JPH0148927B2 - - 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, as coating compositions that are cured by irradiation with active energy such as ultraviolet rays and electron beams, unsaturated polyester resin coating compositions containing an unsaturated polyester resin and an ethylenically unsaturated monomer as main components have generally been used. It is used. This unsaturated polyester resin coating composition is
Although it forms a coating film with almost practical weather resistance and flexibility, various other problems have been pointed out and improvements are desired. That is, since unsaturated polyester resins have poor compatibility with ethylenically unsaturated monomers, the gloss, smoothness, and physical performance of the coating films 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. Furthermore, the composition,
In addition to the above-mentioned defects, cured coatings applied to substrates such as paper surfaces such as gift boxes and book covers, printed surfaces, and metal-deposited surfaces have defects such as adhesion to these substrates, surface hardening properties, and coating slippage. The flexibility, bendability, adhesion to the glue attached to the base material, etc. were insufficient for practical use. Furthermore, when the composition was applied to a metal substrate such as iron, zinc, or aluminum, the adhesion to the substrate, water resistance, and corrosion resistance were insufficient. Furthermore, the coating film obtained by applying the composition to plastic (eg, polyurethane resin, etc.) and curing it has poor adhesion to the substrate and flexibility. In addition, the paint film obtained by applying the composition to wood that has been treated with a filler coating and curing it has insufficient finish appearance, gloss, adhesion with sealants, curing properties, heat resistance, cold resistance, moisture resistance, etc. Moreover, the cutting processability with a saw etc. is also poor. 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 unsaturated polyester resin coating compositions that are cured by irradiation with active energy rays. We have conducted intensive research with the aim of developing an unsaturated polyester resin paint that can be cured by active energy rays and can form coatings with excellent performance on substrates such as paper, metal, plastic, and wood. It was. As a result, it was found that the above objective could be achieved by using an unsaturated monomer with a specific structural formula in the unsaturated polyester resin instead of or in combination with the conventional ethylenically unsaturated monomer. Thus, they completed the present invention. 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 unsaturated polyester resin as essential components, further optionally containing (c) ethylenically unsaturated monomers. The present invention relates to an active energy ray-curing coating material that contains monomers and/or (d) a photopolymerization initiator and is cured by irradiation with active energy rays such as ultraviolet rays and electron beams. A feature of the coating material of the present invention is that an unsaturated monomer represented by the above general formula (component (a)) is used in combination with an unsaturated polyester resin (component (b)). 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 unsaturated polyester resin coating compositions that are cured by irradiating active energy, and have found that the above-mentioned (a) By using these components in combination, the objects of the present invention were completely achieved. This fact was completely unexpected from the above-mentioned known facts regarding component (a), and a surprising technical effect was obtained. Next, each component 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 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. (b) Component: Unsaturated polyester resin Component (b) in the present invention is an unsaturated polybasic acid having a polymerizable unsaturated group and a polyhydric alcohol, and optionally a saturated polybasic acid and/or a monobasic acid. Obtained by ester reaction using an acid or the like. These reactions can be carried out by methods known per se. Examples of unsaturated polybasic acids include maleic acid, fumaric acid, chloromaleic acid, dichloromaleic acid, citraconic acid, mesaconic acid, itaconic acid, tetrahydrophthalic acid, carbicic acid, hexic acid, aconitic acid, glutaconic acid, and these acids. Examples include anhydrous substances. One or more selected from these can be used, and it is particularly preferable to use maleic acid, itaconic acid, and the like. Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, and polyethylene glycol (molecular weight
4000 or less), trimethylene glycol, polypropylene glycol (molecular weight 4000 or less), 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-hexanediol,
Examples include pentaerythritol, dipentaerythritol, mannitol, and glucose. Among these, especially ethylene glycol, butanediol,
It is preferable to use 1,6-hexanediol, trimethylolpropane, or the like. Examples of saturated polybasic acids include phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, methylcyclohexentricarboxylic acid, adipic acid, sebacic acid, azelaic acid, hexahydrophthalic acid, hymic acid, succinic acid, dodecynylsuccinic acid, and methylglutaric acid. Examples include acids, pimelic acid, malonic acid, and anhydrides thereof. One or more selected from these can be used, but
Particularly preferred are phthalic acid, isophthalic acid, adipic acid, hexahydrophthalic acid, and the like. In addition, examples of monobasic acids include benzoic acid,
pt-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, high diene fatty acid, tung oil fatty acid, etc. can be given. Among these, fatty acids are preferably used in an amount of 50% or less based on the oil length. As component (b) in the present invention, the hydroxyl group or carboxyl group contained in the skeleton of the above-mentioned unsaturated polyester resin and a saturated polyester resin obtained from a saturated polybasic acid and a polyhydric alcohol (including those using a monobasic acid in combination) Based on the carboxyl group,
An unsaturated polyester obtained by reacting a polymerizable unsaturated monomer having a glycidyl group, a hydroxyl group, or N-CH ₂ -OR (R is H or an alkyl group) can also be used. That is, examples of the polymerizable unsaturated monomer having a carboxyl group include unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid, and the aforementioned unsaturated polybasic acids. These are reacted with hydroxyl groups in unsaturated polyester resins and saturated polyester resins. Examples of the polymerizable unsaturated monomer having a glycidyl group include glycidyl acrylate and glycidyl methacrylate, which are reacted with the hydroxyl group and carboxyl group in the unsaturated polyester resin and the saturated polyester resin. Further, examples of polymerizable unsaturated monomers having a hydroxyl group include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, butanediol monoacrylate, butanediol monomethacrylate, and the like.
