JP2000063702A - Method of forming cured film - Google Patents

Abstract

(57) [Problem] To provide a method for forming a cured film by an electron beam, which can obtain high curability even in an atmosphere having a high oxygen concentration as in an atmosphere substituted with an inert gas. Kind Code: A1 Abstract: A specific monomer which is liable to generate a radical upon being subjected to hydrogen abstraction by electron beam irradiation, such as tetrahydrofurfuryl (meth) acrylate, a (meth) acrylate compound having an alkylene oxide unit, and a hydroxyl group-containing (meth) acrylate compound. Compound (A), polyfunctional (meth) acrylate compound (B) other than monomer (A), and amine or 3 other than the compound represented by the following general formula (6)
500 pp to the curable composition containing the trivalent phosphorus compound (C)
A method for forming a cured film, comprising irradiating an electron beam under an oxygen concentration of at least m.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for forming a cured film under an oxygen concentration of 500 ppm or more.

[0002]

2. Description of the Related Art A technique for curing active energy rays such as electron beams and ultraviolet rays is (1) fast curing and high in productivity.
(2) Low energy cost, (3) It has the advantages of being able to reduce the emission of volatile components to the environment by eliminating solvent, and is widely used for applications such as paints, inks, and adhesives. . Among the active energy rays, the electron beam has high transparency, is not easily affected by the pigment, does not require the addition of an initiator, and is advantageous in terms of cost and hygiene. The application of technology is expanding. Radical polymerizable compounds having a (meth) acryloyl group are generally used as the electron beam curable compounds used therein.

However, when the active energy ray-curable composition is cured in an atmosphere having a high oxygen concentration, such as in air, the surface layer is impeded by oxygen, which results in insufficient curability. Was. Many proposals have been made to overcome such drawbacks. For example, a method is known in which an inert gas such as nitrogen gas is blown in to reduce the oxygen concentration in the atmosphere. Further, a method of adding an amine to an active energy ray-curable resin is disclosed in JP-B-49-10358, and a method of adding a trivalent phosphorus compound such as phosphite and phosphine is disclosed in JP-A-46-1790. It is disclosed in Japanese Patent Publication No.

The above-mentioned method using an inert gas is not generally used for ultraviolet curing because it has the drawbacks that the inert gas is expensive and the economically applicable applications are limited. . On the other hand, in electron beam curing, electron beam irradiation is performed by adjusting the oxygen concentration to 200 ppm or less with an inert gas. However, when printing and painting are performed at high speed, the irradiated object entrains air, which increases the oxygen concentration and may cause curing inhibition.
Further, the above-mentioned method of adding an amine or a trivalent phosphorus compound requires a large amount of addition in order to obtain practical surface curability, but if they are added excessively, they themselves are radically polymerizable. Since it does not have a group, it has a drawback that the surface hardness is decreased due to the increase of unreacted components.

Further, the polyfunctional (meth) acrylate compound has a higher reactivity as the blending ratio is higher, and a good cured film can be obtained even in a high oxygen atmosphere, but it has a high viscosity, which limits the coating method. receive. Therefore, it is necessary to reduce the viscosity by diluting with a monomer, but the monomer is generally low in reactivity and susceptible to oxygen inhibition.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for forming a cured film by an electron beam, which is capable of obtaining high curability even in an atmosphere having a high oxygen concentration as in an atmosphere in which an inert gas is substituted. To provide.

[0007]

Means for Solving the Problems As a result of intensive studies by the present inventors, a specific monomer which easily receives a hydrogen abstraction by electron beam irradiation to generate a radical, a polyfunctional (meth) acrylate compound, and an amine. Further, it has been found that a good cured film can be formed by irradiating a curable composition in which a trivalent phosphorus compound is combined with an electron beam under an oxygen concentration of 500 ppm or more, and has reached the present invention.

That is, the present invention provides the following general formulas (1) to
At least one monomer (A) selected from the compounds represented by (9), a polyfunctional (meth) acrylate compound (B) other than the monomer (A), and the following general formula (6) The present invention relates to a method for forming a cured film, which comprises irradiating a curable composition containing an amine other than a compound or a trivalent phosphorus compound (C) with an electron beam under an oxygen concentration of 500 ppm or more.

