JP2018165363A - Curable composition, method for producing curable composition, and method for producing active energy ray-curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition that has low viscosity and excellent curability, and forms a cured film with excellent flexibility and yellow discoloration-resistance, preferably an active energy ray-curable composition with excellent curability by UV-LED irradiation.SOLUTION: A curable composition contains the following (A) component. (A) component: a mixture containing a compound having three or more (meth) acryloyl groups, an alkylene oxide unit and a tertiary amino group, produced from Michael addition reaction between the following mixture (a) and compound (b). Mixture (a): a (meth) acrylate mixture containing a compound (a1) having four or more (meth) acryloyl groups and an alkylene oxide unit. Compound (b): a secondary amine.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 a coating agent, an ink, a resist, and an adhesive, and in particular, a coating varnish (or a clear varnish). ) It can be preferably used for applications and belongs to these technical fields. The present invention also relates to a method for producing a curable composition and a method for producing an active energy ray curable composition.
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. When cured with active energy rays, UV lamps such as high-pressure mercury lamps and metal halide lamps are cured as light sources. It has been widely used as a system.

  In recent years, 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 as a curing system replacing these ultraviolet lamps. In particular, in the field of paints such as clear coating agents that irradiate ultraviolet rays in an air atmosphere and in the field of printing such as offset inks, a method for producing a cured film corresponding to a UV-LED light source and a composition used therefor have been studied.

On the other hand, the disadvantage of the UV-LED light source is that the curability (hereinafter also referred to as “surface curability”) of the coating film surface of the ultraviolet curable composition is greatly inferior compared with the conventional ultraviolet lamp light source. .
This is different from an ultraviolet lamp light source that emits ultraviolet light of a wide wavelength range, and a UV-LED light source is a monochromatic light source and does not emit light in a short wavelength region of 300 nm or less. Therefore, generation of radicals generated from a photopolymerization initiator is generated. This is because the polymerization reaction is susceptible to oxygen inhibition due to the small amount.

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, as a composition for suppressing oxygen inhibition, a polyamino compound (a) having a primary or secondary amino group in the molecule, an active hydrogen-containing (meth) acrylic compound (b-1), and a non-functional (meth) acrylic From a multi-branched compound (A) obtained by reacting a vinyl group-containing compound (c) having a functional group capable of reacting with active hydrogen into a core compound formed by Michael addition reaction of a mixture of the system compound (b-2) There has been proposed a reactive oxygen inhibition inhibitor (Patent Document 1).

On the other hand, as a reactive oxygen inhibition inhibitor having a lower viscosity, a Michael adduct (hereinafter referred to as amine-modified acrylate) of a polyfunctional (meth) acrylate having no amine compound and urethane bond has been proposed (Patent Document 2 and Patent Document 3).
Patent Document 2 proposes a Michael adduct of a primary or secondary amine and a tri- or higher functional (meth) acrylate as an amine-modified acrylate.
Patent Document 3 discloses an ultraviolet light emitting diode curable coating varnish characterized by containing an amine-modified acrylate, another ultraviolet curable monomer and / or oligomer component, an acyl phosphine oxide polymerization initiator, and an optical brightener. Proposed.

JP 2000-72831 A JP 2000-86713 A JP 2011-213965 A

In Patent Document 1, since the multi-branched compound has a urethane bond and has a high viscosity, it is not suitable for use in a solventless application.
In Patent Document 2, the amine-modified acrylate having no urethane bond disclosed in Synthesis Examples 1 and 2 was reacted with an amine compound at a ratio of 1.0 mol or more per 1 mol of (meth) acrylate. There was a problem of yellowing of the cured film because it was a mixture of reactants and the tertiary amine value was 65 to 85 mg KOH / g and the amine concentration was high.
Patent Document 3 discloses a Michael adduct of monoethanolamine and propylene oxide-modified glycerin triacrylate (EBECRYL80 manufactured by Daicel Ornex Co., Ltd.) as an amine-modified acrylate. The viscosity of EBECRYL80 is 3,000 mPa · s. Therefore, in order to use as a solventless coating agent, more specifically as a solventless coating varnish, it is necessary to use a large amount of a low viscosity reactive diluent such as polyethylene glycol diacrylate. As a result of the low amine-modified acrylate concentration, the problem is that the curability in the UV-LED light source becomes insufficient. Further, when a thioxanthone compound is used as a photopolymerization initiator for improving curability, there is a problem that yellowing of a cured film becomes remarkable.

  In view of the above problems, the present invention provides a curable composition having a low viscosity and excellent curability, a cured film having excellent flexibility and low yellowing, and also excellent curability by UV-LED irradiation. Objective.

In order to solve the above problems, the inventors of the present invention have a compound having three or more (meth) acryloyl groups, and further comprising an active energy containing a compound having an alkylene oxide unit and a tertiary amino group in the compound. The present invention has been completed by finding that the linear curable composition has low viscosity and excellent curability, and the cured film has excellent flexibility and low yellowing, even though the amine concentration of the composition is lower than the conventional one. .
Hereinafter, the present invention will be described in detail.

  According to the present invention, the curable composition can have a low viscosity and excellent curability, the cured film can have excellent flexibility and low yellowing, and can be excellent in curability by UV-LED irradiation. .

The present invention is a mixture containing a compound having three or more (meth) acryloyl groups, an alkylene oxide unit and a tertiary amino group, which is a Michael addition reaction product of the following mixture (a) and compound (b) [hereinafter, The present invention also relates to a curable composition (hereinafter also referred to simply as “composition”).
-Mixture (a): (meth) acrylate mixture containing compound (a1) having 4 or more (meth) acryloyl groups and alkylene oxide units-Compound (b): secondary amine The mixture (a) and the compound (b) are stirred at room temperature or under heating, and include a compound having three or more (meth) acryloyl groups, alkylene oxide units and tertiary amino groups, which are Michael addition reaction products. The present invention relates to a method for producing a curable composition comprising a step of producing a mixture (A).
Hereinafter, (A) component, a curable composition, and a use are demonstrated.

