JP2000063410A - Electron beam-curing oxygen inhibition suppressor, electron beam-curing composition containing the same, and method of forming cured film and cured material using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an electron beam-curing oxygen inhibition suppressor which is excellent in oxygen inhibition suppressing effect and which can be used in wide fields as resin materials such as film-forming materials e.g. wating materials and inks, encapsulants, molding agents, adhesives and tackiness agents and with which a cured material can be obtained by an electron beam even in the presence of oxygen of 500 ppm or more, a composition containing the same, and to provide a forming method of cured films and cured materials using the same. SOLUTION: An electron beam-curing oxygen inhibition suppressor comprises a (meth)acrylate-based compound having a cycloalkane structure. An electron-curing composition contains the electron beam-curing oxygen inhibition suppressor and another (meth)acrylic-based compound or vinyl ether-based compound and can be cured an electron beam even in the presence of oxygen of 500 ppm or more. A forming method of cured films is to irradiate an electron beam to the electron-curing composition in the presence of oxygen of 500 ppm or more. A cured material is obtained by irradiating an electron beam to the electron-curing composition in the presence of oxygen of 500 ppm or more.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention has an excellent effect of inhibiting oxygen inhibition, and can be used in a wide range of fields as a resin material such as a film forming material such as paints and inks, a sealant, a molding agent, an adhesive, and an adhesive. The present invention relates to an electron beam curable oxygen inhibition inhibitor capable of producing a cured product with an electron beam even under an oxygen concentration of 500 ppm or more, a composition containing the same, a method for forming a cured film using the same, and a cured product. is there.

[0002]

2. Description of the Related Art In recent years, the tendency toward active energy ray curing systems has become remarkable due to increasing interest in the global environment and work environment. Among them, the electron beam curing system is solvent-free and does not require an initiator. Furthermore, the drying time is very short compared to the UV curing system as well as the heat curing system. Its effectiveness has been recognized because it does not cause damage. However, the conventional electron beam curing system has a problem that 1) the apparatus is large and the initial investment is large, and 2) the oxygen concentration is preferably several tens of ppm or less, in order to eliminate the inhibition of surface curing due to the generation of oxygen radicals. However, there is a problem in that running costs are required because inerting with a high-purity inert gas such as nitrogen is required so as to be 200 ppm or less.

[0003] Regarding the inhibition of curing by oxygen, various research institutions have studied and additives such as amine compounds and phosphorus compounds have been investigated. However, all such additives having relatively high effects are cured. The amount of addition is limited due to low water resistance and solvent resistance of the cured product that is extracted later, yellowing is observed, etc., and a sufficient curing inhibition suppressing effect is not obtained. In addition, the cationic resin material, which is said to have relatively low oxygen curing inhibition, is expensive, requires an initiator even though it is an electron beam curing system, and the product lineup is insufficient. Therefore, there are problems such as not meeting a wide range of product specifications.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides an electron beam curable oxygen inhibition inhibitor which has no problem in physical properties such as amino compounds and phosphorus compounds, and an electron beam curable even under an oxygen concentration of 500 ppm or more. An object is to provide an electron beam curable resin composition that can be pressed. Another object of the present invention is to provide a method for forming a cured coating film and a cured product by electron beam irradiation under an oxygen concentration of 500 ppm or more.

[0005]

The inventors of the present invention have found that (meth) acrylic compounds having a cycloalkane structure are highly effective in suppressing curing inhibition by oxygen in electron beam curing. There is no problem in terms of physical properties, and the resin composition containing a (meth) acrylic compound having a cycloalkane structure is 500 ppm.
The inventors have found that the composition can be cured by an electron beam even under the above oxygen concentration, and have completed the present invention.

That is, the present invention relates to an electron beam curable oxygen inhibition inhibitor comprising a (meth) acrylic compound having a cycloalkane structure. The present invention also relates to the electron beam curable oxygen inhibition inhibitor, wherein the cycloalkane structure is a cyclohexane structure. Further, the present invention provides the electron beam curable oxygen inhibition inhibitor, wherein the (meth) acrylic compound having a cyclohexane structure is a (meth) acrylic half ester (A-1) represented by the following general formula (1). Regarding

[0007]

[Chemical 3] (In the formula, R ₁ is a hydrogen atom or a methyl group, R ₃ is an alkyl group having 2 to 25 carbon atoms or an organic residue represented by the following formula (2-a), R ₂ is the following formula (2-b) or (2-c) is an organic residue.)

