JPS5879063A - Active energy radiation curing coating composition - Google Patents

Abstract

PURPOSE:The titled composition that is made by adding a specific unsaturated monomer to a urethane resin containing ethylenically unsaturated groups, thus being suitably used for coating decorative boxes or the like, because of its freeness from unpleasant odor, good coating operability, high adhesion to paper or plastics, good curing properties and flexibility. CONSTITUTION:For example, the objective composition is obtained by adding (A) an ethylenically unsaturated monomer and/or (B) a photopolymerization initiator to (C) an unsaturated monomer formulaI(R1 is H, methyl; R2 is 2-4C alkyl, R3 is 1-20C alkyl, phenyl, alkylphenyl) such as a compound of formula II and (D) a urethane resin containing ethylenically unsaturated groups. EFFECT:Coating films thereof have good luster, smoothness and physical performance without cissing ang shows high adhesion to wood and metal. USE:It is most suitable for the use in the die coating of pipes.

Description

[Detailed description of the invention] The present invention has no unpleasant odor and has good painting workability.

In addition, it has excellent adhesion to paper, plastic, wood, and metal, and is even more durable.

This invention relates to active energy ray hardening coating compositions that form coating films having flexibility, water resistance, weather resistance, gloss, corrosion resistance, etc.

Conventionally, it has been used as a coating composition that is cured by irradiation with active energy such as ultraviolet rays and electron beams.

Urethane resin-based coating compositions containing urethane resins containing ethylenically unsaturated groups and ethylenically unsaturated monomers as main components are generally used.

This urethane resin coating composition forms a coating film that has practical weather resistance and flexibility.

One point in other performance Km has been pointed out, and its improvement is desired. In other words, urethane resins containing ethylenically unsaturated groups have poor compatibility with ethylenically unsaturated monomers, so coating film The gloss, smoothness, and physical performance of these materials are insufficient, and repellency is likely to occur. In addition, an unpleasant odor is generated from the mixture of the two components and the formed coating film, which is unfavorable from a hygienic point of view. Furthermore, the wrinkle composition is applied to substrates such as paper surfaces such as the outer skin of a cosmetic box, printed surfaces, and metal-deposited surfaces. Adhesion 1
Surface hardening properties, m-film sliding properties, and bending properties.

(9) Adhesion to the glue attached to the base material is insufficient for practical purposes. Additionally, when the #composition is applied to metal substrates such as iron, zinc, and aluminum.

9. Adhesion to the base material, water resistance, and corrosion resistance are insufficient. Furthermore, a coating film obtained by coating #composition onto a plastic (eg, polyester resin, etc.) and curing it has poor adhesion to the substrate and flexibility.

9. The wrinkle composition is applied to wood that has been treated with a sealant coating and cured. 9. The coating film has a finish I! It has insufficient gloss, adhesion with fillers, hardenability, heat resistance, cold resistance, moisture resistance, etc., and is also poor in cutting workability with a saw.

In view of the above-mentioned situation, the present inventors have solved the nine defects described above 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 hardening with active energy rays that can form coatings with excellent performance on substrates such as paper, gold, plastic, and wood. It was.

As a result, by using an unsaturated monomer having a specific structural formula in an ethylenically unsaturated group-containing urethane resin instead of or in combination with a conventional ethylenically unsaturated monomer,
It was found that the above object could be achieved and the present invention was completed.

In other words, one aspect of the present invention is.

(&) General formula % Formula % (R1 is hydrogen atom or methyl group, R1 has 2 carbon atoms
~4 alkylene group% R1 is an alkyl group having 1 to 20 longitudinal atoms, phenyl group, 9 is alkyl7 enyl group)
The unsaturated monomer shown by Cb) and the ethylenically unsaturated group-containing urethane resin are essential components, and if necessary, the unsaturated monomer (C) and/or (((
1) The present invention relates to an active energy ray hardening coating composition that contains 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)].

#-) The component is a compound known per se.

