JP2017066347A - Curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a curable composition which is excellent in curability of a composition and further in curability by UV-LED irradiation, is excellent in emulsification resistance and provides a cured product having excellent adhesiveness and abrasion resistance; preferably an active energy ray curable composition; and more preferably an active energy ray curable composition for coating or ink.SOLUTION: There is provided a curable composition which comprises a mixture (A) containing the following mixture (a) and a compound having 3 or more (meth)acryloyl groups and a tertiary amino group and no acidic group which is a Michael addition reaction product of a compound (b) as essential components. Mixture (a): a (meth)acrylate mixture having 4 or more (meth)acryloyl groups and no acidic group. Compound (b): a secondary amine having no acidic group.SELECTED DRAWING: None

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 in particular, for plastic coating applications and offset ink applications. It belongs to these technical fields.
In the present specification, an acryloyl group and / or a methacryloyl group is represented as a (meth) acryloyl group, an acrylate and / or methacrylate is represented as a (meth) acrylate, and acrylic acid and / or methacrylic acid is represented by (meth) acrylic acid. It expresses.

  Active energy ray-curable compositions are used in various applications such as coating agents, inks, resists, and adhesives. In the case of active energy ray curing, UV lamps such as high-pressure mercury lamps and metal halide lamps are used as curing sources. Has been widely used.

  In recent years, as a curing system that replaces these ultraviolet lamps, an ultraviolet device (hereinafter referred to as “UV-LED”) using a light-emitting diode that has a long light source life and excellent energy saving has been developed. In the field of paints such as clear coating agents and printing fields such as offset inks, methods for producing cured products corresponding to UV-LED light sources and compositions used therefor are being studied.

On the other hand, the disadvantage of the UV-LED light source is that the curability (film drying property) of the ultraviolet curable composition is greatly inferior to that of a conventional ultraviolet lamp light source.
This is a monochromatic light source compared to an ultraviolet lamp light source that emits ultraviolet light of a wide wavelength, and 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. It is because it is easy to be influenced by. In addition, since the amount of ultraviolet energy in a relatively short wavelength region is relatively short, an ultraviolet curable composition obtained by UV-LED irradiation generally tends to be inferior in film surface curability.

Conventionally, in order to prevent curing inhibition due to oxygen inhibition, ultraviolet irradiation under a nitrogen atmosphere or ultraviolet irradiation under oxygen interruption by film lamination is known, but the size of the apparatus, cost increase and productivity reduction, etc. There are problems and few cases are introduced.
In addition, compositions containing additives such as amine compounds and phosphorus compounds are known. However, the amount of these relatively highly effective additives is limited because they all bleed out after curing. There is a problem. Therefore, a hyperbranched reactive oxygen inhibition inhibitor using 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 a solvent-free application.

Moreover, the compound which has an acidic group is known as a Michael adduct of an amine compound and polyfunctional (meth) acrylate (patent document 2).
However, although the compound is excellent in various performances, it is insufficient for applications that require emulsification resistance, or has physical properties in applications where adhesion of cured products and scratch resistance are required. It would be insufficient.

On the other hand, when the ink composition is to be cured with a UV-LED, it is necessary to use a photopolymerization initiator having absorption at a wavelength of 350 to 420 nm. In many cases, the pigment used in the ink has a wavelength of 350 Even if a photopolymerization initiator having light absorption at ˜420 nm and simply having absorption at a wavelength of 350 to 420 nm is used as the photopolymerization initiator of the ink, sufficient curing cannot be obtained. Thus, an active energy ray-curable ink containing three specific types of photopolymerization initiators has been proposed (Patent Document 3).
However, although the composition is excellent in 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 referred to as “DPHA”). However, 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 of cured products, scratch resistance, etc. Such physical properties are insufficient.

JP 2000-72831 A International Publication No. 2006/75754 Pamphlet International Publication No. 2009/8226 Pamphlet

  The present inventors are excellent in curability of the composition, further excellent in curability by UV-LED irradiation, excellent in emulsification resistance, and the cured product is excellent in adhesion and scratch resistance, The inventors have intensively studied to find an active energy ray curable composition, preferably an active energy ray curable composition for coating or ink.

In order to solve the above problems, the inventors of the present invention provide a compound having three or more (meth) acryloyl groups, and further having a tertiary amino group without an acidic group in the compound. The curable composition to be contained was found to be excellent in the curability and emulsification resistance of the composition, and the cured product was also excellent in adhesion and scratch resistance, thus completing the present invention.
Hereinafter, the present invention will be described in detail.

  According to the composition of the present invention, the curability of the composition is excellent, the curability by UV-LED irradiation is also excellent, the emulsification resistance is excellent, and the cured product is excellent in adhesion and scratch resistance. It can be.

The present invention is a mixture (A) containing a compound having three or more (meth) acryloyl groups and a tertiary amino group and no acidic group, which is a Michael addition reaction product of the following mixture (a) and compound (b). ) [Hereinafter referred to as “component (A)”].
-Mixture (a): (meth) acrylate mixture containing compound (a1) having 4 or more (meth) acryloyl groups and no acidic group-Compound (b): secondary amine having no acidic group In the invention, the mixture (a) and the compound (b) are stirred at room temperature or under heating to have an acidic group having three or more (meth) acryloyl groups and tertiary amino groups which are Michael addition reaction products. It is related also with the manufacturing method of the curable composition including the process of manufacturing the mixture (A) containing the compound which does not have.
Hereinafter, (A) component, a curable composition, and a use are demonstrated.

1. Component (A) Component (A) is a mixture containing a compound having 3 or more (meth) acryloyl groups and a tertiary amino group and no acidic group.
However, (A) component is manufactured by the Michael addition reaction of the following mixture (a) and compound (b).
-Mixture (a): (meth) acrylate mixture containing compound (a1) having 4 or more (meth) acryloyl groups and no acidic group-Compound (b): secondary amine having no acidic group (A ) Component is a compound having no acidic group, and in the case of a compound having an acidic group, the viscosity is high and the emulsification resistance is deteriorated.
Hereinafter, the mixture (a) and the compound (b), which are 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 4 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 they have 4 or more (meth) acryloyl groups and no acidic groups.
The compound (a1) may be a compound having a hydroxyl group.

Specific examples of the compound (a1) include pentaerythritol tetra (meth) acrylate, diglycerin tetra (meth) acrylate, dipentaerythritol tetra, penta and hexa (meth) acrylate polyol poly (meth) acrylates; and pentaerythritol Polyalkylene oxide adducts such as tetra (meth) acrylate of alkylene oxide adduct, tetra (meth) acrylate of diglycerin alkylene oxide adduct, tetra, penta and hexa (meth) acrylate of dipentaerythritol alkylene oxide adduct (Meth) acrylate is mentioned.
Examples of the alkylene oxide unit in the alkylene oxide adduct include ethylene oxide, propylene oxide, butylene oxide, and the like, and ethylene oxide is preferable.
As the mixture (a), two or more kinds of the aforementioned compounds may be contained.