[Chemical 4] (In the formula, R ₄ and R ₄ 'are hydrogen atoms or alkyl groups having 1 to 25 carbon atoms, p is 2 to 15, q is 0 (direct bond) to 20, r is 2 to 15 and m is 0 (direct Bond) indicates an integer of 10).

Further, in the present invention, the (meth) acrylic half ester (A-1) reacts with a cyclic acid anhydride (a) having a cyclohexane structure and a hydroxyl group-containing (meth) acrylic compound (b). The present invention relates to the above electron beam curable oxygen inhibition inhibitor which is a half ester. Further, the present invention provides an epoxy obtained by reacting a (meth) acrylic compound having a cyclohexane structure with a (meth) acrylic half ester (A-1) represented by the general formula (1) and an epoxy group-containing compound. The present invention relates to the electron beam curable oxygen inhibition inhibitor which is an acrylic compound.

Further, according to the present invention, a (meth) acrylic compound having a cyclohexane structure has a carboxyl group of 1
The present invention relates to the above electron beam curable oxygen inhibition inhibitor, which is an epoxy acrylic compound obtained by reacting a (meth) acrylic compound having one unit with an epoxy group-containing compound having a cyclohexane structure. Further, the present invention relates to the electron beam curable oxygen inhibition inhibitor, wherein the (meth) acrylic compound having a cycloalkane structure has 2 to 6 (meth) acryloyl groups.

Further, the present invention comprises the above-mentioned electron beam curable oxygen inhibition inhibitor and another (meth) acrylic compound or vinyl ether compound, and can be cured by an electron beam even under an oxygen concentration of 500 ppm or more. The present invention relates to an electron beam curable composition. Further, in the present invention, the compounding ratio of the electron beam curable oxygen inhibition inhibitor and the other (meth) acrylic compound or vinyl ether compound is 10: 9.
The present invention relates to the electron beam curable composition having a weight ratio of 0 to 95: 5. The present invention also relates to the above electron beam curable composition for use in printing ink. The present invention also relates to the above electron beam curable composition which is used for coating materials.

The present invention also relates to a method for forming a cured coating by irradiating the above electron beam-curable composition with an electron beam under an oxygen concentration of 500 ppm or more. 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. Further, the present invention is a cured product obtained by irradiating the above electron beam curable composition with an electron beam under an oxygen concentration of 500 ppm or more.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION An electron beam curable oxygen inhibition inhibitor comprising a (meth) acrylic compound having a cycloalkane structure according to the present invention may be used by itself or in a composition containing it.
It is an electron beam curable compound having an oxygen curing inhibition suppressing function of suppressing curing inhibition by oxygen generated when curing with an electron beam under an oxygen concentration of 00 ppm or more. The cycloalkane structure in the present invention has 4 to 20 carbon atoms,
Preferably, it is an organic residue having a saturated aliphatic hydrocarbon type cyclo or bicyclo structure of 4 to 15, more preferably 4 to 8, and hydrogen is easily abstracted by absorption of an electron beam to generate an active radical. Effectively promotes curing and inhibits curing inhibition by oxygen.

As the (meth) acrylic compound having a cycloalkane structure, compounds represented by the following formulas (3-a) to (3-j) can be exemplified.

[Chemical 5] In particular, compounds having a cyclohexane structure include commercially available raw materials and raw materials, which are preferable from the economical viewpoint.

Further, the (meth) acrylic half-ester compound (A-1) represented by the above general formula (1) is preferable because it has a carboxyl group and therefore has a synergistic oxygen inhibition suppressing effect. The (meth) acrylic half ester (A-1) is, for example, a cyclic acid anhydride (a) having a cyclohexane structure and a hydroxyl group-containing (meth) acrylic compound.
It can be synthesized by the reaction with (b). Examples of the cyclic acid anhydride (a) having a cyclohexane structure include cyclohexyldicarboxylic acid anhydride, methylcyclohexyldicarboxylic acid anhydride and bicyclohexyldicarboxylic acid anhydride.

