JPH0488031A - Production of coated article - Google Patents

Abstract

PURPOSE:To obtain a coated article having excellent impact resistance and scratch resistance by applying a photocurable sheet consisting essentially of a specific reactive acrylic resin, low-molecular weight material and light initiator to a body to be applied and curing the sheet by irradiation of light. CONSTITUTION:A curable resin composition obtained by blending (A) a reactive acrylic resin having (meth)acryloyl in the molecule and having 50000-1000000 weight-average molecular weight and being solid at ordinary temperature with (B) a low-molecular-weight material [e.g. ethyl (meth)acrylate] having (meth) acryloyl in the molecule, (C) light initiator (e.g. benzoyl) and as necessary (D) peroxide (e.g. dicumyl peroxide), coloring agent, oxidant, etc., is formed into a sheet (having 5-1000mum thickness) and the sheet is irradiated with a light to provide the aimed coated article. The sheet may be used also as plural layers obtained by laminating adhesive layer and/or surface layer.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a method for manufacturing a coating having a hard coating on its surface, and more specifically, for use in corrosion protection, decoration, display, etc.
The method of applying a photocurable sheet to the surface of an adherend relates to a method for producing a cured coating.

(Prior Art) Paints are generally used to decorate, display, and prevent corrosion of articles, or to impart other functions to the surface of articles.

If organic solvent-based paints or powder paints are used, the working environment will be adversely affected. When a water-based paint is used, it does not impair the working environment, but the drying time becomes longer or a large amount of energy is required to dry the paint.

Therefore, it has recently been proposed to use a photocurable sheet made of a thermoplastic resin such as polyvinyl chloride instead of paint. This sheet is used by being attached to the surface of an adherend such as a steel plate. When such a sheet is used, there is no adverse effect on the working environment and there is no need for drying.

However, since the main component of the material is soft polyvinyl chloride, the resulting coating has poor scratch resistance and is prone to cracking.

As an alternative to these flexible polyvinyl chloride sheets, heat- or photo-curable sheet materials have been proposed. This sheet material is hardened to form a hard film when or after being applied to the surface of an article by heating or irradiating with light.

For example, Japanese Patent Publication No. 61-61873 discloses a self-supporting notebook using a composite sheet formed by laminating a photocurable adhesive layer containing an acrylic photocrosslinkable polymer and a photosensitizing agent. A method of forming a surface protective layer on a plate-shaped article has been proposed. Further, photocurable sheets are generally used for DFR (dry film resist) and the like.

(Problems with the prior art) However, when pasting to a three-dimensional article, it is necessary to stretch the sheet, but the composite sheet with a photocurable adhesive layer used in Japanese Patent Publication No. 61-61873 is self-adhesive. Since a polyvinyl chloride sheet or the like is used as the supporting sheet, the stretchability is poor without heating, and when stretching is performed with heating, the adhesive layer is deformed. In addition, DFR sheets are not designed for the spreadability of the sheet before curing, the adhesion between the coating film and the adherend after curing, hardness, impact resistance, etc., and these performances are insufficient. be.

(Problems to be Solved by the Invention) The present invention solves the above-mentioned drawbacks, and its purpose is to make it easy to apply even to articles with uneven or curved surfaces, and to make it uniform. One object of the present invention is to provide a method for producing a coating using a photocurable sheet that can form a coating with excellent impact resistance and scratch resistance (surface hardness).

(Means for Solving the Problems) The method for producing a coated product according to the present invention according to claim 1 comprises: (a) having a (meth)acryloyl group in the molecule and having a weight average molecular weight of so, ooo to 1.000.000; It is coated with a photocurable sheet whose main components are a reactive acrylic resin that is solid at room temperature, (b) a low molecular weight substance having (meth)acryloyl groups in the molecule, and (c) a photoinitiator. The above object is achieved by including the steps of attaching the sheet to an adherend and curing the sheet by irradiating the sheet attached to the adherend with light.

Further, the method for manufacturing a coating of the present invention according to claim 2 includes:
(a) A reactive acrylic resin having a (meth)acryloyl group in the molecule and having a weight average molecular weight of 50.000 to 1,000.000 and solid at room temperature; (b) A (meth)acryloyl group in the molecule. A low molecular weight compound having (
c) attaching a photocurable sheet containing a photoinitiator and (d) peroxide as main components to an adherend; irradiating the sheet attached to the adherend with light; and curing the sheet by heating the sheet, thereby achieving the above object.

The present invention will be explained in detail below.

The photocurable sheet used in the present invention (a) has a (meth)acryloyl group in the molecule and has a weight average molecular weight of 5.
0.000 to i, ooo, ooo, and a reactive acrylic resin that is solid at room temperature; (b) (meta) in the molecule;
The main components are a low molecular weight substance having an acryloyl group and (c) a photoinitiator.

The reactive acrylic resin contained in the sheet is, for example, a (meth)acrylic acid ester monomer having a functional group such as a hydroxyl group, an amine group, or a carboxyl group, and other (
Acrylic polymers with functional groups are produced by copolymerizing meth)acrylic acid esters, styrene derivative monomers, maleic acid monomers, etc. in the presence of reaction initiators (various peroxides, azo compounds, etc.) and chain transfer agents. It can be obtained by obtaining a polymer and adding a monomer having the above functional group to this acrylic-6= type copolymer.

The (meth)acrylic acid ester monomer having the above functional group includes (meth)acrylic acid having a carboxyl group such as (meth)acrylic acid; 2-hydroxyethyl (
(meth)acrylic acid ester monomers having a hydroxyl group such as meth)acrylate and 4-hydroxybutyl(meth)acrylate; ) Acrylic acid ester monomer; 2-
(1aziridinyl)ethyl(meth)acrylate, 2(
(meth)acrylic acid ester monomers having aziridinyl such as 1-aziridinyl)butyl (meth)acrylate; (meth)acrylic acid ester monomers having epoxy groups such as glycidyl (meth)acrylate; and the like.

