtained by polymerizing an acrylate ester, a styrene derivative monomer or the like, a maleic acid type monomer or the like with various peroxides, chain transfer agents or the like as catalysts.

The above-mentioned reactive acrylic resin has a weight average molecular weight (Mw) of 2
Those of 0,000 to 1,000,000 are preferably used, and more preferably 100,000 to 800,000. Weight average molecular weight is 20,0
If it is less than 00, the thermosetting sheet may not be sufficiently stretched, for example, when it is attached to a molded product, and cracks may occur. When the weight average molecular weight of the reactive acrylic resin exceeds 1,000,000, it is difficult to dissolve in a solvent, and the viscosity of the solution when dissolved becomes too high, and it becomes difficult to form a sheet from the thermosetting resin composition. For example, when a sheet is formed by solvent casting, the viscosity of the solvent increases, and therefore the resin can be cast only at a low concentration, which makes it difficult to increase the thickness of the sheet.

These reactive acrylic resins preferably have a Tg (glass transition point) in the range of −20 to 80 ° C. in view of the relationship between the hardness after sheet curing and the suede feel (soft touch feel). Tg is −20
When the temperature is lower than 0 ° C, the coating film obtained after curing has reduced scratch resistance and is easily scratched. The reactive acrylic resin may be a combination of different types within the molecular weight range. In addition, the functional group value of these reactive acrylic resins (usually OH group value and NH ₂ group value (NH ₂ value: NH added at the time of polymerization)
The amount of ₂ groups is calculated in the same way as the OH value, or the NH ₂ group is reacted with nitrous acid and converted into an OH group and quantified) and the COOH value (COOH
Value: The amount of COOH groups added at the time of weight is calculated in the same manner as the OH value, or a value obtained by titrating COOH groups with KOH)} is preferably in the range of 20 to 200. When the functional group value is below the above range, excellent solvent resistance and scratch resistance cannot be obtained. However, when it is not necessary to have solvent resistance or scratch resistance which is not so high, it is applicable even if it is out of these ranges.

Also, these reactive acrylic resins can be used as a block copolymer in which the reactive portion of the acrylic resin is block-shaped or comb-shaped. In this case, as the material that forms a block with these reactive acrylic resins, not only acrylic materials but also styrene-based, maleic acid-based, and imide-based acrylic resins that have good compatibility with silicone-based and fluorine-based materials Any combination of materials can be used as long as it can be blocked. In this case, there are a method in which the weight average molecular weight of this material is within the above range and a method in which the above-mentioned reactive acrylic resin is blended with these block polymers.

The blocked isocyanate has blocked (masked) an isocyanate group having two or more isocyanate groups in the molecule, for example, a monomer or a modified isocyanate group such as tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate. It is a thing. Examples of the block component include phenols as well as oximes, lactams, malonic acid esters, and the like.
This blocked isocyanate is one in which the block is released by heating and the isocyanate group exhibits activity, and acts as a curing agent for the reactive acrylic resin. The compounding ratio of blocked isocyanate and reactive acrylic resin is usually the total number of functional groups of reactive acrylic resin (total functional group value) / the number of isocyanate groups (NCO value) = 0.5.
It should be -2.0, preferably 0.8-1.2.

The above-mentioned unblocked isocyanate is an isocyanate compound having two or more isocyanate groups in the molecule. For example, tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, tolidine diisocyanate, triphenylmethane triisocyanate, tris (isocyanatophenyl) thiophosphite, p-phenylene diisocyanate, xylylene diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, Hexamethylene diisocyanate,
Monomers such as lysine diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate or trimethylolpropane adducts of these monomers, isocyanurate modified products, biuret modified products, carbodiimide modified products, urethane modified products, allophanate modified products, etc. is there. The amount of this isocyanate added varies depending on the sheet molding method, but NCO is about functional group value: NCO = 1: 0.01 to 0.3 with respect to the functional group value of the reactive acrylic resin.

In the above-mentioned thermosetting sheet, as a melamine-based cross-linking agent, urea, thiourea, guanidine, guanamine, acetoguanamine, benzoguanamine, dicyandiamide, a material having a polyfunctional amino group such as guanamine, and aldehyde are reacted with formaldehyde. There are etherified melamine resins obtained by reacting trimethylol melamine, hexamethylol melamine, dimethylol urea, dimethylol guanidine, dimethylol acetoguanamine, dimethylol benzoguanamine and the like obtained by the reaction with alcohols such as butyl alcohol and propyl alcohol. The addition amount of these melamine-based cross-linking agents is difficult to take a fixed value with respect to the functional group value of the reactive acrylic resin like isocyanate, so when adding them, a preliminary experiment is performed before sheet preparation to determine the addition amount. Is preferred. The addition amount of the melamine-based cross-linking agent is preferably about 0.1 to 0.3 of functional group value: OR (ether value) with respect to the functional group value of the reactive acrylic resin.

Examples of the epoxy cross-linking agent include glycidyl compounds of polyhydric alcohols containing a plurality of epoxy groups, which are usually used together with a Lewis acid catalyst. The Lewis acid is preferably one that is microencapsulated in order to delay the reaction. For example, butadiene dioxide, hexazine dioxide and diglycidyl ester of phthalic acid,
Bisphenol-A diglycidyl ether, bisphenol-F diglycidyl ether, paraaminophenol triglycidyl ether amine, aniline diglycidyl ether, phenylenediamine tetraglycidyl ether, sulfonamide diglycidyl ether, glycerin triglycidyl ether, etc. Glycidyl compound, polyether-modified diglycidyl, polyester-modified diglycidyl, urethane-modified diglycidyl compound (polymer), vinylcyclohexenedioxide, dicyclopentadienedioxide, and the like. The addition amount of this epoxy-based crosslinking agent is such that the functional group: CH ₂ CH ₂ O (epoxy group) = 1: 0.01 to 0.2 with respect to the functional group value of the reactive acrylic resin.
A degree is preferable. Also, since this epoxy-based cross-linking agent reacts with a functional group to generate an OH group, the amount of blocked isocyanate added at the same time is 30 to 80% of the remaining OH group of the functional group of the reactive acrylic resin. It is preferable to add a certain amount.