The hydroxyl group-containing (meth) acrylic compound (b) is a compound having one hydroxyl group and at least one (meth) acryloyl group, and has the following general formula (4):
The compound represented by can be illustrated.

[Chemical 6] In the general formula (4), R ₁ is a hydrogen atom or a methyl group, p is an integer of 2 to 15, preferably 2 to 6, and when p is larger than 15, reactivity decreases. In addition, q is an integer of 0 (direct bond) to 20, preferably 1 to 5, and q is 20.
If it is larger than this, reactivity decreases. Also, r is 2 to 1
5, preferably an integer of 4 to 7, and this range is preferable from the viewpoint of versatility of raw materials and physical properties. Further, m is an integer of 0 (direct bond) to 10, preferably 1 to 5, and m is 10
If it is larger than this, reactivity decreases.

More specifically, the hydroxyalkyl hydroxyl group-containing (meth) acrylic compound (b) represented by the general formula (4) is 2-hydroxyethyl (meth).
Acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate,
2-hydroxybutyl (meth) acrylate, 1,6-
Hexane diol mono (meth) acrylate etc. can be mentioned. Further, as the polyalkylene glycol-based hydroxyl group-containing (meth) acrylic compound (b),
Diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, tripropylene glycol (meth) acrylate, tetrapropylene glycol mono (meth) acrylate, polytetramethylene glycol mono (meth ) Acrylate etc. can be mentioned. Further, as the lactone-modified hydroxyl group-containing (meth) acrylic compound (b), 2- (meth) acryloyloxyethyl hydrogencaprolactonate, 2- (meth) acryloyloxyethyl hydrogendicaprolactonate, 2 Examples thereof include-(meth) acryloyloxyethyl hydrogen polycaprolactonate (polymerization degree 3 to 5) and 2- (meth) acryloyloxyethyl-2-hydroxy-6 hexanolactonate.

Further, as the hydroxyl group-containing (meth) acrylic compound (b), 2- (meth) acryloyloxyethyl 2-hydroxypropyl phthalate, 3-chloro, in addition to the compound represented by the above general formula (4), -2-Hydroxypropyl (meth) acrylate, 2-hydroxy-
There is 3-phenoxypropyl (meth) acrylate,
Glycerol mono (meth) acrylate, pentaerythritol mono (meth) acrylate, ethylene oxide modified pentaerythritol mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, ethylene oxide modified trimethylolpropane mono (meth) acrylate are also used. can do.

Further, the (meth) acrylic compound having a cyclohexane structure is a reaction of the (meth) acrylic half ester (A-1) with an epoxy group-containing compound, or a (meth) acrylic compound having one carboxyl group. It may be an epoxy acrylic compound which can be synthesized by the reaction of a system compound and an epoxy group-containing compound having a cyclohexane structure.

As the epoxy group-containing compound, a bisphenol-based epoxy group-containing compound, a glycidyl ether-based epoxy group-containing compound or a mixture thereof can be used, but the epoxy group-containing compound is not necessarily limited thereto. Examples of the bisphenol epoxy group-containing compound include Epicoat 801, Epicoat 807, Epicoat 808, Epicoat 815, Epicoat 816, Epicoat 819, Epicoat 876, Epicoat 828, Epicoat 834, Epicoat 864, and Epicoat 1001 manufactured by Yuka Shell Epoxy Co., Ltd. , Epicote 1004, epicote 1007, epicote
1009, Epicote 1310, Ciba Geigy's Araldite GY-257, Araldite GY-252, Araldite GY-2
50, Araldite GY-260, Araldite GY-280, Araldite GY-6040, Araldite GY-6060, Araldite
GY-6071, Araldite 6075, Araldite GY-6084,
Araldite GY-6097, Araldite GY-6099, Dow Chemical Japan DER324, DER331, DER
331C, DER332, DER334, DER335, DER33
6, DER337, DER353J, DER732, DER736
, DER661, DER664, DER667 and the like.