Weight average molecular weight (Mw) of these reactive acrylic resins
can be changed depending on the conditions when carrying out the polymerization reaction using a reaction initiator. The reactive acrylic resin used in the present invention has a weight average molecular weight of 50.000.
~1,000,000 are selected. If the weight average molecular weight is less than 50.000, the resulting sheet will have difficulty retaining its shape, and will not have sufficient elongation during stretching during the pasting process, leading to the risk of cracking. When the weight average molecular weight exceeds 1,000,000, it becomes difficult to dissolve in a solvent and it becomes difficult to prepare a sheet from the photocurable resin composition. For example, when a sheet is created by solvent casting, the viscosity of the solvent increases, so the resin can only be cast at a low concentration, which makes it difficult to increase the thickness of the sheet. These reactive acrylic resins have a Tg (glass transition point) of -20°C to
A range of 120'C is preferred. Different types of reactive acrylic resins may be used in combination as long as they have molecular weights within these ranges.

Examples of low molecular weight substances having (meth)acryloyl groups in the molecules contained in the sheet include methyl (meth)acrylate, ethyl (meth)acrylate, benzyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, Monofunctional types such as phenoxydiethylene glycol di(meth)acrylate, 1,6-hexanethiol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(
meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylpropane tri(meth)
There are multifunctional types such as acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate. Further, there are oligomers such as polyester acrylate, polyurethane acrylate, epoxy acrylate, polyether acrylate, oligoacrylate, alkydoacrylate, and polyol acrylate.

The low molecular weight substance is added mainly to maintain the spreadability when the sheet is pasted and to ensure required properties (hardness, chemical resistance, etc.) when the sheet is cured. Therefore, the amount added is approximately related to the Tg of the reactive acrylic resin and the viscosity of the low molecular weight material added. For example, T
When using a reactive acrylic resin with g = 60 to 100'C, a low molecular weight substance with a viscosity of 500 cps (25 °C) or less should be added in an amount of 10 to 1 part by weight per 100 parts by weight of the reactive acrylic resin.
It is preferable to add 50 to 300 parts by weight of a low molecular weight substance having a viscosity of 500 cps (25°C) or more. If the amount added is small, sufficient elongation cannot be obtained after curing.

If the amount added is large, the handling properties of the sheet will deteriorate. The above-mentioned low molecular weight substances may be used in combination of different types.

The photoinitiators that are commonly used can be used, and for example, benzoin alkyl ether-based, acetophenone-based, benzophenone-based, and thioxanthone-based photoinitiators are preferably used. Examples of benzoin ethers include benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, and penzoin impyl ether.

Among the acetophenone types, 2.2-jethoxyacetophenone and 2-hydroxy-2-methylpropiophenone.

p-ter-butyltrichloroacetophenone, 246
Examples include trimethylbenzoyldiphenylphosphine oxide. In the pentsuphenone series, benzophenone, 4
-chlorobenzophenone, 44-dichlorobenzophenone, 33'-dimethyl-4-methoxybenzophenone,
There are things like dibenzosherenone. The thioxanthone series includes thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isofurovirthioxanthone, and 2-chlorothioxanthone.
- Examples include ethyl anthraquinone. The photoinitiator is as described above (
Usually 0.05 to 20 parts by weight, preferably 0.05 to 20 parts by weight, per 100 parts by weight of a low molecular weight substance having a meth)acryloyl group.
It is added in an amount of 5 to 10 parts by weight. Moreover, the number of photoinitiators is not limited to one type, and two or more types may be used in combination.

Peroxide may be added to the photocurable sheet as necessary in order to further heat cure the portions that are difficult to cure by irradiation with light.

As peroxides, common organic peroxides can be used.

From the viewpoint of storage stability at room temperature, organic peroxides with a decomposition degree of 120° C. or higher are more preferred.

These include, for example, 2,2-bis(ter-butylperoxy)butane, ter-butylperoxybenzoate, ter-butylperoxyisophthalate,
Examples include methyl ethyl ketone peroxide, dicumyl peroxide, and ter-butyl peroxy acetate.

The amount of peroxide added is preferably in the range of 05 to 5.0 parts by weight per 100 parts by weight of the above-mentioned low molecular weight substance having a (meth)acryloyl group. Also, the peroxide is not limited to one type,
Two or more types may be used in combination.

The photocurable sheet used in the present invention may further contain materials such as colorants such as pigments and dyes, and antioxidants, if necessary.

As the colorant, pigments and dyes used in paints can be used. Pigments include titanium oxide, iron oxide, carbon black,
These include cyanine pigments and quinacridone pigments. Dyes include azo dyes, anthraquinone dyes, indigoid dyes, and stilbenzene dyes. Further, metal powders such as aluminum flakes, nickel powders, gold powders, and silver powders may be used as the coloring agent. It is preferable that these materials have as fine particles as possible. When using a highly opaque colorant, the amount of these additives should be 10% of the solid content of the resin.
The range of 2 to 400 parts is preferable based on 0 parts by weight. In addition, when these materials are added, it is preferable that the photoinitiator performs the initiation reaction with light having a wavelength that is less absorbed by the colorant.

Various functional agents may be added to impart various functions to the photocurable material used in the present invention. The various functional agents mentioned above include conductive materials, anti-condensation agents, photochromic compounds, gloss control agents made of particles, and rust preventive agents. When these materials are added, it is preferable that the photoinitiator performs the initiation reaction with light of a wavelength that is less absorbed by the functionality-imparting agent.

[Form of photocurable sheet]

A curable resin composition is obtained by kneading the above materials. A base layer is created from the curable resin composition, and when the photocurable sheet is a single layer, this base layer becomes the photocurable sheet as it is.

The sheet used in the present invention may consist of a single layer including only the base layer, or may consist of multiple layers. When the sheet is composed of multiple layers, there are, for example, the following forms.

