JP2018100371A - Curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition which has low viscosity, had quick curability when formed into a thin film, and provides a cured film having high hardness, preferably, an active energy ray-curable composition.SOLUTION: A curable composition contains a mixture (A) that is a mixture of a compound having two or more (meth)acryloyl groups obtained by ester exchange reaction of a compound having polyhydric alcohol and one (meth)acryloyl group in the presence of the following catalysts X and Y, and contains impurities by gel permeation chromatography in an amount of 30 area% in the mixture. Catalyst X: one or more compounds selected from the group consisting of a complex having cyclic tertiary amine having an azabicyclo structure, its salt or its complex, amidine, its salt or its complex, a compound having a pyridine ring, its salt or its complex and phosphine, its salt or its complex. Catalyst Y: compound containing zinc.SELECTED DRAWING: None

Description

The present invention relates to a curable composition, and preferably to an active energy ray curable composition. The composition of the present invention can be used for various applications, and can be preferably used for applications such as coating agents such as hard coats and inks such as offset and ink jet printing, and belongs to these technical fields.
In the present specification, an acryloyl group and / or a methacryloyl group is represented as a (meth) acryloyl group, an acrylate and / or methacrylate is represented as a (meth) acrylate, and acrylic acid and / or methacrylic acid is represented by (meth) acrylic acid. It expresses.

  As an active energy ray-curable composition, a composition containing a compound having two or more (meth) acryloyl groups (hereinafter referred to as “polyfunctional (meth) acrylate”) is used in various applications, particularly dipentaerythritol. A composition mainly composed of a mixture of pentaacrylate and dipentaerythritol hexaacrylate (hereinafter referred to as “DPHA”) or a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (hereinafter referred to as “PETTA”) has excellent physical properties. Is used for various purposes.

A cured film obtained from a composition containing DPHA or / and PETTA is widely used for hard coat applications because of its high surface hardness and resistance to scratching (Patent Document 1).
Since DPHA has high viscosity and PETTA is solid at room temperature, it is difficult to make the composition solvent-free. Patent Document 2 has a compound having one (meth) acryloyl group (hereinafter referred to as “monofunctional (meth) acrylate”) and two (meth) acryloyl groups in order to reduce the viscosity of DPHA. An active energy ray-curable composition containing 30 parts by weight or more of a compound (hereinafter referred to as “bifunctional (meth) acrylate”) is disclosed.
However, the composition of Patent Document 2 has a problem that the hardness of the cured film formed on the plastic film is too low.
DPHA and PETTA are usually produced by dehydration esterification of polyhydric alcohol and acrylic acid, but since these products contain high molecular weight substances, they contribute to a decrease in the hardness of the cured film. Therefore, improvement in hardness is required.

DPHA is widely used as a resin composition for ink applications, particularly active energy ray-curable offset inks, because it has excellent surface curability (Patent Document 3).
Since DPHA and PETTA are produced by dehydration esterification as described above, the product contains a high molecular weight substance, which causes a decrease in emulsion stability.
Patent Document 4 discloses that following the step of removing unreacted acrylic acid, water-soluble components can be removed by washing with a mixture of a specific solvent and water to improve emulsion stability.
However, since waste solvents and waste liquids increase, there is a demand for a production method capable of reducing the high molecular weight material, instead of this method.

  On the other hand, tri (meth) acrylate of glycerin ethylene oxide adduct (hereinafter referred to as “GLY-EO-TA”) and tetra (meth) acrylate of diglycerin ethylene oxide adduct (hereinafter referred to as “DGLY-EO-TA”). An active energy ray-curable composition mainly composed of) is also used in various applications.

  The composition is used for coating applications and ink applications such as offset ink and inkjet ink because of its low viscosity and excellent curability (Patent Documents 5, 6, and 7).

  Since GLY-EO-TA and DGLY-EO-TA all have an ethylene oxide chain, the acryloyl group concentration is lower than that without an ethylene oxide chain, which contributes to a decrease in the hardness of the cured film.

Therefore, diglycerol tetra (meth) acrylate (hereinafter “DGLY-TA”) and glycerol tri (meth) acrylate (hereinafter “GLY-TA”) having a high concentration of acryloyl groups having no ethylene oxide chain are required. It has been.
However, when DGLY-TA and GLY-TA are produced by dehydration esterification of diglycerin and glycerin and acrylic acid, respectively, the reactivity of the secondary hydroxyl group is particularly low and it is difficult to obtain a product. Is not in circulation.

As described above, in a composition containing a polyfunctional (meth) acrylate, if the compound having few impurities such as a high molecular weight substance can be obtained as the raw material polyfunctional (meth) acrylate, it is considered that the above-described various problems can be solved. .
A transesterification method using a tin catalyst or a titanium catalyst is known as a method for producing (meth) acrylate that suppresses the formation of a high molecular weight product (Patent Documents 8 and 9).
However, in a conventional transesterification reaction, when a polyhydric alcohol having 3 or more alcoholic hydroxyl groups is used as a raw material, the reaction rate is low even when reacted for a long time, so the ideal structure (meth) acrylate concentration is low and curing is performed. There was a problem that the hardness of the film was low.

