TW201829537A - Curable composition - Google Patents

Abstract

An object of the present invention is to provide a curable composition having fast curabilitiy, and that can make a cured layer having low yellowing, high flex resistance, and low curl properties. The curable composition of the present invention includes a mixture (A) of compounds having (meth)acryloyl group obtained by transesterification of a polyglycerin having a hydroxy value of 700 to 1,200 mgKOH/g and a compound having one (meth)acryloyl group with catalysts X and Y below. catalyst X: one or more kinds of compounds selected from the group consisting of a cyclic tertialy amine having an azabicyclo structure, or a salt thereof or a complex thereof, amidine, or a salt thereof or a complex thereof, a compound having a pyridine ring, or a salt thereof or a complex thereof, and a phosphine, or a salt thereof or a complex thereof. catalyst Y: a compound include zinc.

Description

Hardened composition

The present invention relates to a hardening type composition and is preferably related to an active energy ray hardening type composition. The hardening type composition of the present invention has excellent rapid hardenability, low yellowing property, high flexibility and low curling property especially when used as an active energy ray-curable composition, even if the light source is an ultraviolet light emitting diode (hereinafter The "UV-LED" is also excellent in curability, and is excellent in low yellowing, high flexibility, and low curling properties, which are difficult to achieve both hardenability, and thus can be applied to a UV-LED hardening type coating agent. And ink on the ink.

Background Art Since an active energy ray-curable composition has advantages such as energy saving, space saving, and high productivity in use of equipment, it is widely used as a clear coat such as paper or film, and lithographic printing. High-pressure mercury lamps and metal halide lamps are widely used in light sources of active energy rays, especially in the case of ultraviolet light sources. However, in recent years, as a light source for further development of energy saving and space saving, introduction of UV-LEDs It is gradually being explored, and compositions having excellent hardenability for UV-LED sources are currently being explored. However, when the conventional active energy ray-curable composition is directly used as a UV-LED hardening type composition, the problem of deterioration of hardenability often occurs.

The problem of deterioration of hardenability caused by introduction of a UV-LED light source is particularly serious in the use of a clear coating containing no pigment such as varnish. The reason for this is that once a photopolymerization initiator having a high sensitivity to light of a UV-LED (usually 385 nm or 365 nm) is used, light absorption of the cured film may cause yellowing of the cured film in any case in the visible light region.

In view of such a background, Patent Document 1 discloses a UV-LED hardening type varnish containing an amine-modified acrylate, a mercaptophosphine oxide-based polymerization initiator, and a fluorescent whitening agent.

Patent Document 2 discloses an ultraviolet curable cover varnish composition comprising: a urethane acrylate obtained by reacting a ring-shaped diisocyanate with pentaerythritol triacrylate; and a polymerizable acrylic acid single body.

Patent Document 3 discloses a transparent ink composition for ink jet printing which has low viscosity but excellent UV-LED hardenability. Advanced technical literature

[Patent Document 1] Japanese Laid-Open Patent Publication No. 2011-072388 [Patent Document 2] International Publication No. 2015/072388 Booklet [Patent Document 3] International Publication No. 2016/009848

Disclosure of the Invention Problems to be Solved by the Invention However, as disclosed in Patent Document 1, a composition containing a fluorescent whitening agent may be discolored by a cured film. For example, when the base material is a plastic film, there may be cases where the cured film has a feeling of yellow or blue, and when the substrate is paper, the whiteness of the paper may be unnatural. Further, the cover varnish composition disclosed in Patent Document 2 cannot sufficiently satisfy both UV-LED curability and low yellow denaturation. Further, the ink composition contained in Patent Document 3 cannot sufficiently satisfy both the UV-LED hardenability and the low yellowing property. As described above, at present, for a UV-LED hardening type composition, a composition having excellent UV-LED hardenability and low yellowing property is required. Further, when a UV-LED hardening type composition is used as a coating agent, a composition having properties such as that the cured film is not easily broken (so-called high flexibility) when bending a substrate, and Low curling of warpage occurs less frequently.

The problem to be solved by the present invention is to provide a hardening type composition which has rapid hardening property and which has excellent low yellowing property, high flexibility and low curling property, and provides active energy ray hardening type composition. Things are appropriate. Means to solve the problem

In order to solve the above problems, the inventors of the present invention have found that a hardening type composition containing a mixture of a (meth)acryl fluorenyl compound is effective, and the (meth)acryl fluorenyl compound is produced as follows. It is obtained by using a specific basic catalyst or a phosphine-based catalyst and a zinc-based catalyst to carry out transesterification of a polyglycerol having a hydroxyl value of 700 to 1,200 mgKOH/g with a compound having one (meth)acryl fluorenyl group. The invention will be described in detail below.

Further, in the specification of the present invention, an acryl fluorenyl group and/or a methacryl fluorenyl group are represented by a (meth) acrylonitrile group, and an acrylate and/or a methacrylate is represented by a (meth) acrylate, and Acrylic acid and/or methacrylic acid is referred to as (meth)acrylic acid. Effect of the invention

According to the composition of the present invention (suitable for the active energy ray-curable composition), it is possible to obtain a material having rapid hardening property and a low-yellowing property, high flexibility and low curling property of the cured film. Further, it is possible to produce a product which exhibits excellent hardenability even when the light source is a UV-LED, and which is excellent in low yellowing property, high flexibility, low curling property, etc., which are difficult to be cured. .

MODE FOR CARRYING OUT THE INVENTION The present invention relates to a hardening type composition comprising a mixture (A) of a compound having a (meth) acrylonitrile group, which is obtained in the following manner: Using the following catalysts X and Y, a polyglycerol having a hydroxyl value of 700 to 1,200 mgKOH/g (hereinafter referred to simply as "polyglycerol") and a compound having one (meth)acrylonitrile group (hereinafter referred to as The "monofunctional (meth) acrylate") is subjected to a transesterification reaction. Catalyst X: selected from the group consisting of a cyclic tertiary amine having a nitrogen abicyclic structure or a salt or complex thereof, hydrazine or a salt thereof or a complex thereof, a compound having a pyridine ring or a salt or a complex thereof, and More than one compound of the group consisting of phosphine or a salt or complex thereof. Catalyst Y: a zinc-containing compound. Hereinafter, the component (A), other components, and methods of use will be described.

1. (A) component (A) component is a mixture of a (meth) acrylate, and the (meth) acrylate is a polyglycerol and a monofunctional (meth)acrylic acid in the presence of the aforementioned catalysts X and Y. The ester is obtained by transesterification. Hereinafter, it is also called a polyglycerol poly(meth)acrylate. Hereinafter, preferred embodiments of the polyglycerol, the monofunctional (meth) acrylate, the catalyst X, the catalyst Y, the method for producing the component (A), and the component (A) will be described.

1-1. Polyglycerol A polyglycerol-based polyether polyol which is used as a raw material of the component (A) has a structure in which glycerin or glycidol is polymerized. It means that the average degree of polymerization of the polyglycerol has a hydroxyl value of 700 to 1,200 mgKOH/g, and preferably 800 to 1,150 mgKOH/g, more preferably 850 to 1,100 mgKOH/g, and more preferably 900 to 1,050 mgKOH/g. When the hydroxyl value of the polyglycerol exceeds 1,200 mgKOH/g, the low crimping property of the cured film of the composition deteriorates, but conversely, if the hydroxyl value is less than 700 mgKOH/g, the production of the component (A) becomes difficult or obtained ( A) The composition has a high viscosity and becomes difficult to handle. Further, the hydroxyl value of the polyglycerol is related to the average degree of polymerization. For example, when the average degree of polymerization is 6, it is approximately 970 mgKOH/g.

In the present invention, one or more polyhydric alcohols other than polyglycerol (hereinafter referred to as "other polyols") may be used arbitrarily in combination within a range that does not impair the effect. When other polyols are used in combination, the proportion is preferably 50 parts by weight or less based on 100 parts by weight of the total of the polyglycerol.

1-2. Monofunctional (meth) acrylate A monofunctional (meth) acrylate which is used as a raw material of the component (A) is a compound having one (meth) acryl fluorenyl group in the molecule, and is exemplified as follows The compound represented by the formula (1).

[Chemical Formula 1]

In the formula (1), R ¹ represents a hydrogen atom or a methyl group. R ² represents an organic group having 1 to 50 carbon atoms.

Preferred specific examples of R ^{2 in} the above formula (1) include carbon number such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group and 2-ethylhexyl group. ~8 alkyl; 2-methoxyethyl, 2-ethoxyethyl and 2-methoxybutyl alkoxyalkyl; and, N,N-dimethylaminoethyl, A dialkylamino group such as N,N-diethylaminoethyl, N,N-dimethylaminopropyl or N,N-diethylaminopropyl. Specific examples of R ^{2 in} the above formula (1), in addition to the above, may be those described in JP-A-2017-39916, JP-A-2017-39917, or International Publication No. 2017/033732. base.

In the present invention, the monofunctional (meth) acrylates may be used singly or in combination of two or more kinds. Among the monofunctional (meth) acrylates, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate and (methyl) a (meth)acrylic acid alkyl ester having a carbon number of 1 to 8 alkyl groups such as 2-ethylhexyl acrylate or a (meth)acrylic acid alkoxyalkyl ester such as 2-methoxyethyl acrylate; N-dimethylaminoethyl (meth) acrylate is preferred, and among them, a (meth) acrylate having a carbon number of 1-4 alkyl groups which is excellent in reactivity with polyglycerol and which is easily obtained is obtained. An alkoxyalkyl (meth)acrylate having a carbon number of 1 to 2 alkyl groups is preferred. Further, an alkoxyalkyl (meth)acrylate having a carbon number of 1 to 2 alkyl groups which promotes dissolution of polyglycerol and exhibits excellent reactivity is more preferable, 2-methoxy (meth)acrylate Ethyl ethyl ester is especially preferred. Further, in the case of a monofunctional (meth) acrylate, an acrylate is particularly preferable because it is excellent in reactivity.

In the method for producing the component (A), the ratio of use of the polyglycerol to the monofunctional (meth) acrylate is not particularly limited, but is 1 mol per unit of the hydroxyl group in the polyglycerol, and the monofunctional (meth)acrylic acid is used. The ester is preferably from 0.4 to 10.0 mol, more preferably from 0.6 to 5.0 mol. The side reaction can be suppressed by making the monofunctional (meth) acrylate at 0.4 m or more. Further, by setting it to 10.0 mol or less, the amount of polyglycerol poly(meth) acrylate produced can be increased to improve productivity.

1-3. In the method for producing the catalyst (A) component, a mixture of polyglycerol (meth) acrylate having excellent hardenability and scratch resistance can be produced in the case of a transesterification catalyst based on a small amount of side reactions. The reason for the catalyst is to use the following catalysts X and Y in combination. Catalyst X: selected from a cyclic tertiary amine having a nitrogen abicyclic structure or a salt or complex thereof (hereinafter referred to as "azabicyclic compound"), hydrazine or a salt thereof or a complex thereof (hereinafter referred to as a "quinone compound", a compound having a pyridine ring or a salt or a complex thereof (hereinafter referred to as "pyridine compound"), and a phosphine or a salt or a complex thereof (hereinafter referred to as "phosphine compound") Forming more than one compound in the group. Catalyst Y: a zinc-containing compound. Hereinafter, the catalyst X and the catalyst Y will be described.

1-3-1. In the method for producing the catalyst X (A) component, the catalyst X is selected from the group consisting of one or more compounds selected from the group consisting of an azabicyclic compound, an anthraquinone compound, a pyridine compound, and a phosphine compound. . In the catalyst X, one or more compounds selected from the group consisting of an azabicyclic compound, an anthraquinone compound, and a pyridine compound are preferred among the above-mentioned compound groups. These compounds are suitable for the production of the component (A) in addition to the excellent catalyst activity, and can form a complex with the catalyst Y described later after completion of the reaction, and the complex can be easily terminated from the reaction by a simple method such as adsorption. After the reaction solution is removed. In particular, a nitrogen heterocyclic compound having a complex with the catalyst Y exhibits poor solubility to the reaction liquid, and can be more easily removed by filtration or adsorption. On the other hand, although the phosphine-based compound has excellent catalytic activity, it is not difficult to form a complex with the catalyst Y, otherwise it is soluble in the reaction liquid when the complex is formed, and the phosphine compound in the reaction liquid after the reaction is completed. Most of the complexes remain in a dissolved state and are difficult to remove from the reaction solution by a simple method such as filtration or adsorption. Therefore, the phosphine-based catalyst remains in the final product, and there is a problem that turbidity, catalyst precipitation, or time-dependent thickening or gelation occurs during storage of the product.

Specific examples of the azabicyclo compound may be any compound which satisfies the conditions of a cyclic tertiary amine having an azabicyclo structure, a salt of the amine or a complex of the amine. Further preferred compounds are quinuclidine, 3-hydroxyquinuclidine, 3-quinuclidinone, 1-azabicyclo[2.2.2]octane-3-carboxylic acid. And triethylene glycol diamine (alias: 1,4-diazabicyclo [2.2.2] octane. Hereinafter referred to as "DABCO"). Specific examples of the azabicyclic compound include, in addition to the above, compounds such as those disclosed in JP-A-2017-39916, JP-A-2017-39917, and International Publication No. 2017/033732.

Specific examples of the lanthanoid compound include imidazole, N-methylimidazole, N-ethylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, and 1-vinylimidazole. , 1-allyl imidazole, 1,8-diazabicyclo[5.4.0]undec-7-ene (hereinafter referred to as "DBU"), 1,5-diazabicyclo[4.3.0] Decane-5-ene (hereinafter referred to as "DBN"), N-methylimidazolium hydrochloride, DBU hydrochloride, DBN hydrochloride, N-methylimidazolium acetate, DBU acetate, DBN acetate, N-methylimidazolium acrylate, DBU acrylate, DBN acrylate and bismuth imine DBU, and the like.

The main specific examples of the pyridine compound include pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 3-ethylpyridine, 4-ethylpyridine, and N. N-dimethyl-4-aminopyridine (hereinafter referred to as "DMAP") or the like. Specific examples of the pyridine-based compound include, in addition to the above, compounds such as those disclosed in JP-A-2017-39916, JP-A-2017-39917, and International Publication No. 2017/033732.

The phosphine-based compound may, for example, be a compound containing a structure represented by the following formula (2).

[Chemical Formula 2]

[In the formula (2), R ³ , R ⁴ and R ⁵ mean a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkenyl group having 1 to 20 carbon atoms, An aryl group having 6 to 24 carbon atoms or a cycloalkyl group having 5 to 20 carbon atoms. R ³ , R ⁴ and R ⁵ may be the same or different from each other].

Specific examples of the phosphine-based compound include triphenylphosphine, stilbene (4-methoxyphenyl)phosphine, tris(p-tolyl)phosphine, tris(m-tolyl)phosphine, and stilbene (4-methoxy-3). , 5-dimethylphenyl)phosphine, tricyclohexylphosphine, and the like. Specific examples of the phosphine-based compound may be, for example, those disclosed in JP-A-2017-39916, JP-A-2017-39917, or International Publication No. 2017/033732.

