JPH07103245B2 - Method of manufacturing coated products - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a coated article having a hard coating provided on the surface thereof. Specifically, for the purpose of anticorrosion, decoration, display, etc., a coating sheet is applied and cured on the surface of the coated article. The present invention relates to a method for manufacturing 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 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 curing sheet capable of forming a coating excellent in impact resistance and scratch resistance (surface hardness).

(Means for Solving the Problems) The method for producing a coated article according to the present invention comprises (a) a hydroxyl group in the molecule,
A reactive acrylic resin having a plurality of at least one functional group selected from the group consisting of an amino group and a carboxyl group and a (meth) acryloyl group, and having a weight average molecular weight of 50,000 to 1,000,000 and being solid at room temperature; (B) a low molecular weight product having a (meth) acryloyl group in the molecule,
A curable sheet containing (c) a photoinitiator and (d) at least one crosslinking agent selected from the group consisting of an isocyanate-based crosslinking agent, a melamine-based crosslinking agent and an epoxy-based crosslinking agent as a main component is coated. The sheet is attached to a body and then irradiated with light to cure the sheet, thereby achieving the above object.

The present invention will be described in detail below.

The curable sheet used in the present invention has (a) a plurality of at least one functional group selected from the group consisting of a hydroxyl group, an amino group and a carboxyl group and a (eth) acryloyl group in the molecule, and has a weight average. Molecular weight 50,000-1,000,
A solid-state reactive acrylic resin having a temperature of 000, or the reactive acrylic resin having a plurality of (meth) acryloyl groups in its molecule together with at least one functional group selected from the above group; A low molecular weight compound having a (meth) acryloyl group in the molecule, (c) a photoinitiator,
(D) At least one crosslinking agent selected from the group consisting of an isocyanate crosslinking agent, a melamine crosslinking agent and an epoxy crosslinking agent as a main component.

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. To add a monomer having a (meth) acryloyl group to a copolymer obtained by copolymerization with an acid-based monomer in the presence of a reaction initiator (various peroxides, azo compounds, etc.) or a chain transfer agent. Can be obtained by 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)
(Meth) acrylic ester monomer having a hydroxyl group such as acrylate and 4-hydroxybutyl (meth) acrylate; (meth) acryl having an amino group such as 2-aminoethyl (meth) acrylate and 3-aminopropyl (meth) acrylate Acid ester monomer; (meth) acrylic acid ester monomer having aziridinyl such as 2- (1-aziridinyl) ethyl (meth) acrylate and 2- (1-aziridinyl) butyl (meth) acrylate; epoxy such as glycidyl (meth) acrylate Examples thereof include (meth) acrylic acid ester monomers having a group.

In the present invention, a reactive acrylic resin having a plurality of functional groups and a plurality of (meth) acryloyl groups may be used.

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,
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, 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.

The reactive acrylic resin has a functional group such as a hydroxyl group, an amino group and a carboxyl group, and thus is crosslinked by the above crosslinking agent, which can improve the flexibility of the sheet. Functional group value of the above-mentioned reactive acrylic resin (usually, OH group value and NH ₂ group value (NH ₂ value: calculation of the amount of NH ₂ group added at the time of polymerization in the same manner as OH value) or NH ₂ group as nitrous acid Reaction and quantification by changing to OH group) and COOH value (COOH value:
The amount of COOH groups added at the time of weight is calculated in the same manner as the OH value, or the sum of COOH groups titrated with KOH)} is preferably in the range of 2 to 100, more preferably in the range of 5 to 50. . If the total functional group value of the reactive acrylic resin is less than 2, the improvement of flexibility cannot be expected. If it exceeds 100, sufficient elongation of the sheet cannot be obtained. However, if the surface hardness is not too high, for example, 2B or less (23 ° C) by the pencil hardness method,
When the elongation of the sheet is hardly required, it is applicable even if it is out of these ranges. The number of (meth) acryloyl groups of the reactive acrylic resin preferably has a molecular weight of 100,000.
The number is 2 to 300, and more preferably 10 to 100. If the amount is less than the above range, the hardness cannot be improved. If the amount is large, it becomes difficult to synthesize an acrylic resin having a (meth) acryloyl group.

