JP2003026709A - Uv ray curable resin composition, coating film forming method and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a UV ray curable resin composition with one liquid type composition in which a pot life is not restricted and which is excellent in adhesion property, heat-resistance and storage stability. SOLUTION: The UV ray curable resin composition contains (A) an acid- modified alkyd resin of which an acid value is 20-80 mgKOH/g; (B) a compound having at least two (meth)acryloyl groups in the molecule; and (C) a photopolymerization initiator.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an ultraviolet-curable resin composition which is a one-pack type and has no limitation on pot life, and is excellent in adhesion, heat resistance and storage stability, and further to FRP molded articles. The present invention relates to an ultraviolet-curable resin composition useful as an anchor coating agent for performing metal vapor deposition.

[0002]

2. Description of the Related Art Conventionally, ultraviolet curable resin compositions have been
Since curing is completed by irradiation of ultraviolet rays for a very short time, it is widely used as a coating agent, an adhesive agent, an anchor coating agent or the like for various substrates. Especially in recent years,
An ultraviolet curable resin composition has been studied as an anchor coating agent for a reflecting mirror of an automobile light. That is, a reflecting mirror of an automobile light is manufactured by vacuum-depositing a metal such as aluminum on the surface of a molded body formed of FRP (fiber reinforced composite material). In order to enhance the adhesion between the FRP and the metal vapor deposition film, and to improve the gloss of the vapor deposition metal and enhance the reflection efficiency of the vapor deposition surface, the metal is vapor deposited prior to vapor deposition.
The surface of the RP is anchor-coated with the ultraviolet curable resin composition.

As such an ultraviolet-curable resin composition, Japanese Patent Application Laid-Open No. 7-26167 discloses an ultraviolet-curable resin for vapor deposition of FRP containing a polyfunctional acrylate of dipentaerythritol and an isocyanurate-type polyisocyanate. Mold base liquid composition is also internationally published W
O95 / 32250 discloses that at least 2 in the molecule.
20-80 having one (meth) acryloyl group
Parts by weight, 80 to 20 parts by weight of oil-modified alkyd resin, and
An ultraviolet curable undercoat liquid composition for metal deposition for FRP, which comprises 2 to 15 parts by weight of a sensitizer, has been proposed.

[0004]

However, in the above disclosed technique, the pot life is necessarily limited because of the two-component type, and the adhesion and heat resistance are still insufficient. Further, in the above disclosed technology, although it is a one-pack type, its storage stability is insufficient, and further, similar to the above, the adhesion and heat resistance are not yet satisfactory, and further improvement is required. It was a thing.

Under these circumstances, the present invention has no limitation on the pot life, and has excellent adhesiveness, heat resistance, and storage stability, and a UV-curable resin composition, and a coating film formation using the same. A method and an automobile reflector using the method are provided.

[0006]

However, as a result of diligent research on such problems, the present inventors have found that the acid value is 20 to 20%.
80 mg KOH / g acid-modified alkyd resin (A),
The present invention found that an ultraviolet curable resin composition containing a compound (B) having at least two (meth) acryloyl groups in the molecule and a photopolymerization initiator (C) meets the above-mentioned object. Was completed.

Further, according to the present invention, a method for forming a coating film of an ultraviolet curable resin composition, which comprises coating the surface of an FRP molded product with the ultraviolet curable resin composition and then irradiating it with ultraviolet rays to form a coating film, and After coating the surface of an FRP molded article for automobile reflectors with such an ultraviolet-curable resin composition, it is irradiated with ultraviolet rays to form a coating film, and a metal is vacuum-deposited on the coating film. The present invention provides an automobile reflecting mirror having a coat layer formed thereon.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.
The acid-modified alkyd resin (A) used in the present invention needs to be an acid-modified alkyd resin having an acid value of 20 to 80 mgKOH / g, and the acid value is 20 mgK.
If it is less than OH / g, the initial adhesion will be insufficient, and 80 mgKOH
If it exceeds / g, the hot water resistance will be poor. A more preferable acid value is 30 to 75 mgKOH / g, and a particularly preferable acid value is 40 to 70 mgKOH / g. Such an acid-modified alkyd resin (A) is obtained by using an oil-modified alkyd resin (a1) obtained by using a fat or oil or a fatty acid fatty acid, in addition to a polyhydric alcohol and a polybasic acid or an acid anhydride thereof, and further adding a polybasic base. It is acid-modified with an acid or its acid anhydride (a2).