1. Component (A) The component (A) is a mixture containing a compound having three or more (meth) acryloyl groups, an alkylene oxide unit and a tertiary amino 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 alkylene oxide units-Compound (b): secondary amine Hereinafter, component (A) A method for producing the mixture (a) and the compound (b), which are raw material compounds of (A), and the component (A) will be described.

1-1. Mixture (a)
The mixture (a) is a (meth) acrylate mixture containing the compound (a1) having 4 or more (meth) acryloyl groups and an alkylene oxide unit [hereinafter also referred to as “compound (a1)”].
As an alkylene oxide unit in a compound (a1), an ethylene oxide unit, a propylene-tylene oxide unit, a butylene oxide unit, etc. are mentioned, An ethylene oxide unit is preferable because it is excellent in the surface curability in an air atmosphere. The number of alkylene oxide units contained in one molecule of the compound (a1) (namely, the number of added alkylene oxides) is preferably 1-20.
As the compound (a1), various compounds can be used as long as they are compounds having four or more (meth) acryloyl groups and an alkylene oxide unit.
The compound (a1) may be a compound having a hydroxyl group.

Specific examples of the compound (a1) include tetra, penta and hexa (meth) acrylates of dipentaerythritol alkylene oxide adduct, tetra (meth) acrylate of pentaerythritol alkylene oxide adduct, and tetra of diglycerin alkylene oxide adduct. Poly (meth) acrylates of polyol alkylene oxide adducts such as (meth) acrylates may be mentioned.
Examples of the alkylene oxide unit in the alkylene oxide adduct include ethylene oxide, propylene oxide, and butylene oxide.
As a mixture (a), 2 or more types of compounds (a1) may be included.

  As the compound (a1), among these compounds, penta and hexa (meth) acrylates of dipentaerythritol ethylene oxide adducts, tetra (pentaerythritol ethylene oxide adducts) are used because the composition has excellent curability. Particularly preferred are (meth) acrylates and tetra (meth) acrylates of diglycerin ethylene oxide adducts.

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 four or more hydroxyl groups and (meth) acrylic acid, one or two or more compounds as the main component ( a1) and a (meth) acrylate 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.
Dipentaerythritol alkylene oxide adduct: A mixture containing tetra, penta and hexa (meth) acrylate as a main component and mono, di and tri (meth) acrylate. Pentaerythritol alkylene oxide adduct: As a main component A mixture containing tetra (meth) acrylate and mono, di and tri (meth) acrylates, diglycerin alkylene oxide adduct: tetra (meth) acrylate as a main component, mono, di and tri (meth) acrylate The mixture (a) in this case is a mixture of a hydroxyl group-containing mono (meth) acrylate, a hydroxyl group-containing poly (meth) acrylate, and a poly (meth) acrylate having no hydroxyl group, and having a hydroxyl value. It becomes the mixture which has.
The preferred hydroxyl value of the mixture (a) is preferably 1 mgKOH / g to 100 mgKOH / g, more preferably 1 mgKOH / g to 90 mgKOH / g.

1-2. Compound (b)
The compound (b) is a secondary amine, and is preferably a compound represented by the following general formula (1).
R ¹ —NH—R ² —General formula (1)
Here, R ¹ and R ² each independently represents an aliphatic hydrocarbon group, a hydroxyl group-containing aliphatic hydrocarbon group, an alkylcarbonyl group, or an aromatic group. These functional groups are preferably groups having no acidic group.
In general formula (1), R ¹ and R ² 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 in which R ¹ and R ² on the nitrogen atom are combined to form a cyclic group include —CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ — and —CH ₂ CH ₂ OCH ₂ CH _2- and the like.
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.
Preferred examples include aliphatic monoamines such as dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-n-octylamine, morpholine, piperidine and 1-methylpiperazine. And hydroxyl monoamines such as N-methylethanolamine, N-acetylethanolamine, diethanolamine and dibutylethanolamine.
Among these, an aliphatic monoamine is particularly preferable in terms of excellent water resistance.

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

In the formula (1), A represents an acryloyloxy group, A ′ represents —COCH ₂ CH ₂ —, EO represents an ethylene oxide group, and R ¹ and R ² are those described in the item of the compound (b). It is synonymous with.
In the above formula (1), for ease of understanding, only hexaacrylate of dipentaerythritol ethylene oxide adduct is described as the compound (a1). Actually, as described above, in the hexaacrylate of dipentaerythritol ethylene oxide adduct obtained industrially, other compounds (a1) include tetra and pentaacrylates of dipentaerythritol ethylene oxide adduct, and dipentaerythritol monoacrylate. , Di- and triacrylates, and these compounds and the compound (b) become a mixture of various compounds obtained by Michael addition reaction.

The reaction ratio of the compound (b) to 1 mol of the mixture (a) is preferably 0.1 mol to 1.0 mol, and more preferably 0.2 mol to 1.0 mol.
A 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 low yellowing of the cured film. This 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 of the mixture (a) (hereinafter also referred to as “Mn”).
Mn in the present invention means a number average molecular weight in terms of polystyrene measured by a gel permeation chromatography (hereinafter also 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 a range of 25 ° C. to 50 ° C. Eluent: tetrahydrofuran (hereinafter also 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 may be introduced into the reaction system for the purpose of maintaining a good color tone of the reaction solution, and a (meth) acryloyl group For the purpose of preventing polymerization of oxygen, an oxygen-containing gas may be introduced into the system.
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. Examples of the method of introducing the oxygen-containing gas include a method of dissolving in the reaction solution or blowing 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 salts such as copper dibutyldithiocarbamate and N-nitroso-N-phenylhydroxylamine aluminum salt System polymerization inhibitors.