JP 2001-278924 A JP 2009-287017 A JP 2000-302997 A Japanese Patent Laid-Open No. 02-279775 JP 2006-335924 A JP 2011-132349 A JP 2010-6913 A JP 2003-190819 A Japanese Patent Laid-Open No. 2002-3444

  The inventors of the present invention are diligent in finding a curable composition, preferably an active energy ray curable composition, having a low viscosity composition, a thin film and a fast curing property, and a cured film of the composition having a high hardness. It was examined.

In order to solve the above-mentioned problems, the present inventors have used a polyfunctional (obtained by transesterifying a polyhydric alcohol and a monofunctional (meth) acrylate in combination with a specific basic catalyst and a zinc-based catalyst. The present inventors have found that a curable composition containing (meth) acrylate and containing impurities at a specific ratio or less has a low viscosity, is a thin film and is fast curable, and has excellent hardness of the cured film.
Hereinafter, the present invention will be described in detail.

  According to the composition of the present invention, it has a low viscosity, is a thin film and has a fast curability, and can further increase the hardness of the cured film of the composition.

The present invention is obtained by subjecting a polyhydric alcohol and a compound having one (meth) acryloyl group (hereinafter referred to as “monofunctional (meth) acrylate”) to an ester exchange reaction in the presence of the following catalysts X and Y. A mixture of two or more (meth) acryloyl group-containing compounds (hereinafter referred to as “polyfunctional (meth) acrylates”)), and impurities determined by gel permeation chromatography (hereinafter referred to as “GPC”) measurement. The present invention relates to a curable composition containing a mixture (A) that is 30 area% or less in the mixture.
Catalyst X: a kind selected from the group consisting of a cyclic tertiary amine having an azabicyclo structure or a salt or complex thereof, an amidine or a salt or complex thereof, a compound having a pyridine ring or a salt or complex thereof, and phosphine or a salt or complex thereof The above compound.
Catalyst Y: Compound containing zinc.
Hereinafter, the component (A), other components, and methods of use will be described.

1. Component (A) Component (A) is a mixture of polyfunctional (meth) acrylates obtained by transesterification of polyhydric alcohol and monofunctional (meth) acrylate in the presence of catalysts X and Y. , Impurities by GPC measurement are a mixture having 30% by area or less in the mixture.

In the present invention, the GPC measurement value means a value measured under the following conditions.
-Detector: RI detector-Column: Guard column Shodex KFG (8 μm 4.6 × 10 mm) manufactured by Showa Denko KK, two types of this column Watergel HR 4E THF (7.8 × 300 mm) + styragel HR 1THF (7.8 × 300 mm)
Column temperature: 40 ° C
Eluent composition: THF (containing 0.03% sulfur as internal standard), flow rate of 0.75 mL / min. Calibration curve: A calibration curve was prepared using standard polystyrene.
Impurity area% = [(RI) / R] × 100 (1)
The symbols and terms in formula (1) mean the following.
-R: total area of detection peak of component (A)-I: area of detection peak containing ideal structure (meth) acrylate-ideal structure (meth) acrylate: the same number as the number of hydroxyl groups contained per molecule of raw alcohol Of (meth) acryloyl groups per molecule.

  Hereinafter, the polyhydric alcohol, the monofunctional (meth) acrylate, the catalyst X, the catalyst Y, the production method of the component (A), and the preferred form of the component (A) will be described.

1-1. The polyhydric alcohol used as a raw material for the polyhydric alcohol (A) component is a compound having at least two or more alcoholic hydroxyl groups in the molecule.
Specific examples of the component (A) include aliphatic alcohols, alicyclic alcohols, aromatic alcohols and polyhydric alcohol ethers, and other functional groups and bonds in the molecule, such as phenolic hydroxyl groups, ketone groups, Acyl group, aldehyde group, thiol group, amino group, imino group, cyano group, nitro group, vinyl group, ether bond, ester bond, carbonate bond, amide bond, imide bond, peptide bond, urethane bond, acetal bond, hemiacetal You may have a coupling | bonding, a hemiketal coupling | bonding, etc.

  Specific examples of the dihydric alcohol having two alcoholic hydroxyl groups include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, trimethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, butanediol, Pentanediol, hexanediol, heptanediol, nonanediol, neopentylglycol, cyclohexanediol, cyclohexanedimethanol, dioxaneglycol, N-methyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine, N-tert-butyldiethanolamine, N- Lauryl diethanolamine, stearyl diethanolamine, N-phenyldi Tanolamine, m-tolyldiethanolamine, p-tolyldiethanolamine, N, N′-bis (2-hydroxypropyl) aniline, N-nitrosodiethanolamine, N- (2-hydroxyethyl) lactamamide, N, N′-bis (2 -Hydroxyethyl) oxamide, 3-morpholino-1,2-propanediol, 2,6-pyridinedimethanol, 3- (dimethylamino) -1,2-propanediol, 3- (diethylamino) -1,2-propane Diol, alloxanthin dihydrate, (+)-N, N, N ′, N′-tetramethyl-L-tartaric acid diamide, (−)-N, N, N ′, N′-tetramethyl-D— Tartaric acid diamide, N-propyl-N- (2,3-dihydroxypropyl) perfluoro-n-octylsulfonamide, thymidine, Chloramphenicol, thiamphenicol, D-erythronolactone, methyl 4,6-O-benzylidene-α-D-glucopyranoside, phenyl 4,6-O-benzylidene-1-thio-β-D-glucopyranoside, 1 , 2: 5,6-di-O-isopropylidene-D-mannitol, 1,2-O-isopropylidene-α-D-xylofuranose, 2,6-di-O-palmitoyl-L-ascorbic acid, isosorbide And these alkylene oxide adducts, hydroquinone, bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S, thiobisphenol, bisphenol Lumpur P, bisphenol PH, alkylene oxide adducts of compounds having a phenolic hydroxyl group such as bisphenol TMC and bisphenol Z, alcohol having a carbonate bond, such as polycarbonate diol.

