JP6915333B2 - Active energy ray-curable composition - Google Patents

Description

The present invention relates to an active energy ray-curable composition containing an oxidase enzyme, an oxidase substrate and a photopolymerization initiator, and a cured product using the same.

It is known that a composition containing a reactive compound such as a (meth) acrylate compound easily undergoes radical polymerization by an active species generated from an initiator to form a cured product. These compositions are used in various fields and include, for example, printing inks, overcoat varnishes, paints, adhesives, photoresists, 3D shaped objects and the like.

In recent years, compositions containing reactive compounds are being used for dental applications, packaging applications for medical products and food products, etc., and it is desirable to use a material having low toxicity for the composition. Since the initiator in the composition that generates the active species that causes radical polymerization is a small molecule compound, those that are not involved in radical polymerization are left behind in the cured product. The initiator remaining in the cured product may have an odor due to exudation to the surface of the cured product, contamination of the content due to penetration into the content, and deterioration of quality. Therefore, among the materials contained in the composition, it is required to reduce the amount of the initiator used as much as possible or to use a material having low potential toxicity.

Redox initiators, thermal polymerization initiators, and photopolymerization initiators are known as types of initiators. Redox initiators function by redox reactions under mild conditions in combination with peroxides and reducing agents. Further, the thermal polymerization initiator or the photopolymerization initiator functions by heating or irradiating with active energy rays, respectively. The initiator is selected according to the application and purpose, but the redox initiator, which is relatively less toxic than the potentially highly toxic thermal polymerization initiator and photopolymerization initiator, is used in medical and dental applications. Has been done.

A typical example of a redox initiator is a combination of hydrogen peroxide and iron (II) sulfate, which is known as a Fenton reaction, and produces hydroxyl radical, which is an active species capable of initiating radical polymerization.

Further, hydrogen peroxide, which is a source of hydroxyl radicals, can be produced by utilizing an enzymatic reaction. Specifically, hydrogen peroxide is generated by a specific combination of an oxidase enzyme typified by glucose oxidase and an oxidase substrate typified by glucose.

That is, there is a report that a radical polymerization initiation reaction is possible by using an enzymatic reaction and a Fenton reaction in combination, and a methacrylate compound which is a reactive compound is radically polymerized (Non-Patent Document 1). Since the enzymatic reaction and the Fenton reaction use materials that are recognized as food additives, they have been proposed as a safer initiator than conventional redox initiators.

However, when the enzyme reaction and the Fenton reaction initiation system are used in combination with the composition containing the reactive compound, the radical polymerization reaction starts instantly when the reducing agent iron (II) sulfate is added, so that the usable applications are limited. The problem is that it is done. In addition, when iron (II) sulfate is used as the reducing agent, coloring derived from metal ions also becomes an issue.

In order to solve the problem of coloring, a starting system in which the reducing agent is changed from iron (II) sulfate to an organic reducing agent is being studied (Patent Document 1). By using ascorbic acid as an organic reducing agent, a colorless and transparent cured product can be obtained.

However, even if the reducing agent is changed to an organic reducing agent, the polymerization reaction of the composition containing the reactive compound gradually proceeds from the time when the reducing agent is added, so that the polymerization initiation reaction cannot be controlled. Further, since a bifunctional methacrylate compound is used as the reactive compound, there is a problem that high-speed curing cannot be performed.

At present, there is no report that it is applied to the application of active energy ray curing using only an enzymatic reaction, but a composition to which a photopolymerization initiator is further added has been proposed (Non-Patent Document 2). It has been proposed as a curing system that is not easily affected by oxygen, which is a polymerization inhibitor, due to an enzymatic reaction.

However, the reactive compound is not excellent in curability because the monofunctional acrylate compound, the bifunctional acrylate compound, and the photopolymerization initiator are limited to 2,2-dimethoxy-2-phenylacetophenone or benzophenone. .. Further, even when the oxidase enzyme and the oxidase substrate are used, there is no description that the amount of the photopolymerization initiator used can be reduced, and there is a concern that the unreacted photopolymerization initiator remains in the cured product.

Special Table 2006-514707

J. Polym. Sci. Part A, Polym. Chem. , 1991, Volume 29, p. 1217-1218 J. Polym. Sci. Part A, Polym. Chem. , 2013, Volume 51, p. 1685-1689

The present invention is an active energy ray-curable composition capable of high-speed curing without using a photoinitiator or in an extremely small amount by using a highly safe oxidase enzyme and an oxidase substrate, and photopolymerization using the same. It is an object of the present invention to provide a cured product in which an initiator does not remain.

（式中、Ｒ^３〜Ｒ^５は、それぞれ独立に、水素原子またはメチル基を表す。式中、ｂ、ｃおよびｄは、それぞれ独立に、２〜４０の整数を表す。）

（式中、Ｒ^６〜Ｒ^８は、それぞれ独立に、水素原子またはメチル基を表す。式中、ｅ、ｆおよびｇは、それぞれ独立に、２〜４０の整数を表す。）

（式中、Ｒ⁹〜Ｒ^１２は、それぞれ独立に、水素原子またはメチル基を表す。式中、ｈ、ｉ、ｊおよびｋは、それぞれ独立に、２〜４０の整数を表す。）

（式中、Ｒ^１３〜Ｒ^１６は、それぞれ独立に、水素原子またはメチル基を表す。式中、ｌ、ｍ、ｎおよびｏは、それぞれ独立に、２〜４０の整数を表す。）

（式中、Ｒ^１７〜Ｒ^２２は、それぞれ独立に、水素原子またはメチル基を表す。式中、ｐ、ｑ、ｒ、ｓ、ｔおよびｕは、それぞれ独立に、２〜４０の整数を表す。） The present inventors have reached the present invention as a result of repeated diligent studies to solve the above problems in consideration of them. That is, the present invention is characterized by containing a hydrophilic radical polymerizable compound (A), an oxidase enzyme (B), an oxidase substrate (C), water, and a radical polymerization initiator (D). , An active energy radical composition,
The hydrophilic radically polymerizable compound (A) is represented by the compound (a1) represented by the following general formula (1), the compound (a2) represented by the following general formula (2), and the following general formula (3). Is one or more selected from the group consisting of the compound (a3), the compound (a4) represented by the following general formula (4), and the compound (a5) represented by the following general formula (5). The present invention relates to an active energy ray-curable composition.

(In the formula, R ^{3 to} R ⁵ each independently represent a hydrogen atom or a methyl group. In the formula, b, c and d each independently represent an integer of 2 to 40.)

(In the formula, R ^{6 to} R ⁸ independently represent a hydrogen atom or a methyl group. In the formula, e, f and g each independently represent an integer of 2 to 40.)

(In the formula, R ^{9 to} R ¹² each independently represent a hydrogen atom or a methyl group. In the formula, h, i, j and k each independently represent an integer of 2 to 40.)

(In the formula, R ^{13 to} R ¹⁶ each independently represent a hydrogen atom or a methyl group. In the formula, l, m, n and o each independently represent an integer of 2 to 40.)

(In the formula, R ^{17 to} R ²² each independently represent a hydrogen atom or a methyl group. In the formula, p, q, r, s, t and u each independently represent an integer of 2 to 40. .)

The present invention relates to the above-described active energy ray-curable composition, wherein the oxidase enzyme (B) is glucose oxidase and the oxidase substrate (C) is glucose.

The oxidase enzyme (B) is contained in the range of 0.03 parts by mass to 0.4 parts by mass with respect to 100 parts by mass of the hydrophilic radically polymerizable compound (A), and the oxidase substrate (C) is 0.4 parts by mass. The present invention relates to the above-mentioned active energy ray-curable composition, which comprises 5.0 parts by mass to 5.0 parts by mass and further contains 1.5 parts by mass or less of the photopolymerization initiator (D).

The active energy according to the above description, wherein the photopolymerization initiator (D) is one or more selected from the group consisting of an acetophenone compound having a hydroxyl group, a dialkylamino group or a morphorn group, a phosphine compound and an oxime ester compound. The present invention relates to a linear curable composition.

The present invention relates to a cured product of the above-mentioned active energy ray-curable composition.

According to the present invention, an active energy ray-curable composition capable of high-speed curing with an extremely small amount of a photoinitiator using a highly safe oxidase enzyme and an oxidase substrate and a photopolymerization initiator using the same do not remain. A cured product could be provided.

Hereinafter, embodiments of the present invention will be described in detail.

First, the hydrophilic radical polymerizable compound (A) used in the active energy ray-curable composition of the present invention will be described.

（式中、Ｒ^３〜Ｒ^５は、それぞれ独立に、水素原子またはメチル基を表す。式中、ｂ、ｃおよびｄは、それぞれ独立に、２〜４０の整数を表す。） The hydrophilic radically polymerizable compound (A) is represented by the following general formulas (1) to (5), has one or more divalent ethylene oxide chains, and has a trifunctional or higher functional group having a polymerizable functional group. It is characterized by being a meta) acrylate compound.

(In the formula, R ^{3 to} R ⁵ each independently represent a hydrogen atom or a methyl group. In the formula, b, c and d each independently represent an integer of 2 to 40.)