The oil-modified alkyd resin (a1) is produced by polycondensing a polyhydric alcohol and a polybasic acid or an acid anhydride thereof, and the polyhydric alcohol constituting the resin is not particularly limited. Ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol, trimethylene glycol, polypropylene glycol, tetramethylene glycol, polytetramethylene glycol, 1,2-butanediol, 1,3-butanediol, 1 , 4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,2-hexylene glycol, 1,6-hexanediol, heptanediol, 1,10-decanediol, cyclohexanediol, 2-butane. Down-1,4-diol, 3-cyclohexene-1,1-dimethanol, 4-methyl-3-cyclohexene-1,1-dimethanol, 3-methylene -
1,5-pentanediol, (2-hydroxyethoxy) -1-propanol, 4- (2-hydroxyethoxy) -1-butanol, 5- (2-hydroxyethoxy) -pentanol, 3- (2-hydroxypropoxy) ) -1-Butanol, 4- (2-hydroxypropoxy) -1-butanol, 5- (2-hydroxypropoxy) -1-pentanol, 1- (2-hydroxyethoxy) -2-butanol, 1- (2 -Hydroxyethoxy) -2-pentanol, hydrogenated bisphenol A, glycerin, diglycerin, polycaprolactone, 1,
2,6-hexanetriol, trimethylolpropane, trimethylolethane, pentanetriol, trishydroxymethylaminomethane, 3- (2-hydroxyethoxy) -1,2-propanediol, 3- (2-
Hydroxypropoxy) -1,2-propanediol,
6- (2-hydroxyethoxy) -1,2-hexanediol, 1,9-nonanediol, neopentyl glycol hydroxypivalate, spiroglycol, 2,2
-Bis (4-hydroxyethoxyphenyl) propane,
2,2-bis (4-hydroxypropoxyphenyl)
Propane, pentaerythritol, dipentaerythritol, trimethylolpropane, trishydroxyethyl isocyanurate, di (2-hydroxyethyl) -1
-Acetoxyethyl isocyanurate, di (2-hydroxyethyl) -2-acetoxyethyl isocyanurate, mannitol, glucose and other polyols can be mentioned, and further, these oxides include ethylene oxide, propylene oxide and ε-caprolactone. , An alkylene oxide-modified or lactone-modified polyol obtained by addition reaction with γ-buterolactone, a polyester polyol having a terminal hydroxyl group obtained by condensing an excess of these polyols with a polybasic acid or an acid anhydride thereof, A polyether polyol etc. can also be mentioned.

Further, a polyhydric alcohol composed of a reaction product of a compound having at least two epoxy groups or glycidyl groups in the molecule with a monovalent acid or a monovalent amine can also be mentioned. The compound having at least two epoxy groups or glycidyl groups in the molecule is not particularly limited, and examples thereof include bisphenol A, bisphenol F,
Glycidyl ether type epoxy resin containing 2,6-xylenol, brominated bisphenol A, phenol novolac, etc., glycidyl ester type epoxy resin containing dimer acid, etc., glycidyl ester type epoxy containing aromatic or heterocyclic amine, etc. Examples thereof include resins, alicyclic epoxy resins, and acrylic resins having an epoxy group or a glycidyl group.

Particularly, as the compound having three or more epoxy groups or glycidyl groups in the molecule, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, sorbitol tetraglycidyl ether, sorbitol pentaglycidyl ether, sorbitan tetraglycidyl ether, sorbitan. Pentaglycidyl ether, triglycerol tetraglycidyl ether, tetraglycerol tetraglycidyl ether,
Pentaglycerol tetraglycidyl ether, triglycerol pentaglycidyl ether, tetraglycerol pentaglycidyl ether, pentaglycerol pentaglycidyl ether, pentaerythritol tetraglycidyl ether, triglycidyl isocyanurate and the like can be mentioned.

The monovalent acid is not particularly limited,
For example, acetic acid, probionic acid, benzoic acid, lauric acid,
Stearic acid, butyric acid, (meth) acrylic acid, etc. can be mentioned.

The monovalent amine is not particularly limited, and examples thereof include monoethylamine, diethylamine, triethylamine, isopropylamine, diisopropylamine, mono-n-butylamine, di-n-butylamine, tri-n-butylamine and mono-amine. 2-ethylhexylamine, monobenzylamine, piperidine, morpholine, n-methylmorpholine, n-ethylmorpholine, cetylmorpholine and the like can be mentioned.

The polybasic acid or its acid anhydride constituting the oil-modified alkyd resin (a1) is not particularly limited, and examples thereof include phthalic acid, isophthalic acid, terephthalic acid,
Trimetic acid, methylcyclohexene tricarboxylic acid,
Adipic acid, sebacic acid, azelaic acid, tetrahydrophthalic acid, hexahydrophthalic acid, hymic acid, succinic acid, dodecynylsuccinic acid, methylglutaric acid, pimelic acid, malonic acid, maleic acid, fumaric acid, chloromaleic acid, dichloromaleic acid , Citraconic acid, mesaconic acid, itaconic acid, tetrahydrophthalic acid, carbic acid, het acid, aconitic acid, glutaconic acid, and their acid anhydrides.

The oil or fat or oil fatty acid constituting the oil-modified alkyd resin (a1) is not particularly limited, and may be any of non-drying oil, semi-drying oil and drying oil. Examples thereof include tall oil, coconut oil, soybean oil, safflower oil, linseed oil, tung oil, castor oil, and fatty acid fatty acids of these fats and oils.

In the present invention, the oil length of the oil-modified alkyd resin (a1) is not particularly limited, and may be any of short oil, medium oil and long oil. In addition, in this specification, "oil length" means the value which represented the content of oil based on weight percentage.

