JPH0715009B2 - Method of manufacturing coated products - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for producing a coated article having a hard coating on the surface, more specifically, for corrosion prevention, decoration, display, etc.
The present invention relates to a method for producing a coated article in which a photocurable sheet is attached and cured on the surface of an adherend.

(Prior Art) A paint is generally used for decoration, display, anticorrosion of an article, or for giving other functions to the article surface.

If an organic solvent-based paint or powder paint is used, the working environment is deteriorated. When a water-based paint is used, it does not impair the working environment, but the drying time becomes long or a large amount of energy is required for drying the paint.

Therefore, recently, it has been proposed to use a photocurable sheet made of a thermoplastic resin such as polyvinyl chloride instead of the paint. This sheet is used by being attached to the surface of an adherend such as a steel plate. When using such a sheet, 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 coating obtained has poor scratch resistance and cracks easily occur.

As an alternative to these soft polyvinyl chloride sheets, heat or light curable sheet materials have been proposed.
This sheet material is hardened to form a hard coating by heating or irradiating with light during or after application of the article surface.

For example, in Japanese Patent Publication No. 61-61873, a composite sheet obtained by laminating a photocurable adhesive layer containing an acrylic photocrosslinkable polymer and a photosensitizer on a self-supporting sheet is used. A method of forming a surface protective layer on a strip-shaped article has been proposed. The photocurable sheet is DFR (dry film resist).
It is generally used for applications.

(Problems of the prior art) However, when attached to a three-dimensional article, it is necessary to stretch the sheet. However, the composite sheet having a photocurable adhesive layer used in Japanese Patent Publication No. 61-61873 is Since a polyvinyl chloride sheet or the like is used as the supporting sheet, the stretchability is poor without heating, and when the sheet is heated and stretched, the adhesive layer is deformed. In addition, the DFR sheet is not designed for spreadability of the sheet before curing, adhesion between the cured coating film and the adherend, hardness, impact resistance, etc. is there.

(Problems to be Solved by the Invention) The present invention is to solve the above-mentioned drawbacks, and an object of the present invention is to easily perform an operation at the time of sticking even on an article having unevenness or a curved surface, and to make it uniform. Another object of the present invention is to provide a method for producing a coated article using a photocuring sheet capable of forming a coating having excellent impact resistance and scratch resistance (surface hardness).

(Means for Solving the Problem) The method for producing a coated article according to the present invention as set forth in claim 1 is (a) having a (meth) acryloyl group in the molecule, having a weight average molecular weight of 50,000 to 1,000,000 and being solid at room temperature. A step of attaching a photocurable sheet containing, as a main component, the reactive acrylic resin (1), a low molecular weight substance (b) having a (meth) acryloyl group in the molecule, and (c) a photoinitiator to an adherend And the step of curing the sheet by irradiating the sheet adhered to the adherend with light, thereby achieving the above object.

The method for producing a coated article according to the second aspect of the present invention is
(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; and (b) a low molecular weight product having a (meth) acryloyl group in the molecule. , (C) a photoinitiator,
(D) A step of sticking a photocurable sheet containing peroxide as a main component to an adherend, irradiating the sheet stuck to the adherend with light, and heating the sheet Curing the sheet by means of which the above objects are achieved.

The present invention will be described in detail below.

The photocurable sheet used in the present invention has a weight average molecular weight of 50,0 having a (meth) acryloyl group in the (a) molecule.
A reactive acrylic resin, which is 00 to 1,000,000 and is solid at room temperature, a (b) low molecular weight compound having a (meth) acryloyl group in the molecule, 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 amino group or a carboxyl group, and other (meth) acrylic acid ester or styrene derivative monomer or maleic acid. An acrylic copolymer having a functional group is obtained by copolymerizing with an acid monomer or the like in the presence of a reaction initiator (various peroxides, azo compounds, etc.), a chain transfer agent, or the like. Can be obtained by adding a monomer having the above functional group.

Examples of the (meth) acrylic acid ester monomer having a functional group include (meth) acrylic acid having a carboxyl group such as (meth) acrylic acid; 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc. (Meth) acrylic acid ester monomer having a hydroxyl group of 2-aminoethyl (meth) acrylate, 3
-(Meth) acrylic acid ester monomer having an amino group such as aminopropyl (meth) acrylate; 2- (1-
Aziridinyl) ethyl (meth) acrylate, 2- (1
An aziridinyl-containing (meth) acrylic acid ester monomer such as aziridinyl) butyl (meth) acrylate;
Examples thereof include (meth) acrylic acid ester monomer having an epoxy group such as glycidyl (meth) acrylate.

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 to 1,00.
A range of 0,000 is selected. Weight average molecular weight is 50,00
When it is less than 0, it becomes difficult to maintain the shape of the obtained sheet, with respect to the stretching during the sticking operation, sufficient elongation cannot be obtained, and a weight average molecular weight which may cause cracking is 1,000,000. If it exceeds, 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 prepared by solvent casting, the solvent viscosity 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 are preferably those having a Tg (glass transition point) in the range of -20 ° C to 120 ° C in view of the hardness after sheet curing. Reactive acrylic resins may be used in combination of different types as long as they have these molecular weight ranges.