The amount of these cross-linking agents to be added is preferably the above-mentioned amount, but actually the functional groups of the reactive acrylic resin and the cross-linking agents are reactive due to the reactivity with the reactive acrylic resin used, for example, melamine-based cross-linking agents, melamine-based Since the reaction between the cross-linking agent and the epoxy-based cross-linking agent or the like occurs, it is preferable to make the determination after conducting a preliminary experiment.

When adding unblocked isocyanate, melamine, or epoxy crosslinking agent, it is necessary to reduce the amount of blocked isocyanate added so that the amount of the crosslinking agent in the entire resin sheet does not increase. The ratio is calculated by the above-mentioned functional group value: amount of the functional group of the crosslinking agent.

The elastic beads have a property of elastically recovering when they are released after being pressed until their shape is deformed.
Examples of the material forming the elastic beads include polyurethane, an acrylic-urethane copolymer, polystyrene, a styrene-isoprene copolymer, polyvinylidene chloride, and a copolymer of vinylidene chloride and another monomer. It is preferable to add 20 to 400 parts by weight of elastic beads having a maximum particle size distribution in the range of 1 to 50 μm to 100 parts by weight of the resin. When the particle size of the elastic beads is less than 1 μm, the obtained sheet does not have a sufficient suede feeling (soft touch feeling), and when the particle size exceeds 50 μm, the surface of the sheet tends to be poor when stretched. . If the added amount of the elastic beads is less than 20 parts by weight, a sufficient suede feeling cannot be obtained, and if the added amount is large, the surface of the sheet tends to be cracked during stretching. The elastic beads are not limited to one type, and two or more types may be used in combination.

The following methods are available for producing the above-mentioned thermosetting sheets. The above-mentioned materials of the thermosetting resin composition are sufficiently dissolved and stirred in an organic solvent or the like, and the resulting solution is processed with a casting method such as a knife coater, a comma coater or a reverse coater (usually silicone release treated PET). : Polyethylene terephthalate, paper, etc.) and dried to remove the solvent to form a base layer (resin layer). Then, a sheet is obtained by peeling the process paper from the base layer.

An uncured or semi-cured thermosetting sheet containing a reactive vinyl monomer and / or oligomer (hereinafter sometimes referred to as a reactive vinyl material), a photopolymerizing agent, a blocked isocyanate, and elastic beads as main components. Such a sheet is obtained by casting the above material and then irradiating it with light.

In addition to the above resin composition, a thermoplastic resin and / or
Alternatively, a thermosetting sheet obtained by containing a reactive resin.

As this reactive vinyl material, a (meth) acrylic resin,
It has a styrene material and a vinyl group such as vinyl acetate. For example, for (meth) acrylic, (meth)
Methyl acrylate, ethyl (meth) acrylate, benzyl (meth) acrylate, 2-ethoxyethyl (meth)
Acrylate, phenoxydiene glycol (meth)
Monofunctional type such as acrylate, 1,6-hexadiol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylpropane tri (meth) acrylate Acrylate, pentaerythritol tri (meth)
Polyfunctional types such as acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate can be applied. For styrene, styrene, α-methylstyrene, α-ethylstyrene, p-methylstyrene, p-methoxystyrene,
Various styrene derivatives such as p-phenylstyrene, p-ethoxystyrene, p-chlorostyrene, m-chlorostyrene and o-chlorostyrene can be applied.

As the photopolymerization initiator, a commonly used one can be used,
For example, benzoin alkyl ether-based, acetophenone-based, benzophenone-based, thioxanthone-based photopolymerization initiators are preferably used. In benzoin ether series,
There are benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether and the like. In the acetophenone system, 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, p-ter-butyltrichloroacetophenone,
2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like. Benzophenone-based compounds include benzophenone, 4-chlorobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-4-methoxybenzophenone and dibenzosuberenone. Thioxanthone, thioxanthone, 2-chlorothioxanthone,
There are 2-methylthioxanthone, 2-isopropylthioxanthone, 2-ethylanthraquinone and the like.

The amount of photopolymerization initiator added varies depending on the material, but it is based on 100 parts by weight of the reactive vinyl monomer.
It is preferably within the range of 0.5 to 5.0 parts by weight. Further, the photopolymerization initiator is not limited to one type, and two or more types may be used in combination.

A crosslinking agent composed of isocyanate, melamine, and epoxy is added as needed, but the above-mentioned materials are used, and the amount of the crosslinking agent is the functional group value relative to the amount of the functional group (functional group value): The amount of functional groups of the cross-linking agent (sum of NCO, OR (ether value) and CHCHO (epoxy group)) = 1: 0.8 to 1.5 is preferable.

Further, the thermoplastic resin added to these is a material which is dissolved in a part of the reactive vinyl monomer and has good compatibility with other reactive vinyl monomers. For example, polyacrylic acid ester, polystyrene-based material, etc., such as polymethylmethacrylate, polymethylmethacrylate copolymer, polystyrene, polyvinyl acetate, polyvinyl chloride, etc. are usually used. The addition amount of this thermoplastic resin is preferably about 1: 0.5 to 2 with respect to the reactive vinyl monomer.

