JPH0722969B2 - Method of manufacturing coated products - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a coated body having a hard coating on the surface, and more specifically, for corrosion prevention, decoration, display, etc.
The present invention relates to a method for producing a coated body in which a coating sheet is attached and cured on the surface of a coated article.

(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 coating 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 to be solved by the invention) However, when attached to a three-dimensional article, it is necessary to stretch the sheet, but the composite sheet having a photocurable pressure-sensitive adhesive layer used in JP-B-61-61873 is Since a polyvinyl chloride sheet or the like is used as the self-supporting sheet, the stretchability is poor without heating, and when the sheet is heated and stretched, the adhesive layer is deformed. Further, the DFR sheet is insufficient in the spreadability of the sheet before curing and the adhesion, hardness, and impact resistance between the coating film and the adherend after curing.

The present invention is to solve the above-mentioned drawbacks, and an object of the present invention is that the work at the time of application is easy even for an article having unevenness or a curved surface, and it is uniform and has impact resistance and scratch resistance ( It is intended to provide a method for producing a coated article using a curable sheet capable of forming a coating having excellent surface hardness).

(Means for Solving the Problems) The method for producing a coated article according to claim 1 of the present invention comprises:
(A) a thermoplastic acrylic resin having a weight average molecular weight of 50,000 to 1,000,000 and solid at room temperature, (b) a low molecular weight product having a (meth) acryloyl group in the molecule, (c)
A step of attaching a curable sheet containing a photoinitiator as a main component to an adherend, and a step of curing the sheet by irradiating the sheet attached to the adherend with light. However, the above-mentioned object is achieved thereby.

Further, the method for producing a coated article according to claim 2 of the present invention comprises: (a) a thermoplastic acrylic resin having a weight average molecular weight of 50,000 to 1,000,000 and solid at room temperature; and (b) (meth) acryloyl in the molecule. A low molecular weight product having a group,
A step of attaching a curable sheet containing (c) a photoinitiator and (d) a peroxide as main components to an adherend, and irradiating the sheet attached to the adherend with light. And curing the sheet by heating the sheet, whereby the above object is achieved.

The present invention will be described in detail below.

The curable sheet used in the present invention, when used as a sheet that is cured only by light irradiation, (a) a thermoplastic acrylic resin having a weight average molecular weight of 50,000 to 1,000,000 and solid at room temperature, and (b) When a low molecular weight product having a (meth) acryloyl group in the molecule and (c) a photoinitiator as main components and used as a sheet which is cured by light irradiation and heating, (d) peroxide is further added. Is the main component.

The thermoplastic acrylic resin contained in the sheet is an acrylic acid ester-based polymer, and examples of the acrylic acid ester-based polymer include (meth) methyl acrylate and (meth) butyl acrylate. There are polymers of acrylic acid esters such as propyl (meth) acrylate, and copolymers of these acrylic acid esters and styrenic monomers, and their blends can also be used.

Weight average molecular weight (Mw) of these thermoplastic acrylic resins
Can be changed depending on the conditions when carrying out the polymerization reaction using a reaction initiator. The thermoplastic acrylic resin used in the present invention has a weight average molecular weight of 50,000 to 1,
Those in the range of, 000,000 are selected. Weight average molecular weight is 50,
When it is less than 000, it becomes difficult to maintain the shape of the obtained sheet, sufficient elongation cannot be obtained with respect to the stretching during the sticking operation, and cracks may occur. When the weight average molecular weight exceeds 1,000,000, the solubility in a solvent becomes poor and it becomes difficult to prepare a sheet from the photocurable resin composition. For example, when creating a sheet by solvent casting, the solvent viscosity increases when the weight average molecular weight of the thermoplastic acrylic resin exceeds 1,000,000, so the resin can be cast only at a low concentration, and therefore the thickness of the sheet should be increased. Becomes difficult. These thermoplastic acrylic resins preferably have a Tg (glass transition point) in the range of -20 ° C to 120 ° C in view of the hardness after curing the sheet. As the thermoplastic acrylic resin, different kinds of materials may be used in combination as long as they have these molecular weight ranges.