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

The low molecular weight substance having a (meth) acryloyl group in the molecule contained in the sheet is, for example, methyl (meth) acrylate, ethyl (meth) acrylate, benzyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate. , Phenoxydiethylene glycol (meth)
Monofunctional type such as acrylate, 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 ) Acrylate, pentaerythritol tri (meth)
There are polyfunctional types such as acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. 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 mainly for plasticizing the reactive acrylic resin. 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, when using a reactive acrylic resin having Tg of 60 to 100 ° C, a low molecular weight substance having a viscosity of 500 cps (25 ° C) or less is 10 to 1 to 100 parts by weight of the reactive acrylic resin.
50 parts by weight, low molecular weight substances with a viscosity of 500 cps (25 ℃) or more, 50
It is preferable to add ˜300 parts by weight. If the added amount is too small, sufficient hardness cannot be obtained after sufficient 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.

The above-mentioned isocyanate cross-linking agent is an isocyanate compound having two or more isocyanate groups in the molecule, and examples thereof include tolylene diisocyanate, diphenylmethane isocyanate, naphthalene diisocyanate, tolidine diisocyanate, triphenylmethane triisocyanate and tris (isocyanatophenyl) thiophos. Fight, P-phenylene diisocyanate, xylylene diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate,
Hexamethylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, monomers such as isophorone diisocyanate, or trimethylolpropane adducts of these monomers, isocyanurate modified products, biuret modified products, carbodiimide modified products,
Examples include urethane modified products and allophanate modified products.

Melamine-based cross-linking agents include melamine, urea, thiourea, guanidine, guanamine, acetoguanamine,
Butyl alcohol, propyl alcohol, etc. Etherified melamine resins reacted with alcohols such as

Examples of the epoxy-based cross-linking agent include glycidyl compounds of polyhydric alcohols containing a plurality of epoxy groups and the like, and are usually used together with a Lewis acid catalyst. The Lewis acid is preferably microencapsulated to control the reaction. For example, butadiene sidioxide, hexazine dioxide and diglycidyl ester of phthalic acid, bisphenol-A diglycidyl ether, bisphenol-F diglycidyl ether, paraaminophenol triglycidyl ether amine, aniline diglycidyl ether, phenylenediamine Glycidyl compounds such as tetraglycidyl ether, diglycidyl ether of sulfonamide, triglycidyl ether of glycerin, polyether modified diglycidyl, polyester modified diglycidyl, urethane modified diglycidyl compound (polymer), vinylcyclohexenedioxide, dicyclopentadienedioxide, etc. Is.

The amount of the cross-linking agent added is preferably such that the functional group value of the reactive acrylic resin: the functional group value of the cross-linking agent = 1: 0.7 to 1.3. However, in reality, the functional group of the reactive acrylic resin and the cross-linking agent are different due to the reactivity with the reactive acrylic resin used, for example,
Since the melamine-based cross-linking agents react with each other and the melamine-based cross-linking agent and the epoxy-based cross-linking agent and the like occur, it is preferable to determine after conducting a preliminary experiment.

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. Examples of the benzophenone series 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 curable sheet used in the present invention, if necessary. As the peroxide, a usual organic peroxide can be used. From the viewpoint of storage stability at room temperature, more preferable is an organic peroxide having a decomposition temperature of 160 ° C or higher. It includes, for example, 2,2-bis (ter-butylperoxy) butane, ter-butylperoxybenzoate, di-ter-butylperoxyisophthalate, methyl ethyl ketone peroxide, dicumyl peroxide, ter.
There is butyl peroxyacetate. The amount of the peroxide added is a low molecular weight product having the (meth) acryloyl group.
The range of 0.5 to 5.0 parts by weight is preferable with respect to 100 parts by weight. 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 cure the portion that is difficult to cure by irradiation with light.

To the curable sheet used in the present invention, materials such as colorants such as pigments and dyes, antioxidants and the like are further added 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 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.

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 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, 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.

A sheet printed on the surface of the base layer of the above-mentioned sheets.

