JP6844105B2 - Curable composition - Google Patents

Description

The present invention relates to a curable composition, preferably an active energy ray-curable composition, and can be used for various applications such as coating agents, inks, resists and adhesives, and particularly for plastic coating applications and offset ink applications. It can be preferably used in and belongs to these technical fields.
In the present specification, an acryloyl group and / or a methacrylic acid group is referred to as a (meth) acryloyl group, an acrylate and / or a methacrylate is referred to as a (meth) acrylate, and an acrylic acid and / or a methacrylic acid is referred to as a (meth) acrylic acid. It is expressed as.

The active energy ray-curable composition is used for various purposes such as coating agents, inks, resists and adhesives, and in the case of active energy ray curing, an ultraviolet lamp such as a high-pressure mercury lamp or a metal halide lamp is used as a light source for a curing system. Has been widely used as.

In recent years, as a curing system to replace these ultraviolet lamps, an ultraviolet device (hereinafter referred to as "UV-LED") using a light emitting diode having a long light source life and excellent energy saving as a light source has been developed, and in particular, ultraviolet irradiation is performed in an air atmosphere. In the field of coatings such as clear coating agents and the field of printing such as offset inks, methods for producing cured products corresponding to UV-LED light sources and compositions used for them are being studied.

On the other hand, as a disadvantage of the UV-LED light source, there is a point that the curability (film drying property) of the ultraviolet curable composition is significantly inferior to that of the conventional ultraviolet lamp light source.
Compared to an ultraviolet lamp light source that emits ultraviolet rays of a wide range of wavelengths, this is a monochromatic light source, the total amount of ultraviolet energy is small, and the amount of radicals generated from the photopolymerization initiator is small, so that the polymerization reaction inhibits oxygen. This is because it is easily affected by. Further, since the amount of ultraviolet energy in a relatively short wavelength region is relatively insufficient, the ultraviolet curable composition obtained by UV-LED irradiation generally tends to have poor curability on the film surface.

Conventionally, in order to prevent curing inhibition due to oxygen inhibition, it has been known to irradiate ultraviolet rays in a nitrogen atmosphere or under oxygen blocking by laminating a film. There are problems and there are few cases where it is introduced.
Further, compositions containing additives such as amine compounds and phosphorus compounds are known, but the amount of such additives having a relatively high effect is limited because they all bleed out after curing. There is a problem to be done. Therefore, a multi-branched reactive oxygen inhibition inhibitor utilizing Michael addition of a polyamine compound and (meth) acrylate has been proposed (Patent Document 1).
However, since the compound has a urethane bond and a high viscosity, it is not suitable for use in solvent-free applications.

Further, as a Michael adduct of an amine compound and a polyfunctional (meth) acrylate, a compound having an acidic group is known (Patent Document 2).
However, although the compound is excellent in various performances, it is insufficient for applications requiring emulsification resistance, or has physical characteristics in applications requiring adhesion and scratch resistance of a cured product. It was inadequate.

On the other hand, when the ink composition is to be cured by UV-LED, it is necessary to use a photopolymerization initiator having absorption at a wavelength of 350 to 420 nm, but the pigment used for the ink is often a wavelength of 350. Sufficient curing cannot be obtained even if a photopolymerization initiator having light absorption at ~ 420 nm and having absorption at a wavelength of 350 to 420 nm is simply used as the photopolymerization initiator of the ink. Therefore, an active energy ray-curable ink containing three specific types of photopolymerization initiators has been proposed (Patent Document 3).
However, although the composition has excellent internal curability, the illuminance of the UV-LED light source developed so far is still low, and a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (hereinafter, "DPHA"). Even if () was used, the surface curability was insufficient.
In addition, some compositions containing polyfunctional (meth) acrylates other than DPHA have excellent curability and emulsification resistance by UV-LED, but in this case, adhesion and scratch resistance of the cured product, etc. The physical characteristics such as were insufficient.

Japanese Unexamined Patent Publication No. 2000-72831 International Publication No. 2006/75754 Pamphlet International Publication No. 2009/8226 Pamphlet

The present inventors have prepared a cured film using a UV-LED curable composition which is excellent in curability by UV-LED irradiation of the composition, excellent in emulsion resistance, and the cured product is excellent in adhesion and scratch resistance. In order to find a method for producing a base material having a cured film, preferably a method for producing a base material having a cured film using a UV-LED curable composition for coating or ink, a diligent study was conducted.

In order to solve the above problems, the present inventors use a compound having three or more (meth) acryloyl groups, which does not have an acidic group in the compound and has a tertiary amino group. The present invention has been completed by finding that the curable composition containing the composition is excellent in curability and emulsion resistance of the composition, and that the cured product is also excellent in adhesion and scratch resistance.
Hereinafter, the present invention will be described in detail.

According to the method for producing a base material having a cured film of the present invention, the composition has excellent curability by UV-LED irradiation, excellent emulsification resistance, and the cured product has excellent adhesion and scratch resistance. can do.

The present invention
The present invention relates to a method for producing a base material having a cured film which is coated with an ultraviolet (hereinafter referred to as "UV-LED") curable composition using the following light emitting diode as a light source and then irradiated with ultraviolet rays by the UV-LED. ..
UV-LED curable composition: It has three or more (meth) acryloyl groups and tertiary amino groups, which are Michael addition reaction products of the following mixture (a) and compound (b), and is an acidic group and an aromatic group. there mixture containing compounds without the hydroxyl value 1~100mgKOH / g which is a mixture (a) and U V-LE D hardening type composition you as essential components hydrogen abstraction type photopolymerization initiator.
Mixture (a): A (meth) acrylate mixture containing a compound (a1) having four or more (meth) acryloyl groups and no acidic group, which is a pentaerythritol tetra (meth) acrylate, diglycerin tetra ( At least one selected from the group consisting of meta) acrylates and penta and hexa (meth) acrylates of dipentaerythritol. Compound (b): A secondary amine having no acidic or aromatic groups, which is an aliphatic monoamine. and the following secondary Amin selected from hydroxy monoamines, described component (A), curable compositions and uses.

1. 1. Component (A) Component (A) has three or more (meth) acryloyl group and a tertiary amino group, a mixture comprising a compound having no acidic group and an aromatic group, a hydroxyl value 1~100mgKOH It is a mixture of / g.
However, the component (A) is produced by the Michael addition reaction of the following mixture (a) and compound (b).
-Mixed (a): (meth) acrylate mixture containing compound (a1) having 4 or more (meth) acryloyl groups and no acidic group-Compound (b): having no acidic group and aromatic group 2 The secondary amine (A) component selected from the aliphatic monoamine and the hydroxymonoamine, which is a secondary amine , is a compound having no acidic group, and in the case of a compound having an acidic group, the viscosity is high and the emulsion resistance is poor. turn into.
Hereinafter, the mixture (a) and the compound (b), which are the raw material compounds of the component (A), and the method for producing the component (A) will be described.

1-1. Mixture (a)
The mixture (a) is a (meth) acrylate mixture containing a compound (a1) having four or more (meth) acryloyl groups and no acidic group [hereinafter referred to as “compound (a1)”].
As the compound (a1), various compounds can be used as long as it is a compound having four or more (meth) acryloyl groups and no acidic group.
The compound (a1) may be a compound having a hydroxyl group.

Specific examples of the compound (a1), pentaerythritol tetra (meth) acrylate, diglycerol tetra (meth) acrylate, tetra dipentaerythritol, polyol poly (meth) acrylate bets such as penta and hexa (meth) acrylate and the like ..
The mixture (a) may contain two or more of the above-mentioned compounds.

As the compound (a1), in that the pairs formed product is excellent in curability, pentaerythritol tetra (meth) acrylate, diglycerol tetra (meth) acrylate, and the penta and hexa (meth) acrylate of dipentaerythritol To use .

The mixture (a) is a (meth) acrylate mixture containing compound (a1).
When the mixture (a) is industrially produced, for example, when it is produced by an esterification reaction of a polyol having 4 or more hydroxyl groups and (meth) acrylic acid, one or more compounds (a1) are the main components. It is obtained as a mixture of (meth) acrylates containing 3 or less (meth) acryloyl groups.
In the present invention, the mixture may be used as the mixture (a).
Specifically, the following examples can be given with reference to the raw material polyol.
・ Pentaerythritol: a mixture containing tetra (meth) acrylate as the main component and containing mono, di and tri (meth) acrylate ・ Dipentaerythritol: containing tetra, penta and hexa (meth) acrylate as the main components, mono, di and tri (meth) mixture, diglycerin containing acrylate: tetra (meth) acrylate as a main component, mono-, mixtures mixtures of this case including di- and tri (meth) acrylate (a) is a hydroxyl-containing mono (meth) acrylate , A mixture of a hydroxyl group-containing poly (meth) acrylate and a hydroxyl group-free poly (meth) acrylate, which is a mixture having a hydroxyl value.
The preferred hydroxyl value of the mixture (a) is preferably 1 to 100 mgKOH / g, more preferably 1 to 90 mgKOH / g.