(2) A sheet having a base layer and an adhesive layer laminated on one side of the base layer.

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

Examples of the pressure-sensitive adhesive include rubber-based, acrylic-based, urethane-based, and silicone-based adhesives. Examples of hot melt adhesives include ethylene-vinyl acetate copolymer (EVA) and styrene isofrene-styrene bronoch copolymer (SIS). Post-curing adhesives include, for example, microcapsule-curing adhesives. Examples of the material include uncrosslinked unsaturated polyester adhesives, uncrosslinked acrylic adhesives, and the like.

(2) A sheet having a base layer and a surface layer laminated on one side of the base layer.

The surface layer is formed by a base layer containing the above-mentioned various functional imparting agents, a transparent layer containing a coloring agent, or a transparent layer containing the above-mentioned various functional imparting agents. It can be formed of a layer containing:

A sheet with a transparent surface layer gives the sheet a sense of depth when viewed.

The transparent layer may be formed of the curable resin composition used for the base layer, except that it does not contain a colorant.

(2) A sheet comprising a base layer, a surface layer laminated on the surface of the base layer, and an adhesive layer laminated on the back surface of the base layer.

Various materials that can be contained in the above-mentioned base layer can be blended into the resin composition forming the surface layer and the adhesive layer.

(2) A sheet comprising the sheets of (1) to (2) above and a protective layer laminated on the surface of the sheet.

=15- The protective layer is laminated to provide shape retention during storage and use of the sheet and surface protection after application.

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

Examples of the thermoplastic resin include polyvinyl chloride, polyurethane, acrylic resin, polyester, ethylene-vinyl acetate copolymer, polyethylene, and polypropylene.

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.

Mixtures of these thermoplastic resins and rubbers can also be used. Alternatively, both films may be laminated.

The protective layer may be peeled off from the adherend immediately after the sheet is applied to the adherend, and then the sheet may be cured, and the sheet may be applied to the adherend and then cured before using these adherends. It may also be used as a protective layer until it is removed. By adding embossing or patterns to the surface of the protective layer, the surface shape (appearance) of the sheet can be changed.

■A sheet with printing applied to the surface of the sheet Φ~■ above.

The thickness of the photocurable sheet obtained in this way is 20 to 500 μm when applied to an uneven adherend surface.
m is preferable, and when pasting on a flat surface, it is 5 to 1.0 m.
It may be about 00 μm. Further, the thickness of other layers laminated on the sheet is usually 10 to 500 μm, and the thickness of the adhesive layer is particularly preferably 10 to 100 μm.

[Preparation of photocurable sheet]

The sheet may be prepared in any manner. When the sheet is a single layer, the following casting method is preferred.

The curable resin composition is sufficiently dissolved or dispersed in an organic solvent. The resulting solution is coated onto processing paper (usually a polyethylene terephthalate film, paper paper, surface treated with silicone) using equipment such as a knife coater, comma coater or reverse coater, and then dried to remove the solvent. to form a base layer. A sheet is obtained by peeling the processing paper from the base layer.

When the sheet is formed of multiple layers, it can be obtained by a casting method or a lamination method. According to the casting method, a solution containing the resin composition of one of the layers is coated onto processing paper, dried to remove the solvent to form a layer, and then the composition of the other layer is coated on top of this layer. Another layer is formed by coating a solution containing the substance and drying to remove the solvent. According to the lamination method, each layer is formed by separately applying a solution containing the resin composition of each layer onto process paper, drying and volatilizing the solvent, and then laminating both layers ( Heating) Press with a roll press.

The process paper used during manufacturing can be used as a protective sheet.

[How to use the photocurable sheet (method for manufacturing the coating)]

The photocurable sheet used in the present invention has a certain degree of flexibility and extensibility at room temperature, so it can be heated or stretched without heating, reduced pressure, pressurized (laminated, etc.), etc. to shape the surface of the adherend. It can be attached to the surface along the

The spreading of the curing sheet and the above-mentioned vacuum or pressurization may be performed simultaneously, or the curing sheet may be spread and then vacuumed or pressurized to be applied to the surface of the adherend. Next, at least the part of the adherend to which the curing sheet is pasted is irradiated with light, and if the sheet contains peroxide, the sheet is further heated to harden the sheet. According to such a method, not only a plate-like member but also a three-dimensional three-dimensional member with unevenness can be easily coated. Further, after the sheet is attached to an adherend, the adherend may be processed into an appropriate shape, and then cured.

[Adherend]

Various types of adherends can be used to attach the photocurable sheet.

For example, metal plates such as steel plates and aluminum plates; galvanized iron;
Metal plated plates such as tin plate; Wood; Ceramics such as gypsum board, cement, and chinaware; Steel plates, ceramics, painted plates with resin film laminated on resin materials; Polyolefin, A
Thermoplastic resins such as BS resin, polyphenylene sulfide (PPS), and polyetherimide; thermosetting resins such as melamine resin, epoxy resin, phenol resin, and polyimide; and the like.

Further, the surface of the adherend may be subjected to various surface treatments.

For example, there are acid treatments such as phosphoric acid and alkali treatments that are normally applied to steel plates, and various surface treatments such as solvent treatment, corona discharge treatment, glow discharge treatment, plasma treatment, ion implantation, etc., and primer treatments for resin surfaces. .

[Applications of photocurable sheet]

The photocurable sheet used in the present invention is applied to the surfaces of various adherends for the purpose of corrosion prevention, decoration, display, and protection. The uses of the sheet are not limited, but include, for example, the following uses.

■Automotive components: body exterior, interior ■Home appliance components: Housings for refrigerators, washing machines, microwave ovens, etc. ■Architectural components: exterior wall components, interior wall components, rain gutters ■Painted steel plates ■OA housing ■Daily necessities: Washbasins , Polybucket (Example) The present invention will be explained in detail based on Examples below.