^{R 3 to} R ⁵ in the general formula (1) independently represent a hydrogen atom or a methyl group, and a hydrogen atom is preferable.

（式中、Ｒ^６〜Ｒ^８は、それぞれ独立に、水素原子またはメチル基を表す。式中、ｅ、ｆおよびｇは、それぞれ独立に、２〜４０の整数を表す。） Each of b, c and d in the general formula (1) independently represents an integer of 2 to 40, and an integer of 3 to 20 is preferable.

(In the formula, R ^{6 to} R ⁸ independently represent a hydrogen atom or a methyl group. In the formula, e, f and g each independently represent an integer of 2 to 40.)

^{R 6 to} R ⁸ in the general formula (2) independently represent a hydrogen atom or a methyl group, and a hydrogen atom is preferable.

（式中、Ｒ⁹〜Ｒ^１２は、それぞれ独立に、水素原子またはメチル基を表す。式中、ｈ、ｉ、ｊおよびｋは、それぞれ独立に、２〜４０の整数を表す。） Each of e, f and g in the general formula (2) independently represents an integer of 2 to 40, and an integer of 3 to 20 is preferable.

(In the formula, R ^{9 to} R ¹² each independently represent a hydrogen atom or a methyl group. In the formula, h, i, j and k each independently represent an integer of 2 to 40.)

^{R 9 to} R ¹² in the general formula (3) independently represent a hydrogen atom or a methyl group, and a hydrogen atom is preferable.

（式中、Ｒ^１３〜Ｒ^１６は、それぞれ独立に、水素原子またはメチル基を表す。式中、ｌ、ｍ、ｎおよびｏは、それぞれ独立に、２〜４０の整数を表す。） H, i, j and k in the general formula (3) independently represent integers of 2 to 40, preferably an integer of 5 to 30, and more preferably an integer of 8 to 20.

(In the formula, R ^{13 to} R ¹⁶ each independently represent a hydrogen atom or a methyl group. In the formula, l, m, n and o each independently represent an integer of 2 to 40.)

^{R 13 to} R ¹⁶ in the general formula (4) independently represent a hydrogen atom or a methyl group, and a hydrogen atom is preferable.

（式中、Ｒ^１７〜Ｒ^２２は、それぞれ独立に、水素原子またはメチル基を表す。式中、ｐ、ｑ、ｒ、ｓ、ｔおよびｕは、それぞれ独立に、２〜４０の整数を表す。） L, m, n and o in the general formula (4) independently represent integers of 2 to 40, preferably an integer of 5 to 30, and more preferably an integer of 8 to 20.

(In the formula, R ^{17 to} R ²² each independently represent a hydrogen atom or a methyl group. In the formula, p, q, r, s, t and u each independently represent an integer of 2 to 40. .)

^{R 17 to} R ²⁰ in the general formula (5) independently represent a hydrogen atom or a methyl group, and a hydrogen atom is preferable.

P, q, r, s, t and u in the general formula (5) independently represent integers of 2 to 40, preferably an integer of 5 to 30, and more preferably an integer of 8 to 20.

Specific examples of the hydrophilic radically polymerizable compound (A) used in the active energy ray-curable composition of the present invention are shown below, but the structure of the hydrophilic radically polymerizable compound (A) used in the present invention is limited thereto. It is not something that is done.

Table 1

The hydrophilic radical polymerizable compound (A) used in the active energy ray-curable composition of the present invention is characterized by having one or more divalent ethylene oxide chains and a trifunctional or higher functional polymerizable functional group. It is a compound. By having this basic structure, it is excellent in hydrophilicity and curability.

These can be used alone or in combination of two or more, and can be arbitrarily mixed and used depending on the properties required for the cured product.

Further, the reason why the hydrophilic radically polymerizable compound (A) is preferable is that the reaction for obtaining the hydrophilic radically polymerizable compound (A) is easy.

The hydrophilic radically polymerizable compound (A) has ethylene oxide added to the hydroxyl groups of trihydric or higher alcohols, phenol derivatives, etc., which can be easily synthesized or obtained, and (meth) acryloyl is added to the hydroxyl groups at the ends thereof. Obtained by adding a group.

Examples of trihydric or higher polyhydric alcohols include, but are not limited to, trimethylolpropane, glycerin, pentaerythritol, ditrimethylolpropane, sorbitol, sucrose, quadrol, dipentaerythritol and the like.

Commercially available products corresponding to the hydrophilic radically polymerizable compound (A) used in the present invention include New Frontier TMP-15 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), SR-502, SR-9035, SR-415 (manufactured by Sertmer). ), NK Ester A-TMPT-9E, NK Ester AT-20E, NK Ester AT-30E, NK Ester A-BPE-4, NK Ester A-GLY-9E, NK Ester A-GLY-20E, NK Ester ATM- 35E, NK Ester ATM-120E, NK Ester A-DPH-48E, NK Ester A-DPH-96E, NK Ester A-PG5024E, NK Ester A-PG5054E, NK Ester TMPT-9EO, NK Ester GLY-9E, NK Ester GLY-20E, NK ester TM-35E, NK (manufactured by Shin-Nakamura Chemical Co., Ltd.) and the like can be mentioned, but the present invention is not limited thereto.

The oxidase enzyme (B) in the present invention will be described. The oxidase enzyme (B) used in the present invention is a kind of oxidoreductase enzyme. This is based on the recommendation (1992) of the International Union of Biochemistry and Molecular Biology (IUBMB) of the International Union of Biochemistry and Molecular Biology (1992). C. It is an enzyme classified into 1 and catalyzes an oxygen reduction reaction (that is, a redox reaction).

The oxidase enzyme (B) acts on oxygen as an electron acceptor to generate hydrogen peroxide, thereby catalyzing the oxidation of the oxidase substrate (C) described later. Such oxidases are classified by the enzyme classification E.I. C. 11.3, E.I. C. 1.2.3, E.I. C. 1.3.3, E.I. C. 1.4.3, E.I. C. 1.5.3, E.I. C. 1.7.3, E.I. C. 1.8.3, E.I. C. It is classified into 1.9.3. Examples of the oxidase enzyme (B) include glucose oxidase, sucrose oxidase, lactate oxidase, (S) -2-hydroxy acid-oxidase, choline oxidase, hexose oxidase, L- or D-amino acid oxidase, xylitol oxidase, xanthin oxidase, Glycolate oxidase, L-sorbose oxidase, alcohol oxidase, glonolactone oxidase and the like can be mentioned, but the present invention is not limited thereto. Examples of the oxidase enzyme (B) used in the present invention include glucose oxidase, lactate oxidase, hexose oxidase, glycolate oxidase, glonolactone oxidase, L-sorbose oxidase, (S) -2-hydroxyate oxidase, choline oxidase, and xanthine. Oxidase is preferred, and glucose oxidase is more preferred.

These can be used alone or in combination of two or more, and can be arbitrarily mixed and used depending on the properties required for the cured product, and the amount of these oxidase enzymes (B) used is hydrophilic radical polymerization. It is contained in the range of 0.001 to 2 parts by mass with respect to 100 parts by mass of the sex compound (A), and is preferably contained in the range of 0.01 to 0.5 parts by mass.

The oxidase substrate (C) in the present invention will be described. The oxidase substrate (C) that can be used in the present invention is an enzyme substrate corresponding to each of the above-mentioned oxidase enzymes (B). Examples of oxidase substrate (C) include β-D-glucose, sucrose, lactate, hexose, choline, glonolactone, (S) -2-hydroxy acid, D-galactose, D-mannose, maltose, cellobiose, L- or Examples include, but are not limited to, D-amino acids, xylitol, xanthin, α-hydroxy acids, L-sorbose, primary alcohols, and L-glono-1,4-lactone. As the oxidase substrate used in the present invention, β-D-glucose, lactate, hexose, choline, glonolactone, L-sorbose, (S) -2-hydroxy acid, and xanthine are preferable, and glucose is more preferable.

These can be used alone or in combination of two or more, but the oxidase substrate (C) corresponding to each oxidase enzyme (B) must be used. When these oxidase substrates (C) are used, the amount used is in the range of 1 to 200 parts by mass and in the range of 10 to 100 parts by mass with respect to 1 part by mass of the oxidase enzyme (B). Is preferable.

The active energy ray-curable composition of the present invention contains water in order to dissolve the above-mentioned oxidase enzyme (B) and oxidase substrate (C). As the water, ultrapure water, pure water, distilled water, deionized water, and tap water can be used. Water is contained in the range of 0.1 to 200 parts by mass with respect to 100 parts by mass of the total amount of the hydrophilic radical polymerizable compound (A) and the polymerizable compound (E) described later which can be used in combination, and is 1 to 100 parts. It is preferably contained in the range of parts by mass.

Further, the active energy ray-curable composition of the present invention may contain various buffers. The buffer is used for the purpose of adjusting the pH of the active energy ray composition. When glucose oxidase is used as the oxidase enzyme (B), it may be a substance having a buffering ability and a pH that can be set to 5.0 to 9.0. Specific examples include phosphates; organic acids such as fumaric acid, maleic acid, glutaric acid, phthalic acid, and citric acid; and Good's buffers such as MOPS, PIPES, HEPES, MES, and TES. It is not limited.