In US LIL Patent No. 14072592, 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 is used in combination with component #←). It is disclosed that the compositions are cured by ultraviolet or electron beam irradiation. The inventors of the present invention also investigated the known technique based on this wrinkle specification, and found that the lack of gloss was due to the poor compatibility between component (a) and the unsaturated epoxy resin.
! They found that it has a serious defect in that it is difficult to form IJllllI and moreover, it is easy to cause scratches on the coating film. Furthermore, the wrinkle composition is applied to the paper surface,
The 9M film, which was applied to wood and cured, was easily yellowed and its adhesion to the ink surface and sealant was insufficient for practical purposes. Adhesion to plastics was also not satisfactory. It has excellent corrosion resistance against metals and has practical performance.

Due to its high viscosity, it is difficult to apply it to steel pipes. As described above, compositions using component (a) in combination with an unsaturated epoxy resin have various defects in terms of 1 kM 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 the above-mentioned and fi (a) components can be applied widely. By using these together, the objects of the present invention can be completely achieved. This fact is completely unexpected from the above-mentioned known facts regarding the ingredients, and a surprising technical effect has been obtained.

Next, the components constituting the stimulant composition of the present invention will be explained.

(a) General formula of component 2 (R1 hydrogen atom or methyl group, R2 is an alkylene group having 2 to rare carbon atoms, Tamaki is an alkyl group having 1 to 20 carbon atoms, phenyl 1tfc is an alkylphenyl group) An unsaturated monomer represented by

In the above general formula, the alkylene group having 2 to 4 carbon atoms for R2 is ethylene group, n-tetrapyrene group, 180
-p-pyrene group, n-butylene group.

Examples include a so-buty-leno group and a tart-butylene group.If the number of carbon atoms in the alkylene group is 5 or more, hardness due to activation energy rays will deteriorate, which is not preferable. In addition, examples of the alkyl group, phenyl group, and arylphenyl group of carbon atoms a1 to a20 of R5 include a methyl group, an ethyl group, an n-tetravir group, a 1-
Globyl groups % n-butyl groups.

1so-butyl group, tart-butyl group, 1so-yl group, n-hexyl group, n-heptyl M% n-octyl group, 2-ethylhexyl group, 1so-nonyl group.

Lauryl group, stearyl group, cyclopropyl group.

Cyclobutyl group, cyclopentyl group, cyclohexyl group, phenyl group, methylphenyl group% 1sio -propylphenyl group a tart-butylphenyl group, methoxyphenyl group Persimmons are mentioned, and the number of carbon atoms in R3 is 2
If it is more than 1, the curability due to active energy ray irradiation deteriorates, which is not preferable.

In the present invention, as the (&) component, 111 and 9 selected from the unsaturated monomers represented by the above general formula can be used in two pairs, and among these, in the general formula, R1 is hydrogen. Atom, R1 is ethylene group, R) is n-propyl group, i! o-propyl group % It is particularly preferred to use unsaturated monomers represented by n-butyl or phenyl groups.

0)) Component: Ethylenically unsaturated group-containing urethane 41II
181 #Q) Component in the present invention, an oligomer having an ethylenically unsaturated group and a urethane bond in one molecule,
Prepolymers and polymers. The urethane bond is formed by a reaction between an incyanate group and a hydroxyl group. .

The component (°C) is known per se and can be produced, for example, by the following method.

(1) Polyisocyanate compound having 2 or more inocyanate groups in 1 molecule. (abbreviated as ``body'') is reacted over 2 molar odors.

(2) Add 2 moles of polyisocyanate compound per mole of polyol having 2 N water groups in one molecule.
For 1 mole of the attached product (having at least 2 incyanate groups on N in 1 molecule) obtained by the reaction,
Water (!i! React two or more J-containing unsaturated monomers.

(5) React the polyisocyanate compound and the water group-containing unsaturated monomer in an approximately equimolar ratio (1 of the #reaction products).
(The molecule has at least one free isocyanate group) 1.Next, 2 mol N of the #reactant raw acid is reacted with 1 mol of polyol.

(2) Acrylic resin having 2 N hydroxyl groups in one molecule CN (abbreviated as acrylic resin polyol) At least two incyanate groups are present in one 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.

a) A polyisocyanate compound and a hydroxyl group-containing unsaturated monomer are reacted at approximately a fat molar ratio (#1 molecule of the reaction product has at least one free incyanate group)%, and then, #Reaction product acrylic 1II11
2 mol of r polyol is reacted.