Examples of the glycidyl ether epoxy group-containing compound include monoglycidyl ether epoxy group-containing compounds such as phenyl glycidyl ether, methyl glycidyl ether and butyl glycidyl ether, 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, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether , Propylene glycol diglycidyl ether, polypropylene Polyglycidyl ether epoxy group-containing compounds such as glycol diglycidyl ether.

As the epoxy group-containing compound having a cyclohexane structure, hydrogenated bisphenol A diglycidyl ether, ethylene oxide modified hydrogenated bisphenol A diglycidyl ether, propylene oxide modified bisphenol A diglycidyl ether, or the following general formula (5 The compounds represented by -a) to (5-c) can be exemplified.

[Chemical 7]

Further, the (meth) acrylic compound having one carboxyl group means, in addition to the above (meth) acrylic half ester (A-1), phthalic acid β- (meth) acryloxyethyl monoester, Isophthalic acid β- (meth) acryloxyethyl monoester, terephthalic acid β
Examples thereof include-(meth) acryloxyethyl monoester, succinic acid β- (meth) acryloxyethyl monoester, acrylic acid and methacrylic acid.

The (meth) acrylic half ester (A
-1) and the epoxy acrylic compound can be synthesized by known methods. During synthesis, tertiary amines such as dimethylbenzylamine and triethylamine can be used as catalysts. The amount of the catalyst added is 0.01 to 3 parts by weight, preferably 0.1 to 1.5 parts by weight, based on 100 parts by weight of the total amount of the reactive compounds as raw materials. The reaction temperature is preferably 50 to 120 ° C. Further, the reaction can be carried out in a solvent-free system, but a general-purpose organic solvent can be used for controlling the reaction. In that case, the active ingredient concentration is 20 to 95% by weight, preferably 30 to 90% by weight.
Is. If the concentration is lower than this range, the reactivity is lowered, which is not preferable.

The (meth) acrylic compound having a cycloalkane structure is not particularly limited in molecular weight and viscosity, but has a number average molecular weight of 30,000 or less, preferably 25.
It is preferably 0 to 10000 from the viewpoint of compatibility with other monomer components and viscosity. The viscosity is not particularly limited as long as the composition containing the (meth) acrylic compound having a cycloalkane structure can form a film, but in terms of handling, it is preferably liquid at 25 ° C., and particularly preferably 30 ° C
At 100,000 cps or less, further 5 to 200
A viscosity of 00 cps is preferred.

The electron beam curable oxygen inhibition inhibitor of the present invention is
It exhibits curability by an electron beam even under an oxygen concentration of 500 ppm or more, and can be used as a resin material such as an electron beam curable coating material, a film forming material such as ink, a molding material and an adhesive. Similarly, a composition in which one or more general-purpose electron beam-curable compounds such as other (meth) acrylic compounds and vinyl ether compounds are blended is also 50
It exhibits curability by an electron beam under an oxygen concentration of 0 ppm or more.

Among the other (meth) acrylic compounds to be blended with the electron beam curable oxygen inhibition inhibitor of the present invention, the monofunctional (meth) acrylic compounds are methyl (meth) acrylate and ethyl (meth). Acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, n-lauryl (meth) acrylate, tridecyl (meth) Acrylate, n-stearyl (meth) acrylate, isostearyl (meth) acrylate, behenyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate , N-butoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2 -Hydroxypropyl (meth) acrylate,
2-hydroxybutyl (meth) acrylate, (meth) acrylic acid, (meth) acryloyloxyethyl hydrogen succinate, (meth) acryloyloxypropyl hydrogen phthalate, (meth) acryloyloxypropyl tetrahydrohydrogen phthalate, (meth) Acryloyloxypropyl hexahydrohydrogen phthalate, (meth) acryloyloxyethyl 2-hydroxypropyl phthalate, glycidyl (meth) acrylate, glycerol mono (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl (meth) acrylate, Examples thereof include, but are not limited to, mono (2- (meth) acryloyloxyethyl) acid phosphate.