In the present invention, the catalysts X may be used singly or in combination of two or more kinds. Among these catalysts X, quinuclidine, 3-quinuclidinone, 3-hydroxyquinuclidine, DABCO, N-methylimidazole, DBU, DBN and DMAP are preferred, and most of the polyols are displayed. 3-hydroxy quinone, DABCO, N-methylimidazole, DBU and DMAP are particularly preferred and are readily available.

The amount of the catalyst X used in the production method of the component (A) is not particularly limited, but it is preferably 0.0001 to 0.5 mol of the catalyst X, more preferably 0.0005 to 0.2 mol, based on 1 mol of the total of the hydroxyl groups in the polyglycerol. ear. By using 0.0001 moles or more of catalyst X, the amount of polyglycerol poly(meth) acrylate produced can be increased, and the amount of by-product formation and reaction can be suppressed by using the amount of 0.5 mol or less. The liquid is colored, and the purification step after the end of the reaction can be simplified.

1-3-2. Catalyst Y Catalyst Y is a zinc-containing compound. The catalyst Y may be any compound as long as it is a compound containing zinc, but it is preferable to use an organic acid zinc or a zinc diketone alkoxide salt from the viewpoint of excellent reactivity. The organic acid zinc may, for example, be a zinc diprotonate such as zinc phthalate or a compound represented by the following formula (3).

[Chemical Formula 3]

[In the formula (3), R ⁶ and R ⁷ mean a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkenyl group having 1 to 20 carbon atoms, and a carbon number of 6 The aryl group of ~24 is a cycloalkyl group having a carbon number of 5-20. R ⁶ and R ⁷ may be the same or different from each other]. The compound of the above formula (3) is preferably a compound wherein R ⁶ and R ⁷ are a linear or branched alkyl or alkenyl group having 1 to 20 carbon atoms. In R ⁶ and R ⁷ , a linear or branched alkyl group or alkenyl group having 1 to 20 carbon atoms is a functional group having no halogen atom such as fluorine or chlorine, and the catalyst Y having the functional group can be produced in a high yield. Polyglycerol poly(meth) acrylate is highly desirable.

The zinc diketone alcohol salt is a compound represented by the following formula (4).

[Chemical Formula 4]

[In the formula (4), R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ mean a linear or branched alkyl group having 1 to 20 carbon atoms and a linear chain having 1 to 20 carbon atoms. a branched or branched alkenyl group, an aryl group having 6 to 24 carbon atoms or a cycloalkyl group having 5 to 20 carbon atoms. R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ may be the same or different from each other].

Specific examples of the zinc-containing compound represented by the above formula (3) include zinc acetate, zinc acetate dihydrate, zinc propionate, zinc octoate, zinc pivalate, zinc laurate, zinc myristate, and stearic acid. Zinc, zinc cyclohexanebutyrate, zinc 2-ethylhexanoate, zinc benzoate, zinc tertiary butyl benzoate, zinc salicylate, zinc naphthenate, zinc acrylate and zinc methacrylate. Further, in the case of such zinc-containing compounds, when the hydrate or solvate thereof or a complex thereof with the catalyst X is present, the hydrate and the solvate thereof and the complex thereof with the catalyst X may also be The component Y is used as a catalyst Y in the production method.

Specific examples of the zinc-containing compound represented by the above formula (4) include zinc acetophenone, zinc acetoacetate hydrate, bis(2,6-dimethyl-3,5-heptanedione) zinc, and bis. (2,2,6,6-tetramethyl-3,5-heptanedion) zinc and bis(5,5-dimethyl-2,4-hexanedione) zinc. Further, in the case of such zinc-containing compounds, when the hydrate or solvate thereof or a complex thereof with the catalyst X is present, the hydrate and the solvate thereof and the complex thereof with the catalyst X may also be The manufacturing method of the component A) is used as the catalyst Y.

As the organic acid zinc and zinc diketo alcohol salt in the catalyst Y, the above compounds can be used as they are, but they can also be used in a reaction system. For example, when other zinc compounds such as zinc oxide, zinc hydroxide, zinc chloride, and zinc nitrate are used as raw materials, and the catalyst Y is zinc organic acid, a method of reacting other zinc compounds with an organic acid may be mentioned, and the catalyst Y When it is a zinc diketo ketene salt, the method of reacting another zinc compound with acetamylacetone, etc. are mentioned. As the organic acid zinc and zinc diketo alcohol salt in the catalyst Y, the above compounds can be used as they are, but they can also be used in a reaction system. For example, when a zinc compound such as zinc metal, zinc oxide, zinc hydroxide, zinc chloride or zinc nitrate (hereinafter referred to as "raw material zinc compound") is used as a raw material, and catalyst Y is an organic acid zinc, it may be mentioned When the method of reacting the raw material zinc compound with the organic acid is a zinc diketo alcohol alkoxide, a method of reacting a raw material zinc compound with a 1,3-diketone or the like can be mentioned.

In the present invention, the catalysts Y may be used singly or in combination of two or more. Among these catalysts Y, zinc acetate, zinc propionate, zinc acrylate, zinc methacrylate and zinc acetonate are preferred, especially zinc acetate which exhibits good reactivity to most of the polyols and which is easily obtained. Zinc acrylate and zinc acetonate are preferred.

The amount of the catalyst Y used in the production method of the component (A) is not particularly limited, but it is preferably 0.0001 to 0.5 mol of the catalyst Y, and 0.0005 to 0.2 mol, more preferably 1 mol of the hydroxyl group in the polyglycerol. good. By using 0.0001 moles or more of catalyst Y, the amount of polyglycerol poly(meth) acrylate can be increased, and by controlling at less than 0.5 mol, the formation of by-products and coloration of the reaction liquid can be suppressed. The purification step after the end of the reaction is simplified.

1-4. Method for Producing Component (A) The component (A) is produced by subjecting polyglycerol to a monofunctional (meth) acrylate in a transesterification reaction in the presence of the above catalysts X and Y. In the method for producing the component (A), the ratio of the catalyst X to the catalyst Y is not particularly limited, but 0.005 to 10.0 mol of the catalyst X is preferably used with respect to 1 mol of the catalyst Y, and 0.05 to 5.0 mol is more preferable. . By using 0.005 mol or more, the amount of the desired polyfunctional (meth) acrylate can be increased, and by controlling at 10.0 mol or less, formation of by-products and coloration of the reaction liquid can be suppressed, and the reaction can be made. The purification step after the end is simple.

In the combination of the catalyst X and the catalyst Y used in the present invention, it is preferred that the catalyst X is an azabicyclic compound and the catalyst Y is a combination of the compounds represented by the above formula (3). Further, nitrogen is used. The heterobicyclic compound is DABCO and the compound represented by the above formula (3) is preferably a combination of zinc acetate and/or zinc acrylate. In addition to the polyglycerol poly(meth)acrylate which can be obtained in good yield, the combination is excellent in color tone after the completion of the reaction (less yellow feeling), and can be applied to transparent varnish or hard coat, etc., which is colorless and transparent. Use of sex. It is also an economically advantageous manufacturing method because it is a catalyst that can be obtained at a lower cost.

The catalyst X and the catalyst Y used in the present invention may be added from the beginning of the above reaction, or may be added from the middle of the reaction. In addition, the required usage can be added in all directions, or added in several steps.

In the production method of the component (A), the reaction temperature is preferably 40 to 180 ° C, more preferably 60 to 160 ° C. By setting the reaction temperature to 40 ° C or higher, the reaction rate can be increased, and by controlling the thermal polymerization of the (meth) acrylonitrile group in the raw material and the product by controlling at 180 ° C or lower, the coloring of the reaction liquid can be suppressed. The purification step after completion of the reaction is simplified.

In the production method of the component (A), the reaction pressure is not particularly limited as long as it can maintain the predetermined reaction temperature, and it can be carried out under reduced pressure or under pressure. It is preferably 0.000001~10MPa (absolute pressure).

In the production method of the component (A), as the transesterification reaction proceeds, a monohydric (meth) acrylate monohydric alcohol will be produced by-produced. When a part of the hydroxyl group of the polyglycerol (for example, about 50 mol%) is (meth) acrylated, the monohydric alcohol is allowed to coexist in the reaction system to be in an equilibrium state, and the catalyst is adsorbed or deactivated or deactivated. After the operation, the monohydric alcohol and the monofunctional (meth) acrylate of the raw material are distilled off, whereby the product having a controlled acrylate ratio can be stably produced. On the other hand, when the hydroxyl group of the polyglycerol is actively subjected to (meth)acrylation, the monohydric alcohol is preferably discharged to the outside of the reaction system to further promote the transesterification reaction.

The method for producing the component (A) may be carried out without using a solvent, but a solvent may be used as needed. Specific examples of the solvent include n-hexane, cyclohexane, methylcyclohexane, n-heptane, n-octane, n-decane, n-decane, benzene, toluene, xylene, ethylbenzene, and diethylbenzene. Benzobenzene, cumene, pentylbenzene, dipentylbenzene, tripentylbenzene, dodecylbenzene, di(dodecyl)benzene, pentyltoluene, isopropyltoluene, decalin and Hydrocarbons such as tetrahydronaphthalene; diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dipentyl ether, diethyl acetal, dihexyl acetal, tertiary butyl methyl ether, Cyclopentyl methyl ether, tetrahydrofuran, tetrahydropyran, three Alkane, two Ethers such as alkane, anisole, diphenyl ether, dimethyl cyanidin, diglyme, triglyme and tetraglyme; 18-crown-6 Equivalent crown ethers; esters such as methyl benzoate and γ-butyrolactone; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone and benzophenone; dimethyl carbonate, Carbonic acid esters such as diethyl carbonate, ethyl carbonate, propyl carbonate, 1,2-butylene carbonate; hydrazine such as cyclobutyl hydrazine; hydrazines such as dimethyl hydrazine; urea or its derivatives a phosphine oxide such as tributylphosphine oxide; an ionic liquid such as an imidazolium salt, a piperidinium salt or a pyridinium salt; a polyoxygenated oil; and water. Among these solvents, hydrocarbons, ethers, carbonate compounds, and ionic liquids are preferred. These solvents may be used singly or in combination of two or more kinds as a mixed solvent.

In the method for producing the component (A), an inert gas such as argon gas, helium gas, nitrogen gas or carbon dioxide can be introduced into the system while maintaining the color tone of the reaction liquid, but the (meth) propylene can also be prevented. For the purpose of sulfhydryl polymerization, an oxygen-containing gas is introduced into the interior of the system. Specific examples of the oxygen-containing gas include air, a mixed gas of oxygen and nitrogen, and a mixed gas of oxygen and helium. The method of introducing the oxygen-containing gas includes a method of dissolving it in the reaction liquid or blowing it into the reaction liquid (so-called foaming).

In the production method of the component (A), it is preferred to add a polymerization inhibitor to the reaction liquid for the purpose of preventing polymerization of (meth) acrylonitrile. Specific examples of the polymerization inhibitor include hydroquinone, tertiary butyl hydroquinone, hydroquinone monomethyl ether, 2,6-di(tertiary butyl)-4-methylphenol, 2,4,6- Tris(tertiary butyl)phenol, 4-tris-butylcatechol, benzopyrene, thiophene , N-nitrous-N-phenylhydroxylamine ammonium, 2,2,6,6-tetramethylpiperidin-1-yloxy, 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 copper dibutyldithiocarbamate, N-nitrous-N-phenylhydroxylamine aluminum salt And other organic salt polymerization inhibitors. The polymerization inhibitor may be added singly or in combination of two or more kinds, and may be added from the beginning of the present invention or may be added from the middle. In addition, the required usage can be added in all directions, or added in several stages. Moreover, it can be continuously added through the rectification column. The addition ratio of the polymerization inhibitor is preferably from 5 to 30,000 wtppm, more preferably from 25 to 10,000 wtppm, in the reaction liquid. When the ratio is 5 wtppm or more, the polymerization effect can be suppressed, and by controlling at 30,000 wtppm or less, the reaction liquid can be suppressed from being colored, the purification step after completion of the reaction can be simplified, and the hardening of the obtained (A) component can be prevented. The speed is reduced.

In the production method of the component (A), the reaction time varies depending on the type and amount of the catalyst, the reaction temperature, the reaction pressure, and the like, and is preferably 0.1 to 150 hours, more preferably 0.5 to 80 hours.

The manufacturing method of the component (A) can be carried out by any one of a batch type, a half batch type, and a continuous type. In one example of the batch type, a polyglycerol, a monofunctional (meth) acrylate, a catalyst, and a polymerization inhibitor are fed into the reactor, and an oxygen-containing gas is bubbled in the reaction liquid. Stir at a predetermined temperature. Thereafter, the monohydric alcohol which is produced by the transesterification reaction is discharged from the reactor under a predetermined pressure, and the target component (A) is produced.

The reaction product obtained by the production method of the component (A) is subjected to a separation and purification operation, and the desired polyglycerol poly(meth)acrylate can be obtained with good purity, which is preferable. The separation and purification operation may be, for example, an adsorption operation, a crystallization operation, a filtration operation, a distillation operation, an extraction operation, or the like, and it is preferred to combine them. The adsorption operation may be carried out by a catalyst using an adsorbent, and the adsorbent may be, for example, aluminum niobate. The crystallization operation may be, for example, cooling crystallization, concentration crystallization, or the like. The filtration operation may be, for example, pressure filtration, suction filtration, or centrifugal filtration. The distillation operation may be, for example, tank distillation, fractional distillation, molecular distillation, or steam distillation. The extraction operation may be, for example, solid-liquid extraction, liquid-liquid extraction, or the like. A solvent can also be used in the separation and purification operation. Further, a neutralizing agent for neutralizing the catalyst and/or the polymerization inhibitor used in the present invention, an acid and/or a base for decomposing or removing the by-product, an activated carbon for improving the color tone, or an activated carbon may be used. To improve the filtration efficiency and filtration speed of the algae soil.

1-5. Preferred Form (A) Component (A) is a mixture of (meth) acrylate obtained by transesterification of polyglycerol with a monofunctional (meth) acrylate, which is a (meth) propylene. A mixture of sulfhydryl groups of different (meth) acrylates.

The hydroxyl value of the component (A) is preferably from 80 to 600 mgKOH/g, more preferably from 100 to 500 mgKOH/g, and particularly preferably from 120 to 400 mgKOH/g. When the hydroxyl value of the component (A) is 80 mgKOH/g or more, the cured film of the composition has excellent low curling property, and by setting the hydroxyl value to 600 mgKOH/g or less, the composition has excellent curability.

The molecular weight distribution index of the component (A) is preferably 1.0 to 2.5, more preferably 1.0 to 2.0, in the main peak of the gel permeation chromatography (hereinafter referred to as "GPC"). It is especially good at 1.0~1.5. Further, Mw means a weight average molecular weight, and Mn means an average molecular weight. When Mw/Mn is 2.5 or less, it means that a high molecular weight body (hereinafter referred to as "side reaction high molecular weight body") due to a side reaction other than (meth) acrylate (such as Michael addition) is less, and it is excellent in hardenability. ideal. On the other hand, the polyglycerol (meth) acrylate obtained by the dehydration esterification reaction has a large amount of side reaction high molecular weight body and the Mw/Mn is more than 2.5 and hardened as compared with the polyglycerol (meth) acrylate obtained by the transesterification reaction. Insufficient.