The acrylic resin polyol in (6) above) and (5) is a polyester having two or more hydroxyl groups in one molecule (hereinafter abbreviated as polyester polyol).
The reaction is performed according to (4) and (5) above except for N in place of N.

The reaction of each component in (1) to (6) of -F can be carried out by a known method.

The component (b) in zero-shot is -F (1 to 0)
Of the methods, % (2), (3), (5) and (6
) is particularly preferred.

In ((9) component -F!e production method α) to (6), the polyisocyanate compounds include 1, for example, tolylene diisocyanate, 4.11'-diphenylmethane diisocyanate, xylylene diisocyanate, xylene diinocyanate, hexamethylene diisocyanate, lysine diisocyanate), IJ, 14'-methylenebis(cyclohexyl isocyanate $-)).

Methylcyclohexane2. # (2,6) diisocyanate), 1. ! 1-(Incyanate methyl) cyclohexane, isophorone diisocyanate, trimethylhexamethylene diisocyanate, dimer acid diisocyanate, dianisidine diisocyanate, phenyl diisocyanate, NOSE2, phenyl diisocyanate, methylene diisocyanate, ethylene diisocyanate, butylene diisocyanate, glopylene diisocyanate, octadecylene diisocyanate), 1.
5-7tale diisocyanate, polymethylene polyphenylene diisocyanate, triphenylmethane triisocyanate, 7-ethylene diisocyanate, trilenodiincyanate polymer, diphenylmethane diisocyanate polymer, hexamethylene diisocyanate polymer, 5-phenyl-2-ethylene diisocyanate , cumene-2,4-diisocya$-), 4-methoxy-1,
5-phinidine diisocyanate, 4-ethoxy-1,
4.4
'-diisocyanate diphenyl ether, benzidine diisocyanate.

9.10-Anthracene diisocyanate%4,4
'-Diinocyanate benzyl% 5.5'-dimethyl-4,4'-diisocyanate diphenylmethane, 2.
6-Simethyl-4,4'-diisocyanate diphenyl.

5.5'-dimethoxy-4,4'-diisoleanatodiphenyl, 1. &&-Anthracene di incyanate.

Phenyl diisocyanate, 2sL6-) 9
triisocyanate), 2. L%'-) diisocyanate diphenyl ether, i, q-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,10-decamethylene diisocyanate)
, 1.5-Schiff tetrahexylene diisocyanate.

Examples include 4.4'-methylene-bis(cyclohexyl isocyanate). These can be used alone or in combination. Among these, inphorone diisocyanate, xylylene diisocyanate, tolylene diisocyanate), 1,6-hexane diisocyanate, etc. are particularly preferred.

In addition, examples of the above-mentioned (1) to (6) K-hydroxyl group-containing unsaturated monomers include 2-hydroxyethyl acrylate, ? - Human axyethyl methacrylate 17ate, hydroxypropyl acrylate, hydroxyethyl acrylate, allyl alcohol.

Examples include butanediol monoacrylate, butanediol monomethacrylate% N-methyl-lylacrylate, crotyl alcohol, 7'oL' rangelicol monoacrylate, and furthermore, glycidyl acrylate or glycidyl methacrylate and carboxyl group-containing fractions ( For example, adducts of adipine a with 2% sebacic acid, azelaic acid, etc.), epoxy compounds with acrylic acid or methacrylic acid (e.g. Aphthalmia rubhydrin, etc.)
etc. can also be used. These properties may be used alone or in combination of two or more. Among these, 2-hydroxyethyl acrylate, butanediol monoacrylate, 2-hydroxyethyl methacrylate, butanediol monomethacrylate, etc. are suitable for 419.

Examples of the polyols used in (2) and C) include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, diglopylene glycol, and polyethylene glycol (molecular weight 6,000 or less).

Trimethylene glycol, polypropylene glycol (
molecular weight 6000 L-1), tetramethylene glycol, polytetramethylene glycol, 1,2-butylene glycol, 1,5-butanediol.

1, II-butanediol, 1,5-bentanediol.