  Among these compounds, compound (a1) includes pentaerythritol tetra (meth) acrylate, diglycerin tetra (meth) acrylate, dipentaerythritol penta and hexa (meth), because the composition has excellent curability. ) Acrylate, tetra (meth) acrylate of pentaerythritol ethylene oxide adduct, tetra (meth) acrylate of diglycerin ethylene oxide adduct, and penta and hexa (meth) acrylate of dipentaerythritol ethylene oxide adduct are particularly preferred.

The mixture (a) is a (meth) acrylate mixture containing the compound (a1).
When the mixture (a) is produced industrially, 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. And a (meth) acrylate mixture containing 3 or less (meth) acryloyl groups.
In the present invention, the mixture may be used as the mixture (a).
Specifically, the following examples are given based on the raw material polyol.
・ Pentaerythritol: A mixture containing tetra (meth) acrylate as the main component and containing mono, di and tri (meth) acrylates. ・ Dipentaerythritol: Mono, di and tri containing tetra, penta and hexa (meth) acrylate as the main components. Mixture containing (meth) acrylate ・ Diglycerin: Tetra (meth) acrylate as the main component, Mixture containing mono, di and tri (meth) acrylate ・ Pentaerythritol alkylene oxide adduct: Tetra (meth) acrylate as the main component , A mixture containing mono, di and tri (meth) acrylate / dipentaerythritol alkylene oxide adduct: a mixture containing tetra, penta and hexa (meth) acrylate as a main component and containing mono, di and tri (meth) acrylate,
Diglycerin alkylene oxide adduct: A mixture containing tetra (meth) acrylate as the main component and containing mono, di and tri (meth) acrylate. In this case, the mixture (a) is a hydroxyl group-containing mono (meth) acrylate, hydroxyl group-containing poly This is a mixture of (meth) acrylate and poly (meth) acrylate having no hydroxyl group, and 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)
The compound (b) is a secondary amine having no acidic group, and is a compound represented by the following general formula (1).
R ¹ —NH—R ² (1)
Here, R ¹ and R ² represent an aliphatic hydrocarbon group, a hydroxyl group-containing aliphatic hydrocarbon group, an alkylcarbonyl group, and an aromatic group, and are groups having no acidic group. However, R ¹ and R ² in one molecule may be the same or different. R ¹ and R ² may be an aliphatic hydrocarbon group that forms a cyclic group together. The aliphatic hydrocarbon group may be a group containing an oxygen atom.
Examples of the aliphatic hydrocarbon group include a linear alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group, a branched alkyl group such as an isopropyl group and an isobutyl group, and an alicyclic group such as a cyclohexyl group. Is mentioned.
Examples of the hydroxyl group-containing aliphatic hydrocarbon group include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, and a hydroxybutyl group.
Examples of the aliphatic hydrocarbon group which forms a cyclic group together 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.
Examples of the aromatic group include a phenyl group.

As the compound (b), various compounds can be used as long as they are secondary amines having no acidic group.
Preferred examples include aliphatic monoamines such as dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine and morpholine; and N-methylethanolamine, N-acetylethanolamine and diethanolamine Of the hydroxyl monoamines.
Among these, aliphatic monoamines are particularly preferable in terms of excellent emulsification resistance.

1-3. (A) Component Production Method Component (A) is obtained by the Michael addition reaction of mixture (a) and compound (b).
A specific example of the component (A) is shown in the following formula (1). Formula (1) is an example using dipentaerythritol hexaacrylate as the compound (a1).

In the formula (1), A represents an acryloyloxy group, A ′ represents —OCOCH ₂ CH ₂ —, and R ¹ and R ² are as defined above.
In the above formula (1), only dipentaerythritol hexaacrylate is described as the compound (a1) for easy understanding. In fact, as described above, industrially obtained dipentaerythritol hexaacrylate includes tetrapentaacrylate and pentaacrylate of dipentaerythritol, and mono, di and triacrylate of dipentaerythritol as other compounds (a1). These compounds and the compound (b) become a mixture of various compounds obtained by Michael addition reaction.

As a reaction rate of the compound (b) with respect to 1 mol of mixtures (a), 0.1-1.0 mol is preferable, More preferably, it is 0.2-1.0 mol.
The reaction product obtained by reacting 0.1 to 1.0 mol of the compound (b) with respect to 1 mol of the mixture (a) 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 the molecular weight cannot be determined uniquely. Therefore, the number of moles of the mixture (a) in the present invention is a value calculated from the number average molecular weight (hereinafter referred to as “Mn”) of the mixture (a).
Mn in the present invention means a number average molecular weight in terms of polystyrene measured by a gel permeation chromatography (hereinafter referred to as “GPC”) method.

In addition, 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: within the range of 25-50 ° C-Eluent: Tetrahydrofuran (hereinafter referred to as "THF")

As a method for the Michael addition reaction, a conventional method may be followed.
Specific examples include a method of reacting the mixture (a) and the compound (b) at room temperature to about 50 ° C. for 1 hour or longer.

In the method for producing the component (A), an inert gas such as argon, helium, nitrogen and carbon dioxide gas may be introduced into the system for the purpose of maintaining the color tone of the reaction solution in good condition, and the (meth) acryloyl group 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 in which the oxygen-containing gas is dissolved in the reaction solution or blown into the reaction solution (so-called bubbling).

In the manufacturing method of (A) component, it is preferable to add a polymerization inhibitor in the reaction liquid for the purpose of preventing the polymerization of the (meth) acryloyl group.
Specific examples of the polymerization inhibitor include hydroquinone, tert-butyl hydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl-4-methylphenol, 2,4,6-tri-tert-butylphenol, 4-tert -Butylcatechol, benzoquinone, phenothiazine, N-nitroso-N-phenylhydroxylamine ammonium, 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 salt systems such as copper dibutyldithiocarbamate and N-nitroso-N-phenylhydroxylamine aluminum salt A polymerization inhibitor is mentioned.

(A) component is a mixture containing the compound which has a 3 or more (meth) acryloyl group, (meth) acryl equivalent 90-250 g / eq is preferable, More preferably, it is 90-230 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, preferably a compound having a tertiary amine value of 5 to 140 mgKOH / g, more preferably 5 to 120 mgKOH / g.
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 and air-cured adhesiveness in an air atmosphere.
As the component (A), a compound having a hydroxyl value of 1 to 100 mgKOH / g is preferable, and 1 to 90 is more preferable.
A compound having a hydroxyl value of 1 to 100 mgKOH as the component (A) is preferable in that it is excellent in surface curability in an air atmosphere and adhesion of a cured product.