The low molecular weight product having a (meth) acryloyl group in the molecule contained in the sheet means a low molecular weight product having an acryloyl group or a methacryloyl group, for example, methyl (meth) acrylate, ethyl (meth) acrylate,
Monofunctional type such as benzyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, and 1,6-
Hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, penta There are polyfunctional types such as erythritol tetra (meth) acrylate and dipentaerythritol hexa (meth) acrylate. Also,
There are also oligomers such as polyester acrylate, polyurethane acrylate, epoxy acrylate, polyether acrylate, oligo acrylate, alkyd acrylate and polyol acrylate.

The low molecular weight substance is added in order to plasticize the main thermoplastic acrylic resin and to impart high hardness after curing the curable sheet. Therefore, the addition amount is almost related to the Tg of the thermoplastic acrylic resin and the viscosity of the low molecular weight substance to be added. For example, when using a thermoplastic acrylic resin with Tg = 60 to 100 ° C, the viscosity is 500 cps (25
It is preferable to add 10 to 150 parts by weight of a low molecular weight substance having a viscosity of 500 cps (25 ° C.) or more to 50 parts by weight to 100 parts by weight of a thermoplastic acrylic resin.
If the addition amount is too small, sufficient elongation of the sheet cannot be obtained. 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.

The photoinitiator can be used those commonly used,
For example, benzoin alkyl ether-based, acetophenone-based, benzophenone-based, thioxanthone-based photoinitiators 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 normal organic peroxide can be used as the above-mentioned peroxide. From the viewpoint of storage stability at room temperature, more preferable is an organic peroxide having a decomposition temperature of 160 ° C or higher. For example, 2,2-bis (ter-butylperoxy) butane, ter
-Butyl peroxybenzoate, di-ter-butyl peroxyisophthalate, methyl ethyl ketone peroxide, dicumyl peroxide, ter-butyl peroxyacetate. The addition amount of the peroxide is preferably in the range of 0, 5 to 5, 0 parts by weight with respect to 100 parts by weight of the low molecular weight product having the (meth) acryloyl group. Further, the peroxide is not limited to one type, and two or more types may be used in combination. By adding these peroxides, it is possible to further harden the portion which is hard to be hardened by irradiation with light.

The thermosetting sheet used in the present invention may further contain materials such as pigments, colorants such as dyes, and antioxidants, 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. Further, aluminum flakes, metal powder such as nickel powder, gold powder, silver powder and the like may be used as the colorant. It is preferable that these materials are fine particles. When a coloring agent having a high hiding property is used, the addition amount thereof is preferably in the range of 2 to 400 parts by weight with respect to 100 parts by weight of the solid content of the resin. 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 curable 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 curable 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 curable sheet is a single layer, the base layer becomes the curable 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.

The sheet formed on the surface layer, when viewing the sheet,
Gives a sense of depth to the seat.

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 layer 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 composed of a film (for example, a thermoplastic resin film or a rubber film) having a malleability 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 and acrylic rubber. It is also possible to use these thermoplastic resins and rubber mixtures. Alternatively, both films may be laminated.

The protective layer may be peeled 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.

A sheet with the surface of the above-mentioned sheets printed.

The thickness of the curable sheet thus obtained is preferably about 20 to 500 μm when it is attached to the surface of an uneven adherend, and may be about 5 to 1,000 μm when it is attached to a flat surface. The thickness of the other layers laminated on the above-mentioned sheet is usually 10 to 500 μm, and the thickness of the adhesive layer is particularly preferably 10 to 100 μm.

[Preparation of Curable 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 curable sheet (method of manufacturing coated product)]

The curable sheet used in the present invention has a certain degree of flexibility and extensibility at room temperature, so that it is uncured or semi-cured (light is irradiated for a short time or is heated for a short time) and is stretched without heating or heating. By adhering to the surface of the adherend, it can be attached to the surface by an operation such as depressurization, pressurization (laminating, etc.). The spreading of the curable sheet and the above-mentioned depressurization or pressurization may be performed 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 attachment portion of the adherend on which the curable sheet is attached is irradiated with light to cure the sheet. When the sheet contains a peroxide as a component, the sheet is cured by light irradiation and heating. 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)

As the adherend to which the curable sheet used in the present invention is attached, various adherends can be used.