Such an oil-modified alkyd resin (a
Specific examples of 1) include beczosol ET-6502-60 (manufactured by Dainippon Ink and Chemicals, Inc., oil length 65%) and arachid 14 as tall oil-modified alkyd resins.
65-60 (manufactured by Arakawa Chemical Industry Co., Ltd., oil length 60%); as a coconut oil-modified alkyd resin, Beckosol 1323-60
-EL (manufactured by Dainippon Ink and Chemicals, Inc., oil length 28%); beczosol ES-65 as soybean oil-modified alkyd resin
05-70 (Dainippon Ink and Chemicals, Inc., oil length 65
%), Arachid 3101X-60 (Arakawa Chemical Industry Co., Ltd., oil length 40%), Beckozole OD-E-198-5.
0 (Dainippon Ink and Chemicals, Inc., oil length 28%), Beckosol ES-4020-55 (Dainippon Ink and Chemicals, Inc., oil length 40%), Beckosol P-470-70 (Dainippon Ink and Chemicals Co., Ltd.) Beckosol J-557 (manufactured by Dainippon Ink and Chemicals, Inc., oil length 51%); as flaxseed oil modified alkyd resin; beccosol 45-163 (Dainippon Ink) Chemical industry company, oil length 28%), Beckosol E
L-4501-50 (manufactured by Dainippon Ink and Chemicals, Inc., oil length 45%), Beckosol EL-6501-70 (manufactured by Dainippon Ink and Chemicals, Inc., oil length 65%) and the like can be mentioned.

In the present invention, the oil length of the oil-modified alkyd resin (a1) can be appropriately selected in consideration of the use of the present invention, but the oil length in the solid content of the composition of the present invention is not limited. Is preferably 80% or less, more preferably 70% or less. If it exceeds 80%, the appearance of the coating film becomes poor and the heat resistance becomes poor, which is not preferable.

Next, the above oil-modified alkyd resin (a1)
The acid-modified alkyd resin (A) used in the present invention is obtained by further acid-modifying the compound with a polybasic acid or an acid anhydride (a2) thereof.

The polybasic acid or its acid anhydride (a2)
Is not particularly limited, and examples thereof include polybasic acids or acid anhydrides thereof as described in the explanation of (a1) above, among which maleic acid, phthalic acid, fumaric acid, tetrahydrophthalic acid, and 3-methyltetrahydro. Phthalic acid or one acid (a2) selected from these acid anhydrides is preferable. Furthermore, the acid-modified alkyd resin (A) is acid-modified by reacting 100 parts by weight of the oil-modified alkyd resin (a1) with 5 to 20 parts by weight of the polybasic acid or the acid anhydride (a2) thereof. Preferably. Such compounding amount is 5
If it is less than part by weight, the initial adhesion to the FRP molded product will be insufficient,
If it exceeds 20 parts by weight, unreacted acid precipitates, resulting in poor adhesion to the FRP molded product, which is not preferable.

Thus, the acid-modified alkyd resin (A) used in the present invention is obtained. The weight-average molecular weight of the acid-modified alkyd resin (A) is 20,000 to 50,
It is preferably 000, more preferably 25.0
00-45,000, particularly preferably 25,000-4
It is 10,000. Such weight average molecular weight is 20,000
If it is less than 0, the cured coating film becomes brittle, and if it exceeds 50,000, the curability becomes poor, which is not preferable.

At least 2 in the molecule used in the present invention
The compound (B) having one (meth) acryloyl group is not particularly limited, and examples thereof include (1) a (meth) acrylic monomer obtained by reacting a polyol with (meth) acrylic acid, and (2) a molecule. Urethane (meth) acrylate obtained by adding a compound having a hydroxyl group and a (meth) acryloyl group to a compound having a terminal isocyanate group therein, (3) a compound having at least two epoxy groups or glycidyl groups in the molecule By reacting (meth) acrylic acid with an epoxy (meth) acrylate obtained by the reaction of (meth) acrylic acid with (4) polyol and a polyester polyol obtained by polycondensing a polybasic acid or an acid anhydride thereof. The obtained polyester (meth) acrylate etc. can be mentioned.

In the (meth) acryl-based monomer of (1) above, the polyol is not particularly limited, and examples thereof include the same as those described in (a1) above. Specific examples of such (meth) acrylic monomers include, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di. (Meth) acrylate, dipropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide modified bisphenol A type di (meth) acrylate , Propylene oxide-modified bisphenol A type di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di (meth) acrylate Rate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, phthalic acid diglycidyl ester di (meth) acrylate, hydroxypivalic acid modified neopentyl glycol di (Meth) acrylate and the like [above, bifunctional acrylic monomer]; trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate,
Pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri (meth) acryloyloxyethoxytrimethylolpropane, glycerin polyglycidyl ether poly (meth) acrylate, etc. [above, Trifunctional or higher functional acrylic monomers].

In the urethane (meth) acrylate of (2) above, examples of the compound having a terminal isocyanate group in the molecule include polyisocyanates or those exemplified as the polyol in the compound of (1) above. Examples thereof include those obtained by reacting polyisocyanate.

Among the urethane (meth) acrylates of (2) above, as the polyol, a compound having at least two epoxy groups or glycidyl groups in the molecule is reacted with a monovalent acid or monovalent amine. The product obtained by using the above-mentioned product has, for example, one isocyanate group in one molecule obtained by reacting a compound having one hydroxyl group and (meth) acryloyl group in the molecule with polyisocyanate in advance. The compound is reacted with a compound having at least two epoxy groups or glycidyl groups in the molecule and a polyol obtained by reacting a monovalent acid or a monovalent amine, and urethane-modified having an ester bond and a urethane bond. It can be obtained as an epoxy acrylate.