Neopentyl glycol, 1,2-hexylene glycol, 1,6-hexanediol, heptanediol,
1.10-f candiol, cyclohexanediol, 2-butene-1,4-diol, 5-Schifftetrahexene-1,1-dimetatool, tt-methyl-5-cyclohexene-1,1-dimetatool, 5-methylene -1,5
-bentanediol, (2-hydroxyethoxy)-1
-Propertool, 4-(2-hydroxyethoxy)-1
-butanol, 5-(2-hydroxyethoxy)-benfi/-l, lar(2-hydroxypropoxy)-1-
7' lovanol, 1l-(2-hydroxy-propoxy)-1-butanol, 5-(2-hydroxypropoxy)-1-pentanol, 1-(2-hydroxyethoxyl)-2-butanol, 1-(2- Hydroxyethoxy)-2-pentanol, hydrogen 4F bisphenol, glycerin, polycaprolactone, 1.2.6-hexanediol, trimethylolethane, trimethylolethane, pentanetriol, trishydrogenoxymethylacrylatemethane, 5-(2- hydroxyethoxy) -1,2
-Propanediol, 5-(2-hydroxypropoxy)-1,2-furopanediol, 6-(2-hydroxyethoxy)-1,2-hexanediol, pentaerythritol, dipentaerydrift, mannitol.

Examples include glucose. Among these, polyethylene glycol, polycaprotictone, polypropylene glycol, tetramethylene glycol, trimethylene glycol,
Lupropane and the like are preferred.

Furthermore, in the above 6) and υ) K & t-j acrylic resin polyol, the above-mentioned hydroxyl group-containing unsaturated monomer and acrylic monomer are copolymerized together with other vinyl monomers as required. This is what I did.

The number average molecular weight of wrinkled acrylic resin polyol is approximately 1000
~10,000, and the amount of hydroxyl group i is preferably from 500 to 5,000, respectively.

Examples of the acrylic monomer include esters of acrylic elIt and methacrylic acid and monohydric alcohols having 1 to 20 carbon atoms. Specifically, methyl acrylate,
Pure methyl methacrylate, ethyl acrylate, ethyl methacrylate, acrylic #In-butyl, n-methacrylate
Butyl, 1so-butyl acrylate, methacrylic r! 1
180-butyl, tert-butyl acrylate, 49-t@rt-butyl methacrylate, propyl acrylate, propyl methacrylate.

Hexyl acrylate, hexyl methacrylate, octyl acrylate, octyl methacrylate, acrylic acrylate, lauryl methacrylate, acrylic J12-ethylhexyl, methacrylic I! [2-Ethylhexyl, cyclohexyl acrylate, cyclohexyl methacrylate, stearyl acrylate.

Examples include stearyl methacrylate. Furthermore, acrylic monomers such as acrylic acid, methacrylic M, glycidyl acrylate, glycidyl methacrylate, acrylamide/methacrylamide, and diacetone acryl azide can be used alone or in combination.

Ota. Other vinyl monomers include styrene, vinyltoluene, and methylstyrene.

Chlorstyrene, vinyl acetate, vinyl chloride, vinyl isophthyl ether, methyl vinyl ether.

Acrylonitrile? -Ethylhexyl vinyl ether, divinylbenzene, etc. In the wrinkled acrylic resin polyol, the content of the other vinyl monomers is preferably 50 weight tatami or less.

Furthermore, the polyester polyol in the above (6) has a hydroxyl group in the terminal and/or side chain, and the amount of hydroxyl groups is preferably 200 to 5,000. The wrinkled polyester polyol is obtained by reacting a polybasic acid and a polyhydric alcohol together with a monobasic acid depending on the necessary IFK.

Examples of the polybasic acids include thalic anhydride, isophthalic acid, terephthalic anhydride, and succinic anhydride. Adipic acid, azelaic acid, sepacic acid, tetrahydrophthalic anhydride,
Hexahydrophthalic anhydride, % hexahydrophthalic anhydride, Hymi anhydride, Rikami, Maleic anhydride.

Examples thereof include itaconic acid, trimellitic anhydride, methylcyclohexenetricarboxylic anhydride, bilomel anhydride, and these may be used alone or in combination.

Examples of the polyhydric alcohol include the polyols described above.

Examples of the -basic acid include benzoic acid, p-t-butylbenzoic acid, coconut oil fatty acid, and castor oil fatty acid.