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

The viscosity of the component (A) is preferably 100 to 15,000 mPa · s, and 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 TECHNICAL FIELD This invention relates to the curable composition containing the said (A) component.
As a method for producing the composition, the mixture (a) and the compound (b) are stirred at room temperature or under heating, and three or more (meth) acryloyl groups and tertiary amino groups, which are Michael addition reaction products, are added. The method including the process of manufacturing the mixture (A) containing the compound which has and does not have an acidic group is preferable.
What is necessary is just to follow the manufacturing method of above-described (A) component as the said process.

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

As other components, specifically, a polymerization initiator (hereinafter referred to as “component (B)”), a compound having an ethylenically unsaturated group other than the component (A) [hereinafter referred to as “component (C)”. And organic solvents [hereinafter referred to as “component (D)”] and the like.
Hereinafter, these components will be described.
In addition, the other component mentioned later may use only 1 type of the illustrated compound, and may use 2 or more types together.

2-1. (B) Component The composition of the present invention is a curable composition, and preferably contains a component (B) (polymerization initiator).
When the composition of the present invention is used as an active energy ray-curable composition, it is preferable to blend a photopolymerization initiator (hereinafter referred to as “component (B1)”) as the component (B), and the thermosetting type When used as a composition, it is preferable to blend a thermal polymerization initiator [hereinafter referred to as “component (B2)”] 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, it does not contain the component (B1) (photopolymerization initiator), It can also be cured by a 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 active energy rays, the component (B1) is further added from the viewpoint of ease of curing and cost. It is preferable to contain.
When an electron beam is used as the active energy ray, it is not always necessary to add it, but a small amount can be added as necessary in order to improve curability.

Specific examples of the component (B1) include benzylic compounds such as benzyldimethyl ketal and benzyl;
Benzoin compounds such as benzoin, benzoin ethyl ether, methyl benzoin formate, benzoin isopropyl ether and benzoin isobutyl ether;
1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-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-) Α-hydroxyalkylphenone compounds such as propionyl) benzyl] phenyl] -2-methylpropan-1-one;
2-methyl-1- [4- (methylthio)] phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-Dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) butan-1-one and 3,6-bis (2-methyl-2-morpholinopropionyl) Α-aminoalkylphenone compounds 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-Benzoylphenylsulfanyl) 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] -2-hydroxypropyl-thioxanthone such as N, N, N-trimethylammonium chloride and fluorothioxanthone Compounds, and the like.

Among these compounds, a hydrogen abstraction type photopolymerization initiator is preferable as the component (B1) because it is excellent in curability and adhesiveness of the cured product. Examples of the hydrogen abstraction type photopolymerization initiator include benzophenone compounds and thioxanthone compounds.
Furthermore, the α-hydroxyalkylphenone compound is preferable because it has a good surface curability even under the atmosphere even if it is a thin film coating. Specifically, 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-2-methyl More preferred is -1-phenyl-propan-1-one.
Also, 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 using an ultraviolet absorber or a pigment together For the purpose of improving the curability of the composition, it is preferable to use a plurality of types of compounds selected from acylphosphine oxide compounds, thioxanthone compounds and α-aminoalkylphenone compounds.
Preferable examples of the compound in this case include acylphosphine oxide compounds such as bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl- (2, 4,6-trimethylbenzoyl) phenyl phosphinate and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and the like, and as the thioxanthone compound, 2,4-diethylthioxanthone , Isopropylthioxanthone, 1-chloro-4-propoxythioxanthone and the like, and α-aminoalkylphenone compounds include 2-methyl-1- [4- (methylthio)] phenyl] -2-morpholinopropane. − -One, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholine-4- Yl-phenyl) -butan-1-one and the like.

When a UV-LED is used as the 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, and 2,4-diethylthioxanthone, 4,4′-bis (dimethylamino) benzophenone and 4,4′-bis (diethylamino) benzophenone are preferable.
Examples of the cleavage type photopolymerization initiator include α-hydroxyalkylphenone compounds, α-aminoalkylphenone compounds, acylphosphine oxide compounds, and the like. 1- [4- (2-hydroxyethoxy) phenyl] -2 -Hydroxy-2-methyl-1-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-dimethylamino-2- (4-methyl) Benzyl) -1- (4-morpholin-4-yl-phenyl) butan-1-one, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide Is preferred.
The combined ratio of the hydrogen abstraction type photopolymerization initiator and the cleavage type photopolymerization initiator is 5 to 95% by weight of the hydrogen abstraction type photopolymerization initiator based on the total amount of 100% by weight, and the cleavage type. The photopolymerization initiator is preferably 5 to 95% by weight.

As for the content rate of (B1) component, 0.1-10 weight part is preferable with respect to 100 weight part of sclerosing | hardenable component total amount, More preferably, it is 0.5-8 weight part. By making the ratio of the component (B1) 0.1 parts by weight or more, the photocurability of the composition can be improved and the adhesiveness can be improved, and by setting it to 10 parts by weight or less, a cured film The internal curability can be improved, and the adhesion to the substrate can be improved.
In addition, a sclerosing | hardenable component is a component hardened | cured with a heat | fever or an active energy ray, means (A) component, and when mix | blending (C) component mentioned later, it means (A) and (C) component To do.

2-1-2. (B2) Component When the composition of the present invention is used as a thermosetting composition, it is preferable to incorporate a component (B2) (thermal polymerization initiator).
As the component (B2), various compounds can be used, and organic peroxides and azo 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, , 1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, , 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- , 5-di (m-toluoylperoxy) hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy 2-ethylhexyl monocarbonate, 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-butyl) Peroxy) 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-butylperoxide P-menthane hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, diisopropylbenzene hydroperoxide, t-butyltrimethylsilyl peroxide, 1,1,3 Examples include 3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, and t-butyl hydroperoxide.
Specific examples of the azo compound include 1,1′-azobis (cyclohexane-1-carbonitrile), 2- (carbamoylazo) isobutyronitrile, 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. Moreover, an organic peroxide can also be made into a redox reaction by combining with a reducing agent.

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 components.
When component (B2) is used alone, it may be carried out in accordance with conventional radical thermal polymerization conventional methods. In some cases, it is used in combination with component (B1) and heat-cured for the purpose of further improving the reaction rate after photocuring. Curing can also be performed.

2-2. Component (C) The 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 component (C) include a (meth) acryloyl group, a (meth) acrylamide group, a vinyl group, and a (meth) allyl group, with a (meth) acryloyl group being preferred.
In the following, “monofunctional” means a compound having one ethylenically unsaturated group, “◯ functional” means a compound having ○ ethylenically unsaturated groups, and “polyfunctional”. Means a compound having two or more ethylenically unsaturated groups.