These are reacted with carboxyl groups in unsaturated polyester resins and saturated polyester resins. In addition, examples of the polymerizable unsaturated monomer having N-CH ₂ -OR include N-methylol acrylamide, N-methylol methacrylamide,
Examples include N-butoxymethylacrylamide and N-butoxymethylmethacrylamide, which are reacted with hydroxyl groups in unsaturated polyesters and saturated polyesters. The unsaturated polyester resin [component (b)] used in the present invention is obtained as described above, and is a polyester resin having polymerizable unsaturated bonds in the main skeleton and/or side chains of the resin. The component (b) has a molecular weight of 400 to 3000,
Particularly preferred are those having an unsaturation equivalent of 100 to 1000. The paint of the present invention essentially contains the above components (a) and (b), and the proportion of both components is preferably 5 to 95% by weight of component (a), based on the total amount of both components. 20-80% by weight, component (b) 95-5% by weight,
Preferably it is in the range of 80 to 20% by weight. When component (a) is less than 5% by weight, the flexibility and gloss of the coating film decreases.
Smoothness, physical performance etc. are reduced while 95% by weight
If the amount is too large, the curability, weather resistance, etc. of the coating film will deteriorate, so both are not preferable. (c) Component: Ethylenically unsaturated monomer The above (a) is an essential component in the coating of the present invention.
If necessary, an ethylenically unsaturated monomer [component (c)] can be further used in combination with the system consisting of the component and the component (b). As the component (c), common monomers and oligomers having radical polymerizability can be used, and specific examples include the following. Examples of the monomer include esters 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. Also, styrene, vinyltoluene, methylstyrene, chlorostyrene, vinyl acetate, vinyl chloride, vinyl isobutyl ether, methyl vinyl ether, acrylonitrile, 2-ethylhexyl vinyl ether,
Divinylbenzene and the like can also be used. Furthermore, the above-mentioned polymerizable unsaturated monomers having a carboxyl group, glycidyl group, hydroxyl group, or N-CH ₂ -OR can also be used. Radically polymerizable oligomers are mainly di, tri and tetravinyl compounds, including 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 methacrylate, 1.4-butanediol diacrylate, 1.4-butanediol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 1.6-hexanediol diacrylate, 1.6
-Hexanediol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, adduct of bisphenol A and ethylene oxide with acrylic acid and/or a product obtained by reacting methacrylic acid, and a product obtained by reacting an adduct of bisphenol A and propylene oxide with acrylic acid and/or 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 paint and the physical performance of the cured coating film can be adjusted. (d) Component: Photopolymerization initiator The paint film of the present invention is cured by irradiation with active energy such as electron beams and ultraviolet rays.
When curing by ultraviolet irradiation, it is necessary to add a photopolymerization initiator to the composition 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 blending amount thereof is preferably 0.1 to 10% by weight of the total amount of components (a) and (b), or, if component (c) is used in combination, the total amount including them. 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 coating material of the present invention essentially contains the components (a) and (b), and further contains the component (c) and/or the component (d) if necessary. Furthermore, the paint 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 organic solvent with a low boiling point (below 180°C). . The paint of the present invention can be applied using a roll coater, curtain flow coater, brush, dipping, electrostatic atomizer, 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. Moreover, the thickness of the coating film on these surfaces to be coated is preferably 3 to 500 μm. The paint film 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. Electron beam sources include Kotskucroft type, Kotskucroft-Walton type, Van de Graaff type,
There are resonant transformer types, transformer types, insulated core transformer types, dynamitron types, linear filament types, and high frequency types. The electron beam irradiation conditions are not particularly limited, but 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 in air or under an inert gas atmosphere for several seconds or more.