The (meth) acrylate is preferably an acrylate from the viewpoint of rapid hardenability.

2. Hardening type composition The present invention relates to a hardening type composition containing the above (A) component. In the method for producing a composition, it is preferred to produce a polyacrylic acid by subjecting a polyglycerol to a transesterification reaction with a monofunctional (meth) acrylate in the presence of the catalysts X and Y. A mixture of alcohol (meth) acrylates. According to this production method, the amount of the side reaction high molecular weight body in the component (A) is small, the viscosity is low, the handling is easy, and the curability and the scratch resistance are excellent. This step may be carried out only in accordance with the production method of the above component (A). Further, in the case of blending other components described later, it is only necessary to stir and mix the component (A) with other components.

The content ratio of the component (A) is preferably 20% by weight based on the total amount of the curable component, from the viewpoint that the composition has rapid curability and the obtained cured film has excellent low yellowing, high flexibility, and low curling property. 100% by weight, more preferably 30 to 100% by weight. In the present invention, the "curable component" is "a component which is hardened by heat or an active energy ray", and means (A) component, and means (A) and (D) when blending the component (D) described later. )ingredient. Further, when a polymerizable functional group compound (hereinafter referred to as "other polymerizable component") other than the components (A) and (D) such as a cationically curable compound (for example, an epoxy compound or an oxonium compound) is blended, "hardening" "Sexual component" means "(A) component and other polymerizable component" and "(A) component, (D) component and other polymeric component".

The composition of the present invention can be used for any of an active energy ray-curable composition and a thermosetting composition, but it is preferably an active energy ray-curable composition. In the composition of the present invention, the above (A) is an essential component, but various components may be blended depending on the purpose. The other components are preferably a photopolymerization initiator (hereinafter referred to as "component (B)"), a thermal polymerization initiator (hereinafter referred to as "component (C)"), and ethylene other than the component (A). Unsaturated compound [hereinafter referred to as "(D) component"], pigment or dye [hereinafter referred to as "(E) component"], organic solvent or water [hereinafter referred to as "(F) component"], colloidal Inorganic fine particles [hereinafter referred to as "(G) component"] and a polymer (hereinafter referred to as "(H) component"). Hereinafter, these components will be described. In addition, as for the other components mentioned later, only one of the exemplified compounds may be used, and two or more kinds may be used in combination.

2-1. (B) Component When the composition of the present invention is used as an active energy ray-curable composition and further used as an electron beam hardening type composition, it may be made free of the component (B) (photopolymerization initiator) ) and harden it with an electronic wire. When the composition of the present invention is used as an active energy ray-curable composition, in particular, when ultraviolet rays or visible rays are used for the active energy ray, it is necessary to further contain the component (B). When the electron beam is used for the active energy ray, although it is not necessary to blend, it may be blended in a small amount as needed in order to improve the hardenability.

Specific examples of the component (B) include benzyldimethylacetal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1-[ 4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, oligo[2-hydroxy-2-methyl-1-[4-1-( Methylvinyl)phenyl]acetone, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propenyl)benzyl]phenyl}-2-methylpropane-1 -ketone, 2-methyl-1-[4-(methylthio)][phenyl]-2- Lolinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4- Polinylphenyl)butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4- Physo-4-yl-phenyl)butan-1-one and 3,6-bis(2-methyl-2- Acetophenone-based compounds such as phenylpropanyl)-9-n-octylcarbazole; benzoin compounds such as benzoin, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; benzophenone, 2-methyldiphenyl Ketone, 3-methylbenzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, methyl-2-di Benzophenone, 1-[4-(4-benzylidenephenylhydrogenthio)phenyl]-2-methyl-2-(4-methylphenylindenyl)propan-1-one, 4 , 4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone and 4-methoxy-4'-dimethylamino group II Benzophenone-based compound such as benzophenone; bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide, 2,4,6-trimethylbenzhydryldiphenylphosphine a mercaptophosphine oxide compound such as an oxide and bis(2,6-dimethoxybenzylidene)-2,4,4-trimethylpentylphosphine oxide; and 9-oxothiolane 2-chloro-9-oxopurine 2,4-diethyl-9-oxothione Isopropyl-9-oxoxime 1-chloro-4-propyl-9-oxopurine , 3-[3,4-dimethyl-9-oxo-oxy-9H-9-oxathioprine -2-yl-oxy]-2-hydroxypropyl-N,N,N-trimethylammonium chloride and fluoro-9-oxothiolane 9-oxopurine A compound or the like. The compound other than the above may, for example, be a benzyl group, an ethyl (2,4,6-trimethylbenzylidene) phenylphosphinate, a methyl phenylglyoxylate, an ethyl hydrazine or a phenanthrenequinone. Camphor and so on.

Among the active energy rays, a preferred component (B) for using a UV-LED as an ultraviolet light source will be described. In this case, the compound is preferably a mercaptophosphine oxide-based compound (hereinafter referred to as "(B-1) component") from the viewpoint of achieving both UV-LED curability and low-yellowing. Particularly, in the use of the UV-LED hardening type transparent coating agent, the component (B-1) is more preferable. Specific examples of the component (B-1) include the above compounds.

Further, when the composition of the present invention is used for ink printing, in order to further improve the UV-LED hardenability of the component (B), it is intended to contain 9-oxosulfuron. A compound (hereinafter referred to as "(B-2) component") or 4,4'-bis(dialkylamino)benzophenone (hereinafter referred to as "(B-3) component") is preferred. The component (B-2) and the component (B-3) may be used in combination. Further, in addition to the component (B-2) or/and the component (B-3), the component (B-1) may be used in combination.

When the component (B-2) is used, in order to improve the efficiency of dehydrogenation and active radical generation by the photosensitive (B-2) component, it is preferred to add a tertiary amine compound. The tertiary amine compound is preferably an aromatic ring-containing amine compound such as ethyl 4-dimethylaminobenzoate. Specific examples of the component (B-2) include the above compounds.

Specific examples of the component (B-3) include 4,4'-bis(dimethylamino)benzophenone and 4,4'-bis(diethylamino)benzophenone.

The content ratio of the component (B) is preferably from 1 to 20 parts by weight, more preferably from 2 to 18 parts by weight, per 100 parts by weight of the total of the curable component, from the viewpoint of the composition curability and the yellowing resistance of the cured film. And 3 to 15 parts by weight is more preferable.

The component (B) may be used in combination with the above-mentioned compound only for the purpose of use, and the preferred combination and ratio thereof are, for example, the following. When the composition of the present invention is used as a UV-LED curable transparent coating agent, the content of the component (B-1) is preferably from 1 to 15 parts by weight, more preferably from 3 to 5 parts by weight based on 100 parts by weight of the total of the curable component. 12 parts by weight. Further, in the viewpoint of making the cured film have a low yellowing property, the component (B-2) is preferably not contained in an amount of 2 parts by weight or more, more preferably not more than 1 part by weight. Further, in the same manner, the component (B-3) is preferably not contained in an amount of 1 part by weight or more, and more preferably 0.5 part by weight or more, from the viewpoint of imparting low-yellowing of the cured film.

When the composition of the present invention is used as a UV-LED curable ink composition, the content ratio of the component (B-2) and/or the component (B-3) is 100 parts by weight based on the total amount of the curable component. It is preferably 1 to 15 parts by weight, more preferably 2 to 12 parts by weight. In addition to the component (B-2) or/(B-3), when the component (B-1) is used in combination, it preferably contains 1 to 15 parts by weight of the component (B-1), more preferably 2 to 10 Parts by weight. However, the total amount of the component (B) is preferably 20 parts by weight or less based on 100 parts by weight of the curable component.

2-2. (C) Component When the composition of the present invention is used as a thermosetting composition, a thermal polymerization initiator may be blended. As the thermal polymerization initiator, various compounds can be used, and an organic peroxide and an azo initiator are preferred. Specific examples of the organic peroxide include 1,1-bis(tri-butylperoxy)2-methylcyclohexane and 1,1-bis(tri-hexylperoxy)-3,3,5- Trimethylcyclohexane, 1,1-bis(tri-hexylperoxy)cyclohexane, 1,1-bis(tertiarybutylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tri-butylperoxy)cyclohexane, 2,2-bis(4,4-dibutylperoxycyclohexyl)propane, 1,1-bis(tri-butylperoxy) Cyclododecane, tertiary hexylperoxyisopropylmonocarbonate, tertiary butylperoxy maleic acid, tertiary butylperoxy-3,5,5-trimethylhexanoate, three Butyl butylperoxylaurate, 2,5-dimethyl-2,5-di(m-tolylmethyl peroxy)hexane, tertiary butyl peroxyisopropyl monocarbonate, tertiary butyl Base peroxy 2-ethylhexyl monocarbonate, tertiary hexylperoxybenzoate, 2,5-dimethyl-2,5-bis(benzhydrylperoxy)hexane, tert-butyl Peroxyacetate, 2,2-bis(tertiary butylperoxy)butane, tertiary butyl peroxybenzoate, n-butyl-4,4-bis(tri-butylperoxy) Valerate, di(tertiary butyl)peroxyisophthalate, α,α'-bis(tri-butylperoxy)diisopropylbenzene, dicumyl Dicumyl peroxide, 2,5-dimethyl-2,5-di(tri-butylperoxy)hexane, tertiary butyl cumyl peroxide, di(tertiary butyl) Peroxide, p-menthane peroxide, 2,5-dimethyl-2,5-di(tri-butylperoxy)hexane-3, diisopropylbenzene hydroperoxide, tertiary tributyl Trimethylsulfonyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, tertiary hexyl hydroperoxide and tertiary butyl hydrogen peroxide Oxide, etc. Specific examples of the azo compound include 1,1'-azobis(cyclohexane-1-carbonitrile), 2-(aminomercaptoazo)isobutyronitrile, and 2-phenylazo- 4-methoxy-2,4-dimethylvaleronitrile, azobis(trioctane), azobis(tertiary butane), and the like. These may be used alone or in combination of two or more. Further, the organic peroxide can also be subjected to a redox reaction by being combined with a reducing agent.

The content ratio of the component (C) is preferably 10 parts by weight or less based on 100 parts by weight of the total amount of the curable component. When the component (C) is used alone, it may be carried out according to the usual method of general radical thermal polymerization, and may be used in combination with the component (B) (photopolymerization initiator) as appropriate, and the reaction rate is further improved after photocuring. Thermal hardening is carried out under the purpose.

2-3. (D) Component The component (D) is an ethylenically unsaturated compound other than the component (A), which is blended for the purpose of imparting various physical properties of the cured film of the composition. The ethylenically unsaturated group in the component (D) may, for example, be a (meth) acrylonitrile group, a (meth) acrylamide group, a maleimide group, a vinyl group or a (meth)allyl group. And the like, and a (meth) acrylonitrile group is preferred. In the following, "monofunctional" means a compound having one ethylenically unsaturated group, "○ functional" means a compound having ○ ethylenically unsaturated groups, and "polyfunctional" means having 2 More than one ethylenically unsaturated group of compounds. Specific examples of the component (D) include (meth) acrylate, (meth) acrylamide, vinyl ether, and maleimide, and a (meth) acrylate is preferable. Among these compounds, acrylate, acrylamide, and vinyl ether are preferred from the viewpoint of curability, and acrylate is more preferable.

In the component (D), the polyfunctional ethylenically unsaturated compound may be a compound (D-1) having two ethylenically unsaturated groups (hereinafter referred to as "(D-1) component"), and having three or more. The ethylenically unsaturated group compound (D-2) [hereinafter referred to as "(D-2) component"] and a monofunctional ethylenically unsaturated compound [hereinafter referred to as "(D-3) component"). The following (D-1) to (D-3) components will be described.

2-3-1. (D-1) Component The component (D-1) is a compound having two ethylenically unsaturated groups other than the component (A), and may be a low molecular weight compound or an oligomer.

When a low molecular weight monomer is blended as the component (D-1), a composition having a low viscosity can be obtained without a solvent. Further, when a high molecular weight urethane (meth) acrylate oligomer is used, the cured film can be imparted with elasticity or adhesion to the adherend.

Specific examples of the component (D-1) include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, and neopentyl glycol di( Methyl) acrylate, hexanediol di(meth) acrylate and decanediol di(meth) acrylate, cyclohexane dimethanol di(meth) acrylate, lower a di(meth) acrylate of an aliphatic diol such as an alkyl dimethylol di(meth) acrylate or a tricyclodecane dimethylol di(meth) acrylate; a polyethylene glycol di(methyl) a polyalkylene glycol di(meth)acrylate such as acrylate, polypropylene glycol di(meth)acrylate or polytetramethylene glycol di(meth)acrylate; and an alkylene oxide of bisphenol A a dialkylated oxide adduct of a compound having two phenolic hydroxyl groups in one molecule, such as an adduct of a di(meth)acrylate and an alkylene oxide adduct of bisphenol F. Acrylate; bisphenol A type epoxy resin added with (meth)acrylic acid compound, etc., so-called epoxy (meth) acrylate; ethylene glycol, phthalic anhydride and (meth) acrylate ester Compounds and the like, so-called polyester (meth) acrylate; and isophorone diisocyanate, polymer diol and hydroxyalkyl (meth) acrylate by urethane reaction A compound or the like, a so-called urethane (meth) acrylate or the like. Here, the polymer diol may, for example, be a polyether diol, a polyester diol, a polycarbonate diol, or a diol having a plurality of such skeletons.

Specific examples of the component (D-1) may further include 2-vinyloxyethyl (meth)acrylate, 2-vinyloxyethoxyethyl (meth)acrylate, and 1,4-butanediol. Divinyl ether, neopentyl glycol divinyl ether, cyclohexane dimethanol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether and dipropylene glycol divinyl ether, etc. A difunctional monomer containing a functional group other than (meth) acrylate.

When the composition of the present invention is used as a UV-LED hardening type varnish, the (D-1) component preferably contains a polyalkylene glycol di(meth)acrylate (D-1-1) [hereinafter referred to as "(D) -1-1) Ingredients"]. By including the component (D-1-1), the excellent rapid hardenability of the component (A) can be prevented from being greatly lowered, and the viscosity can be reduced and the flexibility can be further improved. In the case of the component (D-1-1), polyethylene glycol (average degree of polymerization 2 to 10) diacrylate is used in view of low viscosity and excellent hardenability of the composition and excellent flexibility of the cured film. More ideal.

When the component (D-1) is blended, the preferred content ratio varies depending on the use of the composition of the present invention. In addition, it varies depending on the type of (D-1-1) component. The use ratio of the component (D-1-1) to the varnish for paper or plastic film is preferably 0 to 80 parts by weight, more preferably 0 to 70 parts by weight, per 100 parts by weight of the curable component. On the other hand, in the case of the hard coat layer, the content of the component (D-1) is preferably from 0 to 40 parts by weight, more preferably from 0 to 20 parts by weight, per 100 parts by weight of the curable component.

2-3-2. The component (D-2) is a compound having three or more ethylenically unsaturated groups other than the component (A), and may be a low molecular weight compound or an oligomer. .