The thickness of the curable sheet of the present invention thus obtained is 20 to 50 in the case of sticking to an adherend surface having irregularities.
0 μm is preferable, and 5 to 1,0 when affixing to a flat surface
It may be about 00 μm. 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 it can be stretched without heating or reduced in shape by applying pressure, pressure (lamination, etc.) to the surface of the adherend. It can be attached along its surface. 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. Then, 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 cured by 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)

Various adherends can be used as the adherend to which the curable 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 curable sheet]

The curable 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".

(A) Preparation of Curing Sheet Example 1 Reactive acrylic resin (copolymer of methyl methacrylate, butyl methacrylate, 2-hydroxylethyl acrylate and acrylic acid, Mw = 86,000, Tg = 35 ° C., COOH value = 5, average double bond per molecule = 20) 100 parts Acrylate monomer (Nippon Kayaku Co., Ltd., KAYARAD DPC)
A-20) 150 parts Photoinitiator (Kayacure DETX manufactured by Nippon Kayaku Co., Ltd.) 1 part Photopolymerization accelerator (Kayacure EPA manufactured by Nippon Kayaku Co., Ltd.) 2
Isocyanate cross-linking agent (Nippon Polyurethane Industry Co., Ltd.)
Manufactured by Coronate L, NCO = 13.0%, solid content 75%) 2.2 parts by solid content (this cross-linking agent has an equivalent amount of isocyanate groups to the functional groups of the above-mentioned reactive acrylic resin) Ethyl acetate 300 parts Stirring above While mixing.

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 curing sheet. The thickness of the obtained curing sheet was 100 μm.

Example 2 Reactive acrylic resin (copolymer of methyl methacrylate, butyl methacrylate, 2-hydroxyethyl acrylate and acrylic acid, Mw = 184,000, Tg = 65 ° C., COOH
Value = 15, average double bond per molecule = 40) 100 parts Acrylate monomer (Nippon Kayaku Co., KAYARAD R
604) 80 parts Photoinitiator (Nippon Ciba Geigy Co., Ltd., Irgacure 18)
4) 2 parts isocyanate cross-linking agent (Japan Polyurethane Industry Co., Ltd.)
Manufactured by Coronate L, NCO = 13.0%, solid content 75%) 6.5 parts by solid content (this crosslinking agent has an equivalent amount of isocyanate groups to the functional groups of the reactive acrylic resin) N-methyldiethanolamine 2 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 curing sheet. The thickness of the obtained curing sheet was 100 μm.

Example 3 Reactive acrylic resin (copolymer of methyl methacrylate, butyl methacrylate, 2-aminoethyl acrylate, 2-hydroxyethyl acrylate and acrylic acid, Mw
= 143,000, Tg = 55 ° C, NH ₂ value = 10, COOH value = 5, average double bond per molecule = 40) 100 parts Acrylate monomer (Nippon Kayaku Co., KAYARAD M
ANDA) 20 parts Acrylate monomer (Nippon Kayaku Co., Ltd., KAYARAD D
PCA20) 80 parts Photoinitiator (Ciba Geigy Co., Ltd., Irgacure 65)
1) 2 parts epoxy crosslinking agent (Ciba-Geigy, Araldide CY17
5, epoxy equivalent 160, epoxy value corresponding to functional group value
220) 3.6 parts (80% of the functional groups of the reactive acrylic resin react) 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 curing sheet. The thickness of the obtained curing sheet was 50 μm.

Example 4 Reactive acrylic resin (copolymer of methyl methacrylate, butyl methacrylate, 2-hydroxyethyl acrylate and acrylic acid, Mw = 243,000, Tg = 45 ° C., COOH value = 10, per molecule Average double bond = 60) 100 parts Acrylate monomer (Nippon Kayaku Co., Ltd., KAYARAD R
604) 80 parts Photoinitiator (2,4,6, -trimethyl benzoyl diphenylphosphine oxide) 4 parts Isocyanate crosslinking agent (Nippon Polyurethane Industry Co., Ltd.)
Manufactured by Coronate L, NCO = 13.0%, solid content 75%) 5.2 parts by solid content (this crosslinking agent has 1.2 equivalents of isocyanate groups based on the functional groups of the reactive acrylic resin) 100 parts of rutile type titanium oxide 300 parts of ethyl acetate 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 curing sheet. The thickness of the obtained curing sheet was 80 μm.