The photopolymerization initiator (D) in the present invention is a compound that generates radicals that are active species by irradiation with various energies, especially active energy rays such as ultraviolet rays, and the generated radicals promptly start a radical polymerization reaction. Can be cured and cured.

As the photopolymerization initiator (D) used in the present invention, a conventionally known photopolymerization initiator can be used. Specifically, for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzylmethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl). ) Ketone, 1-Hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) ) Butane, oligo {2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone}, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) propionyl) ) Acetophenone compounds such as benzyl] phenyl} -2-methylpropan-1-one; benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; 2,4,6-trimethylbenzoyl- Hosphin compounds such as diphenyl-phosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; other phenylglycoxymethyl esters and the like can be mentioned.

More specifically, Irgacure 184, Irgacure 1173, Irgacure 500, Irgacure 1000, Irgacure 2959, Irgacure 907, Irgacure 369, Irgacure 379, Irgacure 1700, Irgacure 149, Irgacure 1800, Irgacure 1850, Irgacure 819, Irgacure 784, Irgacure 261, Irgacure OXE-01 (CGI124), CGI242 (manufactured by BASF), Adecaoptomer N1414, Adecaoptomer N1717, EsacureONE (manufactured by Lamberti), Esac (Manufactured by Lamberti), Triazine Derivatives described in JP-A-59-1281, JP-B-61-9621 and JP-A-60-60104, JP-A-59-1504 and JP-A-61-243807. Organic peroxides described in Japanese Patent Publication No. 43-23684, Japanese Patent Publication No. 44-6413, Japanese Patent Publication No. 47-1604, and Diazonium Compound Publication No. USP No. 3567453, USP No. 2848328. , USP No. 2852379 and USP No. 2940853, Organic Azide Compounds, Japanese Patent Publication No. 36-22062, Japanese Patent Publication No. 37-13109, Japanese Patent Publication No. 38-18015, and Japanese Patent Publication No. 45-9610. Ortho-quinone diazides described in Japanese Patent Publication No. 55-39162, Japanese Patent Application Laid-Open No. 59-140203, and iodonium described in "MACROMOLECULES", Vol. 10, p. 1307 (1977). Various onium compounds including compounds, azo compounds described in JP-A-59-142205, JP-A-1-54440, European Patent No. 109851, European Patent No. 126712, "Journal of "Imaging Science (J.IMAG.SCI.)", Vol. 30, p. 174 (1986), Metal Allen Complex, Titanosens, JP-A-61-151197, "Coordination Chemistry Review". (COORDINATION CHEMISTRY REVIEW) ”, Vol. 84, pp. 85-277 (1988), and a transition metal containing a transition metal such as ruthenium described in JP-A-2-182701. Complex, aluminate complex described in JP-A-3-209477, borate compound described in JP-A-2-157760, JP-A-55-127550 and JP-A-60-202437, 2. 4,5-Triarylimidazole dimer, carbon tetrabromide, organic halogen compounds described in JP-A-59-107344, sulfonium complexes or oxosulfonium complexes described in JP-A-5-255347, JP-A54. -99185, JP-A-63-264560, and acetophenone compounds described in JP-A-10-299777, JP-A-2001-264530, JP-A-2001-261716, JP-A-2000-80068, JP-A-2000-80068 2001-233842, JP-A-2004-534977, JP-A-2006-342166, JP-A-2008-09470, JP-A-2009-40762, JP-A-2010-15025, JP-A-2010-189279, JP-A-2010-189280. , Special Table 2010-526846, Special Table 2010-527338, Special Table 2010-527339, USP3558309 (1971), USP4202697 (1980), and oxime ester compounds described in JP-A-61-24558. And so on.

Among these, an acetophenone compound, a phosphine compound, and an oxime ester compound are preferably used.

As the acetophenone compound of the photopolymerization initiator (D) used in the present invention, a compound having a hydroxyl group, a dialkylamino group or a morphorn group is preferable.

The acetophenone compound having a hydroxyl group is a compound having one or more hydroxyl groups in the molecule, and specifically, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4- (2-hydroxyethoxy). ) Phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenyl ketone, oligo {2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone} 2-hydroxy- Examples thereof include 1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one.

A specific example of an acetophenone compound having a dialkylamino group is a compound having one or more dialkylamino groups in the molecule, and a specific example is 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl). ) Butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone and the like.

Specific examples of the acetophenone compound having a morphorno group are compounds having one or more morphorno groups in the molecule, and specific examples are 2-methyl-1- [4- (methylthio) phenyl] -2-. Examples thereof include morpholinopropane-1-one.

These can be used alone or in combination of two or more, and can be arbitrarily mixed and used depending on the properties required for the cured product. The amount used when these photopolymerization initiators (D) are used is , Is contained in the range of 0.01 to 100 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable compound (E) described later that can be used in combination with the hydrophilic radical polymerizable compound (A), and is 0.1 to 20 parts by mass. It is preferable that it is contained in the range of.

Further, in the active energy ray-curable composition of the present invention, the polymerizable compound (E) may be used in combination depending on the properties required for the cured product. The polymerizable compound (E) is a compound having at least one radically polymerizable skeleton in the molecule and not contained in the hydrophilic radically polymerizable compound (A). In addition, all of these have chemical forms of liquid or solid monomers, oligomers or polymers at normal temperature and pressure.

Examples of such a polymerizable compound (E) include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid and maleic acid, and salts, esters, acid amides and acid anhydrides thereof. Furthermore, acrylates such as urethane acrylates, acrylonitrile, styrene derivatives, various unsaturated polyesters, unsaturated polyethers, unsaturated polyamides, unsaturated polyurethanes, methacrylates, allylates, acid amides, styrenes, etc. , Other vinyl compounds, radically polymerizable cyclic compounds, oligomers, prepolymers and the like, but the present invention is not limited thereto. Specific examples of the polymerizable compound (E) in the present invention will be given below.

Among the polymerizable compounds (E), examples of the (meth) acrylates include the following compounds. In addition, "(meth) acrylate" means "acrylate" or "methacrylate", and "(meth) acrylic acid" means "acrylic acid" or "methacrylic acid".

Examples of monofunctional alkyl (meth) acrylates:
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Octyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl ( Meta) acrylate, benzyl (meth) acrylate.

Examples of monofunctional hydroxy (meth) acrylates:
2-Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxy-3-3 Allyloxypropyl (meth) acrylate, (meth) acrylate-2-hydroxy-3-allyloxypropyl, 2- (meth) acryloyloxyethyl-2-hydroxypropylphthalate.

Examples of monofunctional halogen-containing (meth) acrylates:
2,2,2-Trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1H-hexafluoroisopropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl ( Meta) acrylate, 1H, 1H, 2H, 2H-heptadecafluorodecyl (meth) acrylate, 2,6-dibromo-4-butylphenyl (meth) acrylate, 2,4,6-tribromophenoxyethyl (meth) acrylate , 2,4,6-Tribromophenol 3EO (ethylene oxide) -added (meth) acrylate.

Examples of monofunctional ether-containing (meth) acrylates:
2-methoxyethyl (meth) acrylate, 1,3-butylene glycol methyl ether (meth) acrylate, butoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypolyethylene glycol # 400 (meth) acrylate, methoxydi Propylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, ethylcarbitol (meth) acrylate, 2-ethylhexylcarbitol (meth) acrylate, tetrahydro Flufuryl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, cresylpolyethylene glycol (meth) acrylate, (meth) acrylate-2- (vinyloxyethoxy) ) Ethyl, p-nonylphenoxyethyl (meth) acrylate, p-nonylphenoxypolyethylene glycol (meth) acrylate, glycidyl (meth) acrylate.

Examples of monofunctional carboxyl-containing (meth) acrylates:
β-carboxyethyl (meth) acrylate, monoacryloyloxyethyl succinate ester, ω-carboxypolycaprolactone mono (meth) acrylate, 2- (meth) acryloyloxyethyl hydrogenphthalate, 2- (meth) acryloyloxypropylhydrogenphthalate, 2- (Meta) acryloyloxypropyl hexahydrohydrogenphthalate, 2- (meth) acryloyloxypropyltetrahydrohydrogenphthalate.

Examples of other monofunctional (meth) acrylates:
N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, morpholinoethyl (meth) acrylate, trimethylsiloxyethyl (meth) acrylate, diphenyl-2- (meth) acryloyloxyethyl phosphate , 2- (Meta) acryloyloxyethyl acid phosphate, caprolactone-modified -2- (meth) acryloyloxyethyl acid phosphate, 2-hydroxy-1- (meth) acryloyl-3-methacryloxypropane.