The component (A) is a mixture containing a compound having three or more (meth) acryloyl groups, and the (meth) acryl equivalent is preferably 90 g / eq to 250 g / eq, more preferably 90 g / eq to 230 g. / Eq.
In the present invention, (meth) acrylic equivalent means a value (unit: g / eq) converted to mass (g) of a mixture of (meth) acrylate per mole of (meth) acryloyl group, and bromine value That is, it means a value calculated from the mass (g) of bromine added to the unsaturated component in 100 g of the sample.
When the (meth) acrylic equivalent of the component (A) is 90 g / eq to 250 g / eq, it is preferable in terms of excellent surface curability and a cured film flexibility in an air atmosphere.
The component (A) is a mixture containing a compound having a tertiary amino group, and the tertiary amine value is preferably 5 mgKOH / g to 60 mgKOH / g, more preferably 5 mgKOH / g to 50 mgKOH / g. .
When the tertiary amine value of the component (A) is 5 mgKOH / g to 60 mgKOH / g, it is preferable from the viewpoint of excellent surface curability in an air atmosphere and low yellowing of the cured film.
As the component (A), the hydroxyl value is preferably 1 mgKOH / g to 100 mgKOH / g, more preferably 1 mgKOH / g to 90 mgKOH / g.
When the hydroxyl value of the component (A) is 1 mgKOH / g to 100 mgKOH / g, it is preferable in terms of excellent surface curability in an air atmosphere and excellent adhesion of the cured film.

The weight average molecular weight (hereinafter also 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 of GPC are as described in the item of the number average molecular weight of the mixture (a).

The viscosity of the component (A) is preferably 100 mPa · s to 1,000 mPa · s, and more preferably 100 mPa · s to 900 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 polyalkylene oxide units which are Michael addition reaction products are used. And the method including the process of manufacturing the mixture (A) containing the compound which has a tertiary amino group is preferable.
What is necessary is just to follow the manufacturing method of above-described (A) component as the said process.

Although the composition of this invention contains the said (A) component, it may contain various components according to the objective.
The composition of the present invention can be used for both the active energy ray-curable composition and the thermosetting composition, but is preferably used for the active energy ray-curable composition.

As other components, specifically, a polymerization initiator [hereinafter also referred to as “component (B)”], a compound having an ethylenically unsaturated group other than the component (A) [hereinafter referred to as “component (C)”. And a polymerization inhibitor (hereinafter also referred to as “component (D)”), an organic solvent (hereinafter also referred to as “component (E)”), 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. Component (B) The composition of the present invention preferably contains a component (B) (that is, a polymerization initiator).
When the composition of the present invention is used as an active energy ray-curable composition, it preferably contains a photopolymerization initiator (hereinafter referred to as “component (B1)”) as the component (B). When used as a product, it is preferable to include a thermal polymerization initiator (hereinafter referred to as “component (B2)”) as 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) (ie, photopolymerization initiator) is not included. It may be cured by an electron beam.
When ultraviolet rays and visible rays are used as the active energy rays, the composition of the present invention preferably further contains a component (B1) from the viewpoint of ease of curing and cost.
When the composition of the present invention is used as an electron beam curable composition, it can be cured with an electron beam without containing the component (B), but if necessary to improve curability ( B) Component may be contained in a small amount.

Specific examples of the component (B1) include:
Benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl- 1-propan-1-one, oligo [2-hydroxy-2-methyl-1- [4-1- (methylvinyl) phenyl] propanone, 2-hydroxy-1- [4- [4- (2-hydroxy- 2-methylpropionyl) 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- ( - morpholin-4-yl-phenyl) - butan-1-one and 3,6-bis (2-methyl-2-morpholinophenyl propionyl) acetophenone compounds such as -9-n-octyl carbazole;
Benzoin compounds such as benzoin, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether;
Benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, methyl-2-benzophenone, 1- [4- (4-benzoylphenylsulfanyl) phenyl ] -2-Methyl-2- (4-methylphenylsulfonyl) propan-1-one, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone and 4-methoxy-4 ′ -Benzophenone compounds such as dimethylaminobenzophenone;
Such as bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide. Acyl phosphine oxide compounds; and thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 1-chloro-4-propylthioxanthone, 3- [3,4-dimethyl-9-oxo-9H-thioxanthone-2 Thioxanthone compounds such as -yl-oxy] -2-hydroxypropyl-N, N, N-trimethylammonium chloride and fluorothioxanthone,
Etc.
Examples of the compound other than the above include benzyl, ethyl (2,4,6-trimethylbenzoyl) phenyl phosphinate, methyl phenylglyoxylate, ethyl anthraquinone, phenanthrenequinone, and camphorquinone.

  Among these compounds, the component (B1) preferably contains an acyl phosphine oxide compound and does not contain a thioxanthone compound in that the composition has excellent curability and is excellent in low yellowing of the cured film.

When it is necessary to increase the film thickness of the cured film, for example, when the film thickness of the cured film needs to be 50 μm or more, an acylphosphine oxide compound, a thioxanthone compound, and It is preferable to use a plurality of compounds selected from α-aminoalkylphenone compounds in combination. Further, when an ultraviolet absorber or a pigment is used in combination, a plurality of compounds selected from acylphosphine oxide compounds, thioxanthone compounds and α-aminoalkylphenone compounds are used in combination for the purpose of improving the curability of the composition. It is preferable.
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.

The content ratio of the component (B1) is preferably 0.1 to 15 parts by weight, more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the total amount of the curable components. . (B) By making the ratio of a component into 0.1 weight part or more, the photocurability of a composition can be made favorable and it can be excellent in adhesiveness, and a cured film can be made into 15 weight part or less. The internal curability can be improved, and the adhesion to the substrate can be improved.
The content ratio of the thioxanthone compound is preferably 1 part by weight or less, more preferably 0.1 part by weight or less, and 0.01 part by weight or less with respect to 100 parts by weight of the total amount of the curable component. More preferably, it is still more preferably 0.001 part by weight or less, and particularly preferably 0.0001 part by weight or less.
In addition, a sclerosing | hardenable component is a component hardened | cured with an active energy ray or a heat | fever, and means (A) component, and when (C) component mentioned later is included, it means (A) and (C) component. .