1-2. Compound (b)
Compound (b) is a secondary amine having no acidic group or aromatic group , which is a secondary amine selected from aliphatic monoamines and hydroxymonoamines, and is a compound represented by the following general formula (1). is there.
R ^1- NH-R ² ... (1)
Here, R ¹ and R ² represent an aliphatic hydrocarbon group, a hydroxyl group-containing aliphatic hydrocarbon group, and an alkylcarbonyl group , and are groups having no acidic group. However, R ¹ and R ² in one molecule may be the same or different. Further, R ¹ and R ² may be an aliphatic hydrocarbon group that forms a cyclic group as one. Further, the aliphatic hydrocarbon group may be a group containing an oxygen atom.
Examples of aliphatic hydrocarbon groups include linear alkyl groups such as methyl group, ethyl group, propyl group and butyl group, branched alkyl groups such as isopropyl group and isobutyl group, alicyclic groups such as cyclohexyl group and the like. Can be mentioned.
Examples of the hydroxyl group-containing aliphatic hydrocarbon group include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group and the like.
Examples of aliphatic hydrocarbon groups that form a cyclic group as one include −CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ − and −CH ₂ CH ₂ OCH ₂ CH ₂ −.
Examples of the alkylcarbonyl group include an acetyl group and the like .

As the compound (b), various compounds can be used as long as it is a secondary amine having no acidic group or aromatic group and is a secondary amine selected from an aliphatic monoamine and a hydroxymonoamine.
Preferred specific examples include aliphatic monoamines such as dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine and morpholine; and N-methylethanolamine, N-acetylethanolamine and diethanolamine and the like. Hydroxylmonoamine is mentioned.
Among these, aliphatic monoamines are particularly preferable because they are excellent in emulsification resistance.

1-3. Method for Producing Component (A) Component (A) is obtained by the Michael addition reaction of the mixture (a) and the compound (b).
Specific examples of the component (A) are shown in the following formula (1). Formula (1) is an example in which dipentaerythritol hexaacrylate is used as compound (a1).

In formula (1), A represents an acryloyloxy group, A'represents −OCOCH ₂ CH ₂ −, and R ¹ and R ² have the same meanings as described above.
In the above formula (1), only dipentaerythritol hexaacrylate is described as compound (a1) for easy understanding. In fact, as described above, the industrially obtained dipentaerythritol hexaacrylate contains dipentaerythritol tetra and pentaacrylate as other compounds (a1), and dipentaerythritol mono, di and triacrylate. This compound and compound (b) form a mixture of various compounds obtained by the Michael addition reaction.

The reaction ratio of the compound (b) to 1 mol of the mixture (a) is preferably 0.1 to 1.0 mol, more preferably 0.2 to 1.0 mol.
The reaction product obtained by reacting 1 mol of the mixture (a) with 0.1 to 1.0 mol of the compound (b) is excellent in surface curability in an air atmosphere and adhesion of the cured product. Is preferable.
The mixture (a) is a mixture containing a plurality of types of (meth) acrylates, and its molecular weight cannot be uniquely determined. Therefore, the number of moles of the mixture (a) in the present invention is a value calculated from the number average molecular weight of the mixture (a) (hereinafter referred to as “Mn”).
Mn in the present invention means a polystyrene-equivalent number average molecular weight measured by a gel permeation chromatography (hereinafter referred to as “GPC”) method.

The molecular weight measured by GPC in the present invention means a value measured under the following conditions.
・ Detector: Differential refractometer (RI detector)
-Column type: Cross-linked polystyrene column-Column temperature: In the range of 25 to 50 ° C.-Eluent: tetrahydrofuran (hereinafter referred to as "THF")

As the method of the Michael addition reaction, a conventional method may be followed.
Specifically, for example, a method of reacting the mixture (a) and the compound (b) at room temperature to about 50 ° C. for 1 hour or more can be mentioned.

In the method for producing the component (A), an inert gas such as argon, helium, nitrogen or carbon dioxide may be introduced into the system for the purpose of maintaining a good color tone of the reaction solution, and the (meth) acryloyl group may be introduced. An oxygen-containing gas may be introduced into the system for the purpose of preventing polymerization.
Specific examples of the oxygen-containing gas include air, a mixed gas of oxygen and nitrogen, a mixed gas of oxygen and helium, and the like. As a method for introducing the oxygen-containing gas, there is a method of dissolving it in the reaction solution or blowing it into the reaction solution (so-called bubbling).

In the method for producing the component (A), it is preferable to add a polymerization inhibitor to the reaction solution for the purpose of preventing the polymerization of the (meth) acryloyl group.
Specific examples of the polymerization inhibitor include hydroquinone, tert-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl-4-methylphenol, 2,4,6-tri-tert-butylphenol, 4-tert. -Butylcatechol, benzoquinone, phenothiazine, N-nitroso-N-phenylhydroxylamineammonium, 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine Organic polymerization inhibitors such as -1-oxyl, inorganic polymerization inhibitors such as copper chloride, copper sulfate and iron sulfate, and organic salts such as copper dibutyldithiocarbamate and N-nitroso-N-phenylhydroxylamine aluminum salt. Polymerization inhibitors can be mentioned.

The component (A) is a mixture containing a compound having three or more (meth) acryloyl groups, and the (meth) acrylic equivalent is preferably 90 to 250 g / eq, more preferably 90 to 230 g / eq.
The compound having a (meth) acrylic equivalent of 90 to 250 g / eq as the component (A) is preferable in that it is excellent in surface curability in an air atmosphere and scratch resistance of the cured product.
The component (A) is a mixture containing a compound having a tertiary amino group, and a compound having a tertiary amine value of 5 to 140 mgKOH / g is preferable, and 5 to 120 mgKOH / g is more preferable.
The compound having a tertiary amine value of 5 to 140 mgKOH / g as the component (A) is preferable in that it is excellent in surface curability in an air atmosphere and adhesion of a cured product.
Component (A) has a hydroxyl value is a compound of 1~100mgKOH / g, the good Mashiku a. 1 to 90 mg KOH / g.
A compound having a hydroxyl value of 1 to 100 mgKOH as a component (A) is preferable because it is excellent in surface curability in an air atmosphere and adhesion of a cured product.

The weight average molecular weight of the component (A) (hereinafter referred to as “Mw”) is preferably 400 to 3,000, and more preferably 400 to 2,000.
Mw in the present invention means a polystyrene-equivalent weight average molecular weight measured by GPC. The measurement conditions of GPC are as described above.

The viscosity of the component (A) is preferably 100 to 15,000 mPa · s, more preferably 100 to 10,000 mPa · s.
In the present invention, the viscosity means a value measured at 25 ° C. using an E-type viscometer.

2. Curable Composition The present invention relates to a curable composition containing the component (A).
As a method for producing the composition, the mixture (a) and the compound (b) are stirred at room temperature or under heating to obtain three or more (meth) acryloyl groups and tertiary amino groups which are Michael addition reaction products. A method including a step of producing a mixture (A) containing a compound having an acidic group and not having an acidic group is preferable.
As the step, the method for producing the component (A) described above may be followed.

The composition of the present invention contains the component (A) as an essential component, but various components can be blended depending on the purpose.
The composition of the present invention can be used for both the active energy ray-curable composition and the thermosetting composition, but the active energy ray-curable composition is preferable.

Specific examples of the other components include a polymerization initiator [hereinafter referred to as "(B) component"] and a compound having an ethylenically unsaturated group other than the (A) component [hereinafter referred to as "(C) component". ] And an organic solvent [hereinafter referred to as "component (D)"] and the like.
Hereinafter, these components will be described.
As the other components described later, only one of the illustrated compounds may be used, or two or more of them may be used in combination.

2-1. Component (B) The composition of the present invention is a curable composition, and preferably contains the component (B) (polymerization initiator).
When the composition of the present invention is used as an active energy ray-curable composition, it is preferable to add a photopolymerization initiator [hereinafter referred to as "(B1) component"] as the component (B), and it is a thermosetting type. When used as a composition, it is preferable to add a thermal polymerization initiator [hereinafter, referred to as "(B2) component"] as the component (B).
Hereinafter, the components (B1) and (B2) will be described.

2-1-1. (B1) component When the composition of the present invention is used as an active energy ray-curable composition and further used as an electron beam-curable composition, the component (B1) component (photopolymerization initiator) is not contained and electrons are used. It can also be cured by wire.
When the composition of the present invention is used as an active energy ray-curable composition, particularly when ultraviolet rays and visible rays are used as the active energy rays, the component (B1) is further added from the viewpoint of easiness of curing and cost. It is preferable to contain it.
When an electron beam is used as the active energy ray, it is not always necessary to blend it, but it can be blended in a small amount if necessary in order to improve the curability.