The polyisocyanate in the above (2) may be, for example, any of an aliphatic type, an alicyclic type, an aromatic type and an aromatic-aliphatic type. Examples thereof include tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, 4,4′-
Methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4-diisocyanate, methylcyclohexane-2,6-diisocyanate, 1,3-
(Isocyanate methyl) cyclohexane, isophorone diisocyanate, trimethylhexamethylene diisocyanate, dimer acid diisocyanate, dianisidine diisocyanate, phenyl diisocyanate, halogenated phenyl diisocyanate, methylene diisocyanate, ethylene diisocyanate, butylene diisocyanate, propylene diisocyanate, octadecylene diisocyanate, 1,5 -Naphthalene diisocyanate, polymethylene polyphenylene diisocyanate, triphenylmethane triisocyocyanate, naphthylene diisocyanate, 3-phenyl-2-ethylene diisocyanate, cumene-2,4-diisocyanate, 4-methoxy-1,3-phenylene Diisocyanate, 4-ethoxy-1,3-phenyl Two diisocyanate, 2,
4'-diisocyanate diphenyl ether, 5,6-
Dimethyl-1,3-phenylene diisocyanate, 4,
4'-diisocyanate diphenyl ether, benzidine diisocyanate, 9,10-anthracene diisocyanate, 4,4'-diisocyanate dibenzyl,
3,3-dimethyl-4,4'-diisocyanate diphenyl, 2,6-dimethyl-4,4'-diisocyanate diphenyl, 3.3-dimethoxy-4.4'-diisocyanate diphenyl, 1,4-anthracene diisocyanate, Diisocyanates such as phenylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,10-decane methylene diisocyanate and 1,3-cyclohexylene diisocyanate; nurate, buret, adduct of these diisocyanates;
4,6-Tolylenetriisocyanate, 2,4,4'-
Examples thereof include triisocyanates such as triisocyanate diphenyl ether.

Examples of the compound having a hydroxyl group and a (meth) acryloyl group in the above (2) include, for example, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, epoxy (meth) acrylate, and 2-hydroxyethyl. (Meta)
Acrylate, glycerol di (meth) acrylate,
And examples thereof include alkylene oxide-modified or lactone-modified compounds obtained by adding ethylene oxide, propylene oxide, ε-caprolactone, γ-butyrolactone and the like to these, and polyisocyanate is added to these compounds. Compounds can also be used.

At least 2 in the molecule in the above (3).
Examples of the compound having one epoxy group or glycidyl group include those exemplified as the compounds having at least two epoxy groups or glycidyl groups in the molecule as described above. In the above (4), examples of the polyol, polybasic acid or acid anhydride thereof include the same ones as described above. Compound (B) having at least two (meth) acryloyl groups in the molecule
Are used alone or in combination of two or more.

In the present invention, at least 2 in the molecule.
As the compound (B) having one (meth) acryloyl group, the above-mentioned compounds (1) to (4) and the like can be used, and these compounds cause a polymerization reaction due to the involvement of the unsaturated bond contained therein. However, if desired, it may further contain a compound having another unsaturated bond, such as diallyl fumarate or triallyl isocyanurate.

In the present invention, the compound (B) having at least two (meth) acryloyl groups in the molecule.
Is preferably one having at least three (meth) acryloyl groups in the molecule from the viewpoint of heat resistance.

The photopolymerization initiator (C) used in the present invention is not particularly limited as long as it generates a radical by the action of light, and specific examples thereof include 4-phenoxydichloroacetophenone and 4-t-. Butyl-dichloroacetophenone, diethoxyacetophenone, 2-hydroxy-
2-methyl-1-phenylpropan-1-one, 1-
(4-isopropylenephenyl) -2-hydroxy-2
-Methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) -phenyl (2-
Hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4-
(Methylthio) phenyl] -2-morpholinopropane-
1, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether,
Benzoin isobutyl ether, benzyl dimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3′-dimethyl-4-methoxybenzophenone, Thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone,
Camphorquinone, dibenzosuberone, 2-ethylanthraquinone, 4 ', 4 "-diethylisophthalophenone, 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, α-acyloxime ester , Acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, 4- (2-hydroxyethoxy) phenyl-
(2-Hydroxy-2-propyl) ketone, dimethylaminobenzoic acid, dimethylaminobenzoic acid alkyl ester and the like can be mentioned. Among them, benzyl dimethyl ketal, 1
-Hydroxycyclohexyl phenyl ketone, benzoyl isopropyl ether, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, dimethylamino Benzoic acid and dimethylaminobenzoic acid alkyl ester are preferable, and dimethylaminobenzoic acid and dimethylaminobenzoic acid alkyl ester are particularly preferably used. These photopolymerization initiators (C) are used alone or in combination of two or more.

In the present invention, the acid-modified alkyd resin (A), the compound (B) having at least two (meth) acryloyl groups in the molecule and the photopolymerization initiator (C) are contained. The content of each of these components is not particularly limited, but 25 to 400 parts by weight of the compound (B) having at least two (meth) acryloyl groups in the molecule is based on 100 parts by weight of the acid-modified alkyd resin (A). Department,
It is particularly preferably 30 to 300 parts by weight, and further preferably 40 to 200 parts by weight. The acid-modified alkyd resin (A) 1
If the amount of the compound (B) is less than 25 parts by weight with respect to 00 parts by weight, the heat resistance and the adhesiveness are deteriorated, and if the amount of the compound (B) exceeds 400 parts by weight, the adhesiveness is deteriorated, which is not preferable.

