JPH0142287B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention has no unpleasant odor, has good coating workability, has excellent adhesion to paper, plastic, wood, metal, etc., and has excellent hardening properties, flexibility, water resistance, weather resistance, gloss, corrosion resistance, etc. The present invention relates to an active energy ray-curable coating composition that forms a coating film having the following properties. Conventionally, urethane resin-based coating compositions containing urethane resins containing ethylenically unsaturated groups and ethylenically unsaturated monomers as main components have been used as coating compositions that are cured by irradiation with active energy such as ultraviolet rays and electron beams. is commonly used. This urethane resin coating composition forms a coating film with almost practical weather resistance and flexibility, but
Various other performance problems have been pointed out, and improvements are desired. That is, since urethane resins containing ethylenically unsaturated groups have poor compatibility with ethylenically unsaturated monomers, the gloss, smoothness and physical performance of the coating film are insufficient, and repellency is likely to occur. Further, the mixture of both components and the formed coating film generate an unpleasant odor, which is unfavorable from a hygienic standpoint in terms of handling. moreover,
In addition to the above-mentioned defects, the cured coating film obtained by applying the composition to substrates such as paper surfaces such as gift boxes and book covers, printed surfaces, and metal-deposited surfaces has problems such as adhesion to these substrates and surface hardening. properties, smoothness of the coating film, bendability,
Adhesion to the glue adhering to the base material was insufficient for practical use. Furthermore, when the composition is applied to a metal substrate such as iron, zinc, or aluminum,
Adhesion to the base material, water resistance, and corrosion resistance were insufficient. Furthermore, the coating film obtained by applying the composition to plastic (eg, polyester resin, etc.) and curing it has poor adhesion to the substrate and flexibility. In addition, the coating film obtained by applying the composition to wood that has been treated with a sealing coating and curing it has a good finish appearance, gloss,
It has insufficient adhesion with fillers, hardenability, heat resistance, cold resistance, moisture resistance, etc., and is also poor in cutting processability with a saw or the like. In view of the above-mentioned situation, the present inventors have solved the above-mentioned defects without reducing the weather resistance and flexibility of conventional urethane resin-based coating compositions that are cured by irradiation with active energy rays. We have conducted intensive research with the aim of developing a urethane resin coating composition for curing with active energy radiation that can form coatings with excellent performance on substrates such as paper, metal, plastic, and wood. be. As a result, the above purpose can be achieved by using an unsaturated monomer having a specific structural formula in an ethylenically unsaturated group-containing urethane resin instead of or in combination with the conventional ethylenically unsaturated monomer. It was found that this could be achieved, and the present invention was completed. That is, the present invention provides (a) general formula (R ₁ is a hydrogen atom or a methyl group, R ₂ is an alkylene group having 2 to 4 carbon atoms, R ₃ is a carbon atom number 1
~20 alkyl groups, phenyl groups, or alkylphenyl groups) and (b) an ethylenically unsaturated group-containing urethane resin as essential components, further optionally containing (c) The present invention relates to a coating composition for curing with active energy rays, which is formulated with an ethylenically unsaturated monomer and/or (d) a photopolymerization initiator, and is cured by irradiation with active energy rays such as ultraviolet rays and electron beams. The coating composition of the present invention is characterized by the combination of the ethylenically unsaturated group-containing urethane resin [component (b)] and the unsaturated monomer represented by the above general formula [component (a)]. Component (a) is a compound known per se,