[0009]

[Chemical 10] (In the formula, R1 is a hydrogen atom or a methyl group, and n is 0.
Is an integer of ˜2. )

[0010]

[Chemical 11] (In the formula, R1 is a hydrogen atom or a methyl group, R2 is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a phenyl group,
It is a nonylphenyl group or a (meth) acryloyl group. In addition, n is an integer of 1 to 23. )

[0011]

[Chemical 12] (In the formula, R1 is a hydrogen atom or a methyl group.
l, m, and n are integers of 0 to 6, and l + m + n is 1 to 6.
Is. )

[0012]

[Chemical 13] (In the formula, R1 is a hydrogen atom or a methyl group.
m and n are integers of 0 to 30, and m + n is 1 to 30. )

[0013]

[Chemical 14] (In the formula, n is an integer of 1 to 3, R 1 is a hydrogen atom or a methyl group, and R 3 is a hydrogen atom, a methyl group,
It is an ethyl group, a methylol group, a phenoxymethyl group, or a (meth) acryloyloxymethyl group. )

[0014]

[Chemical 15] (In the formula, R1 is a hydrogen atom or a methyl group, and R4 is a methyl group or an ethyl group.)

[0015]

[Chemical 16] (In the formula, R5 is an alkyl group having 2 to 18 carbon atoms, a hydroxyalkyl group having 2 to 9 carbon atoms, a cyclohexyl group,
Alternatively, it is an organic residue represented by any of the general formulas (7a) to (7d). Further, in the general formula (7a), n is an integer of 2 to 6, R
1 is a hydrogen atom or a methyl group. )

[0016]

[Chemical 17] (In the formula, R6 is an organic residue represented by the general formulas (8a) to (8e). In the general formula (8a), n is an integer of 4 to 9. Further, the general formula (8b). In the formula, n is an integer of 2 to 6, R1 is a hydrogen atom or a methyl group, and in the general formula (8e), R1 is a hydrogen atom or a methyl group.
Further, m and n are integers of 0 to 6, and m + n is 0 to 6. )

[0017]

[Chemical 18] (In the formula, R7 is a methylol group, an ethyl group, or a vinyloxymethyl group.)

In the present invention, the compounding ratio of the monomer (A) and the polyfunctional (meth) acrylate compound (B) in the curable composition is 10:90 to 90:10 (weight ratio). , The amine or the trivalent phosphorus compound (C) is 0.1 to 5 parts by weight based on 100 parts by weight of the total of (A) and (B), and the method for forming a cured film. The present invention also relates to a method for forming the above-mentioned cured film, which comprises irradiating an electron beam with an acceleration voltage of 30 to 100 kV. The present invention also relates to the method for forming a cured coating, wherein the electron beam irradiation dose is 1 to 10 kGy. Furthermore, the present invention relates to a method for forming the above-mentioned cured film, wherein the composition is used for ink or paint.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the monomer (A) is a monomer which easily undergoes hydrogen abstraction by electron beam irradiation to generate a radical, and is represented by the above general formulas (1) to (9). It is at least one monomer selected from the compounds shown.

Specific examples of the compound represented by the general formula (1) include tetrahydrofurfuryl (meth) acrylate, KAYARAD TC-110 manufactured by Nippon Kayaku Co., Ltd.
Caprolactone-modified tetrahydrofurfuryl acrylate such as S may be mentioned.

Of the compounds represented by the general formula (2), the compound having an ethylene oxide unit is
Methoxydiethylene glycol (meth) acrylate,
Methoxytriethylene glycol (meth) acrylate, methoxytetraethylene glycol (meth) acrylate, butoxytriethylene glycol (meth) acrylate, ethylcarbitol (meth) acrylate,
2-ethylhexyldiethylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate,
Phenoxytetraethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate Is mentioned.