  In the component (C), specific examples of the monofunctional ethylenically unsaturated compound include (meth) acrylic acid, Michael addition dimer of acrylic acid, ω-carboxy-polycaprolactone mono (meth) acrylate, 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 of phenol alkylene oxide adduct, (meta) of alkylphenol alkylene oxide adduct (meta Of alkylene oxide adduct of acrylate, cyclohexyl (meth) acrylate, tert-butylcyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl acrylate, paracumylphenol (Meth) acrylate, orthophenylphenol (meth) acrylate, (meth) acrylate of alkylene oxide adduct of orthophenylphenol, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanemethylol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, N- (2- (meth) acryloxyethyl) hexahydrophthalimide, N- (2- (meth) acryloxyethyl) tetrahydrophthalimide, N, N-dimethylacrylamide, acryloylmorpholine, N-vinylpyrrolidone, N-vinylcaprolactam and the like can be mentioned.

  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 bisphenol A alkylene oxide adduct, di (meth) acrylate of bisphenol F alkylene oxide adduct, butanediol di (meth) Examples include acrylate, hexanediol di (meth) acrylate, and nonanediol di (meth) acrylate. In addition, epoxy (meth) acrylate having a bisphenol skeleton, polyether skeleton, polyalkylene skeleton, polyester skeleton, urethane (meth) acrylate having a polyether skeleton or a polycarbonate skeleton, and polyester (meth) acrylate may also be used. Can do.

Examples of the trifunctional or higher functional (meth) acrylate compound include various compounds as long as the compound has three or more (meth) acryloyl groups. For example, glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate. , Diglycerin tri or tetra (meth) acrylate, pentaerythritol tri or tetra (meth) acrylate, ditrimethylolpropane tri or tetra (meth) acrylate and dipentaerythritol tri, tetra, penta or hexa (meth) acrylate Polyol poly (meth) acrylates such as;
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
Tris (meth) acrylates of isocyanuric acid alkylene oxide adducts; and compounds having 3 or more (meth) acryloyl groups and hydroxyl groups, such as pentaerythritol tri (meth) acrylate and dipentaerythritol penta (meth) acrylate Examples thereof include urethane (meth) acrylate that is a reaction product with polyisocyanate.
Examples of the alkylene oxide adduct include ethylene oxide adduct, propylene oxide adduct, ethylene oxide and propylene oxide adduct, and the like.
Examples of the organic polyisocyanate include hexamethylene diisocyanate, tetramethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, norbornane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated 4,4′-diphenylmethane diisocyanate, hydrogenated xylylene. Examples include diisocyanate, trimer of 4,4′-dicyclohexylmethane diisocyanate and hexamethylene diisocyanate.

(C) It is preferable that the content rate of a component is 0-60 weight% in 100 weight part of total amounts of a sclerosing | hardenable component, More preferably, it is 0-30 weight%.
By making the content rate of (C) component 60 weight% or less, when a (C) component is a polyfunctional ethylenically unsaturated compound, it can prevent that a cured film becomes weak.

2-3. Component (D) The composition of the present invention is most preferably solvent-free, but can contain an organic solvent as component (D) for the purpose of improving the coating property to the 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, toluene And aromatic compounds such as xylene; ester compounds such as propylene glycol monomethyl ether acetate, ethyl acetate and butyl acetate; ketone compounds such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ether compounds such as dibutyl ether; and N-methylpyrrolidone 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 more preferably 0 to 300 parts by weight with respect to 100 parts by weight of the total amount of the curable components. More preferably, it is part 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 application method described later.

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

3-1. Coating composition The composition of the present invention is excellent in thin film curability and has a high hardness of a 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 substrate include plastic films used for polarizer protective films and antireflection films, resin molded products used for home appliances and automotive interior / exterior parts, and the like. .

The coating composition contains the component (A) as an essential component, but various components can be blended depending on the purpose.
Specifically, as other components, in addition to the components (B), (C) and (D) described above, antioxidants, ultraviolet absorbers, pigments / dyes, silane coupling agents, surface modifiers and polymers. Etc.
Hereinafter, these components will be described.
In addition, the other component mentioned later may use only 1 type of the illustrated compound, and may use 2 or more types together.

1) Antioxidant Antioxidant is mix | blended in order to improve durability, such as heat resistance of a cured film, and weather resistance.
Examples of the antioxidant include phenol-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants.
Examples of phenolic antioxidants include hindered phenols such as di-t-butylhydroxytoluene. As what is marketed, Ade-20 Co., Ltd. AO-20, AO-30, AO-40, AO-50, AO-60, AO-70, AO-80 etc. are mentioned.
Examples of the phosphorus-based antioxidant include phosphines such as trialkylphosphine and triarylphosphine, and trialkyl phosphites and triaryl phosphites. Examples of commercially available products of these derivatives include Adeka Co., Ltd., ADK STAB PEP-4C, PEP-8, PEP-24G, PEP-36, HP-10, 260, 522A, 329K, 1178, 1500, 135A, 3010. Etc.
Examples of the sulfur-based antioxidant include thioether compounds, and examples of commercially available products include AO-23, AO-412S, and AO-503A manufactured by Adeka Corporation.
These may be used alone or in combination of two or more. Preferred combinations of these antioxidants include the combined use of phenolic antioxidants and phosphorus antioxidants, and the combined use of phenolic antioxidants and sulfurous antioxidants.
What is necessary is just to set suitably as content rate of antioxidant according to the objective, 0.01-5 weight part is preferable with respect to 100 weight part of sclerosing | hardenable component total amount, More preferably, it is 0.1-1 weight part. It is.
When the content ratio is 0.1 parts by weight or more, the durability of the composition can be improved. On the other hand, when the content ratio is 5 parts by weight or less, curability and adhesion can be improved.

2) Ultraviolet absorber An ultraviolet absorber is mix | blended in order to improve the light resistance of a cured film.
Examples of the UV absorber include triazine UV absorbers such as TINUVIN400, TINUVIN405, TINUVIN460, and TINUVIN479 manufactured by BASF, and benzotriazole UV absorbers such as TINUVIN900, TINUVIN928, and TINUVIN1130.
What is necessary is just to set suitably as a content rate of a ultraviolet absorber according to the objective, 0.01-5 weight part is preferable with respect to 100 weight part of sclerosing | hardenable component total amount, More preferably, it is 0.1-1 weight part. It is. When the content ratio is 0.01% by weight or more, the light resistance of the cured film can be improved, and when it is 5% by weight or less, the curability of the composition is excellent. be able to.