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 ceramics; steel plate, ceramics, coated plate with resin film laminated on resin material; thermoplastic resin such as polyolefin, ABS resin, polyphenylene sulfide (PPS) and polyetherimide; melamine resin, epoxy resin, phenol resin , Thermosetting resin such as 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 curable sheet]

The curable sheet used in the present invention is attached and cured on 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 based on Examples. In addition, "part" means "part by weight".

(A) Preparation of curable sheet Example 1 100 parts of acrylic resin (Kyowa Gas Chemical Co., Ltd., Parapet beads G1P8) Acrylate monomer (Nippon Kayaku Co., Ltd., KAYARAD DP)
CA-20) 100 parts Photopolymerization accelerator (Nippon Kayaku Co., Ltd., KAYACURE EPA) 2 parts Photoinitiator (Nippon Kayaku Co., Ltd., Kayacure DETX) 1.0
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 coated on the release surface at 80 ℃
After drying for 5 minutes, the PET film was peeled off to obtain an uncured curable sheet. The thickness of the obtained curable sheet was 100 μm.

Example 2 100 parts of acrylic resin (Kyowa Gas Chemical Co., Ltd., Parapet beads G1P8) Acrylate monomer (Nippon Kayaku Co., Ltd., KAYARAD R5)
51) 80 parts Photoinitiator (Nippon Ciba Geigy Co., Ltd., Irgacure)
184) 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 being dried for a minute, the PET film was peeled off to obtain a curable sheet in an uncured state. The thickness of the obtained curable sheet was 100 μm.

Example 3 100 parts of acrylic resin (Kyowa Gas Chemical Co., Ltd., parapet beads EH1000P) Acrylate monomer (Nippon Kayaku Co., Ltd., KAYARAD MA)
NDA) 20 parts Acrylate monomer (Nippon Kayaku Co., Ltd., KAYARAD DP
CA20) 80 parts photoinitiator (manufactured by Nippon Ciba Geigy Ltd., Irgacure)
651) 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 being dried for a minute, the PET film was peeled off to obtain a curable sheet in an uncured state. The thickness of the obtained curable sheet was 50 μm.

Example 4 100 parts of acrylic resin (Kyowa Gas Chemical Co., Ltd., Parapet beads EH1000P) Acrylate monomer (Nippon Kayaku Co., Ltd., KAYARAD R5)
51) 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.

Apply this mixture to the release surface of PET film and apply at 80 ℃ for 5
After being dried for a minute, the PET film was peeled off to obtain a curable sheet in an uncured state. The thickness of the obtained curable sheet was 80 μm.

Example 5 Acrylic resin (Delpet 8200, manufactured by Asahi Kasei Corporation)
100 parts acrylate monomer (Nippon Kayaku Co., Ltd., KAYARAD DP
HA) 80 parts Acrylate monomer (Nippon Kayaku Co., Ltd., KAYARAD R6
04) 40 parts Photoinitiator (Made by MERCK Japan Ltd, Darocur 4043) 6
Part photoinitiator (Nippon Kayaku Co., Ltd., Kayacure DETX) 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 being dried for a minute, the PET film was peeled off to obtain a curable sheet in an uncured state. The thickness of the obtained curable sheet was 50 μm.

Example 6 Acrylic resin (Kyowa Gas Chemical Co., Ltd., Parapet beads (G1P8) 100 parts Acrylate monomer (Nippon Kayaku Co., Ltd., KAYARAD R5)
51) 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 being dried for a minute, the PET film was peeled off to obtain a curable sheet in an uncured state. The thickness of the obtained curable sheet was 50 μm.

Example 7 100 parts of acrylic resin (Kyowa Gas Chemical Co., Ltd., Parapet beads EH1000P) Acrylate monomer (Nippon Kayaku Co., Ltd., KAYARAD MA)
NDA) 80 parts Photoinitiator (2,4,6, -trimethylbenzoyldiphenylphosphine oxide) 2.0 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. The thickness of the obtained curable sheet (thickness of sheets other than PET) was 20 μm (referred to as a clear layer).

Acrylic resin (Kyowa Gas Chemical Co., Ltd., Parapet beads EH1000P) 100 parts Acrylate monomer (Shin Nakamura Kogyo Co., Ltd., NPA-10
G) 80 parts Photoinitiator (2,4,6, -trimethylbenzoyldiphenylphosphine oxide) 4 parts N-methyldiethanolamine 2.0 parts Rutin-type 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 being dried for a minute, the PET film was peeled off to obtain a curable sheet in an uncured state. The thickness of the obtained curable sheet was 70 μm (clear layer 20 μm, colored layer 50 μm
m).