Specific examples of the component (D-2) include glycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, and neopentyl alcohol tris or tetra(meth)acrylate. , tris or tetra (meth) acrylate of di(trimethylol)propane, tri or tetra (meth) acrylate of diglycerol, three, four, five or six of dipentaerythritol Poly(meth)acrylates such as acrylates and tripentaerythritol, such as tris, tetra, penta, hexavalent or octa (meth) acrylates; glycerol alkylene oxide adducts Tris(meth)acrylate, trimethylolpropane alkylene oxide adducts of tris(meth)acrylate, pentaerythritol alkylene oxide adducts of three or four (methyl) a poly(meth) acrylate of an acrylate, a diglycerin alkylene oxide adduct, or a poly(meth) acrylate of a polyglycerol alkylene oxide adduct (but three a functional or higher (meth) acrylate), a bis(trimethylol)propane alkylene oxide adduct of a tri- or tetra(meth) acrylate, a dipentaerythritol alkylene oxide addition Three, four, five or six (methyl a poly(alkyl) oxide adduct of a acrylate or a pentaerythritol alkylene oxide adduct of three, four, five, six, seven or eight (meth) acrylates. Acrylate; tris(meth)acrylate of isomeric cyanuric acid alkylene oxide adduct; polyhydroxyl of neopentyl alcohol triacrylate by Michael addition to acrylate Acrylate, etc., Michael addition molding polymer containing hydroxyl polyfunctional acrylate; polyfunctional amine ethyl formate (meth) acrylate, which is neopentyl alcohol tri(meth) acrylate or dipentaerythritol a reaction product of a compound having a hydroxyl group and three or more (meth) acrylonitrile groups and an organic polyisocyanate such as penta (meth) acrylate; a novolak type epoxy resin and a trifunctional or higher (meth) group added with acrylic acid a polyfunctional epoxy (meth) acrylate such as acrylate; and a polyhydric alcohol having three or more hydroxyl groups, an acid anhydride such as phthalic anhydride, and a polyester composed of (meth)acrylic acid in one molecule such as trimethylolpropane ( A polyfunctional polyester (meth) acrylate such as a methyl acrylate or the like. Examples of the alkylene oxide adducts in the above-mentioned examples include ethylene oxide adducts, propylene oxide adducts, and ethylene oxide and propylene oxide adducts. Further, the organic polyisocyanate may, for example, be hexamethylene diisocyanate, tetramethylene diisocyanate, trimethylhexamethylene diisocyanate, isocyanuric acid diisocyanate or isophorone diisocyanate. Alkyl diisocyanate, hydrogenated methyl phenyl diisocyanate, hydrogenated 4,4'-diphenylmethane diisocyanate, hydrogenated deuterated diisocyanate, 4,4'-dicyclohexylmethane diisocyanate and hexamethylene diisocyanate Terpolymer and the like.

When the composition of the present invention is used as a hard coat layer, the component (D-2) preferably contains dipentaerythritol poly(meth)acrylate (D-2-1) [hereinafter referred to as "(D-2-1) )ingredient"]. In addition, as for the component (D-2), it is also preferred to contain ethyl urethane (meth) acrylate (D-2-2) having three or more (meth) acrylonitrile groups [hereinafter referred to as "( D-2-2) component "] is used as the component (D-2-2). The component (D-2-1) and the component (D-2-2) may also be used in combination. The scratch resistance of the cured film of the composition can be improved by including the component (D-2-1) and/or the component (D-2-2).

When the component (D-2) is blended, the preferred content ratio varies depending on the use of the composition of the present invention. The hard coat use is preferably 0 to 80 parts by weight, more preferably 0 to 70 parts by weight, per 100 parts by weight of the curable component. On the other hand, the use of the active energy ray-curable varnish for paper or plastic film is preferably 0 to 40 parts by weight, more preferably 0 to 20 parts by weight, per 100 parts by weight of the curable component.

2-3-3. (D-3) Component The component (D-3) is a compound having one ethylenically unsaturated group in one molecule, and may be a low molecular weight compound or an oligomer. The adhesion of the cured film can be imparted or the adhesion to the adherend can be improved by blending the component (D-3).

Specific examples of the component (D-3) include the same compounds as the above-mentioned monofunctional (meth)acrylate. Examples of the compound other than the monofunctional (meth) acrylate include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. , 4-cyclohexanedimethylol mono(meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, (meth)acrylate of phenylalkylene oxide adduct, (meth) acrylate of p-cumylphenol alkylene oxide adduct, (meth) acrylate of o-phenylphenol alkylene oxide adduct, nonyl phenol alkylene oxide a (meth) acrylate of an adduct, a (meth) acrylate of an alkylene oxide adduct of 2-ethylhexyl alcohol, a pentanediol mono(meth) acrylate, a hexane diol ( Methyl) acrylate, mono(meth) acrylate of diethylene glycol, mono (meth) acrylate of triethylene glycol, mono (meth) acrylate of tetraethylene glycol, polyethylene glycol Mono (meth) acrylate, mono (meth) acrylate of dipropylene glycol, mono (meth) acrylate of tripropylene glycol, mono (meth) acrylate of polypropylene glycol, 2-hydroxyl (meth) acrylate - 3-phenoxy Propyl ester, 2-hydroxy-3-butoxypropyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, caprolactone modified tetrahydrofurfuryl (meth)acrylate, (meth)acrylic acid (2-ethyl-2-methyl-1,3-di Pentane-4-yl)methyl ester, (meth)acrylic acid (2-isobutyl-2-methyl-1,3-di Pentane-4-yl)methyl ester, (meth)acrylic acid (1,4-di) Spiro[4,5]decane-2-yl)methyl ester, 2-sided oxytetrahydrofuran-3-yl (meth) acrylate, (meth)acrylic acid (5-ethyl-1,3-di Alkan-5-yl)methyl ester, glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, (meth)acrylic acid (3-ethyloxonium-3) -yl)methyl ester, 2-(methyl)propenyloxyethyl isocyanate, N-(methyl)propenyloxyethyl hexahydroindenimide, N-(methyl)acryloxyloxy Tetrahydroindenimide, 2-(methyl)propenyloxyethyl hexahydrophthalic acid, 2-(meth)acryloxyethyl succinic acid, ω-carboxy-polycaprolactone mono( Methyl) acrylate, 3-(meth) propylene methoxy propyl trimethoxy decane, 3-(methyl) propylene methoxy propyl dimethoxy methyl decane, 3-(methyl) propylene Alkoxypropyltriethoxydecane, 2-(meth)acrylomethoxyethyl phosphate, and the like. Further, a compound having both an ethylenically unsaturated group and an alkoxyfluorenyl group is also referred to as a decane coupling agent. When it is desired to improve the adhesion to the inorganic substrate, a decane coupling agent or a compound having both an ethylenically unsaturated group and a phosphoric acid group is preferred.

The (D-3) component other than the monofunctional (meth) acrylate may, for example, be N-vinylpyrrolidone, N-vinyl caprolactam, (meth) acrylamide, or (meth) acrylonitrile. Porphyrin, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-hydroxyethyl(meth)acrylamide, N-isopropyl (Methyl) acrylamide, maleic anhydride, N-phenyl maleimide, N-hydroxyethyl maleimide, N-hydroxyethyl citrate, Cyclohexyl vinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 1,4-cyclohexane dimethanol monovinyl ether, diethylene glycol monovinyl ether, dipropylene glycol monovinyl ether, ethoxy Ethyl vinyl ether, ethoxybutyl vinyl ether, acetonitrile cyclohexane dimethanol monovinyl ether, acetyl bisethylene glycol monovinyl ether, glycidoxy ethyl vinyl ether, propylene oxide Oxybutyl butyl vinyl ether, epoxypropyl cyclohexane dimethanol monovinyl ether, and epoxy propylene diethylene glycol monovinyl ether.

When the component (D-3) is blended, the preferred content ratio varies depending on the use of the composition of the present invention, the type of the adherend, the light source, and the hardened gas atmosphere. In the case of a hard coat layer or a UV-LED hardening type clear coating agent and an ink which are hardened by air, the content ratio of the component (D-3) is from the viewpoint of rapid hardenability, and the curable component is 100% by weight. % should preferably contain 0~30% by weight, more preferably 0~15% by weight. On the other hand, when it is applied to an adherend having difficulty in adhesion, or when an ink for inkjet or the like is required to have an ultra-low viscosity, the component (D-3) may be contained in an amount of 80% by weight based on 100% by weight of the curable component. At this time, the rapid hardenability was impaired, but the hardenability was improved as compared with the composition without using the component (A).

2-4. Component (E) The component (E) is a coloring component selected from a pigment or a dye, and is essential when the composition of the present invention is used as a composition for ink. The pigment may, for example, be an organic pigment or an inorganic pigment. Specific examples of the organic pigment include insoluble azo pigments such as toluidine red, toluidine maroon, Hansa yellow, benzidine yellow, and pyrazole ruthenium; , Helio Bordeaux, pigment scarlet and permanent red 2B soluble azo pigments; valerin, indanthrene and Thioindigo-maroon derived from anthraquinone dyes; indigo blue and indigo green Isocyanin-based organic pigment; quinacridone red and quinophthalone ketone and other quinacone organic pigments; ruthenium and scorpion red and other lanthanide organic pigments; isoindolinone yellow and isoindolinone orange Isoindolinone organic pigment; anthrone organic pigment such as anthrone red and anthrone orange; thioindigo organic pigment; condensed azo organic pigment; benzimidazolone organic pigment; quinoline yellow Isoquinoline yellow-based organic pigment; isoporphyrin-based organic pigment such as isoporphyrin yellow; and other pigments such as Flavanthrone yellow, decyl guanamine yellow, nickel azo yellow (nickel) Azo yellow), copper azomethine Yellow), perinone orange, Anseron orange, dimercapto red and Purple and so on. Further, specific examples of the inorganic pigment include carbon black, titanium oxide, barium sulfate, calcium carbonate, zinc oxide, lead sulfate, yellow lead, zinc yellow, Bengala (red iron oxide (III)), cadmium red, ultramarine blue, Prussian blue, chrome oxide green, cobalt green, amber, titanium black and synthetic iron black. The dye may, for example, be an azo dye or a plant-derived extract. The content of the component (E) may be appropriately adjusted depending on the use and the film thickness. However, in the case of the ink composition, the total amount of the curable component is preferably from 5 to 200 parts by weight, more preferably from 5 to 200 parts by weight. 10 to 100 parts by weight.

2-5. (F) Component The composition of the present invention can be blended with an organic solvent or water as the component (F) for the purpose of reducing the viscosity. Specific examples of the organic solvent include low molecular weight alcohol compounds such as methanol, ethanol, isopropanol and butanol; alkylene glycol monoether compounds such as ethylene glycol monomethyl ether and propylene glycol monomethyl ether; diacetone alcohol and the like. Acetyl alcohol; aromatic compounds such as benzene, toluene and 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; An ether compound such as ether; and N-methylpyrrolidone. Among these, an ethylene glycol monoether compound and a low molecular weight alcohol compound are preferred.

When the essential component (A) component of the composition of the present invention has a large proportion of hydroxyl groups in one molecule, water can be dissolved to some extent. Therefore, the composition of the present invention can be blended with water as the component (F). The efficiency of water dilution is extremely high and safe. Therefore, a solvent-free, low-viscosity, low-odor, and fast-hardening composition can be produced by using water.

The preferred content ratio of the component (F) varies depending on the use of the composition of the present invention, but is preferably 0 to 1,000 parts by weight, more preferably 0 to 500 parts by weight, based on 100 parts by weight of the total amount of the curable component. More preferably 300 parts by weight.

2-6. (G) component The composition of the present invention may also contain colloidal inorganic particles as the component (G). Examples of the inorganic particles include metal oxides such as cerium oxide, aluminum oxide, titanium oxide, zinc oxide, tin oxide, and indium oxide; metals such as gold, silver, platinum, and palladium; metal chalcogenides such as zinc sulfide and zinc arsenide; . Among them, in the use of a hard coat layer or the like which requires scratch resistance and colorless transparency, a colorless metal oxide is preferable, specifically, cerium oxide, titanium oxide, zinc oxide, tin oxide, or the like. Indium oxide is preferred, and cerium oxide is particularly preferred. In this case, the average particle diameter is preferably from 1 to 200 nm, more preferably from 5 to 150 nm, and more preferably from 10 to 100 nm, as determined by the specific surface area measured by the BET method.

The component (G) may be a colloidal inorganic particle (hereinafter referred to as "(G-1) component") having an ethylenically unsaturated group or a photoreactive group bonded to the surface, and having no ethylenically unsaturated group and photoreaction. Colloidal inorganic particles (hereinafter referred to as "(G-2) component"). In the case of the component (G), it is preferable to use the component (G-1) when the durability against scratch resistance is used, and the component (G-2) is preferably used when the film is applied to a thin substrate such as a film. Specific examples of the component (G-1) include a reaction product of (meth)acryloxypropyltrimethoxydecane and colloidal cerium oxide.

When the component (G-1) is blended, the content of the component (G-1) is preferably 0 to 60 parts by weight, more preferably 0 to 30 parts by weight, per 100 parts by weight of the curable component. On the other hand, when the component (G-2) is blended, the blending amount of the component (G-2) is preferably from 0 to 100 parts by weight, more preferably from 0 to 50 parts by weight, per 100 parts by weight of the curable component. Further, the component (G-1) is contained in the curable component, and the component (G-2) is not included in the curable component.

2-7. (H) component The composition of the present invention can be blended with a polymer as the component (H). When the polymer is blended as the component (H), it is possible to improve the curl of the substrate when the thickness is thin or to improve the adhesion to plastics and metals. The polymer may be preferably a (meth)acrylic polymer. Preferred structural monomers may be methyl (meth)acrylate, cyclohexyl (meth)acrylate, (meth)acrylic acid, (A). Glycidyl acrylate, N-(2-(methyl) propylene methoxyethyl) tetrahydrofurinimide, and the like. When the (meth)acrylic acid is copolymerized to form a polymer, a (meth)acrylonitrile group may be added to the polymer chain by addition of glycidyl (meth)acrylate. In addition to (meth)acrylic polymers, polyesters, polyurethanes, polycarbonates, polyvinylpyrrolidone, polyvinyl acetate, vinylpyrrolidone and ethylene acetate may be blended. Various polymers such as copolymers, polyvinyl alcohol, cellulose alkylate, and diallyl phthalate resins.

The component (H) may, for example, be a polymer having an ethylenically unsaturated group and a photoreactive group (hereinafter referred to as "(H-1) component") and a polymerization having no ethylenically unsaturated group and a photoreactive group. (hereinafter referred to as "(H-2) component"]. In the case of the component (H), when the composition of the present invention is used as a hard coat layer, the component (H-1) is preferred.

When the component (H-1) is blended, the content of the component (H-1) is preferably 0 to 60 parts by weight, more preferably 0 to 30 parts by weight, per 100 parts by weight of the curable component. On the other hand, when the component (H-2) is blended, the blending amount of the component (H-2) is preferably 0 to 50 parts by weight, more preferably 0 to 25 parts by weight, per 100 parts by weight of the curable component. Further, the component (H-1) is contained in the curable component, and the component (H-2) is not contained in the curable component.