Examples of the low molecular weight substance having a (meth) acryloyl group in the molecule contained in the sheet include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, benzyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, Monofunctional type such as phenoxydiethylene glycol (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, Polyfunctional type such as trimethylpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate A. There are also oligomers such as polyester acrylate, polyurethane acrylate, epoxy acrylate, polyether acrylate, oligo acrylate, alkyd acrylate, and polyol acrylate.

The above-mentioned low molecular weight substance is added mainly in order to maintain the malleability at the time of sticking the above-mentioned sheet and to secure the required characteristics (hardness, chemical resistance, etc.) when the sheet is cured. Therefore, the added amount is almost related to the Tg of the reactive acrylic resin and the viscosity of the low molecular weight substance to be added. For example, Tg
When using a reactive acrylic resin of 60 to 100 ° C,
Low molecular weight substances with a viscosity of 500 cps (25 ℃) or less are 10 to 150 parts by weight to 100 parts by weight of reactive acrylic resin, and a viscosity of 500 cps (25
It is preferable to add 50 to 300 parts by weight of a low molecular weight substance having a temperature of (° C.) Or higher. If the added amount is too small, sufficient elongation cannot be obtained after curing. If the amount of addition is large, the handleability of the sheet will deteriorate. The low molecular weight substances may be used in combination of different types.

As the above-mentioned photoinitiator, those usually used can be used, and for example, photoinitiators such as benzoin alkyl ether type, acetophenone type, benzophenone type and thioxanthone type are preferably used. Examples of the benzoin ether type include benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin propyl ether. 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, 2-chlorothioxanthone, 2 in thioxanthone system
-Methylthioxanthone, 2-isopropylthioxanthone, 2-ethylanthraquinone and the like. The photoinitiator is a low molecular weight compound 100 having the (meth) acryloyl group.
Usually, 0.05 to 20 parts by weight, preferably 0.5
It is added in the range of up to 10 parts by weight. Further, the photoinitiator is not limited to one type, and two or more types may be used in combination.

A peroxide may be added to the light-curable sheet, if necessary, in order to further heat-cure a portion that is hard to be cured by irradiation with light.

As the peroxide, a usual organic peroxide can be used.
From the viewpoint of storage stability at room temperature, an organic peroxide having a decomposition temperature of 120 ° C. or higher is more preferable. For example, 2,2-bis (ter-butylperoxy) butane, ter-
There are butyl peroxybenzoate, di-ter-butyl peroxyisophthalate, methyl ethyl ketone peroxide, dicumyl peroxide, and ter-butyl peroxyacetate. The amount of peroxide added is the above (meta)
The range of 0.5 to 5.0 parts by weight is preferable to 100 parts by weight of the low molecular weight product having an acryloyl group. Further, the peroxide is not limited to one type, and two or more types may be used in combination.

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

As the colorant, pigments and dyes used in paints can be used. Examples of pigments include titanium oxide, iron oxide, carbon black, cyanine pigments, and quinacridone pigments.
Examples of dyes include azo dyes, anthraquinone dyes, indigoid dyes, and stilbenzene dyes. Also,
Aluminum flakes, metal powder such as nickel powder, gold powder, and silver powder may be used as the colorant. It is preferable that these materials are fine particles. When using a colorant having a high hiding property, the addition amount of these is the solid content of the resin.
The range of 2 to 400 parts is preferable with respect to 100 parts by weight. Further, when these materials are added, it is preferable that the photoinitiator undergoes an initiation reaction with light having a wavelength at which absorption of the colorant is small.

Various functionalizing agents may be added to impart various functions to the photocurable sheet used in the present invention. The above-mentioned various functional imparting agents include conductive materials, anti-condensation agents, photochromic compounds, gloss control agents composed of particles, rust preventive agents and the like. When these materials are added, it is preferable that the photoinitiator undergoes an initiation reaction with light having a wavelength at which absorption of the functionalizing agent is small.

[Form of Photocurable Sheet] A curable resin composition is obtained by kneading the above materials. A base layer is prepared from the curable resin composition, and when the photocurable sheet is a single layer, the base layer becomes the photocurable sheet as it is.

The sheet used in 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, there are the following forms.

A sheet having a base layer and an adhesive layer laminated on one surface of the base 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, and silicone-based 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 a base layer and a surface layer laminated on one surface of the base layer.

The surface layer is formed of a layer containing the above-mentioned various functionalizing agents in the base layer, or a layer of the transparent layer containing a coloring agent, or the above-mentioned various functionalizing agents in the transparent layer. It may be formed of contained layers.

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

The transparent layer can be formed of the curable resin composition used for the base layer, except that the transparent layer does not contain a coloring agent.