Examples of bifunctional (meth) acrylates:
1,4-Butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene Glycoldi (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polypropylene glycol # 400 di (meth) acrylate, polypropylene glycol # 700 di ( Meta) acrylate, neopentyl glycol di (meth) acrylate, neopentyl glycol PO (propylene oxide) modified di (meth) acrylate, hydroxypivalate neopentyl glycol ester di (meth) acrylate, hydroxypivalate neopentyl glycol ester caprolactone Additives Di (meth) acrylate, 1,6-hexanediol bis (2-hydroxy-3- (meth) acryloyloxypropyl) ether, bis (4- (meth) acryloxypolyethoxyphenyl) propane, 1,9- Nonanediol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol di (meth) acrylate monostearate, pentaerythritol di (meth) acrylate monobenzoate, bisphenol A di (meth) acrylate, EO-modified bisphenol A di. (Meta) Acrylate, PO Modified Bisphenol A Di (Meta) Acrylate, Hydrogenated Bisphenol A Di (Meta) Acrylate, EO Modified Bisphenol A Di (Meta) Acrylate, PO Modified Bisphenol A Di (Meta) Acrylate, Bisphenol F di (meth) acrylate, EO modified bisphenol F di (meth) acrylate, PO modified bisphenol F di (meth) acrylate, EO modified tetrabromobisphenol A di (meth) acrylate, tricyclodecanedimethylol di (meth) acrylate, EO-modified di (meth) acrylate of isocyanuric acid, 2-hydroxy-1,3-di (meth) acryloxipropane.

Examples of (meth) acrylic acid esters containing vinyl ether groups:
-2-Vinyloxyethyl (meth) acrylate, -3-vinyloxypropyl (meth) acrylate, -1-methyl-2-vinyloxyethyl (meth) acrylate, -2-vinyloxypropyl (meth) acrylate, (meth) ) -4-Vinyloxybutyl acrylate, -1-methyl-3-vinyloxypropyl (meth) acrylate, -1-vinyloxymethylpropyl (meth) acrylate, -2-methyl-3-bini (meth) acrylate Propylpropyl, (meth) acrylate-3-methyl-3-vinyloxypropyl, (meth) acrylate-1,1-dimethyl-2-vinyloxyethyl, (meth) acrylate-3-vinyloxybutyl, (meth) acrylic acid -1-Methyl-2-vinyloxypropyl, (meth) acrylate-2-vinyloxybutyl, (meth) acrylate-4-vinyloxycyclohexyl, (meth) acrylate-5-vinyloxypentyl, (meth) acrylic acid -6-Vinyloxyhexyl, (meth) acrylate-4-vinyloxymethylcyclohexylmethyl, (meth) acrylate-3-vinyloxymethylcyclohexylmethyl, (meth) acrylate-2-vinyloxymethylcyclohexylmethyl, ( Meta) acrylate-p-vinyloxymethylphenylmethyl, (meth) acrylate-m-vinyloxymethylphenylmethyl, (meth) acrylate-o-vinyloxymethylphenylmethyl, (meth) acrylate-2-( Vinyloxyisopropoxy) ethyl, (meth) acrylate-2- (vinyloxyethoxy) propyl, (meth) acrylate-2- (vinyloxyethoxy) isopropyl, (meth) acrylate-2- (vinyloxyisopropoxy) ) Propyl, -2- (vinyloxyisopropoxy) isopropyl (meth) acrylate, -2- (vinyloxyethoxyethoxy) ethyl (meth) acrylate, -2- (vinyloxyethoxyisopropoxy) (meth) acrylate Ethyl, -2- (vinyloxyisopropoxyethoxy) ethyl (meth) acrylate, -2- (vinyloxyisopropoxyisopropoxy) ethyl (meth) acrylate.

Examples of trifunctional (meth) acrylates:
Glycerin PO-modified tri (meth) acrylate, trimethylolpropane PO-modified tri (meth) acrylate, trimethylolpropane PO-modified tri (meth) acrylate, isocyanuric acid EO-modified tri (meth) acrylate, isocyanuric acid EO-modified ε-caprolactone-modified tri (meth) ) Acrylate, 1,3,5-tri (meth) acryloylhexahydro-s-triazine, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate tripropionate.

Examples of tetrafunctional or higher (meth) acrylates:
Pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate monopropionate, dipentaerythritol hexa (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, oligoester Tetra (meth) acrylate, tris (acryloyloxy) phosphate.

Among the polymerizable compounds (E), examples of the allylate include the following compounds.

Allyl glycidyl ether, diallyl phthalate, triallyl trimerite, isocyanuric acid trialilate.

Among the polymerizable compounds (E), examples of the acid amides include the following compounds.

Acrylamide, N-methylolacrylamide, diacetoneacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-isopropylacrylamide, acryloylmorpholin, methacrylamide, N-methylolmethacrylamide, diacetonemethacrylamide, N, N -Dimethylmethacrylamide, N, N-diethylmethacrylamide, N-isopropylmethacrylamide, methacryloylmorpholin.

Among the polymerizable compounds (E), examples of the styrenes include the following compounds.

Styrene, p-hydroxystyrene, p-chlorostyrene, p-bromostyrene, p-methylstyrene, p-methoxystyrene, pt-butoxystyrene, pt-butoxycarbonylstyrene, pt-butoxycarbonyloxystyrene , 2,4-Diphenyl-4-methyl-1-pentene.

Among the polymerizable compounds (E), examples of other vinyl compounds include the following compounds.

Vinyl acetate, monochloroacetate, vinyl benzoate, vinyl pivalate, vinyl butyrate, vinyl laurate, divinyl adipic acid, vinyl methacrylate, vinyl crotonic acid, vinyl 2-ethylhexanoate, N-vinylcarbazole, etc.

Among the polymerizable compounds (E), examples of the monofunctional N-vinyl compounds include the following compounds.

N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylformamide, N-vinylacetamide.

The above-mentioned polymerizable compound (E) can be easily obtained as a commercially available product of the following manufacturers. For example, "Light Acrylate", "Light Ester", "Epoxy Ester", "Urethane Acrylate" and "Highly Functional Monomer" series manufactured by Kyoei Co., Ltd., and "Shin Nakamura Chemical Co., Ltd." "NK ester" and "NK oligo" series, "Funkril" series manufactured by Hitachi Kasei Kogyo Co., Ltd., "Aronix M" series manufactured by Toa Synthetic Chemical Co., Ltd., manufactured by Daihachi Kagaku Kogyo Co., Ltd. "Functional Monomer" Series, "Special Acrylic Monomer" Series manufactured by Osaka Organic Chemical Industry Co., Ltd., "Acrylate" and "Diabeam Oligomer" Series manufactured by Mitsubishi Rayon Co., Ltd., Nippon Kayaku Co., Ltd. "Kayarad" and "Kayamer" series manufactured by Nippon Catalyst Co., Ltd., "(Meta) acrylic acid / methacrylic acid ester monomer" series manufactured by Nippon Catalyst Co., Ltd., "NICHIGO-UV purple light urethane" manufactured by Nippon Synthetic Chemical Industry Co., Ltd. Examples include the "acrylate ligomer" series, the "carboxylic acid vinyl ester monomer" series manufactured by Shinetsu Vinyl Acetate Co., Ltd., and the "functional monomer" series manufactured by Kojin Co., Ltd.

Further, the following radically polymerizable cyclic compounds such as vinylcyclopropanes and vinyloxylanes, and cyclic ketenacetals are also mentioned as the polymerizable compound (E).

Examples of the three-membered ring compounds are described in, for example, Journal of Polymer Science Polymer Chemistry Edition (J. Polym. Sci. Polymer. Chem. Ed.), Vol. 17, p. 3169 (1979). Vinyl Cyclopropanes, 1-Phenyl-2-vinyl Cyclopropanes, 1-phenyl-2-vinylcyclopropanes, described in Macromol. Chem. Rapid Commun., Vol. 5, p. 63 (1984), Journal of the Journal of. Polymer Science Polymer Chemistry Edition (J. Polym. Sci. Polymer. Chem. Ed.), Vol. 23, p. 1931 (1985) and Journal of Polymer Science Polymer Letter Edition (J). Polymer. Sci. Polymer. Lett. Ed.), Vol. 21, p. 4331 (1983), 2-phenyl-3-vinyloxylans, Proceedings of the 50th Annual Meeting of the Chemical Society of Japan, p. 1564 ( 1985) The 2,3-divinyloxylanes described.

Examples of cyclic keten acetals include, for example, Journal of Polymer Science Polymer Chemistry Edition (J. Polym. Sci. Polymer. Chem. Ed.), Vol. 20, p. 3021 (1982) and Journal. 2-Methylene-1,3-dioxepan, Polymer, described in J. Polym. Sci. Polym. Lett. Ed., Vol. 21, p. 373 (1983). Pre-Preprints, Vol. 34, p. 152 (1985), Dioxorans, Journal of Polymer Science Polymer Letter Edition (J. Polym. Sci. Polymer. Lett. Ed.) , Vol. 20, p. 361 (1982), Macropolymer. Chem., Vol. 183, p. 1913 (1982) and Macropolymer. Chem., Vol. 186, 1543. 2-Methylene-4-phenyl-1,3-dioxepan, described on page (1985), Macropolymers, Vol. 15, p. 17,11 (1982), 4,7-dimethyl-2-methylene. -1,3-Dioxepan, Polymer. Preprints, Vol. 34, p. 154 (1985), 5,6-benzo-2-methylene-1,3-diosepan.