Example 5 Reactive acrylic resin (copolymer of methyl methacrylate, butyl methacrylate, 2-hydroxyethyl acrylate, acrylic acid and 3-aminopropyl acrylate, Mw = 153,000, Tg = 45 ° C., OH Value = 5, COOH value = 5, N
H ₂ value = 10, average double bond per molecule = 60) 100 parts Acrylate monomer (Nippon Kayaku Co., 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 (Kayakyu DETX manufactured by Nippon Kayaku Co., Ltd.) 0.5 part Melamine crosslinking agent (Dainippon Ink and Chemicals Co., Ltd., Superbaccamin J-820-60) 18.4 parts by solid content (the above reactive acrylic) 80% of the functional groups of the resin react) 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 curing sheet. The thickness of the obtained curing sheet was 50 μm.

Example 6 Reactive acrylic resin (copolymer of methyl methacrylate, butyl methacrylate, 2-hydroxyethyl acrylate, 3-aminopropyl acrylate and acrylic acid, Mw = 278,000, Tg = 65 ° C., COOH Value = 5, NH ₂ value = 10,
Average double bond per molecule = 15) 100 parts Acrylate monomer (Nippon Kayaku Co., KAYARAD R)
551) 80 parts Photoinitiator (2,4,6, -trimethyl benzoyl diphenylphosphine oxide) 4 parts Isocyanate crosslinking agent (Nippon Polyurethane Industry Co., Ltd.)
Manufactured by Coronate L, NCO = 13.0%, solid content 75%) 6.5 parts by solid content (this cross-linking agent has 1.0 equivalent of isocyanate groups based on the functional groups of the reactive acrylic resin) Iron Fire Iron 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 curing sheet. The thickness of the obtained curing sheet was 50 μm.

Example 7 Reactive acrylic resin (copolymer of methyl methacrylate, butyl methacrylate, 2-hydroxyl ethyl acrylate and acrylic acid, Mw = 153,000, Tg = 45 ° C., OH value = 10, COOH value = 5, average double bond per molecule = 45)
100 parts acrylate monomer (Nippon Kayaku Co., Ltd., KAYARAD R
604) 80 parts Photoinitiator (2,4,6-trimethylbenzoyl diphenylphosphine oxide) 2 parts Isocyanate crosslinking agent (Nippon Polyurethane Industry Co., Ltd.)
Manufactured by Coronate L, NCO = 13.0%, solid content 75%) 7.8 parts by solid content (this crosslinking agent has 1.2 equivalents of isocyanate groups with respect to the functional groups of the reactive acrylic resin) N-methyldiethanolamine 2 parts acetic acid More than 300 parts of ethyl 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 curing sheet (thickness of sheets other than PET) was 20 μm (referred to as a clear layer).

Reactive acrylic resin (copolymer of methyl methacrylate, butyl methacrylate and 2-hydroxyethyl acrylate, Mw = 153,000, Tg = 45 ° C., OH value = 10) 100 parts Acrylate monomer (Shin Nakamura Kogyo ( Co., Ltd., NPA-10
G) 80 parts Photoinitiator (2,4,6, -trimethyl benzoyl diphenylphosphine oxide) 4 parts Isocyanate crosslinking agent (Nippon Polyurethane Industry Co., Ltd.)
Manufactured by Coronate L, NCO = 13.0%, solid content 75%) 5.2 parts by solid content (this crosslinking agent has 1.2 equivalents of isocyanate groups based on the functional groups of the reactive acrylic resin) 100 parts of rutile type titanium oxide N-methyldiethanolamine 2 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 a curing sheet. The thickness of the obtained curing sheet is 70μ
m (clear layer 20 μm, colored layer 50 μm).