As the polyfunctional (meth) acrylic compound, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate,
Polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide modified bisphenol A di (meth) acrylate, propylene oxide modified bisphenol A di (meth) acrylate, trimethylol Propane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipenta Erythritol hexa (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol Rutori (meth) acrylate,
3- (meth) acryloyloxyglycerin mono (meth)
Acrylate, dipentaerythritol tetra (meth)
Acrylate, dipentaerythritol penta (meth)
In addition to polyfunctional (meth) acrylate monomers such as acrylates, urethane acryl, epoxy acryl, ester acryl, etc. may be mentioned, but not limited to these. If a (meth) acrylic compound having a functionality of 3 or more is used among the above polyfunctional compounds, the reactivity is increased and the inhibition of curing by oxygen can be further improved.

Among the vinyl ether compounds, examples of monofunctional vinyl ether compounds include hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, dodecyl vinyl ether, cyclohexanedimethanol monovinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether and octadecyl vinyl ether. .

The polyfunctional vinyl ether compounds include ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol, pentaerythritol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether and triethylene glycol divinyl ether. Propylene glycol divinyl ether, neopentyl glycol divinyl ether, 1,4-
Butanediol divinyl ether, 1,6-hexanediol divinyl ether, glycerol divinyl ether,
Trimethylolpropane divinyl ether, 1,4-dihydroxycyclohexanedivinyl ether, 1,4-dihydroxymethylcyclohexanedivinyl ether, hydroquinone divinyl ether, hydroquinone diethoxydivinyl ether, resorcindiethoxydivinyl ether, bisphenol A diethoxydivinyl ether,
Divinyl ether compounds such as bisphennol S diethoxydivinyl ether, glycerol trivinyl ether, sorbitol tetravinyl ether, trimethylolpropane trivinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol hexavinyl ether, dipentaerythritol polyvinyl ether , Ditrimethylolpropane tetravinyl ether,
3 such as ditrimethylolpropane polyvinyl ether
Examples thereof include polyvinyl ether compounds having a functionality or higher, but are not necessarily limited thereto.

The compounding ratio of the electron beam curable oxygen inhibition inhibitor to the other (meth) acrylic monomer or vinyl monomer is such that the content of the cycloalkane structure and other (meth) acrylic compound to be blended are It depends on the structure of the vinyl-based monomer or vinyl-based monomer and the oxygen concentration during curing, but is preferably 10:90.
~ 95: 5 (weight ratio), more preferably 30: 70 ~.
It is 95: 5 (weight ratio).

The electron beam curable oxygen inhibition inhibitor of the present invention or the electron beam curable composition containing it contains an amino resin in order to control viscosity, film-forming property and film performance.
Phenolic resin, polyamide resin, cellulose derivative,
General-purpose resin materials such as vinyl resin, polyolefin, natural rubber derivative, acrylic resin, epoxy resin, polyester, polystyrene, alkyd resin, rosin-modified alkyd resin, and linseed oil-modified alkyd resin, and dryness of linseed oil, tung oil, soybean oil, etc. You may mix oil etc. However,
The amount of each of these compounds is preferably 60% by weight or less, more preferably 40% by weight or less, based on the total amount of the composition.

Further, water, an organic solvent, a compatibilizer, a surfactant, a lubricant and the like may be added for the purpose of controlling fluidity. The blending amount thereof is preferably 20% by weight or less, more preferably 10% by weight or less, based on the total amount of the composition. To the electron beam curable composition of the present invention, an appropriate amount of a colorant composed of a pigment such as carbon black, titanium white, phthalocyanine, an azo dye, quinacridone or an inorganic filler such as Si fine particles, mica or calcium carbonate is added. Therefore, it can be used as various printing inks, colored paints and the like.

The electron beam curable oxygen inhibition inhibitor of the present invention and the composition containing the same can be used for various metals, plastics, papers,
Plate, sheet or film-like substrate made of ceramic or composite material, coating method such as roll coater, bar coater, knife coater, or offset printing,
Film formation or filling can be performed with a film thickness of 0.1 to 500 μm by a printing method such as gravure printing, letterpress printing, and silk screen printing. The coating film formed or filled by the above method can be cured by irradiation with an electron beam even under an oxygen concentration of 500 ppm or more.