In particular, when irradiating in air, it is preferable to use a high-pressure mercury lamp. Since the paint 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 paint obtained according to the present invention and the cured coating film made from the paint exhibit 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. Furthermore, 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 paint of the present invention is applied to paper, metal, vapor-deposited surfaces, ink-printed surfaces, etc. used for cosmetic cases and book covers, a coating film with excellent adhesion and gloss is formed, which significantly improves aesthetics and lasts 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 excessively. Furthermore, since the paint has a relatively low viscosity, it has good wetting 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 paint of the present invention can also be applied to wood, and when active energy is irradiated to a paint film applied to wood that has undergone sealing treatment, the inside and surface of the paint film is very well cured, preventing scratches. This resulted in improvements in the finished appearance, gloss, and adhesion with fillers. 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 paint 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. Furthermore, since the paint of the present invention has a relatively low viscosity, it is most suitable for ironing pipes and the like. As described above, the coating material of the present invention can be applied to almost any object to be coated, and has excellent coating film 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. Parts and % in Examples and Comparative Examples are parts by weight and % by weight. Example 1 (a) Ingredients (b) Component 50 parts of an ethylenically unsaturated group-containing polyester resin () was mixed to obtain a coating material targeted by the present invention. The ethylenically unsaturated group-containing polyester resin (2) was produced in the following manner. Put 148 parts of phthalic acid, 146 parts of adipic acid, and 354 parts of 1.6-hexanediol into a 4-necked flask and add 220 parts of phthalic acid.
After keeping at ℃ for 5 hours while performing azeotropic dehydration using toluene, it is cooled to 100℃. 144 parts of acrylic acid,
Component (b) was obtained by adding 10 parts of para-toluenesulfonic acid and keeping it at 120°C for 5 hours while azeotropically dehydrating with toluene while blowing in a small amount of air. . Example 2 Paint obtained in Example 1 100 parts Benzyl dimethyl ketal [component (d)] 5 parts Example 3 (a) component (b) Component 40 parts of polyester resin containing ethylenically unsaturated groups (c) Component 10 parts of styrene were mixed to obtain the paint object of the present invention. The above ethylenically unsaturated group-containing polyester resin ()
was manufactured according to the following. 490 parts of maleic acid, 146 parts of adipic acid, 400 parts of hexahydrophthalic acid, 310 parts of ethylene glycol,
1.4 Put 450 parts of butanediol into a four-necked flask, hold at 200°C for 4 hours while azeotropically dehydrating with toluene, and then remove the toluene from the solvent while cooling. The resulting product is called component (b). did. Example 4 Paint obtained in Example 3 100 parts Benzoin ethyl ether [component (d)] 3 parts Example 5 (a) component (b) Component 60 parts of ethylenically unsaturated group-containing polyester resin (2) were mixed to obtain a coating composition targeted by the present invention. 584 parts of adipic acid, 118 parts of 1.6 hexanediol,
134 parts of trimethylolpropane was placed in a four-necked flask and kept at 220°C for 5 hours while azeotropically dehydrating with toluene, then cooled to 120°C, 426 parts of glycidyl methacrylate and 4 parts of tetraammonium bromide were added, After keeping the mixture at 120°C for 5 hours while blowing a small amount of air, the toluene was removed from the solvent and the mixture was cooled to obtain component (b). Comparative Example 1 A paint was prepared in the same manner as in Example 1, except that component (a) in the paint of Example 1 was replaced with phenoxyethyl acrylate. Comparative Example 2 A paint obtained by replacing component (a) in the paint of Example 1 with diethylene glycol diacrylate, and further adding 5 parts of benzophenone and 2 parts of triphenylphosphine. Comparative Example 3 A paint produced by replacing component (b) in Example 1 with an epoxy resin containing an ethylenically unsaturated group. The ethylenically unsaturated group-containing epoxy resin was produced as follows. 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
1 part was heated to 100°C and reacted at the same temperature until the acid value reached 5 to 10. Comparative Example 4 A paint obtained by replacing component (b) in Example 1 with the ethylenically unsaturated group-containing epoxy resin used in Comparative Example 3, and further adding 5 parts of benzophenone and 2 parts of triphenylphosphine. Various performance tests were conducted on the paints of Examples and Comparative Examples produced as described above, and the results are shown in Table 1.