Rice bran oil fatty acids, soybean oil fatty acids, tall oil fatty acids.

Examples include dehydrated castor oil fatty acids, safflower oil fatty acids, linseed oil fatty acids, high diene fatty acids, and tung oil fatty acids.

The coating composition of the present invention contains component (a) and Cb.
) component is essential, and the ratio of both components is based on the total amount of both components, (a) component 5 to 95% by weight, preferably 20 to sol. It is preferably in the range of 5% to 20% by weight. (
&) If the amount of the component is less than 5% by weight, the flexibility, gloss, smoothness, physical performance, etc. of the f# film will decrease, while if it is more than 95% by weight, the hardness, weather resistance, etc. of the coating film will be affected. Therefore, the deviation by %b is also not desirable.

(0) Component: Ethylenically unsaturated monomer In the composition of the present invention, the above (IL) is an essential component.
If necessary, an ethylenically unsaturated monomer (l) component can be further used in combination with the system consisting of the component and the (+) component.

# (0) A normal product that has radical polymerizability as a component! - and oligomers can be used, and specific examples include the following.

Radically polymerizable things! Examples of - include the water aL1 group-containing unsaturated monomers, acrylic monomers, and other vinyl monomers disclosed in the description of component (1)).

Also, as a radically polymerizable oligomer.

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% 1.5-butanediol diacrylate) , 1.3-butanediol dimethacrylate)
, 1.14-butanediol diacrylate),
1,4-butanediol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 1,6-hexanethiol diacrylate), 1,6-hexanethiol dimethacrylate.

Trimethylolpropane triacrylate, trimethylpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate,
Pentaerythritol tetramethacrylate, a product obtained by reacting an addition product of bisphenol A and ethylene oxide with acrylic acid and/or methacrylic acid, a product obtained by reacting an adduct of bisphenol A and propylene oxide with acrylic acid and/or methacrylic acid. There are products etc. One or two of these monomers or oligomers
Species N± can be mixed and used.

These (0) components can be used together in an amount of 5 to 95% by weight, preferably 20 to 80% by weight of the component (e) above, in place of the pattern (0) component.

By using component #(C) in combination, the viscosity of the coating composition and the physical performance of the cured coating film can be adjusted.

11I film formed from the composition 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 generates radicals when excited by ultraviolet irradiation is used.
For example, benzoin, benzoin methyl ether, benzoin ethyl ether, pentuin n-propyl ether, benzoin isopropyl ether, benzoin n-
Butyl ether, benzophenone, IP-methylbenzophenone.

ζHiraketone, acetophenone, 2-chlorothioxanthone, anthraquinone, 2-methylan)laquinone,
Examples include phenyl disulfide% 2-nitrofluorene. These photopolymerization initiators may be one or two types of N
Can be used by mixing the above.

Its blending amount is 0.1 to 1% of the total amount of the above ingredients and component (b), or if component (0) is used together, the total amount including it.
A proportion of greater than 0 weight is preferred.

(9) In order to promote the photopolymerization reaction by the photopolymerization initiator, a photosensitization accelerator may be used in combination with the photopolymerization initiator. 1
As a photosensitizer, 1 such as triethylamine, triethanolamine, 2-dimethylaminoethanol, etc.
Class aquine series, alkyl phosphine series such as triphenylphosphine,! -Thioethers such as thiodiglycol can be used. These photosensitizers may be one or two types.
Can be used in combination with more than one species. Its arrangement amount ti, h period (
The ratio of 0.1 to 10% by weight of the total amount of component (-) in component), or the total amount including component (Q) when used in combination is preferably 0.1-10% by weight.

The composition of the present invention is composed of the above-mentioned components (a) and (b) as essential components, and optionally in combination with (Q) component and /i or (d) component. be.

Furthermore, the composition can contain pigments and dyes that do not interfere with the radical polymerization that occurs when irradiated with active energy rays, and also contain a small amount of an organic solvent with a low boiling point (under the odor of 110°C). I can't help it.

The composition of the present invention can be coated using a roll coater, curtain flow coater, brush, dip, electrostatic coater, spray gun, or the like. The object to be coated is not limited to %, and can be applied to plastic, paper, metal-deposited surfaces, metal, wood, etc.