In addition, "part" means "part by weight." Further, the number of "double bonds per molecule" described in the reactive acrylic resin means the average number of double bonds per molecule.

(A) Adjustment of photocurable sheet 110 = Reactive acrylic resin (manufactured by Nippon Shokubai Chemical Co., Ltd., AE
G-15S, weight average molecular weight = 54.300. Double bonds per molecule - 26) 100 parts acrylate monomer (manufactured by Nippon Kayaku Co., Ltd., KAYAR
AD R604) 80 parts photoinitiator (Nippon Kayaku Co., Ltd. Kayacure DETX) 1
2 parts photopolymerization accelerator (Kayacure EPA, manufactured by Nippon Kayaku ■) 300 parts or more of ethyl acetate were mixed with stirring.

This mixture was applied to a silicone release-treated polyethylene terephthalate film (manufactured by Kaisho Kako Co., Ltd., film thickness 50 μm).
Coating on the release surface of the PET film (hereinafter referred to as PET film),
After drying at 80° C. for 5 minutes, the PET film was peeled off to obtain an uncured photocurable sheet. The thickness of the obtained photocurable sheet was ioo μm.

Support plate Takumi reactive acrylic resin (manufactured by Nippon Shokubai Chemical Co., Ltd., AE
G-15S, weight average molecular weight = 54.300. Double bonds per molecule -26) 100 parts acrylate monomer (manufactured by Nippon Kayaku Co., Ltd., KAYAR
AD R604) 80 parts photoinitiator (manufactured by Nippon Ciba Geigy Co., Ltd., Irgacure
184) 2 parts N methyljetanolamine 2 parts Ethyl acetate 300 parts or more were mixed with stirring.

Coat this mixture on the release surface of the PET film and
After drying at C for 5 minutes, the PET film was peeled off to obtain an uncured photocurable sheet.

The thickness of the obtained photocurable sheet was 100 μm.

Oarashi Takumi reactive acrylic resin (manufactured by Nippon Shokubai Chemical Co., Ltd., AE
G-153, weight average molecular weight = 54,300. Double bond per molecule = 26) 100 parts acrylate monomer (manufactured by Nippon Kayaku Co., Ltd., KAYAR
AD MANDA) 20 parts acrylate monomer (manufactured by Nippon Kayaku Co., Ltd., KAYAR
AD DPCA20) 80 parts Photoinitiator (manufactured by Nihon Ciba Geigy Co., Ltd., Irgacure 651) 2 parts N-methyljetanolamine 2 parts Ethyl acetate 300 parts or more were mixed with stirring.

Coat this mixture on the release surface of the PET film and
After drying at C for 5 minutes, the PET film was peeled off to obtain an uncured photocurable sheet.

The thickness of the obtained photocurable sheet was 50 μm.

Shiran Takumi soil reactive acrylic resin (manufactured by Nippon Shokubai Chemical Co., Ltd., AE
G-143, weight average molecular weight = 80.700.Double bond per molecule -37)
AD DPCA-20) 120 parts photoinitiator (2゜4
,5. -trimethyl hendiyl diphenylphosphine oxide) 4 parts N-methyljetanolamine 2 parts rutile titanium oxide 100 parts At least 300 parts of ethyl acetate were mixed with stirring.

Coat this mixture on the release surface of the PET film and
After drying at C for 5 minutes, the PET film was peeled off to obtain an uncured photocurable sheet.

The thickness of the obtained photocurable sheet was 80 μm.

Friend is Salmon 1 Reactive acrylic resin (manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd., AE
G-14S, weight average molecular weight = 80.700. Double bond per molecule -37) 100 parts acrylate monomer (manufactured by Nippon Kayaku Co., Ltd., KAYAR
AD DPI (A) 80 parts acrylate monomer (manufactured by Nippon Kayaku Co., Ltd., KAYAR
AD MANI) A) 40 parts photoinitiator (MERCK)
Made by Japan Ltd, Tarocure 404
3) 6-part photoinitiator (Kayacure DETX manufactured by Nippon Kayaku Co., Ltd.) 0
．． 5 parts N-methyljetanolamine 2 parts quinacridone 100 parts At least 300 parts of ethyl acetate were mixed with stirring.

This mixture was coated on the release surface of the PET film, and 80'
After drying at C for 5 minutes, the PET film was peeled off to obtain an uncured photocurable sheet.

The thickness of the obtained photocurable sheet was 50 μm.

Reactive acrylic resin (manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd., AE
G-14S, weight average molecular weight = 80.700. Double bonds per molecule - 37) 100 parts acrylate monomer (manufactured by Nippon Kayaku Co., Ltd., KAYA
RAD R551) 80 parts Photoinitiator (2,4,6-trimethyl benzoyl diphenylphosphine oxide) 4 parts N-methyljetanolamine 2 parts Iron oxide 100 parts At least 300 parts of ethyl acetate were mixed with stirring.

Coat this mixture on the release surface of the PET film and
After drying at C for 5 minutes, the PET film was peeled off to obtain an uncured photocurable sheet.

The thickness of the obtained photocurable sheet was 50 μm.

manufactured by AEG-153, weight average molecular weight -54,300,
Double bond per molecule -26) 100 parts acrylate monomer (manufactured by Nippon Kayaku Co., Ltd., KAYAR
AD R604) 80 parts Photoinitiator (2,4,6-trimethyl benzoyl diphenylphosphine oxide) 2 parts N-methyljetanolamine 2 parts At least 300 parts of ethyl acetate were mixed with stirring.

Coat this mixture on the release surface of the PET film and
It was dried at C for 5 minutes. The thickness of the obtained photocurable sheet (thickness of sheet other than PET) was 20 μm (referred to as clear layer).