Specific examples of the component (B1) include benzyl compounds such as benzyl dimethyl ketal and benzyl;
Benzoin compounds such as benzoin, benzoin ethyl ether, methyl benzoinate, benzoin isopropyl ether and benzoin isobutyl ether;
1-Hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propane- 1-one, oligo [2-hydroxy-2-methyl-1- [4-1- (methylvinyl) phenyl] propanone and 2-hydroxy-1- [4- [4- (2-hydroxy-2-methyl-) Propionyl) benzyl] phenyl] -2-methylpropan-1-one and other α-hydroxyalkylphenone compounds;
2-Methyl-1- [4- (methylthio)] phenyl] -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1-one, 2-Dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) butane-1-one and 3,6-bis (2-methyl-2-morpholinopropionyl) Α-Aminoalkylphenyl compound such as -9-n-octylcarbazole;
Quinone compounds such as ethyl anthraquinone and phenanthrenequinone;
Benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, 4- (methylphenylthio) phenylphenylmethane, methyl-2-benzophenone, 1- [4- (4-benzoylphenyl sulfanyl) phenyl] -2-methyl-2- (4-methylphenylsulfonyl) propan-1-one, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis Benzophenone compounds such as (diethylamino) benzophenone and 4-methoxy-4'-dimethylaminobenzophenone;
Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate and bis (2,6-- Acylphosphine oxide compounds such as dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide; thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 1-chloro-4-propylthioxanthone, 3- [3,4-Dimethyl-9-oxo-9H-thioxanthone-2-yl-oxy] Examples thereof include thioxanthone compounds such as -2-hydroxypropyl-N, N, N-trimethylammonium chloride and fluorothioxanthone.

Among these compounds, as the component (B1), a hydrogen abstraction type photopolymerization initiator is preferable because it is excellent in curability and adhesion of the cured product. Examples of the hydrogen abstraction type photopolymerization initiator include benzophenone compounds and thioxanthone compounds.
Further, the α-hydroxyalkylphenone compound is preferable because it has good surface curability even when it is coated with a thin film in the atmosphere. Specifically, 1-hydroxycyclohexylphenylketone and 2-hydroxy-2-methyl. -1-phenyl-Propane-1-one is more preferred.
When it is necessary to increase the thickness of the cured product, for example, when it is necessary to make it 50 μm or more, for the purpose of improving the curability inside the cured product, or when an ultraviolet absorber or pigment is used in combination. For the purpose of improving the curability of the composition, it is preferable to use a plurality of kinds of compounds selected from an acylphosphine oxide compound, a thioxanthone compound and an α-aminoalkylphenone compound in combination.
Preferred examples of the compound in this case include bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and ethyl- (2,6-trimethylbenzoyl) as the acylphosphine oxide compound. 4,6-trimethylbenzoyl) phenylphosphinate and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and the like can be mentioned. Examples of the thioxanthone compound include 2,4-diethylthioxanthone. , Isopropylthioxanthone, 1-chloro-4-propoxythioxanthone and the like, and examples of the α-aminoalkylphenone compound include 2-methyl-1- [4- (methylthio)] phenyl] -2-morpholinopropane. -1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-) 4-Il-phenyl) -butane-1-one and the like can be mentioned.

When a UV-LED is used as a light source, it is preferable to use a combination of a hydrogen abstraction type photopolymerization initiator and a cleavage type photopolymerization initiator.
Examples of the hydrogen abstraction type photopolymerization initiator include the same compounds as described above, including 2,4-diethylthioxanthone, 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone. preferable.
Examples of the cleavage-type photopolymerization initiator include α-hydroxyalkylphenone-based compounds, α-aminoalkylphenone-based compounds, and acylphosphine oxide compounds, and 1- [4- (2-hydroxyethoxy) phenyl] -2. -Hydroxy-2-methyl-1-propane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1-one, 2-dimethylamino-2- (4-methyl) Benzyl) -1- (4-morpholin-4-yl-phenyl) butane-1-one, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide Is preferable.
The combined ratio of the hydrogen abstraction type photopolymerization initiator and the cleavage type photopolymerization initiator is 5 to 95% by weight based on the total amount of 100% by weight of these, and the cleavage type photopolymerization initiator. The photopolymerization initiator of the above is preferably 5 to 95% by weight.

The content ratio of the component (B1) is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 8 parts by weight, based on 100 parts by weight of the total amount of the curable component. By setting the ratio of the component (B1) to 0.1 parts by weight or more, the photocurability of the composition can be improved and the adhesion can be improved. By setting the ratio to 10 parts by weight or less, the cured film can be obtained. The internal curability of the material can be improved, and the adhesion to the substrate can be improved.
The curable component is a component that is cured by heat or active energy rays, and means the component (A), and when the component (C) described later is blended, it means the components (A) and (C). To do.

2-1-2. (B2) component When the composition of the present invention is used as a thermosetting composition, it is preferable to add the (B2) component (thermopolymerization initiator).
As the component (B2), various compounds can be used, and organic peroxides and azo-based initiators are preferable.
Specific examples of the organic peroxide include 1,1-bis (t-butylperoxy) 2-methylcyclohexane, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, and 1 , 1-bis (t-hexyl peroxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2, , 2-bis (4,4-di-butylperoxycyclohexyl) propane, 1,1-bis (t-butylperoxy) cyclododecane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-Butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di (m-toluoleperoxy) hexane, t-butylper Oxyisopropyl monocarbonate, t-butylperoxy2-ethylhexylmonocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate, 2, 2-bis (t-butylperoxy) butane, t-butylperoxybenzoate, n-butyl-4,4-bis (t-butylperoxy) valerate, di-t-butylperoxyisophthalate, α, α '-Bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-butyl Peroxide, p-menthan hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexin-3, diisopropylbenzenehydroperoxide, t-butyltrimethylsilyl peroxide, 1,1,3 , 3-Tetramethylbutylhydroperoxide, cumenehydroperoxide, t-hexylhydroperoxide, t-butylhydroperoxide and the like.
Specific examples of azo compounds include 1,1'-azobis (cyclohexane-1-carbonitrile), 2- (carbamoylazo) isobutyronitrile, and 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile. , Azodi-t-octane, azodi-t-butane and the like.
These may be used alone or in combination of two or more. In addition, the organic peroxide can be combined with a reducing agent to cause a redox reaction.

The blending ratio of the component (B2) is preferably 10 parts by weight or less with respect to 100 parts by weight of the total amount of the curable component.
When the component (B2) is used alone, it may be carried out according to the conventional method of radical thermal polymerization. In some cases, it may be used in combination with the component (B1) and heat-cured for the purpose of further improving the reaction rate. It can also be cured.

2-2. Component (C) Component (C) is an ethylenically unsaturated compound other than the component (A), and is blended for the purpose of imparting various physical properties to the cured product of the composition.
Examples of the ethylenically unsaturated group in the component (C) include a (meth) acryloyl group, a (meth) acrylamide group, a vinyl group and a (meth) allyl group, and a (meth) acryloyl group is preferable.
In the following, "monofunctional" means a compound having one ethylenically unsaturated group, and "○ functional" means a compound having ○ ethylenically unsaturated groups, and is "polyfunctional". Means a compound having two or more ethylenically unsaturated groups.

Specific examples of the monofunctional ethylenically unsaturated compound in the component (C) include (meth) acrylic acid, a Michael-added dimer of acrylic acid, ω-carboxy-polycaprolactone mono (meth) acrylate, and monohydroxy phthalate. Ethyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethyl carbitol (meth) acrylate, butyl carbitol (meth) acrylate, 2- Ethylhexyl carbitol (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, (meth) acrylate with alkylene oxide adduct of phenol, (meth) acrylate with alkylene oxide adduct of alkylphenol, cyclohexyl (meth) acrylate, tert-Butylcyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl acrylate, (meth) acrylate of alkylene oxide adduct of paracumylphenol, orthophenylphenol (Meta) acrylate, (meth) acrylate of alkylene oxide adduct of orthophenylphenol, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanemethylol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (Meta) Acrylate, N- (2- (Meta) Acryloxyethyl) Hexahydrophthalimide, N- (2- (Meta) Acryloxyethyl) Tetrahydrophthalimide, N, N-Dimethylacrylamide, Acryloylmorpholin, N-Vinylpyrrolidone , N-vinylcaprolactam and the like.

Specific examples of the bifunctional (meth) acrylate compound include polyethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and tetramethylene glycol. Di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, di (meth) acrylate of alkylene oxide adduct of bisphenol A, di (meth) acrylate of alkylene oxide adduct of bisphenol F, butanediol di (meth) Examples thereof include acrylate, hexanediol di (meth) acrylate and nonanediol di (meth) acrylate. In addition, a bisphenol skeleton, a polyether skeleton, an epoxy (meth) acrylate having a polyalkylene skeleton, a polyester skeleton, a urethane (meth) acrylate having a polyether skeleton or a polycarbonate skeleton, a polyester (meth) acrylate, and the like are also used. Can be done.