In the present invention, the oxygen concentration of 500 ppm or more includes the concentration range achieved by performing inerting with an inert gas such as nitrogen or argon. The permissible concentration of oxygen curable by an electron beam of the composition of the present invention is determined by irradiation conditions (accelerating voltage, irradiation dose, etc.), blending amount of an oxygen curing inhibition inhibitor, other (meth) acrylic compound or vinyl ether type. Depending on the type of compound, etc., under the best conditions, it can be cured even in air without oxygen inhibition. Economically (price of inerting gas), more than 1000ppm, and even 10
It is preferable to cure under an oxygen concentration of 000 ppm or more.

The electron beam used as a curing trigger in the present invention is obtained by an electron beam irradiation device having an accelerating voltage in the range of preferably 10 to 300 kV, more preferably 30 to 100 kV. Irradiation with an electron beam having an accelerating voltage of 100 kV or less is preferable because it causes less damage to the coating film and the substrate. Also, the acceleration voltage 30 to
In the electron beam irradiation device with a low acceleration voltage in the range of 70 kV, energy is concentrated on the surface, so that the electron beam is intensively absorbed on the coating / printing surface where curing inhibition is likely to occur due to oxygen, and the curability is improved. Since it is possible, it is effective for curing a thin film and is particularly preferable. The electron beam irradiation dose (DOSE) is preferably 1 to 1000 kG.
y, and more preferably 5 to 200 kGy.
If it is less than this range, it is difficult to obtain a sufficiently cured product, and if it is more than this range, the coating film or the base material is greatly damaged.

[0036]

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. ◎ Measurement method of number average molecular weight and viscosity 1) Number average molecular weight (Mn) Gel permeation chromatography (manufactured by Tosoh Corporation: SC-80)
20) 2) Viscosity (30 ° C.) Rheometer RDS-II (high viscosity type) manufactured by Rheometrics Co., Ltd. or RFS-I according to the viscosity of the sample.
Steady-state viscosity measured by I (low viscosity type) (sliding speed = 1
The value of -10 / sec) was adopted.

◎ Electron beam irradiation device and irradiation conditions 1) Area beam type electron beam irradiation device Curetron EBC-200
-20-30 (manufactured by Nisshin High Voltage Co., Ltd.) Electron beam acceleration: 200 kV Absorbed dose (Dose): A range of 5 to 80 kGy was adjusted by the amount of current and the transport speed. 2) MIN-EB (manufactured by AIT) Electron beam acceleration; 30 kV output; 10 W, 30 W absorbed dose (Dose); The range of 5 to 50 kGy was adjusted by the transport speed.

The abbreviations of the compounds used in Examples and Comparative Examples are shown below. 1) Cycloalkane structure-containing (meth) acrylate BISDA; hydrogenated bisphenol A diacrylate DAPA; compound represented by the above formula (3-i)

2) Hydroxyl group-containing (meth) acrylic compound HEA; 2-hydroxyethyl acrylate 4HBA; 4-hydroxybutyl acrylate PPG2A; dipropylene glycol monoacrylate PEG3A; triethylene glycol monoacrylate FA1; 2- (meth) acryloyloxy Ethyl hydrogen caprolactonate (OH value = 244KOHmg / g) FA2; 2- (meth) acryloyloxyethyl hydrogen dicaprolactonate (OH value = 163KOHmg / g) PE3A; pentaerythritol triacrylate (OH value = 1)
30KOHmg / g)

3) Cyclic acid anhydride HPAH; cis-1,2 cyclohexanedicarboxylic acid anhydride MHPAH; 4-methylcyclohexane 1,2-dicarboxylic acid anhydride NBAH; norbornanedicarboxylic acid anhydride PAH; phthalic anhydride 4) ( Carboxyl group-containing (meth) acrylic compound AA other than (meth) acrylic half ester (A-1); acrylic acid SA; 2-acryloyloxyethyl ethyl hydrogen succinate CCA; ω-carboxy-dicaprolactone acrylate