  Specific examples of the trihydric alcohol having three alcoholic hydroxyl groups include trimethylolethane, trimethylolpropane, glycerin, tris (2-hydroxyethyl) isocyanurate, hexanetriol, octanetriol, decantriol, triethanolamine, triethanolamine Isopropanolamine, 1- [bis2- (hydroxyethyl) amino] -2-propanol, D-panthenol, DL-panthenol, uridine, 5-methyluridine, cytidine, inosine, adenosine, leuomycin A3, leucomomycin A4 , Leucomycin A6, leucomycin A8, clindamycin hydrochloride monohydrate, prednisolone, methyl β-D-arabinopyranoside, methyl β-L-fucopyranoside, methyl α-L-fucopyranoside, D-galac Tar, 4-methoxyphenyl 3-O-allyl-β-D-galactopyranoside, 4-methoxyphenyl 3-O-benzyl-β-D-galactopyranoside, 1,6-anhydro-β-D- Glucose, α-chloralose, β-chloralose, 4,6-O-ethylidene-α-D-glucopyranose, D-glucal, 1,2-O-isopropylidene-α-D-glucofuranose, D-glucurono-6 , 3-lactone, 2-deoxy-D-ribose, methyl β-D-ribofuranoside, D-(+)-ribono-1,4-lactone, methyl-β-D-xylopyranoside, 6-O-palmitoyl-L- Examples include ascorbic acid, 6-O-stearoyl-L-ascorbic acid, 3-O-ethyl-L-ascorbic acid, and alkylene oxide adducts thereof.

  Specific examples of the tetrahydric alcohol having four alcoholic hydroxyl groups include ditrimethylolethane, ditrimethylolpropane, diglycerin, pentaerythritol, N, N, N ′, N′-tetrakis (2-hydroxyethyl) butanediamide, N, N, N ′, N′-tetrakis (2-hydroxypropyl) butanediamide, N, N, N ′, N′-tetrakis (2-hydroxyethyl) hexanediamide, N, N, N ′, N′-tetrakis (2-hydroxypropyl) hexanediamide, N, N, N ′, N′-tetrakis (2-hydroxyethyl) ethylenediamine, N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine, N-hexanoyl -D-glucosamine, N-valeryl-D-glucosamine, N-trifluoroacetyl-D- Lucosamine, N-benzoyl-D-glucosamine, 5-acetamido-N, N′-bis (2,3-dihydroxypropyl) -2,4,6-triiodoisophthalamide, spiramycin, clarithromycin, leucomycin A1 , Leucomycin A5, leucomycin A7, leucomycin A9, leucomycin A13, lincomycin hydrochloride monohydrate, diazolidinyl urea, D-(-)-arabinose, DL-arabinose, L-(+)-arabinose, meso -Erythritol, D-(+)-fucose, L-(-)-fucose, allyl α-D-galactopyranoside, methyl β-D-galactopyranoside, methyl α-D-galactopyranoside monohydrate Japanese, 4-methoxyphenyl β-D-galactopyranoside, 2-nitrophenyl β-D-ga Ctopyranoside, 4-nitrophenyl α-D-galactopyranoside, 4-nitrophenyl β-D-galactopyranoside, phenyl β-D-galactopyranoside, N-acetyl-D-galactosamine hydrate, D -(+)-Galactosamine hydrochloride, arbutin, 2-deoxy-D-glucose, esculin hemihydrate, D-(+)-glucono-1,5-lactone, D-glucuronamide, helicin, methyl α -D-glucopyranoside, methyl β-D-glucopyranoside hemihydrate, 4-methoxyphenyl β-D-glucopyranoside, 4-nitrophenyl β-D-glucopyranoside monohydrate, 4-nitrophenyl α-D- Glucopyranoside, nonyl β-D-glucopyranoside, n-octyl β-D-glucopyranoside, phenyl β-D-glucopyranos Hydrate, phlorizin hydrate, picaide, puerarin, N-acetyl-D-glucosamine, N-benzoyl-D-glucosamine, D-(+)-glucosamine hydrochloride, N-hexanoyl-D-glucosamine, N- Valeryl-D-glucosamine, L-(+)-gulonic acid γ-lactone, D-(−)-lyxose, L-(+)-lyxose, 3,4-O-isopropylidene-D-mannitol, methyl α- D-mannopyranoside, D-mannono-1,4-lactone, 4-methoxyphenyl α-D-mannopyranoside, N-acetyl-D-mannosamine monohydrate, D-(−)-ribose, L-ribose, D- (+)-Xylose, DL-xylose, L-(-)-xylose, D-araboascorbic acid, L-ascorbic acid, L-threitol and the same And the like of the alkylene oxide adduct.