The above-mentioned and curable sheets are produced by using a knife coater, a comma coater, a reverse coater, or the like to cast these materials on a process paper (usually, PET release-treated with silicone: polyethylene terephthalate, paper, etc.).
It is coated with a coating on top and then irradiated with light from a high pressure mercury lamp, a metal halide lamp or a xenon lamp.

An uncured or semi-cured thermosetting sheet mainly composed of a reactive silicone resin having a weight average molecular weight of 20,000 to 1,000,000, having a plurality of hydroxyl groups, amino groups, and carboxyl groups, a blocked isocyanate, and elastic beads.

An uncured or semi-cured thermosetting sheet mainly composed of a reactive fluororesin having a plurality of hydroxyl groups, amino groups and carboxyl groups having a weight average molecular weight of 20,000 to 1,000,000, a blocked isocyanate and elastic beads.

An uncured or semi-cured thermosetting sheet comprising a reactive polyester resin having a plurality of hydroxyl groups, amino groups and carboxyl groups having a weight average molecular weight of 20,000 to 1,000,000, a blocked isocyanate and elastic beads as main components.

As for the materials (1) to (3), the main chains thereof are silicone-based, for example, siloxane polymer and the like; fluorine-based, for example, alternating copolymers of polyethylene and trifluoroethylene, polyethylene and difluoroethylene, etc. Etc .; Polyester type, for example, those in which a hydroxyl group, amino group, or carboxyl group is introduced into the side chain of various material types such as saturated ether type of terephthalic acid and ethylene glycol type material, unsaturated type of terephthalic acid and butadiene, etc. Is.

Further, a cross-linking agent composed of isocyanate, melamine and epoxy can be added if necessary.

The relationship between each functional group value and the cross-linking agent is the same as the above item.

Further, the thermosetting sheet obtained by any of the above items 1 to 3 may contain a colorant such as a pigment or a dye. As the colorant, pigments, dyes and the like used in ordinary coating can be used. For example,
Examples of pigments include titanium oxide, iron oxide, carbon black, and cyanine pigments; examples of dyes include azo dyes, anthraquinone dyes, indigoid dyes, and stilbene dyes. In addition, metal powder such as aluminum flakes, nickel powder, gold powder, and silver powder can also be used. For the amount of colorant,
When obtaining a thermosetting sheet with high hiding power, the total amount of colorant is 2 per 100 parts of solid content of the sheet material.
A range of up to 400 parts is preferred. Further, the thermosetting sheet may contain a reaction control catalyst, an inorganic filler, a metal material, an antiaging agent, an anticorrosive agent, etc. for surface control and functional enhancement.

[Form of thermosetting sheet]

A thermosetting resin composition is obtained by kneading the above materials.
A base layer (resin layer) is prepared from the fat composition, and when the thermosetting sheet is a single layer, the base layer becomes the thermosetting sheet as it is. The sheet of the present invention may be composed of a single layer having only a base layer, or may be composed of a plurality of layers. When the sheet has a plurality of layers, for example, the following forms are available.

A sheet having a base layer and a back surface layer laminated on the back surface of the base layer.

This back surface layer is provided to further improve the handleability of the sheet, to improve the adhesion with the injection resin when the sheet is used for sheet insert injection molding, or to withstand the shear stress of the injection resin. To be When the adhesion between the base layer and the back surface layer is poor, a primer layer may be provided between both layers, or a plurality of back surface layers may be provided.

Since the sheet of the present invention is stretched as needed and attached to an adherend, it is preferable that these back surface layers (and primer layers) are composed of a film that is malleable at least under heating.

As the resin used for the back surface layer, for example, polystyrene, acrylic polymer, polycarbonate, polyvinyl chloride, polyethylene, polypropylene, ABS (acrytonitrile-butadiene-styrene copolymer), modified polyphenylene oxide, polyphenylene sulfide, poly Examples thereof include ether imide, polyether ether ketone, and polyethylene sulfide.

A sheet having a base layer or the sheet obtained above, and an adhesive layer laminated on one surface of the sheet (in the case of the sheet, the outer surface of the back surface layer).

As the adhesive used in the adhesive layer, a pressure sensitive adhesive, a hot melt adhesive, and a post-curable adhesive are preferably used. Mixtures of these adhesives may be used. A plurality of different types of adhesive may be sequentially laminated.

Examples of the pressure-sensitive adhesive include rubber-based, acrylic-based, urethane-based, silicone-based and other pressure-sensitive adhesives. Examples of hot melt adhesives include ethylene-vinyl acetate copolymer (EVA) -based adhesives and styrene-isoprene-styrene block copolymer (SIS) -based adhesives. The post-curing type adhesive includes, for example, a microcapsule curing type adhesive. Examples of the material include an uncrosslinked unsaturated polyester adhesive and an uncrosslinked acrylic adhesive.

A sheet having the sheet obtained in the above and and a protective layer laminated on one surface of the sheet.

The protective layer is laminated in order to provide shape retention during storage and use of the sheet and surface protection after attachment.

Since the sheet of the present invention is stretched as necessary and attached to an adherend, it is preferable that the protective layer is composed of a film (for example, a thermoplastic resin film or a rubber film) having a malleability property at least under heating.

Examples of the thermoplastic resin include soft vinyl chloride, polyurethane, acrylic resin, polyester, ethylene-vinyl acetate copolymer, polyethylene, polypropylene and the like. Examples of the rubber film include natural rubber, styrene-butadiene rubber, nitrile-butadiene rubber, isoprene rubber, butadiene rubber, chloroprene rubber, urethane rubber, silicone rubber and acrylic rubber. It is also possible to use these thermoplastic resins and rubber mixtures. Alternatively, both films may be laminated.