Further, as the polymerizable compound (E), those described in the following documents can also be mentioned. For example, Shinzo Yamashita et al., "Crosslinking Agent Handbook" (1981, Taiseisha) and Kiyomi Kato, "UV / EB Curing Handbook (Raw Materials)", (1985, Polymer Publishing Association), Radtech Research Kai, Kiyoshi Akamatsu, "New Practical Technology for Photosensitive Resins", (1987, CMC), Tsuyoshi Endo, "Precision of Thermosetting Polymers", (1986, CMC), Takiyama Examples include "Polyester Resin Handbook" by Eiichiro, (1988, Nikkan Kogyo Shimbun), edited by Radtech Study Group, "Application and Market of UV / EB Curing Technology", (2002, CMC).

As the polymerizable compound (E) used in the present invention, those called oligomers and prepolymers can be used in addition to the above-mentioned monomers. Specifically, Daicel UCB's "Ebecry" series, "KRM" series, "KRM" series, "IRR" series, "RDX" series, Sartmer's "CN" series, BASF's "Laromer" series, Examples include the "Photomer" series manufactured by Cognis, the "Art Resin" series manufactured by Negami Kogyo, the "Shikou" series manufactured by Nippon Synthetic Chemistry, and the "Kayarad" series manufactured by Nippon Kayaku.

As the polymerizable compound (E) in the present invention, only one type may be used, or two or more types may be mixed in an arbitrary ratio in order to improve the desired properties.

Further, the active energy ray-curable composition of the present invention has sufficient sensitivity without using a sensitizer, but for the purpose of further improving the sensitivity and improving the film characteristics after curing, a sensitizer is used. It can be used together.

Examples of the sensitizer that can be mixed with the active energy ray-curable composition of the present invention and used in combination include unsaturated ketone derivatives such as benzophenone derivatives, chalcone derivatives and dibenzalacetone, and benzyl and camphorquinone. Representative 1,2-diketone derivatives, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives , Cyanine derivatives, merocyanine derivatives, polymethine pigments such as oxonoll derivatives, aclysine derivatives, azine derivatives, thiadin derivatives, oxazine derivatives, indolin derivatives, azulene derivatives, azurenium derivatives, squarylium derivatives , Porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives , Naphthalocyanine derivatives, Subphthalocyanine derivatives, Pyrylium derivatives, Thiopyrylium derivatives, Tetraphyllin derivatives, Anurene derivatives, Spiropyran derivatives, Spiroxazine derivatives, Thiospyropyran derivatives, Metal arene complexes, Organic ruthenium Complexes are mentioned, and other specific examples include Nobu Okawara et al., "Dye Handbook" (1986, Kodansha), Nobu Okawara et al., "Chemistry of Functional Dyes" (1981, CMC), Ikemori. Dyes and sensitizers described in "Special Functional Materials" (1986, CMC), edited by Chuzaburo et al. Examples thereof include dyes and sensitizers that exhibit absorption, and two or more of these may be used in any ratio as required.
Among the above-mentioned sensitizers, the thioxanthone derivatives include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, and 1-chloro-4-propoxy. Examples thereof include thioxanthone, and examples of benzophenones include benzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4,4'-dimethylbenzophenone, 4,4'-dimethoxybenzophenone, and 4,4'-. Examples of coumarins include bis (diethylamino) benzophenone, and examples of coumarins include coumarin 1, coumarin 338, and coumarin 102. Examples of coumarins include 3,3'-carbonylbis (7-diethylaminocoumarin). Etc., but are not limited to these.

The amount of the sensitizer used in the present invention is preferably in the range of 0.01 to 100 parts by mass, more preferably in the range of 0.1 to 50 parts by mass with respect to 100 parts by mass of the photopolymerization initiator (D). ..

Further, in the active energy ray-curable composition of the present invention, a polymerization inhibitor can be added for the purpose of preventing polymerization during storage.

Specific examples of the polymerization inhibitor that can be added to the active energy ray-curable composition of the present invention include p-methoxyphenol, hydroquinone, alkyl-substituted hydroquinone, catechol, tert-butylcatechol, phenothiazine, and the like. The polymerization inhibitor is preferably added in the range of 0.001 to 5 parts by mass with respect to 100 parts by mass of the photopolymerization initiator (D).

A surface conditioner can be added to the active energy ray-curable composition of the present invention for the purpose of improving the adhesion to the substrate. Specific examples of the surface conditioner include "BYK-300, 302, 306, 307, 310, 315, 320, 322, 323, 325, 330, 331, 333, 337, 340, 344, 370, 375" manufactured by Big Chemie. 377, 350, 352, 354, 355, 356, 358N, 361N, 357, 390, 392, UV3500, UV3510, UV3570 "Tegokemy's" Tegorad-2100, 2200, 2250, 2500, 2700 "and the like. These surface conditioners may be used alone or in combination of two or more as required.

The surface conditioner that may be used in combination in the present invention is used in the range of 0 to 5.0% by mass with respect to the active energy ray-curable composition.

The active energy ray-curable composition of the present invention further has an oxygen removing agent such as a dye, an organic and inorganic pigment, a pigment dispersant, a phosphine, a phosphonate, and a phosphite, a reducing agent, an antifog agent, and an antifading agent, depending on the purpose. , Anti-halation agent, fluorescent whitening agent, surfactant, colorant, bulking agent, plasticizer, flame retardant, antioxidant, pigment precursor, ultraviolet absorber, foaming agent, antifungal agent, antistatic agent, magnetic Dispersants such as body and resin type dispersants Silane coupling agents, storage stabilizers such as quaternary ammonium chloride, plasticizers, surface tension modifiers, slipping agents, antiblocking agents, light stabilizers, leveling agents, erasing agents It may be mixed with a foaming agent, an infrared absorber, a surfactant, a thixotropy agent, an antibacterial agent, fine particles such as silica, other additives imparting various properties, a diluting solvent and the like.

The active energy ray-curable composition of the present invention can be polymerized by applying energy by heat or active energy rays such as ultraviolet rays, visible rays, near infrared rays, and electron beams during a polymerization reaction to obtain a desired polymer. Although it is possible, as a light source for applying energy, irradiation of active energy rays by a light source having a main wavelength of light emission in a wavelength region of 250 nm to 450 nm is preferable. Examples of light sources having a main emission wavelength in the 250 nm to 450 nm wavelength range are ultra-high pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, mercury xenon lamps, metal halide lamps, high power metal halide lamps, xenon lamps, pulsed emission xenon. Lamps, heavy hydrogen lamps, fluorescent lamps, Nd-YAG triple wave lasers, He-Cd lasers, nitrogen lasers, Xe-Cl xenon lasers, Xe-F xenon lasers, semiconductor-pumped solid-state lasers, emission wavelengths at 365 nm, 375 nm, and 385 nm. Examples thereof include various light sources such as an LED lamp light source having the light source. The definition of active energy rays such as ultraviolet rays, visible light, and near infrared rays in the present specification is based on "Iwanami Physics and Chemistry Dictionary 4th Edition" (1987, Iwanami) edited by Ryogo Kubo et al.

Therefore, the active energy ray-curable composition of the present invention can be printed or applied on various substrates, and the substrate on which the active energy ray-curable composition of the present invention is printed or applied is glass. , Plastic, metal and paper can be appropriately selected from the group. Furthermore, a composite base material composed of a plurality of base materials can also be selected. These base materials may have a flat shape such as a plate, a film, or paper, or may have a three-dimensional shape. As the plastic film, a transparent film is preferable.

Examples of printing and coating methods include an inkjet method, a blade coating method, a gravure coating method, a gravure offset coating method, a bar coating method, a roll coating method, a knife coating method, an air knife coating method, a comma coating method, and a U comma coating method. Examples thereof include an AKKU coating method, a smoothing coating method, a microgravure coating method, a reverse roll coating method, a 4- to 5-roll coating method, a dip coating method, a curtain coating method, a slide coating method, a die coating method, and a spray coating method.

Examples of the base material of the plastic include transparent polymers such as polyester-based polymers, cellulosic-based polymers, polycarbonate-based polymers, and polyacrylic-based polymers. Examples of the polyester-based polymer include polyethylene terephthalate (PET) and polyethylene naphthalate. Examples of the cellulosic polymer include diacetyl cellulose and triacetyl cellulose (TAC). Examples of the polyacrylic polymer include polymethyl methacrylate and the like.

Examples of the base material of the plastic include transparent polymers such as polystyrene-based polymers, polyolefin-based polymers, polyvinyl chloride-based polymers, and polyamide-based polymers. Examples of the polystyrene-based polymer include polystyrene, an acrylonitrile / styrene copolymer polymer, and the like. Examples of the polyolefin-based polymer include polyethylene, polypropylene, a polyolefin polymer having a cyclic or norbornene structure, and an ethylene / propylene copolymer polymer. Examples of the polyamide polymer include nylon and aromatic polyamide polymers.

Furthermore, polyimide-based polymers, polysulfone-based polymers, polyether sulfone-based polymers, polyether ketone-based polymers, polyphenylsulfide-based polymers, polyvinyl alcohol-based polymers, polyvinylidene chloride-based polymers, polyvinyl butyral-based polymers, polyarylate-based polymers, poly Examples thereof include oximethylene-based polymers, polyepoxy-based polymers, and transparent polymers such as blends of the polymers. In particular, those having a small birefringence are preferably used.