In U.S. Patent No. 4,072,592, component (a) is used in combination with an unsaturated epoxy resin such as an adduct of an epoxy resin and acrylic acid and a modified product obtained by further modifying the adduct with an acid anhydride. composition,
Disclosures are made regarding curing by ultraviolet or electron beam irradiation. The inventors of the present invention also studied the known technology according to this specification, and found that it was difficult to form a coating film with excellent gloss due to the poor compatibility between component (a) and the unsaturated epoxy resin. However, they discovered that it has a serious defect in that it tends to cause repellency in the coating film. Furthermore, the coating film obtained by applying the composition to a paper surface, wood, etc. and curing it was prone to yellowing, and its adhesion to the ink surface and the sealant was insufficient from a practical point of view. Adhesion to plastics was also unsatisfactory. For metals, it has excellent corrosion resistance and has practical performance, but its high viscosity makes it difficult to apply it to steel pipes. As described above, compositions containing component (a) in combination with unsaturated epoxy resins have various defects in coating film performance, and their range of use is extremely limited. The present inventors have conducted research to eliminate the various defects described above in urethane resin coating compositions that are cured by irradiating active energy, and have found that component (a) as described above can be used in a wide range of applications. By using them together, the object of the present invention was completely achieved. This fact was completely unexpected from the above-mentioned known facts regarding component (a), and a surprising technical effect was obtained. Next, the components constituting the coating composition of the present invention will be explained. (a) Component: General formula (R ₁ is a hydrogen atom or a methyl group, R ₂ is an alkylene group having 2 to 4 carbon atoms, R ₃ is a carbon atom number 1
~20 alkyl, phenyl or alkylphenyl groups). In the above general formula, R ₂ has 2 to 4 carbon atoms
Examples of the alkylene group include ethylene group, n-propylene group, iso-propylene group, n-butylene group,
Examples include iso-butylene group and tert-butylene group. If the number of carbon atoms in the alkylene group is 5 or more, it is not preferable because the curability upon irradiation with active energy rays deteriorates. In addition, the number of carbon atoms in R ₃ is 1 to
Examples of the alkyl group, phenyl group, and alkylphenyl group of 20 include methyl group, ethyl group, n-
Propyl group, i-propyl group, n-butyl group,
iso-butyl group, tert-butyl group, iso-amyl group,
n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, iso-nonyl group, lauryl group, stearyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, phenyl group, methylphenyl group, Examples include iso-propylphenyl group, tert-butylphenyl group, methoxyphenyl group, etc. If the number of carbon atoms in R ₃ is 21 or more, curability by active energy ray irradiation deteriorates, which is not preferable. In the present invention, as component (a), one or more selected from the unsaturated monomers represented by the above general formula can be used, and among these, in the general formula, R ₁ is a hydrogen atom. It is particularly preferable to use an unsaturated monomer in which R ₂ is an ethylene group, and R ₃ is an n-propyl group, iso-propyl group, n-butyl group, or phenyl group. Component (b): Ethylenically unsaturated group-containing urethane resin The component (b) in the present invention is an oligomer, prepolymer, and polymer having an ethylenically unsaturated group and a urethane bond in one molecule. The urethane bond is formed by the reaction between an isocyanate group and a hydroxyl group. Component (b) is known per se and can be produced, for example, by the following method. (1) Per mole of polyisocyanate compound having two or more isocyanate groups in one molecule,