Example 8 Reactive acrylic resin (copolymer of methyl methacrylate, butyl methacrylate, 2-hydroxyethyl acrylate, 3-aminopropyl acrylate and acrylic acid, Mw = 728,000, Tg = 50 ° C., OH Value = 15, NH ₂ value = 10, 1
Average double bond per molecule = 25) 100 parts Acrylate monomer (Nippon Kayaku Co., KAYARAD R)
604) 80 parts Photoinitiator (2,4,6, -trimethyl benzoyl diphenylphosphine oxide) 2 parts Isocyanate crosslinking agent (Nippon Polyurethane Industry Co., Ltd.)
Manufactured by Coronate L, NCO = 13.0%, solid content 75%) 10.8 parts by solid content (this cross-linking agent has an equivalent amount of isocyanate groups to the functional groups of the above-mentioned reactive acrylic resin) Ethyl acetate 300 parts Stirring above While mixing.

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 curing sheet (thickness of sheets other than PET) was 20 μm (referred to as a clear layer).

Reactive acrylic resin (copolymer of methyl methacrylate, butyl methacrylate, 2-hydroxyethyl acrylate, 3-aminopropyl acrylate and acrylic acid, Mw = 728,000, Tg = 50 ° C., OH value = 15 , NH ₂ value = 10, 1
Average double bond per molecule = 25) 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 (Kayakyu DETX manufactured by Nippon Kayaku Co., Ltd.) 0.5 part Isocyanate crosslinking agent (Nippon Polyurethane Industry Co., Ltd.)
Manufactured by Coronate L, NCO = 13.0%, solid content 75%) 10.8 parts by solid content (this cross-linking agent has an equivalent amount of isocyanate groups to the above functional acrylic resin) Cyanine blue 100 parts Ethyl acetate 300 The above parts 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 a curing sheet. The thickness of the obtained curing sheet is 70μ
m (clear layer 20 μm, colored layer 50 μm).

Example 9 Reactive acrylic resin (copolymer of methyl methacrylate, butyl methacrylate, 2-hydroxyethyl acrylate, acrylic acid and 3-aminopropyl acrylate, Mw = 353,000, Tg = 45 ° C., OH Value = 5, COOH value = 5, N
H ₂ value = 10, average double bond per molecule = 25) 100 parts Acrylate monomer (Nippon Kayaku Co., KAYARAD O
PCA-20) 150 parts Photoinitiator (Nippon Ciba Geigy Co., Ltd., Irgacure 18)
4) 2 parts Melamine cross-linking agent (manufactured by Dainippon Ink and Chemicals, Inc., Superbaccamin J-820-60) 9.2 parts by solid content (40% of the functional groups of the reactive acrylic resin react) N-methyldiethanolamine 2 parts isocyanate cross-linking agent (Japan Polyurethane Industry Co., Ltd.)
Manufactured by Coronate L, NCO = 13.0%, solid content 75%) 5.2 parts by solid content (this cross-linking agent has 0.6 equivalent of isocyanate groups based on the functional groups of the reactive acrylic resin) 300 parts or more of ethyl acetate 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 curing 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 Reactive acrylic resin (copolymer of methyl methacrylate, butyl methacrylate, 2-hydroxyethyl acrylate and acrylic acid, Mw = 53,000, Tg = 0 ° C., OH value =
35, COOH value = 5, average double bond per molecule = 10) 10
0 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 Isocyanate crosslinking agent (Nippon Polyurethane Industry Co., Ltd.)
Manufactured by Coronate L, NCO = 13.0%, solid content 75%) 18.2 parts by solid content (this crosslinking agent has 1.2 equivalents of isocyanate groups to the functional groups of the reactive acrylic resin) 100 parts of rutile type titanium oxide 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 removing the PET film, a curing sheet was obtained. The thickness of the obtained curing sheet was 70 μm (coloring layer 50 μm, protective layer 20 μm).