5) Epoxy group-containing compound HDDG; 1,6 hexanediol diglycidyl ether (epoxy equivalent = 153 g / eg) CHDG; 1,2-cyclohexanedicarboxylic acid diglycidyl ester (epoxy equivalent = 176 g / eg) HBADG; 2 , 2-Bis [4- (2,3-epoxypropyl) cyclohexane] propane (epoxy equivalent = 216g / eg) 6) (meth) acrylic monomer or vinyl monomer HDDA; 1,6-hexane Diol diacrylate PE3A; pentaerythritol triacrylate DPHA; dipentaerythritol hexaacrylate HDVA; 1,6-hexanediol vinyl ether

Synthesis Example Synthesis of (meth) acrylic half ester (Synthesis Example 1)
9 to Comparative Synthesis Example 1) A four-necked round bottom flask equipped with a stirrer, a nitrogen inlet tube, a temperature sensor, and a condenser was charged with the hydroxyl group-containing (meth) acrylic compound shown in Table 1 and a cyclic acid anhydride. Molar charge (the amount of hydroxyl group-containing (meth) acrylic compound was calculated from the hydroxyl value), and dimethylbenzylamine.
5 phr was added. This was set in a hot water bath set at 85 ° C., and heating and stirring was started. When it was confirmed that the inside of the reaction system became uniform, the temperature of the water bath was further raised to 90 ° C., and heating and stirring were continued. After 2 to 3 hours, the characteristic absorption of the acid anhydride (around 1820 cm ^-1 ) was checked by IR, and when the peak disappeared, it was removed from the water bath and allowed to cool. The product obtained is GPC
It was confirmed by the number average molecular weight and the residual ratio of the raw materials measured in.

Synthesis of Epoxy Acrylic Compounds (Synthesis Examples 10 to 18, Comparative Synthesis Example 2) Epoxy compounds shown in Table 1 in a four-necked round bottom flask equipped with a stirrer, a nitrogen inlet tube, a temperature sensor, and a condenser. Group-containing compound and double molar amount of carboxyl group (meta)
An acrylic compound was charged, and 0.5 phr of dimethylbenzylamine was further added. This was set in a hot water bath set at 85 ° C., and heating and stirring was started. When it was confirmed that the inside of the reaction system became uniform, the temperature of the water bath was further raised to 95 ° C., and heating and stirring were continued. The acid value was measured every hour, and when the acid value became 5 mgKOH / g or less, the reaction was stopped by removing it from the hot water bath. The obtained compound was confirmed by the molecular weight measured by GPC and the residual ratio of raw materials.

Table 1 shows the number average molecular weight, viscosity and purity of the raw materials used for the synthesis of the (meth) acrylic half ester and epoxy acrylic compound and the products obtained.

[Table 1]

The (meth) acrylic compounds obtained in Synthetic Examples 1 to 18 and Comparative Synthetic Examples 1 and 2 and the various (meth) acrylic monomers or vinyl monomers are shown in Table 3. The mixed curable composition was applied onto an aluminum plate with a # 6 bar coater and irradiated with an electron beam. Tables 2 and 3
And electron beam irradiation conditions (irradiation dose, oxygen concentration, accelerating voltage)
And curing characteristics of the obtained coating film (tack test → ×: with tack, △: without tack, but with scratches on nails, ○: without tack, without scratches due to nails, MEK rubbing test → about absorbent cotton containing MEK Surface condition after rubbing 50 times under a load of 500 g; ○:
No change, Δ: surface whitening, ×: background visible).