A sheet having a base layer, a surface layer laminated on the front surface of the base layer, and an adhesive laminated on the back surface of the base layer.

The resin composition forming the surface layer and the adhesive layer may be blended with various materials that can be contained in the base layer.

A sheet comprising the above-mentioned sheets and a protective layer laminated on the 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 is stretched as necessary and attached to the adherend, it is preferable that the protective layer is made of a film (for example, a thermoplastic resin film or a rubber fill) 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 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, acrylic rubber and the like. It is also possible to use these thermoplastic resins and rubber mixtures. Alternatively, both films may be laminated.

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

Sheets on which the surfaces of the above-mentioned sheets are printed.

The thickness of the photocurable sheet thus obtained is preferably about 20 to 500 μm when it is attached to the surface of an uneven adherend, and 5 to 1,000 μm when it is attached to a flat surface.
It does not matter how much. 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.

[Preparation of photocurable sheet]

The sheet may be prepared by any method. When the sheet has a single layer, the following casting method is preferable.

The curable resin composition is sufficiently dissolved or dispersed in an organic solvent. The resulting solution is coated on a process paper (usually a polyethylene terephthalate film whose surface is treated with silicone, or paper) using a device 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 process paper from the base layer.

When the sheet is formed of a plurality of layers, it can be obtained by a casting method or a laminating method. According to the casting method, a solution containing the resin composition of one of the layers is coated on the process paper and dried to remove the solvent to form a layer, and then the composition of the other layer is formed on this layer. The solution containing the substance is coated and dried for removing the solvent to form another layer. According to the laminating method, a solution containing the resin composition of each layer is separately applied onto the process paper, dried to volatilize the solvent to form each layer, and then both layers are laminated ( Heat it) Press it with a roll press.

The process paper used in the production can be used as a protective sheet.

[Method of using photocurable sheet (method of manufacturing coating)]

Since the photocurable sheet used in the present invention has a certain degree of flexibility and extensibility at room temperature, the shape of the adherend surface can be obtained by heating or stretching without heating, depressurizing, pressing (laminating, etc.). It can be attached to the surface along with. The spreading of the curing sheet and the above-mentioned depressurization or pressurization may be carried out at the same time, or the curable sheet may be spread and then depressurized or pressurized to be attached to the surface of the adherend. Next, at least the pasting portion of the adherend to which the curing sheet is pasted is irradiated with light, and when the sheet contains a peroxide, the sheet is further heated to cure the sheet. According to such a method, not only a plate-shaped member but also a three-dimensional three-dimensional member having irregularities can be easily covered. Further, after the sheet is attached to an adherend, the adherend may be processed into an appropriate shape and then cured.

(Substrate)

Various adherends can be used as the adherend to which the photocurable sheet is attached.

For example, metal plates such as steel plates and aluminum plates; metal plated plates such as galvanized iron and tin plate; wood; gypsum board, cement,
Ceramics such as crockery; steel plate, ceramics, coated plate with resin film laminated on resin material; polyolefin, ABS
Resins, thermoplastic resins such as 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 various acid treatments such as phosphoric acid that are usually performed on steel sheets, alkali treatments, various surface treatments such as solvent treatment, corona discharge treatment, glow discharge treatment, plasma treatment, and ion implantation on the resin surface, and primer treatment. .

[Uses of photocurable sheet]

The photocurable sheet used in the present invention is attached to the surface of various adherends for the purpose of anticorrosion, decoration, display and protection. The use of the sheet is not limited, but examples thereof include the following.

Automotive parts: Exterior and interior of body: Home appliance parts: Housings for refrigerators, washing machines, microwave ovens, etc. Building parts: Outer wall members, inner wall members, rain gutters Painted steel sheet OA housing Daily necessities: Washbasins, poly buckets (Example) Hereinafter, the present invention will be described in detail with reference to Examples. In addition,
"Parts" means "parts by weight". The number of "double bonds per molecule" described in the reactive acrylic resin means the average number of double bonds per molecule.

(A) Preparation of photocurable sheet Example 1 Reactive acrylic resin (manufactured by Nippon Shokubai Chemical Co., Ltd., AEG
-15S, weight average molecular weight = 54,300, double bond per molecule = 26) 100 parts Acrylate monomer (Nippon Kayaku Co., KAYARAD R
604) 80 parts Photoinitiator (Nippon Kayaku Co., Ltd. Kayacure DETX) 1 part Photopolymerization accelerator (Nippon Kayaku Co., Ltd., Kayacure EPA) 2
Part Ethyl acetate 300 parts The above components were mixed with stirring.

This mixture was treated with a silicone release treatment polyethylene terephthalate film (Soken Kako Co., Ltd., film thickness 50μ
m, hereinafter referred to as PET film), and apply at 80 ℃
After being dried 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.