Moreover, the thickness of the coating film on these deposited surfaces is preferably 5 to 500 seconds.

The coating film formed from the composition of the present invention is cured by irradiation with active energy.

As the active energy ray, any of electron beams and ultraviolet rays may be used.

As an electron beam source, Kotsukcroft type, Ko! There are four types: Croft-Walton type, Pan de Graz type, common loss transformer type, transformer type, insulated core transformer type, dynamidron type, linear filament type, and ^frequency type. The electron beam irradiation conditions are not limited to e, but a dose of 1 to 20 megarads is suitable. Also, as the ultraviolet irradiation source, there are mercury lamps, xenon lamps, carbon arcs, metal height lamps, sunlight, etc. . 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 under 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 (IL) component and (b) component, it has been able to obtain various unexpected technical effects.

That is, since no or almost no unpleasant odor is observed from the composition obtained by 1 #1 light and from the cured film made from the composition, the hygienic problem in handling has been solved. In addition, the % (&) component has excellent compatibility with the (b) component, so it can significantly improve the gloss, smoothness, physical performance, etc. of %aS, and no cissing was observed at all. It was no longer possible to do so. Especially (b)
No decrease in electrocompatibility due to the high molecular weight of the components, and adhesion to paper, gold-tone vapor-deposited surfaces, printing ink surfaces, plastics (e.g., polyvinyl chloride, polyurethane, polyester, etc.), wood, metals, etc. It has an excellent roundness and has a wider range of uses than conventional urethane resin paints.

First, paper used for cosmetic cases and book covers, metal-deposited N,
When the composition of the present invention is applied to an ink-printed surface, a coating with excellent adhesion and gloss can be formed, resulting in a marked improvement in emotionality, and even after a long period of time, no gloss or yellowing occurs. . Also.

MS also has excellent smoothness, so it does not stick even when stacked or pressed together. Furthermore, since it has excellent bendability, the coating film will not crack or peel even if it is bent appropriately. Moreover, since the #composition flow line has a relatively low viscosity, it has good wetting on the surface to be coated, and the coating workability has been improved.

It also has excellent adhesion to plastic,
Because of its good flexibility, it can sufficiently respond to these deformations.

Furthermore, the composition of the present invention can be applied to wood, and when active energy is irradiated to the m-film painted on wood that has undergone sealing treatment, the inside and surface of the coating are extremely hard and scratch-free. As a result, the finished appearance, gloss, and adhesion with sealants have been improved.Furthermore, the flexibility of the coating film is even better than conventional ones, so it can be used with saws, etc. It is easy to cut and process, and exhibits excellent heat and cold resistance. In addition, water resistance,
It also had good moisture resistance.

Furthermore, the composition of the present invention can also be applied to iron, aluminum, zinc, and alloys containing these metals. The MS coated on these objects was 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 uniquely suitable for ironing into 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 film performance.

Next, the content of the present invention will be explained in more detail using examples and comparative examples. Note that the present invention is not limited to this embodiment. Example.

In the comparative examples, parts and - are parts by weight.

Example 1 (→Component: 50 parts of HOO OH La and -) component: 50 parts of ethylenically unsaturated group-containing urethane resin (1) were mixed to obtain a coating composition aimed at by the present invention.

The above-mentioned ethylenically unsaturated group-containing urethane resin 0) was produced according to the following procedure, and 90 polyethylene glyfur (molecular weight i4 o o ) qo
.

part (1 mol), inphorone diisocyanate) 14111
Put 1 part (2 moles) into 4 loaf flasks, stir,
After being kept at 00°C for 1 hour, it is cooled to a temperature of 70tK. At 70°C, 5 parts of hydroquinone L and 232 parts (2 moles) of 2-hydroxyethyl acrylate were added into four Lof flasks, and the temperature was raised to 80°C by stirring while blowing air.
and keep for 5 hours.

After confirming that almost no remaining isocyanate groups were observed, the mixture was cooled and used as component (a).

Example 2 Coating composition obtained in Example 1 100 parts Benzophenone (← component) 5111 Triphenylphosphin [Photosensitization accelerator] 2 parts Example 5 Component Ethylenically unsaturated group-containing urethane resin (■ ) 40
Part (e) component (trimethylolpropane triacrylate) 10 parts were mixed to obtain a coating composition which is the object of the present invention.