A coloring component can be added to the active energy ray-curable composition of the present invention. Conventionally known pigments can be used as the coloring component. Further, for the purpose of obtaining a desired hue, a dye may be contained within a range that does not reduce heat resistance and weather resistance. These can be used alone or in admixture of two or more in order to obtain a desired color density and hue.

As the pigment, for example, an organic pigment or an inorganic pigment can be used, and two or more kinds of pigments can be mixed and used.

Examples of organic pigments include diketopyrrolopyrrole pigments, azo pigments (eg, azo, disazo, polyazo, etc.), phthalocyanine pigments (eg, copper phthalocyanine, halogenated copper phthalocyanine, metal-free phthalocyanine, etc.), and anthraquinone pigments. Pigments (eg, aminoanthraquinone, diaminodianthraquinone, antrapyrimidine, flavantron, antoanthron, indantron, pyranthron, biolantron, etc.), quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thioindigo pigments, iso Examples thereof include indolin-based pigments, isoindolinone-based pigments, quinophthalone-based pigments, slene-based pigments, and metal complex-based pigments.

Examples of inorganic pigments include titanium oxide, zinc white, zinc sulfide, lead white, calcium carbonate, precipitated barium sulfate, white carbon, alumina white, kaolin clay, talc, bentonite, black iron oxide, carbon black, and cadmium red. Bengara, Molybdenum Red, Molybdate Orange, Chrome Vermillion, Yellow Lead, Cadmium Yellow, Yellow Iron Oxide, Titanium Yellow, Chromium Oxide, Viridian, Titanium Cobalt Green, Cobalt Green, Cobalt Chrome Green, Victoria Green, Ultramarine Blue, Navy Blue, Cobalt Examples thereof include blue, cerulean blue, cobalt silica blue, cobalt zinc silica blue, manganese violet, cobalt violet and the like.

Examples of carbon black include "Special Black 350, 250, 100, 550, 5, 4, 4A, 6" manufactured by Degussa, "Printex U, V, 140U, 140V, 95, 90, 85, 80, 75, 55, 45". , 40, P, 60, L6, L, 300, 30, 3, 35, 25, A, G ", Cabot" REGAL 400R, 660R, 330R, 250R "" MOGUL E, L ", Mitsubishi Chemical Corporation" MA7, 8, 11, 77, 100, 100R, 100S, 220, 230 "" # 2700, # 2650, # 2600, # 200, # 2350, # 2300, # 2200, # 1000, # 990, # 980, # 970, # 960, # 950, # 900, # 850, # 750, # 650, # 52, # 50, # 47, # 45, # 45L, # 44, # 40, # 33, # 332, # 30, # 25, # 20, # 10, # 5, CF9, # 95, # 260 "and the like.

In addition, the pigments that can be used in the active energy ray-curable composition of the present invention are shown below by a color index (CI) number.

Examples of the red pigment include C.I. I. Pigment Red 7, 9, 14, 19, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 97, 122, 123, 146, 149, 168, 177, 178, 180, 184, 185, 187, 192, 200, 202, 208, 210, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 246, 254, 255, 264, 272 and the like can be used, but the present invention is not limited thereto.

Examples of the yellow pigment include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1,37,37: 1,40,42,43,53,55,60,61,62,63,65,73,74,77,81,83,86,93,94,95,97,98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199 and the like can be used, but the present invention is not limited thereto.

Examples of the orange pigment include C.I. I. Pigment Orange 36, 43, 51, 55, 59, 61 and the like can be used, but are not limited thereto.

Examples of the green pigment include C.I. I. Pigment Green 7, 10, 36, 37 and other green pigments can be used, but are not limited thereto.

Examples of the blue pigment include C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64 and the like can be used, but are not limited thereto.

Examples of the purple pigment include C.I. I. Pigment Violet 1, 23, 27, 29, 30, 32, 37, 40, 42, 50 and the like can be used, but are not limited thereto.

Examples of the black pigment include C.I. I. Pigment Black 1, 6, 7, 12, 20, 31, and the like can be used, but are not limited thereto.

Two or more of these pigments can be mixed and used at an arbitrary ratio.

When the pigment as a coloring component is added, the amount used is 0.01 to 100 parts by mass with respect to 100 parts by mass of the total amount of the hydrophilic radically polymerizable compound (A) and the polymerizable compound (E). , Preferably 1 to 60 parts by mass.

The particle size of the pigment is preferably sufficiently smaller than the wavelength of visible light from the viewpoint of the absorption coefficient of visible light (appropriate spectrum) and transparency. That is, the pigment preferably has an average primary particle size of 0.01 μm or more and 0.3 μm or less, particularly 0.01 μm or more and 0.1 μm or less. The primary particle size refers to the diameter of the pigment particle, which is the smallest unit, and is measured with an electron microscope.

The primary particle size of the pigment can be controlled within an appropriate range using a known dispersion device, for example, a sand mill, a kneader, two rolls, or the like.

Further, when a pigment is added to the active energy ray-curable composition of the present invention, a pigment derivative or a pigment dispersant is used for the purpose of improving the dispersibility of the pigment and the storage stability of the active energy ray-curable composition. Can be done.

Here, the pigment derivative is a compound in which a substituent is introduced into an organic dye. Organic dyes also include pale yellow aromatic polycyclic compounds such as phthalimide-based, naphthalene-based, naphthoquinone-based, anthracene-based, and anthraquinone-based, which are not generally called dyes.

Examples of the pigment derivative include Japanese Patent Application Laid-Open No. 63-305173, Japanese Patent Application Laid-Open No. 57-15620, Japanese Patent Application Laid-Open No. 59-40172, Japanese Patent Application Laid-Open No. 63-17102, Japanese Square Root 5-2469, Japanese Patent Application Laid-Open No. 06- Those described in JP-A-306301, JP-A-2001-220520, JP-A-2003-238842, etc. can be used, and these can be used alone or in combination of two or more.

Examples of the pigment dispersant include hydroxyl group-containing carboxylic acid esters, long-chain polyaminoamide and high-molecular-weight acid ester salts, high-molecular-weight polycarboxylic acid salts, long-chain polyaminoamide and polar acid ester salts, and high-molecular-weight unsaturated acid esters. High molecular weight copolymer, modified polyurethane, modified polyacrylate, polyether ester type anionic activator, naphthalene sulfonic acid formalin condensate salt, aromatic sulfonic acid formalin condensate salt, polyoxyethylene alkyl phosphate, polyoxyethylene Nonylphenyl ether, stearylamine acetate and the like can be used.

Specific examples of the pigment dispersant include "Anti-Terra-U (polyaminoamide phosphate)", "Anti-Terra-203 / 204 (high molecular weight polycarboxylate)" and "DISPERBYK-101" manufactured by BYK Chemie. Polyaminoamide phosphate and acid ester), 107 (hydroxyl-containing carboxylic acid ester), 110, 111 (acid group-containing copolymer), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 ( (Polymer copolymer)", "400", "Bycumen" (high molecular weight unsaturated acid ester), "BYK-P104, P105 (high molecular weight unsaturated acid polycarboxylic acid)", "P104S, 240S (high molecular weight unsaturated acid)" Saturated acid polycarboxylic acid and silicon-based) ”,“ Lactimon (long-chain amine and unsaturated acid polycarboxylic acid and silicon) ”.

In addition, "Fuka 44, 46, 47, 48, 49, 54, 63, 64, 65, 66, 71, 701, 764, 766", "Fuka Polymer 100 (modified polyacrylate), 150 (aliphatic)" manufactured by Efka CHEMICALS. (Modified polymer), 400, 401, 402, 403, 450, 451, 452, 453 (modified polyacrylate), 745 (copper phthalocyanine) "," Fuka PX4701 "," Floren TG-710 (urethane) manufactured by Kyoeisha Chemical Co., Ltd. (Oligomer), "Flownon SH-290, SP-1000", "Polyflow No. 50E, No. 300 (acrylic copolymer)", Kusumoto Kasei Co., Ltd. "Disparon KS-860, 873SN, 874 (Polymer dispersant) ), # 2150 (aliphatic polyvalent carboxylic acid), # 7004 (polyether ester type) ”.

Furthermore, Kao Co., Ltd. "Demor RN, N (Naphthalene Sulfonic Acid Formarin Condensate Sodium Salt), MS, C, SN-B (Aromatic Sulfonic Acid Formarin Condensate Sodium Salt), EP", "Homogenol L-18 (Poly) Carous acid type polymer), "Emulgen 920, 930, 931, 935, 950, 985 (polyoxyethylene nonylphenyl ether)," acetamine 24 (coconut amine acetate), 86 (stearyl amine acetate) ", manufactured by Lubrizol. "Sols Spurs 5000 (phthalocyanine ammonium salt type), 13940 (polyester amine type), 17000 (fatty acid amine type), 24000GR, 32000, 33000, 35000, 39000, 41000, 53000", Nikko Chemical Co., Ltd. "Nikkor T106 (polyoxyethylene)" Sorbitan monoolate), MYS-IEX (polyoxyethylene monostearate), Hexagline 4-0 (hexaglyceryl tetraolate) ", Ajinomoto Fine Techno Co., Ltd." Azisper PB821, 822, 824 "and the like.