Example 11 Reactive acrylic resin (reactive acrylic resin obtained by adding 2-hydroxyethyl to a copolymer of methyl methacrylate, butyl acrylate and acrylic acid, weight average molecular weight =
175,000, Tg = 60 ° C, COOH value = 5, average double bond per molecule = 1) 100 parts Acrylate monomer (Nippon Kayaku Co., KAYARAD R
604) 50 parts Photoinitiator (2,4,6, -trimethyl benzoyl diphenylphosphine oxide) 4 parts N-methyldiethanolamine 2 parts Isocyanate crosslinking agent (Nippon Polyurethane Industry Co., Ltd.)
Manufactured by Coronate L, NCO = 13.0%, solid content 75%) 2.2 parts by solid content (this cross-linking agent has an equivalent amount of isocyanate groups to the functional groups of the above-mentioned reactive acrylic resin) Ethyl acetate 300 parts Stirring above While mixing.

This mixture was coated on a PET film and dried at 80 ° C for 5 minutes. By removing the PET film, a curing sheet was obtained. The thickness of the obtained curing sheet was 50 μm.

(B) Performance Evaluation of Curing Sheet Spreadability Test Strip-shaped test pieces (20 mm × 50 mm) were obtained by cutting from the curing sheets obtained in Examples 1 to 11, and the test piece was cut at room temperature and 80 ° C. in the longitudinal direction. 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 curing 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) that is curved like a convex lens.
When the end portions of the steel sheet were spread so as to reach both ends of the steel sheet, and the resin layers were opposed to each other and vacuum pressure bonding was performed at 50 ° C., good coating was possible without generation of wrinkles.

Performance evaluation of coatings Coatings 1, 2, 3, 9 coated with curable sheets 1 to 11,
Reference numeral 11 was a high pressure mercury lamp, and coatings 4 to 8 and 10 were light (100 mW / cm) from a metal halide lamp for 60 seconds and 40 seconds, respectively, and cured. Then JI
The hardness of the coating was measured by a pencil hardness test according to SK5400. The results are shown in Table 1.

(Comparative Example) (A) Preparation of Curable Sheet Comparative Example 1 Reactive acrylic resin (copolymer of methyl methacrylate, butyl methacrylate and 2-hydroxylethyl acrylate, Mw = 13,000, Tg = 45 ° C.) , OH value = 5) 100 parts Acrylate monomer (Nippon Kayaku Co., Ltd., KAYARAD M
ANNDA) 80 parts Photoinitiator (Nippon Ciba Geigy Co., Ltd., Irgacure)
184) 4 parts Isocyanate cross-linking agent (Nippon Polyurethane Industry Co., Ltd.)
Made by Coronate L, NCO = 13.0%, solid content 75%)
2.2 parts (this cross-linking agent has 1.0 equivalent of isocyanate groups to the functional groups of the reactive acrylic resin) 300 parts of ethyl acetate The above components were mixed while 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 Reactive acrylic resin (copolymer of methyl methacrylate, butyl methacrylate and 2-hydroxyl ethyl acrylate, Mw = 11,113,000, Tg = 45 ° C., OH value = 5) 100 parts Acrylate monomer (Japan Kayaku Co., Ltd., KAYARAD D
PCA) 120 parts Photoinitiator (Nippon Ciba Geigy Co., Ltd., Irgacure)
184) 4 parts Isocyanate cross-linking agent (Nippon Polyurethane Industry Co., Ltd.)
Made by Coronate L, NCO = 13.0%, solid content 75%)
2.2 parts (This cross-linking agent has 1.0 equivalent of isocyanate groups with respect to the functional groups of the above-mentioned reactive acrylic resin) Ethyl acetate 150 parts It was difficult to uniformly dissolve the reactive acrylic resin, although the above components were stirred. It was

Comparative Example 3 Reactive acrylic resin (copolymer of methyl methacrylate, butyl methacrylate and 2-hydroxyl ethyl acrylate, Mw = 13,000, Tg = 45 ° C., OH value = 5) 100 parts Acrylate monomer (Japan KAYARAD R manufactured by Kayaku Co., Ltd.
551) 80 parts Photoinitiator (Nippon Ciba Geigy Co., Ltd., Irgacure)
184) 4 parts Isocyanate cross-linking agent (Nippon Polyurethane Industry Co., Ltd.)
Made by Coronate L, NCO = 13.0%, solid content 75%)
2.2 parts (This cross-linking agent has 1.0 equivalent of isocyanate groups to the functional groups of the above-mentioned reactive acrylic resin) 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). A curable sheet was obtained by peeling off the PET film. The thickness of the obtained curable sheet was 70 μm (clear layer 50 μm, protective layer 20 μm).