Example 2 Reactive acrylic resin (manufactured by Nippon Shokubai Chemical Co., Ltd., AEG
-15S, weight average molecular weight = 54,300, double bond per molecule = 26) 100 parts Acrylate monomer (Nippon Kayaku Co., KAYARAD R
604) 80 parts Photoinitiator (Nippon Ciba Geigy Co., Ltd., Irgacure 18)
4) 2 parts N-methyldiethanolamine 2 parts Ethyl acetate 300 parts The above components were mixed with stirring.

Apply this mixture to the release surface of PET film and apply at 80 ℃ for 5
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 100 μm.

Example 3 Reactive acrylic resin (manufactured by Nippon Shokubai Chemical Industry Co., Ltd., AEG
-15S, weight average molecular weight = 54,300, double bond per molecule = 26) 100 parts Acrylate monomer (Nippon Kayaku Co., KAYARAD MA)
NDA) 20 parts Acrylate monomer (Nippon Kayaku Co., Ltd., KAYARAD D
PCA20) 80 parts Photoinitiator (Nippon Ciba Geigy Co., Ltd., Irgacure 65)
1) 2 parts N-methyldiethanolamine 2 parts Ethyl acetate 300 parts The above components were mixed with stirring.

Apply this mixture to the release surface of PET film and apply at 80 ℃ for 5
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 50 μm.

Example 4 Reactive acrylic resin (manufactured by Nippon Shokubai Chemical Industry Co., Ltd., AEG
-14S, weight average molecular weight = 80,700, double bond per molecule = 37) 100 parts Acrylate monomer (Nippon Kayaku Co., Ltd., KAYARAD D
PCA-20) 120 parts Photoinitiator (2,4,6, -trimethylbenzoyldiphenylphosphine oxide) 4 parts N-methyldiethanolamine 2 parts Rutile titanium oxide 100 parts Ethyl acetate 300 parts The above components were mixed with stirring.

Apply this mixture to the release surface of PET film and apply at 80 ℃ for 5
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 80 μm.

Example 5 Reactive acrylic resin (manufactured by Nippon Shokubai Chemical Co., Ltd., AEG
-14S, weight average molecular weight = 80,700, double bond per molecule = 37) 100 parts Acrylate monomer (Nippon Kayaku Co., Ltd., KAYARAD D
PHA) 80 parts Acrylate monomer (Nippon Kayaku Co., Ltd., KAYARAD M
ANDA) 40 parts Photoinitiator (Made by MERCK Japan Ltd, Darocur-4043)
6 parts Photoinitiator (Kayacure-DETX manufactured by Nippon Kayaku Co., Ltd.) 0.5 part N-methyldiethanolamine 2 parts Quinacridone 100 parts Ethyl acetate 300 parts The above components were mixed with stirring.

Apply this mixture to the release surface of PET film and apply at 80 ℃ for 5
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 50 μm.

Example 6 Reactive acrylic resin (manufactured by Nippon Shokubai Chemical Co., Ltd., AEG
-14S, weight average molecular weight = 80,700, double bond per molecule = 37) 100 parts Acrylate monomer (Nippon Kayaku Co., KAYARAD R
551) 80 parts Photoinitiator (2,4,6, -trimethylbenzoyldiphenylphosphine oxide) 4 parts N-methyldiethanolamine 2 parts Iron oxide 100 parts Ethyl acetate 300 parts The above components were mixed with stirring.

Apply this mixture to the release surface of PET film and apply at 80 ℃ for 5
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 50 μm.

Example 7 Reactive acrylic resin (manufactured by Nippon Shokubai Chemical Industry Co., Ltd., AEG
-15S, weight average molecular weight = 54,300, double bond per molecule = 26) 100 parts Acrylate monomer (Nippon Kayaku Co., KAYARAD R
604) 80 parts Photoinitiator (2,4,6, -trimethylbenzoyldiphenylphosphine oxide) 2 parts N-methyldiethanolamine 2 parts Ethyl acetate 300 parts The above components were mixed with stirring.

Apply this mixture to the release surface of PET film and apply at 80 ℃ for 5
Allow to dry for minutes. Thickness of the resulting photocurable sheet (PET
The thickness of the sheet other than) was 20 μm (referred to as a clear layer).

Reactive acrylic resin (Nippon Shokubai Chemical Co., Ltd., AEG
-15S, weight average molecular weight = 54,300, double bond per molecule = 26) 100 parts Acrylate monomer (Shin Nakamura Industry Co., Ltd., NPA-10
G) 80 parts Photoinitiator (2,4,6, -trimethylbenzoyldiphenylphosphine oxide) 4 parts N-methyldiethanolamine 2 parts Rutile titanium oxide 100 parts Ethyl acetate 300 parts The above components were mixed with stirring.

This mixture was applied onto the clear layer, dried at 80 ° C. for 5 minutes, and then 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
m).