Further, specific examples of the commercially available products thereof include Bremmer PE-90 and Bremmer PE- manufactured by NOF CORPORATION.
200, polyethylene glycol mono (meth) acrylates such as Bremmer PE-350, light acrylate 130A manufactured by Kyoeisha Chemical Co., Ltd., NK ester AM-90G, NK ester M-230 manufactured by Shin Nakamura Chemical Co., Ltd.
G, NK ester M-90G, methoxypolyethylene glycol (meth) acrylate such as BLEMMER PME-400 manufactured by NOF CORPORATION, light acrylate 9 EGA, light acrylate 14 EGA manufactured by Kyoeisha Chemical Co., Ltd.,
Light ester 14EG, light ester 9EG, Toagosei Co., Ltd. Aronix M-245, Aronix M
-260, KAYARAD PEG4 manufactured by Nippon Kayaku Co., Ltd.
00DA, Bremmer PDE-40 manufactured by NOF CORPORATION
0, KS-PEG400DA, SR manufactured by Kayaku Sartomer Co., Ltd.
-210A, SR-252, SR-34 manufactured by Sartomer Company.
4, NK ester 9G, NK ester 14G, NK ester 23G, NK ester A-, manufactured by Shin-Nakamura Chemical Co., Ltd.
400, polyethylene glycol di (meth) acrylates such as NK ester A-600, Kyoeisha Chemical Co., Ltd. light acrylate NP-4EA, light acrylate N
P-8EA, Aronix M-11 manufactured by Toagosei Co., Ltd.
1, nonylphenol polyethylene glycol (meth) acrylate such as Aronix M-113, phenoxy polyethylene glycol (meth) acrylate such as biscoat 193 manufactured by Osaka Organic Chemical Industry Co., Ltd., and the like.

Further, as the compound having a propylene oxide unit, methoxydipropylene glycol (meth) acrylate, phenoxydipropylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, nonylphenoxypropylene glycol (meth) acrylate, Examples include tripropylene glycol di (meth) acrylate. Specific examples of the commercially available products include Viscoat 312 manufactured by Osaka Organic Chemical Industry Co., Ltd. and N manufactured by Shin Nakamura Chemical Industry Co., Ltd.
K ester 9PG, NK ester APG-400, NK
Ester APG-700, polypropylene glycol di (meth) acrylates such as Aronix M-270 manufactured by Toagosei Co., Ltd., SR-604 manufactured by Sartomer, Bremmer PP-330 manufactured by NOF CORPORATION, Bremmer PP.
Examples include polypropylene glycol mono (meth) acrylates such as -500 and Bremmer PP-800.

Specific examples of the compound represented by the general formula (3) include VISCOAT 36 manufactured by Osaka Organic Chemical Industry Co., Ltd.
0, Kayaku Sartomer's CD-499, CD-502,
SR-454, Kyoeisha Chemical Co., Ltd. light acrylate TMP-3EO-A, light acrylate TMP-6E
O-3A, Aronix M-35 manufactured by Toagosei Co., Ltd.
0, Aronix M-360, KAY manufactured by Nippon Kayaku Co., Ltd.
Polyethylene oxide-modified trimethylolpropane tri (meth) acrylate such as ARAD THE-330, SR-492 manufactured by Kayaku Sertomer Co., Photomer 4072 manufactured by San Nopco, Aronix M-310 manufactured by Toagosei Co., Ltd., and Aronix M-320. , Nippon Kayaku Co., Ltd.
KAYARAD TPA-310, KAYARAD
Examples include polypropylene oxide-modified trimethylolpropane tri (meth) acrylate such as TPA-320 and KAYARAD TPA-330.