The protective layer may be peeled from the adherend immediately after the sheet is attached to the adherend, and then the sheet may be cured, or after the sheet is adhered to the adherend and cured, until these adherends are used. It may be used as a protective layer between. By embossing or patterning the surface of the protective layer, the surface shape (appearance) of the sheet can be changed.

A sheet comprising a transparent base layer (surface layer) and a colored layer containing a colorant.

The colored layer can be formed from the thermosetting resin composition used for the base layer. In this case, the colored layer may not contain elastic beads.

A sheet obtained by printing on the front surface or the back surface of the base layer of the thermosetting sheet obtained in any of above.

When the back surface of the base layer is printed, the printed surface can be protected by the base layer.

The thickness of the thermosetting sheet obtained in any of above is preferably about 20 to 1,000 μm when it is attached to the surface of an adherend having irregularities, and may be about 10 to 500 μm when it is attached to a flat surface. The thickness of the other layers laminated on the above-mentioned sheet is usually 10 to 500 μm, and the thickness of the adhesive layer is particularly preferably 10 to 100 μm.

[Method of Using Thermosetting Sheet (Method of Manufacturing Coated Material)]

The thermosetting sheet of the present invention can give a desired adherend a suede tone (soft touch feeling) by being used as follows, for example.

The thermosetting sheet is heated or stretched without heating and attached to the surface of the adherend so as to conform to the shape of the surface. Alternatively, a method such as a method of injecting a resin into the mold after closing the mold by heating the sheet inside the mold for injection molding at room temperature or by heating and making the sheet adhere by vacuum and / or air pressure molding is performed. A sheet-attached molded product is obtained by sheet insert injection molding. After that, the sheet is cured by heating at least the sheet of the pasted part of the article to which the sheet is pasted to obtain a covering body.

(Effect of the invention) Since the thermosetting sheet of the present invention has excellent stretchability before curing, it can be stretched when it is attached to the surface of an adherend having irregularities or curved surfaces. . For example, when attaching a sheet to the surface of an adherend that has a concave portion on the surface, place the sheet on the outside of the concave portion and press the sheet toward the concave portion so that the sheet is attached exactly to the outer surface of the concave portion. You can

After the sheet is attached to the adherend, it is heated and cured to form a hard and suede-like (soft touch) coating.

(Example) Below, this invention is demonstrated based on an Example.

In addition, "part" means "part by weight".

I. Preparation of thermosetting sheet (1) 300 parts of ethyl acetate, reactive acrylic resin (copolymer of methyl methacrylate, methacrylic acid and 2-aminoethyl acrylate, Mw = 75,000, Tg35 ° C, COOH value) 20
And NH ₂ value 40) in a solid content of 100 parts, blocked isocyanate (Takeda Yakuhin K.K., Takenate XB-72, hexamethylene diisocyanate isocyanurate oxime block NCO = 10.1%, solid content 70%) 31 parts by solid content (this crosslinking agent has 1.0 equivalent of isocyanate groups with respect to the functional groups of the above-mentioned reactive acrylic resin) and 200 parts of elastic beads (Nippon Shokubai Kagaku Kogyo Co., Ltd., EBS100) were well stirred. While mixing. Polyethylene terephthalate film (hereinafter PE
The release surface of (T film) was coated with an applicator and dried at 70 ° C. for 10 minutes to obtain a thermosetting sheet. The thickness of the sheet was 50 μm.

(2) Ethyl acetate 300 parts, reactive acrylic resin (copolymer of methyl methacrylate, 2-hydroxyethyl methacrylate and ethyl acrylate, Mw = 250,000, Tg15
C, OH value 40 and COOH value 40) 100 parts in solid content, blocked isocyanate (Takenate B-815N, manufactured by Takeda Pharmaceutical Co., Ltd.,
59 parts of hydrogenated paraphenylene diisocyanate ketoxime block NCO = 7.3%, solid content 60% in solid content (this crosslinking agent is 1.
2 equivalents of isocyanate group), 2 parts of dibutyltin laurylate, elastic beads (Nippon Shokubai Kagaku Kogyo Co., Ltd.)
(Manufactured by EBS100) was mixed with good stirring. This mixture was applied to the release surface of a PET film with an applicator and dried at 70 ° C for 30 minutes to obtain a thermosetting sheet. The thickness of the sheet was 200 μm.

(3) 300 parts of ethyl acetate, reactive acrylic resin (copolymer of methyl methacrylate, 2-hydroxyethyl methacrylate, butyl acrylate and 4-aminobutyl methacrylate, Mw = 368,000, Tg10 ° C., OH Value 40 and NH ₂ value
40) in 100 parts by solid content, block acrylic polycarboxylic acid (copolymer of stearyl methacrylate and methacrylic acid, Mw = 25,000, Tg 20 ° C, acid value 20) in 10 parts by solid content
Parts, Block isocyanate (Coronate 2513, manufactured by Nippon Polyurethane Industry Co., Ltd., ethyl acetoacetate block of isocyanurate of hexamethylene diisocyanate, NCO = 10.2%, solid content 80%) 47 parts (this crosslinking agent is the above-mentioned reactive acrylic resin) 100 parts of elastic beads (manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd., EBS300) were mixed with good stirring. ABS sheet (A20 manufactured by Sanpo Resin Co., Ltd.)
5,500 μm) was coated with an applicator and dried at 70 ° C. for 15 minutes to obtain a thermosetting sheet. Sheet thickness is 600μ
m (including ABS sheet).