Example 8 Reactive acrylic resin (manufactured by Nippon Shokubai Chemical Co., Ltd., AEG
-15S, weight average molecular weight = 54,300, double bond per molecule = 26) 100 parts Acrylate monomer (Nippon Kayaku Co., KAYARAD R
604) 80 parts Photoinitiator (2,4,6, -trimethylbenzoyldiphenylphosphine oxide) 2 parts N-methyldiethanolamine 2 parts Ethyl acetate 300 parts The above components were mixed with stirring.

Apply this mixture to the release surface of PET film and apply at 80 ℃ for 5
Allow to dry for minutes. Thickness of the resulting photocurable sheet (PET
The thickness of the sheet other than) was 20 μm (referred to as a clear layer).

Reactive acrylic resin (Nippon Shokubai Chemical Co., Ltd., AEG
-15S, weight average molecular weight = 54,300, double bond per molecule = 26) 100 parts Acrylate monomer (Shin Nakamura Industry Co., Ltd., NPA-10
G) 80 parts Photoinitiator (Nippon Ciba Geigy Co., Ltd., Irgacure 90)
7) 2 parts Photoinitiator (Kayacure-DETX manufactured by Nippon Kayaku Co., Ltd.) 0.5 part N-methyldiethanolamine 2 parts Cyanine blue 100 parts Ethyl acetate 300 parts The above components were mixed with stirring.

This mixture was applied onto the clear layer, dried at 80 ° C. for 5 minutes, and then 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
m).

Example 9 Reactive acrylic resin (methyl methacrylate, butyl methacrylate, acrylic acid copolymer 2-
Reactive acrylic resin with hydroxyethyl methacrylate added, weight average molecular weight = 654,300, average double bond per molecule = 98) 100 parts Acrylate monomer (Nippon Kayaku Co., KAYARAD R
604) 80 parts Photoinitiator (Nippon Ciba Geigy Co., Ltd., Irgacure 18)
4) 2 parts N-methyldiethanolamine 2 parts Ethyl acetate 300 parts The above components were mixed with stirring.

Apply this mixture to the release surface of PET film and apply at 80 ℃ for 5
Allow to dry for minutes. Thickness of the resulting photocurable sheet (PET
The thickness of the sheets other than) was 100 μm (called a clear layer).

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

Example 10 Reactive acrylic resin (methyl methacrylate, butyl methacrylate, acrylic acid copolymer 2-
Reactive acrylic resin added with hydroxyethyl methacrylate, weight average molecular weight = 358,300, average double bond per molecule = 126) 100 parts Acrylate monomer (manufactured by Shin-Nakamura Industry Co., Ltd., NPA-10
G) 80 parts Photoinitiator (2,4,6, -trimethylbenzoyldiphenylphosphine oxide) 4 parts N-methyldiethanolamine 2 parts Rutile titanium oxide 100 parts Ethyl acetate 300 parts The above components were mixed with stirring.

This mixture was applied on a PET film, dried at 80 ° C. for 5 minutes, and then laminated with an ethylene-methyl acrylate film (PE2255 manufactured by Chevron Chemical, film thickness 20 μm) (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 was 70 μm (coloring layer 50 μm + protective layer 20 μm).

Example 11 Reactive acrylic resin (manufactured by Nippon Shokubai Chemical Co., Ltd., AEG
-15S, weight average molecular weight = 54,300, double bond per molecule = 26) 100 parts Acrylate monomer (Nippon Kayaku Co., KAYARAD R
604) 80 parts Photoinitiator (Nippon Kayaku Co., Ltd., Kayacure-DETX) 1 part Photopolymerization accelerator (Nippon Kayaku Co., Ltd., Kayacure EPA) 2
Part Peroxide (Nippon Oil & Fats Co., Ltd., Perbutyl P) 0.5 part Ethyl acetate 300 parts The above components were mixed with stirring.

Apply this mixture to the release surface of PET film and apply at 80 ℃ for 5
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 100 μm.

Example 12 Reactive acrylic resin (manufactured by Nippon Shokubai Chemical Co., Ltd., AEG
-15S, weight average molecular weight = 54,300, double bond per molecule = 26) 100 parts Acrylate monomer (Nippon Kayaku Co., KAYARAD R
604) 80 parts Photoinitiator (Nippon Ciba Geigy Co., Ltd., Irgacure 18)
4) 2 parts Peroxide (manufactured by NOF Corporation, Perbutyl P) 1 part N-methyldiethanolamine 2 parts Ethyl acetate 300 parts The above components were mixed with stirring.

Apply this mixture to the release surface of PET film and apply at 80 ℃ for 5
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 100 μm.

Example 13 Reactive acrylic resin (manufactured by Nippon Shokubai Chemical Co., Ltd., AEG
-15S, weight average molecular weight = 54,300, double bond per molecule = 26) 100 parts Acrylate monomer (Nippon Kayaku Co., KAYARAD M
ANDA) 20 parts Acrylate monomer (Nippon Kayaku Co., Ltd., KAYARAD D
PCA20) 80 parts Photoinitiator (Nippon Ciba Geigy Co., Ltd., Irgacure 65)
1) 2 parts Peroxide (Nippon Oil & Fats Co., Ltd., Perbutyl P) 1 part Peroxide (Nippon Oil & Fats Co., Ltd., Perbutyl Z) 1 part N-methyldiethanolamine 2 parts Ethyl acetate 300 parts While stirring the above Mixed.