Specific examples of the compound represented by the above general formula (4) include VISCOAT 70 manufactured by Osaka Organic Chemical Industry Co., Ltd.
0, Kayaku Sartomer SR-349, SR-348,
Kyoeisha Chemical Co., Ltd. light acrylate BP-4EA,
Light ester BP-2EM, NK ester A-BPE-4, NK ester BPE-1 manufactured by Shin Nakamura Chemical Co., Ltd.
00, NK ester BPE-200, NK ester BP
E-500, NK ester BPE-1300, Toon Gosei Co., Ltd. Aronix M-210, Nippon Kayaku Co., Ltd. KAYARAD R-551, and other polyethylene oxide-modified bisphenol A di (meth) acrylate, Kyoeisha Chemical Co., Ltd. ) Light acrylate BP-4PA manufactured by Sannopco Ltd., polypropylene oxide-modified bisphenol A di (meth) acrylate such as Photon 4020 manufactured by San Nopco,
Examples include polyethylene oxide-modified bisphenol F di (meth) acrylate such as KAYARADR-712 manufactured by Nippon Kayaku Co., Ltd.

Specific examples of the compound represented by the above general formula (5) include 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate.
Hydroxy group-containing (meth) acrylate such as hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, glycerin di (meth) acrylate, glycerin methacrylate acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and glycerol (meth) acrylate. ) Acrylate compounds are mentioned.

Specific examples of the compound represented by the above general formula (6) include N, N-dimethylaminoethyl (meth) acrylate and N, N-diethylaminoethyl (meth) acrylate.

Specific examples of the compound represented by the above general formula (7) include ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether, dodecyl vinyl ether,
Octadecyl vinyl ether, cyclohexyl vinyl ether, allyl vinyl ether, 2-hydroxyethyl vinyl ether, 2-hydroxybutyl vinyl ether, 4-hydroxybutyl vinyl ether, 9-hydroxynonyl vinyl ether, 4-hydroxycyclohexyl vinyl ether, cyclohexanedimethanol monovinyl ether, diethylene glycol monovinyl ether, tri Examples thereof include ethylene glycol monovinyl ether, tetraethylene glycol monovinyl ether, pentaethylene glycol monovinyl ether, and hexaethylene glycol monovinyl ether.

Specific examples of the compound represented by the above general formula (8) include ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol, pentaerythritol divinyl ether, propylene glycol divinyl ether and dipropylene. Glycol divinyl ether, tripropylene glycol divinyl ether, 1,4-butanediol divinyl ether, 1,6-hexanediol divinyl ether, glycerol divinyl ether, 1,9-nonanediol divinyl ether, 1,4-dihydroxycyclohexanedivinyl ether, 1,4-dihydroxymethylcyclohexane divinyl ether, polyethylene oxide modified bisphenol A di Vinyl ether and the like.

Specific examples of the compound represented by the above general formula (9) include trimethylolpropane trivinyl ether, pentaerythritol trivinyl ether and pentaerythritol tetravinyl ether.

The number of (meth) acryloyl groups in the polyfunctional (meth) acrylate compound (B) other than the monomer (A) in the present invention is 2 or more, preferably 2 to 9, and particularly preferably 3 to 6. It is an individual. Since the monofunctional (meth) acrylate compound has low reactivity, a sufficient cured film cannot be obtained in a high oxygen atmosphere. Further, the larger the number of (meth) acryloyl groups, the higher the reactivity becomes, and although a good cured film can be obtained even in a high oxygen atmosphere, the viscosity of the compound tends to increase, and the compounding amount in the composition or Since there are cases where there are restrictions on the coating method, the range of 3 to 6 is particularly preferable. However, when it has a polar group such as a hydroxyl group, a carboxyl group, an amino group, an amide bond or a urethane bond, it can be preferably used even if the number of (meth) acryloyl groups is two.

Polyfunctional (meth) acrylate compound (B)
Specific examples of 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate
Acrylate, neopentyl glycol di (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ethylene oxide modified Examples thereof include pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate and ester (meth) acrylate.