2-1-2. (B2) Component When the composition of the present invention is used as a thermosetting composition, it preferably contains a component (B2) (that is, a 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-butyl peroxide , P-menthane hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, diisopropylbenzene hydroperoxide, t-butyltrimethylsilyl peroxide, 1,1,3,3 -Tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, t-butyl hydroperoxide and the like.
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, you may advance a redox reaction by combining an organic peroxide with a reducing agent.

As a content rate of (B2) component, it is preferable that it is 10 weight part or less with respect to 100 weight part of sclerosing | hardenable component total amount.
When the component (B2) is used alone, it may be cured according to a known means of radical thermal polymerization, and is used in combination with the component (B1), and is thermoset for the purpose of further improving the reaction rate after photocuring. May be performed.

2-2. Component (C) The component (C) is an ethylenically unsaturated compound other than the component (A). The curable composition may contain a component (C) for the purpose of imparting various physical properties to the cured film of the curable composition.
Examples of the ethylenically unsaturated group that component (C) has 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 ethylenically unsaturated compound” means a compound having one ethylenically unsaturated group, and “X functional ethylenically unsaturated compound” means X ethylenically unsaturated groups. The “polyfunctional ethylenically unsaturated compound” means a compound having two or more ethylenically unsaturated groups.

  Specific examples of monofunctional ethylenically unsaturated compounds include (meth) acrylic acid, Michael addition dimer of acrylic acid, ω-carboxy-polycaprolactone mono (meth) acrylate, monohydroxyethyl (meth) acrylate phthalate, 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, (meth) acrylate of alkylphenol alkylene oxide adduct, Hexyl (meth) acrylate, tert-butylcyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl acrylate, paracumylphenol alkylene oxide adduct (meta ) Acrylate, orthophenylphenol (meth) acrylate, (meth) acrylate of orthophenylphenol alkylene oxide adduct, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanemethylol (meth) acrylate, 2- Hydroxy-3-phenoxypropyl (meth) acrylate, N- (2- (meth) acryloxyethyl) hexahydrophthalimide, N- (2- (meth) a Acryloxyethyl) tetrahydrophthalimide, N, N-dimethylacrylamide, acryloylmorpholine, N-vinylpyrrolidone, N-vinylcaprolactam and the like.

  Specific examples of the bifunctional ethylenically unsaturated 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, the epoxy (meth) acrylate having at least one selected from the group consisting of a bisphenol skeleton, a polyether skeleton, and a polyalkylene skeleton, a polyester skeleton, a polyether skeleton, and a polycarbonate skeleton are selected. Urethane (meth) acrylate having at least one kind, polyester (meth) acrylate, and the like can also be used.

Examples of the trifunctional or higher functional ethylenically unsaturated compound include various compounds as long as the compound has three or more ethylenically unsaturated groups.
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 Polyol poly (meth) acrylates such as dipentaerythritol tri, tetra, penta or hexa (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) acrylates of isocyanuric acid alkylene oxide adducts; and compounds having three or more (meth) acryloyl groups and hydroxyl groups such as pentaerythritol tri (meth) acrylate and dipentaerythritol penta (meth) acrylate Urethane (meth) acrylate which is a reaction product with polyisocyanate,
Etc.
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.

The content ratio of the component (C) is preferably 0% to 50% by weight, more preferably 0.0001% to 50% by weight, and still more preferably 100 parts by weight of the total amount of the curable component. 0.0001 wt% to 20 wt%.
By making the content rate of (C) component 50 weight% or less, especially when (C) component is a polyfunctional ethylenically unsaturated compound, it can prevent that a cured film becomes weak.

2-3. (D) Component (D) A component is a polymerization inhibitor. The composition of the present invention may contain a component (D) for the purpose of improving the thermal stability of the composition.
Examples of the component (D) include organic polymerization inhibitors, inorganic polymerization inhibitors, and organic salt polymerization inhibitors.
Specific examples of the organic polymerization inhibitor include hydroquinone, tert-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl-4-methylphenol, 2,4,6-tri-tert-butylphenol and 4 Phenol compounds such as tert-butylcatechol; quinone compounds such as benzoquinone; phenothiazine; N-nitroso-N-phenylhydroxylamine ammonium; 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy- 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidine-1-oxyl and 4-methoxy-2,2,6,6-tetramethyl N-oxyl compounds such as piperidine-1-oxyl; and N Aromatic diamine compounds such as N′-di-sec-butyl-p-phenylenediamine, N, N′-diphenyl-1,4-phenylenediamine, 4,4′-dioctyldiphenylamine, 4,4′-dicumyldiphenylamine Etc.
Examples of the inorganic polymerization inhibitor include copper chloride, copper sulfate, and iron sulfate.
Examples of organic salt polymerization inhibitors include copper butyldithiocarbamate and N-nitroso-N-phenylhydroxylamine aluminum salt.
(D) The use of an aromatic diamine compound among the compounds as component (D) can improve the thermal stability without lowering the curability of the composition, and further, like an aliphatic diamine. (A) It is preferable because the Michael addition reaction is difficult to the (meth) acryloyl group in the component.
The content ratio of the component (D) may be appropriately set according to the purpose, and is preferably 0.0001 to 1 part by weight, more preferably 0.0005 to 100 parts by weight of the total amount of the curable component. Parts by weight to 0.1 parts by weight.
(D) By making the content rate of a component 0.0001 weight part or more, the thermal stability of a composition can be improved, On the other hand, sclerosis | hardenability is made favorable by being 0.1 weight part or less. can do.

2-4. (E) Component Most preferably, the composition of the present invention does not contain a solvent, but it contains a component (E) (that is, an organic solvent) for the purpose of improving the coating property to the substrate. Also good.

Specific examples of the component (E) 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 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.

  (E) It is preferable that the content rate of a component is 0 weight part-1,000 weight part with respect to 100 weight part of total amounts of a sclerosing | hardenable component, and is 0.0001 weight part-1,000 weight part. More preferred is 0.0001 to 500 parts by weight, and particularly preferred is 0.0001 to 300 parts by weight. When the content is in 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 coating varnish compositions.
Hereinafter, more preferable uses will be described.

3-1. Composition for Coating Varnish The composition of the present invention can be preferably used as a composition for coating varnish because the composition has low viscosity and excellent curability, and the cured film has flexibility and low yellowing.