Two or more moles of a monomer having a hydroxyl group and an ethylenically unsaturated group (hereinafter abbreviated as a hydroxyl group-containing unsaturated monomer) are reacted. (2) An adduct obtained by reacting 2 or more moles of a polyisocyanate compound per mole of a polyol having two or more hydroxyl groups in one molecule (having at least two or more isocyanate groups in one molecule) 2 or more moles of the hydroxyl group-containing unsaturated monomer are reacted per mole. (3) A polyisocyanate compound and a hydroxyl group-containing unsaturated monomer are reacted in a substantially equimolar ratio (one molecule of the reaction product has at least one free isocyanate group), and then, The reaction product is reacted in an amount of 2 or more moles per mole of polyol. (4) An acrylic resin having two or more hydroxyl groups in one molecule (hereinafter abbreviated as acrylic resin polyol) is reacted with about 1 mol of a polyisocyanate compound per 1 mol of the hydroxyl group to obtain 1 mol of the acrylic resin polyol. At least two isocyanate groups are present in the molecule. Next, a hydroxyl group-containing unsaturated monomer is added to the reaction product so that each molecule of the adduct contains at least two ethylenically unsaturated bonds. (5) A polyisocyanate compound and a hydroxyl group-containing unsaturated monomer are reacted in a substantially equimolar ratio (one molecule of the reaction product has at least one free isocyanate group), and then, 2 moles or more of the reaction product is reacted with an acrylic resin polyol. (6) Except for replacing the acrylic resin polyol in (4) and (5) above with a polyester having two or more hydroxyl groups in one molecule (hereinafter abbreviated as polyester polyol), ). The reactions of each component in (1) to (6) above can be carried out by known methods. As the component (b) in the present invention, among the above methods (1) to (6), those obtained by methods such as (2), (3), (5) and (6) are particularly preferable. . In the above manufacturing methods (1) to (6) for component (b), examples of the polyisocyanate compound include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate,
xylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, 4,
4'-methylenebis(cyclohexyl isocyanate), methylcyclohexane 2,4(2,6) diisocyanate, 1,3-(isocyanatomethyl)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 triisocyanate, naphthylene diisocyanate, tolylene diisocyanate polymer,
Diphenylmethane diisocyanate polymer, hexamethylene diisocyanate polymer, 3-phenyl-2-ethylene diisocyanate, cumene-2,4-diisocyanate, 4-methoxy-
1,3-phenylene diisocyanate, 4-ethoxy-1,3-phenylene 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'-benzyl diisocyanate, 3,3'-dimethyl-4,
4'-diisocyanate diphenylmethane, 2,6
-dimethyl-4,4'-diisocyanate diphenyl, 3,3'-dimethoxy-4,4'-diisocyanate diphenyl, 1,4-anthracene diisocyanate, phenylene diisocyanate, 2,
4,6-tolylene triisocyanate, 2,4,
4′-triisocyanate diphenyl ether,
1,4-tetramethylene diisocyanate, 1,
6-hexamethylene diisocyanate, 1,10-
Examples include decamethylene diisocyanate, 1,3-cyclohexylene diisocyanate, and 4,4'-methylene-bis(cyclohexyl isocyanate). These can be used alone or in combination of two or more. Among these, isophorone diisocyanate, xylylene diisocyanate, tolylene diisocyanate, 1,6-hexane diisocyanate, and the like are particularly preferred. In addition, examples of the hydroxyl group-containing unsaturated monomers in (1) to (6) above include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, allyl alcohol, butanediol monoacrylate. , butanediol monomethacrylate, N-methylol acrylamide, crotyl alcohol, propylene glycol monoacrylate, etc. Furthermore, glycidyl acrylate or glycidyl methacrylate and a carboxyl group-containing compound (for example, adipic acid, sebacic acid, azelaic acid, etc.) Adducts of acrylic acid or methacrylic acid and epoxy compounds (e.g. epichlorohydrin, etc.) can also be used. These may be used alone or in a mixture of two or more. Among these, 2-hydroxyethyl acrylate, butanediol monoacrylate, 2-hydroxyethyl methacrylate, butanediol monomethacrylate, etc. are particularly preferred. The polyols used in (2) and (3) above include, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol (molecular weight 6000 or less), trimethylene glycol, polypropylene glycol (molecular weight 6000 or less). (below), tetramethylene glycol,
Polytetramethylene glycol, 1,2-butylene glycol, 1,3-butanediol, 1,4
-butanediol, 1,5-pentanediol,
Neopentyl glycol, 1,2-hexylene glycol, 1,6-hexanediol, heptanediol, 1,10-decanediol, cyclohexanediol, 2-butene-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-propanol, 4-(2-hydroxypropoxy)-1-butanol, 5-(2-hydroxypropoxy)-1-pentanol, 1-(2-
hydroxyethoxyl)-2-butanol, 1-
(2-hydroxyethoxy)-2-pentanol,