(4) 300 parts of ethyl acetate, reactive acrylic resin (copolymer of methyl methacrylate, 2-hydroxyethyl methacrylate, acrylic acid, butyl acrylate and 4-aminoethyl methacrylate, Mw = 360,000, Tg35 ℃, O
H value of 20, COOH value of 20 and NH ₂ value of 40) in solid content of 100 parts, blocked isocyanate (Takenate B-815N manufactured by Takeda Pharmaceutical Co., Ltd.) 59 parts (this cross-linking agent is a functional group of the reactive acrylic resin). Based on the group, it has 1.2 equivalents of isocyanate group), elastic beads (manufactured by Nippon Shokubai Chemical Industry Co., Ltd., EBS30)
0) 200 parts were mixed with good stirring. PE this mixture
The release surface of the T film was coated with an applicator, dried at 80 ° C for 5 minutes, and further subjected to initial curing treatment at 160 ° C for 2 minutes to prepare a thermosetting sheet. As for the initial curing of this thermosetting sheet, 10% of the total functional groups had been initially cured by quantitative analysis such as infrared absorption spectrometry (IR). The thickness of the sheet was 50 μm.

(5) 400 parts of ethyl acetate, reactive acrylic resin (copolymer of methyl methacrylate, methacrylic acid, butyl acrylate and 3-aminopropyl acrylate, Mw = 621,
000, Tg10 ℃, COOH value 40 and NH ₂ value 40) 100 parts by solid content,
59 parts of blocked isocyanate (Takenate B-815N manufactured by Takeda Pharmaceutical Co., Ltd.) (this cross-linking agent has 1.2 equivalents of isocyanate groups based on the functional groups of the reactive acrylic resin), titanium oxide 100 parts, elastic beads (Nippon Catalyst) 200 parts of EBS300 manufactured by Kagaku Kogyo Co., Ltd. were mixed with good stirring. This mixture was applied to the release surface of a PET film with an applicator and dried at 80 ° C for 5 minutes to obtain a thermosetting sheet. The thickness of the sheet was 100 μm.

(6) Ethyl acetate 300 parts, reactive acrylic resin (copolymer of methyl methacrylate, methacrylic acid, butyl acrylate and 2-aminoethyl acrylate, Mw = 492,00
0, Tg 35 ° C, COOH value 40 and NH ₂ value 40) as solid content 100 parts, blocked isocyanate (Takeda Yakuhin K.K., Takenate B-870N, isophorone diisocyanate keto oxime block NCO = 12.6%, solid content 60%) 23 parts (this cross-linking agent has 0.8 equivalent of isocyanate groups with respect to the functional groups of the above-mentioned reactive acrylic resin), epoxy cross-linking agent (manufactured by Ciba-Geigy, Araldide CY175, epoxy equivalent 16
0, epoxy value 220 corresponding to the functional group value) 4.9 parts (10% of the functional groups of the reactive acrylic resin is initially cured), elastic beads (Nippon Shokubai Chemical Co., Ltd., EBS3100) 100 parts well Mixed with stirring. This mixture was applied to the release surface of a PET film with an applicator and dried at 80 ° C for 5 minutes to obtain a thermosetting sheet. The thickness of the sheet was 80 μm.

(7) 300 parts of ethyl acetate, reactive acrylic resin (methyl methacrylate, 2-hydroxyethyl methacrylate, butyl acrylate and acrylic acid copolymer, Mw =
90,000, Tg15 ℃, OH number 40 and COOH number 40) 100 as solid content
Part, blocked isocyanate (manufactured by Takeda Pharmaceutical Company Limited,
Takenate B-815N) 59 parts (this crosslinking agent has 1.2 equivalents of isocyanate groups with respect to the functional groups of the above-mentioned reactive acrylic resin) and isocyanate (Nippon Polyurethane Industry Co., Ltd., Coronate L, NCO = 13.0). 15 in solids
Part (30% of the functional groups of reactive acrylic resin is initially cured),
Elastic beads (EBS300, manufactured by Nippon Shokubai Chemical Co., Ltd.) 100
The parts were mixed with good stirring. This mixture was applied to the release surface of a PET film with an applicator and dried at 80 ° C for 5 minutes to obtain a thermosetting sheet. Sheet thickness is 100μ
It was m.

(8) 300 parts of ethyl acetate, reactive acrylic resin (copolymer of methyl methacrylate, 2-hydroxyethyl methacrylate, butyl acrylate and 4-aminobutyl methacrylate, Mw = 368,000, Tg10 ° C., OH Value 40 and NH ₂ value
40) in a solid content of 100 parts, block copolymer reactive acrylic resin (copolymer of methyl methacrylate and 2-hydroxyethyl methacrylate, Mw = 36,000, Tg95 ° C., OH
Valency 40) in solid content of 10 parts, blocked isocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate 2513) 40 parts (this cross-linking agent is 1.0% relative to the functional groups of the reactive acrylic resin and the block reactive acrylic resin). Polyisocyanate NCO = 13.0%, solid content of which is obtained by reacting an equivalent amount of isocyanate group) with isocyanate (Japan Polyurethane Industry Co., Ltd., Coronate L, 3 mol of tolylene diisocyanate and 1 mol of trimethylolpropane) %)
2.4 parts by solid content (10% of the total functional groups of the above-mentioned reactive acrylic resin and block reactive acrylic resin is initially cured), elastic beads (manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd., EBS10)
0) 200 parts were mixed with good stirring. PE this mixture
The release surface of the T film was coated with an applicator and dried at 70 ° C for 10 minutes to obtain a thermosetting sheet. The thickness of the sheet
It was 60 μm.