3) Examples of the pigment / dye pigment include organic pigments and inorganic pigments.
Specific examples of organic pigments include insoluble azo pigments such as toluidine red, toluidine maroon, Hansa Yellow, benzidine yellow and pyrazolone red; soluble azo pigments such as Ritol Red, Helio Bordeaux, Pigment Scarlet and Permanent Red 2B; Alizarin, Indantron And derivatives from vat dyes such as thioindigo maroon; 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 scarlet; Isoindolinone organic pigments such as indolinone yellow and isoindolinone orange; pyranthrone organic pigments such as pyranthrone red and pyranthrone orange Thioindigo organic pigments; condensed azo organic pigments; benzimidazolone organic pigments; quinophthalone organic pigments such as quinophthalone yellow; isoindoline organic pigments such as isoindoline yellow; and other pigments such as flavanthrone yellow and acylamide Examples include yellow, nickel azo yellow, copper azomethine yellow, perinone orange, anthrone orange, dianthraquinonyl red, and dioxazine violet.

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

4) Silane coupling agent A silane coupling agent is mix | blended in order to improve the interface adhesive strength of a cured film and a base material.
The silane coupling agent is not particularly limited as long as it can contribute to improvement in adhesion to the substrate.

  Specific examples of the silane coupling agent include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3- Glycidoxypropyltriethoxysilane, 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-mercaptopropylmethyldi Tokishishiran, 3-mercaptopropyltrimethoxysilane, and the like.

The blending ratio of the silane coupling agent may be appropriately set according to the purpose, and is preferably 0.1 to 10 parts by weight, more preferably 1 to 5 parts by weight with respect to 100 parts by weight of the total amount of the curable component. .
When the blending ratio is 0.1 parts by weight or more, the adhesive strength of the composition can be improved. On the other hand, when the blending ratio is 10 parts by weight or less, it is possible to prevent the adhesive force from changing over time.

5) Surface modifying agent The composition of the present invention may be added with a surface modifying agent for the purpose of increasing the leveling property at the time of coating, the purpose of increasing the slipping property of the cured film and enhancing the scratch resistance, and the like. Good.
Examples of the surface modifier include a surface modifier, a surfactant, a leveling agent, an antifoaming agent, a slipperiness imparting agent, and an antifouling imparting agent, and these known surface modifiers can be used. .
Of these, silicone-based surface modifiers and fluorine-based surface modifiers are preferred. Specific examples include silicone polymers and oligomers having a silicone chain and a polyalkylene oxide chain, silicone polymers and oligomers having a silicone chain and a polyester chain, and fluorine polymers having a perfluoroalkyl group and a polyalkylene oxide chain. And a fluorine-based polymer and an oligomer having a perfluoroalkyl ether chain and a polyalkylene oxide chain.
Further, for the purpose of increasing the slidability, a surface modifier having an ethylenically unsaturated group, preferably a (meth) acryloyl group, in the molecule may be used.

  It is preferable that the content rate of a surface modifier is 0.01-1.0 weight part with respect to 100 weight part of total amounts of a sclerosing | hardenable component. It is excellent in the surface smoothness of a coating film as it is the said range.

6) Polymer The composition of the present invention may further contain a polymer for the purpose of further improving the curl resistance of the resulting 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- (meth) acryloxyethyl) tetrahydrophthalimide and the like. In the case of a polymer copolymerized with (meth) acrylic acid, glycidyl (meth) acrylate may be added to introduce a (meth) acryloyl group into the polymer chain.
It is preferable that the content rate of a polymer is 0.01-10 weight part with respect to 100 weight part of total amounts of a sclerosing | hardenable component. It is excellent in the curl resistance of the cured film obtained as it is the said range.

3-2. Ink composition Since the composition of the present invention is excellent in thin film curability, it is suitable for color printing such as transparent overprint varnish ink and yellow, red, indigo, black ink, etc., which are further printed by a printing machine after single-color or multicolor printing. It can be preferably used for ink.

  Printing methods include offset printing (normal lithographic plates that use dampening water and waterless lithographic plates that do not use fountain solution), relief printing (flat pressure relief printing, relief half-rotation, rotary rotation, intermittent rotation, flexo), intaglio printing Various printing methods such as (gravure printing), stencil printing (screen printing), ink jet printing and the like can be mentioned, and since it is excellent in emulsion stability, it can be preferably used for offset printing using fountain solution. Moreover, since it is low-viscosity, it can be preferably used as inkjet printing.

The ink composition contains the component (A) as an essential component, but various components can be blended depending on the purpose.
As a method for producing an ink composition, a conventional method for producing an ink composition may be followed. The component (A), the component (B) (when the active energy ray is ultraviolet light), the component (E), (F ) Component, a polymerization inhibitor, a wax and other additives and the like, and then a pigment is added and dispersed by a dispersing machine such as a three-roll mill or a bead mill.

As other components, specifically, in addition to the component (C) described above, a binder (hereinafter referred to as “(E) component”), a pigment (hereinafter referred to as “(F) component”), a plasticizer, an antifriction agent, and the like Is mentioned.
Hereinafter, these components will be described.
In addition, as for another component, only 1 type of the illustrated compound may be used, and 2 or more types may be used together.

1) Component (E) In the present invention, the component (E) includes, for example, a diallyl phthalate resin having no polymerizable group, such as an epoxy acrylate compound or urethane acrylate having at least one polymerizable group in one molecule. And polyester acrylate.

  Among the binder components described above, diallyl phthalate resin refers to a prepolymer synthesized from diallyl phthalate monomer or diallyl isophthalate monomer, and there are several commercially available products depending on the types and molecular weights of orthophthalic and isophthalic monomers. it can. Specific examples include Daiso Dup A, Daiso Dup S, Daiso Dup K, and Daiso Isodap sold by Daiso Corporation. Among these, Daiso Dup A is the most preferable among the above-mentioned commercial products in consideration of 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 with respect to the total amount of ink. When the amount is less than 10% by weight, sufficient film curability and offset printability cannot be obtained, and when the amount exceeds 65% by weight, the binder having a polymerizable group generally has a high viscosity. In the composition described in the examples, it becomes difficult to obtain a viscosity suitable as an offset ink.

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

In the present invention, inorganic fine particles may be used as the extender pigment. As inorganic fine particles, inorganic coloring pigments such as titanium oxide, kraftite, zinc white; lime carbonate powder, precipitated calcium carbonate, gypsum, clay (ChinaClay), silica powder, diatomaceous earth, talc, kaolin, alumina white, barium sulfate, Inorganic pigments such as aluminum stearate, magnesium carbonate, barite powder, and abrasive powder; inorganic pigments such as silicone, glass beads, and the like.
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 ink fluidity adjustment, prevention of misting, and prevention of penetration into printing substrates such as paper. is there.