Hydrogenated bisphenol A, glycerin, 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-
Examples include hexanediol, pentaerythritol, dipentaerythritol, mannitol, and glucose. Among these, polyethylene glycol, polycaprolactone, polypropylene glycol, tetramethylene glycol, trimethylolpropane and the like are particularly preferred. Furthermore, the acrylic resin polyols in (4) and (5) above are obtained by copolymerizing the above-mentioned hydroxyl group-containing unsaturated monomer and acrylic monomer in combination with other vinyl monomers as necessary. It is something. The number average molecular weight of the acrylic resin polyol is approximately
The preferable range is 1000 to 10000, and the hydroxyl equivalent is preferably 300 to 3000. Examples of the acrylic monomer include esterified products of acrylic acid or methacrylic acid and a monohydric alcohol having 1 to 20 carbon atoms. Specifically, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isoacrylate
-butyl, iso-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate,
Propyl acrylate, propyl methacrylate, hexyl acrylate, hexyl methacrylate, octyl acrylate, octyl methacrylate, lauryl acrylate, lauryl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, cyclohexyl acrylate, methacrylic acid Examples include cyclohexyl, stearyl acrylate, and stearyl methacrylate. Furthermore, acrylic acid, methacrylic acid, glycidyl acrylate, glycidyl methacrylate, acrylamide, methacrylamide, diacetone acrylamide, and the like can also be used as the acrylic monomer. These may be used alone or in combination. In addition, examples of other vinyl monomers include styrene, vinyltoluene, methylstyrene,
Chlorstyrene, vinyl acetate, vinyl chloride, vinyl isobutyl ether, methyl vinyl ether,
Examples include acrylonitrile, 2-ethylhexyl vinyl ether, and divinylbenzene. In the acrylic resin polyol, the content of the other vinyl monomers is preferably 30% by weight or less. Furthermore, the polyester polyol in the above (6) has a hydroxyl group at the terminal and/or side chain, and the hydroxyl equivalent thereof is preferably 200 to 5,000.
The polyester polyol is obtained by reacting a polybasic acid and a polyhydric alcohol, optionally using a monobasic acid in combination. Examples of the polybasic acids include phthalic anhydride, isophthalic acid, terephthalic acid, succinic anhydride, adipic acid, azelaic acid, sebacic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, hexic anhydride, hemicic anhydride, and anhydride. Examples include maleic acid, fumaric acid, itaconic acid, trimellitic anhydride, methylcyclohexentricarboxylic anhydride, pyromellitic anhydride, and these may be used alone or in combination. Examples of the polyhydric alcohol include the polyols described above. In addition, as monobasic acids, benzoic acid, p-t-
Examples include butylbenzoic acid, coconut oil fatty acid, castor oil fatty acid, rice bran oil fatty acid, soybean oil fatty acid, tall oil fatty acid, dehydrated castor oil fatty acid, safflower oil fatty acid, linseed oil fatty acid, hydene fatty acid, and tung oil fatty acid. The coating composition of the present invention comprises the above-mentioned component (a) and
Component (b) is essential, and the ratio of both components is 5 to 95% by weight, preferably 20 to 80% by weight of component (a), and 95% by weight of component (b), based on the total amount of both components. ~
5% by weight, preferably in the range 80-20% by weight. If component (a) is less than 5% by weight, the flexibility, gloss, smoothness, physical performance, etc. of the coating film will decrease, while if it is more than 95% by weight, the curing properties, weather resistance, etc. of the coating film will deteriorate. Both are unfavorable. (c) Component: Ethylenically unsaturated monomer The above-mentioned essential component in the composition of the present invention
If necessary, an ethylenically unsaturated monomer [component (c)] can be further used in combination with the system consisting of components (a) and (b). As the component (c), common monomers and oligomers having radical polymerizability can be used, and specific examples include the following. Examples of radically polymerizable monomers include the hydroxyl group-containing unsaturated monomers, acrylic monomers, and other vinyl monomers disclosed in the explanation regarding component (b) above. In addition, as radically polymerizable oligomers,