Examples of the trifunctional or higher (meth) acrylate compound include various compounds as long as they have three or more (meth) acryloyl groups. For example, glycerintri (meth) acrylate and trimethylolpropane tri (meth) acrylate. , Diglycerin tri or tetra (meth) acrylate, pentaerythritol tri or tetra (meth) acrylate, dimethylolpropane tri or tetra (meth) acrylate and dipentaerythritol tri, tetra, penta or hexa (meth) acrylate. Such as polyol poly (meth) acrylate;
Tri or tetra (meth) acrylate of pentaerythritol alkylene oxide adduct, tri or tetra (meth) acrylate of ditrimethylolpropane alkylene oxide adduct, tri, tetra, penta or hexa (meth) acrylate of dipentaerythritol alkylene oxide adduct Poly (meth) acrylates of polyol alkylene oxide adducts such as
Tri (meth) acrylate of isocyanurate alkylene oxide adduct; and compounds having hydroxyl groups such as pentaerythritol tri (meth) acrylate and dipentaerythritol penta (meth) acrylate and having three or more (meth) acryloyl groups and organic Examples thereof include urethane (meth) acrylate, which is a reaction product with polyisocyanate.
Examples of the alkylene oxide adduct described above include ethylene oxide adducts, propylene oxide adducts, ethylene oxide and propylene oxide adducts, and the like.
Examples of the organic polyisocyanate include hexamethylene diisocyanate, tetramethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, norbornan diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated 4,4'-diphenylmethane diisocyanate, and hydride Examples thereof include range isocyanate, 4,4'-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate trimeric, and the like.

The content ratio of the component (C) is preferably 0 to 60% by weight, more preferably 0 to 30% by weight, in 100 parts by weight of the total amount of the curable component.
By setting the content ratio of the component (C) to 60% by weight or less, it is possible to prevent the cured film from becoming brittle, particularly when the component (C) is a polyfunctional ethylenically unsaturated compound.

2-3. Component (D) The composition of the present invention is most preferably solvent-free, but may contain the organic solvent of component (D) for the purpose of improving coatability on a substrate.

Specific examples of the component (D) include alcohol compounds such as methanol, ethanol, isopropanol and butanol; alkylene glycol monoether compounds such as ethylene glycol monomethyl ether and propylene glycol monomethyl ether; acetone alcohols such as diacetone alcohol; benzene and toluene. And aromatic compounds such as xylene; ester compounds such as propylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate; ketone compounds such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ether compounds such as dibutyl ether; and N-methylpyrrolidone and the like. Can be mentioned.
Among these, alkylene glycol monoether compounds and ketone compounds are preferable, and alkylene glycol monoether compounds are more preferable.

The content ratio of the component (D) is preferably 0 to 1,000 parts by weight, more preferably 0 to 500 parts by weight, and 0 to 300 parts by weight with respect to 100 parts by weight of the total amount of the curable component. It is more preferably by weight. Within the above range, the composition can have a viscosity suitable for coating, and the composition can be easily applied by a known coating method described later.

3. 3. Applications The compositions of the present invention can be used for various purposes.
Examples of preferable uses include coating agents, inks, resists, adhesives, and the like, and examples of more preferable uses include compositions for plastic coatings, compositions for offset printing inks, and the like.
Hereinafter, more preferable uses will be described.

3-1. Coating Composition The composition of the present invention has excellent thin film curability and high hardness of the cured product, and therefore can be preferably used as a coating composition.

The coating composition can be preferably used for plastic coating applications, and examples of the base material include plastic films used for polarizer protective films and antireflection films, resin molded products used for home appliances and automobile interior / exterior parts, and the like. ..

The coating composition contains the above (A) as an essential component, but various components can be blended depending on the purpose.
Specific examples of the other components include the above-mentioned components (B), (C) and (D), as well as antioxidants, ultraviolet absorbers, pigments / dyes, silane coupling agents, surface modifiers and polymers. And so on.
Hereinafter, these components will be described.
As the other components described later, only one of the illustrated compounds may be used, or two or more of them may be used in combination.

1) Antioxidant Antioxidant is added for the purpose of improving the durability such as heat resistance and weather resistance of the cured film.
Examples of the antioxidant include phenolic antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants and the like.
Examples of the phenolic antioxidant include hindered phenols such as dit-butylhydroxytoluene. Examples of commercially available products include AO-20, AO-30, AO-40, AO-50, AO-60, AO-70, and AO-80 manufactured by ADEKA CORPORATION.
Examples of the phosphorus-based antioxidant include phosphines such as trialkylphosphine and triarylphosphine, and trialkyl phosphite and triaryl phosphine. Commercially available products of these derivatives include, for example, ADEKA CORPORATION PEP-4C, PEP-8, PEP-24G, PEP-36, HP-10, 260, 522A, 329K, 1178, 1500, 135A, 3010. And so on.
Examples of the sulfur-based antioxidant include thioether-based compounds, and examples of commercially available products include AO-23, AO-212S, and AO-503A manufactured by ADEKA CORPORATION.
These may use one kind or two or more kinds. Preferred combinations of these antioxidants include a combination of a phenolic antioxidant and a phosphorus-based antioxidant, and a combination of a phenolic antioxidant and a sulfur-based antioxidant.
The content ratio of the antioxidant may be appropriately set according to the purpose, and is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 1 part by weight, based on 100 parts by weight of the total amount of curable components. Is.
When the content ratio is 0.1 parts by weight or more, the durability of the composition can be improved, while when the content ratio is 5 parts by weight or less, the curability and adhesion can be improved.

2) Ultraviolet absorber The ultraviolet absorber is added for the purpose of improving the light resistance of the cured film.
Examples of the ultraviolet absorber include triazine-based ultraviolet absorbers such as TINUVIN400, TINUVIN405, TINUVIN460, and TINUVIN479 manufactured by BASF, and benzotriazole-based ultraviolet absorbers such as TINUVIN900, TINUVIN928, and TINUVIN1130.
The content ratio of the ultraviolet absorber may be appropriately set according to the purpose, and is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 1 part by weight, based on 100 parts by weight of the total amount of the curable component. Is. When the content ratio is 0.01% by weight or more, the light resistance of the cured film can be improved, while when it is 5% by weight or less, the curability of the composition is excellent. be able to.

3) Pigments / dyes Examples of pigments include organic pigments and inorganic pigments.
Specific examples of organic pigments include insoluble azo pigments such as toluidine red, toluidine maroon, hanza ero, benzidine ero and pyrazolone red; soluble azo pigments such as litol red, heliobordeaux, pigment scarlet and permanent red 2B; alizarin, indantron. And derivatives from building dyes such as thioindigomaroon; phthalocyanine organic pigments such as phthalocyanine blue and phthalocyanine green; quinacridone organic pigments such as quinacridone red and quinacridone magenta, perylene organic pigments such as perylene red and perylene carlet; iso Isoindolinone-based organic pigments such as indolinone yellow and isoindolinone orange; pyranthron-based organic pigments such as pyranthron red and pyranthron orange; thioindigo-based organic pigments; condensed azo-based organic pigments; benzimidazolone-based organic pigments; quinophthalone Kinophthalone-based organic pigments such as ero, isoindrin-based organic pigments such as isoindrin ero; and other pigments include flavanthron ero, acylamide ero, nickel azo ero, copper azomethine ero, perinone orange, anthron orange, and dianthra. Examples thereof include quinonyl red and dioxazine violet.

Specific examples of inorganic pigments include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, lead yellow lead, zinc yellow, red iron oxide (III), cadmium red, ultramarine blue, dark blue, and chromium oxide green. Examples thereof include cobalt green, amber, titanium black and synthetic iron black.
The carbon black exemplified in the filler can also be used as an inorganic pigment.
As the dye, various conventionally known compounds can be used.

4) Silane coupling agent The silane coupling agent is blended for the purpose of improving the interfacial adhesive strength between the cured film and the substrate.
The silane coupling agent is not particularly limited as long as it can contribute to improving the adhesiveness with the base material.

Specific examples of the silane coupling agent include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-. Glycydoxypropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-Aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3 -Aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like can be mentioned.

The blending ratio of the silane coupling agent may be appropriately set according to the intended purpose, and is preferably 0.1 to 10 parts by weight, more preferably 1 to 5 parts by weight, based on 100 parts by weight of the total amount of the curable components. ..
By setting the blending ratio to 0.1 parts by weight or more, the adhesive strength of the composition can be improved, while by setting the blending ratio to 10 parts by weight or less, it is possible to prevent the adhesive strength from changing with time.