Example 8 100 parts of acrylic resin (Kyowa Gas Chemical Co., Ltd., Parapet beads G1P8) Acrylate monomer (Nippon Kayaku Co., Ltd., KAYARAD MA)
NDA) 80 parts Photoinitiator (2,4,6, -trimethylbenzoyldiphenylphosphine oxide) 2.0 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. The thickness of the obtained curable sheet (thickness of sheets other than PET) was 20 μm (referred to as a clear layer).

Acrylic resin (Kyowa Gas Chemical Co., Ltd., Parapet beads EH1000P) 100 parts Acrylate monomer (Shin Nakamura Kogyo Co., Ltd., NPA-10
G) 80 parts Photoinitiator (Nippon Ciba Geigy Co., Ltd., Irgacure)
907) 2.0 parts Photoinitiator (Kayakyu 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.

Apply this mixture to the release surface of PET film and apply at 80 ℃ for 5
After being dried for a minute, the PET film was peeled off to obtain a curable sheet in an uncured state. The thickness of the obtained curable sheet was 70 μm (clear layer 20 μm, colored layer 50 μm
m).

Example 9 100 parts of acrylic resin (Kyowa Gas Chemical Co., Ltd., Parapet beads G1P8) Acrylate monomer (Nippon Kayaku Co., Ltd., KAYARAD R5)
51) 80 parts Photoinitiator (Nippon Ciba Geigy Co., Ltd., Irgacure)
184) 2 parts N-methyldiethanolamine 2.0 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. The thickness of the resulting curable sheet (thickness of sheets other than PET) was 100 μm (referred to as a clear layer).

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

Example 10 Acrylic resin (Kyowa Gas Chemical Co., Ltd., Parapet beads EH1000P) 100 parts Acrylate monomer (Shin Nakamura Kogyo KK, NPA-10)
G) 80 parts Photoinitiator (2,4,6, -trimethylbenzoyldiphenylphosphine oxide) 4 parts N-methyldiethanolamine 2.0 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 removing the PET film, a curable sheet in an uncured state was obtained. The thickness of the obtained curable sheet was 70 μm (coloring layer 50 μm, protective layer 20 μm
m).

Example 11 Acrylic resin (Kyowa Gas Chemical Co., Ltd., Parapet beads G1P8) 100 parts Acrylate monomer (Nippon Kayaku Co., Ltd., KAYARAD R6)
04) 80 parts Photopolymerization accelerator (Nippon Kayaku Co., Ltd., KAYACURE EPA) 2 parts Photoinitiator (Nippon Kayaku Co., Ltd., Kayacure DETX) 1.0
Part Peroxide (Nippon Yushi Co., Ltd., Perbutyl Z) 0.5 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 a PET film), and dried at 80 for 5 minutes, and then the PET film was peeled off to obtain an uncured curable sheet. The thickness of the obtained curable sheet was 100 μm.

Example 12 100 parts of acrylic resin (Kyowa Gas Chemical Co., Ltd., Parapet beads G1P8) Acrylate monomer (Nippon Kayaku Co., Ltd., KAYARAD R5)
51) 80 parts Photoinitiator (Nippon Ciba Geigy Co., Ltd., Irgacure)
184) 2 parts Peroxide (manufactured by NOF CORPORATION, Perbutyl Z) 0.5 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 being dried for a minute, the PET film was peeled off to obtain a curable sheet in an uncured state. The thickness of the obtained curable sheet was 100 μm.

Example 13 100 parts of acrylic resin (Kyowa Gas Chemical Co., Ltd., Parapet beads EH1000P) Acrylate monomer (Nippon Kayaku Co., Ltd., KAYARAD MA)
NDA) 20 parts Acrylate monomer (Nippon Kayaku Co., Ltd., KAYARAD DP
CA20) 80 parts photoinitiator (manufactured by Nippon Ciba Geigy Ltd., Irgacure)
651) 2 parts Peroxide (manufactured by NOF CORPORATION, Perbutyl P) 0.5 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 being dried for a minute, the PET film was peeled off to obtain a curable sheet in an uncured state. The thickness of the obtained curable sheet was 50 μm.