Mainly di-, tri- and tetravinyl compounds, diethylene glycol diacrylate, diethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, 1,3-butanediol diacrylate,
1,3-butanediol dimethacrylate, 1,
4-Butanediol diacrylate, 1,4-butanediol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane triacrylate Acrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate,
Pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, products obtained by reacting an adduct of bisphenol A and ethylene oxide with acrylic acid and/or methacrylic acid, products obtained by reacting an adduct of bisphenol A and propylene oxide with acrylic acid and/or There are products made by reacting methacrylic acid. These monomers and oligomers can be used alone or in combination of two or more. These component (c) can be used in combination in an amount of 5 to 95% by weight, preferably 20 to 80% by weight of the component (b). By using component (c) in combination, the viscosity of the coating composition and the physical performance of the cured coating film can be adjusted. (d) Component: Photopolymerization initiator The coating film made from the composition of the present invention is cured by irradiation with active energy such as electron beams and ultraviolet rays. It is necessary to add a polymerization initiator in advance. As the photopolymerization initiator, a normal photopolymerization initiator that is excited by ultraviolet irradiation to generate radicals is used, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, Examples include benzoin n-butyl ether, benzophenone, P-methylbenzophenone, Michler's ketone, acetophenone, 2-chlorothioxanthone, anthraquinone, 2-methylanthraquinone, phenyl disulfide, and 2-nitrofluorene. These photopolymerization initiators can be used alone or in combination of two or more. The amount to be blended is the total amount of component (a) and component (b) above, or the total amount including component (c) if used together.
A proportion of 0.1 to 10% by weight is preferred. Moreover, in order to promote the photopolymerization reaction by the photopolymerization initiator, a photosensitization accelerator may be used in combination with the photopolymerization initiator. As the photosensitization accelerator, for example, tertiary amine type such as triethylamine, triethanolamine, 2-dimethylaminoethanol, alkylphosphine type such as triphenylphosphine, β
- Examples include thioethers such as thiodiglycol. These photosensitizers can be used alone or in combination of two or more. Its compounding amount is as above.
The proportion of component (a) and component (b) is preferably 0.1 to 10% by weight of the total amount of component (b), or, if component (c) is used in combination, the total amount including the component. As described above, the composition of the present invention essentially contains components (a) and (b), and optionally contains components (c) and/or (d) in combination. Furthermore, the composition may contain pigments and dyes that do not interfere with the radical polymerization that occurs when irradiated with active energy rays, and may also contain a small amount of an organic solvent with a low boiling point (180°C or less). do not have. The composition of the present invention can be coated by a roll coater, curtain flow coater, brush, dip, electrostatic coater, spray gun, or the like. The object to be coated is not particularly limited, and it can be applied to plastic, paper, metal-deposited surfaces, metal, wood, etc. Further, the thickness of the coating film on these surfaces to be coated is preferably 3 to 500 μm. The coating film made from the composition of the present invention is cured by irradiation with active energy rays.
Examples of active energy rays include electron beams and ultraviolet rays, and any of them may be used. Examples of electron beam sources include Kotskucroft type, Kotscroft-Walton type, Van de Graaff type, resonant transformer type, transformer type, insulated core transformer type, dynamitron type, linear filament type, and high frequency type. . The electron beam irradiation conditions are:
Although not particularly limited, a dose of 1 to 20 megarads is suitable. Further, examples of the ultraviolet irradiation source include a mercury lamp, a xenon lamp, a carbon arc, a metal height lamp, and sunlight. The irradiation conditions for ultraviolet rays are not particularly limited either, but it is preferable to irradiate for several seconds or more in air or in an inert gas atmosphere.