Epoxy (meth) acrylate is a compound obtained by reacting an epoxy compound with a (meth) acrylic compound having a carboxyl group. Examples of the epoxy compound include a bisphenol type epoxy compound, a phenol novolac type epoxy compound, and an aliphatic epoxy compound. Specific examples of the bisphenol type epoxy compound include Epicoat 801, Epicoat 807, Epicoat 808 manufactured by Yuka Shell Epoxy Co., Ltd.
Epicoat 815, Epicoat 816, Epicoat 81
9, Epicoat 828, Epicoat 834, Epicoat 1001, Epicoat 4010P, Ciba Geigy Corporation
Made Araldite GY-257, Araldite GY-2
52, Araldite GY-250, Araldite GY-
260, Araldite GY-280, D.C. E. R. 324, D.I. E. R. 331,
D. E. R. 332, D.I. E. R. 334, D.I. E.
R. 335, D.I. E. R. 336, D.I. E. R. 33
7, D.I. E. R. 353J, D.I. E. R. 732, D.I.
E. R. 736 and the like.

Specific examples of the aliphatic epoxy compound include neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether,
Dibromoneopentyl glycol diglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether,
Examples thereof include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether.

Examples of the (meth) acrylic compound having a carboxyl group include (meth) acrylic acid and 2- (meth) acrylic acid.
Acryloyloxyethyl succinic acid, 2- (meth) acryloyloxypropyl succinic acid, 3- (meth) acryloyloxypropyl succinic acid, 4- (meth) acryloyloxybutyl succinic acid, 2- (meth) acryloyl Roxyethylphthalic acid, 2- (meth) acryloyloxypropylphthalic acid, 3- (meth) acryloyloxypropylphthalic acid, 4- (meth) acryloyloxybutylphthalic acid, 2
-(Meth) acryloyloxyethyl maleic acid, 2-
(Meth) acryloyloxypropyl maleic acid, 3-
(Meth) acryloyloxypropyl maleic acid, 4-
(Meth) acryloyloxybutyl maleic acid, 2- (meth) acryloyloxyethyl tetrahydrophthalic acid, 2
-(Meth) acryloyloxypropyl tetrahydrophthalic acid, 3- (meth) acryloyloxypropyl tetrahydrophthalic acid, 4- (meth) acryloyloxybutyl tetrahydrophthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid Acid, 2- (meth) acryloyloxypropylhexahydrophthalic acid, 3- (meth) acryloyloxypropylhexahydrophthalic acid, 4- (meth) acryloyloxybutylhexahydrophthalic acid and the like can be mentioned.

The urethane (meth) acrylate is obtained by subjecting a polyisocyanate compound, a polyol compound and a hydroxyl group-containing (meth) acrylate compound to a urethane reaction by a conventional method, or a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate compound. It is a compound obtained by reacting. Examples of the polyisocyanate compound include isophorone diisocyanate, 1,6-hexamethylene diisocyanate,
2,6-tolylene diisocyanate, 2,4-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,5-naphthalene diisocyanate, dicyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate, etc. Diisocyanate compound, a burette type polyisocyanate compound obtained from the reaction of various diisocyanate compounds as described above with water, an adduct type polyisocyanate compound obtained by reacting a low molecular polyol such as trimethylolpropane with the above diisocyanate compound, Examples thereof include polyisocyanate compounds obtained by converting the above-mentioned diisocyanate compound to isocyanurate.

As the polyol compound, ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, neopentyl glycol, 1,3-butanediol, 1,4-butanediol, 1 , 6-hexanediol, 1,9-nonanediol, cyclohexanedimethanol, 1,4-cyclohexanediol, trimethylolethane, trimethylolpropane, glycerin, hydrogenated bisphenol A and the like.

Further, a polyester polyol compound obtained by esterifying the above-mentioned polyol compound with the following carboxylic acids or their acid anhydrides can also be used. As the carboxylic acids, maleic acid, itaconic acid,
Examples include fumaric acid, adipic acid, succinic acid, tetrahydrophthalic acid, hymic acid, dimer acid, sebacic acid, azelaic acid, terephthalic acid, trimellitic acid, hexahydrophthalic acid, pyromellitic acid, and their acid anhydrides. To be

As the hydroxyl group-containing (meth) acrylate compound, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2
-Hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, pentaerythritol tri (meth) acrylate, glycidyl methacrylate (meth) acrylic acid addition The thing etc. are mentioned. Ester (meth) acrylate is a compound obtained by esterifying the polyester polyol compound and (meth) acrylic acid.