2-8. Various Additives In addition to the aforementioned components, the composition of the present invention may be blended with various additives depending on the purpose. Various additives may be used as surface modifiers, antioxidants, ultraviolet absorbers, light stabilizers, decane coupling agents, particles, polymerization inhibitors, conductivity imparting agents, pigment dispersants, antifoaming agents, antibacterial agents, photoacids. Agent, photobase generator, thermal radical polymerization initiator, and the like. The following also briefly supplements one of the parts.

2-8-1. Surface Modifier The surface modifier can be added to the composition of the present invention for the purpose of improving the leveling property at the time of coating, and for improving the lubricity of the cured film to improve the scratch resistance. The surface modifier may, for example, be a surface conditioner, a surfactant, a leveling agent, an antifoaming agent, a lubricity imparting agent, or an antifouling imparting agent, and such a conventional surface modifying agent can be used. Among them, a polyfluorene-based surface modifier and a fluorine-based surface modifier may be mentioned, and specific examples thereof include a polyfluorene-based chain having a polyfluorene chain and a polyalkylene oxide chain. Polymers and oligomers, polyfluorene-based polymers and oligomers having a polyfluorene chain and a polyester chain, fluorine-based polymers and oligomers having a perfluoroalkyl group and a polyalkylene oxide chain And a fluorine-based polymer having a perfluoroalkyl ether chain and a polyalkylene oxide chain, an oligomer, and the like. Further, it is also possible to use a surface modifier having an ethylenically unsaturated group (preferably a (meth) acrylonitrile group) in the molecule for the purpose of improving the sustainability of lubricity. The content ratio of the surface modifier is preferably 0.01 to 1.0 part by weight based on 100 parts by weight of the total amount of the curable component. When it is in the above range, the surface of the cured film is excellent in smoothness.

2-8-2. Antioxidant The antioxidant is blended for the purpose of improving durability such as heat resistance and weather resistance of the cured film. The antioxidant may, for example, be a phenol-based antioxidant, a phosphorus-based antioxidant, or a sulfur-based antioxidant. The phenolic antioxidant may, for example, be a hindered phenol such as di(tri-butyl)hydroxytoluene. Commercially available products are AO-20, AO-30, AO-40, AO-50, AO-60, AO-70, and AO-80 manufactured by ADEKA. Examples of the phosphorus-based antioxidant include phosphines such as trialkylphosphine and triarylphosphine, trialkylphosphonium phosphate, and triaryl phosphite. Commercial products of such derivatives may be, for example, ADK STAB PEP-4C, PEP-8, PEP-24G, PEP-36, HP-10, 260, 522A, 329K, 1178, 1500, 135A, and ADEKA. 3010 and so on. Examples of the sulfur-based antioxidant include a thioether compound, and commercially available products include AO-23, AO-412S, and AO-503A manufactured by ADEKA. These may be used alone or in combination of two or more. A preferred combination of these antioxidants may be a combination of a phenolic antioxidant and a phosphorus antioxidant, and a phenolic antioxidant and a sulfur-based antioxidant. The content ratio of the antioxidant may be appropriately set depending on the purpose, and is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 1 part by weight, per 100 parts by weight of the total amount of the curable component. The durability of the composition can be improved by setting the content to be 0.1 part by weight or more, and the curability and the adhesion can be improved by setting it to 5 parts by weight or less.

2-8-3. Ultraviolet absorber The ultraviolet absorber can be blended for the purpose of improving the light resistance of the cured film. Examples of the ultraviolet absorber include TINUVIN400, TINUVIN405, TINUVIN460, and TINUVIN479 manufactured by BASF. It is a UV absorber and a benzotriazole-based UV absorber such as TINUVIN900, TINUVIN928, and TINUVIN1130. The content ratio of the ultraviolet absorber may be appropriately set depending on the purpose, and is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 1 part by weight, per 100 parts by weight of the total amount of the curable component. When the content ratio is 0.01% by weight or more, the light resistance of the cured film can be improved. On the other hand, by setting it to 5% by weight or less, the composition can be excellent in curability.

2-8-4. Light stabilizer The light stabilizer can be blended for the purpose of improving the light resistance of the cured film. The light stabilizer is preferably a hindered amine light stabilizer (so-called HALS). The HALS can be, for example, TINUVIN 123, TINUVIN 144, TINUVIN 111 FDL, TINUVIN 152, TINUVIN 292, TINUVIN 5100, and the like manufactured by BASF Corporation.

2-8-5. Decane coupling agent not belonging to the component (D-3) The decane coupling agent can be blended for the purpose of improving the interface strength between the cured film and the substrate. The decane coupling agent is only required to contribute to the improvement of adhesion to the substrate, and is not particularly limited. Further, the decane coupling agent used herein is a compound having no ethylenically unsaturated group and is different from the compound of the component (D-3). Even if there is no ethylenically unsaturated group, there is sometimes a case where the adhesion is improved. Specific examples of the decane coupling agent different from the component (D-3) include 2-(3,4-epoxycyclohexyl)ethyltrimethoxynonane and 3-glycidoxypropyltrimethoxynonane. 3-glycidoxypropylmethyldiethoxydecane, 3-glycidoxypropyltriethoxydecane, N-2-(aminoethyl)-3-aminopropylmethyl Dimethoxy decane, N-2-(aminoethyl)-3-aminopropyltrimethoxydecane, N-2-(aminoethyl)-3-aminopropyltriethoxy Decane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-triethoxyindolyl-N-(1,3-dimethyl-butylene)propyl Amine, N-phenyl-3-aminopropyltrimethoxydecane, 3-mercaptopropylmethyldimethoxydecane, 3-mercaptopropyltrimethoxydecane, and the like. The blending ratio of the decane coupling agent may be appropriately set depending on the purpose, and is preferably 0.1 to 10 parts by weight, more preferably 1 to 5 parts by weight, per 100 parts by weight of the total amount of the curable component. By setting the blending ratio to 0.1 part by weight or more, the adhesion of the composition can be increased, and on the other hand, it can be set to 10 parts by weight or less to prevent the change in the force over time.

2-8-6. Particles not belonging to the component (G) The composition of the present invention may be blended under the purpose of imparting anti-glare properties to the cured film or imparting lubricity to the cured film substrate during lamination. ) Particles other than ingredients. The particle size of the particles varies depending on the application, and is generally applicable to 0.2 to 100 μm. The particles are either inorganic or organic. The inorganic particles may be metal oxides such as cerium oxide, aluminum oxide or titanium oxide, and are not colloidal. The organic substance may be, for example, a particle obtained by crosslinking a polymer of a monomer such as an alkyl (meth)acrylate or styrene.

2-8-7. Polymerization Inhibitor The composition of the present invention may further contain a polymerization inhibitor in addition to the polymerization inhibitor contained in the component (A). The polymerization inhibitor is preferably the same compound as that added in the case of synthesizing the component (A).

2-8-8. Conductivity imparting agent The composition of the present invention may be added with a conductivity imparting agent such as an antistatic agent. The antistatic agent may be a nonionic surfactant such as glycerol fatty acid ester, polyoxyalkylene alkyl ether or alkyl diethanolamine; alkyl sulfonate, alkyl benzene sulfonate, alkyl phosphate Anionic surfactant such as salt; cationic surfactant such as tetraalkylammonium salt and trialkylbenzylammonium salt; amphoteric surfactant such as alkylbetaine, alkylimidazolium betaine; polyether ester, poly a polymer type antistatic agent such as an ether ester decylamine, a polystyrene sulfonate, a quaternary ammonium salt-containing (meth) acrylate polymer, and a polyether polyoxyalkylene; a phosphoric acid (meth) acrylate or the like a monomer of an acidic group; a metal salt of bis(fluoroalkylsulfonyl) ruthenium such as lithium bis(trifluoromethanesulfonyl) sulfoxide; ginseng (trifluoromethanesulfonyl) lithium An alkali metal salt of a fluoroalkylsulfonyl)methide; an alkali metal salt of a trifluoromethanesulfonate ion such as lithium trifluoromethanesulfonate; an imidazolium-based ionic liquid; a pyridinium-based ionic liquid plasma liquid; Lithium imide lithium salts and ionic liquids not only reduce surface resistance, but also have the effect of reducing volume resistivity.

3. Method of use The method of using the composition of the present invention can be carried out only in accordance with the usual method. For example, a method in which a composition is applied to a substrate and then cured by irradiation with an active energy ray or heating may be mentioned. Specifically, when the composition is coated or printed on a substrate to be applied by a general coating method, and the composition is an active energy ray-curable composition, the active energy ray may be used to cure the composition, or When the composition is a thermosetting composition, it may be a method of hardening by heating or the like. When the composition is used for a molding material or the like, the composition is injected into a predetermined mold frame, and when the composition is an active energy ray-curable composition, the active energy ray may be used to cure the composition, or the composition may be a thermosetting composition. In the case, it may be, for example, a method of hardening by heating. The method of irradiating the active energy ray and the heating method need only be a general method which has been known as a conventional hardening method. Further, it is also possible to employ a method in which the component (B) (photopolymerization initiator) and (C) component (thermal polymerization initiator) are irradiated with an active energy ray and then heated and hardened, thereby improving Adhesion to the substrate.

The substrate may be, for example, paper, plastic film, plastic plate, wood, metal, inorganic materials other than metal, nails, bones, and leather. The composition of the present invention is particularly suitable for use on a substrate having a relatively small thickness such as a paper or a plastic film, since the composition does not curl when it is cured and the cured film has excellent flexibility.

Specific examples of the plastic include cellulose acetate resins such as triacetonitrile cellulose and diacetyl cellulose; polyvinyl alcohol, acrylic resin, polyethylene terephthalate, polycarbonate, and polyacrylate. Polyether oxime, drop A cyclic polyolefin resin having a cyclic olefin as a monomer such as a olefin; a polyvinyl chloride, an epoxy resin, a polyurethane resin, or the like. Wood can be found in natural wood and synthetic wood. Examples of the inorganic material include metals such as steel sheets, stainless steel, aluminum, gold, silver, copper, and chromium, and metal oxides such as zinc oxide (ZnO), tin oxide, aluminum oxide, and indium tin oxide (ITO). Other inorganic materials include glass, mortar, cement, and stone. In the case of nails, bones, and leather, it may be an animal source for decoration or the like or a coating agent for human nails.

The thickness of the cured film of the composition of the substrate may be appropriately set depending on the substrate to be used and the use of the cured film substrate to be obtained. The film thickness of the cured film of the composition is preferably 0.5 to 100 μm, more preferably 1 to 20 μm.

The coating method of the composition of the present invention on the substrate may be appropriately set depending on the purpose, and may be, for example, a pen, a bristles, a bar coater, an applicator, a doctor blade, a dip coater, a roll coater, or the like. Spin coater, flow coater, knife coater, comma coater, reverse roll coater, die coater, lip coater, gravure coater, micro gravure coater and spray A method of coating or printing ink or the like.

When the composition of the present invention contains an organic solvent or water as the component (F), it is preferred to dry it after coating. When manufacturing the production line, a hot air dryer should be provided. The hot air dryer should be equipped with a local exhaust device. However, when water is only used as the component (F), the drying step is not necessarily required. When the water content is small, even if it is directly hardened in a water-containing state, a cured film which is transparent and has no problem in performance can be obtained in some cases. In addition, even when the water content is large (for example, when it contains 50% by weight or more of the whole), in the case where the film thickness is as thin as about 2 μm, most of the water volatilizes at normal temperature, and sometimes transparency and performance can be obtained. A hardened film with no problem.

The active energy ray for curing the composition of the present invention may be, for example, ultraviolet light, visible light or electronic light, but ultraviolet light is preferred. Examples of the ultraviolet light source include a high pressure mercury lamp, a metal halide lamp, an ultraviolet (UV) electrodeless lamp, a UV-LED (ultraviolet light emitting diode), and sunlight. The irradiation energy may be appropriately set depending on the type and amount of the light source, the application, and the component (B). If a high-pressure mercury lamp is used as an example, the irradiation energy in the UV-A region is 100 to 5,000 mJ/cm ^{2 .} Preferably, 200~1,000mJ/cm ^{2 is} better. Further, in the case of using a UV-LED, a case of using a transparent varnish of a 365 nm UV-LED is preferably 100 to 1,000 mJ/cm ² at 365 nm, more preferably 200 to 700 mJ/cm ² .

4. Use The hardening type composition of the present invention is preferably used as an active energy ray-curable composition, which can achieve the effects of the aforementioned rapid hardening property, low yellowing property, high flexibility, and low curling property, and can utilize the effect. For a variety of uses. Examples of preferred applications include a coating agent such as a clear coating agent and a coating material, an ink such as a slab ink or an inkjet ink, an adhesive, a photoresist, and a molding material. The use of the composition of the present invention is particularly useful as a clear coat such as a UV-LED curable clear varnish, a UV-LED curable ink, a hard coat layer, an ink for ink jet, and a paint for nails.

The active energy ray-curable composition has the following effects in various applications in addition to the aforementioned rapid hardening property, low yellowing property, high flexibility, and low curling property. (1) The composition of the active energy ray-curable transparent coating agent (including the clear varnish) exhibits excellent hardenability even when the light source is a UV-LED, and can be made into an excellent low-yellow denaturation and high scratching which is difficult to combine with hardenability. Flexibility and low curling. (2) The active energy ray-curable ink composition exhibits excellent hardenability even when the light source is a UV-LED, and can be made into an article having excellent high flexibility and low curling property. (3) The active energy ray-curable hard coat composition can be made into a product having excellent scratch resistance, high flexibility, and low curl. (4) The active energy ray-curable water-based inkjet composition can be made into a composition containing no organic solvent or a composition which is made to contain only a small amount of an organic solvent such as a small amount of ethanol, even if it contains an organic solvent, and can be produced. It has excellent low viscosity, fast hardenability, low yellowing and high flexibility. (5) The active energy ray-curable nail coating composition can be formed into a composition containing no organic solvent or a composition which is made to contain only a small amount of an organic solvent such as a small amount of ethanol, even if it contains an organic solvent, and can be used. Made of excellent low viscosity, fast hardenability, low yellowing properties. Hereinafter, the active energy ray-curable transparent coating agent composition, the active energy ray-curable ink composition, the active energy ray-curable hard coat composition, and the solventless active energy ray-curable composition will be described in detail. .

4-1. The active energy ray-curable transparent coating agent composition is used as a UV-LED hardening type transparent coating agent for an active energy ray-curable transparent coating agent composition (including a clear varnish). The component (B-1) (mercaptophosphine oxide compound) is preferably a component of the component (B). Further, in the case of the use, it is preferred to contain a component (D-1) (a compound having two ethylenically unsaturated groups) as a component (D), and a component (D-1-1) is contained. The alkylene glycol di(meth)acrylate] is more preferably a composition of the component (D-1).

4-2. Active energy ray-curable ink composition For the active energy ray-curable ink composition, when used as a UV-LED hardening ink composition, it contains (B-2) component (9- Oxysulfuron The compound () and/or the component (B-3) [4,4'-bis(dialkylamino)benzophenone] is preferably a component of the component (B).

4-3. Composition for active energy ray-curable hard coat layer The active energy ray-curable composition of the present invention has excellent rapid hardenability, low yellowing property, high flexibility and low curling property, and is also resistant to abrasion resistance. It is excellent and can be suitably used as a composition for a hard coat layer.