Reactive acrylic resin (manufactured by Nippon Shokubai Chemical Co., Ltd., AE
G-153, weight average molecular weight = 54,300. Double bond per molecule = 26) 100 parts acrylate monomer (manufactured by Shin Nakamura Kogyo Co., Ltd., NPA-
10G) 80 parts Photoinitiator (2,4,6-trimethyl benzoyl diphenylphosphine oxide) 4 parts N-methyljetanolamine 2 parts Rutile titanium oxide 10 parts Ethyl acetate or more 300 parts were mixed with stirring.

Coat this mixture on the clear layer and go'c.
After drying for a minute, the PET film was peeled off to obtain an uncured photocurable sheet.

The thickness of the obtained photocurable sheet was 70 μm (clear layer: 20 μm, colored layer: 50 μm).

x Blood-reactive acrylic resin (manufactured by Nippon Shokubai Chemical Co., Ltd., AE
G-15S, weight average molecular weight = 54.300. Double bond per molecule = 26) 100 parts acrylate monomer (manufactured by Nippon Kayaku Co., Ltd., KAYAR
AD R604) 80 parts Photoinitiator (2,46-trimethyl benzoyl diphenylphosphine oxide) 2 parts N-methyljetanolamine 2 parts At least 300 parts of ethyl acetate were mixed with stirring.

Coat this mixture on the release surface of the PET film and
It was dried at C for 5 minutes. The thickness of the obtained photocurable sheet (thickness of sheet other than PET) was 20 μm (referred to as clear layer).

Reactive acrylic resin (manufactured by Nippon Shokubai Chemical Co., Ltd., AE
G-15S, weight average molecular weight = 54.300. Double bonds per molecule = 26) 100 parts acrylate monomer (manufactured by Shin Nakamura Kogyo Co., Ltd., NPA-
10G) 80 parts photoinitiator (manufactured by Nippon Ciba Geigy Co., Ltd., Irgacure
907) Two-part photoinitiator (Kayacure DETX manufactured by Nippon Kayaku Co., Ltd.) 0
．． 5 parts N-methyljetanolamine 2 parts Cyanine Blue 100 parts At least 300 parts of ethyl acetate were mixed with stirring.

This mixture was coated on the above clear layer and heated at 80°C for 5 minutes.
After drying for a minute, the PET film was peeled off to obtain an uncured photocurable sheet.

The thickness of the obtained photocurable sheet was 70 μm (clear layer: 20 μm, colored layer: 50 μm).

Reactive acrylic resin (copolymer of methyl methacrylate, butyl methacrylate, and acrylic acid with 2-
Reactive acrylic resin with added hydroxyethyl methacrylate, weight average molecular weight -654,300, average double bond per molecule = 98) 100 parts acrylate monomer (manufactured by Nippon Kayaku Co., Ltd., KAYARAD R60
4) 80 parts photoinitiator (manufactured by Nippon Ciba Geigy Co., Ltd., Irgacure)
184) 2 parts N methyljetanolamine 2 parts Ethyl acetate 300 parts or more were mixed with stirring.

Coat this mixture on the release surface of the PET film and
It was dried at C for 5 minutes. The thickness of the obtained photocurable sheet (thickness of sheet other than PET) was 100 μm (
(referred to as the clear layer).

A 20 μm thick layer made of an acrylic pressure-sensitive adhesive (SK Dyne 1386, manufactured by Soken Kagaku Co., Ltd., Tg - 30° C.) was laminated on the clear layer to obtain a photocurable sheet.

Support n highly reactive acrylic resin (copolymer of methyl methacrylate, butyl methacrylate, and acrylic acid with 2-
Reactive acrylic resin with addition of hydroxyethyl methacrylate + 7 ray 1-, weight average molecular weight -358,300,1
Average double bond per molecule = 126) 100 parts acrylate monomer (manufactured by Shin Nakamura Kogyo Co., Ltd., NPA-
LOG) 80 parts Photoinitiator (2,4,6,-1)methyl benzoyl
4 parts of diphenylphosphine oxide) 2 parts of N-methyljetanolamine 100 parts of rutile titanium oxide 300 parts or more of ethyl acetate were mixed with stirring.

This mixture was coated on PET film and heated at 80°C for 5 minutes.
After drying for minutes, ethylene-methyl acrylate film (PE2255 manufactured by Chevron Chemical, film thickness 20
μm) was laminated (referred to as a protective layer). By peeling off the PET film, an uncured photocurable sheet was obtained. The thickness of the obtained photocurable sheet is 70 μm
(Colored layer 50 μm + protective layer 20 μm).

Outer layer, LLL Reactive acrylic resin (manufactured by Nippon Shokubai Chemical Co., Ltd., AE
G-153, weight average molecular weight -54,300, double bond per molecule = 26) 100 parts acrylate monomer (manufactured by Nippon Kayaku Co., Ltd., KAYAl
i'AD R604) 80 parts photoinitiator (Nippon Kayaku Co., Ltd., Kayacure DETX)
1 part photopolymerization accelerator (Nippon Kayaku (ready made, Kayacure EPA) 2 parts
0.5 parts peroxide (Perbutyl P, manufactured by NOF Corporation) and 300 parts or more of ethyl acetate were mixed with stirring.

This mixture was coated on the release surface of the PET film, and
After drying at C for 5 minutes, the PET film was peeled off to obtain an uncured photocurable sheet.

The thickness of the obtained photocurable sheet was 100 μm.

Reactive acrylic resin (manufactured by Nippon Shokubai Chemical Co., Ltd., AE
G-15S, weight average molecular weight = 54.300. double bond per molecule = 26) 100 parts acrylate monomer (manufactured by Nippon Kayaku Co., Ltd., KAYAR
AD R604) 80 parts photoinitiator (manufactured by Nippon Ciba Geigy Co., Ltd., Irgacure
184) 2 parts peroxide (Perbutyl P, manufactured by NOF Corporation) 1 part N-methyljetanolamine 2 parts At least 300 parts of ethyl acetate were mixed with stirring.