The content of the photopolymerization initiator (C) is 100 in total of the acid-modified alkyd resin (A) and the compound (B) having at least two (meth) acryloyl groups in the molecule.
The amount is preferably 2 to 10 parts by weight, more preferably 2.5 to 9 parts by weight, and particularly preferably 3 to 8 parts by weight. If the amount of the photopolymerization initiator is less than 2 parts by weight, the adhesion and heat resistance will be poor,
If the amount exceeds 10 parts by weight, the effect does not change and it is economically disadvantageous, which is not preferable.

In the present invention, an amino resin may be added, if necessary, in addition to the components (A) to (C). The content of the amino resin is about 1 to 20 parts by weight, and further about 5 to 15 parts by weight, based on 100 parts by weight of the acid-modified alkyd resin (A).

In the present invention, in addition to the above-mentioned components (A) to (C), a solvent, a surface conditioner, a polymerization inhibitor and the like can be further added. Such a solvent has a function of diluting the resin composition of the present invention to facilitate coating. The solvent is not particularly limited, but a low surface tension solvent is preferable in order to improve wettability, and examples of such a solvent include alcohol solvents, ketone solvents, and the like. In addition, ethyl acetate, butyl acetate, toluene, xylene and the like can be used in combination in view of the evaporation rate and cost. The blending amount of such a solvent can be increased or decreased as necessary.

The surface conditioner is not particularly limited, and examples thereof include a fluorine-based additive and a cellulose-based additive. Such a fluorine-based additive has the effect of preventing cissing when applied to the FRP material by lowering the surface tension and improving the wettability. Specific examples of the fluorine-based additive include Megafac F-17.
7 (manufactured by Dainippon Ink and Chemicals, Inc.) and the like.

Such a cellulosic additive has a function of imparting a film-forming property during coating. The cellulose-based additive has a number average molecular weight of 150 in order to reduce fluidity.
A high molecular weight product of 00 or more is preferable, and examples of such a product include a cellulose-acetate-butyrate resin.

In the present invention, when the amount of the above-mentioned fluorine-based additive is increased, the adhesion of vapor-deposited aluminum or top coat is deteriorated, and when the amount of the above-mentioned cellulose-based additive is increased, the resin composition of the present invention is obtained. It is preferable to use the above-mentioned fluorine additive and the above-mentioned cellulose-based additive in combination, since the solid content of the above-mentioned will decrease and the coating film will not adhere easily.

In the present invention, the total amount of the surface modifier is 100 parts by weight of the total of the components (A) to (C), and the total amount of the fluorine-based additive and the cellulose-based additive is 100 parts by weight. The amount is preferably 0.01 to 3.0 parts by weight. When the above-mentioned fluorine-based additive is used alone,
01 to 1.0 parts by weight is preferable, and when the above-mentioned cellulose-based additive is used alone, 0.5 to 5.0 parts by weight is preferable.

Examples of the polymerization inhibitor include p-benzoquinone, naphthoquinone, toluquinone, 2,5-diphenyl-p-benzoquinone, hydroquinone and 2,5-di-t.
-Butyl hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, mono-t-butyl hydroquinone, pt-butyl catechol and the like can be mentioned.

Further, an antioxidant, a flame retardant, an antistatic agent, a filler, a leveling agent, a stabilizer, a reinforcing agent, a delustering agent, a grinding agent, etc. should be added to the ultraviolet curable resin composition of the present invention. Is also possible.

Thus, the ultraviolet curable resin composition of the present invention is obtained, and is effectively used as a coating agent or anchor coating agent for various substrates. In applying the ultraviolet resin composition to the substrate, it can be dissolved in a solvent to be in a solution state or heated to be in a molten state and applied by a general applicator, roll coater, bar coater or the like. .

The ultraviolet-curable resin composition of the present invention is cured by ultraviolet rays after being coated on a substrate. As a method of ultraviolet irradiation curing, a high pressure mercury lamp that emits light in the wavelength range of 150 to 450 nm is used. , Metal halide lamp, xenon lamp, chemical lamp, etc.
Irradiation may be performed at about 0 to 3000 mJ / cm ² .

The UV-curable resin composition of the present invention is a polyolefin resin, polyester resin, polycarbonate resin, ABS, polystyrene resin or the like, or molded products (film, sheet, cup, etc.), metal, glass. It also has excellent adhesion performance to, but especially FR
It has particularly excellent adhesion to the P molded body.

The ultraviolet-curable resin composition of the present invention is particularly effective for use in automobile reflectors, and when producing an automobile reflector using such an ultraviolet-curable resin composition,
For example, after washing the FRP molded body with an aqueous detergent, the ultraviolet curable resin composition is applied to the surface of the molded body, and then irradiated with ultraviolet rays to form a coating film of an anchor coat layer, and the coating film is formed on the coating film. The metal is vacuum-deposited, and the topcoat layer is further formed thereon.

FRP of the ultraviolet curable resin composition of the present invention
The surface of the molded body can be coated by air spray coating, electrostatic coating, dip coating, or the like. The coating is performed so that the dry film thickness is 10 to 40 μm, and if necessary, 70 to 13 before the irradiation with the ultraviolet rays.
The solvent is evaporated by preheating at 0 ° C. for 5 to 25 minutes, preferably 10 to 20 minutes. If the preheating temperature is lower than 70 ° C, the water resistance and heat resistance are poor,
If it exceeds 130 ° C, the performance is not affected, but it is economically disadvantageous.