Apply this mixture to the release surface of PET film and apply at 80 ℃ for 5
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 50 μm.

Example 14 Reactive acrylic resin (manufactured by Nippon Shokubai Chemical Co., Ltd., AEG
-14S, weight average molecular weight = 80,700, double bond per molecule = 37) 100 parts Acrylate monomer (Nippon Kayaku Co., KAYARAD M
ANDA) 80 parts Photoinitiator (2,4,6, -trimethyl benzoyl diphenylphosphine oxide) 4 parts Peroxide (Nippon Yushi Co., Ltd., Perbutyl Z) 1 part N-methyldiethanolamine 2 parts Rutile titanium oxide 100 parts 300 parts or more of ethyl acetate were mixed with stirring.

Apply this mixture to the release surface of PET film and apply at 80 ℃ for 5
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 80 μm.

Example 15 Reactive acrylic resin (manufactured by Nippon Shokubai Chemical Industry Co., Ltd., AEG
-14S, weight average molecular weight = 80,700, double bond per molecule = 37) 100 parts Acrylate monomer (Nippon Kayaku Co., Ltd., KAYARAD D
PHA) 80 parts Acrylate monomer (Nippon Kayaku Co., Ltd., KAYARAD M
ANDA) 40 parts Photoinitiator (Made by MERCK Japan Ltd, Darocur-4043)
6 parts Photoinitiator (Nippon Kayaku Co., Ltd., Kayacure-DETX) 0.5
Part Peroxide (Perbutyl Z manufactured by NOF CORPORATION) 1 part N-methyldiethanolamine 2 parts Quinacridone 100 parts Ethyl acetate 300 parts The above components were mixed with stirring.

Apply this mixture to the release surface of PET film and apply at 80 ℃ for 5
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 50 μm.

Example 16 Reactive acrylic resin (manufactured by Nippon Shokubai Chemical Co., Ltd., AEG
-14S, weight average molecular weight = 80,700, double bond per molecule = 37) 100 parts Acrylate monomer (Nippon Kayaku Co., KAYARAD R
551) 80 parts Photoinitiator (2,4,6, -trimethyl benzoyl diphenylphosphine oxide) 4 parts Peroxide (Nippon Yushi Co., Ltd., Perhexa 3M) 2 parts N-methyldiethanolamine 2 parts Iron oxide 100 parts Ethyl acetate 300 parts or more were mixed with stirring.

Apply this mixture to the release surface of PET film and apply at 80 ℃ for 5
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 50 μm.

Example 17 Reactive acrylic resin (manufactured by Nippon Shokubai Chemical Co., Ltd., AEG
-15S, weight average molecular weight = 54,300, double bond per molecule = 26) 100 parts Acrylate monomer (Nippon Kayaku Co., KAYARAD M
ANDA) 80 parts Photoinitiator (2,4,6, -trimethylbenzoyl diphenylphosphine oxide) 2 parts Peroxide (Nippon Yushi Co., Ltd., Perhexa 3M) 1 part N-methyldiethanolamine 2 parts Ethyl acetate 300 parts or more Mixed with stirring.

Apply this mixture to the release surface of PET film and apply at 80 ℃ for 5
Allow to dry for minutes. Thickness of the resulting photocurable sheet (PET
The thickness of the sheet other than) was 20 μm (referred to as a clear layer).

Reactive acrylic resin (Nippon Shokubai Chemical Co., Ltd., AEG
-15S, weight average molecular weight = 54,300, double bond per molecule = 26) 100 parts Acrylate monomer (Shin Nakamura Industry Co., Ltd., NPA-10
G) 80 parts Photoinitiator (2,4,6, -trimethylbenzoyl diphenylphosphine oxide) 4 parts Peroxide (Nippon Yushi Co., Ltd., Perhexa 3M) 1 part N-methyldiethanolamine 2 parts Rutile titanium oxide 100 parts 300 parts or more of ethyl acetate were mixed with stirring.

This mixture was applied onto the clear layer, dried at 80 ° C. for 5 minutes, and then 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
m).

Example 18 Reactive acrylic resin (manufactured by Nippon Shokubai Chemical Co., Ltd., AEG
-15S, weight average molecular weight = 54,300, double bond per molecule = 26) 100 parts Acrylate monomer (Nippon Kayaku Co., KAYARAD M
ANDA) 80 parts Photoinitiator (2,4,6, -trimethyl benzoyl diphenylphosphine oxide) 2 parts Peroxide (Nippon Yushi Co., Ltd., Perhexa 3M) 1 part N-methyldiethanolamine 2 parts Ethyl acetate 300 parts or more Mixed with stirring.