3) Plasticizers and anti-friction agents As plasticizers and anti-friction agents, paraffin wax, carnauba wax, beeswax, microcrystalline wax, polyethylene wax, oxidized polyethylene wax, polytetrafluoroethylene wax, amide wax and other wax compounds, palm oil Fatty acids and the like in the range of about C8 to C18 such as fatty acids and soybean oil fatty acids 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, after apply | coating a composition to a base material, the method of making it harden | cure by irradiating an active energy ray or heating, etc. are mentioned.
Specifically, after applying the composition to the substrate to be applied by an ordinary coating method, in the case of an active energy ray curable composition, a method of irradiating and curing active energy rays, or a thermosetting composition In the case of a thing, the method of heating and hardening etc. is mentioned.
A general method known as a conventional curing method may be adopted as the active energy ray irradiation method and heating method.
In addition, (B1) component (photopolymerization initiator) and (B2) component (thermal polymerization initiator) are used in combination with the composition, and this is irradiated with active energy rays and then heat-cured, thereby adhering to the substrate. A method for improving the property can also be adopted.
Hereinafter, the coating composition and ink patent, which are preferred uses of the composition of the present invention, will be described in detail.

4-1. Method of Using Coating Composition The substrate to which the composition of the present invention can be applied can be applied to various materials, and examples thereof include plastic, wood, metal, inorganic material, and paper.
Specific examples of plastics include cellulose acetate resins such as polyvinyl alcohol, triacetyl cellulose and diacetyl cellulose, cyclic polyolefin resins having cyclic olefins such as acrylic resin, polyethylene terephthalate, polycarbonate, polyarylate, polyethersulfone, norbornene as monomers. , Polyvinyl chloride, epoxy resin, polyurethane resin and the like.
Examples of the 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 inorganic materials include glass, mortar, concrete, and stone.
Among these, a plastic substrate is particularly preferable.

  What is necessary is just to set the film thickness of the composition cured film with respect to a base material suitably according to the objective. The thickness of the cured film may be selected according to the substrate to be used and the use of the substrate having the produced cured film, but is preferably 1 to 500 μm, more preferably 5 to 200 μm. .

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

Examples of the active energy ray for curing the composition of the present invention include ultraviolet rays, visible rays, and electron beams, and ultraviolet rays are preferred.
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 composition of the active energy ray. As an 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. Method of using ink composition The printing substrate used in the printed material of the present invention is not particularly limited. For example, paper such as fine paper, coated paper, art paper, imitation paper, thin paper, cardboard, various synthetic papers, Polyester resin, acrylic resin, vinyl chloride resin, vinylidene chloride resin, polyvinyl alcohol, polyethylene, polypropylene, polyacrylonitrile, ethylene vinyl acetate copolymer, ethylene vinyl alcohol copolymer, ethylene methacrylic acid copolymer, nylon, polylactic acid, Examples thereof include films or sheets such as polycarbonate, cellophane, aluminum foil, and other various base materials conventionally used as printing base materials.
Among these, a paper base material is particularly preferable.

  What is necessary is just to set the film thickness of the composition cured film with respect to a base material suitably according to the objective. The thickness of the cured film may be selected according to the use of the substrate to be used or the substrate having the produced 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 an offset ink, it can be suitably used as an application method to a substrate by using an offset printing machine that continuously supplies water onto the plate surface. Further, the present invention can be suitably used in any sheet feeding method, such as a sheet-fed offset printing machine using sheet-type printing paper, an offset rotary printing machine using reel-type printing paper.

  When the composition of the present invention is used for inkjet ink, it can be suitably used as a coating method on a substrate by using a known inkjet recording apparatus or the like that forms an image by discharging by an inkjet method. .

  In the ink jet 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 discharge properties. 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, and electron beams, and ultraviolet rays are preferred.
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 composition of the active energy ray, and examples include the same irradiation energy as described above.

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

1. Production example
1) Comparative production example 1 [ Production of compounds other than component (A)]
EO6 mol adduct of dipentaerythritol (Aoki Yushi Kogyo Co., Ltd., Brownon DPE-E6, hydroxyl value 643 mg KOH / g) is added to a 2 L side-tube four-necked flask equipped with a thermometer, stirrer and reflux tube. , 575 g of acrylic acid (a ratio of 1.16 mol to 1 mol of all hydroxyl groups in the alcohol), 24 g of 70% methanesulfonic acid (hereinafter referred to as “MSA”), 1.9 g of cupric chloride and 520 g of toluene did.
The mixture was heated and stirred at a reaction liquid temperature of 85 to 95 ° C. while oxygen-containing gas was blown into the flask. While water generated with the progress of the reaction was taken out of the system through a Dean-Stark tube, a 6-hour dehydration esterification reaction was performed.
After completion of the reaction, 1250 g of toluene was added for dilution. Further, 300 g of distilled water was added, stirred and allowed to stand, and then the lower layer was removed. Next, 490 g of a 20% aqueous sodium hydroxide solution was added with stirring, and the mixture was sufficiently stirred and 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 allowed to stand and then the lower layer was removed. The upper organic phase was heated under reduced pressure to distill off toluene.
The obtained reaction product 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, EO 4 mol adduct of pentaerythritol (Aoki Yushi Kogyo Co., Ltd., BROWNON PE-240N, hydroxyl value 717 mg KOH / g) 520 g, acrylic acid 570 g, MSA 25 g, cupric chloride 2 g, MEHQ0 .2 g and 480 g of toluene were charged.
The mixture was heated and stirred at a reaction liquid temperature of 82 to 97 ° C. while oxygen-containing gas was blown into the flask. While water generated with the progress of the reaction was taken out of the system through a Dean-Stark tube, a 6-hour dehydration esterification reaction was performed.
After completion of the reaction, 1050 g of toluene was added for dilution. Further, 250 g of distilled water was added and stirred and allowed to stand, and then the lower layer was removed. Next, 360 g of a 20% aqueous sodium hydroxide solution was added with stirring, and the mixture was sufficiently stirred and 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 allowed to stand and then the lower layer was removed. The upper organic phase was heated under reduced pressure to distill off toluene.
The obtained reaction product 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 4.00 g (0.02 mol) of zinc acetate, 1.42 g of hydroquinone monomethyl ether as a polymerization inhibitor (2000 wtppm based on the total weight of the charged raw materials), oxygen-containing gas (oxygen 5% by volume, nitrogen Was volatilized into the liquid.
2-methoxyethanol and 2-methoxyethyl acrylate by-produced as the transesterification progresses while adjusting the pressure in the reaction system in the range of 110 to 760 mmHg while heating and stirring at a reaction liquid temperature of 105 to 130 ° C. Was extracted from the reaction system via a rectification column and a cooling tube. Further, 2-methoxyethyl acrylate in the same weight part as the extracted liquid was added to the reaction system as needed. 27 hours after the start of heating and stirring, the pressure in the reaction system was returned to normal pressure, and the extraction was completed.
The reaction solution was cooled to room temperature, 200 ml of normal hexane was added, and the precipitate was separated by filtration. Then, 2.0 g of aluminum silicate [KYOWARD 700 (trade name) manufactured by Kyowa Chemical Industry Co., Ltd.] and activated carbon [ Futamura Chemical Co., Ltd. made Dazai S (trade name)] was introduced, and under reduced pressure distillation for 8 hours at a temperature of 70 to 95 ° C. and a pressure of 0.001 to 100 mmHg while bubbling dry air. A 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 liquid and subjected to pressure filtration, 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, diglycerin EO 4 mol adduct [Kao Co., Ltd., Emulgen G2E-4, 625 mg KOH / 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 oxygen-containing gas was blown into the flask, the mixture was heated and stirred under conditions of a reaction liquid temperature of 80 to 100 ° C. and a reaction system pressure of 400 to 760 Torr. A dehydration esterification reaction was carried out for 7 hours while removing water generated as the reaction progressed out of the system using a Dean-Stark tube.
After completion of the reaction, the obtained reaction solution is added to a separatory 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 purified with pure water. After washing and liquid separation, and leaving to stand, the lower layer was removed. The upper organic phase was heated under reduced pressure to distill off toluene.
The obtained reaction product 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)]
A 500 mL 4-neck flask with a side tube equipped with a thermometer, a stirrer, and a reflux tube was charged with 16 g of succinic anhydride, 250 g of A′1 component, and 0.13 g of methoquinone, and the temperature was raised to 85 ° C. The reaction was carried out for 4 hours after adding 1.3 g of the catalyst triethylamine. 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”).
Subsequently, 17.4 g of di-n-butylamine (0.3 mol with respect to 1 mol of A ″ component) was added at room temperature, followed by reaction at 50 ° C. for 4 hours. The reaction was carried out under a mixed atmosphere of air / nitrogen.
The obtained reaction product was a mixture containing a Michael adduct of di-n-butylamine. Hereinafter, it is referred to as “A′7 component”.
Moreover, the hydroxyl value of 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 Comparative Production Example 5, dipentaerythritol penta and hexaacrylate mixture (Mw 1,020, Mn 1,012, viscosity 7,280 mPa · s (25 ° C.), hydroxyl value 32 mg KOH / g, Aronix M-402 manufactured by Toagosei Co., Ltd. , 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 with respect to 1 mol of A′1 component) Was allowed to react at 50 ° C. for 4 hours. The reaction was carried out under a mixed atmosphere of air / nitrogen.
The obtained reaction product was a mixture containing a Michael adduct of di-n-butylamine. Hereinafter, it is referred to as “component (A1)”.