The above ethylenically unsaturated group-containing urethane resin (Rin) is manufactured according to the following procedure.
550 parts (1 mol) of xylylene diisocyanate and 576 parts (2 mol) of xylylene diisocyanate were stirred and kept at 100°C for 1 hour, then cooled and heated for 7 hours.
Bring to 0℃. At 70°C, 15 parts of hydroquinone, butanediol monoacrylate 2111! 4 parts into the flask.

While stirring while blowing air, the temperature was raised to 80°C and maintained for 5 hours until the remaining isocyanate groups reached t1! After confirming that it has completely reacted, cool it down and add the ingredients.

Example 4 Example 9 Paint composition 100 parts Benzoin ethyl ether 5 parts Example 5 ←) Component HOO φ) Component 57 Ethylenically unsaturated group-containing urethane resin (厘) 70
A coating composition targeted by the present invention was obtained by mixing the two parts.

The ethylene saturated group-containing urethane resin was produced according to the following procedure.

300 parts of methyl methacrylate, 6 parts of n-butyl acrylate
00 parts, 100 parts of acrylic #2 hydroxyethyl, 1500 parts of Shef, and 50 parts of azobisin butytetranitrile were placed in a 4 flask and kept at 110°C for 5 hours to produce an acrylic resin polyol. This acrylic resin polyol has a molecular weight of 5,000 and a hydroxyl group weight of 1,160. To this acrylic resin polyol, 222 parts of isophorone diisocyanate and 116 parts of diacrylate in dihydroacrylic acid were added.
Example 6: 1014 parts of a monoisocyanate compound added with 100% and 10% were added and reacted at 100°C for 5 hours, and after confirming that the remaining incyanate groups had completely reacted, the mixture was cooled and used as component (b). (a) Component ((9) Component ethylene saturated group-containing urethane tree 1ti4v) 5 parts (0) Component 16 Hexane diol diacrylate 20 parts were mixed to prepare the desired coating composition. Obtained.

The ethylenically unsaturated group-containing urethane resin (Of) was produced according to the following procedure.

11,252 parts of adipine and 424 parts of diethylene glycol were placed in a 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°C, 2 parts of medium shark diisocyanate 6 was added to L6 and kept at 100°C for 1 hour.

After cooling to 80°C, after death, add 464 parts of 2-hydroxyethyl acrylic and keep at 80°C for 5 hours.After confirming that the remaining isocyanate has almost completely reacted, cool the resulting product. And so.

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 N2 was replaced with diethylene glycol diacrylate.

Comparative Example Example 10 A coating composition was prepared in the same manner as in Example 1 except that the following components were replaced with the following ethylenically unsaturated group-containing epoxy resin.

82 g of Epicote (diglycidyl ether of bisphenol A, epoxy equivalent 1 g 5-19; ?, z poxy value α50-o, 51+) 660 parts, acrylic acid 24
8 parts, 5 parts of triethylamine L and 0 parts of hydroquinone
．． Heat 1 part to 100°C.

It was obtained by reacting at the same temperature until the acid value reached 5 to 10.

Comparative Example 4 The components ~) in Example 2 were used in Comparative Example 9. A coating composition that replaces epoxy resins containing ethylenically unsaturated groups.

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.

Notes: (Qinl) Odor: Investigated on coating compositions and cured coatings prepared in real and comparative examples.9.

S: Almost no unpleasant odor Δ: Slightly unpleasant odor Coating amount 10 with Clavia coater)
It was painted so that it was v/-.

The paint compositions obtained in Examples 1.5.5 and 6 and Comparative Examples 1 and 5 were applied to 5 megaland at 45 rms in 500 El- using a Ford scanning W11 child accelerator. It was irradiated and hardened.

It was. Examples 2 and 4. The coating compositions obtained in Comparative Examples 2 and 4 were applied, and the coatings were cured by irradiation for 2 seconds with a 1201 flW/- high-pressure mercury lamp (UBO62-5A manufactured by Nozakiden 41).

(1115) Adhesion: After the adhesive cellophane tape applied with IFIIIK was rapidly peeled off, the m-plane was examined.