(9) 300 parts of ethyl acetate, reactive acrylic resin (copolymer of methyl methacrylate, 2-hydroxyethyl methacrylate, acrylic acid, butyl acrylate and 4-aminoethyl methacrylate, Mw = 480,000, Tg35 ℃, O
H value of 20, COOH value of 20 and NH ₂ value of 40) in solid content of 100 parts, blocked isocyanate (Takenate B-815N manufactured by Takeda Pharmaceutical Co., Ltd.) 39 parts (this crosslinking agent is a functional group of the reactive acrylic resin). With an isocyanate group of 0.8 equivalent to the group) and a melamine cross-linking agent (manufactured by Dainippon Ink and Chemicals, Super Beckamine (butylated melamine resin) J-820-60)
4.6 parts by solids (5% of the functional groups of the reactive acrylic resin)
Was mixed with 200 parts of elastic beads (manufactured by Nippon Shokubai Kagaku Kogyo KK, EBS100). This mixture was applied to the release surface of a PET film with an applicator and dried at 80 ° C for 5 minutes to obtain a thermosetting sheet. Then, a polyhexamethylene terephthalate sheet (50 μm) was heat laminated. The thickness of the thermosetting sheet was 60 μm.

(10) 300 parts of ethyl acetate, reactive acrylic resin (copolymer of methyl methacrylate, methacrylic acid, butyl acrylate and 3-aminopropyl acrylate, Mw = 621,
000, Tg10 ℃, COOH value 40 and NH ₂ value 40) 100 parts by solid content,
Acrylic polycarboxylic acid oligomer (copolymer of ethyl acrylate, butyl acrylate and acryl acid, Mw = 2
5,000, Tg-30 ° C, COOH value 100) in solid content of 20 parts, blocked isocyanate (Nippon Polyurethane Industry Co., Ltd., Coronate 2513) in solid content of 58 parts (this crosslinker is functional of the above reactive acrylic resin). Group (having 1.0 equivalent of isocyanate group with respect to the carboxyl group of the acrylic polycarboxylic acid oligomer) and isocyanate (Coronate L, manufactured by Nippon Polyurethane Industry Co., Ltd.) in solid content of 4.4 parts (functionality of reactive acrylic resin) While 10% of the carboxyl groups of the base group and the acrylic polycarboxylic acid oligomer are initially cured), 50 parts of phthalocyanine blue, and 200 parts of elastic beads (EBS100 manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd.) are well kneaded with a triple roll. Mixed. This mixture was applied to the release surface of a PET film and dried at 70 ° C for 10 minutes to obtain a thermosetting sheet. The thickness of the sheet was 80 μm.

(11) Methyl methacrylate 70 parts, paranonylphenoxydiethylene glycol acrylate 15 parts, 2-hydroxyethyl acrylate 15 parts, 2,4,6-trimethylbenzoyldiphenylphosphine oxide 2.8 parts, blocked isocyanate (Nippon Polyurethane Industry Co., Ltd.) Manufactured by Coronate 2513 with 100% solid content, NCO = 12.8%)
34 parts (1 equivalent amount of isocyanate with respect to the total functional groups), elastic beads (manufactured by Nippon Shokubai Chemical Co., Ltd., EB
S100) 200 parts were well stirred. This mixture was applied to an ABS sheet (A205, 500 μm, manufactured by Sanpo Resin Co., Ltd.) and irradiated with a metal halide lamp (100 W / cm) for 20 seconds to obtain a thermosetting sheet. The thickness of the sheet was 580 μm (including the ABS sheet).

(12) 60 parts of methyl acrylate, 20 parts of phenoxyethyl acrylate, 20 parts of acrylic acid, 2.8 parts of 2,4-diethylthioxanthone, 5.6 parts of paradimethylaminobenzoic acid isoamino ester, blocked isocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd.) , Coronate 2513 with a solid content of 100%, NCO = 12.8%) 90 parts (1 equivalent amount of isocyanate with respect to the total functional groups), elastic beads (Nippon Catalysis Chemical Co., Ltd., EBS100) 300 The parts were well stirred. This mixture was applied to the release surface of a PET film and irradiated with a metal halide lamp (100 W / cm) for 20 seconds to obtain a thermosetting sheet. The thickness of the sheet was 80 μm.

(13) 70 parts methyl methacrylate, 10 parts paranonylphenoxydiethylene glycol acrylate, 5 parts 2-hydroxyethyl acrylate, reactive acrylic resin (methyl methacrylate, butyl acrylate, 2-hydroxyethyl methacrylate, acrylic acid And 4-aminoethyl methacrylate copolymer, Mw = 480,000, Tg35
℃, OH value 20 and COOH value 20 and NH ₂ value 40, solid content 100%) 15 parts,
2.8 parts of 2,4,6-trimethylbenzoyldiphenylphosphine oxide, blocked isocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., 100% solid content of Coronate 2513, NCO = 12.8%) 21 parts (total functional groups On the other hand, 250 parts of an elastic bead (manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd., EBS300) was thoroughly stirred. This mixture was applied to the release surface of a PET film and irradiated with a metal halide lamp (100 W / cm) for 20 seconds to obtain a thermosetting sheet. The thickness of the sheet was 60 μm.

(14) Methyl acrylate 60 parts, acrylic acid 20 parts, thermoplastic acrylic resin (Asahi Kasei Co., Ltd., Delpet SR85
00) 20 parts, 2,4-diethylthioxanthone 2.8 parts, paradimethylaminobenzoic acid isoamino ester 5.6 parts, blocked isocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd.,
Coronate 2513 with 100% solids, NCO = 12.8
%) 90 parts, elastic beads (manufactured by Nippon Shokubai Chemical Co., Ltd., EB
S300) 100 parts was well stirred. This mixture is applied to the release surface of PET film, and metal halide lamp (100W / cm)
And irradiated for 20 seconds to obtain a thermosetting sheet. The thickness of the sheet is 80
was μm.