In particular, when irradiating in air, it is preferable to use a high-pressure mercury lamp. Since the composition of the present invention uses the above-mentioned components (a) and (b), it has been able to obtain various unexpected technical effects. That is, the composition obtained according to the present invention and the cured coating film made from the composition generate no or almost no unpleasant odor, so that the hygienic problem in handling has been solved. Furthermore, since component (a) has extremely good compatibility with component (b), it can significantly improve the gloss, smoothness, physical performance, etc. of the paint film, and there is no occurrence of repelling. I couldn't do it anymore. In particular, no decrease in compatibility is observed even when the molecular weight of component (b) increases. Moreover, it has excellent adhesion to paper, metal-deposited surfaces, printing ink surfaces, plastics (e.g., polyvinyl chloride, polyurethane, polyester, etc.), wood, and metals, so it has a wider range of applications than conventional urethane resin-based paints. became wider. First, when the composition of the present invention is applied to paper, metal-deposited surfaces, ink-printed surfaces, etc. used for cosmetic cases and book covers, a coating film with excellent adhesion and gloss can be formed, and the aesthetics will be significantly improved and the product will last for a long time. Even after a period of time, there will be no shine or yellowing. In addition, the coating film has excellent smoothness, so it does not stick even when stacked or pressed together. Furthermore, since it has excellent flexibility, the coating film will not crack or peel even if it is bent appropriately. Furthermore, since the composition has a relatively high viscosity, it has good wettability on the surface to be coated, and the coating workability is improved. Furthermore, it has excellent adhesion to plastics and good flexibility, so it can sufficiently respond to these deformations. Furthermore, the composition of the present invention can also be applied to wood,
When active energy is applied to a paint film applied to wood that has undergone sealing treatment, the inside and surface of the paint film is extremely well cured, making it difficult to scratch, improving the finished appearance, gloss, and adhesion with sealants. etc. were improved. Moreover, the flexibility of the coating film
Because it is superior to conventional products, it is easy to cut and process with a saw, and exhibits excellent heat and cold resistance. Furthermore, the water resistance and humidity resistance were also good. Furthermore, the composition of the present invention can also be applied to iron, aluminum, zinc, and alloys containing these metals. The coating films applied to these objects were excellent in terms of adhesion, corrosion resistance, weather resistance, water resistance, etc. Moreover, since the composition of the present invention has a relatively low viscosity, it is most suitable for ironing onto pipes and the like. As described above, the composition of the present invention can be applied to almost any object to be coated and has excellent coating performance. Next, the content of the present invention will be explained in more detail with reference to Examples and Comparative Examples. Note that the present invention is not limited to this example. Example,
Parts and % in comparative examples are parts by weight and % by weight. Example 1 (a) Ingredients: and (b) component: ethylenically unsaturated group-containing urethane resin () 50
A coating composition targeted by the present invention was obtained by mixing the following parts. The ethylenically unsaturated group-containing urethane resin () was produced in the following manner. 400 parts (1 mol) of polyethylene glycol (molecular weight 400) and 444 parts (2 mol) of isophorone diisocyanate were placed in a four-necked flask and stirred.
After keeping at 100℃ for 1 hour, cool to 70℃. Add 1.5 parts of hydroquinone and 232 parts (2 moles) of 2-hydroxyethyl acrylate to a four-necked flask at 70°C, stir while blowing air, raise the temperature to 80°C, and keep for 5 hours to remove residual isocyanate groups. After confirming that almost no oxidation was observed, the mixture was cooled and designated as component (b). Example 2 Coating composition obtained in Example 1 100 parts Benzophenone [component (d)] 5 parts Triphenylphosphine [photosensitization accelerator]
Part 2 Example 3

[Table] were mixed to obtain a coating composition targeted by the present invention. The ethylenically unsaturated group-containing urethane resin () was produced in the following manner. 550 parts (1 mol) of polycaprolactone (trade name: Plaxel 205, manufactured by Daicel Corporation) and 376 parts (2 mol) of xylylene diisocyanate were placed in a four-necked flask, stirred, kept at 100°C for 1 hour, and then cooled. to bring the resin temperature to 70℃. Hydroquinone at 70℃
Add 1.5 parts of butanediol monoacrylate and 288 parts of butanediol monoacrylate into a four-necked flask, stir while blowing air, raise the temperature to 80°C and keep it for 5 hours, and confirm that the remaining isocyanate groups have almost completely reacted. The mixture was cooled and used as component (b). Example 4 Coating composition obtained in Example 3 100 parts Benzoin ethyl ether 5 parts Example 5 (a) Component (b) Component 70 parts of a 57% ethylenically unsaturated group-containing urethane resin () was mixed to obtain a coating composition targeted by the present invention. The ethylenically unsaturated group-containing urethane resin () was produced in the following manner. 300 parts of methyl methacrylate, 600 parts of n-butyl acrylate, 100 parts of dihydroxyethyl acrylate
1,500 parts of toluene, and 50 parts of azobisisobutyronitrile were placed in a four-necked flask and kept at 110°C for 5 hours to produce an acrylic resin polyol. This acrylic resin polyol has a molecular weight of 5000 and a hydroxyl equivalent.