The composition for an active energy ray-curable hard coat layer having excellent scratch resistance, high flexibility, and low curling property has been studied variously. Japanese Laid-Open Patent Publication No. 2012-229412 discloses that a composition containing a specific ethyl urethane (meth) acrylate has excellent scratch resistance, pencil hardness, and low curling property, but its performance is not sufficient. Japanese Laid-Open Patent Publication No. 2013-23585 discloses that a composition containing urethane (meth) acrylate and tripentaerythritol octa (meth) acrylate exhibits low curl, high hardness, and high flexibility, but It is still seeking further performance improvements. JP-A-2016-6161 discloses that a composition containing two specific urethane (meth) acrylates is excellent in terms of scratch resistance, high flexibility, and hardness, but low curl is unknown. .

Japanese Laid-Open Patent Publication No. 2015-120860 discloses that a (meth) acrylate having a structure in which an alkylene oxide is added to a polyglycerol is contained in the range of 95/5 to 50/50 (A)/(B). The composition of (A) and ethyl urethane (meth) acrylate (B) has excellent scratch resistance and substrate followability (flexibility). However, it still seeks further performance improvements.

Here, polyglycerol (meth) acrylate ((meth) acrylate of polyglycerol which is not added with an alkylene oxide) has few use cases due to difficulty in synthesis. Japanese Laid-Open Patent Publication No. 2015-44955 discloses the description of the (meth) acrylate of polyglycerol, but the addition ratio of the acrylonitrile group is extremely low, and the physical properties thereof are unknown. Japanese Laid-Open Patent Publication No. 2006-182725 contains a process for acetalization of polyglycerol, but it is conceivable that the (meth) acrylate ratio is low because of a high hydroxyl value. Further, the curable property of the composition containing polyglycerol (meth) acrylate obtained is difficult to be fast, and although it has excellent flexibility, the scratch resistance is unknown. As described above, the polyglycerol (meth) acrylate obtained by the conventional production method is not suitable as a blending raw material for producing a composition having excellent hardenability and/or scratch resistance.

The inventors of the present invention have revealed a composition in which the cured film is excellent in all viewpoints of scratch resistance, high flexibility, and low curling property (JP-A-2016-23203), the composition is specific The ratio includes: tetra(meth)acrylate obtained from the addition of 4-8 mol of ethylene oxide to diglycerol, and penta and hexa(meth)acrylic acid of dipentaerythritol. Ester, but still strive for further improvement in its performance.

According to the composition for a hard coat layer of the present invention, the above problems can be solved, and an article having excellent rapid hardenability, low yellowing property, high flexibility, low curling property, and excellent scratch resistance can be obtained. The composition for a hard coat layer preferably contains a component (D-2) (a compound having three or more ethylenically unsaturated groups) as a component (D), and further contains (D) -2-1) Ingredients [dipentaerythritol poly(methyl) acrylate] and/or (D-2-2) component [Ethyl urethane having 3 or more (meth) acrylonitrile groups (A The acrylate] is preferably a composition of the component (D-2).

4-4. Solvent-free active energy ray-curable composition The active energy ray-curable composition of the present invention can be used for a low-viscosity solvent-free active energy ray-curable composition which does not contain an organic solvent or even The organic solvent contains only a small amount of an almost harmless organic solvent such as ethanol, or is a water-based composition. In the composition, an active energy ray-curable inkjet composition and an active energy ray-curable nail coating composition (which is applied to a nail paint) can be further used.

In recent years, there has been an increase in demand for a solvent-free active energy ray-curable inkjet composition, and it is difficult to fully satisfy all properties such as low viscosity, rapid hardenability, and flexibility. In order to enhance the physical properties, although it is important to select which compound is used as the photopolymerization initiator, it is still difficult to enhance the physical properties only by this.

Among such backgrounds, acrylate 2-(vinyloxyethoxy)ethyl ester has been attracting attention as a monomer excellent in all properties such as low viscosity, rapid hardenability, and high flexibility (for example, Japanese patent) Bulletin 5790234). However, there is still a need for further rapid hardenability. 9-oxopurine Although it is a combination of a photopolymerization initiator suitable for the photopolymerization initiator, and the curing property is improved, the yellowing is a problem and the hardenability is still insufficient due to the combination with the photocuring initiator which enhances the hardenability.

On the other hand, the composition of the active energy ray-curable nail coating agent applied to the paint for the appearance of nails is first safe. In addition, since it is applied to the nail, it needs to have a low viscosity, and in order not to adversely affect the human body, it is also required to be hardened by a low-illumination UV-LED at a long wavelength. Solar light can also be used instead of UV-LED. However, the conventional active energy ray-curable nail paint is usually made of a low-odor odor-free (meth) acrylate monomer (for example, JP-A-2013-43853). The health of the operator creates doubts.

According to the solvent-free composition of the present invention, the above-mentioned problem can be solved, and it is possible to obtain an object which does not contain an organic solvent or which has rapid curability, low yellowing property, high flexibility, and low curling property even in the case of a water-based composition. Example

The present invention will be more specifically described below by showing examples and comparative examples. In addition, the following "parts" means parts by weight.

1. Production Example 1-1) Production Example 1 [Production of component (A), hydroxyl value: 299 mgKOH/g] 146 g was fed into a 1 liter flask equipped with a stirrer, a thermometer, a gas introduction tube, and a cooling tube ( Polypropylene glycol having a hydroxyl group of 2.5 mol [polyglycerol 06 manufactured by DAICEL, hydroxyl value 960 mgKOH/g (17.1 meq/g), hereinafter referred to as "D-PGL6"], 585 g (4.5 mol) of acrylic acid 2 -methoxyethyl ester (hereinafter referred to as "MEA"), 1.4 g (0.0125 mol) of DABCO used as catalyst X, and 5.2 g (0.025 mol) of zinc acrylate used as catalyst Y (hereinafter referred to as "ZnAc") ), 0.35 g of hydroquinone monomethyl ether (hereinafter referred to as "MQ") and 0.012 g of morphine While the oxygen-containing gas (oxygen 5 vol%, nitrogen 95 vol%) was bubbled in the liquid, the mixture was heated and stirred at 130 ° C for 7 hours to carry out a transesterification reaction. The acrylation ratio of the hydroxyl group by the transesterification reaction was determined from the amount of 2-methoxyethanol produced by liquid chromatography, and was 50 mol%. 30 g of aluminum niobate [KYOWAAD 700 manufactured by Kyowa Chemical Industry Co., Ltd., hereinafter referred to as "KD700") was placed in the reaction liquid which had been cooled to room temperature, and then the mixture was stirred at 100 ° C for 1 hour to adsorb the catalyst. The pressure-treated filter is used to separate the adsorbed aluminum citrate. The obtained filtrate was placed in a flask to which a stirrer, a thermometer, a gas introduction tube, a cooling tube for distillation, and a pressure reduction tube were connected, and the dry air was bubbled at a temperature of 90 to 100 ° C and a pressure of 0.01 to 200 mmHg. While stirring for 13 hours, the unreacted MEA and the by-product 2-methoxyethanol were distilled off to obtain a polyglycerol acrylate of the reaction product. The residual amount of MEA in the product was analyzed by gas chromatography and found to be 100 ppm or less. The product did not feel odor at all. The obtained polyglycerol acrylate had a viscosity of 7.3 Pa·s (25 ° C) and a hydroxyl value of 299 mg KOH/g. The Mw, Mn and polydispersity (Mw/Mn) of the GPC main peak-converted polystyrene were 1,291, 1,016 and 1.3, respectively. Hereinafter, the polyglycerol acrylate of Production Example 1 is referred to as pGlyAc-1.

Further, the hydroxyl value and GPC were measured in the following manner. ◆Measurement conditions of hydroxyl value Add the acetamidine reagent to the sample and heat it in a warm bath. After allowing to cool, the phenolphthalein solution was used as an indicator, and the acid was titrated in a potassium hydroxide ethanol solution to determine the hydroxyl value. ◆GPC measurement conditions and equipment: GPC by Waters, system name 1515 2414 717P RI ・Detector: differential refractive index (RI) detector ・column: protection column, Shodex KFG (8μm) 4.6×10mm); 2 main columns, styragel HR 4E THF (7.8×300mm) + styragel HR 1THF (7.8×300mm) • Column temperature: 40°C ・Dissolve composition: THF (internal standard) Sulfur 0.03%), flow rate 0.75 mL/min. Calibration line: Calibration curve was prepared using standard polystyrene.・Method for calculating the dispersion of the main peak (Mw/Mn) Among the peaks of Mw300 or more measured, the peak with the largest area is regarded as the main peak, and Mw, Mn, and polydispersity are calculated. In addition, the peak of insufficient spike separation is not divided, and it is regarded as a spike.

1-2) Production Example 2 [Production of component (A), hydroxyl value: 114 mgKOH/g] 146 g (hydroxyl 2.5 mol) was fed into a 1 liter flask equipped with a stirrer, a thermometer, a gas introduction tube, and a cooling tube. D-PGL6 (hydroxyl value 960 mg KOH/g), 585 g (4.5 mol) of MEA, 1.4 g (0.0125 mol) of DABCO used as catalyst X, 5.2 g (0.025 mol) used as catalyst Y ZnAc, 0.35g of MQ and 0.047g of morphine The oxygen-containing gas (oxygen 5% by volume, nitrogen 95% by volume) was bubbled in the liquid, and the mixture was heated and stirred at 130 ° C for 5 hours to carry out a transesterification reaction. Then, the reaction liquid is heated and stirred at a temperature of 115 to 125 ° C, and the pressure in the reaction system is adjusted within a range of 150 to 300 mmHg to cause 2-methoxyethanol which is produced by the transesterification reaction. The MEA mixture is discharged from the reaction system through a rectification column and a cooling pipe. Further, the effluent and the same part by weight of the MEA were added to the reaction system at any time. After heating and stirring for 9 hours under reduced pressure, the pressure in the reaction system was returned to normal pressure and the discharge was terminated. The acrylation rate of the hydroxyl group by the transesterification reaction was determined from the amount of 2-methoxyethanol produced by liquid chromatography, and was found to be 75 mol%. After 30 g of KD700 (aluminum silicate) was added to the reaction liquid which had been cooled to room temperature, it was further stirred at 100 ° C for 2 hours to adsorb the catalyst. The pressure-treated filter is used to separate the adsorbed aluminum citrate. The obtained filtrate was placed in the same flask as in Production Example 1, and the mixture was stirred for 6 hours while bubbling dry air at a temperature of 80 to 100 ° C and a pressure of 0.01 to 100 mmHg to distill off unreacted MEA and by-products. The 2-methoxyethanol was used to prepare a polyglycerol acrylate of the reaction product. The residual amount of MEA in the product was analyzed by gas chromatography and found to be 100 ppm or less. The product did not feel odor at all. The obtained polyglycerol acrylate had a viscosity of 4.2 Pa·s (25 ° C) and a hydroxyl value of 114 mg KOH/g. The Mw, Mn and polydispersity (Mw/Mn) of the GPC main peak-converted polystyrene were 1,417, 1,098 and 1.3, respectively. Hereinafter, the polyglycerol acrylate of Production Example 2 is referred to as pGlyAc-2.

1-3) Production Example 3 [Production of component (A), hydroxyl value: 367 mgKOH/g] 234 g (hydroxyl 4.0 mol) was fed into a 1 liter flask equipped with a stirrer, a thermometer, a gas introduction tube, and a cooling tube. D-PGL6 (hydroxyl value 960 mgKOH/g), 520 g (4.0 mol) of MEA, 2.2 g (0.020 mol) of DABCO used as catalyst X, and 8.3 g (0.040 mol) used as catalyst Y ZnAc, 0.31g of MQ and 0.010g of morphine While the oxygen-containing gas (oxygen 5% by volume, nitrogen 95% by volume) was foamed in the liquid, the mixture was heated and stirred at 130 ° C for 6 hours to carry out a transesterification reaction. The acrylation rate of the hydroxyl group by the transesterification reaction was determined from the amount of 2-methoxyethanol produced by liquid chromatography, and found to be 43 mol%. After 32 g of KD700 (aluminum silicate) was placed in the reaction liquid which had been cooled to room temperature, it was further stirred at 100 ° C for 1 hour to adsorb the catalyst. The pressure-treated filter is used to separate the adsorbed aluminum citrate. The obtained filtrate was placed in the same flask as in Production Example 1, and stirred at a temperature of 90 to 100 ° C and a pressure of 0.01 to 200 mmHg while stirring the dry air for 13 hours to distill off unreacted MEA and by-products. The 2-methoxyethanol was used to prepare a polyglycerol acrylate of the reaction product. The residual amount of MEA was analyzed by gas chromatography, and the result was 100 ppm or less. The obtained polyglycerol acrylate had a viscosity of 29.4 Pa·s (25 ° C) and a hydroxyl value of 367 mg KOH/g. The Mw, Mn and polydispersity (Mw/Mn) of the GPC main peak-converted polystyrene were 1,407, 1,054 and 1.3, respectively. Hereinafter, the polyglycerol acrylate of Production Example 3 is referred to as pGlyAc-3.

1-4) Production Example 4 [Production of component (A), hydroxyl value: 269 mgKOH/g] 161 g (alcoholic hydroxyl group 2.5) was fed into a 1 liter flask equipped with a stirrer, a thermometer, a gas introduction tube, and a cooling tube. The average degree of polymerization of 6 moles of polyglycerol [Sakamoto Pharmaceutical Industry Co., Ltd. produced polyglycerol #6, hydroxyl value 973 mgKOH / g (17.3 meq / g), water 10.3% by mass, hereinafter referred to as "S-PGL6 In the case where an oxygen-containing gas (oxygen 5 vol%, nitrogen 95 vol%) is foamed in the liquid, the water is separated by distillation under the conditions of a temperature of 98 to 110 ° C and a pressure of 28 to 300 mmHg for 2 hours. 16.6g. The residue after distillation was fed with 585 g (4.5 mol) of MEA, 1.4 g (0.0125 mol) of DABCO used as catalyst X, 5.2 g (0.025 mol) of ZnAc used as catalyst Y, and 0.35 g. MQ and 0.012g of morphine The oxygen-containing gas (oxygen 5 vol%, nitrogen 95 vol%) was bubbled in the liquid, and the mixture was heated and stirred at 120 to 130 ° C for 8 hours to carry out a transesterification reaction. Then, the mixture is heated and stirred at a temperature of the reaction solution at a temperature of 80 to 130 ° C, and the pressure in the reaction system is adjusted within a range of 55 to 700 mmHg to cause 2-methoxyethanol which is produced by the transesterification reaction. The MEA mixture is discharged from the reaction system through a rectification column and a cooling pipe. Further, the effluent and the same part by weight of the MEA were added to the reaction system at any time. After heating and stirring for 6 hours under reduced pressure, the pressure in the reaction system was returned to normal pressure, and the discharge was completed. The acrylation rate of the hydroxyl group by the transesterification reaction was determined from the amount of 2-methoxyethanol produced by liquid chromatography, and found to be 42 mol%. After 25 g of KD700 (aluminum silicate) was placed in the reaction liquid which had been cooled to room temperature, it was further stirred at 90 to 100 ° C for 1 hour to adsorb the catalyst. The pressure-treated filter is used to separate the adsorbed aluminum citrate. The obtained filtrate was placed in the same flask as in Production Example 1, and after adding 10 g of KD700 (aluminum silicate), the mixture was stirred for 9 hours while bubbling dry air at a temperature of 80 to 100 ° C and a pressure of 0.01 to 100 mmHg. The unreacted MEA and the by-product 2-methoxyethanol were distilled off to obtain a polyglycerol acrylate of the reaction product. To the residue after the distillation, 2 g of diatomaceous earth [manufactured by Showa Chemical Industry Co., Ltd., Radiolite (trade name)] was added and filtered under pressure to obtain a polyglycerol acrylate of the reaction product as a filtrate. The residual amount of MEA in the product was analyzed by gas chromatography and found to be 100 ppm or less. The product did not feel odor at all. The obtained polyglycerol acrylate had a viscosity of 6.8 Pa·s (25 ° C) and a hydroxyl value of 269 mg KOH/g. The Mw, Mn and polydispersity (Mw/Mn) of the GPC main peak-converted polystyrene were 1,038, 849 and 1.2, respectively. Hereinafter, the polyglycerol acrylate of Production Example 4 is referred to as pGlyAc-4.