In the present invention, the amine or trivalent phosphorus compound (C) is blended for the purpose of reacting with oxygen radicals which cause the inhibition of curing of the film surface and reducing the concentration thereof. Examples of the amine include trimethylamine, triethylamine, tributylamine, trihexylamine, trioctylamine, trilaurylamine, dimethyloctylamine, dimethylstearylamine, pentamethyldiethyltetramine, tetramethyldiaminohexamine, triethanolamine, N-methyl-N, N-diethanolamine, butyldiethanolamine, dimethylaminopropanol, N, N-dimethylethanolamine, N,
N-diethylethanolamine, N, N-dibutylethanolamine, dimethylbenzylamine, N-methyl-
3-piperidinemethanol, dipiperidinomethane, N-
Tertiary amines such as methylmorpholine and tetramethylethylenediamine, N-methylethanolamine, diisopropylamine, diethylamine, morpholine, di2-
Secondary amines such as ethylhexylamine, diethanolamine and N-methylpiperazine, and primary amines such as aminoethylethanolamine, 3-amino-1-propanol, isopropylamine, monoethylamine, 2-ethylhexylamine and t-butylamine can be mentioned.

The trivalent phosphorus compounds include phosphines and phosphites. Typical examples of phosphines are tributylphosphine, trioctylphosphine,
Tricyclohexylphosphine, triphenylphosphine, tribenzylphosphine, tritolylphosphine,
p-styryldiphenylphosphine and the like, and typical examples of the phosphite ester are triphenylphosphite, tri-p- (nonylphenyl) phosphite,
Tri-p-tolyl phosphite, diphenyl decyl phosphite, monophenyl didecyl phosphite, etc. are mentioned. The amine or trivalent phosphorus compound (C) can be used alone or in combination of two or more as necessary from the above compounds.

The compounding ratio of the monomer (A) and the polyfunctional (meth) acrylate compound (B) in the curable composition is as follows: monomer (A): polyfunctional (meth) acrylate compound (B) =
10:90 to 90:10 (weight ratio), and further 30: 7
It is preferably 0 to 70:30 (weight ratio). When the compounding ratio of the monomer (A) is less than the above range, the expected viscosity lowering effect is low, and when it exceeds the above range, the number of functional groups in the composition is insufficient, and it is difficult to obtain sufficient curability.

The content of the amine or trivalent phosphorus compound (C) in the curable composition is 100 parts by weight based on the total of 100 parts by weight of the monomer (A) and the polyfunctional (meth) acrylate compound (B). It is preferably 0.1 to 5 parts by weight, more preferably 0.3 to 3 parts by weight. When the content is less than 0.1 parts by weight, the effect of suppressing curing inhibition by oxygen is low, and when it exceeds 5 parts by weight, unreacted amine or phosphorus compound increases and the film hardness decreases.

The curable composition may be in a liquid state when the above compound is blended, but in order to apply the composition easily and smoothly, the viscosity in the blended state is 100 to 10,000 cp.
It is preferably s (25 ° C.). The liquid state here includes not only a liquid state in which two or more kinds of compounds are completely compatible with each other, but also a heterogeneous system in which a powdery compound is dispersed in a liquid compound. In the curable composition, any compound can be used as long as it is liquid at the time of mixing, but it is liquid from the viewpoint of working environment and safety,
It is preferable to select a substance having a flash point of 70 to 300 ° C. (hazardous substance, fourth class, third class petroleum, fourth class petroleum) and having a small odor.

In the curable composition, for various purposes,
Various additive components can be added. For example, to add a filler, a diluent or a resin component to improve the cured properties, to adjust the viscosity or to reduce the cost, to add an antibacterial agent, a fungicide or an antiseptic agent to give added value, or to add a color. Pigments can be added. Further, a matting agent such as silicon fine particles and organic fine particles can be added for the purpose of improving the design. Also,
An organic solvent can be added to reduce the viscosity. Examples of the organic solvent include isopropyl alcohol, methyl ethyl ketone, toluene, xylene, ethyl acetate and the like.