It is 1160. 222 parts of isophorone diisocyanate and 2 parts of acrylic acid are added to this acrylic resin polyol.
1014 parts of a monoisocyanate compound to which 116 parts of hydroxyacrylate had been added were added and reacted at 100°C for 3 hours, and after confirming that the remaining isocyanate groups had completely reacted, the mixture was cooled and used as component (b). Example 6

【table】

[Table] were mixed to obtain a coating composition targeted by the present invention. The above ethylenically unsaturated group-containing urethane resin () was manufactured according to the following method. 232 parts of adipic acid and 424 parts of diethylene glycol were placed in a four-necked flask, stirred and kept at 220°C for 5 hours while azeotropically dehydrating with toluene, and then the toluene was removed from the solvent while cooling. After cooling to 80℃, add 672 parts of 1.6 hexamethylene diisocyanate and keep at 100℃ for 1 hour.After cooling to 80℃, add 464 parts of 2-hydroxyethyl acrylate and keep at 80℃ for 3 hours to remove residual isocyanate. After confirming that almost complete reaction had occurred, the mixture was cooled and the resulting product was designated as component (b). Comparative Example 1 A coating composition was produced in the same manner as in Example 1 except that component (a) in Example 1 was replaced with diethylene glycol diacrylate. Comparative Example 2 A coating composition was produced in the same manner as in Example 1, except that component (a) in Example 2 was replaced with diethylene glycol diacrylate. Comparative Example 3 A coating composition was produced in the same manner as in Example 1, except that component (b) in Example 1 was replaced with the following ethylenically unsaturated group-containing epoxy resin. Epicote 828 (diglycidyl ether of bisphenol A, epoxy equivalent 185-192, epoxy value 0.50-0.54) 660 parts, acrylic acid 248 parts,
1.3 parts of triethylamine and 0.1 part of hydroquinone
100°C and reacted at the same temperature until the acid value reached 5 to 10. Comparative Example 4 A coating composition in which component (b) in Example 2 was replaced with the ethylenically unsaturated group-containing epoxy resin used in Comparative Example 3. Various performance tests were conducted on the coating compositions of Examples and Comparative Examples produced as described above.
The results are shown in Table 1.

【table】

【table】

【table】

Claims (1)

[Claims] 1 (a) General formula (R ₁ is a hydrogen atom or a methyl group, R ₂ is an alkylene group having 2 to 4 carbon atoms, and R ₃ is an alkyl group, phenyl group, or alkylphenyl group having 1 to 20 carbon atoms). A coating composition for curing with active energy rays, the main components of which are a saturated monomer and (b) a urethane resin containing an ethylenically unsaturated group. 2. The active energy ray-curable coating composition according to claim 1, the main component of which is a mixture of components (a) and (b) with (c) an ethylenically unsaturated monomer. . 3 Claim 1 whose main component is a product obtained by blending (d) a photopolymerization initiator with the components (a) and (b).
The coating composition for curing with active energy rays as described in 1. 4. The active energy ray-curable coating composition according to claim 2, which contains the component (d) as a main component in addition to the components (a), (b), and (c).