The amount of the pigment derivative and the pigment dispersant added is not particularly limited, but is preferably 0.1 to 40 parts by mass, more preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the pigment. be.

Examples of the dyes that may be contained in order to obtain a desired hue include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes. Be done.

Examples of the azo dye include C.I. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. Disperse thread 58, C.I. I. Disperse Blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Moldant Red 7, C.I. I. Moldant Yellow 5, C.I. I. Examples include, but are not limited to, Moldant Black 7.

Examples of the anthraquinone dye include C.I. I. Bat Blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disperse thread 60, C.I. I. Disperse Blue 56, C.I. I. Disperse blue 60 and the like can be mentioned, but the present invention is not limited thereto.

In addition, examples of the phthalocyanine dye include C.I. I. Pad Blue 5 and the like are examples of quinoneimine dyes such as C.I. I. Basic Blue 3, C.I. I. Basic blue 9 and the like are examples of quinoline dyes such as C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 and the like can be used as nitro dyes, for example, C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Disperse Yellow 42 and the like can be mentioned, but the present invention is not limited thereto.

When these dyes are added, the amount used is 0.01 to 100 parts by mass, preferably 0.01 to 100 parts by mass, based on 100 parts by mass of the total amount of the hydrophilic radically polymerizable compound (A) and the polymerizable compound (E). Although it is 1 to 60 parts by mass, as described above, it is not preferable that the amount used is too large from the viewpoint of heat resistance and weather resistance.

Further, in order to reduce the viscosity of the active energy ray-curable composition and improve the wettability and spreadability to the substrate, the active energy ray-curable composition may contain an organic solvent.

Organic solvents include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, and dipropylene glycol monomethyl. Ether acetate, ethylene glycol monomethyl ether propionate, ethylene glycol monoethyl ether propionate, ethylene glycol monobutyl ether propionate, diethyl diglycol, diethylene glycol dialkyl ether, tetraethylene glycol dialkyl ether, diethylene glycol monomethyl ether propionate, diethylene glycol Monoethyl ether propionate, diethylene glycol monobutyl ether propionate, propylene glycol monomethyl ether propionate, dipropylene glycol monomethyl ether propionate, ethylene glycol monomethyl ether butyrate, ethylene glycol monoethyl ether butyrate, ethylene glycol monobutyl ether Glycol monoacetates such as butyrate, diethylene glycol monomethyl ether butyrate, diethylene glycol monoethyl ether butyrate, diethylene glycol monobutyl ether butyrate, propylene glycol monomethyl ether butyrate, dipropylene glycol monomethyl ether butyrate, ethylene glycol diacetate, diethylene glycol di Acetate, propylene glycol diacetate, dipropylene glycol diacetate, ethylene glycol acetate propionate, ethylene glycol acetate butyrate, ethylene glycol propionate butyrate, ethylene glycol dipropionate, ethylene glycol acetate dibutyrate, diethylene glycol acetate propio Nate, Diethylene Glycol Acetate Butyrate, Diethylene Glycol Propionate Butyrate, Diethylene Glycol Dipropionate, Diethylene Glycol Acetate Dibutylate, Propylene Glycol Acetate Propionate, Propylene Glycol 1 Acetate Butyrate, Propylene Glycol Propionate Butyrate, Propylene Glycol Dipropionate, Propylene Glycol Acetate Dibutyrate, Dipropylene Glycol Acetate Propionate, Dipropylene Glycol Acetate Butyrate, Dipropylene Glycol Propionate Butyrate, Dipropylene Glycol diacetates such as glycol dipropionate and dipropylene glycol acetate dibutyrate, glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and dipropylene glycol, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol Monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, propylene glycol n-propyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether , Glycol ethers such as triethylene glycol monobutyl ether and tripropylene glycol monomethyl ether, and lactic acid esters such as methyl lactate, ethyl lactate, propyl lactate and butyl lactate. Of these, tetraethylene glycol dialkyl ether, ethylene glycol monobutyl ether acetate, and diethyl diglycol are preferable.

To use the active energy ray-curable composition of the present invention, the active energy ray-curable composition is printed or applied on a substrate, and then irradiated with active energy rays such as ultraviolet rays or the like. As a result, the active energy ray-curable composition on the print medium is rapidly cured.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to the following Examples.

Examples of synthesis of the compounds shown in Table 1 are shown below.
<Synthesis Example 1> Hydrophilic radically polymerizable compound (A): Compound (A-9)
92 g (1.0 mol) of glycerin, 36 g of distilled water, and 0.3 g of potassium hydroxide were placed in an autoclave having a capacity of 2 L equipped with a stirrer, heated to 90 ° C., and stirred to obtain a slurry-like liquid. Then, the mixture was heated to 130 ° C., and 1365 g (31 mol) of ethylene oxide was gradually introduced into the autoclave for reaction. With the introduction of ethylene oxide, the temperature inside the autoclave increased. Cooling was added as needed to keep the reaction temperature below 140 ° C. After the reaction, excess ethylene oxide and by-produced ethylene glycol polymers were removed by reducing the pressure at 140 ° C. with a mercury column of 10 mmHg or less. Then, it was neutralized with acetic acid to adjust the pH to 6-7.
Subsequently, 141 g (0.1 mol) of the obtained glycerin 30 mol ethylene oxide addition compound, 230 g (3.2 mol) of acrylic acid, 16 g of paratoluenesulfonic acid, 500 g of toluene, and 1 g of hydroquinone were charged into a glass four-necked flask and air was charged. The heating reaction was carried out while blowing. The water generated in the reaction was azeotropically boiled with toluene to remove it from the system at any time. The reaction temperature was adjusted to maintain 100-110 ° C. After the reaction, the reaction was carried out with alkaline water and water, the upper toluene layer was separated, toluene was distilled off under reduced pressure, and 352 g (yield 86%) of glycerin 30 mol ethylene oxide-added acrylate represented by compound (A-9) was added. Obtained.

<Synthesis Example 2> Hydrophilic radically polymerizable compound (A): Compound (A-19)
In an autoclave with a capacity of 2 L equipped with a stirrer, 137 g (1.0 mol) of trimethylolpropane, 36 g of distilled water, and 0.3 g of potassium hydroxide were charged, heated to 90 ° C., and stirred to obtain a slurry-like liquid. .. Then, the mixture was heated to 130 ° C., and 1365 g (31 mol) of ethylene oxide was gradually introduced into the autoclave for reaction. With the introduction of ethylene oxide, the temperature inside the autoclave increased. Cooling was added as needed to keep the reaction temperature below 140 ° C. After the reaction, excess ethylene oxide and by-produced ethylene glycol polymers were removed by reducing the pressure at 140 ° C. with a mercury column of 10 mmHg or less. Then, it was neutralized with acetic acid to adjust the pH to 6-7.
Subsequently, 146 g (0.1 mol) of the obtained trimethylolpropane 30 mol ethylene oxide addition compound, 230 g (3.2 mol) of acrylic acid, 16 g of paratoluenesulfonic acid, 500 g of toluene, and 1 g of hydroquinone were charged into a glass four-necked flask. , The heating reaction was carried out while blowing air. The water generated in the reaction was azeotropically boiled with toluene to remove it from the system at any time. The reaction temperature was adjusted to maintain 100-110 ° C. After the reaction, the reaction was carried out with alkaline water and water, the upper toluene layer was separated, toluene was distilled off under reduced pressure, and 303 g of trimethylolpropane 30 mol ethylene oxide-added acrylate represented by compound (A-19) was added (yield 84). %)Obtained.

<Synthesis Example 3> Hydrophilic radically polymerizable compound (A): Compound (A-38)
256 g (1.0 mol) of ditrimethylolpropane, 36 g of distilled water, and 0.3 g of potassium hydroxide were charged into a 2 L-capacity autoclave equipped with a stirrer, heated to 110 ° C. and stirred to obtain a slurry-like liquid. .. Then, it was heated to 130 degreeC, and 1585 g (36 mol) of ethylene oxide was gradually introduced into an autoclave and reacted. With the introduction of ethylene oxide, the temperature inside the autoclave increased. Cooling was added as needed to keep the reaction temperature below 140 ° C. After the reaction, excess ethylene oxide and by-produced ethylene glycol polymers were removed by reducing the pressure at 140 ° C. with a mercury column of 10 mmHg or less. Then, it was neutralized with acetic acid to adjust the pH to 6-7.
Subsequently, 180 g (0.1 mol) of the obtained ditrimethylolpropane 35 mol ethylene oxide addition compound, 273 g (3.8 mol) of acrylic acid, 16 g of paratoluenesulfonic acid, 500 g of toluene, and 1 g of hydroquinone were charged into a glass four-necked flask. , The heating reaction was carried out while blowing air. The water generated in the reaction was azeotropically boiled with toluene to remove it from the system at any time. The reaction temperature was adjusted to maintain 100-110 ° C. After the reaction, the reaction was carried out with alkaline water and water, the upper toluene layer was separated, toluene was distilled off under reduced pressure, and 367 g of ditrimethylolpropane 35 mol ethylene oxide-added acrylate represented by compound (A-9) (yield 85%). ) Was obtained.