The monomer (A), the polyfunctional (meth) acrylate compound (B) other than the monomer (A), and the amine or trivalent phosphorus compound (C) other than the compound represented by the general formula (6). A curable composition containing a) is applied to a base material such as various steel plates, metal plates such as aluminum plates, plastic films, paper, plastic film laminated paper, etc. by a roll coater, knife coater, etc., or offset printing, gravure coating. Forming or filling a film with a film thickness of 0.1 to 500 μm by a printing method such as printing, letterpress printing, silk screen printing, and irradiating with an electron beam under an oxygen concentration of 500 ppm or more to form a cured film. You can The oxygen concentration of 500 ppm or more also includes the concentration range achieved by performing inerting with an inert gas such as nitrogen or argon.

The acceleration voltage of electron beam irradiation is 30 to 250 k.
Although a cured film can be formed by setting it in the range of V, it is preferable to set it in the range of 30 to 100 kV so that the same curability can be obtained at a lower irradiation dose. 30 to 10
By irradiating with an electron beam of 0 kV, the electron beam concentrates on the coating / printing surface where curing inhibition is likely to occur, and the curability can be improved. Therefore, in order to obtain high curability under high oxygen concentration, it is preferable to irradiate with an electron beam with an acceleration voltage of 30 to 100 kV.

Further, the acceleration voltage of the electron beam is set to 30 to 100 k.
When it is set in the range of V, it is possible to set the irradiation dose of the electron beam to a value lower than usual and to achieve energy saving by high energy efficiency and improvement of production efficiency by speeding up coating and printing. . Accelerating voltage is 100 ~ 250k
In the ordinary electron beam irradiation of V, the curable composition can be cured under an oxygen concentration of 500 ppm or more in the irradiation dose region of 3 to 30 kGy, but the accelerating voltage is 3
When the range is set to 0 to 100 kV, the irradiation dose is suppressed to 1 to 10 kGy, which is one-third, and similar curability is obtained.

[0049]

EXAMPLES Next, the present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto. The surface tack and surface hardness were evaluated by the following methods. (1) Surface tack: A curable composition was applied on a glass plate so that the film thickness after curing was 5 μm, and then “Curetron” EBC-200-manufactured by Nisshin High Voltage Co., Ltd.
20-30 and Min-EB manufactured by AIT were used to perform electron beam irradiation, and the surface tack of the cured film was evaluated. "Curetron" is performed at an accelerating voltage of 150 kV, irradiation dose of 5 and 20 kGy, and Min-EB is at an accelerating voltage of 50 k
V, irradiation dose 2 and 5 kGy. The oxygen concentration in the irradiation atmosphere is 500, 500 using nitrogen gas.
It was adjusted to 0, 50,000 and 200,000 ppm.

(2) Surface hardness: (1) Maximum pencil hardness at which the coating film is not damaged by a pencil ("Uni" manufactured by Mitsubishi Pencil Co., Ltd.) after being irradiated with an electron beam under the same conditions as the surface tack. Was measured.

The abbreviations used in Examples and Comparative Examples are shown below. UA-306H: Kyoeisha Chemical Co., Ltd. urethane acrylate MDA: N-methyl-N, N-diethanolamine TMP-3EO-A: Kyoeisha Chemical Co., Ltd. light acrylate TMP-3EO-A, polyethylene oxide modified trimethylolpropane tri (Meth) acrylate A-BPE-4: NK ester A-BPE-4 manufactured by Shin Nakamura Chemical Co., Ltd., polyethylene oxide modified bisphenol A diacrylate M-9050: manufactured by Toagosei Co., Ltd., polyester acrylate R-167: Nippon Kayaku Co., Ltd., 1,6-hexanediol diglycidyl ether terdiacrylate DPHA: dipentaerythritol hexaacrylate

(Examples 1 to 9 and Comparative Examples 1 to 3) Tables 1 and 2
Mix each component (numbers show weight%) in the ratio shown in
A curable composition was obtained. Then, the surface tack and the surface hardness were evaluated. The results are shown in Tables 1 and 2.