The composition for coating varnish contains the component (A), but may further contain other components depending on the purpose.
Specifically, as other components, in addition to the components (B), (C), (D) and (E) described above, fluorescent whitening agents, antioxidants, ultraviolet absorbers, silane couplings Agents, surface modifiers, plasticizers and antifriction agents.
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) The composition for optical brightener coating varnish may contain an optical brightener for the purpose of preventing yellowing of the cured film.
Examples of the optical brightener include benzoxazal, pyrazoline, stilbene, triazine, thiazole, triazole, oxazole, thiophene, xanthone, and coumarin derivatives, such as 2,5-thiophenediyl (5-tert-butyl). -1,3-benzoxazole), 4,4′-bis (diphenyltriazinyl) stilbene, stilbenyl-naphthotriazole, 2,2 ′-(thiophendiyl) -bis (tert-butyl-benzoxazole), 2- (Stilbyl-4)-(naphth-1 ′, 2 ′, 4,5) -1,2,3-triazole-2 ″ -sulfonic acid phenyl ester, 7- (4′-chloro-6 ″ -diethylamino) -1 ′, 3 ′, 5′-triazin-4′-yl) -amino-3-phenyl-coumarin, 2,5-bis (6,6′- (Tert-butyl) -benzoxazol-2-yl) thiophene, 4,4′-bis (benzoxazol-2-yl) stilbene, dibenzoxazolylethylene, N-methyl-5-methoxynaphtholimide and the like Can be mentioned.
Among these compounds, 2,5-thiophenediyl (5-tert-butyl-1,3-benzoxazole) benzoxazole derivative, 2,2 ′-(thiophenediyl) -bis (tert-butyl-benzoxazole) The benzoxazole derivative of 2,5-thiophenediyl (5-tert-butyl-1,3-benzoxazole) is particularly preferably used in that excellent curability is obtained and the yellowing of the cured film is small. More preferred.

These fluorescent brighteners may be used alone or in combination of two or more.
The maximum absorption wavelength of the fluorescent brightening agent is preferably in the range of 360 nm to 400 nm, whereby the curability of the composition by the ultraviolet light emitting diode of 350 nm to 420 nm can be improved.

What is necessary is just to set suitably as a content rate of a fluorescent whitening agent according to the objective, 0.05 weight part-1 weight part is preferable with respect to 100 weight part of sclerosing | hardenable component total amount, More preferably, it is 0.1. Parts by weight to 0.5 parts by weight.
When the content of the fluorescent brightening agent is 0.05 parts by weight or more, curability can be improved, and when it is 1 part by weight or less, yellowing of the cured film can be prevented. it can.

2) The composition for antioxidant coating varnish may further contain an antioxidant for the purpose of improving durability such as heat resistance and weather resistance of the cured film.
Examples of the antioxidant include phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, and the like.
Examples of phenolic antioxidants include hindered phenols such as 2,6-di-t-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 antioxidant include phosphines such as trialkylphosphine and triarylphosphine, trialkyl phosphite, and triaryl phosphite. Examples of commercially available products of these derivatives include ADEKA STAB PEP-4C, PEP-8, PEP-24G, PEP-36, HP-10, 260, 522A, 329K, 1178, 1500, 135A, 3010 manufactured by Adeka Corporation. Etc.
Examples of sulfur-based antioxidants include thioether-based 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 a combination of a phenolic antioxidant and a phosphorus antioxidant, a combination of a phenolic antioxidant and a sulfur antioxidant, and the like.
What is necessary is just to set suitably as content rate of antioxidant according to the objective, 0.01 weight part-5 weight part are preferable with respect to 100 weight part of sclerosing | hardenable component total amount, More preferably, it is 0.1 weight. Part to 1 part by weight.
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.

3) The composition for ultraviolet absorber coating varnish may further contain an ultraviolet absorber for the purpose of improving the light resistance of the cured film.
Examples of the ultraviolet absorber include triazine ultraviolet absorbers such as TINUVIN400, TINUVIN405, TINUVIN460, and TINUVIN479 manufactured by BASF, and benzotriazole ultraviolet 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 weight part-5 weight part are preferable with respect to 100 weight part of sclerosing | hardenable component total amount, More preferably, it is 0.1 weight. Part to 1 part by weight. By setting the content ratio to 0.01 parts by weight or more, the light resistance of the cured film can be improved, and by setting it to 5 parts by weight or less, the curability of the composition is excellent. be able to.

4) The silane coupling agent coating varnish composition may further contain a silane coupling agent 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 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.

What is necessary is just to set suitably the content rate of a silane coupling agent according to the objective, 0.1 weight part-10 weight part are preferable with respect to 100 weight part of sclerosing | hardenable component total amount, More preferably, 1 weight part- 5 parts by weight.
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) The composition for surface modifier coating varnish further contains a surface modifier for the purpose of increasing the leveling property at the time of application, or for the purpose of enhancing the slipping property of the cured film and enhancing the scratch resistance. Also good.
Examples of the surface modifier include a surface conditioner, a surfactant, a leveling agent, an antifoaming agent, a slipperiness imparting agent, and an antifouling imparting agent, and a known surface modifier 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 weight part-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 cured film as it is the said range.

6) The plasticizer and antifriction agent coating varnish composition may further contain a plasticizer or antifriction agent.
Plasticizers and antifriction agents include: wax compounds such as paraffin wax, carnauba wax, beeswax, microcrystalline wax, polyethylene wax, oxidized polyethylene wax, polytetrafluoroethylene wax, amide wax, and the like;
Fatty acids in the range of about 8 to 18 carbon atoms, such as coconut oil fatty acid and soybean oil fatty acid,
Can be used as long as the object of the present invention is not impaired.

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 etc. are mentioned.
Specifically, when the composition is an active energy ray-curable composition, the composition is applied to a substrate to be applied by a normal coating method and then cured by irradiating active energy rays. Is mentioned.
The active energy ray irradiation method may be a general method known as a conventional curing method.
Hereinafter, the coating varnish composition, which is a preferred application of the composition of the present invention, will be described in detail.