5) Surface modifier The composition of the present invention may be added with a surface modifier for the purpose of improving the leveling property at the time of application, improving the slipperiness of the cured film and improving the scratch resistance, and the like. Good.
Examples of the surface modifier include a surface conditioner, a surfactant, a leveling agent, a defoaming agent, a slipperiness-imparting agent, an antifouling agent, and the like, and these known surface modifiers can be used. ..
Among them, a silicone-based surface modifier and a fluorine-based surface modifier are preferably mentioned. Specific examples include a silicone polymer and oligomer having a silicone chain and a polyalkylene oxide chain, a silicone polymer and an oligomer having a silicone chain and a polyester chain, and a fluoropolymer having a perfluoroalkyl group and a polyalkylene oxide chain. And oligomers, and fluoropolymers and oligomers having a perfluoroalkyl ether chain and a polyalkylene oxide chain.
Further, a surface modifier having an ethylenically unsaturated group, preferably a (meth) acryloyl group in the molecule may be used for the purpose of enhancing the sustainability of slipperiness.

The content ratio of the surface modifier is preferably 0.01 to 1.0 parts by weight with respect to 100 parts by weight of the total amount of the curable components. Within the above range, the surface smoothness of the coating film is excellent.

6) Polymer The composition of the present invention may further contain a polymer for the purpose of further improving the curl resistance of the obtained cured film.
Suitable polymers include (meth) acrylic polymers, and suitable constituent monomers include methyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylic acid, glycidyl (meth) acrylate, N-(. 2- (Meta) acrylicoxyethyl) tetrahydrophthalimide and the like can be mentioned. In the case of a polymer copolymerized with (meth) acrylic acid, a (meth) acryloyl group may be introduced into the polymer chain by adding glycidyl (meth) acrylate.
The content ratio of the polymer is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the total amount of the curable components. Within the above range, the curl resistance of the obtained cured film is more excellent.

3-2. Compositions for Inks Since the compositions of the present invention have excellent thin film curability, they are used for transparent overprint varnish inks that are printed by a printing machine after single-color or multicolor printing, and for color printing such as yellow, red, indigo, and ink. It can be preferably used for ink.

Printing methods include offset printing (normal flat plate that uses dampening water and waterless flat plate that does not use dampening water), letterpress printing (flat pressure letterpress, letterpress half-rotation, rotation, intermittent rotation, flexo), and concave printing. Various printing methods such as (gravure printing), stencil printing (screen printing), and inkjet printing can be mentioned, and since they are excellent in emulsion stability, they can be preferably used for offset printing using dampening water. Moreover, since it has a low viscosity, it can be preferably used for inkjet printing.

The composition for ink contains the above (A) as an essential component, but various components can be blended depending on the purpose.
As the method for producing the composition for ink, the conventional method for producing the composition for ink may be followed, and the component (A), the component (B) (when the active energy ray is ultraviolet rays), the component (E), and (F). ) Ingredients, polymerization inhibitors, waxes and other additives, and then pigments are added and dispersed by a disperser such as a three-roll mill or a bead mill.

Specific examples of the other components include a binder [hereinafter referred to as "(E) component"], a pigment [hereinafter referred to as "(F) component"], a plasticizer, an anti-friction agent, and the like, in addition to the above-mentioned component (C). Can be mentioned.
Hereinafter, these components will be described.
As the other components, only one of the illustrated compounds may be used, or two or more of them may be used in combination.

1) Component (E) The component (E) in the present invention includes an epoxy acrylate mixture having at least one polymerizable group in one molecule, such as a diallyl phthalate resin having no polymerizable group, and urethane acrylate. , Polyester acrylate and the like.

Among the above-mentioned binder components, the diallyl phthalate resin refers to a prepolymer synthesized from a diallyl phthalate monomer or a diallyl isophthalate monomer, and there are several commercially available products depending on the monomer type and molecular weight of orthophthal and isophthalate, which are used in the present invention. it can. Specific examples include Daiso Dup A, Daiso Dup S, Daiso Dap K, and Daiso Isodap sold by Daiso. Of these, Daiso Dup A is the most preferable among the above-mentioned commercially available products, considering the film strength after ink curing, compatibility with the component (A), and the like.

The content of the component (E) in the ink composition is preferably in the range of 10 to 65% by weight based on the total amount of the ink. If it is less than 10% by weight, sufficient film curability and offset printing suitability cannot be obtained, and if the amount is more than 65% by weight, the binder having these polymerizable groups generally has a high viscosity. In the composition described in the example, it becomes difficult to obtain a viscosity suitable for the offset ink.

2) Component (F) The pigment of the component (F) includes organic pigments and inorganic pigments.
As specific examples of the organic pigment and the inorganic pigment, the same compounds as described above can be used.

In the present invention, inorganic fine particles may be used as the extender pigment. Inorganic fine particles include inorganic coloring pigments such as titanium oxide, clafite, and zinc oxide; lime carbonate powder, precipitated calcium carbonate, plaster, ChinaClay, silica powder, diatomaceous earth, talc, kaolin, alumina white, barium sulfate, etc. Inorganic pigments such as aluminum stearate, magnesium carbonate, barite powder, abrasive powder; and other inorganic pigments, silicone, glass beads, and the like can be mentioned.
By using these inorganic fine particles in the ink in the range of 0.1 to 20% by weight, it is possible to obtain effects such as adjusting the fluidity of the ink, preventing misting, and preventing penetration into a printing substrate such as paper. is there.

3) Plasticizers and anti-friction agents As plastic agents and anti-friction agents, wax compounds such as paraffin wax, carnauba wax, mitsuro, microcrystallin wax, polyethylene wax, polyethylene oxide wax, polytetrafluoroethylene wax, amide wax, and coconut oil. A fatty acid in the range of C8 to C18, such as a fatty acid or a soybean oil fatty acid, can be blended and used within a range that does not interfere with the object of the present invention.

4. Method of use As a method of using the composition of the present invention, a conventional method may be followed.
For example, a method of applying the composition to a base material and then curing it by irradiating it with active energy rays or heating it to cure it can be mentioned.
Specifically, a method of applying the composition to the applied substrate by a usual coating method and then irradiating the active energy ray-curable composition with active energy rays to cure the composition, or a thermosetting composition. In the case of a product, a method of heating and curing may be mentioned.
As the method of irradiating the active energy rays and the method of heating, a general method known as a conventional curing method may be adopted.
Further, the composition is adhered to the substrate by using the component (B1) (photopolymerization initiator) and the component (B2) (thermal polymerization initiator) in combination, irradiating the composition with active energy rays, and then heating and curing the composition. A method of improving the sex can also be adopted.
Hereinafter, the coating composition and the patent for ink, which are preferable uses of the composition of the present invention, will be described in detail.

4-1. Method of using coating composition Examples of the base material to which the composition of the present invention can be applied include plastics, woods, metals, inorganic materials, paper and the like, which can be applied to various materials.
Specific examples of plastics include cellulose acetate resins such as polyvinyl alcohol, triacetyl cellulose and diacetyl cellulose, acrylic resins, cyclic polyolefin resins using cyclic olefins such as polyethylene terephthalate, polycarbonate, polyarylate, polyether sulfone and norbornene as monomers. , Polyvinyl chloride, epoxy resin, polyurethane resin and the like.
Examples of wood include natural wood and synthetic wood.
Examples of the metal include steel plates, metals such as aluminum and chromium, and metal oxides such as zinc oxide (ZnO) and indium tin oxide (ITO).
Examples of the inorganic material include glass, mortar, concrete and stone.
Among these, a plastic base material is particularly preferable.

The film thickness of the composition cured film with respect to the base material may be appropriately set according to the intended purpose. The thickness of the cured film may be selected depending on the use of the substrate to be used and the application of the produced substrate having the cured film, but is preferably 1 to 500 μm, more preferably 5 to 200 μm. ..

The method for applying the composition of the present invention to the substrate may be appropriately set according to the intended purpose, and is a bar coater, an applicator, a doctor blade, a dip coater, a roll coater, a spin coater, a flow coater, a knife coater, and a comma. Examples thereof include a method of coating with a coater, a reverse roll coater, a die coater, a lip coater, a gravure coater, a micro gravure coater, an inkjet, and the like.

Examples of the active energy ray for curing the composition of the present invention include ultraviolet rays, visible rays, electron beams and the like, but ultraviolet rays are preferable.
Examples of the ultraviolet irradiation device include a high-pressure mercury lamp, a metal halide lamp, an ultraviolet (UV) electrodeless lamp, and a light emitting diode (LED).
The irradiation energy may be appropriately set according to the type and compounding composition of the active energy rays. For example, when a high-pressure mercury lamp is used, the irradiation energy in the UV-A region is 100 to 5,000 mJ / cm ² Is preferable, and 200 to 1,000 mJ / cm ² is more preferable.