The above-mentioned ultraviolet irradiation is carried out after the above preheating.
It is performed under the condition of about 500 to 5000 mJ / cm ² . The ultraviolet-curable resin composition of the present invention can be cured by the above-mentioned ultraviolet irradiation.

A metal such as aluminum is vacuum-deposited on the cured coating film obtained by coating and curing the ultraviolet curable resin composition of the present invention. Then, a clear coating is applied on the vapor-deposited metal and baked at 100 to 120 ° C. for about 5 to 15 minutes to form a top coat layer having a dry film thickness of 3 to 15 μm. A reflector can be obtained.

Examples of the clear coating used in the clear coating include acrylic lacquer coating, acrylic melamine curing clear coating, aluminum chelate curing acrylic coating and the like. The FRP molded body to which the ultraviolet curable resin composition of the present invention can be applied is not particularly limited, and examples thereof include automobile mirrors such as head lamps, tail lamps, side lamps, and the like. It can be suitably used for a headlamp that requires a relatively large amount of light.

Further, the composition of the present invention containing the above-mentioned components (A) to (C) should be applied not only to the above-mentioned automobile reflecting mirror, but also to, for example, offset printing printing paper. By protecting the printing paper and imparting a cosmetic effect, it is possible to obtain a processed paper product having excellent adhesion with the offset ink and the paper.

[0051]

EXAMPLES The present invention will be specifically described below with reference to examples. In the examples, "%" and "parts" mean weight basis unless otherwise specified.

Example 1 [Production of acid-modified alkyd resin (A)] In a flask, a soybean oil-modified alkyd resin (a1) having an oil length of 41% (Arakawa Chemical Co., Ltd., "Arachid 3101X-60", resin content 60) was used.
%) 100 parts and maleic acid (a2) 6 parts were charged, and 9
The reaction was carried out by stirring at 0 ° C. for 2 hours to give an acid-modified alkyd resin (A-1) (resin content 62%, weight average molecular weight 30,
000, an acid value of 66.7 mgKOH / g) as a resin was obtained.

[Production of UV-Curable Resin Composition] 100 parts of the above acid-modified alkyd resin (A-1) (6 parts as a resin component)
2 parts), 15 parts of trimethylolpropane triacrylate (B), 15 parts of dipentaerythritol hexaacrylate (B), 1.35 parts of benzophenone (C),
1.35 parts of isoamyl dimethylaminobenzoate (C),
And 67.3 parts of ethyl acetate, and as a surface conditioner, Megafac F-177 (manufactured by Dainippon Ink and Chemicals, Inc., perfluoroalkyl group-containing nonionic oligomer) 0.0
2 parts and 0.2 part of methylhydroquinone as a polymerization inhibitor were mixed to obtain an ultraviolet curable resin composition of the present invention.

[Manufacture of FRP molded body automobile reflecting mirror] The FRP molded body for automobile reflecting mirror was washed with isopropyl alcohol and dried, and then the UV curable resin composition obtained above was dried to a film thickness of 10 to 10. Air spray coating was applied to the surface so that the thickness was 20 μm. After that, the solvent is removed by preheating at 100 ° C. for 10 minutes, and 80 W / cm ²
Using the ozone type diffusion type high pressure mercury lamp,
An anchor coat layer was formed on the surface of the FRP molded product by curing it by irradiating it with ultraviolet rays at a dose of mJ / cm ² .

Next, after vacuum-depositing aluminum on the surface of the obtained anchor coat layer, 20 parts of Yupica Coat 3002A (manufactured by Japan Upica Co.), 35 parts of toluene, and 40 parts of Solvesso # 100 are further deposited thereon. Parts, n-butanol, a topcoat prepared by the composition of 5 parts,
Air spray coating to a dry film thickness of 3μm,
The top coat layer was formed by baking at 120 ° C. for 10 minutes to prepare an FRP molded automobile mirror. The following evaluation was performed on the obtained FRP molded automobile reflecting mirror.

(Appearance of coating film) The appearance was visually observed to inspect for defects such as rainbow, whitening, cracks and blisters, and evaluated as follows. ○: No defect △: Slightly defective ×: Defective

(Glossiness) The glossiness was evaluated by visual observation as follows. ○ ・ ・ ・ Sufficient gloss × ・ ・ ・ Insufficient gloss

(Adhesiveness) The surface of the reflecting mirror was cut into 100 pieces of 2 mm-width cross-cuts with a cutter knife, and the cellophane sticky tape was affixed from above to the number of squares left without peeling. Was measured.

(Heat resistance) After leaving in a hot air circulation type drying oven at 180 ° C. for 100 hours, taking out and allowing to cool to room temperature, the appearance and adhesion were evaluated by the same method as above.

(Storage Stability) The ultraviolet curable resin composition obtained above was stored at 60 ° C., and the period until the viscosity increased and gel formation was measured.