<Example of active energy ray-curable composition>

<Examples 1 to 76, Comparative Examples 1 to 4> Preparation of active energy ray-curable composition An active energy ray-curable composition was obtained by the formulation shown in Table 2. Using the obtained polymerizable composition, the curability and the residual amount of the photopolymerization initiator were evaluated by the following methods. The results are shown in Table 2.

<Curability evaluation test>
The prepared active energy ray-curable composition was applied onto a polyethylene terephthalate (PET) substrate by a bar coating method using a K control coater so that the wet film thickness was 10 μm, and seven coating films were prepared. did. The coating film was irradiated with ultraviolet rays as active energy rays at a conveyor speed of 10 m / min using a belt conveyor type ultraviolet irradiation device (metal halide lamp 100 W / cm1 lamp). The seven coating films were irradiated with ultraviolet rays at seven levels of 1, 2, 3, 4, 5, 6, and 7 times, and then dried at 40 ° C. for 5 minutes. The surface of the cured product was rubbed with a cotton cloth, and the curability was judged by the number of irradiations at which the film was not scratched. It was judged that the smaller the number of irradiations, the better the curability. The judgment criteria are as follows.

Judgment criteria ◎: Curing in 1 to 3 times. Especially good.
◯: Hardened in 4 to 6 times. Somewhat good.
X: Uncured even after 7 irradiations, not suitable for practical use. Bad.

<Residual rate evaluation test of photopolymerization initiator>
The prepared active energy ray-curable composition was applied onto a polyethylene terephthalate (PET) substrate by a bar coating method using a K control coater so that the wet film thickness was 10 μm to prepare a coating film. The coating film was irradiated with ultraviolet rays as active energy rays 5 times at a conveyor speed of 10 m / min using a belt conveyor type ultraviolet irradiation device (metal halide lamp 100 W / cm 1 lamp), and then dried at 40 ° C for 5 minutes to cure the cured product. Got The obtained cured product (10 cm × 10 cm) was cut into 1 cm squares together with the base material, and immersed in 100 ml of methyl ethyl ketone in a closed container at 60 ° C. for 3 days to retain low molecule residual components in the cured film. The rate was extracted. After 2 days, the methyl ethyl ketone homogenized by stirring was taken out from the container, and the extracted component was identified by HPLC (manufactured by Shimadzu Corporation). The residual rate of the photopolymerization initiator in the cured film was calculated by preparing a calibration curve of the detected compound and quantifying each compound. It was judged that the smaller the residual rate of the photopolymerization initiator, the better. The judgment criteria are as follows.

<Mass of cured film>
The cured film mass was calculated as follows.
Cured film mass = mass of cured product (cured film + base material) after UV irradiation-base material mass before UV irradiation

<Residual rate of photopolymerization initiator>
The residual rate of the unreacted photopolymerization initiator remaining in the cured film was calculated as follows.
Residual rate of photopolymerization initiator = total amount of photopolymerization initiator extracted / mass of cured film (g)

◯: Photoinitiator residual rate is less than 0.5%. Especially good.
Δ: Photoinitiator residual rate is 0.5% to less than 1%. Somewhat good.
X: The photoinitiator residual rate is 1% or more, which is not suitable for practical use. Bad.

Table 2

The raw materials in Table 2 are shown below.
PEGDA: (polyethylene glycol (molecular weight 400) diacrylate); NK ester A-400 (manufactured by Shin-Nakamura Kogyo Co., Ltd.)
PET-3A: Pentaerythritol triacrylate; Light acrylate PE-3A (manufactured by Kyoeisha Chemical Co., Ltd.)
GOx: Glucose oxidase activity 190 U / mg (manufactured by Wako Pure Chemical Industries, Ltd.)
GaOx: Galactose oxidase (manufactured by Wako Pure Chemical Industries, Ltd.)
ChOx: Choline oxidase (manufactured by Wako Pure Chemical Industries, Ltd.)
Gl: β-D-glucose (manufactured by Tokyo Chemical Industry Co., Ltd.)
Ga: D-galactose (manufactured by Tokyo Chemical Industry Co., Ltd.)
Ch: Colin (manufactured by Tokyo Chemical Industry Co., Ltd.)
Water: Deionized water Irg. 184: 1-Hydroxy-cyclohexyl-phenyl-ketone (manufactured by BASF)
TPO: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (manufactured by BASF)
Irg. 1173: 2-Hydroxy-2-methyl-1-phenyl-propane-1-one (manufactured by BASF)
Irg. 2959: 1- [4- (2-Hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one (manufactured by BASF)
Irg. 651: 2,2-dimethoxy-2-phenylacetophenone (manufactured by BASF)
BP: Benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.)

The active energy ray-curable composition containing the hydrophilic radically polymerizable compound (A) having a trifunctional or higher functional (meth) acrylate group of the present invention can be cured at high speed by ultraviolet irradiation, and is a photopolymerization initiator. It was obtained in a cured product with a low residual rate of. (Examples 1 to 76)

The active energy ray-curable composition containing PEGDA having a bifunctional acrylate group has moderately good curability, but has a large residual ratio of the photopolymerization initiator in the cured film. (Comparative Examples 1 and 2)

Further, the active energy ray-curable composition containing PEGDA having a bifunctional acrylate group has poor curability when the amount of the photopolymerization initiator is small, and the degree of curing is low, so that the remaining photopolymerization initiator remains. Is easily extracted, and the residual rate of the photopolymerization initiator is not excellent. (Comparative Examples 3 and 4)

Based on the above, the active energy ray-curable composition of the present invention is characterized by containing an oxidase enzyme, an oxidase substrate, and a hydrophilic radically polymerizable compound (A), and is characterized by high speed with a small amount of a photopolymerization initiator. It was possible to provide a cured product showing curability and having a low residual rate of the photoinitiator.

The use of the active energy ray-curable composition of the present invention is not restricted in various applications. Examples of applications that can be expected to improve sensitivity, cured product properties, and safety by the present invention include molding resins, casting resins, opto-molding resins, and sealants that utilize polymerization or cross-linking reactions. , Dental polymerized resin, printing ink, printing varnish, paint, photosensitive resin for printing plate, color proof for printing, resist for color filter, resist for black matrix, photo spacer for liquid crystal, screen material for rear projection, optical fiber, plasma Rib material for display, dry film resist, resist for printed substrate, solder resist, photo resist for semiconductor, resist for microelectronics, resist for manufacturing parts for micromachine, resist for etching, micro lens array, insulating material, hologram material, optical switch Compositions for waveguide materials, overcoating agents, powder coatings, adhesives, adhesives, mold release agents, optical recording media, adhesives, release coating agents, image recording materials using microcapsules, Various devices and the like can be mentioned.

Claims (4)

Active energy ray curing, which comprises a hydrophilic radical polymerizable compound (A), an oxidase enzyme (B), an oxidase substrate (C), water, and a radical polymerization initiator (D). It is a mold composition
The hydrophilic radically polymerizable compound (A) is represented by the compound (a1) represented by the following general formula (1), the compound (a2) represented by the following general formula (2), and the following general formula (3). that compound (a3), Ri compound der one or more chosen from the group consisting of (a5) represented by compounds represented by the following general formula (4) (a4) and the following general formula (5),
The active energy ray-curable type, wherein the radical polymerization initiator (D) is one or more selected from the group consisting of an acetophenone compound having a hydroxyl group, a dialkylamino group or a morphorn group, a phosphine compound and an oxime ester compound. Composition.

(In the formula, R ^{3 to} R ⁵ each independently represent a hydrogen atom or a methyl group. In the formula, b, c and d each independently represent an integer of 2 to 40.)

(In the formula, R ^{6 to} R ⁸ independently represent a hydrogen atom or a methyl group. In the formula, e, f and g each independently represent an integer of 2 to 40.)

(In the formula, R ^{9 to} R ¹² independently represent a hydrogen atom or a methyl group. In the formula, h,
i, j and k each independently represent an integer of 2-40. )

(In the formula, R ^{13 to} R ¹⁶ each independently represent a hydrogen atom or a methyl group. In the formula, l, m, n and o each independently represent an integer of 2 to 40.)

(In the formula, R ^{17 to} R ²² each independently represent a hydrogen atom or a methyl group. In the formula, p, q, r, s, t and u each independently represent an integer of 2 to 40. .) The active energy ray-curable composition according to claim 1, wherein the oxidase enzyme (B) is glucose oxidase and the oxidase substrate (C) is glucose. The oxidase enzyme (B) is contained in the range of 0.03 parts by mass to 0.4 parts by mass with respect to 100 parts by mass of the hydrophilic radically polymerizable compound (A), and the oxidase substrate (C) is 0.4 parts by mass. The active energy ray-curable type according to claim 1 or 2, which comprises 5.0 parts by mass to 5.0 parts by mass, and further contains 1.5 parts by mass or less of the photopolymerization initiator (D). Composition. A cured product of the active energy ray-curable composition according to any one of claims 1 to 3.