Coat this mixture on the release surface of the PET film and
After drying at C for 5 minutes, the PET film was peeled off to obtain an uncured photocurable sheet.

The thickness of the obtained photocurable sheet was 100 μm.

Table f1 Reactive acrylic resin (manufactured by Nippon Shokubai Chemical Co., Ltd., AE
G-153, weight average molecular weight = 54.300. double bond per molecule = 26) 100 parts acrylate monomer (manufactured by Nippon Kayaku Co., Ltd., KAYAR
AD MANDA) 20 parts acrylate monomer (manufactured by Nippon Kayaku Co., Ltd., KAYAR
AD DPCA20) 80 parts Photoinitiator (manufactured by Nippon Ciba Geigy Co., Ltd., Irgacure 651) 2 parts peroxide (manufactured by NOF Corporation, Perbutyl P) 1 part peroxide (manufactured by NOF Corporation, Perbutyl Z ) 1 part N-methyljetanolamine 2 parts Ethyl acetate 300 parts or more were mixed with stirring.

Coat this mixture on the release surface of the PET film and
After drying at C for 5 minutes, the PET film was peeled off to obtain an uncured photocurable sheet.

The thickness of the obtained photocurable sheet was 50 μm.

JLf Hit 1” engineering-reactive acrylic resin (manufactured by Nippon Shokubai Chemical Co., Ltd., AE
G-143, weight average molecular weight = 80.700.Double bonds per molecule-37) 100 parts acrylate monomer (Nippon Kayaku Co., Ltd. L KAY
ARAD MANOA) 80 parts Photoinitiator (2,4,6-trimethyl benzoyl diphenylphosphine oxide) 4 parts Peroxide (Perbutyl Z, manufactured by NOF Corporation) 1 part N-methyljetanolamine 2 parts Rutile type oxidation 100 parts of titanium and 300 parts or more of ethyl acetate were mixed with stirring.

Coat this mixture on the release surface of the PET film and
After drying at C for 5 minutes, the PET film was peeled off to obtain an uncured photocurable sheet.

The thickness of the obtained photocurable sheet was 80 μm.

Maruketaku Takumi Reactive Acrylic Resin (manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd., AE
G-143, weight average molecular weight -80,700, double bond per molecule = 37) 100 parts acrylate monomer (manufactured by Nippon Kayaku Co., Ltd., KAYAR
AD DP) [A) 80 parts acrylate monomer (manufactured by Nippon Kayaku Co., Ltd., KAYAR
AI) MANI) A) 40 parts photoinitiator (MERC)
Manufactured by K Japan Ltd, Darocure 404
3) 6-part photoinitiator (Nippon Kayaku Co., Ltd., Kayacure DETX
) 0.5 parts peroxide (Perbutyl Z, manufactured by NOF Corporation) 1 part N-methyljetanolamine 2 parts Quinacridone 100 parts At least 300 parts of ethyl acetate were mixed with stirring.

This mixture was applied to the release surface of the PBT film and heated to 80°C.
After drying for 5 minutes, the PET film was peeled off to obtain an uncured photocurable sheet.

The thickness of the obtained photocurable sheet was 50 μm.

Reactive acrylic resin (manufactured by Nippon Shokubai Chemical Co., Ltd., AE
G-14S, weight average molecular weight = 80.700.Double bond per molecule -37) loop part agua acrylate monomer manufactured by Honkayaku Co., Ltd., KAYAR
AD 1551) 80 parts Photoinitiator (2,4,6,-trimethyl benzoyl diphenylphosphine oxide) 4 parts Peroxide (manufactured by NOF Corporation, 1<-hexa 3M) 2 parts N-methyljetanolamine 2 100 parts of iron oxide and 300 parts of ethyl acetate were mixed with stirring.

Coat this mixture on the release surface of the PET film and
After drying at C for 5 minutes, the PET film was peeled off to obtain an uncured photocurable sheet.

The thickness of the obtained photocurable sheet was 50 μm.

Shio Takumi-ari reactive acrylic resin (manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd., AE
G-15S, weight average molecular weight -54,300, double bond per molecule = 26) 100 parts acrylate monomer (manufactured by Nippon Kayaku Co., Ltd., KAYAR
AD MANDA) 80 parts Photoinitiator (2,4,6-trimethyl benzoyl diphenylphosphine oxide) 2 parts Peroxide (manufactured by NOF Corporation, Barhexa 3M) 1 part N-methyljetanolamine 2 parts Acetic acid More than 300 parts of ethyl was mixed with stirring.

This mixture was coated on the release surface of the PET film, and 80'
It was dried at C for 5 minutes. The thickness of the obtained photocurable sheet (thickness of sheet other than PET) was 20 μm (referred to as clear layer).

Reactive acrylic resin (manufactured by Nippon Shokubai Chemical Co., Ltd., AE
G-15S, weight average molecular weight -54,300, double bond per molecule -26) 100 parts acrylate monomer (manufactured by Shin Nakamura Kogyo Co., Ltd., =37-NPA-10G) 80 parts photoinitiator (2, (4,6,-trimethyl benzoyl diphenylphosphine oxide) 4 parts peroxide (manufactured by NOF Corporation, Perhexa 3M) 1 part N-methyljetanolamine 2 parts rutile titanium oxide 100 parts Ethyl acetate or more 300 parts Mixed with stirring.

This mixture was coated on the above clear layer and heated at 80°C for 5 minutes.
After drying for a minute, the PET film was peeled off to obtain an uncured photocurable sheet.

The thickness of the obtained photocurable sheet was 70 parts and 1 m (clear layer: 20 μm, colored layer: 50 μm).

``Reactive acrylic resin (manufactured by Nippon Shokubai Chemical Co., Ltd., AE
G-15S, weight average molecular weight -54,300, double bond per molecule -26) 100 parts acrylate monomer (manufactured by Nippon Kayaku Co., Ltd., KAYAR
AD MANDA) 80 parts Photoinitiator (2,4,6,-)limethyl benzoyl diphenylphosphine oxide) 2 parts Peroxide (manufactured by NOF Corporation, Perhexa 3M) 1 part N-methyljetanolamine 2 parts More than 300 parts of ethyl acetate were mixed with stirring.