Example 14 Acrylic resin (Kyowa Gas Chemical Co., Ltd., Parapet beads EH1000P) 100 parts Acrylate monomer (Nippon Kayaku Co., Ltd., KAYARAD R5)
51) 80 parts Photoinitiator (2,4,6, -trimethyl benzoyl diphenylphosphine oxide) 4 parts Peroxide (manufactured by NOF Corporation, perbutyl P) 0.5 part Peroxide (manufactured by NOF Corporation, Perbutyl Z) 0.5 part 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 being dried for a minute, the PET film was peeled off to obtain a curable sheet in an uncured state. The thickness of the obtained curable sheet was 80 μm.

Example 15 Acrylic resin (Asahi Kasei Kogyo KK, Delpet 8200)
100 parts acrylate monomer (Nippon Kayaku Co., Ltd., KAYARAD DP
HA) 80 parts Acrylate monomer (Nippon Kayaku Co., Ltd., KAYARAD MA
NDA) 20 parts photoinitiator (Made by MERCK Japan Ltd, Darocur 4043) 6
Part photoinitiator (Nippon Kayaku Co., Ltd., Kayacure DETX) 0.5
Part Peroxide (manufactured by NOF CORPORATION, Perhexa 3M) 2.0 parts 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 being dried for a minute, the PET film was peeled off to obtain a curable sheet in an uncured state. The thickness of the obtained curable sheet was 50 μm.

Example 16 Acrylic resin (Kyowa Gas Chemical Co., Ltd., parapet beads (G1P8) 100 parts Acrylate monomer (Nippon Kayaku Co., Ltd., KAYARAD R5)
51) 80 parts Photoinitiator (2,4,6, -trimethylbenzoyldiphenylphosphine oxide) 4 parts Peroxide (Nippon Yushi Co., Ltd., Perhexa 3M) 2.0 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 being dried for a minute, the PET film was peeled off to obtain a curable sheet in an uncured state. The thickness of the obtained curable sheet was 50 μm.

Example 17 100 parts of acrylic resin (Kyowa Gas Chemical Co., Ltd., Parapet beads EH1000P) Acrylate monomer (Nippon Kayaku Co., Ltd., KAYARAD MA)
NDA) 80 parts Photoinitiator (2,4,6, -trimethylbenzoyl diphenylphosphine oxide) 2.0 parts Peroxide (Nippon Yushi Co., Ltd., Perhexa 3M) 2.0 parts 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. The thickness of the obtained curable sheet (thickness of sheets other than PET) was 20 μm (referred to as a clear layer).

Acrylic resin (Kyowa Gas Chemical Co., Ltd., Parapet beads EH1000P) 100 parts Acrylate monomer (Shin Nakamura Kogyo Co., Ltd., NPA-10
G) 80 parts Photoinitiator (2,4,6, -trimethyl benzoyl diphenylphosphine oxide) 4 parts Peroxide (Nippon Yushi Co., Ltd., Perhexa 3M) 2.0 parts N-methyldiethanolamine 2.0 parts Rutile titanium oxide 100 parts 300 parts of ethyl acetate The above components were mixed with stirring.

This mixture was applied on the clear layer, dried at 80 ° C. for 5 minutes, and then the PET film was peeled off to obtain an uncured curable sheet. The thickness of the obtained curable sheet was 70 μm (clear layer 20 μm, colored layer 50 μm).

Example 18 100 parts of acrylic resin (Kyowa Gas Chemical Co., Ltd., Parapet beads G1P8) Acrylate monomer (Nippon Kayaku Co., Ltd., KAYARAD MA)
NDA) 80 parts Photoinitiator (2,4,6, -trimethyl benzoyl diphenylphosphine oxide) 2.0 parts Peroxide (Nippon Yushi Co., Ltd., Perhexa 3M) 1.0 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. The thickness of the obtained curable sheet (thickness of sheets other than PET) was 20 μm (referred to as a clear layer).