4-1. Method of using composition for coating varnish The base material to which the composition of the present invention can be applied is not particularly limited. For example, polyester resin, acrylic resin, vinyl chloride resin, vinylidene chloride resin, polyvinyl alcohol, polyethylene, polypropylene, poly Acrylonitrile, ethylene vinyl acetate copolymer, ethylene vinyl alcohol copolymer, ethylene methacrylic acid copolymer, plastic film or sheet such as nylon, polylactic acid, polycarbonate, fine paper, coated paper, art paper, imitation paper, thin paper, Examples include paper such as cardboard, various synthetic papers, cellophane, aluminum foil, and other various base materials conventionally used as printing base materials.
Among these, a plastic film or sheet and a paper substrate are particularly preferable.

  What is necessary is just to set the film thickness of a cured film suitably according to the objective. The thickness of the cured film may be selected according to the use of the substrate to be used and the substrate having the produced cured film, but is preferably 1 μm to 100 μm, and more preferably 1 μm to 20 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 electrodeless lamp, and an ultraviolet light emitting diode (UV-LED).
Irradiation energy may be appropriately set according to the type of active energy ray and the composition of the composition, and varies depending on the thickness and illuminance of the coating film. For example, when using a high-pressure mercury lamp, irradiation in the UV-A region preferably 5mJ / cm ² ~2,000mJ / cm ² at an ^{energy, 10mJ / cm 2 ~1,000mJ / cm} 2 is more preferable. Further, when using a UV-LED, preferably has its emission peak wavelength is 350Nm～420nm, preferably 5mJ / cm ² ~2,000mJ / cm ² irradiation energy, 10mJ / cm ² ~1,000mJ / cm ² is more preferred.

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”.
In the following, “room temperature” means 23 ° C.

1. Production example
1) Comparative production example 1
To a 4 L flask with 2 L side tube equipped with a thermometer, stirrer and reflux tube, EO6 mol adduct of dipentaerythritol [Aoki Yushi Kogyo Co., Ltd., Brownon DPE-E6, hydroxyl value 643 mg KOH / g] 600 g, Add 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 also referred to as “MSA”), 1.9 g of cupric chloride and 520 g of toluene. It was.
While oxygen-containing gas was blown into the flask, the mixture was heated and stirred at a reaction liquid temperature of 85 ° C to 95 ° C. The water produced as the reaction progressed was taken out of the reaction system with a Dean-Stark tube, and the dehydration esterification reaction was carried out for 6 hours.
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 aqueous phase was removed. Next, 490 g of a 20% aqueous sodium hydroxide solution was added with stirring, the mixture was sufficiently stirred, and allowed to stand, and then the aqueous 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 aqueous phase was removed. The remaining organic phase was heated under reduced pressure to distill off toluene.
The obtained reaction product was a mixture containing pentaacrylate and hexaacrylate. Hereinafter, this mixture is referred to as “A′1 component”.

2) Comparative production example 2
In a flask similar to Comparative 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, 0.2 g of MEHQ (4-methoxyphenol) and 480 g of toluene were added.
While oxygen-containing gas was blown into the flask, the mixture was heated and stirred at a reaction liquid temperature of 82 ° C to 97 ° C. The water produced as the reaction progressed was taken out of the reaction system with a Dean-Stark tube, and the dehydration esterification reaction was carried out for 6 hours.
After completion of the reaction, 1050 g of toluene was added for dilution. Further, 250 g of distilled water was added, stirred and allowed to stand, and then the lower aqueous phase 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 aqueous phase was removed. Subsequently, 250 g of distilled water was added to the organic phase with stirring, and the mixture was stirred and allowed to stand, and then the aqueous phase was removed. The remaining organic phase was heated under reduced pressure to distill off toluene.
The obtained reaction product was a mixture containing triacrylate and tetraacrylate. Hereinafter, this mixture is referred to as “A′2 component”.

3) Comparative production example 3
In a flask similar to Comparative Production Example 1, 500 g of diglycerin EO 4 mol adduct [Kao Corporation, Emulgen G2E-4, 625 mg KOH / g], 518 g of acrylic acid, 41 g of paratoluenesulfonic acid monohydrate, second chloride 1.59 g of copper, 1.59 g of MEHQ and 550 g of toluene were added.
While oxygen-containing gas was blown into the flask, the mixture was heated and stirred under the conditions of a reaction solution temperature of 80 ° C. to 100 ° C. and a reaction system pressure of 400 Torr to 760 Torr. A dehydration esterification reaction was carried out for 7 hours while removing water generated as the reaction progressed out of the reaction 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 allowing to stand, the lower aqueous phase was removed. The remaining organic phase was heated under reduced pressure to distill off toluene.
The obtained reaction product was a mixture containing triacrylate and tetraacrylate. Hereinafter, this mixture is referred to as “A′3 component”.

4) Comparative production example 4
In a flask similar to Comparative Production Example 1, dipentaerythritol penta and hexaacrylate mixture (Mw 1,020, Mn 1,012, viscosity 7,280 mPa · s (25 ° C.), hydroxyl value 32 mgKOH / g, Aronix manufactured by Toagosei Co., Ltd. M-402, hereinafter referred to as “DPHA component”) 250 g (0.247 mol) is added, and 17.3 g of di-n-butylamine (0.134 mol, 0.54 mol with respect to 1 mol of DPHA component) is added. After adding at room temperature, reaction was performed at 50 degreeC 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, this mixture is referred to as “component (A′4)”.

5) Production Example 1 [Production of component (A)]
In Comparative Production Example 4, 250 g (0.220 mol) of A′1 component (Mn1,138) was used instead of DPHA component, and 11.9 g (0.092 mol, A′1 component 1) of di-n-butylamine was used. The reaction was performed in the same manner as in Comparative Production Example 4 except that 0.42 mol) was used.
The obtained reaction product was a mixture containing a Michael adduct of di-n-butylamine. Hereinafter, this mixture is referred to as “A1 component”.