Apply this mixture to the release surface of PET film and apply at 80 ℃ for 5
Allow to dry for minutes. Thickness of the resulting photocurable sheet (PET
The thickness of the sheet other than) was 20 μm (referred to as a clear layer).

Reactive acrylic resin (Nippon Shokubai Chemical Co., Ltd., AEG
-15S, weight average molecular weight = 54,300, double bond per molecule = 26) 100 parts Acrylate monomer (manufactured by Shin-Nakamura Industry Co., Ltd., NPA-10
G) 80 parts Photoinitiator (Nippon Ciba Geigy Co., Ltd., Irgacure 90)
7) 2 parts Photoinitiator (Nippon Kayaku Co., Ltd. Kayacure-DETX) 0.5 part Peroxide (Nippon Yushi Co., Ltd., Perhexa 3M) 1 part N-methyldiethanolamine 2 parts Cyanine blue 100 parts Ethyl acetate 300 parts The above was mixed with stirring.

This mixture was applied onto the clear layer, dried at 80 ° C. for 5 minutes, and then 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
m).

Example 19 A reactive acrylic resin (a copolymer of methyl methacrylate, butyl methacrylate and acrylic acid
Reactive acrylic resin with hydroxyethyl methacrylate added, weight average molecular weight = 654,000, average double bond per molecule = 198) 100 parts acrylate monomer (Nippon Kayaku Co., KAYARAD M
ANDA) 80 parts Photoinitiator (Nippon Ciba Geigy Co., Ltd., Irgacure 18)
4) 2 parts Peroxide (manufactured by NOF CORPORATION, perbutyl O) 1 part N-methyldiethanolamine 2 parts Ethyl acetate 300 parts The above components were mixed with stirring.

Apply this mixture to the release surface of PET film and apply at 80 ℃ for 5
Allow to dry for minutes. Thickness of the resulting photocurable sheet (PET
The thickness of the sheets other than) was 100 μm (called a clear layer).

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

Example 20 Reactive acrylic resin (a copolymer of methyl methacrylate, butyl methacrylate and acrylic acid
Reactive acrylic resin added with hydroxyethyl methacrylate, weight average molecular weight = 358,300, average double bond per molecule = 126) 100 parts Acrylate monomer (manufactured by Shin-Nakamura Industry Co., Ltd., NPA-10
G) 80 parts Photoinitiator (2,4,6, -trimethyl benzoyl diphenylphosphine oxide) 4 parts Peroxide (Nippon Yushi Co., Ltd., Perbutyl O) 1.5 parts N-methyldiethanolamine 2 parts Rutile titanium oxide 100 parts 300 parts or more of ethyl acetate were mixed with stirring.

This mixture was applied on a PET film, dried at 80 ° C. for 5 minutes, and then laminated with an ethylene-methyl acrylate film (PE2255 manufactured by Chevron Chemical, film thickness 20 μm) (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 was 70 μm (coloring layer 50 μm + protective layer 20 μm).

(B) Performance evaluation of photocurable sheet Spreadability test Strip-shaped test pieces (20 mm x 50 mm) were obtained by cutting from the photocurable sheets obtained in Examples 1 to 20 and long at room temperature and 80 ° C. A tensile test in the depth direction was performed. As a result, even with 100% elongation, the specimen showed uniform elongation without cracking or cracking.

Coating test Light curable sheet (20 cm x 20 cm) on the convex surface of a steel plate (radius of curvature 50 cm: bottom diameter is 30 cm) curved in a convex lens shape.
Was stretched so that its ends reached both ends of the steel sheet, and the resin layers were opposed to each other and vacuum-pressed at 50 ° C., and good coating was possible without generation of wrinkles.

Performance evaluation of coatings Coatings 1, 2, 3 coated with photocurable sheets 1-20,
9, 11, 12, 19 are 4-8, 10, 14-1 by high pressure mercury lamp
8 and 20 light by metal halide lamp (100mW / cm)
Was irradiated for 60 seconds and 40 seconds from the upper and side surfaces, and the sheets 11 to 20 were further heated at 160 ° C. for 30 minutes to be cured. Then, the hardness of the film was measured by a pencil hardness test according to JIS K5400. The results are shown in Tables 1 and 2.

(Comparative Example) (A) Preparation of Light-Curable Sheet Comparative Example 1 Reactive acrylic resin (methyl methacrylate, butyl methacrylate, acrylic acid copolymer 2-
Reactive acrylic resin with hydroxyethyl methacrylate added, weight average molecular weight = 21,300, average double bond per molecule = 6) 100 parts Acrylate monomer (Nippon Kayaku Co., KAYARAD M
ANNDA) 80 parts Photoinitiator (Nippon Ciba Geigy Co., Ltd., Irgacure)
184) 4 parts Ethyl acetate 300 parts The above components were mixed with stirring.