Coat this mixture on the release surface of the PET film and
It was dried for 5 minutes at C. The thickness of the obtained photocurable sheet (thickness of sheet other than PET) was 20 μm (referred to as clear layer).

Reactive acrylic resin (manufactured by Nippon Shokubai Chemical Co., Ltd., AE
G-15S, weight average molecular weight -54,300, double bond per molecule -26) 100 parts acrylate monomer (manufactured by Shin Nakamura Kogyo Co., Ltd., NPA-
JOG) 80 parts Photoinitiator (manufactured by Nippon Ciba Geigy Co., Ltd., Irgacure
907) Two-part photoinitiator (Nippon Kayaku Co., Ltd. Kayagyunia-DETX) 0
5 parts peroxide (manufactured by NOF Corporation, Perhexa 3M) 1 part N-methyljetanolamine 2 parts cyanine blue 100 parts At least 300 parts of ethyl acetate were mixed with stirring.

This mixture was coated on the above clear layer and heated at 80°C for 5 minutes.
After drying for a minute, the PET film was peeled off to obtain an uncured photocurable sheet.

The thickness of the obtained photocurable sheet was 70 μm (clear layer: 20 μm, colored layer: 50 μm).

Tomodara Takudoyu reactive acrylic resin (copolymer of methyl methacrylate, butyl methacrylate, and acrylic acid with 2-
Reactive acrylic resin with added hydroxyethyl methacrylate, weight average molecular weight -654,000, average double bond per molecule = 198) 100 parts acrylate monomer (manufactured by Nippon Kayaku Co., Ltd., KAYAR)
AD MANDA) 80 parts Photoinitiator (manufactured by Nippon Ciba Geigy Co., Ltd., Irgacure)
184) 2 parts peroxide (manufactured by NOF Corporation, Perbutyl ○) 1 part N-methyljetanolamine 2 parts Ethyl acetate or more 300 parts or more were mixed with stirring.

Coat this mixture on the release surface of the PET film and
It was dried at C for 5 minutes. The thickness of the obtained photocurable sheet (thickness of sheet other than PET) was 100 μm (
(referred to as the clear layer).

The above clear layer is made of acrylic adhesive (SK Dyne 1386, manufactured by Soken Kagaku Co., Ltd. Tg - 30°C) with a thickness of 2
A photocurable sheet was obtained by laminating layers of 0 μm.

1 hill group Mainly reactive acrylic resin (copolymer of methyl methacrylate, butyl methacrylate, and acrylic acid with 2-
Reactive acrylic resin with added hydroxyethyl methacrylate, weight average molecular weight -358,300, average double bond per molecule -126) 100 parts acrylate monomer (manufactured by Shin Nakamura Kogyo Co., Ltd., NPA-
10G) 80 parts Photoinitiator (2,4,6,-trimethyl benzoyl diphenylphosphine oxide) 4 parts Peroxide (Noku-butyl O, manufactured by NOF Corporation) 1.5 parts N-methyljetanolamine 2 100 parts of rutile titanium oxide and 300 parts or more of ethyl acetate were mixed with stirring.

This mixture was coated on PET film and heated at 80°C for 5 minutes.
After drying for minutes, ethylene-methyl acrylate film (PE2255 manufactured by Chevron Chemical, film thickness 20
I want to laminate the protective layer (μm). By peeling off the PET film, an uncured photocurable sheet was obtained. The thickness of the obtained photocurable sheet is 70 μm
(5071 m of colored layer + 20 μm of protective layer).

(B) Performance evaluation of photocurable sheets ■ Spreadability test Strip-shaped test pieces (20 mm x 50 mm) were cut from the photocurable sheets obtained in Examples 1 to 20, and were carried out at room temperature and 80°C. A longitudinal tensile test was conducted. As a result, even at 100% elongation, the test piece exhibited uniform elongation without any cracks or cracks.

■Covering test A photocurable sheet (20cm
20cm) was spread so that its ends reached both ends of the steel plate, and the resin layers were vacuum-pressed at 50°C with the resin layers facing each other. As a result, good coverage was achieved without any formation of wrinkles. .

■Performance evaluation of coated products Coated products coated with photocurable sheets 1 to 20 1.2.3.
9.1112.19 was 4-8 by high pressure mercury lamp, toS
14-18.20 is lit by a metal halide lamp (
100 mW/Cm) was irradiated from the top and side for 60 seconds and 40 seconds, respectively, and sheets 11 to 20 were further irradiated with 16
It was cured by heating at 0°C for 30 minutes. After that, JIS
The hardness of the coating was measured by a pencil hardness test according to K5400=44-. The results are shown in Tables 1 and 2.

(Leaving space below) Table 1 Table 2 6- (Comparative example) (A) Preparation of photocurable sheet Clean water m Reactive acrylic resin (copolymer of methyl methacrylate, butyl methacrylate, and acrylic acid) −
Reactive acrylic resin added with hydroxyethyl methacrylate, weight average molecular weight = 21.300. Average double bond per molecule = 6) 100 parts acrylate monomer (manufactured by Nippon Kayaku Co., Ltd., KAYARAD MAN)
NDA) 80 parts photoinitiator (Nippon Ciba Gaiki Co., Ltd.)
4 parts (manufactured by Irgacure 184) and 300 parts or more of ethyl acetate were mixed with stirring.

Coat this mixture on the release surface of the PET film and
It was dried at C for 5 minutes. The obtained photocurable sheet was
When I tried to peel it off from the T, I was unable to peel it off because the photocurable sheet had poor self-supporting properties.