4-2. How to use the composition for ink The printing base material used in the printed matter of the present invention is not particularly limited, and for example, high-quality paper, coated paper, art paper, imitation paper, thin paper, thick paper and other papers, various synthetic papers, etc. Polyester resin, acrylic resin, vinyl chloride resin, vinylidene chloride resin, polyvinyl alcohol, polyethylene, polypropylene, polyacrylonitrile, ethylene vinyl acetate copolymer, ethylene vinyl alcohol copolymer, ethylene methacrylate copolymer, nylon, polylactic acid, Examples thereof include films or sheets such as polypropylene, cellophane, aluminum foil, and various other substrates that have been conventionally used as printing substrates.
Among these, a paper base material is particularly preferable.

The film thickness of the composition cured film with respect to the base material may be appropriately set according to the intended purpose. The thickness of the cured film may be selected depending on the use of the substrate to be used and the application of the produced substrate having the cured film, but is preferably 1 to 20 μm, more preferably 1 to 10 μm. ..

When the composition of the present invention is used for offset ink, it can be suitably used as a coating method on a base material by using an offset printing machine that continuously supplies water on a plate surface. Further, it can be suitably used in any paper supply method, that is, a sheet-fed offset printing machine that uses sheet-type printing paper and an offset rotary printing machine that uses reel-type printing paper.

When the composition of the present invention is used for an inkjet ink, it can be suitably used as a coating method on a base material by using a known inkjet recording device or the like that ejects an image by an inkjet method. ..

In the inkjet method, the viscosity of the composition is 7 mPa · s to 30 mPa · s at the temperature at the time of discharge (for example, 40 ° C. to 80 ° C., preferably 25 ° C. to 30 ° C.) in consideration of the ejection property. preferable. More preferably, it is 7 mPa · s to 20 mPa · s.

Examples of the active energy ray for curing the composition of the present invention include ultraviolet rays, visible rays, electron beams and the like, but ultraviolet rays are preferable.
Examples of the ultraviolet irradiation device include the same devices as described above.
The irradiation energy may be appropriately set according to the type of active energy ray and the compounding composition, and the same irradiation energy as described above can be mentioned.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
In the following, "part" means a part by weight, and "%" means% by weight.
Further, in the following, ethylene oxide is abbreviated as "EO".

1. 1. Manufacturing example
1) Comparative production example 1 [Production of compounds other than component (A)]
600 g of dipentaerythritol EO6 mol adduct [Brownon DPE-E6, hydroxyl value 643 mgKOH / g] in a 2 L 4-necked flask equipped with a thermometer, agitator and a reflux tube. , 575 g of acrylic acid (1.16 mol to 1 mol of total hydroxyl groups in alcohol), 24 g of 70% methanesulfonic acid (hereinafter referred to as "MSA"), 1.9 g of cupric chloride and 520 g of toluene were added. did.
While blowing the oxygen-containing gas into the flask, the mixture was heated and stirred at a reaction solution temperature of 85 to 95 ° C. The dehydration esterification reaction was carried out for 6 hours while taking out the water generated as the reaction proceeded out of the system with a Dean-Stark tube.
After completion of the reaction, 1250 g of toluene was added for dilution. Further, 300 g of distilled water was added, and the mixture was stirred, allowed to stand, and then the lower layer was removed. Next, 490 g of a 20% aqueous sodium hydroxide solution was added under stirring, and the mixture was sufficiently stirred, allowed to stand, and then the lower phase was removed. Subsequently, 280 g of distilled water was added to the organic phase under stirring, and the mixture was stirred, allowed to stand, and then the lower layer was removed. The organic phase of the upper layer was heated under reduced pressure to distill off toluene.
The resulting reaction was a mixture containing pentaacrylate and hexaacrylate. Hereinafter, it is referred to as "A'2 component".

2) Comparative production example 2 [Production of compounds other than component (A)]
In the same flask as in Production Example 1, EO4 mol adduct of pentaerythritol [Aoki Yushi Kogyo Co., Ltd., Braunon PE-240N, hydroxyl value 717 mgKOH / g] 520 g, acrylic acid 570 g, MSA 25 g, cupric chloride 2 g, MEHQ0 .2 g and 480 g of toluene were added.
While blowing the oxygen-containing gas into the flask, the mixture was heated and stirred at a reaction solution temperature of 82 to 97 ° C. The dehydration esterification reaction was carried out for 6 hours while taking out the water generated as the reaction proceeded out of the system with a Dean-Stark tube.
After completion of the reaction, 1050 g of toluene was added for dilution. Further, 250 g of distilled water was added, and the mixture was stirred, allowed to stand, and then the lower layer was removed. Next, 360 g of a 20% aqueous sodium hydroxide solution was added under stirring, and the mixture was sufficiently stirred, allowed to stand, and then the lower phase was removed. Subsequently, 250 g of distilled water was added to the organic phase under stirring, and the mixture was stirred, allowed to stand, and then the lower layer was removed. The organic phase of the upper layer was heated under reduced pressure to distill off toluene.
The resulting reaction was a mixture containing triacrylate and tetraacrylate. Hereinafter, it is referred to as "A'4 component".

3) Comparative production example 3 [Production of compounds other than component (A)]
In the same flask as in Production Example 1, 77.00 g (0.46 mol) of diglycerin, 627.21 g (4.82 mol) of 2-methoxyethyl acrylate, and 2.45 g (0.02 mol) of DABCO as a catalyst. And zinc acetate 4.00 g (0.02 mol), hydroquinone monomethyl ether as a polymerization inhibitor 1.42 g (2000 wtppm with respect to the total weight of the charged raw materials), oxygen-containing gas (5% by volume of oxygen, nitrogen) 95% by volume) was bubbled in the liquid.
The pressure in the reaction system was adjusted in the range of 110 to 760 mmHg while heating and stirring in the reaction solution temperature range of 105 to 130 ° C., and 2-methoxyethanol and 2-methoxyethyl acrylate produced as by-products as the transesterification reaction proceeded. The mixed solution of the above was withdrawn from the reaction system via a rectification column and a cooling tube. In addition, 2-methoxyethyl acrylate in the same weight as the withdrawal solution was added to the reaction system at any time. Twenty-seven hours after the start of heating and stirring, the pressure in the reaction system was returned to normal pressure to complete the extraction.
The reaction solution is cooled to room temperature, 200 ml of normal hexane is added, the precipitate is separated by filtration, and then 2.0 g of aluminum silicate [Kyoward 700 (trade name) manufactured by Kyowa Chemical Industry Co., Ltd.] is added to the filtrate, and activated carbon [ Futamura Chemical Co., Ltd. Taiko S (trade name)] was added in 0.5 g, and while bubbling dry air, vacuum distillation was performed at a temperature of 70 to 95 ° C. and a pressure of 0.001 to 100 mmHg for 8 hours under reduced pressure. The distillate containing unreacted 2-methoxyethyl acrylate was separated. 2.0 g of diatomaceous earth [Radiolite (trade name) manufactured by Showa Chemical Industry Co., Ltd.] was added to the kettle solution and pressure filtration was performed, and the obtained filtrate was used as a purified product.
The obtained reaction product was a mixture containing tetraacrylate as a main component. Hereinafter, it is referred to as "A'5 component".

4) Comparative production example 4 [Production of compounds other than component (A)]
In the same flask as in Production Example 1, EO4 mol adduct of diglycerin [Kao Corporation, Emargen G2E-4, 625 mgKOH / g] 500 g, acrylic acid 518 g, p-toluenesulfonic acid monohydrate 41 g, cupric chloride 1.59 g, MEHQ 1.59 g and toluene 550 g were added.
While blowing the oxygen-containing gas into the flask, the mixture was heated and stirred under the conditions of a reaction solution temperature of 80 to 100 ° C. and a reaction system pressure of 400 to 760 Torr. The dehydration esterification reaction was carried out for 7 hours while removing the water generated as the reaction proceeded from the system with a Dean-Stark tube.
After completion of the reaction, the obtained reaction solution is added to a separating funnel, washed and separated with pure water, the organic layer is further washed and separated with an aqueous sodium hydroxide solution, and the organic layer is further washed with pure water. After washing and separating the liquid with, and letting it stand, the lower layer was removed. The organic phase of the upper layer was heated under reduced pressure to distill off toluene.
The resulting reaction was a mixture containing triacrylate and tetraacrylate. Hereinafter, it is referred to as "A'6 component".