Example 2 [Production of acid-modified alkyd resin (A)] In a flask, tall oil-modified alkyd resin (a1) having an oil length of 66% (Arakawa Chemical Co., Ltd., "Arachid 1465-60", resin content 60) was used.
%) 100 parts and maleic acid (a2) 6 parts were charged, and 9
The reaction was carried out by stirring at 0 ° C. for 2 hours to give an acid-modified alkyd resin (A-2) (resin content 62%, weight average molecular weight 38,
000, an acid value of 54.2 mgKOH / g) as a resin was obtained.

[Production of UV-Curable Resin Composition] 100 parts of the above acid-modified alkyd resin (A-2) (6 parts as resin content)
2 parts), 20 parts of trimethylolpropane triacrylate (B), 20 parts of dipentaerythritol hexaacrylate (B), 1.5 parts of benzophenone (C), 1.5 parts of isoamyl dimethylaminobenzoate (C), and acetic acid. 79 parts of ethyl, 0.02 part of Megafac F-177 (Dainippon Ink and Chemicals, Inc., nonionic oligomer containing a perfluoroalkyl group) as a surface modifier, and mono-t-butylhydroquinone 0.2 as a polymerization inhibitor.
Parts were blended to obtain the ultraviolet curable resin composition of the present invention.

[Production of FRP molded automobile reflector] Example 1 was prepared using the ultraviolet curable resin composition obtained above.
An FRP molded automobile reflecting mirror was produced in the same manner as in. The same evaluation as in Example 1 was performed on the obtained FRP molded automobile reflecting mirror.

Example 3 [Production of acid-modified alkyd resin (A)] The same acid-modified alkyd resin (A-1) as in Example 1 was used.

[Production of UV-Curable Resin Composition] 100 parts of the above acid-modified alkyd resin (A-1) (6 parts as a resin component)
2 parts), ethylene oxide modified (n = 3) trimethylolpropane triacrylate (B) 20 parts, trimethylolpropane triacrylate (B) 20 parts, benzophenone (C) 1.5 parts, dimethylaminobenzoic acid isoamyl (C) ) 1.5 parts, and ethyl acetate 79 parts, and as a surface conditioner, Megafac F-177 (manufactured by Dainippon Ink and Chemicals, Inc., perfluoroalkyl group-containing nonionic oligomer) 0.02 part, and hydroquinone as a polymerization inhibitor. 0.2 part of monomethyl ether was blended to obtain the ultraviolet curable resin composition of the present invention.

[Production of FRP molded automobile reflecting mirror] Using the ultraviolet curable resin composition obtained above, Example 1
An FRP molded automobile reflecting mirror was produced in the same manner as in. The same evaluation as in Example 1 was performed on the obtained FRP molded automobile reflecting mirror.

Example 4 [Production of acid-modified alkyd resin (A)] The same acid-modified alkyd resin (A-2) as in Example 2 was used.

[Production of UV-Curable Resin Composition] 100 parts of the above acid-modified alkyd resin (A-2) (6 parts as resin content)
2 parts), pentaerythritol tetraacrylate (B) 20 parts, dipentaerythritol hexaacrylate (B) 20 parts, benzophenone (C) 1.5 parts, dimethylaminobenzoic acid isoamyl (C) 1.5 parts, and ethyl acetate 79 parts, as a surface modifier, Megafac F-177 (manufactured by Dainippon Ink and Chemicals, Inc., perfluoroalkyl group-containing nonionic oligomer) 0.02 part, and mono-t-butylhydroquinone 0.2 as a polymerization inhibitor.
Parts were blended to obtain the ultraviolet curable resin composition of the present invention.

[Manufacture of FRP molded automobile reflecting mirror] The ultraviolet curable resin composition obtained above was used in Example 1.
An FRP molded automobile reflecting mirror was produced in the same manner as in. The same evaluation as in Example 1 was performed on the obtained FRP molded automobile reflecting mirror.

Comparative Example 1 In Example 1, instead of the acid-modified alkyd resin (A-1), a tall oil-modified alkyd resin (a) having an oil length of 66% was used.
1) ("Arakawad 1465-60", manufactured by Arakawa Chemical Co., Ltd.,
Resin content 60%, acid value as resin 7.7mgKOH / g)
A UV-curable resin composition was obtained in the same manner except that was used. Using the obtained ultraviolet curable resin composition, an FRP molded automobile reflecting mirror was prepared in the same manner as in Example 1,
Similar evaluation was performed.

Comparative Example 2 In Example 1, the acid-modified alkyd resin (A-
An ultraviolet curable resin composition was obtained in the same manner except that the following acid-modified alkyd resin was used instead of 1). [Production of acid-modified alkyd resin] Oil length of 41
% Soybean oil modified alkyd resin (a1) (Arakawa Chemical Co.,
"Araquid 3101X-60", resin content 60%) 10
0 parts and 15 parts of maleic acid (a2) were charged and reacted by stirring at 90 ° C. for 2 hours to give an acid-modified alkyd resin (resin content 62%, weight average molecular weight 30,000, acid value 82 mgKOH / resin as resin / g) was obtained. Using the obtained ultraviolet curable resin composition, in the same manner as in Example 1, F
An RP molded automobile reflecting mirror was prepared and the same evaluation was performed.

Comparative Example 3 An ultraviolet curable resin was prepared in the same manner as in Example 1 except that 15 parts of phenoxyethyl acrylate was used instead of trimethylolpropane triacrylate (B) and dipentaerythritol hexaacrylate (B). A composition was obtained. Using the obtained ultraviolet-curable resin composition, an FRP molded automobile reflecting mirror was prepared in the same manner as in Example 1, and the same evaluation was performed. Table 1 shows the evaluation results of the examples and comparative examples.