1-5) Comparative Production Example 1 [Production of Polyglycerol Acrylate by Dehydration Esterification Method] 107 g (hydroxyl 1.8 mol) was fed into a 1 liter flask equipped with a stirrer, a thermometer, a gas introduction tube, and a cooling tube. D-PGL6 (hydroxyl value 960 mgKOH/g), 237 g (3.3 mol) of acrylic acid, 348 g of toluene, 5.3 g (0.0276 mol) of p-toluenesulfonic acid monohydrate used as a catalyst (hereinafter referred to as "PTS"), 2.14g of MQ, and 1.07g of copper chloride dihydrate, while the oxygen-containing gas (oxygen 5 vol%, nitrogen 95 vol%) is foamed in the liquid, and the internal pressure of the reaction system is 600 mmHg. This is heated to reflux, and the water which is generated as a result of the transesterification reaction is discharged from the reaction system through the rectification column and the cooling pipe. In the meantime, the temperature of the reaction liquid was changed in the range of 109 to 115 °C. Starting from the start of heating and stirring, the reaction liquid was heated after 2 hours and 30 minutes, and the pressure in the reaction system was returned to normal pressure and the discharge was terminated. The esterification reaction rate of the hydroxyl group was determined from the amount of water discharged from the reaction system to be 44 mol%. The reaction solution was pipetted to a separatory funnel to carry out extraction purification for removing unreacted acrylic acid. After adding 205 g of n-hexane and vigorously shaking it, it was allowed to stand. After standing, the liquid is separated into two layers, and the upper liquid contains n-hexane, toluene and acrylic acid, but the polyglycerol acrylate of the object contains only trace amounts. After the upper layer was discharged, n-hexane was again added and the same extraction and purification operation was carried out. Next, a neutralization operation for removing the PTS is performed. To the lower layer obtained by the extraction and purification operation, 2070 g of tetrahydrofuran and 207 g of magnesium oxide were added, and the mixture was stirred at room temperature for 1 hour, and then subjected to pressure filtration. By this operation, the residue of the PTS and the magnesium oxide neutralizing salt is removed as a filter residue to obtain a filtrate containing the polyglycerol acrylate of the target. Add 0.49g of MQ and 0.06g of morphine to the filtrate. While bubbling dry air, the mixture was subjected to vacuum distillation at a temperature of 40 to 80 ° C and a pressure of 0.001 to 700 mmHg for 7 hours to separate a distillate containing tetrahydrofuran, and a reaction product was produced in the form of a residual liquid after distillation. Polyglycerol acrylate. The obtained polyglycerol acrylate had a viscosity of 477.8 Pa·s (25 ° C) and a hydroxyl value of 196 mg KOH/g. The Mw, Mn and polydispersity (Mw/Mn) of the main peak of GPC converted to polystyrene were 6,245, 2,002 and 3.1, respectively. Hereinafter, the polyglycerol acrylate of Comparative Production Example 1 is referred to as pGlyAc-5.

1-6) Comparative Production Example 2 [Production of Polyglycerol Acrylate by Transesterification Using Ti Catalyst] 117 g (hydroxyl 2.0) was fed to a 1 liter flask equipped with a stirrer, a thermometer, a gas introduction tube, and a cooling tube. M-) D-PGL6 (hydroxyl value 960 mgKOH/g), 468 g (3.6 mol) of MEA, 20.4 g (0.06 mol) of tetra-n-butoxytitanium used as a transesterification catalyst (hereinafter referred to as "TiBO""), 0.28g of MQ, 0.009g of morphine While the oxygen-containing gas (oxygen 5% by volume, nitrogen 95% by volume) was foamed in the liquid, the mixture was heated and stirred at a reaction liquid temperature of 127 to 132 ° C for 8 hours to carry out a transesterification reaction. The transesterification reaction rate of the hydroxyl group was determined from the amount of 2-methoxyethanol produced by liquid chromatography, and as a result, it was 4 mol%, and a practical reaction rate could not be obtained.

1-7) Summary The polyglycerol acrylate obtained in Production Example 1 to Production Example 4 and Comparative Production Examples 1 and 2 was subjected to the following Table 1 in terms of the reaction form, raw materials, catalyst, and physical properties.

[Table 1] ※Unit: Pa•s (25°C)

2. Example 1 to Example 3, Comparative Example 1, 2 (UV-LED Curable Transparent Coating Agent-1) 2-1) Production of Compositions The components shown in Table 2 were blended in respective parts. The photocurable composition is prepared by stirring and mixing according to a usual method. In addition, the abbreviations of the synthetic components in the table are as follows except as defined above. (B) component, TPO: (2,4,6-trimethylbenzylidene) diphenylphosphine oxide, Lucirin TPO [(B-1) component manufactured by BASF Corporation] (D) component, DPHA: two A mixture of pentaerythritol 5 and hexaacrylate, ARONIX M-402 (five: six = 30:70) [(D-2) component] of East Asian Synthetic Co., Ltd. ・pGlyAc-5: Comparative Polypropylene III of Manufacturing Example 1. Alcohol acrylate [(D-2) component]

2-2) Evaluation of UV-LED hardenability The composition obtained in Table 2 was applied to a polyethylene terephthalate film (manufactured by Toyobo Co., Ltd., COSMOSHINE A4300) having a thickness of 50 μm. Hereinafter referred to as "PET". ], coated with a bar coater to a film thickness of 8 μm. Next, a UV-LED irradiation apparatus (light emission wavelength: 385 nm) made of a SENTEC (stock) equipped with a stage moving device was irradiated with ultraviolet rays in an air atmosphere at a rate of 50 mJ/cm ² per pass of UV-A. The hardening state of the coating film is confirmed by fingers every time, and the ultraviolet rays are irradiated once more when it is not hardened. When it has been hardened, the surface of the cured film is rubbed by a non-woven fabric (BEMCOT manufactured by Asahi Kasei) with a force of about 1 kg/cm ² , and when there is a flaw, it is irradiated with ultraviolet rays once more. The curing was carried out up to 10 times, and the hardening property was evaluated by the number of times of ultraviolet irradiation in which the nonwoven fabric did not cause scratches. In addition, when there are still scratches in 10 passes of ultraviolet rays, it is rated as "10<". In this manner, the hardenability was evaluated by the number of passes of the nonwoven fabric without rubbing and causing no scratches, and the results are shown in Table 2.

2-3) Evaluation of cured film For the cured film produced by the method of the above 2-2) (however, 6 to 10 times of Examples 1 to 3 and Comparative Example 1 and 10 times for Comparative Example 2) were as follows. Evaluation of low curling property and flexibility. <Low Curlability> The low curl property was evaluated by the height average 値 (mm) of the four corners of the cured film cut into a square of 10 cm in side length. When the height is less than 1mm, it is rated as "<1". However, when the film is greatly curled to exceed a semicircular arc, its state is described. For example, when the film is wound into a cylindrical shape, it is described as "one turn". <Flexibility> Flexibility According to the mandrel test (JIS K5600-5-1), a PET film formed with a cured film is wound around a core rod having a diameter of 2 mm, 3 mm, 4 mm, 5 mm, 6 mm, and 8 mm (hardening) The film is on the outside and records the smallest diameter where no cracking or peeling occurs. Here, when the core rod had a diameter of 2 mm and no cracking or peeling occurred, the test was performed by bending the film without using a mandrel bar. Even if cracking did not occur, it was evaluated as 0 mm because there was no core rod.

2-4) Evaluation results As is apparent from the results of Table 2, the compositions of Examples 1 to 3 in which the photopolymerization initiator was added to the component (A) had excellent UV-LED hardenability and also had Low curling property and high flexibility, overwhelmingly superior to Comparative Example 1. In particular, Examples 1 and 3 in which the (A) component has a hydroxyl value of 120 mgKOH/g or more have almost no curl, and the flexibility is also excellent to the extent that the bent film does not break. On the other hand, the composition of Comparative Example 1 containing no polyfunctional acrylate (DPHA) different from the component (A), which contains the component (A) of the present invention, has excellent curability but low curling property and high flexibility. It is greatly degraded. Further, the composition of Comparative Example 2 using the polyglycerol acrylate different from the component (A) of the present invention was significantly deteriorated in hardenability as compared with the compositions of Examples 1 to 3.

[Table 2]

3. Examples 4 and 5, Comparative Examples 3 and 4 (UV-LED hardening type transparent coating agent-2) 3-1) Composition and viscosity measurement of the composition The components shown in Table 3 were mixed in respective parts. The mixture was stirred and mixed according to a usual method to prepare a photocurable composition. The viscosity of the obtained composition at 25 ° C was measured by an E-type viscometer, and the results are shown in Table 3. In addition, the abbreviations of the mixed components in the table are synonymous with the above Table 2. The abbreviations of the ingredients in Table 2 above are as follows. (D) Component: M-240: Polyethylene glycol (average degree of polymerization 4) diacrylate, ARONIX M-240 [(D-1) component of East Asia Synthetic Co., Ltd.] ・SP-1509: Pair of bisphenol A Epoxy acrylate based on epoxy resin addition acryl, RIPOXY SP-1509 [(D-1) component] (other components) made by Showa Denko Co., Ltd. ・8019add: Polyoxane leveling agent, Dow 8019ADDITIVE manufactured by Corning Toray Co., Ltd.

3-2) Evaluation of UV-LED hardenability Experiments were carried out in the same manner as in the above 2-2) except that the thickness of the PET film of the above 2-2) was changed to 100 μm.

3-3) Evaluation of Cured Film After the hardening property was evaluated in the above 3-2), the number of irradiations of the UV-LED was unified to 10 times in total. Thereafter, after standing for 1 hour in a 50% room (with fluorescent lamp illumination) at 23 ° C, low curling property, flexibility, abrasion resistance, and yellowing were evaluated in the following manner, and the results are shown in Table 3. <Low curl property> Evaluation was performed in the same manner as in the above 2-3). <Flexibility> First, evaluation was performed in the same manner as in the above 2-3). Here, even if the sample is completely bent without cracking, the nail is used to compress the bend. Including this result, the judgment is as follows. A: After the sample is completely bent, there is no crack even if the nail is used to compress the bend. B: The sample is completely bent without cracking, but cracking occurs when the nail is forced to compress the bend. C: There is no crack when wound around a 2 mmφ mandrel, but cracking occurs if it is completely bent. D: Cracking occurred after winding on a 2 mmφ mandrel, and no crack was observed at 3 mmφ. E: Cracking also occurred in the 3 mmφ mandrel. <Friction resistance> The nonwoven fabric which was bent into 1 cm ² was rubbed back and forth 10 times on the cured film at 1 kgf or 4 kgf, and the presence or absence of scratches was observed and determined as follows. A: No damage at 4 kgf/cm ² . B: No damage at 1 kgf/cm ² and scratch at 4 kgf/cm ² . C: There is a scar under 1 kgf/cm ² . <Yellow Density> The integral spherical spectroscopic transmittance measuring device DOT-3 manufactured by Murakami Color Technology Research Institute was evaluated by the D65 light source and the yellowness (YI) measured under the condition of a 10-degree field of view.

3-4) Evaluation results As is apparent from the results of Table 3, the compositions of Examples 4 and 5 of the composition of the present invention have excellent UV-LED hardenability, low curling property, high flexibility, and scratch resistance. Sexual and low yellow degeneration. In Example 5, the flexibility was improved as compared with Example 4, and the level at which cracking did not occur even if the laminate of the cured film and the film was bent hard. On the other hand, the composition of Comparative Example 3 which does not contain the component (A) of the present invention has a large deterioration in low curling property and flexibility compared with the composition of Example 5, and the UV-LED hardenability is also poor. The composition of Comparative Example 4 containing no component (A) of the present invention was inferior in hardenability to the compositions of Example 4, Example 5 and Comparative Example 3. Although the abrasion resistance is improved by being placed under a fluorescent lamp just after the UV-LED is hardened, it is scarred when rubbed by a force of 4 kgf/cm ² , which is inferior to the other three.

[table 3]

4. Examples 6 and 7 and Comparative Example 5 (UV-LED hardening type ink composition) The components shown in Table 4 were mixed with each other in a number of parts, stirred and mixed, and then dispersed in an agate mortar to prepare a pigment. A light-curing ink composition. The hardenability of the compositions was evaluated in the same manner as in the above 2-2), and the results are shown in Table 4. However, when there are injuries in 6 passes, it is recorded as "6<". In addition, the abbreviations of the mixed components in the table are synonymous with the above Table 2. The abbreviations of the ingredients in Table 2 above are as follows. (B) Ingredients DETX: 2,4-Diethyl-9-oxothiopurine , KAYACURE DETX-s[(B-2) component] manufactured by Nippon Kayaku Co., Ltd. ・EAB: 4,4'-bis(diethylamino)benzophenone, SB-PI701 manufactured by SHUANG-BANG INDUSTRIAL [(B-3) component] (E) component, FA5375: blue pigment, CI pigment blue 15:3, DIC (share), Fastogen Blue FA5375 (other components) ・EPA: ethyl-4-(dimethyl Amino) benzoate, manufactured by Nippon Kayaku Co., Ltd., KAYACURE EPA

From the results of Table 4, it is apparent that the composition of Example 6 in which the curable component is pGlyAc-2 and the component (B) is a combination of TPO and EAB is the same as the hardening component is DPHA and the component (B) is the same. The composition of Example 5 showed twice or more UV-LED hardenability. Further, in the composition of Example 7, the component (B) was a combination of TPO and EAB which was not excellent in curability, but exhibited UV-LED curability which was superior to the composition of Comparative Example 5. As described above, the composition of the present invention also has very excellent hardenability when used as a UV-LED hardening type ink composition.

[Table 4]

5. Examples 8 to 12, Comparative Examples 6 to 8 (hard coat composition-1) 5-1) Manufacture of the composition The components shown in Tables 5 and 6 were mixed in the respective parts and as usual. The mixture was stirred and mixed to prepare a photocurable composition. In addition, the abbreviations of the mixed components in the table are synonymous with the above Tables 2 and 3. The abbreviations of the ingredients in Tables 2 and 3 above are as follows. In addition, although the component (G) is supplied in a state of being dispersed in the solvent of the component (F), it is described in Tables 5 and 6 as components.