5) Comparative production example 5 [Production of compounds other than component (A)]
16 g of succinic anhydride, 250 g of A'1 component, and 0.13 g of methquinone were placed in a 500 mL 4-necked flask equipped with a thermometer, a stirrer and a reflux tube, and the temperature was raised to 85 ° C. After adding 1.3 g of the catalyst triethylamine into it, the reaction was carried out for 4 hours. The reaction was carried out in a mixed atmosphere of air / nitrogen to obtain a compound having an acid value of 34 mgKOH / g (hereinafter referred to as “A''1 component”).
Then, 17.4 g of di-n-butylamine (0.3 mol with respect to 1 mol of A''1 component) was added at room temperature, and then the reaction was carried out at 50 ° C. for 4 hours. The reaction was carried out in a mixed atmosphere of air / nitrogen.
The resulting reaction was a mixture containing a Michael adduct of di-n-butylamine. Hereinafter, it is referred to as "A'7 component".
The hydroxyl value of the A'7 component was 11 mgKOH / g, and the acid value was 32 mgKOH / g.

6) Production Example 1 [Production of component (A)]
In the same flask as in Comparative Production Example 5, a mixture of dipentaerythritol penta and hexaacrylate (Mw1,020, Mn1,012, viscosity 7,280 mPa · s (25 ° C.), hydroxyl value 32 mgKOH / g, Toagosei Aronix M-402 , Hereinafter referred to as "A'1 component") 250 g (0.247 mol) was added, and 17.3 g of di-n-butylamine (0.134 mol, 0.54 mol per 1 mol of A'1 component). Was charged at room temperature and then reacted at 50 ° C. for 4 hours. The reaction was carried out in a mixed atmosphere of air / nitrogen.
The resulting reaction was a mixture containing a Michael adduct of di-n-butylamine. Hereinafter, it is referred to as "(A1) component".

7) Reference production example 1 [Production of compounds other than component (A)]
Except for 250 g (0.220 mol) of A'2 component (Mn1,138) and 11.9 g of di-n-butylamine (0.092 mol, 0.42 mol for 1 mol of A'2 component). , The reaction was carried out according to the same method as in Production Example 1.
The resulting reaction was a mixture containing a Michael adduct of di-n-butylamine. Hereinafter referred to as "A 1 'component".

8) Production Example 2 [Production of component (A)]
Pentaerythritol tetraacrylate (Mw560, Mn560, viscosity 570 mPa · s (25 ° C.), hydroxyl value 6 mgKOH / g, Toagosei Aronix M-450, hereinafter referred to as “A'3 component”) 250 g (0.446 mol) ), Di-n-butylamine was 27.5 g (0.213 mol, 0.48 mol with respect to 1 mol of A'3 component), and the reaction was carried out in the same manner as in Production Example 1.
The resulting reaction was was a mixture containing a Michael adduct of di -n- butylamine [hereinafter referred to as "A 2 component"].

9) Reference production example 2 [Production of compounds other than component (A)]
Manufactured except 250 g (0.338 mol) of A'4 component (Mn739) and 18.7 g (0.145 mol, 0.43 mol for 1 mol of A'4 component) of di-n-butylamine. The reaction was carried out according to the same method as in Example 1.
The resulting reaction was a mixture containing a Michael adduct of di-n-butylamine. Hereinafter referred to as "A 2 'component".

10) Production Example 3 [Production of component (A)]
Manufactured except 250 g (0.463 mol) of A'5 component (Mn540) and 25.4 g (0.197 mol, 0.42 mol for 1 mol of A'5 component) of di-n-butylamine. The reaction was carried out according to the same method as in Example 1.
The resulting reaction was a mixture containing a Michael adduct of di-n-butylamine. Hereinafter referred to as "A 3 component".

11) Reference production example 3 [Production of compounds other than component (A)]
Except for 250 g (0.205 mol) of A'6 component (Mn1,218) and 16.9 g of di-n-butylamine (0.131 mol, 0.64 mol per 1 mol of A'6 component). , The reaction was carried out according to the same method as in Production Example 1.
The resulting reaction was a mixture containing a Michael adduct of di-n-butylamine. Hereinafter referred to as "A 3 'component".

2. Evaluation Method of Reactants For the reactants obtained in Production Examples 1 to 3 , Reference Production Examples 1 to 3, and Comparative Production Examples 1 to 5, the acrylic equivalent, tertiary amine value, according to the method described below. The hydroxyl value, Mw and viscosity were measured.
The results are shown in Table 1.

(1) Acrylate equivalent The bromine value of acrylate (the number of g of bromine added to the unsaturated component in 100 g of the sample) measured based on JIS K 2605 was converted into the number of g of acrylate per mol of acryloyl group. Represents a value (unit: g / eq).

(2) 5 ml of acetic anhydride was added to 0.2 g of a tertiary amine value sample and 50 g of acetone, reacted at room temperature for 30 minutes, and then titrated with 0.01N perchloric acid by a potentiometric titration method. A blank test was carried out in the same manner, and the tertiary amine value was calculated from the following formula.
Tertiary amine value = {(AB) x f x 0.01 x 56.11} / C
A: Consumption of 0.01N perchloric acid required for sample titration (ml)
B: Consumption of 0.01N perchloric acid required for titration of blank test (ml)
f: 0.01N Perchloric acid factor C: Amount of sample (g)

(3) Hydroxyl group value Indicates the number of mg of potassium hydroxide equivalent to the hydroxyl group in 1 g of the sample, which is measured based on JIS K 0070-1992.

(4) Mw (GPC measurement conditions)
-Device: Waters Co., Ltd. GPC system name 1515 2414 717P RI
-Detector: RI detector-Column: Guard column Showa Denko Co., Ltd. Shodex KFG (8 μm 4.6 x 10 mm), 2 types of this column Waters Co., Ltd. stylel HR 4E THF (7.8 x 300 mm) + stylel HR 1 THF (7.8 x 300 mm)
-Column temperature: 40 ° C
-Eluent composition: THF (containing 0.03% sulfur as an internal standard), flow rate 0.75 mL / min

(5) Viscosity The viscosity was measured at 25 ° C. using an E-type viscometer.

(6) Emulsification resistance 3 g of the obtained reaction product was dissolved in 6 g of xylene, and 9 g of distilled water was placed in a glass test tube (18 mφ hard glass) and stoppered. After shaking this up and down 10 times, it was allowed to stand and the time until the aqueous layer and the organic layer were completely separated was measured, and the transparency of the upper layer and the lower layer was judged at the following four levels. There is a correlation between water separability and emulsification resistance, and the better the water separation property, the better the emulsification resistance when applied to ink.
⊚: Transparent ○: Slightly turbid △: turbid ×: Emulsified.
The overall evaluation was judged on the following four levels.
⊚: Separation time is within 4 minutes and upper layer transparency is ◎ or ○, lower layer transparency is ◎ or ○
〇: Separation time is within 4 minutes, upper layer transparency is △, lower layer transparency is ◎ or ○
Δ: Separation time is within 4 minutes, upper layer transparency is ×, lower layer transparency is ◎ or ○
×: Separation time is 5 minutes or more, or upper layer transparency is ×

As is clear from the results of preparation. 1 to 3, A1 to 3 component corresponding to component (A) of the present invention, was excellent in耐乳resistance.
On the other hand, the A'1 to A'6 components, which are raw material compounds or obtained in Comparative Production Examples 1 to 5, were inferior in emulsification resistance because they were compounds having no tertiary amino group. .. Further, since the A'7 component is a compound having a tertiary amino group and an acidic group, the viscosity was as high as 18,590 mPa · s or more, and the emulsification resistance was remarkably inferior.

3. 3. Active energy ray-curable composition
1) Production method The compounds shown in Tables 2 and 4 below were stirred and mixed at the ratios shown in Tables 2 and 4 to produce an active energy ray-curable composition.
The obtained composition was used for the evaluation described later. The results are shown in Tables 2 and 4.

The numbers in Tables 2 and 4 mean the number of copies.
The abbreviations in Tables 2 and 4 mean the following.
-DETX: 2,4-diethylthioxanthone, KAYACURE DETX-s manufactured by Nippon Kayaku
-IRG379: 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1-one, BASF IRGACURE379
-TPO: (2,4,6-trimethylbenzoyl) diphenylphosphine oxide, BASF Lucillin TPO
-EAB: 4,4'-bis (diethylamino) benzophenone, EAB manufactured by Hodogaya Chemical Co., Ltd.

2) Evaluation method of composition
(1) Curability [1] (Evaluation under standard UV irradiation conditions)
The composition obtained in Table 2 was prepared into a polyethylene terephthalate film [Cosmo Shine A4300 (thickness 100 μm) manufactured by Toyobo Co., Ltd.) so as to have a film thickness of 2 μm. Hereinafter referred to as "PET"] with a bar coater, and a UV-LED irradiation device (emission wavelength: 365 nm, peak intensity: 820 mW / cm ² ) manufactured by Centec Co., Ltd. equipped with a stage moving device, per pass. Irradiation was performed at 200 mJ / cm ^2, and the mixture was transported in an air atmosphere, and the number of passes until the surface tack was eliminated was determined. The results are shown in Table 3.