(15) 300 parts ethyl acetate, reactive acrylic resin (methyl methacrylate and butyl acrylate, methacrylic acid 2
-Hydroxyethyl, acrylic acid and methacrylic acid 4-
Copolymer with aminoethyl, Mw = 480,000, Tg35 ℃, OH
No. 20 and COOH No. 20 and NH ₂ No. 40) as solids, 100 parts, Blocked isocyanate (Takenate B, manufactured by Takeda Pharmaceutical Co., Ltd.)
-815N) 39 parts (this crosslinking agent has an isocyanate group of 0.8 equivalent to the functional group of the reactive acrylic resin), melamine crosslinking agent (manufactured by Dainippon Ink and Chemicals, Super Beckamine (butylated melamine resin) J −820−60 of 100
% Solid content) 4.6 parts (5% of the reactive acrylic resin is initially cured), elastic beads (manufactured by Nippon Shokubai Chemical Industry Co., Ltd.,
200 parts of EBS100) were mixed with good stirring. Apply this mixture to the release surface of PET film with an applicator,
The resin layer was formed by drying at 0 ° C. for 5 minutes. The thickness of the resin layer was 20 μm. This was used as the surface layer. Next, 500 parts of ethyl acetate, thermoplastic acrylic resin (Asahi Kasei Co., Ltd.)
Manufactured by Delpet SR8200), 40 parts of 1,6-hexadiol dimethacrylate, 40 parts of neopentyl glycol dimethacrylate, and 2.5 parts of ter-butyl peroxyisobutyrate were mixed while stirring well. Overcoat the mixture with an applicator on the surface layer described above,
It was dried at 60 ° C for 30 minutes to form a resin layer. The thickness of the resin layer
The thickness of the sheet was 60 μm, and the total thickness of the sheet was 80 μm.

(16) 300 parts of ethyl acetate, reactive acrylic resin (methyl methacrylate, 2-hydroxyethyl methacrylate, butyl acrylate, copolymer of acrylic acid and 4-aminoethyl methacrylate, Mw = 360,000, Tg35 ℃, O
H value of 20, COOH value of 20 and NH ₂ value of 40) in solid content of 100 parts, blocked isocyanate (Takenate B-815N manufactured by Takeda Pharmaceutical Co., Ltd.) 59 parts (this cross-linking agent is a functional group of the reactive acrylic resin). Based on the group, it has 1.2 equivalents of isocyanate group), elastic beads (manufactured by Nippon Shokubai Chemical Co., Ltd., EBS10)
0) 200 parts were mixed with good stirring. PE this mixture
The release surface of the T film was coated with an applicator and dried at 80 ° C. for 5 minutes to form a resin layer. Resin layer thickness is 20μ
It was m. This was used as the surface layer. Next, ethyl acetate 30
0 parts, reactive acrylic resin (copolymer of methyl methacrylate and butyl acrylate, methacrylic acid and 3-aminopropyl acrylate, Mw = 621,000, Tg10 ° C, COOH
Valency 40 and NH ₂ valency 40) in solid content of 100 parts, blocked isocyanate (Takenate B-815N manufactured by Takeda Pharmaceutical Co., Ltd.) 59 parts (this cross-linking agent is 1.
100 parts of titanium oxide were mixed with good stirring. This mixture is applied over the surface layer described above with an applicator and coated at 70 ° C for 20
After drying for a minute, a resin layer was formed. Resin layer thickness is 100 μm
The total sheet thickness was 120 μm.

(17) Toluene 300 parts, reactive silicone resin (polymethyl polyol siloxane, weight average molecular weight 50,000, OH
Value 80) 100 parts, blocked isocyanate (Takenate B-815N, manufactured by Takeda Pharmaceutical Co., Ltd.) 47 parts (this crosslinking agent has 1.0 equivalent of isocyanate groups based on the functional groups of the resin), titanium oxide 100 parts, elastic beads. 200 parts (manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd., EBS300) were mixed while thoroughly kneading with a triple roll. This mixture was applied to the release surface of a PET film with an applicator and dried at 90 ° C for 10 minutes to obtain a thermosetting sheet. The thickness of the sheet was 100 μm.

(18) Toluene 300 parts, reactive fluororesin (alternate copolymer of ethylene and hydroxytrifluoroethylene, weight average molecular weight 100,000, OH value 455) 100 parts, blocked isocyanate (Takenate B-815N manufactured by Takeda Pharmaceutical Co., Ltd.) 140
Parts (this cross-linking agent has 0.5 equivalents of isocyanate groups with respect to the functional groups of the resin) and 100 parts of elastic beads (EBS300, manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd.) were mixed with good stirring. This mixture was applied to the release surface of a PET film with an applicator and dried at 90 ° C for 10 minutes to obtain a thermosetting sheet. The thickness of the sheet was 100 μm.

(19) Toluene 300 parts, reactive fluororesin (alternating copolymer of ethylene and hydroxytrifluoroethylene, weight average molecular weight 250,000, OH number 455) 100 parts, blocked isocyanate (Takenate B-815N manufactured by Takeda Pharmaceutical Co., Ltd.) 140
Parts (this cross-linking agent has 0.5 equivalents of isocyanate groups with respect to the functional groups of the resin), isocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate L) 26 parts (this cross-linking agent has functional groups of the above resin) , 0.1 equivalents of isocyanate groups) and 300 parts of elastic beads (EBS300, manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd.) were mixed with good stirring. This mixture was applied to the release surface of a PET film with an applicator and dried at 90 ° C for 10 minutes to obtain a thermosetting sheet. The thickness of the sheet was 100 μm.