6) Production Example 2 [Production of Component (A)]
In Comparative Production Example 4, 250 g (0.338 mol) of A′2 component (Mn739) was used instead of DPHA component, and 18.7 g (0.145 mol, 1 mol of A′2 component was added to 1 mol of A′2 component. The reaction was carried out in the same manner as in Comparative Production Example 4 except that 0.43 mol) was used.
The obtained reaction product was a mixture containing a Michael adduct of di-n-butylamine. Hereinafter, this mixture is referred to as “A2 component”.

7) Production Example 3 [Production of Component (A)]
In Comparative Production Example 4, 250 g (0.205 mol) of A′3 component (Mn1,218) was used instead of DPHA component, and 16.9 g (0.131 mol, A′3 component 1) of di-n-butylamine was used. The reaction was carried out in the same manner as in Comparative Production Example 4 except that 0.64 mol) was used.
The obtained reaction product was a mixture containing a Michael adduct of di-n-butylamine. Hereinafter, this mixture is referred to as “A3 component”.

8) Production Example 4 [Production of Component (A)]
In Comparative Production Example 4, 250 g (0.205 mol) of A′3 component (Mn1,218) was used instead of DPHA component, and 24.9 g (0.103 mol, A′3 component) of di-n-octylamine was used. The reaction was carried out according to the same method as in Comparative Production Example 4 except that 0.50 mol) was used.
The obtained reaction product was a mixture containing a Michael adduct of di-n-octylamine. Hereinafter, this mixture is referred to as “A4 component”.

9) Production Example 5 [Production of component (A)]
In Comparative Production Example 4, 250 g (0.205 mol) of A′3 component (Mn1,218) was used instead of DPHA component, and 14.1 g of diethanolamine (0.134 mol, based on 1 mol of A′3 component) The reaction was conducted in the same manner as in Comparative Production Example 4 except that 0.65 mol) was used.
The obtained reaction product was a mixture containing a Michael adduct of diethanolamine. Hereinafter, this mixture is referred to as “A5 component”.

2. Evaluation method of mixture According to the method described later, the acrylic equivalent, tertiary amine value, hydroxyl value, Mw and viscosity of the mixture obtained in Comparative Production Example 1 to Comparative Production Example 4 and Production Example 1 to Production Example 5 were determined. It was measured.
The results are shown in Table 1.

(1) Acrylic equivalent Measured based on JIS K 2605, bromine number of acrylate (mass of bromine added to unsaturated component in 100 g of sample (g)), mass of acrylate per mol of acryloyl group (g ) (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 and reacted at room temperature for 30 minutes, followed by titration with 0.01 N (mol / L) 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 mass (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 made 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 Co., Ltd. Two types of this column: Stylgel HR 4E THF (7.8 × 300 mm) manufactured by Waters Co., Ltd. and styrgel 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.

3. Active energy ray-curable composition
1) Production method The compounds shown in Table 2 below were stirred and mixed in the proportions shown in Table 2 to produce an active energy ray-curable composition.
Each composition obtained was used and evaluated below. The results are shown in Table 3.

The numbers in Table 2 mean the number of copies.
Moreover, "-" in Table 2 means not containing.
Moreover, the symbol in Table 2 means the following.
TPO: (2,4,6-trimethylbenzoyl) diphenylphosphine oxide, Irgacure TPO manufactured by BASF

2) Composition evaluation method
(1) LED curability Polyethylene terephthalate film [manufactured by Toyobo Co., Ltd., Cosmo Shine A4300 (thickness: 100 μm) so that each composition obtained has a film thickness of 5 μm. (Hereinafter referred to as “PET film”) with a bar coater and a UV-LED irradiation device (light emission wavelength: 365 nm, peak intensity: 800 mW / cm ² ) manufactured by Sentec Co., Ltd. equipped with a stage moving device. 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.

(2) Flexibility When the flexibility of the PET film with a cured film obtained in (1) is wound around a cylindrical core rod with the cured film facing outward according to a mandrel test (JIS K5600-5-1) The minimum diameter at which the cured film did not crack was determined. The results are shown in Table 3.
In Table 3, “<2” means that no crack occurs even when a PET film with a cured film is wound around a core rod having a diameter of 2 mm.

(3) Yellowing of yellowing of PET film with cured film obtained in yellowing (1) is measured using a high-speed integrating sphere type spectral transmittance measuring device [SPECTROTOPOMETER DOT-3C manufactured by Murakami Color Research Laboratory Co., Ltd.] It was evaluated by doing.

3) Evaluation results As is clear from the results of Examples 1 to 5, the composition of the present invention is excellent in LED curability in spite of low viscosity, and further excellent in flexibility and low yellowing of the cured film. there were.
On the other hand, the compositions of Comparative Examples 1 to 3 are compositions containing a compound having an ethylene oxide unit but no tertiary amino group, and are inferior in curability as compared with the compositions of the examples. It was a thing. Further, the composition of Comparative Example 4 is a composition containing a compound having a tertiary amino group but not having an ethylene oxide unit, and the flexibility of the cured film is significantly inferior to the composition of the example. Met.

4). Active energy ray-curable composition
1) Production method The compounds shown in Table 4 below were stirred and mixed in the proportions shown in Table 4 to produce an active energy ray-curable composition.
Each composition obtained was used and evaluated below. The results are shown in Table 5.

The numbers in Table 4 mean the number of copies.
Moreover, "-" in Table 4 means not containing.
The abbreviations in Table 4 mean the following, except for those defined above.
◆ (C) component M240: Polyethylene glycol (ethylene oxide unit repeat number 4) diacrylate, Aronix M-240 manufactured by Toagosei Co., Ltd.
MT3547: Glycerin triacrylate, Aronix MT-3547 manufactured by Toagosei Co., Ltd.
ACMO: acryloylmorpholine, ACMO manufactured by KJ Chemicals
BC230: 1,6-hexanediol diacrylate, Osaka Organic Chemical Industry Co., Ltd. Biscoat # 230
◆ (D) component BPDA: N, N′-di-sec-butyl-p-phenylenediamine (polymerization inhibitor), BASF Kerobit BPD
◆ Other ingredients・ Add: Polyether-modified silicone leveling agent, 8019 ADDITIVE manufactured by Toray Dow Corning Co., Ltd.
UVTEX: 2,5-thiophenediylbis (5-tert-butyl-1,3-benzoxazole) (fluorescent whitening agent), UVITEX OB manufactured by BASF

2) Composition evaluation method
(1) Viscosity Each composition obtained was measured by the same method as described above.