7) Production Example 2 [Production of 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 with respect to 1 mol of A′2 component). The reaction was performed according to the same method as in Production Example 1.
The obtained reaction product was a mixture containing a Michael adduct of di-n-butylamine. Hereinafter, it is referred to as “A2 component”.

8) Production Example 3 [Production of Component (A)]
250 g (0.446 mol) of pentaerythritol tetraacrylate (Mw 560, Mn 560, viscosity 570 mPa · s (25 ° C.), hydroxyl value 6 mg KOH / g, Aronix M-450 manufactured by Toagosei, hereinafter referred to as “A′3 component”) ), Di-n-butylamine was reacted in the same manner as in Production Example 1, except that it was changed to 27.5 g (0.213 mol, 0.48 mol relative to 1 mol of A′3 component).
The obtained reaction product was a mixture containing a Michael adduct of di-n-butylamine [hereinafter referred to as “component A3”].

9) Production Example 4 [Production of Component (A)]
Manufactured except for 250 g (0.338 mol) of A′4 component (Mn739) and 18.7 g of di-n-butylamine (0.145 mol, 0.43 mol with respect to 1 mol of A′4 component). The reaction was carried out in the same manner as in Example 1.
The obtained reaction product was a mixture containing a Michael adduct of di-n-butylamine. Hereinafter, it is referred to as “A4 component”.

10) Production Example 5 [Production of Component (A)]
Manufactured except for 250 g (0.463 mol) of A′5 component (Mn540) and 25.4 g of di-n-butylamine (0.197 mol, 0.42 mol with respect to 1 mol of A′5 component). The reaction was carried out in the same manner as in Example 1.
The obtained reaction product was a mixture containing a Michael adduct of di-n-butylamine. Hereinafter, it is referred to as “A5 component”.

11) Production Example 6 [Production of 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 with respect to 1 mol of A′6 component). The reaction was performed according to the same method as in Production Example 1.
The obtained reaction product was a mixture containing a Michael adduct of di-n-butylamine. Hereinafter, it is referred to as “A6 component”.

2. Reactant Evaluation Method For the reactants obtained in Production Examples 1 to 6 and Comparative Production Examples 1 to 5, the acrylic equivalent, tertiary amine value, hydroxyl value, Mw, and viscosity were measured according to the methods described below. did.
The results are shown in Table 1.

(1) Acrylic equivalent The bromine number of acrylate (g number of bromine added to the unsaturated component in 100 g of the sample ) measured based on JIS K 2605 was converted to g number of acrylate per mol of acryloyl group. Value (unit: g / eq) is represented.

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

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

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

(5) Viscosity Using an E-type viscometer, the viscosity was measured at 25 ° C.

(6) Emulsion resistance 3 g of the obtained reaction product was dissolved in 6 g of xylene, and 9 g of distilled water was put into 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 water layer and the organic layer were completely separated was measured, and the transparency of the upper layer and the lower layer was determined according to the following four levels. There is a correlation between water separability and emulsification resistance. The better the water separability, the better the emulsification resistance when applied to ink.
◎: Transparent ○: Slightly cloudy △: Cloudy ×: Milky.
Comprehensive evaluation was determined according to the following four levels.
A: Separation time is within 4 minutes, upper layer transparency is A or B, lower layer transparency is A or B
○: Separation time is within 4 minutes, upper layer transparency is Δ, lower layer transparency is ◎ or ○
Δ: Separation time within 4 minutes, upper layer transparency x, lower layer transparency ◎ or ○
X: Separation time is 5 minutes or more, or upper layer transparency is x

As is clear from the results of Production Examples 1 to 6, the A1 to A6 components corresponding to the component (A) of the present invention were excellent in emulsification resistance.
On the other hand, since the A′1 to A′6 components that are raw material compounds or obtained in Comparative Production Examples 1 to 5 are compounds that do not have a tertiary amino group, they have poor emulsification resistance. . In addition, 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. 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 active energy ray-curable compositions.
The obtained composition was used and evaluated as described later. The results are shown in Tables 2 and 4.