Apply this mixture to the release surface of PET film and apply at 80 ℃ for 5
Allow to dry for minutes. When the obtained photocurable sheet was tried to be peeled from PET, the photocurable sheet was inferior in self-supporting property and could not be peeled off.

Comparative Example 2 Reactive acrylic resin (methyl methacrylate, butyl methacrylate, acrylic acid copolymer 2-
Reactive acrylic resin with hydroxyethyl methacrylate added, weight average molecular weight = 1,151,300, average double bond per molecule = 330) 100 parts Acrylate monomer (Nippon Kayaku Co., KAYARAD D)
PCA) 120 parts Photoinitiator (Nippon Ciba Geigy Co., Ltd., Irgacure)
184) 4 parts Ethyl acetate 150 parts The above was stirred, but it was difficult to uniformly dissolve the reactive acrylic resin.

Comparative Example 3 Reactive acrylic resin (methyl methacrylate, butyl methacrylate, acrylic acid copolymer 2-
Reactive acrylic resin with hydroxyethyl methacrylate added, weight average molecular weight = 21,300, average double bond per molecule = 6) 100 parts Acrylate monomer (Nippon Kayaku Co., KAYARAD R
551) 80 parts Photoinitiator (Nippon Ciba Geigy Co., Ltd., Irgacure)
184) 4 parts Ethyl acetate 150 parts The above components were mixed with stirring.

This mixture was applied on a PET film, dried at 80 ° C. for 5 minutes, and then laminated with an ethylene-methyl acrylate film (PE2255 manufactured by Chevron Chemical, film thickness 20 μm) (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 (clear layer 50 μm +
The protective layer was 20 μm).

Comparative Example 4 Reactive acrylic resin (methyl methacrylate, butyl methacrylate, acrylic acid copolymer 2-
Reactive acrylic resin with hydroxyethyl methacrylate added, weight average molecular weight = 21,300, average double bond per molecule = 6) 100 parts Acrylate monomer (Nippon Kayaku Co., KAYARAD M
ANNDA) 80 parts Photoinitiator (Nippon Ciba Geigy Co., Ltd., Irgacure)
184) 4 parts Peroxide (manufactured by NOF CORPORATION, perbutyl O) 1.5 parts Ethyl acetate 300 parts The above components were mixed with stirring.

Apply this mixture to the release surface of PET film and apply at 80 ℃ for 5
Allow to dry for minutes. When the obtained photocurable sheet was tried to be peeled from PET, the photocurable sheet was inferior in self-supporting property and could not be peeled off.

Comparative Example 5 Reactive acrylic resin (methylmethacrylate, butylmethacrylate, acrylic acid copolymer 2-
Reactive acrylic resin with hydroxyethyl methacrylate added, weight average molecular weight = 1,151,300, average double bond per molecule = 330) 100 parts Acrylate monomer (Nippon Kayaku Co., KAYARAD D)
PCA) 120 parts Photoinitiator (Nippon Ciba Geigy Co., Ltd., Irgacure)
184) 4 parts Peroxide (manufactured by NOF Corporation, Perbutyl O) 1.5 parts Ethyl acetate 150 parts The above was stirred, but it was difficult to uniformly dissolve the reactive acrylic resin.

Comparative Example 6 Reactive acrylic resin (a copolymer of methyl methacrylate, butyl methacrylate and acrylic acid
Reactive acrylic resin with hydroxyethyl methacrylate added, weight average molecular weight = 21,300, average double bond per molecule = 6) 100 parts Acrylate monomer (Nippon Kayaku Co., KAYARAD R
551) 80 parts Photoinitiator (Nippon Ciba Geigy Co., Ltd., Irgacure)
184) 4 parts Peroxide (manufactured by NOF CORPORATION, perbutyl O) 1.5 parts Ethyl acetate 150 parts The above components were mixed with stirring.

This mixture was applied on a PET film, dried at 80 ° C. for 5 minutes, and then laminated with an ethylene-methyl acrylate film (PE2255 manufactured by Chevron Chemical, film thickness 20 μm) (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 (clear layer 50 μm +
The protective layer was 20 μm).

(B) Performance evaluation of photocurable sheet Spreadability test A strip-shaped test piece (20 mm x 50 mm) was cut from the photocurable sheet obtained in Comparative Examples 3 and 6, and was cut at room temperature and 80 ° C for a long time. A tensile test in the vertical direction was performed. When stretched 100%,
The photocurable sheet was cracked.

(Effect of the invention) The constitution of the method for producing a coated article of the present invention is as described above,
The photocurable sheet before application has excellent spreadability, flexibility and extensibility, and can be favorably applied by stretching it on the surface of an adherend having not only a flat surface but also irregularities or a curved surface. Further, this light-curable sheet can form a strong coating excellent in hardness and scratch resistance by irradiating light, and obtain a coating having a coating excellent in impact resistance and scratch resistance. Can be done.

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Claims (2)

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