[Table 1] Appearance of coating film Glossiness Adhesion Heat resistance Storage stability Appearance Adhesion Example 1 ○ ○ 100/100 ○ 100/100 3 months 〃 2 ○ ○ 100/100 ○ 100/100 3 months 〃 3 ○ ○ 100/100 ○ 100/100 3 months 〃 4 ○ ○ 100/100 ○ 100/100 3 months Comparative example 1 ○ ○ 90/100 ○ 80/100 2 months 〃 2 × × 10/100 × 0/100 2 days 3 △ × 20/100 × 0/100 2 months

[0074]

The ultraviolet-curable resin composition of the present invention comprises an acid-modified alkyd resin (A) having an acid value of 20 to 80 mgKOH / g, a compound having at least two (meth) acryloyl groups in the molecule ( B), and a photopolymerization initiator (C)
Since it is a one-component type, it has no limitation on pot life and has excellent effects on adhesion, heat resistance, and storage stability. In particular, an anchor coat for performing metal vapor deposition on FRP molded bodies. It is useful as an agent.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09D 4/02 C09D 4/02 4/06 4/06 5/00 5/00 Z 163/10 163/10 167/00 167/00 167/06 167/06 167/08 167/08 175/14 175/14 (72) Inventor Mamoru Akiyama 2-13-1 Muroyama, Ibaraki City, Osaka Prefecture Nippon Synthetic Chemical Industry Co., Ltd. Chuo Institute within the F-term (reference) 4D075 AE03 BB42Y BB46Y BB85Z CA13 CA18 CA38 CB04 CB06 DA04 DA06 DA23 DB01 DB13 DB18 DB35 DB36 DB37 DB43 DB48 DB61 DC13 EA07 EA21 EA41 EA43 EB20 EB22 EB24 EB32 EB33 EB34 EB35 EB36 EB37 EB38 EB45 EB55 EB56 EC07 EC37 EC54 4J011 AA05 PA88 QA12 QA13 QA17 QA22 QA23 QA24 QB12 QB14 QB16 QB19 QB20 QB24 RA07 SA01 SA21 SA31 SA41 SA51 SA61 SA64. AG07 AJ08 BA19 BA20 BA21 BA23 BA26 CB10 CC05 CD08 4J038 DD001 DD002 DD231 DD232 FA151 FA152 FA251 FA252 FA261 FA262 FA281 FA282 GA06 KA03 NA12 NA14 NA26 PA17 PB07 PB08 PC08

Claims (9)

[Claims] 1. An acid-modified alkyd resin (A) having an acid value of 20 to 80 mgKOH / g, a compound (B) having at least two (meth) acryloyl groups in the molecule, and a photopolymerization initiator (C). An ultraviolet-curable resin composition comprising: 2. The acid-modified alkyd resin (A) is based on 100 parts by weight of the oil-modified alkyd resin (a1), and maleic acid, phthalic acid, fumaric acid, tetrahydrophthalic acid,
The ultraviolet-curable resin composition according to claim 1, which is modified with 5 to 20 parts by weight of at least one acid (a2) selected from 3-methyltetrahydrophthalic acid or an acid anhydride thereof. 3. The oil-modified alkyd resin (a1) is
Tall oil, coconut oil, soybean oil, safflower oil, linseed oil,
The ultraviolet curable resin composition according to claim 2, wherein the ultraviolet curable resin composition is modified with at least one selected from tung oil, castor oil and fatty acids of these oils and fats. 4. The compound (B) having at least two (meth) acryloyl groups in the molecule is a (meth) acrylic monomer, urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate. It is at least 1 sort (s) selected, The ultraviolet curable resin composition in any one of Claims 1-3. 5. The ultraviolet curable resin composition according to claim 1, wherein the photopolymerization initiator (C) is at least one of dimethylaminobenzoic acid and dimethylaminobenzoic acid alkyl ester. . 6. The content of the acid-modified alkyd resin (A) and the compound (B) having at least two (meth) acryloyl groups in the molecule is 100 parts by weight of the molecule of the acid-modified alkyd resin (A). The ultraviolet-curable resin composition according to any one of claims 1 to 5, wherein the compound (B) having at least two (meth) acryloyl groups therein is 25 to 400 parts by weight. 7. A photopolymerization initiator (C) 2 to 10 relative to 100 parts by weight in total of the acid-modified alkyd resin (A) and the compound (B) having at least two (meth) acryloyl groups in the molecule. The ultraviolet curable resin composition according to any one of claims 1 to 6, wherein the ultraviolet curable resin composition comprises parts by weight. 8. An ultraviolet curable resin, characterized in that the ultraviolet curable resin composition according to any one of claims 1 to 7 is applied to the surface of an FRP molded article and then irradiated with ultraviolet rays to form a coating film. Method for forming coating film of composition. 9. An ultraviolet ray curable resin composition according to any one of claims 1 to 7 is applied to the surface of an FRP molded article for an automobile reflecting mirror and then irradiated with ultraviolet rays to form a coating film. An automobile reflecting mirror, characterized in that a metal is vacuum-deposited on the above, and a top coat layer is further formed thereon.