(20) The sheet obtained in (18) above was coated on the release surface of the PET film with an applicator so that the film thickness was 20 μm. Next, 300 parts of toluene, 100 parts of reactive fluororesin (alternate copolymer of ethylene and hydroxytrifluoroethylene, weight average molecular weight 100,000, OH value 455),
Blocked isocyanate (Takeda Yakuhin Kogyo, Takenate B-815N) 140 parts (this cross-linking agent has 0.5 equivalent of isocyanate groups based on the functional groups of the resin), phthalocyanine blue 20 parts, elastic beads (Nippon Shokubai Kagaku Kogyo ( Co., Ltd., EBS300) 200 parts was well mixed with a triple roll. This mixture was applied onto the above-mentioned sheet with an applicator and dried at 90 ° C for 10 minutes to form a thermosetting resin layer. The resin layer has a thickness of 100 μm, and the sheet has a thickness of 1
It was 20 μm.

(21) Toluene 300 parts, reactive fluororesin (alternating copolymer of ethylene and hydroxytrifluoroethylene, weight average molecular weight 250,000, OH value 455) 100 parts, blocked isocyanate (Takenate B-815N manufactured by Takeda Pharmaceutical Co., Ltd.) 140
Parts (this cross-linking agent has 0.5 equivalents of isocyanate groups with respect to the functional groups of the resin), isocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate L) 26 parts (this cross-linking agent has functional groups of the above resin) , 0.1 equivalent of isocyanate group) and 100 parts of elastic beads (EBS300, manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd.) were mixed with good stirring. This mixture was applied to the release surface of a PET film with an applicator and dried at 90 ° C for 10 minutes to obtain a thermosetting sheet. The thickness of the sheet was 100 μm.

(22) 300 parts of xylene, reactive polyester resin (2-
A copolymer of aminoterephthalic acid and hexamethylene glycol, weight average molecular weight 65,000, amino value 226) 100 parts,
Blocked isocyanate (Takeda Yakuhin Kogyo, Takenate B-815N) 111 parts (this cross-linking agent has 0.8 equivalent of isocyanate groups based on the functional groups of the resin), elastic beads (Nippon Shokubai Chemical Co., Ltd., EBS300) ) 200 parts were mixed with good stirring. This mixture was applied to the release surface of a PET film with an applicator and dried at 90 ° C for 10 minutes to obtain a thermosetting sheet. The thickness of the sheet was 80 μm.

(B) Performance Evaluation of Thermosetting Sheet Spreadability Test A strip-shaped test piece (20 mm × 100 mm) was cut from the thermosetting sheet obtained in Examples (1) to (22) to obtain Example 3. , 11 sheets were subjected to a tensile test in the longitudinal direction at 150 ° C and the other sheets at 80 ° C. As a result, all the sheets showed uniform elongation at 300% elongation without cracking or cracking of the test piece.

Coating test Sheets (20 cm x 20 cm) obtained in Examples (1) to (22)
On a convex surface of a steel plate (radius of curvature 50 cm: bottom diameter is 30 cm) curved in the shape of a convex lens so that the ends reach both ends of the steel plate and the resin layer is opposed to the convex surface side.
C. (However, the sheets of Examples 3 and 11 were 160.degree. C.), and vacuum pressure bonding was performed. All the sheets could be covered well without wrinkles.

Then, the curable sheet on the surface of the coating was cured by adding these coatings. Adhesion and softness were evaluated by a taper wear test (taper 1 Kg, CS17, 1000 rotations) after curing and a cross-cut test. The results are shown in Table 1
4 shows.

Further, the sheet obtained in Example 3 was placed in a female mold for injection molding having a suction hole for sucking to a vacuum so that the curable resin layer was in contact with the surface of the mold, and then vacuum and pressure molding were performed. (The sheet is heated to 150 ° C with a heating plate), the mold is closed and ABS
A resin (ABS-ME, manufactured by Denki Kagaku Kogyo KK) was injected.
Then, the curable sheet on the surface of the coating was cured by heating these coatings. After that, the curable sheet after curing was evaluated by the same method as described above. The results are shown in Table 5.

Comparative Example ABS resin sheet (A205, manufactured by Sanpo Resin Co., Ltd., thickness m) was coated with a soft touch paint (Cenosoft II, manufactured by Cashew Co., Ltd.) to a film thickness of 50 μm, and the temperature was kept at 80 ° C for 30 minutes. Heat cured. A strip-shaped test piece (20 mm × 100 mm) was cut from the obtained coating sheet, and a tensile test in the length direction was performed at 150 ° C. As a result, the sheet broke when stretched by about 80%.

Claims (2)

[Claims] 1. All of them have a weight average molecular weight of 20,000 to 1,000,
000, reactive acrylic resin, hydroxyl group, amino group,
Reactive silicone resin having a plurality of carboxyl groups,
Thermosetting resin containing one or more resins selected from reactive fluororesin having multiple hydroxyl groups, amino groups and carboxyl groups, reactive polyester resin having multiple hydroxyl groups, amino groups and carboxyl groups, blocked isocyanate and elastic beads An uncured or semi-cured thermosetting sheet formed of a resin composition. 2. An uncured or semi-cured thermosetting sheet formed of a composition containing a reactive vinyl monomer and / or oligomer, a photopolymerization initiator, a blocked isocyanate and elastic beads.