ΔCarp main reactive acrylic resin (copolymer of methyl methacrylate, butyl methacrylate, and acrylic acid with 2-
Reactive acrylic resin with added hydroxyethyl methacrylate, weight average molecular weight -1,151,300,
Average double bond per molecule -330) 100 parts acrylate monomer (manufactured by Nippon Kayaku Co., Ltd., KAYAR
AD DPCA) 120 parts Photoinitiator (manufactured by Nippon Ciba Geigy Co., Ltd., Irgacure 184) 4 parts Ethyl acetate 150 parts or more were stirred, but it was difficult to uniformly dissolve the reactive acrylic resin.

Main reactive acrylic resin (copolymer of methyl methacrylate, butyl methacrylate, and acrylic acid with 2-
Reactive acrylic resin with added hydroxyethyl methacrylate, weight average molecular weight -21,300, average double bond per molecule = 6) 100 parts acrylate monomer (manufactured by Nippon Kayaku Co., Ltd., KAYARAD R551)
) 80 parts photoinitiator (manufactured by Nippon Ciba Geigy Co., Ltd.,
Irgacure 184) 4 parts and 150 parts or more of ethyl acetate were mixed with stirring.

This mixture was coated onto a PET film and dried at 80'C for 5 minutes, followed by ethylene-methyl acrylate.
Film (PE2255 manufactured by Chevron Chemical, film thickness 2
0 μm) was laminated (referred to as a protection notification). By peeling off the PET film, an uncured photocurable sheet was obtained. The thickness of the obtained photocurable sheet is 70 μm
(50 μm of clear layer + 20 μm of protective layer).

Reactive acrylic resin (a copolymer of methyl methacrylate, butyl methacrylate, and acrylic acid)
Reactive acrylic resin added with hydroxyethyl methacrylate, weight average molecular weight -21,300, average double bond per molecule 6) 100 parts acrylate resin /
KAYARAD MANN (manufactured by Nippon Kayaku Co., Ltd.)
DA) 80 parts photoinitiator (manufactured by Nippon Ciba Geigy Co., Ltd., Irgacure 184) 4 parts peroxide (manufactured by NOF (1), Barbutyl O) 1.5 parts
300 parts or more of ethyl acetate were mixed with stirring.

This mixture was coated on the release surface of the PET film, and 80'
It was dried at C for 5 minutes. The obtained photocurable sheet was
When an attempt was made to peel the sheet from T, the sheet could not be peeled off because the photocurable sort had poor self-supporting properties.

Anonymous reactive acrylic resin (copolymer of methyl methacrylate, butyl methacrylate, and acrylic acid with 2-
Reactive acrylic resin added with hydroquine ethyl methacrylate, weight average molecular weight -1,151,300,
Average double bond per molecule = 330) 100 parts acrylate monomer (manufactured by Nippon Kayaku Co., Ltd., KAYAR
AD DPCA) 120 parts Photoinitiator (manufactured by Nippon Ciba Geigy Co., Ltd., Irgacure-184) 4 parts Peroxide (manufactured by NOF ■, Verbutyl O) 1.5 parts More than 150 parts of ethyl acetate was stirred, but the reactivity It was difficult to uniformly dissolve the acrylic resin.

Anonymous reactive acrylic resin (copolymer of methyl methacrylate, butyl methacrylate, and acrylic acid with 2-
Reactive acrylic resin with added hydroxyethyl methacrylate, weight average molecular weight = 21,300. Average double bond per molecule = 6) 100 parts acrylate monomer (manufactured by Nippon Kayaku Co., Ltd., KAYARAD R551)
) 80 parts photoinitiator (manufactured by Nippon Ciba Geigy Co., Ltd., Irgacure 184) 4 parts peroxide (NOF (off-the-shelf, Verbutyl ○) 1.5 parts ethyl acetate 150 parts or more were mixed with stirring.

This mixture was coated on PET film and heated at 80°C for 5 minutes.
After drying for minutes, ethylene-methyl acrylate film (PE2255 manufactured by Chevron Chemical, film thickness 20
μm) to be laminated (called a protective layer). By peeling off the PET film, an uncured photocurable sheet was obtained. The thickness of the obtained photocurable sheet is 70 μm
(50 μm of clear layer + 20 μm of protective layer).

(B) Performance evaluation of photocurable sheet ■ Spreadability test A strip-shaped test piece (20 mm x 50 mm) was cut from the photocurable notebook obtained in Comparative Example 3.6, and heated in a room and at 80°C. A longitudinal tensile test was conducted.

Cracks occurred in the photocurable sheet when it was stretched 100%.

(Effects of the invention) The structure of the method for manufacturing a coating of the present invention is as described above,
The photocurable sheet before being pasted has excellent spreadability, flexibility, extensibility, etc., and can be well pasted by stretching it not only on a flat surface but also on an irregular or curved surface of an adherend. In addition, this photocurable sheet can form a strong film with excellent hardness and scratch resistance by irradiating it with light, and it is possible to obtain a coating having a film with excellent impact resistance and scratch resistance. I can do it.

that's all

Claims (1)

[Scope of Claims] 1. (a) a reactive acrylic resin having a (meth)acryloyl group in the molecule and having a weight average molecular weight of 50,000 to 1,000,000 and being solid at room temperature; (b) A step of attaching to an adherend a photocurable sheet containing as main components a low molecular weight material having a (meth)acryloyl group in the molecule; (c) a photoinitiator; A method for producing a coating comprising the step of curing the sheet by irradiating the sheet with light. 2. (a) a reactive acrylic resin having a (meth)acryloyl group in the molecule and having a weight average molecular weight of 50,000 to 1,000,000 and being solid at room temperature; (b) a (meth)acryloyl group in the molecule; A step of attaching to an adherend a photocurable sheet containing as main components a low molecular weight material having an acryloyl group, (c) a photoinitiator, and (d) a peroxide; irradiating the sheet with light;
and curing the sheet by heating the sheet.