  Specific examples of the pentahydric alcohol having 5 alcoholic hydroxyl groups include tritrimethylolethane, tritrimethylolpropane, triglycerin, bis (2-hydroxyethyl) aminotris (hydroxymethyl) methane, and bis (2-hydroxypropyl). Aminotris (hydroxymethyl) methane, N, N, N ′, N ″, N ″ -pentakis (2-hydroxyethyl) diethylenetriamine, N, N, N ′, N ″, N ″ -pentakis (2 -Hydroxypropyl) diethylenetriamine, miglitol, erythromycin, azithromycin dihydrate, D-(+)-arabitol, DL-arabitol, L-(-)-arabitol, D-(-)-fructose, L-(+)- Fructose, D-(+)-galactose, L-(-)-galactose, β-D-glucose, D-(+)-glucose, L-(−)-glucose, D-glucose diethyl mercaptal, salicin, L-gulose, D-(+)-mannose, L-(−) − Mannose, ribitol, L-(−)-sorbose, D-tagatose, xylitol, sucralose, glyceryl ascorbate, and alkylene oxide adducts thereof can be mentioned.

  Specific examples of the polyhydric alcohol having 6 or more alcoholic hydroxyl groups include polytrimethylolethane, polytrimethylolpropane, polyglycerin, dipentaerythritol, tripentaerythritol, polypentaerythritol, iohexol, galactitol, D- Sorbitol, L-sorbitol, myo-inositol, scyllo-inositol, D-mannitol, L-mannitol, icariin, amygdalin, D-(+)-cellobiose, diosmine, 2-O-α-D-glucopyranosyl-L-ascorbic acid , Hesperidin, D-(+)-lactose monohydrate, lactulose, D-(+)-maltose monohydrate, D-(+)-melibiose monohydrate, methyl hesperidin, maltitol, naringin hydrate Thing Hesperidin dihydrochalcone hydrate, palatinose hydrate, rutin hydrate, D-(+)-sucrose, stevioside, D-(+)-turanose, D-(+)-trehalose (anhydrous), D-(+ ) -Trehalose dihydrate, D-(+)-meletitol hydrate, D-(+)-raffinose pentahydrate, rebaudioside A, stachyose, α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin , Starch, polyvinyl alcohol, and these alkylene oxide adducts.

In this invention, these polyhydric alcohol can be used individually or in combination of 2 or more types.
Among these polyhydric alcohols, polyhydric alcohols having 3 or more alcoholic hydroxyl groups are preferable, and in particular, dipentaerythritol, pentaerythritol, diglycerin and glycerin are obtained. Is preferable in that it is high.

1-2. The monofunctional (meth) acrylate used as a raw material for the monofunctional (meth) acrylate (A) component is a compound having one (meth) acryloyl group in the molecule. For example, it is represented by the following general formula (1). Compounds.

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

Preferable specific examples of R ² in the general formula (1) include carbon such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, and 2-ethylhexyl group. Alkyl groups of formulas 1-8, alkoxyalkyl groups such as 2-methoxyethyl group, 2-ethoxyethyl group and 2-methoxybutyl group, and N, N-dimethylaminoethyl group, N, N-diethylaminoethyl group, N , N-dimethylaminopropyl groups, and N, N-diethylaminopropyl groups and the like.
Specific examples of R ² in the general formula (1) include functional groups mentioned in the specifications of Japanese Patent Application Nos. 2015-163808, 2015-163910, and 2015-164092.

In the present invention, these monofunctional (meth) acrylates can be used alone or in combination of two or more.
Among these monofunctional (meth) acrylates, carbon such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate Alkyl (meth) acrylates having an alkyl group of 1 to 8 and alkoxyalkyl (meth) acrylates such as 2-methoxyethyl acrylate, and N, N-dimethylaminoethyl (meth) acrylate are preferred, particularly good for glycerin (Meth) acrylate having an alkyl group having 1 to 4 carbon atoms, and an alkoxyalkyl (meth) acrylate having an alkyl group having 1 to 2 carbon atoms, which are easy to obtain, are preferable.
Furthermore, the alkoxyalkyl (meth) acrylate which has a C1-C2 alkyl group which accelerates | stimulates melt | dissolution of glycerol and shows very favorable reactivity is more preferable, and 2-methoxyethyl (meth) acrylate is especially preferable.
Furthermore, as monofunctional (meth) acrylate, acrylate is particularly preferable because of its excellent reactivity.

  (A) Although there is no restriction | limiting in particular in the usage rate of glycerol and monofunctional (meth) acrylate in the manufacturing method of component, 0.4-10.0 mol of monofunctional (meth) acrylate is with respect to 1 mol of hydroxyl groups of glycerol. Preferably, it is 0.6-5.0 mol. By making the monofunctional (meth) acrylate 0.4 mol or more, side reactions can be suppressed. Moreover, the production amount of (A) component can be increased by making it 10.0 mol or less, and productivity can be improved.