Acrylic resin (Kyowa Gas Chemical Co., Ltd., Parapet beads EH1000P) 100 parts Acrylate monomer (Shin Nakamura Kogyo Co., Ltd., NPA-10
G) 80 parts Photoinitiator (Nippon Ciba Geigy Co., Ltd., Irgacure)
907) 2.0 parts Photoinitiator (Kayakyu DETX manufactured by Nippon Kayaku Co., Ltd.) 0.5 part Peroxide (Nippon Yushi Co., Ltd., Perhexa 3M) 1.0 N methyldiethanolamine 2 parts Cyanine blue 100 parts Ethyl acetate 300 parts or more Mixed with stirring.

This mixture was applied on the clear layer, dried at 80 ° C. for 5 minutes, and then the PET film was peeled off to obtain an uncured curable sheet. The thickness of the obtained curable sheet was 70 μm (clear layer 20 μm, colored layer 50 μm).

Example 19 100 parts of acrylic resin (Kyowa Gas Chemical Co., Ltd., Parapet beads G1P8) Acrylate monomer (Nippon Kayaku Co., Ltd., KAYARAD R5)
51) 80 parts Photoinitiator (Nippon Ciba Geigy Co., Ltd., Irgacure)
184) 2 parts Peroxide (manufactured by NOF CORPORATION, perbutyl O) 1.0 part N-methyldiethanolamine 2.0 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. The thickness of the resulting curable sheet (thickness of sheets other than PET) was 100 μm (referred to as a clear layer).

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

Example 20 Acrylic resin (Kyowa Gas Chemical Co., Ltd., Parapet beads EH1000P) 100 parts Acrylate monomer (Shin Nakamura Kogyo KK, NPA-10
G) 80 parts Photoinitiator (2,4,6, -trimethylbenzoyldiphenylphosphine oxide) 4 parts Peroxide (Nippon Yushi Co., Ltd., Perbutyl O) 1.0 part N-methyldiethanolamine 2.0 parts Rutile titanium oxide 100 parts 300 parts of ethyl acetate The above components were mixed with stirring.

This mixture was applied on a PET film and dried at 80 ° C. for 5 minutes, and then an 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, a curable sheet in an uncured state was obtained. The thickness of the obtained curable sheet was 70 μm (coloring layer 50 μm, protective layer 20
μm).

(B) Performance evaluation of curable sheet Spreadability test Strip-shaped test pieces (20 mm x 50 mm) were cut from the curable sheets obtained in Examples 1 to 20 to obtain lengthwise direction at room temperature and 80 ° C. Was subjected to a tensile test. As a result, even with 100% elongation, the specimen showed uniform elongation without cracking or cracking.

Coating test A curable sheet (20 cm x 20 cm) is placed on the convex surface of a steel plate (radius of curvature 50 cm: bottom diameter is 30 cm) curved in the shape of a convex lens.
When the resin layer was spread so that its ends reached both ends of the steel sheet, and the resin layer was opposed to the convex side and vacuum-pressed at 50 ° C., good coating could be performed without wrinkles.

Performance evaluation of coatings Coatings coated with curable sheets 1-20 1,2,3,9,11,12,1
3,19 are high pressure mercury lamps 4,5,6,7,8,10,14,15,16,17,18,
20 is a metal halide lamp that emits light (100 mW / cm) from the top and side for 30 seconds and 20 seconds, respectively,
Coatings 1-5 and 11-15 are 5 minutes at 160 ℃, 6-8 and 16-18
Was heated at 130 ° C. for 5 minutes, and 9,10 and 19,20 were heated at 110 ° C. for 5 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 Table 1.

(Comparative Example) (A) Preparation of Curable Sheet Comparative Example 1 Acrylic resin (copolymer of methyl methacrylate and butyl methacrylate, weight average molecular weight 14,000) 100
Part Acrylic monomer (Nippon Kayaku Co., Ltd.
NNDA) 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 curable sheet was peeled from PET, the curable sheet was inferior in self-supporting property and could not be peeled off.

Comparative Example 2 Acrylic resin (copolymer of methyl methacrylate and butyl methacrylate, weight average molecular weight of 1,280,000) 1
00 parts acrylate monomer (Nippon Kayaku Co., Ltd., KAYARAD DP
CA) 120 parts Photoinitiator (Nippon Ciba Geigy Co., Ltd., Irgacure)
184) 4 parts Ethyl acetate 150 parts The above components were stirred, but it was difficult to uniformly dissolve the thermoplastic acrylic resin.