[0046]

[Table 2]

[0047]

[Table 3]

[0048]

INDUSTRIAL APPLICABILITY According to the present invention, a film forming material such as a paint or an ink, an encapsulant, a molding agent, which has an excellent effect of suppressing oxygen inhibition,
An electron beam curable oxygen inhibition inhibitor which can be used in a wide range of fields as a resin material such as an adhesive or a pressure sensitive adhesive, and 5
It has become possible to obtain an electron beam curable composition that can be cured with an electron beam even under an oxygen concentration of 00 ppm or more.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Masashi Arishima             Toyo Inn, 2-3-13 Kyobashi, Chuo-ku, Tokyo             Ki Manufacturing Co., Ltd. F-term (reference) 4J011 QA03 QA07 QA15 QA18 QA25                       QA34 QA35 QA38 QA45 QB07                       TA08 UA03 VA06 WA01 WA02                       WA05 WA06                 4J100 AE02Q AE05Q AE09Q AE10Q                       AE70Q AE76Q AJ02Q AL03Q                       AL04Q AL05Q AL08P AL08Q                       AL09Q AL10Q AL62Q AL63Q                       AL66P AL66Q AL67P AL67Q                       BA03P BA03Q BA04Q BA05Q                       BA06Q BA08P BA08Q BA11P                       BA15P BA16P BA16Q BA21P                       BA27P BA62Q BC04P BC07Q                       BC08P BC21Q BC32Q BC43Q                       BC45Q BC53Q CA01 CA04                       FA00 FA18 JA01 JA03 JA05                       JA07

Claims (14)

[Claims] 1. An electron beam curable oxygen inhibition inhibitor comprising a (meth) acrylic compound having a cycloalkane structure. 2. The electron beam curable oxygen inhibition inhibitor according to claim 1, wherein the cycloalkane structure is a cyclohexane structure. 3. A (meth) acrylic compound having a cyclohexane structure is represented by the following general formula (1) (meth).
The electron beam curable oxygen inhibition inhibitor according to claim 2, which is an acrylic half ester (A-1). [Chemical 1] (In the formula, R ₁ is a hydrogen atom or a methyl group, R ₃ is an alkyl group having 2 to 25 carbon atoms or an organic residue represented by the following formula (2-a), R ₂ is the following formula (2-b) or It is an organic residue represented by (2-c).) (In the formula, R ₄ and R ₄ 'are hydrogen atoms or alkyl groups having 1 to 25 carbon atoms, p is 2 to 15, q is 0 (direct bond) to 20, r is 2 to 15 and m is 0 (direct Bond) indicates an integer of 10). 4. A (meth) acrylic half ester (A-1)
The electron beam curable oxygen inhibition inhibitor according to claim 3, wherein is a half ester formed by reacting a cyclic acid anhydride (a) having a cyclohexane structure with a hydroxyl group-containing (meth) acrylic compound (b). 5. An epoxy acrylic obtained by reacting a (meth) acrylic compound having a cyclohexane structure with a (meth) acrylic half ester (A-1) represented by the general formula (1) and an epoxy group-containing compound. The electron beam curable oxygen inhibition inhibitor according to claim 2, which is a system compound. 6. A (meth) acrylic compound having a cyclohexane structure has one carboxyl group (meth).
The electron beam curable oxygen inhibition inhibitor according to claim 2, which is an epoxy acrylic compound obtained by reacting an acrylic compound with an epoxy group-containing compound having a cyclohexane structure. 7. The electron beam curable oxygen inhibition inhibitor according to claim 1, wherein the (meth) acrylic compound having a cycloalkane structure has 2 to 6 (meth) acryloyl groups. 8. An electron beam curable oxygen inhibition inhibitor according to any one of claims 1 to 7, and another (meth) acrylic compound or vinyl ether compound, 500
An electron beam curable composition capable of being cured with an electron beam even under an oxygen concentration of ppm or more. 9. The compounding ratio of the electron beam curable oxygen inhibition inhibitor and the other (meth) acrylic compound or vinyl ether compound is 10:90 to 95: 5 (weight ratio). Electron beam curable composition. 10. The use as a printing ink, as claimed in claim 8 or 9.
The electron beam-curable composition described. 11. The electron beam curable composition according to claim 8, which is used for paints. 12. A method for forming a cured film, which comprises irradiating an electron beam-curable composition according to claim 8 with an electron beam under an oxygen concentration of 500 ppm or more. 13. The method for forming a cured film according to claim 12, wherein the electron beam having an accelerating voltage of 30 to 100 kV is irradiated. 14. A cured product obtained by irradiating the electron beam curable composition according to claim 8 with an electron beam under an oxygen concentration of 500 ppm or more.