1-3. As the transesterification catalyst in the method for producing the catalyst (A) component, the following catalysts X and Y are used in combination as a catalyst because a reaction product containing glycerin di (meth) acrylate can be produced in a high yield.
Catalyst X: a cyclic tertiary amine having an azabicyclo structure or a salt or complex thereof (hereinafter referred to as “azabicyclo compound”), an amidine or a salt or complex thereof (hereinafter referred to as “amidine compound”), a compound having a pyridine ring, or One or more compounds selected from the group consisting of salts or complexes thereof (hereinafter referred to as “pyridine compounds”) and phosphines or salts or complexes thereof (hereinafter referred to as “phosphine compounds”).
Catalyst Y: Compound containing zinc.
Hereinafter, the catalyst X and the catalyst Y will be described.

1-3-1. Catalyst X
The catalyst X in the method for producing the component (A) is one or more compounds selected from the group consisting of an azabicyclo compound, an amidine compound, a pyridine compound, and a phosphine compound.
The catalyst X is preferably at least one compound selected from the group consisting of azabicyclo compounds, amidine compounds and pyridine compounds among the compound groups described above. These compounds are excellent in catalytic activity and can preferably produce the component (A), and also form a complex with catalyst Y described later during and after the reaction, and the complex is a reaction solution after completion of the reaction by a simple method such as adsorption. Can be easily removed from. In particular, since the complex with the catalyst Y becomes hardly soluble in the reaction solution, the azacyclo compound can be more easily removed by filtration and adsorption.
On the other hand, although the phosphine compound is excellent in catalytic activity, it is difficult to form a complex with the catalyst Y, or when the complex is formed, it is easily soluble in the reaction solution, and the phosphine compound in the reaction solution after the completion of the reaction. Since most of the compound or complex remains dissolved, it is difficult to remove from the reaction solution by a simple method such as filtration and adsorption. For this reason, the phosphine-based catalyst remains in the final product, thereby causing turbidity and catalyst precipitation during storage of the product, and increasing the viscosity or gelation over time. May cause problems.

Specific examples of the azabicyclo compound include various compounds as long as the compound satisfies the cyclic tertiary amine having an azabicyclo structure, a salt of the amine, or a complex of the amine. Preferred compounds include quinuclidine, 3 -Hydroxyquinuclidine, 3-quinuclidinone, 1-azabicyclo [2,2,2] octane-3-carboxylic acid, and triethylenediamine (also known as 1,4-diazabicyclo [2,2,2] octane. DABCO ”).
Specific examples of the azabicyclo compounds include the compounds mentioned in the specifications of Japanese Patent Application Nos. 2015-163808, 2015-163910, and 2015-164092.

  Specific examples of the amidine compound include imidazole, N-methylimidazole, N-ethylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-vinylimidazole, 1-allylimidazole, 1 , 8-diazabicyclo [5,4,0] undec-7-ene (hereinafter referred to as “DBU”), 1,5-diazabicyclo [4,3,0] non-5-ene (hereinafter referred to as “DBN”) N-methylimidazole hydrochloride, DBU hydrochloride, DBN hydrochloride, N-methylimidazole acetate, DBU acetate, DBN acetate, N-methylimidazole acrylate, DBU acrylate, DBN acrylate, phthalimide DBU etc. are mentioned.

Principal examples of pyridine-based compounds 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”) and the like.
Specific examples of the pyridine-based compound include the compounds mentioned in the specifications of Japanese Patent Application Nos. 2015-163808, 2015-163910, and 2015-164092.

  Examples of the phosphine compound include compounds having a structure represented by the following general formula (2).

[In Formula (2), R < ³ >, R < ⁴ > and R < ⁵ > are a C1-C20 linear or branched alkyl group, a C1-C20 linear or branched alkenyl group, carbon number 6 Means an aryl group of ˜24 or a cycloalkyl group of 5 to 20 carbon atoms. R ³ , R ⁴ and R ⁵ may be the same or different.

Specific examples of the phosphine compound include triphenylphosphine, tris (4-methoxyphenyl) phosphine, tri (p-tolyl) phosphine, tri (m-tolyl) phosphine, tris (4-methoxy-3,5-dimethylphenyl). ) Phosphine and tricyclohexylphosphine.
Specific examples of the phosphine compound include the compounds mentioned in the specifications of Japanese Patent Application Nos. 2015-163808, 2015-163910, and 2015-164092.

  In this invention, these catalysts X can be used individually or in combination of 2 or more types. Among these catalysts X, quinuclidine, 3-quinuclidinone, 3-hydroxyquinuclidine, DABCO, N-methylimidazole, DBU, DBN and DMAP are preferable, and particularly have good reactivity with most polyhydric alcohols. Preference is given to 3-hydroxyquinuclidine, DABCO, N-methylimidazole, DBU and DMAP, which are readily available.