[0053]

[Table 1]

[0054]

[Table 2]

[0055]

According to the present invention, a cured film having high curability and high surface hardness can be obtained even in a high oxygen atmosphere.

Front page continuation (51) Int.Cl. ⁷ Identification code FI theme code (reference) // C08F 290/06 C08F 290/06 F term (reference) 4J027 AB03 AC02 AC03 AC04 AC06 AC07 AE02 AE03 AE04 AG01 AG03 AG12 AG13 AG14 AG15 AG23 AG24 AG27 AJ02 AJ08 AJ09 BA02 BA07 BA08 BA13 BA17 BA20 BA21 BA23 BA24 BA26 BA27 CA25 CA27 CC06 CD08 4J038 CE051 CG141 CH021 CH051 CH061 CH071 CH121 CH141 CH161 CH201 DB371 DD211 DG211 GA09 JB03 AD10 AD34 AD09 4 EA04 FA01 FA02 FA04 GA16

Claims (5)

[Claims] 1. At least one monomer (A) selected from compounds represented by the following general formulas (1) to (9) and a polyfunctional (meth) acrylate compound (B other than the monomer (A). ), And a curable composition containing an amine other than the compound represented by the following general formula (6) or a trivalent phosphorus compound (C) is irradiated with an electron beam under an oxygen concentration of 500 ppm or more. Method of forming a film. [Chemical 1] (In the formula, R1 is a hydrogen atom or a methyl group, and n is 0.
Is an integer of ˜2. ) [Chemical 2] (In the formula, R1 is a hydrogen atom or a methyl group, R2 is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a phenyl group,
It is a nonylphenyl group or a (meth) acryloyl group. In addition, n is an integer of 1 to 23. ) [Chemical 3] (In the formula, R1 is a hydrogen atom or a methyl group.
l, m, and n are integers of 0 to 6, and l + m + n is 1 to 6.
Is. ) [Chemical 4] (In the formula, R1 is a hydrogen atom or a methyl group.
m and n are integers of 0 to 30, and m + n is 1 to 30. ) [Chemical 5] (In the formula, n is an integer of 1 to 3, R 1 is a hydrogen atom or a methyl group, and R 3 is a hydrogen atom, a methyl group,
It is an ethyl group, a methylol group, a phenoxymethyl group, or a (meth) acryloyloxymethyl group. ) [Chemical 6] (In the formula, R1 is a hydrogen atom or a methyl group, and R4 is a methyl group or an ethyl group.) (In the formula, R5 is an alkyl group having 2 to 18 carbon atoms, a hydroxyalkyl group having 2 to 9 carbon atoms, a cyclohexyl group,
Alternatively, it is an organic residue represented by any of the general formulas (7a) to (7d). Further, in the general formula (7a), n is an integer of 2 to 6, R
1 is a hydrogen atom or a methyl group. ) [Chemical 8] (In the formula, R6 is an organic residue represented by the general formulas (8a) to (8e). In the general formula (8a), n is an integer of 4 to 9. Further, the general formula (8b). In the formula, n is an integer of 2 to 6, R1 is a hydrogen atom or a methyl group, and in the general formula (8e), R1 is a hydrogen atom or a methyl group.
Further, m and n are integers of 0 to 6, and m + n is 0 to 6. ) [Chemical 9] (In the formula, R7 is a methylol group, an ethyl group, or a vinyloxymethyl group.) 2. The compounding ratio of the monomer (A) and the polyfunctional (meth) acrylate compound (B) in the curable composition is 10:
90 to 90:10 (weight ratio), and the total content of amine or trivalent phosphorus compound (C) is 10 (A) and (B).
The method for forming a cured film according to claim 1, wherein the amount is 0.1 to 5 parts by weight with respect to 0 parts by weight. 3. The method for forming a cured film according to claim 1, wherein the electron beam having an accelerating voltage of 30 to 100 kV is irradiated. 4. The method for forming a cured film according to claim 3, wherein the irradiation dose of the electron beam is 1 to 10 kGy. 5. The method for forming a cured film according to claim 1, wherein the composition is used for ink or paint.