Comparative Example 4 Reactive acrylic resin (copolymer of methyl methacrylate, butyl methacrylate, 2-hydroxyethyl acrylate and acrylic acid, Mw = 13,000, Tg = 45 ° C., OH value =
5, average double bond per molecule = 5) 100 parts Acrylate monomer (Nippon Kayaku Co., KAYARAD R
604) 80 parts Photoinitiator (Nippon Ciba Geigy Co., Ltd., Irgacure)
184) 4 parts Isocyanate cross-linking agent (Nippon Polyurethane Industry Co., Ltd.)
Made by Coronate L, NCO = 13.0%, solid content 75%)
2.2 parts (this cross-linking agent has 1.0 equivalent of isocyanate groups with respect to the functional groups of the reactive acrylic resin) 300 parts of ethyl acetate The above components were mixed while 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 Reactive acrylic resin (copolymer of methyl methacrylate, butyl methacrylate, 2-hydroxyl ethyl acrylate and acrylic acid, Mw = 1113,000, Tg = 45 ° C., OH
Value = 5, average double bond in molecule = 150) 100 parts Acrylate monomer (Nippon Kayaku Co., Ltd., KAYARAD D
PCA20) 120 parts Photoinitiator (Nippon Ciba Geigy Co., Ltd., Irgacure)
184) 4 parts Isocyanate cross-linking agent (Nippon Polyurethane Industry Co., Ltd.)
Made by Coronate L, NCO = 13.0%, solid content 75%)
2.2 parts (This cross-linking agent has 1.0 equivalent of isocyanate groups with respect to the functional groups of the above-mentioned reactive acrylic resin) Ethyl acetate 150 parts It was difficult to uniformly dissolve the reactive acrylic resin, although the above components were stirred. It was

Comparative Example 6 Reactive acrylic resin (copolymer of methyl methacrylate, butyl methacrylate, 2-hydroxyethyl acrylate and acrylic acid, Mw = 13,000, Tg = 45 ° C., OH value =
5, average double bond in molecule = 5) 100 parts Acrylate monomer (Nippon Kayaku Co., Ltd., KAYARAD R
551) 80 parts Photoinitiator (Nippon Ciba Geigy Co., Ltd., Irgacure)
184) 4 parts Isocyanate cross-linking agent (Nippon Polyurethane Industry Co., Ltd.)
Made by Coronate L, NCO = 13.0%, solid content 75%)
2.2 parts (This cross-linking agent has 1.0 equivalent of isocyanate groups to the functional groups of the above-mentioned reactive acrylic resin) 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). A curable sheet was obtained by peeling off the PET film. The thickness of the obtained curable sheet was 70 μm (clear 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 obtained by cutting from the curable sheets obtained in Comparative Examples 3 and 6, and lengthwise at room temperature and 80 ° C. When a tensile test of No. 1 was conducted, the curable sheet was cracked when stretched 100%.

(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 a flat surface but also irregularities or a curved surface. Further, this curable sheet can form a strong coating excellent in hardness and scratch resistance by irradiating light, and a coated product having a coating excellent in impact resistance and scratch resistance can be obtained. I can.

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Claims (1)

[Claims] 1. A compound having at least one functional group selected from the group consisting of a hydroxyl group, an amino group and a carboxyl group and a (meth) acryloyl group in the molecule (a) and having a weight average molecular weight of 50,000 to 1,000,000. Which is a solid at room temperature, (b) a low molecular weight product having a (meth) acryloyl group in the molecule, (c) a photoinitiator, (d) an isocyanate crosslinking agent, and a melamine crosslinking At least one cross-linking agent selected from the group consisting of agents and epoxy-based cross-linking agents, and a curable sheet having as a main component affixed to an adherend and then irradiating light to cure the sheet. Manufacturing method.