  (A) Although the usage-amount of the catalyst X in the manufacturing method of a component does not have a restriction | limiting in particular, It is preferable to use 0.0001-0.5 mol of catalyst X with respect to 1 mol of hydroxyl groups of a polyhydric alcohol, More preferably Is 0.0005 to 0.2 mol. By using the catalyst X in an amount of 0.0001 mol or more, the yield of the reaction product containing the target polyfunctional (meth) acrylate can be increased. And coloring of the reaction solution can be suppressed, and the purification step after completion of the reaction can be simplified.

1-3-2. Catalyst Y
The catalyst Y is a compound containing zinc.
As the catalyst Y, various compounds can be used as long as they contain zinc, but organic acids zinc and zinc diketone enolate are preferable because of excellent reactivity.
Examples of the organic acid zinc include dibasic acid zinc such as zinc oxalate and a compound represented by the following general formula (3).

[In Formula (3), R < ⁶ > and R < ⁷ > are C1-C20 linear or branched alkyl groups, C1-C20 linear or branched alkenyl groups, C6-C24 An aryl group or a C5-C20 cycloalkyl group is meant. R ⁶ and R ⁷ may be the same or different.
As a compound of the said Formula (3), the compound whose R < ⁶ > and R < ⁷ > is a C1-C20 linear or branched alkyl group or an alkenyl group is preferable. In R ⁶ and R ⁷ , the 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 and chlorine, and the catalyst Y having the functional group is This is preferable because a reaction product containing the desired polyfunctional (meth) acrylate can be produced in high yield.

  Examples of the zinc diketone enolate include compounds represented by the following general formula (4).

[In Formula (4), R < ⁸ >, R < ⁹ >, R < ¹⁰ >, R < ¹¹ >, R < ¹² > and R < ¹³ > are C1-C20 linear or branched alkyl groups, C1-C20 linear Or a branched alkenyl group, a C6-C24 aryl group, or a C5-C20 cycloalkyl group is meant. R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ may be the same or different.

Specific examples of the compound containing zinc represented by the general formula (3) include zinc acetate, zinc acetate dihydrate, zinc propionate, zinc octylate, zinc neodecanoate, zinc laurate, zinc myristate, Examples include zinc stearate, zinc cyclohexanebutyrate, zinc 2-ethylhexanoate, zinc benzoate, zinc t-butylbenzoate, zinc salicylate, zinc naphthenate, zinc acrylate, and zinc methacrylate.
In addition, about these compounds containing zinc, when the complex with the hydrate, solvate, or catalyst X exists, this complex with the hydrate, solvate, and catalyst X is also component (A). It can be used as catalyst Y in the production method of

  Specific examples of the compound containing zinc represented by the general formula (4) include zinc acetylacetonate, zinc acetylacetonate hydrate, bis (2,6-dimethyl-3,5-heptanedionato) zinc, bis (2,2,6,6-tetramethyl-3,5-heptanedionato) zinc, bis (5,5-dimethyl-2,4-hexanedionato) zinc and the like. In addition, about these compounds containing zinc, when the complex with the hydrate or solvate, or the catalyst X exists, this complex with the hydrate, the solvate, and the catalyst X is also component (A). It can be used as the catalyst Y in the production method.

As the organic acid zinc and zinc diketone enolate in the catalyst Y, the aforementioned compounds can be used directly, but these compounds can also be generated and used in the reaction system.
For example, zinc compounds such as metal zinc, zinc oxide, zinc hydroxide, zinc chloride and zinc nitrate (hereinafter referred to as “raw zinc compounds”) are used as raw materials. In the case of organic acid zinc, raw zinc compounds and organic acids are used. In the case of zinc diketone enolate, a method of reacting a raw material zinc compound with 1,3-diketone and the like can be mentioned.

  In this invention, these catalysts Y can be used individually or in combination of 2 or more types. Among these catalysts Y, zinc acetate, zinc propionate, zinc acrylate, zinc methacrylate, and zinc acetylacetonate are preferable, and particularly shows good reactivity with most polyhydric alcohols and is easily available. Zinc acetate, zinc acrylate and zinc acetylacetonate are preferred.

  Although there is no restriction | limiting in particular in the usage-amount of the catalyst Y in the manufacturing method of (A) component, It is preferable to use 0.0001-0.5 mol of catalyst Y with respect to 1 mol of total hydroxyl groups of glycerol, More preferably 0.0005 to 0.2 mol. By using 0.0001 mol or more of catalyst Y, the yield of the reaction product containing the target polyfunctional (meth) acrylate can be increased. And coloring of the reaction solution can be suppressed, and the purification step after completion of the reaction can be simplified.

1-4. (A) Component Production Method Component (A) is produced by subjecting glycerol and a monofunctional (meth) acrylate to an ester exchange reaction in the presence of the catalysts X and Y.
(A) Although the usage-amount of the catalyst X and the catalyst Y in the manufacturing method of a component does not have a restriction | limiting in particular, It is preferable to use 0.005-10.0 mol of catalyst X with respect to 1 mol of catalyst Y, and more. Preferably it is 0.05-5.0 mol. By using 0.005 mol or more, the yield of the reaction product containing the target polyfunctional (meth) acrylate can be increased, and by making it 10.0 mol or less, by-product formation and reaction solution The coloring process can be suppressed, and the purification process after completion of the reaction can be simplified.