(B) Component: Irg-184: 1-hydroxy-cyclohexyl-phenyl-ketone, manufactured by BASF Corporation, IRGACURE 184 (D) component, M-460: 4 molar ethylene oxide adduct of diglycerol A acrylate, ARONIX M-460 [(D-2) component] ・UA-306H: synthesized by the addition reaction of pentaerythritol triacrylate and hexamethylene diisocyanate Polyfunctional urethane acrylate (mixture with pentaerythritol tetraacrylate), UA-306H [(D-2) component manufactured by Kyoeisha Chemical Co., Ltd. (F) component, PGM: propylene glycol monomethyl Ether, IPA: Isopropyl alcohol, MEK: methyl ethyl ketone (G) component, AC2140: ORGANOSILICASOL MEK-AC-2140Z manufactured by Nissan Chemical Industries Co., Ltd. (Polymer modified by methyl methacrylate ruthenium on an average particle size of 10 to 15 nm) Cerium oxide, the cerium oxide moiety [(G-1) component] in the dispersion medium MEK). AC2140 (NET) in the table means a solid component.・IPA-ST: Osmium oxide fraction [(G-2) component] in ORGANOSILICASOL IPA-ST (average particle size 10~15nm without surface modified colloidal cerium oxide, dispersion medium IPA) manufactured by Nissan Chemical Industries Co., Ltd. IPA-ST (NET) in the table means a solid component.

5-2) Preparation of Hard Coat Curing Film The composition obtained in Tables 5 and 6 was applied to PET having a thickness of 100 μm by drying to a thickness of 8 μm by a bar coater, and dried at 90 ° C. 2 minute. Next, using a concentrating high-pressure mercury lamp (output power 120/cm) manufactured by EYE GRAPHICS CO., LTD., the height of the lamp was adjusted and the illuminance of the UV-A region was 1,000 mW/cm ² at an irradiation amount of 300 mJ/cm ^{2 .} Under the conditions, ultraviolet rays are irradiated and the coating film is hardened.

5-3) Evaluation of cured film The scratch resistance, pencil hardness, flexibility, and curl were evaluated as follows. <Scratch Resistance> While pressing steel wool #0000 at 500 gf/cm ² and 1 kgf/cm ² and rubbing back and forth for 10 turns, the number of scratches in the range of 1 cm ^{2 was} counted and evaluated as follows. A: no flaws B: one or more scars and less than 5 C: 5 or more scars and less than 10 D: 10 or more flaws <pencil hardness> According to JIS K5600-5-4, the evaluation was carried out under a load of 750 g. <Flexibility> Evaluation was carried out in the same manner as in the above 2-3). <Low curl property> Evaluation was performed in the same manner as in the above 2-3).

5-4) Evaluation results As is apparent from the results of Tables 5 and 6, the compositions of Examples 8 to 12 which are compositions of the present invention have scratch resistance, high hardness, high flexibility and low curling property. Balanced and high performance. The compositions of Examples 8 to 12 were compared with the compositions of Comparative Examples 6 to 8 which did not contain the component (A). Compared with the composition of Comparative Example 6, the composition of Example 8 had the same flexibility, but the scratch resistance, the pencil hardness, and the low curl property were all improved. Further, the composition of Example 8 had the same scratch resistance and pencil hardness as the composition of Comparative Example 7 and Comparative Example 8, but was excellent in flexibility and low curling property. In the composition of Example 9, the pencil hardness and the flexibility were the same as those of Comparative Example 7 and Comparative Example 8, but the scratch resistance and the low curl property were excellent. The composition of Example 10 was not only excellent in scratch resistance and pencil hardness, but also excellent in low curling property. The compositions of Examples 11 and 12 were excellent not only in scratch resistance and pencil hardness but also in low curling properties. In addition, it is noted that the cured films of the compositions of Examples 8 to 12 have excellent colorless transparency.

[table 5]

[Table 6]

6. Examples 13 to 15 and Comparative Examples 9 to 10 (Composition for inkjet) 6-1) Production of the composition The components shown in Table 7 were blended in respective parts, and stirred and mixed according to a usual method. A photohardenable composition is prepared. In addition, the abbreviations of the mixed components in the table are synonymous with the above Tables 2 to 6. The meanings of the ingredient abbreviations not found in the tables are as follows. (B) Ingredients, Irg-2959: IRGACURE 2959, 1-SF-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, Irg -819: IRGACURE 819 manufactured by BASF Corporation, bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide [(B-1) component] (D) component, VEEA: (share) Japan touch VEEA, (meth) acrylate 2-vinyloxyethoxyethyl ester [(D-1) component] ・HBA: 4-HBA made from Osaka Organic Chemical Industry Co., Ltd., 4-hydroxybutyl acrylate [ (D-3) Ingredients] ・POA: POA of Kyoeisha Chemical Co., Ltd., phenoxyethyl acrylate [(D-3) component] (F) component, EtOH: ethanol

6-2) Evaluation of ink-jet suitability The viscosity of the obtained composition at 25 ° C was measured by an E-type viscometer, and the results are shown in Table 7. Further, the inkjet suitability was evaluated by the viscosity at 25 ° C in the following manner. A: 10 mPa·s or less B: 11 to 50 mPa·s C: 51 to 100 mPa·s D: More than 100 mPa·s

6-3) Evaluation of ultraviolet curability The composition obtained in Table 7 was applied to a PET having a thickness of 50 μm by a bar coater at a film thickness of 2 μm after drying. Next, a concentrating metal halide lamp manufactured by EYE GRAPHICS CO., LTD. was used, and the illuminance in the UV-A region was 500 mW/cm ² and the irradiation amount was 50 mJ/cm ² per pass, and each pass was confirmed by a finger. The film is hardened. When it is not hardened, it is irradiated with ultraviolet rays once more. When it is hardened, the surface of the cured film is rubbed with a non-woven fabric (BEMCOT manufactured by Asahi Kasei) with a force of about 1 kg/cm ² , and one time of ultraviolet rays is irradiated when the flaw is caused. This was carried out up to 10 times, and the hardenability was evaluated by the number of times of ultraviolet irradiation in which the non-woven fabric became no longer causing scratches. In addition, it was rated as "10<" when there were still scratches in 10 passes of ultraviolet rays. In this manner, the hardenability was evaluated by the number of passes of the nonwoven fabric without rubbing or causing the flaw, and the results are shown in Table 7. Further, even in the case of a composition containing water, a heating and drying step in which a dryer or the like is placed is not performed. In this method, whitening occurs when the film thickness is approximately 10 μm. However, even if it is naturally dried in 1 minute at 2 μm, a colorless transparent cured film can be obtained.

6-4) Evaluation of cured film <Low yellowing> Observe the appearance of the cured film obtained in the above 6-3), and judge A without yellow feeling, B with a slight yellow feeling, and obviously with yellow feeling. For C. <Bending resistance> When the cured film was completely bent toward the outside, the crack was evaluated as A, and the crack was evaluated as B.

6-5) Evaluation results As is apparent from the results of Table 7, the compositions of Examples 13 and 14 contained no organic solvent and exhibited a low viscosity at which the ink jetting step was performed, and at the same time, the hardenability was compared. In the examples 9 and the comparative example 10 (corresponding to the conventional photocurable inkjet composition, the composition of the pigment and the additive is removed from the seventh embodiment of Japanese Patent No. 5790234). The compositions of Examples 13 and 14 also had low yellowing and bending resistance. Further, the hardening property of the composition of Comparative Example 9 was such that the cured film could not be evaluated. The composition of Example 15 contained 7 wt% of ethanol instead of a completely solvent-free system, but it contained only ethanol of a low alcohol content, so that it was not harmful to the human body as long as it was not used in a large amount in a narrow room. The composition of the fifteenth embodiment is extremely excellent in terms of both low viscosity and rapid hardenability, and is also excellent in low yellowing resistance and flexural resistance. The composition of Example 13 also had a characteristic of no odor at all. The composition of Example 14 was extremely odorous. This is because the hydroxyl group-containing (meth) acrylate is mostly weak in odor and the same in HBA. Here, 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate are highly irritating to the skin, but the skin irritation of HBA is weaker than that of HBA, and HBA is suitable as a component of a low odor ink composition. one. On the other hand, the compositions of Example 15, Comparative Example 9, and Comparative Example 10 were odor-prone. In particular, the composition of Comparative Example 10 was odorous. Further, in the compositions of Examples 13 and 15, the skin irritation was expected to be low because the low molecular weight acrylate monomer was not contained.

[Table 7]

7. Examples 16 to 18 (ink composition for inkjet) The following commercially available dye-based inkjet ink was mixed with the composition of Example 15 at a weight ratio of 1:1 to prepare an inkjet ink composition. Example 16: INK-E50 series (magenta) manufactured by SANWA SUPPLY Co., Ltd. Example 17: INK-E50 series (blue) made by SANWA SUPPLY (Example): INK-E50 series (SANWA SUPPLY) Yellow) Next, the hardenability was evaluated in the same manner as in Example 15. As a result, all of Examples 16 to 18 were cured in four passes. Different from the above, the substrate was changed to paper, and the composition of Examples 16 to 18 which had been coated and cured by ultraviolet rays was prepared. In addition, it is also prepared to apply the dye-based ink to the paper and dry it separately. The water was poured into the water and the degree of dyeing was compared. As a result, the degree of bleeding by the ultraviolet curing was small, and the water resistance was improved.

8. Example 19 (Nail paint composition) The composition of Example 4 was applied to the nail with bristles, and exposed to the sun at noon on March, and the result was completely hardened after 1 minute to obtain a fold-free and lustrous color. A cured film. No appearance defects such as cracks or turbidity were observed. The ease of peeling of the cured film is not peeled off by the degree of finger rubbing, but peeling off by scratching with a nail. If it is expressed in other ways, it can be removed without using an organic solvent. Therefore, it can be said that it is a composition for nail beauty which is excellent in safety and simplicity (speed hardening). Industrial availability

The hardened composition of the present invention can be suitably used as an active energy ray-curable composition, and has excellent rapid hardenability, low yellowing property, high flexibility, and low curling property, and is suitable as an active energy ray-curable transparent coating. The agent is particularly suitable for use when the light source is a UV-LED. The substrate of the transparent coating agent may be a protective coating of plastic and wood or a clear varnish of paper. Further, the pigment-containing composition can also be suitably used as a UV-LED hardening type ink composition. The active energy ray-curable composition of the present invention also has excellent scratch resistance and is therefore suitable for use as a hard coat layer, and is particularly suitable for use as a hard coat layer of a plastic film because of its remarkable characteristics of small curl. Furthermore, the active energy ray-curable composition of the present invention can also be suitably used as a water-based inkjet ink or nail coating paint.

Claims (27)

A hardening type composition comprising a mixture (A) of a compound having a (meth) acrylonitrile group, which is obtained by the following method: in the presence of the following catalysts X and Y a transesterification reaction of a polyglycerol having a hydroxyl value of 700 to 1,200 mgKOH/g with a compound having one (meth)acrylonitrile group; a catalyst X: selected from a cyclic 3 grade having a nitrogen heterobicyclic structure a compound or a salt or a complex thereof, a hydrazine or a salt thereof or a complex thereof, a compound having a pyridine ring or a salt or a complex thereof, and a phosphine or a salt or a complex thereof Catalyst Y: a zinc-containing compound. The hardened composition of claim 1, wherein the compound having one (meth) acrylonitrile group is an alkoxyalkyl (meth) acrylate. The hardening type composition of claim 1, wherein the catalyst X is selected from the group consisting of a cyclic tertiary amine having a nitrogen abicyclic structure or a salt or a complex thereof, hydrazine or a salt or a complex thereof, and a pyridine One or more compounds of the group consisting of a cyclic compound or a salt or a complex thereof. The hardened composition of claim 1, wherein the catalyst Y is an organic acid zinc or/and a diketoenolate zinc salt. The hardening type composition of claim 1, wherein the hydroxyl value of the component (A) is in the range of 80 to 600 mgKOH/g. The hardening type composition of claim 1, wherein the component (A) has a dispersion (Mw/Mn) of a main peak obtained by gel permeation chromatography (GPC) in a range of 1.0 to 2.5. The hardening type composition of claim 1, which further contains the compound (D) having an ethylenically unsaturated group other than the component (A). The hardening type composition of claim 7, wherein the component (D) comprises a compound (D-1) having two ethylenically unsaturated groups or/and a compound having three or more ethylenically unsaturated groups (D-2). . The hardened composition of claim 8, wherein the component (D-1) comprises a polyalkylene glycol di(meth)acrylate (D-1-1). The hardened composition of claim 8, wherein the component (D-2) comprises (D-2-1) dipentaerythritol poly(meth)acrylate and/or (D-2-2) has 3 The above (meth) acrylonitrile-based urethane (meth) acrylate. The hardened composition of claim 1, which further contains water. An active energy ray-curable composition comprising the composition of claim 1. The active energy ray-curable composition of claim 12, which further contains a photopolymerization initiator (B). An ultraviolet curable composition using a light-emitting diode (UV-LED) containing the composition of claim 13. The active energy ray-curable composition of claim 13 which contains 1 to 20 parts by weight of the (B-1) fluorenylphosphine oxide-based compound as the component (B) per 100 parts by weight of the curable component. An active energy ray-curable composition according to claim 13 which contains (B-2) 9-oxothione A compound and/or (B-3) 4,4'-bis(dialkylamino)benzophenone as the component (B). An active energy ray-curable coating composition comprising the composition of any one of claim 12 to claim 16. The active energy ray-curable coating composition of claim 17, which further comprises colloidal particles. An active energy ray-curable hard coat composition comprising the composition of claim 17. An active energy ray-curable nail coating composition comprising the composition of claim 17. An active energy ray-curable ink composition comprising the composition of any one of claim 12 to claim 16. An active energy ray-curable inkjet ink containing the composition of claim 21. A method for producing a hardened composition comprising the steps of: a polyglycerol having a hydroxyl value of 700 to 1,200 mgKOH/g and a compound having a (meth)acrylonitrile group in the presence of the catalysts X and Y described below Performing a transesterification reaction to produce a mixture (A) of a compound having a (meth) acrylonitrile group; Catalyst X: selected from a cyclic tertiary amine having an azabicyclo structure or a salt or a complex thereof, hydrazine Or a salt or complex thereof, a compound having a pyridine ring or a salt or a complex thereof, and a compound of the group consisting of phosphine or a salt or a complex thereof; Catalyst Y: a zinc-containing compound. The method for producing a hardened composition according to claim 23, wherein the compound having one (meth) acrylonitrile group is an alkoxyalkyl (meth) acrylate. The method for producing a hardened composition according to claim 23, wherein the catalyst X is selected from the group consisting of a cyclic tertiary amine having a nitrogen abicyclic structure or a salt or a complex thereof, hydrazine or a salt or a complex thereof, And one or more compounds in the group consisting of a compound having a pyridine ring or a salt or a complex thereof. The method for producing a hardened composition according to claim 23, wherein the catalyst Y is an organic acid zinc or/and a diketoenolate zinc salt. The method for producing a hardened composition according to any one of the preceding claims, comprising the step of: mixing the photopolymerization initiator (B) after the component (A) is produced.