(2) Thermal stability test Each composition obtained was left in an aluminum block type heating apparatus at 90 ° C for 48 hours to conduct a thermal stability test.
The viscosity after the thermal stability test was measured by the same method as described above. Using the viscosity before the thermal stability test and the viscosity after the thermal stability test, the thickening rate (%) was calculated by the following formula (2).
Thickening rate (%) =
[([Viscosity after test]-[Viscosity before test]) / [Viscosity before test]] × 100 Formula (2)
Furthermore, based on the results of the thickening rate, the determination was made at the following three levels.
A: Thickening rate is 10% or less B: Thickening rate is more than 10% and less than 100% C: Thickening rate is 100% or more

(3) LED curability Each of the obtained compositions was cardboard (Makiruto, manufactured by Hokuetsu Kishu Paper Co., Ltd.) so that the film thickness was 5 μm. (Hereinafter referred to as “paper”) with a bar coater to prepare a test specimen.
Using a UV-LED irradiation device (Emission wavelength: 385 nm, peak intensity: 200 mW / cm ² ) manufactured by Sentech Co., Ltd. equipped with a stage moving device, the test specimen was irradiated with ultraviolet rays in an air atmosphere. The amount of integrated light was changed by changing the conveyance speed, and the minimum amount of integrated light until the surface tack was eliminated was obtained.

(4) Surface tension The surface tension of each composition obtained was measured by the Wilhelmy method using a platinum plate using an automatic surface tension meter CBVP-Z manufactured by Kyowa Interface Science Co., Ltd.

3) Evaluation results As is clear from the results of Examples 6 to 14, the composition of the present invention has excellent LED curability, excellent thermal stability, and low surface tension despite its low viscosity. there were.
Moreover, as a result of evaluating the bendability and low yellowing of the cured film in the same manner as described above for the compositions of Examples 6 to 14, the results were the same as described above, and these performances were excellent.

  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 varnish applications.

Claims (17)

A curable composition containing the following component (A).
Component (A): A mixture comprising a compound having three or more (meth) acryloyl groups, an alkylene oxide unit and a tertiary amino group, which is a Michael addition reaction product of the following mixture (a) and compound (b).
-Mixture (a): (meth) acrylate mixture containing compound (a1) having four or more (meth) acryloyl groups and alkylene oxide units-Compound (b): secondary amine   The curable composition according to claim 1, wherein the alkylene oxide unit is an ethylene oxide unit.   The (A) component is a mixture of a (meth) acryl equivalent of 90 g / eq to 250 g / eq and a tertiary amine value of 5 mgKOH / g to 60 mgKOH / g. A curable composition.   The curable composition according to any one of claims 1 to 3, wherein the component (A) is a mixture having a hydroxyl value of 1 mgKOH / g to 100 mgKOH / g.   The curable composition according to any one of claims 1 to 4, wherein the component (A) is a mixture having a viscosity at 25 ° C of 100 mPa · s to 1,000 mPa · s.   The component (A) is a mixture of reactants obtained by reacting the compound (b) at a ratio of 0.1 mol to 1.0 mol with respect to 1 mol of the mixture (a). Item 6. The curable composition according to any one of Items 5.   The compound (a1) having the four or more (meth) acryloyl groups and an alkylene oxide unit is obtained by adding penta (hexa) of a dipentaerythritol alkylene oxide adduct, tetra (hexa (meth) acrylate), tetra (pentaerythritol alkylene oxide adduct). The curable composition according to any one of claims 1 to 6, which is at least one selected from the group consisting of (meth) acrylates and tetra (meth) acrylates of diglycerin alkylene oxide adducts.   The curable composition according to any one of claims 1 to 7, wherein the compound (b) is an aliphatic monoamine.   Component (C): An ethylenically unsaturated group-containing compound other than the component (A) is further included, and the component (A) is added to 100% by weight of the total amount of the component (A) and the component (C). The curable composition according to any one of claims 1 to 8, comprising 50% by weight or more.   (D) component: The curable composition of any one of Claims 1-9 which further contains a polymerization inhibitor and the said (D) component is an aromatic diamine compound.   (B) Component: The curable composition of any one of Claims 1-10 which further contains a photoinitiator.   The curable composition according to claim 11, wherein the component (B) contains an acylphosphine oxide compound and does not contain a thioxanthone compound.   The curable composition according to any one of claims 1 to 12, which is an active energy ray curable composition.   The curable composition of Claim 13 which is an ultraviolet-ray (UV-LED) curable composition which uses a light emitting diode as a light source.   The curable composition according to claim 13 or 14, which is an active energy ray-curable composition for coating varnish. The following mixture (a) and compound (b) are stirred at room temperature or under heating to prepare a compound having three or more (meth) acryloyl groups, alkylene oxide units and tertiary amino groups, which are Michael addition reaction products. The manufacturing method of a curable composition including the process of manufacturing the mixture (A) containing.
-Mixture (a): (meth) acrylate mixture containing compound (a1) having four or more (meth) acryloyl groups and alkylene oxide units-Compound (b): secondary amine The following mixture (a) and compound (b) are stirred at room temperature or under heating to prepare a compound having three or more (meth) acryloyl groups, alkylene oxide units and tertiary amino groups, which are Michael addition reaction products. A step of producing a mixture (A), and a step of stirring and mixing the mixture (A) and the photopolymerization initiator (B),
The manufacturing method of an active energy ray hardening-type composition containing this.
-Mixture (a): (meth) acrylate mixture containing compound (a1) having four or more (meth) acryloyl groups and alkylene oxide units-Compound (b): secondary amine