The combination of the catalyst X and the catalyst Y used in the present invention is preferably a combination of the catalyst X being an azabicyclo compound, the catalyst Y being a compound represented by the general formula (3), and the azabicyclo compound being DABCO. And a combination in which the compound represented by the general formula (3) is zinc acetate and / or zinc acrylate is particularly preferable.
In addition to obtaining a reaction product containing a polyfunctional (meth) acrylate in good yield, this combination is excellent in color tone after the reaction is finished (small yellowishness). It can be suitably used for applications. Furthermore, since the catalyst is available at a relatively low cost, it is an economically advantageous production method.

  The catalyst X and catalyst Y used in the present invention may be added from the beginning of the above reaction or may be added midway. Moreover, a desired use ratio may be added all at once or may be added in divided portions.

  (A) It is preferable that the reaction temperature in the manufacturing method of a component is 40-180 degreeC, More preferably, it is 60-160 degreeC. By setting the reaction temperature to 40 ° C. or higher, the reaction rate can be increased, and by setting it to 180 ° C. or lower, thermal polymerization of (meth) acryloyl groups in raw materials and products is suppressed, and coloring of the reaction liquid is performed. And the purification process after completion of the reaction can be simplified.

  The reaction pressure in the method for producing the component (A) is not particularly limited as long as the predetermined reaction temperature can be maintained, and may be performed in a reduced pressure state or in a pressurized state. Usually, it is 0.000001-10MPa (absolute pressure).

In the manufacturing method of (A) component, the monohydric alcohol derived from monofunctional (meth) acrylate byproduces with progress of transesterification.
When a part of the hydroxyl group of glycerin (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 removed by adsorption or deactivation. By distilling off the monohydric alcohol and the raw material monofunctional (meth) acrylate, a product having a controlled acrylate ratio can be stably produced.
On the other hand, when the hydroxyl group of glycerin is positively (meth) acrylated, it is preferable to discharge the monohydric alcohol out of the reaction system to further promote the progress of the transesterification reaction.

In the method for producing the component (A), the reaction can be carried out without using a solvent, but a solvent may be used as necessary.
Specific examples of the solvent include n-hexane, cyclohexane, methylcyclohexane, n-heptane, n-octane, n-nonane, n-decane, benzene, toluene, xylene, ethylbenzene, diethylbenzene, isopropylbenzene, amylbenzene, diamyl. Hydrocarbons such as benzene, triamylbenzene, dodecylbenzene, didodecylbenzene, amyltoluene, isopropyltoluene, decalin and tetralin; diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, diethyl acetal, dihexyl acetal , T-butyl methyl ether, cyclopentyl methyl ether, tetrahydrofuran, tetrahydropyran, trioxane, dioxane, anisole, diphenyl ether Ethers such as tellurium, dimethylcellosolve, diglyme, triglyme and tetraglyme; crown ethers such as 18-crown-6; esters such as methyl benzoate and γ-butyrolactone; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone And ketones such as benzophenone; carbonate compounds such as dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, and 1,2-butylene carbonate; sulfones such as sulfolane; sulfoxides such as dimethyl sulfoxide; ureas or derivatives thereof Ionic liquids such as phosphine oxides such as tributylphosphine oxide, imidazolium salts, piperidinium salts and pyridinium salts; silicon oil and water Etc.
Of these solvents, hydrocarbons, ethers, carbonate compounds and ionic liquids are preferred.
These solvents may be used alone, or two or more kinds may be arbitrarily combined and used as a mixed solvent.

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

In the manufacturing method of (A) component, it is preferable to add a polymerization inhibitor in the reaction liquid for the purpose of preventing the polymerization of the (meth) acryloyl group.
Specific examples of the polymerization inhibitor include hydroquinone, tert-butyl hydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl-4-methylphenol, 2,4,6-tri-tert-butylphenol, 4-tert -Butylcatechol, benzoquinone, phenothiazine, N-nitroso-N-phenylhydroxylamine ammonium, 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine Organic polymerization inhibitors such as -1-oxyl, inorganic polymerization inhibitors such as copper chloride, copper sulfate and iron sulfate, and organic salt systems such as copper dibutyldithiocarbamate and N-nitroso-N-phenylhydroxylamine aluminum salt A polymerization inhibitor is mentioned.
A polymerization inhibitor may be added individually by 1 type, or may be added in combination of 2 or more types, may be added from the beginning of this invention, and may be added from the middle. Moreover, a desired use amount may be added all at once, or may be added in divided portions. Moreover, you may add continuously via a rectification column.
The addition ratio of the polymerization inhibitor is preferably 5 to 30,000 wtppm in the reaction solution, and more preferably 25 to 10,000 wtppm. By setting this ratio to 5 wtppm or more, the polymerization inhibition effect can be exerted, and by setting it to 30,000 wtppm or less, coloring of the reaction solution can be suppressed, and the purification step after completion of the reaction can be simplified. Moreover, the fall of the cure rate of the (A) component obtained can be prevented.

  Although the reaction time in the manufacturing method of (A) component changes with the kind and usage-amount of a catalyst, reaction temperature, reaction pressure, etc., it is 0.1 to 150 hours normally, Preferably it is 0.5 to 80 hours.