◎: No flaking of the 1/11 membrane was observed.

Δ: Slight adhesion of adhesive cello/non-tape K11.

x: @Most of the membrane was peeled off.

(*4) Flexing resistance: The coating film was examined at the IBO@bent portion with the coating film outside.

◎: No abnormality observed at all.

Δ: Some cracks are observed in the folded part. ×: Many cracks and scratches are observed in the folded part.

(Hata 5) Yellowing Resistance 2 The sample obtained as described above (*2) was left near a window for 6 months, and the painted surface was examined after 9 months.

◎：J! Δ: Slight yellowing. ×: Yellow 1* turned brown.

(Qin 6) Two-sight judgment of gloss ◎: Good at first glance Δ: Slightly inferior ×: Significantly inferior (Case 7) Cured film 2 on lauan plywood treated with wood second sealing
I painted it with a knife coulter to make it 50jlC.

Examples 1.5.5 and 6. The coating compositions obtained in Comparative Examples 1 and 5 were coated with an electron beam, and the coating compositions obtained in Comparative Examples 1 and 5 were irradiated with an electron beam.
．． Comparative example? The coatings coated with the coating compositions obtained in 4 and 4 were cured by irradiation with ultraviolet rays ◎The irradiation conditions are as above (*2
) is the same as

(*8) Adhesiveness: Use a cutter to cut 1 x 1 square squares in a grid pattern to reach the substrate.

An adhesive cellobane tip was attached to the surface, and the number of coatings remaining after rapid peeling was examined.

0299 to 100 pieces remaining Δ: 98 to gO: Remaining .

◎: Abnormalities are not introduced at all.

Δ: Slight blistering and yellowing occurs. ×: Blisters occur on the entire surface and yellowing is also significant.

(*10) Workability: Cut the covered part with a saw.

The IIM at the cut surface was examined.

◎:: No abnormality (cracking, peeling) is observed in the coating film at the cut section.

Δ: Slight peeling was observed. ×: Many cracks and peeling occur. (*11) Gold lR: Dull mild steel plate (thickness αg■) K.

Use a roll coater to obtain a cured film thickness of 20sK!
I installed it. The curing method for ** was the same as for (urn?).

(Hata 12) Adhesion 2 The same procedure as above (*8) was carried out.

(*15) Corrosion resistance: Apply the coating to the base! Toshi, the coated surface was examined after 48 hours of testing using a salt spray tester.

◎: Absolutely not observed.

Δ: 7 cracks, rust occurred.

×: 7 cracks, rust occurs almost on the entire surface.

(*114) Layer resistance: The test plate was folded with the film on the outside using a bending tester, and the bending angle at which cracking, peeling, etc. occurred in the coating film was examined.

◎: No abnormality is observed even after bending by 180'.

Δ: Cracks, peeling, etc. occur between 120 and 180 degrees x: 1
Cracking, peeling, etc. occur when soaking at 20 degrees (*15) Water resistance: The test plate was immersed in tap water at 20 degrees Celsius for two days, and then the painted surface was examined.

◎: No abnormality is observed.

Δ: Occurrence of blistering equipped. The coating film was cured in the same manner as (urn 2).

(*17) Adhesion: Tested in the same manner as above (*8).

018) Flexibility Resistance 2 Tested in the same manner as above (urn 1&&).

(*19) Weather resistance 2 Test in the same manner as above (*9).

Patent applicant (140) Kansai Paint Co., Ltd. 446-

Claims (1)

[Claims] L) general formula % formula % (RL is a hydrogen atom or a methyl group % phantom is a carbon atom number of 2 to
(4) alkylene group, R1 is an alkyl group, phenyl group, or alkylphenyl group having 1 to 20 carbon atoms); A coating composition for curing with active energy rays. 2. The Aspergillus composition for active energy curing according to claim 1, wherein %←) of an ethylenically unsaturated monomer is blended in components #←) and #←). 5. Claims t characterized in that (+1) a photopolymerization initiator is blended into components (5) and (1)).
The active energy ray hard coating composition according to item 1E1. The active energy ray hard coating according to claim 2, the main component of which is a mixture of the (IL), (1)) and (0) components with #). Composition O