Comparative Example 3 Acrylic resin (copolymer of methyl methacrylate and butyl methacrylate, weight average molecular weight 32,000) 100
Part Acrylate monomer (Nippon Kayaku Co., Ltd., KAYARAD R5
51) 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 and dried at 80 ° C. for 5 minutes, and then an ethylene-methyl acrylate film (PE2255 manufactured by Chevron Chemical, film thickness 20 μm) was laminated (protective layer). By peeling off the PET film, a curable sheet in an uncured state was obtained. The thickness of the obtained curable sheet was 70 μm (clear layer 50 μm, protective layer 20 μm
m).

Comparative Example 4 Acrylic resin (copolymer of methyl methacrylate and butyl methacrylate, weight average molecular weight 14,000) 100
Part Acrylic monomer (Nippon Kayaku Co., Ltd., KAYARAD MA)
NNDA) 80 parts Photoinitiator (Nippon Ciba Geigy Co., Ltd., Irgacure)
184) 4 parts Peroxide (manufactured by NOF CORPORATION, perbutyl O) 1.0 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
Allow to dry for minutes. When the obtained curable sheet was peeled from PET, the curable sheet was inferior in self-supporting property and could not be peeled off.

Comparative Example 5 Acrylic resin (copolymer of methyl methacrylate and butyl methacrylate, weight average molecular weight of 1,280,000) 1
00 parts acrylate monomer (Nippon Kayaku Co., Ltd., KAYARAD DP
CA) 120 parts Photoinitiator (Nippon Ciba Geigy Co., Ltd., Irgacure)
184) 4 parts Peroxide (manufactured by NOF CORPORATION, Perbutyl O) 1.0 part Ethyl acetate 150 parts The above was stirred, but it was difficult to uniformly dissolve the thermoplastic acrylic resin.

Comparative Example 6 Acrylic resin (copolymer of methyl methacrylate and butyl methacrylate, weight average molecular weight 32,000) 100
Part Acrylate monomer (Nippon Kayaku Co., Ltd., KAYARAD DP
CA-20) 80 parts Photoinitiator (Nippon Ciba Geigy Co., Ltd., Irgacure)
184) 4 parts Peroxide (manufactured by NOF CORPORATION, perbutyl O) 1.0 part Ethyl acetate 150 parts The above components were mixed with stirring.

This mixture was applied onto a PET film and dried at 80 ° C. for 5 minutes, and then an ethylene-methyl acrylate film (PE2255 manufactured by Chevron Chemical, film thickness 20 μm) was laminated (protective layer). By peeling off the PET film, a curable sheet in an uncured state was obtained. The thickness of the obtained curable sheet was 70 μm (clear layer 50 μm, protective layer 20 μm
m).

(B) Performance evaluation of curable sheet Spreadability test A strip-shaped test piece (20 mm x 50 mm) was cut from the curable sheet obtained in Comparative Examples 3 and 6 in which a sheet could be prepared, and obtained at room temperature and 80 ° C. Was subjected to a tensile test in the length direction. 100
When the film was stretched%, cracks were generated in all the curable sheets.

(Effect of the invention) The constitution of the method for producing a coated article of the present invention is as described above,
The curable 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 flat surfaces but also irregularities and curved surfaces. Further, this curable sheet can form a strong coating film excellent in hardness and scratch resistance by irradiating light, or by heating while irradiating light, and has excellent impact resistance and scratch resistance. A coated article having a coating can be obtained.

Claims (2)

[Claims] 1. A weight average molecular weight of 50,000 to 1,000,00
A thermosetting acrylic resin which is 0 and is solid at room temperature; (b) a low molecular weight product having a (meth) acryloyl group in the molecule; and (c) a photoinitiator as a main component, A method for producing a coated article, comprising: a step of sticking to an adherend; and a step of curing the sheet by irradiating the sheet stuck to the adherend with light. 2. A weight average molecular weight of 50,000 to 1,000,00.
0, which is a solid at room temperature and is mainly a thermoplastic acrylic resin, (b) a low molecular weight product having a (meth) acryloyl group in the molecule, (c) a photoinitiator, and (d) a peroxide. A step of attaching a curable sheet as a component to an adherend, and irradiating the sheet attached to the adherend with light;
And a step of curing the sheet by heating the sheet, the method for producing a coated article.