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

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

(2) Scratch 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 transported in three passes under an air atmosphere under the same conditions as in (1) above.
The obtained cured product was subjected to a rubbing test (load 500 g, 10 reciprocations) using a non-woven fabric (Bencot manufactured by Asahi Kasei). The appearance was visually observed and evaluated according to the following two levels. The results are shown in Table 5.
○: Not scratched.
×: Scratched.

(3) Curability [2] (Evaluation with low illumination 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 irradiation device (emission wavelength: 365 nm, peak intensity: 130 mW / cm ² ). Irradiation was carried out so as to be 10 mJ / cm ^2, and transport was performed in an air atmosphere, and the number of passes until surface tack was eliminated was determined. The results are shown in Table 5.

(4) Scratch resistance [2] (Evaluation with low illumination 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 transported in three passes under 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 nonwoven fabric, the appearance was visually observed, and the following two levels were evaluated. 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 the emulsion resistance method.
The evaluation results were the same as those in Table 1. Tables 3 and 5 list only the overall evaluation.

3) Evaluation results As is clear from the results of Examples 1 to 5, the composition of the present invention was excellent in curability and further excellent in scratch resistance and emulsification resistance. In particular, the compositions of Examples 1 to 3 were compositions containing DETX, which is a hydrogen abstraction type photopolymerization initiator, as the photopolymerization initiator, and were extremely excellent in curability.
On the other hand, the compositions of Comparative Examples 1 to 5 are compositions containing a compound that does not have a tertiary amino group, and are less curable or slightly inferior to the compositions of the 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, and is slightly inferior in curability and inferior in scratch resistance as compared with the compositions of Examples. It was a thing. Furthermore, about the emulsification resistance, the composition of Comparative Examples 1-3 and 5-6 was inferior.

As is apparent from the results of Examples 6 to 11, the composition of the present invention was excellent in curability, scratch resistance and emulsification resistance even when UV-LEDs having low illuminance and low exposure were used. .
On the other hand, the compositions of Comparative Examples 7 to 12 are compositions containing a compound that does not have a tertiary amino group, and the curability is inferior or slightly inferior as compared with the compositions of Examples. On the other hand, the scratch resistance was all inferior. Further, the composition of Comparative Example 13 is a composition containing a compound having a tertiary amino group and an acidic group, and the curability was comparable to the compositions of the Examples, but the scratch resistance was high. Was inferior. Furthermore, about the emulsification resistance, the composition of Comparative Examples 7-8 and 11-13 was inferior.

4). Production of active energy ray-curable composition for ink
1) Composition Production Method After stirring and mixing the compounds shown in Table 6 below in the ratio shown in Table 6, the mixture was further kneaded with a three-roll mill to produce an active energy ray-curable composition for ink.
The obtained composition was used and evaluated as described later. The results are shown in Table 7.

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

2) Composition evaluation method
(1) Curability [2] (Evaluation with low illumination 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. Under the same conditions as in (1) [Curability [2]], air atmosphere Below, three-pass conveyance was performed.
The adhesiveness of the obtained cured product was subjected to a rubbing test (load 500 g, 10 reciprocations) using a nonwoven fabric, the appearance was visually observed, and the following two levels were evaluated. A result is shown in Table 7. (circle): There is no peeling of an ink.
X: There is peeling of ink.

(3) Emulsification resistance The compositions obtained in Table 6 were also evaluated in the same manner as the emulsion resistance method.
The evaluation results were the same as those in Table 1. Table 7 lists only the overall evaluation.

3) Evaluation results As is clear from the results of Examples 12 to 17, the composition of the present invention is curable, ink adhesion and anti-emulsification even when UV-LEDs having low illuminance and low exposure are used. Excellent in properties.
On the other hand, the compositions of Comparative Examples 14 to 19 are compositions containing a compound that does not have a tertiary amino group, and the curability is inferior 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 is slightly inferior in curability and inferior in ink adhesion as compared with the compositions of Examples. there were. Furthermore, about the emulsification resistance, the composition of Comparative Examples 14-15 and 18-20 was inferior.

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

Claims (15)

A mixture (A) containing a compound having 3 or more (meth) acryloyl groups and a tertiary amino group and having no acidic group, which is a Michael addition reaction product of the following mixture (a) and compound (b), is an essential component. A curable composition contained as
-Mixture (a): (meth) acrylate mixture containing compound (a1) having 4 or more (meth) acryloyl groups and no acidic group-Compound (b): secondary amine having no acidic group The curable composition 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 curable composition according to claim 1 or 2, wherein the component (A) is a mixture having a hydroxyl value of 1 to 100 mgKOH / g. The component (A) is a mixture of reactants obtained by reacting the compound (b) at a ratio of 0.1 to 1.0 mol with respect to 1 mol of the mixture (a). 2. The curable composition according to item 1. The compound (a1) having four or more (meth) acryloyl groups and no acid group is pentaerythritol tetra (meth) acrylate, diglycerin tetra (meth) acrylate, dipentaerythritol penta and hexa (meth) At least selected from the group consisting of acrylate, tetra (meth) acrylate of pentaerythritol ethylene oxide adduct, tetra (meth) acrylate of diglycerin ethylene oxide adduct, and penta and hexa (meth) acrylate of dipentaerythritol ethylene oxide adduct It is 1 type, The curable composition of any one of Claims 1-4. The said compound (b) is an aliphatic monoamine, The curable composition containing the composition of any one of Claims 1-5. The active energy ray hardening-type composition containing the composition of any one of Claims 1-6. Furthermore, the active energy ray hardening-type composition of Claim 7 containing a photoinitiator (B1). The active energy ray-curable composition according to claim 8, wherein the component (B1) is a hydrogen abstraction type photopolymerization initiator. The ultraviolet-ray (UV-LED) curable composition which uses the light emitting diode containing the composition of any one of Claims 7-9 as a light source. The active energy ray hardening-type composition for coating containing the composition of any one of Claims 7-10. The active energy ray hardening-type composition for plastic coating containing the composition of Claim 11. The active energy ray hardening-type composition for ink containing the composition of any one of Claims 7-10. The active energy ray hardening-type composition for offset inks containing the composition of Claim 13. The following mixture (a) and compound (b) are stirred at room temperature or under heating, and are compounds having three or more (meth) acryloyl groups and tertiary amino groups, which are Michael addition reaction products and no acidic groups The manufacturing method of the curable composition including the process of manufacturing the mixture (A) containing this.
-Mixture (a): (meth) acrylate mixture containing compound (a1) having 4 or more (meth) acryloyl groups and no acidic group-Compound (b): secondary amine having no acidic group