[Table] Notes: (*1) Odor: The coating compositions and cured coatings produced in Examples and Comparative Examples were investigated. ◎: Almost no or no unpleasant odor △: Slightly unpleasant odor ×: Significant unpleasant odor (*2) Paper: Printed hot paper for cosmetic boxes (thickness
0.5mm), roll coater (gravure coater)
The coating was applied at a coating amount of 10g/ ^m2 . The coating films coated with the paints obtained in Examples 1 and 3 and Comparative Examples 1 and 3 were heated at 300K.W.-45mA for 5 minutes using a scanning type electron accelerator manufactured by Ford.
It was hardened by irradiation with Megarad. Further, the coating films coated with the paints obtained in Examples 2 and 4 and Comparative Examples 2 and 4 were cured by irradiation for 2 seconds with a 120 mW/cm ² high-pressure mercury lamp (UBO62-5A manufactured by Iwasaki Electric). (*3) Adhesion: The painted surface was examined after the adhesive cellophane tape attached to the paint film was suddenly peeled off. ◎: No peeling of the coating film was observed. △: The coating film was slightly attached to the adhesive cellophane tape. ×: Most of the coating film was peeled off. (*4) Flexibility: The coating film was examined by bending it 180 degrees with the coating film on the outside. ◎: No abnormality observed at all. △: Cracking is observed in the bent portion. ×: Many cracks and peelings are observed in the bent portion. (*5) Yellowing resistance: The sample obtained in the above (*2) was left near a window for 6 months, and then the painted surface was examined. ◎: No abnormality, no yellowing observed at all. △: Slight yellowing. ×: Changed to yellow or brown. (*6) Gloss: Visual judgment ◎: Very good △: Slightly inferior ×: Significantly inferior (*7) Wood: Painted with a knife coater on sealed lauan plywood so that the cured film was 250μ. Those coated with the paint compositions obtained in Examples 1 and 3 and Comparative Examples 1 and 3 were irradiated with electron beams, and those coated with the coating compositions obtained in Examples 2 and 4 and Comparative Examples 2 and 4 were irradiated with ultraviolet rays. and hardened it. The irradiation conditions are the same as above (*2). (*8) Adhesion: Cut out squares of size 1 x 1 mm in a gong shape with a cutter to reach the substrate, stick adhesive cellophane tape on the surface, and quickly peel off the coating film. I checked the remaining numbers. ◎: 99 to 100 pieces remaining △: 98 to 80 pieces remaining ×: 79 pieces or less remaining (*9) Weather resistance: The condition of the painted surface after exposing the test plate outdoors at a 45° angle facing south for 30 days. Examined. ◎: No abnormality is observed. Δ: Slight blistering and yellowing occurred. ×: Blistering and yellowing occurred on the entire surface. (*10) Workability: The painted part was cut with a saw, and the coating film at the cut part was examined. ◎: No abnormality (cracking, peeling) is observed in the coating film at the cut portion. △: Some peeling was observed. ×: Many cracks and peeling occurred. (*11) Metal: Dull mild steel plate (0.8 mm thick).
It was coated with a roll coater so that the cured film thickness was 20μ. The coating film was cured in the same manner as in (*2). (*12) Adhesion: Same as above (*8). (*13) Corrosion resistance: The paint film was cross-cut to reach the substrate, and the painted surface was examined after testing in a salt spray tester for 48 hours. ◎: No abnormality is observed. △: Blisters and rust occurred. ×: Blisters and rust occurred almost on the entire surface. (*14) Flexibility: The test plate was bent using a bending tester with the paint film on the outside, and the bending angle at which cracks, peeling, etc. occurred in the paint film was examined. ◎: No abnormality is observed even when bent by 180°. △: Cracking, peeling, etc. occur at 120-180° ×: Cracking, peeling, etc. occur at 120° or less (*15) Water resistance: The painted surface after immersing the test plate in tap water at 20°C for 2 days. Examined. ◎: No abnormalities observed △: Blisters occur ×: Blisters occur almost on the entire surface (*16) Plastic: Polyester terephthalate film (thickness 100μ) and plate (thickness 3cm) are checked with a bar coder to determine the cured film thickness. It was painted so that the thickness was 5μ. The coating film was cured in the same manner as in (*2). (*17) Adhesion: Tested in the same manner as above (*8). (*18) Flexibility: Tested in the same manner as above (*14). (*19) Weather resistance: Tested in the same manner as above (*9).

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). An active energy ray-curable coating whose main components are a saturated monomer and (b) an unsaturated polyester resin. 2. The active energy ray-curable paint 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 active energy ray-curing paint described in . 4. The active energy ray-curable paint according to claim 2, the main component of which is a mixture of components (a), (b), and (c) with component (d).