(2) Abrasion resistance [1] (evaluation under standard irradiation conditions)
The composition obtained in Table 2 was applied to PET with a bar coater so as to have a film thickness of 2 μm, and carried out for 3 passes in an air atmosphere under the same conditions as in (1) above.
The scratch resistance of the obtained cured product was subjected to a rubbing test (load 500 g, 10 reciprocations) using a non-woven fabric (Asahi Kasei Bencot), the appearance was visually observed, and the evaluation was made according to the following two levels. The results are shown in Table 5.
◯: Not scratched.
×: Scratched.

(3) Curability [2] (Evaluation at low illuminance and low exposure)
The composition obtained in Table 4 was applied to PET with a bar coater so as to have a film thickness of 2 μm, and per pass ^{with a UV-LED irradiator (emission wavelength: 365 nm, peak intensity: 130 mW / cm 2).} Irradiation was performed at 10 mJ / cm ^2, and the mixture was transported in an air atmosphere, and the number of passes until the surface tack was eliminated was determined. The results are shown in Table 5.

(4) Scratch resistance [2] (Evaluation at low illuminance and low exposure)
The composition obtained in Table 4 was applied to PET with a bar coater so as to have a film thickness of 2 μm, and carried out for 3 passes in an air atmosphere under the same conditions as in (3) above.
The scratch resistance of the obtained cured product was subjected to a rubbing test (load 500 g, 10 reciprocations) using a non-woven fabric, the appearance was visually observed, and evaluation was performed at the following two levels. The results are shown in Table 5.
◯: Not scratched.
×: Scratched.

(5) Emulsification resistance The compositions obtained in Tables 2 and 4 were also evaluated in the same manner as in the above emulsion resistance method.
The evaluation results were the same as those in Table 1 above. Tables 3 and 5 show only the overall evaluation.

3) Evaluation Results As is clear from the results of Examples 1 to 3 , the composition of the present invention was excellent in curability, scratch resistance and emulsification resistance. In particular, the compositions of Examples 1 and 2 are compositions containing DETX, which is a hydrogen abstraction type photopolymerization initiator, as a photopolymerization initiator, and are remarkably excellent in curability.
On the other hand, the compositions of Comparative Examples 1 to 5 are compositions containing a compound having no tertiary amino group, and are inferior or slightly inferior in curability to the compositions of Examples. On the other hand, the scratch resistance was all inferior. Further, the composition of Comparative Example 6 is a composition containing a compound having a tertiary amino group and an acidic group, which is slightly inferior in curability and inferior in scratch resistance as compared with the composition of Example. It was a thing. Further, the compositions of Comparative Examples 1 to 3 and 5 to 6 were inferior in terms of emulsification resistance.

As is clear from the results of Examples 4 to 6 , the composition of the present invention was excellent in curability, scratch resistance and emulsification resistance even when using a UV-LED having a low illuminance and a low exposure amount. ..
On the other hand, the compositions of Comparative Examples 7 to 12 are compositions containing a compound having no tertiary amino group, and are inferior or slightly inferior in curability to the compositions of Examples. On the other hand, the scratch resistance was all inferior. Further, the composition of Comparative Example 13 was a composition containing a compound having a tertiary amino group and an acidic group, and had the same degree of curability as the composition of Example, but was scratch resistant. Was inferior. Further, regarding the emulsification resistance, the compositions of Comparative Examples 7 to 8 and 11 to 13 were inferior.

4. Manufacture of active energy ray-curable composition for ink
1) Method for Producing Composition The compounds shown in Table 6 below were stirred and mixed at the ratios shown in Table 6 and then further kneaded with a three-roll mill to produce an active energy ray-curable composition for ink.
The obtained composition was used for the evaluation described later. The results are shown in Table 7.

The numbers in Table 6 mean the number of copies.
The abbreviations in Table 6 have the same meanings as described above, and other than the above, they mean the following.
-DAP-A: Dialyl phthalate prepolymer, Daiso Dap A manufactured by Daiso Co., Ltd.
FA5375: blue pigment, C.I. I. Pigment Blue 15: 3, DIC Co., Ltd. Fastogen Blue FA5375

2) Evaluation method of composition
(1) Curability [2] (Evaluation at low illuminance and low exposure)
The compositions obtained in Table 6 were used and evaluated in the same manner as described above.

(2) Ink Adhesion The composition obtained in Table 6 was applied to PET with a bar coater so as to have a film thickness of 2 μm, and the air atmosphere was the same as in (1) [Curability [2]] above. Below, 3-pass transport was performed.
The adhesion of the obtained cured product was subjected to a rubbing test (load 500 g, 10 reciprocations) using a non-woven fabric, the appearance was visually observed, and evaluation was performed at the following two levels. The results are shown in Table 7. ◯: No ink peeling.
X: There is ink peeling.

(3) Emulsification resistance The composition obtained in Table 6 was also evaluated in the same manner as in the above emulsion resistance method.
The evaluation results were the same as those in Table 1 above. Table 7 shows only the comprehensive evaluation.

3) Evaluation Results As is clear from the results of Examples 7 to 9 , the composition of the present invention has curability, ink adhesion and emulsion resistance even when UV-LEDs having low illuminance and low exposure are used. Excellent in sex.
On the other hand, the compositions of Comparative Examples 14 to 19 are compositions containing a compound having no tertiary amino group, and are inferior in curability or slightly inferior to the compositions of Examples. On the other hand, the ink adhesion was all inferior. Further, the composition of Comparative Example 20 is a composition containing a compound having a tertiary amino group and an acidic group, and has slightly inferior curability and inferior ink adhesion as compared with the composition of Example. there were. Further, regarding the emulsification resistance, the compositions of Comparative Examples 14 to 15 and 18 to 20 were inferior.

The composition of the present invention can be preferably used as an active energy ray-curable composition, and can be used for various purposes such as coating agents, inks, resists and adhesives, and in particular. , Plastic coating applications and offset ink applications can be preferably used.

Claims (8)

A method for producing a base material having a cured film obtained by applying an ultraviolet (hereinafter referred to as "UV-LED") curable composition using the following light emitting diode as a light source to the base material and then irradiating the base material with ultraviolet rays by the UV-LED.
UV-LED curable composition: It has three or more (meth) acryloyl groups and tertiary amino groups, which are Michael addition reaction products of the following mixture (a) and compound (b), and is an acidic group and an aromatic group. there mixture containing compounds without the hydroxyl value 1~100mgKOH / g which is a mixture (a) and U V-LE D hardening type composition you as essential components hydrogen abstraction type photopolymerization initiator.
Mixture (a): A (meth) acrylate mixture containing a compound (a1) having four or more (meth) acryloyl groups and no acidic group, such as pentaerythritol tetra (meth) acrylate and diglycerin tetra ( At least one compound (b) selected from the group consisting of meta) acrylate and penta and hexa (meth) acrylate of dipentaerythritol : a secondary amine having no acidic group or aromatic group, and an aliphatic monoamine. And secondary amines selected from hydroxymonoamines The method for producing a substrate having a cured film according to claim 1, wherein the component (A) is a mixture having a (meth) acrylic equivalent of 90 to 250 g / eq and a tertiary amine value of 5 to 140 mgKOH / g. The first or second claim, wherein the component (A) is a mixture of a reaction product obtained by reacting 1 mol of the mixture (a) with the compound (b) at a ratio of 0.1 to 1.0 mol. A method for producing a base material having a cured film of. A method for producing a base material having a cured film for coating, which comprises the production method according to any one of claims 1 to 3 . A method for producing a base material having a cured film for plastic coating, which comprises the production method according to claim 4. A method for producing a base material having a cured film for ink, which comprises the production method according to any one of claims 1 to 3 . A method for producing a base material having a cured film for offset ink, which comprises the production method according to claim 6 . The following mixture (a) and compound (b) are stirred at room temperature or under heating to have three or more (meth) acryloyl groups and tertiary amino groups, which are Michael addition reaction products, and are acidic and aromatic. A step of producing a mixture (A) containing a compound having no group and having a hydroxyl value of 1 to 100 mgKOH / g, and a step of mixing the obtained component (A) with a hydrogen abstraction type photopolymerization initiator. The process of producing a UV-LED curable composition containing,
A method for producing a base material having a cured film, which comprises a step of applying the UV-LED curable composition obtained above to the base material and a step of irradiating the base material with ultraviolet rays by the UV-LED.
- mixture (a): A four or more (meth) compound having no acidic group having an acryloyl group containing (a1) (meth) acrylate mixture, pentaerythritol tetra (meth) acrylate, diglycerol tetra ( At least one compound (b) selected from the group consisting of meta) acrylate and penta and hexa (meth) acrylate of dipentaerythritol: a secondary amine having no acidic group or aromatic group, and an aliphatic monoamine. And secondary amines selected from hydroxymonoamines