  (A) The manufacturing method of a component can be implemented by any method of a batch type, a semibatch type, and a continuous type. As an example of a batch system, glycerin, monofunctional (meth) acrylate, a catalyst and a polymerization inhibitor are charged into a reactor, and stirred at a predetermined temperature while bubbling oxygen-containing gas into the reaction solution. Then, it can implement by the method of producing | generating the target (A) component by extracting the monohydric alcohol byproduced with progress of transesterification from a reactor by predetermined | prescribed pressure.

For the reaction product obtained by the production method of component (A), it is preferable to carry out separation and purification operations because the reaction product containing the desired polyfunctional (meth) acrylate can be obtained with high purity. .
Examples of the separation / purification operation include an adsorption operation, a crystallization operation, a filtration operation, a distillation operation, and an extraction operation, and these are preferably combined. The adsorption operation includes adsorption of a catalyst by an adsorbent, and examples of the adsorbent include aluminum silicate. Examples of the crystallization operation include cooling crystallization and concentrated crystallization. Examples of the filtration operation include pressure filtration, suction filtration, and centrifugal filtration. Examples of the distillation operation include simple distillation, fractional distillation, molecular distillation, and steam distillation. Examples of the extraction operation include solid-liquid extraction and liquid-liquid extraction.
A solvent may be used in the separation and purification operation. Further, a neutralizing agent for neutralizing the catalyst and / or polymerization inhibitor used in the present invention, an acid and / or alkali for decomposing or removing by-products, activated carbon for improving the color tone, filtration You may use diatomaceous earth etc. for improving efficiency and filtration speed.

1-5. A preferred component (A) component (A) is a mixture of polyfunctional (meth) acrylate obtained by transesterification of polyhydric alcohol and monofunctional (meth) acrylate, and has a polyfunctional (meth) acrylate having no hydroxyl group and It is a mixture of polyfunctional (meth) acrylates having a hydroxyl group.
For example, a case where dipentaerythritol, pentaerythritol, diglycerin and glycerin, which are preferable polyhydric alcohols, are used as raw materials will be described.
In the case of dipentaerythritol, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate It is a mixture of In this case, a (meth) acrylate mixture containing dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate as main components is preferable.
In the case of pentaerythritol, it is a mixture of pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol tetra (meth) acrylate. In this case, a mixture mainly composed of pentaerythritol tetra (meth) acrylate is preferable.
In the case of diglycerin, it is a mixture of diglycerin di (meth) acrylate, diglycerin tri (meth) acrylate and diglycerin tetra (meth) acrylate. In this case, a (meth) acrylate mixture mainly composed of diglycerin tri (meth) acrylate and diglycerin tetra (meth) acrylate is preferable.
In the case of glycerol, it is a mixture of glycerol di (meth) acrylate and glycerol tri (meth) acrylate. In this case, a (meth) acrylate mixture containing glycerin tri (meth) acrylate as a main component is preferable.
The mixture of polyfunctional (meth) acrylates may contain a small amount of mono (meth) acrylate.

What is necessary is just to set suitably as a hydroxyl value of (A) component according to the objective and the obtained polyvalent (meth) acrylate.
(A) As a hydroxyl value when using a component for preferable uses, such as a coating agent, ink, and pattern formation, a thing with a low hydroxyl value is preferable. Specifically, the hydroxyl value is preferably 60 mgKOH / g or less, more preferably 45 mgKOH / g or less.
By setting the hydroxyl value of the component (A) within this range, the composition can have a low viscosity, and a composition excellent in the hardness of the cured product can be obtained.
In the present invention, the hydroxyl value means the number of mg of potassium hydroxide equivalent to the hydroxyl group in 1 g of a sample.

1-6. Impurity (A) component in component (A) is a mixture of the various (meth) acrylates described above. As impurities, for example, a side reaction product having a Michael addition type structure, a Rauhut-Currier reaction type structure is used. And a side reaction product derived from the polymerization inhibitor. Depending on the production conditions, it contains a small amount of unreacted polyhydric alcohol used as a raw material. In addition to these compounds, high molecular weight substances that are difficult to identify are also included.
The present invention is a composition containing 30% by area or less of these impurities as a value by GPC measurement in the mixture.

  Examples of the side reaction product having a Michael addition type structure include a compound represented by the following general formula (5).

In [Equation (5), R ¹⁴ represents a hydrogen atom or a methyl group. R ¹⁵ and R ¹⁶ represent an organic group having 1 to 50 carbon atoms. R ¹⁵ and R ¹⁶ may be the same or different.

In the formula (5), as R ¹⁵ and R ¹⁶ , a hydrogen atom, an organic group exemplified by R ² in (formula 1), a (meth) acryloyl group, an organic group represented by the following general formula (6), etc. Can be mentioned.

In [Equation (6), R ¹⁷ and R ¹⁸ represents an organic group having 1 to 50 carbon atoms. R ¹⁷ and R ¹⁸ may be the same or different.

In formula (6), specific examples of R ¹⁷ and R ¹⁸ include a hydrogen atom and a (meth) acryloyl group.

As a specific example of the side reaction product having a Michael addition type structure represented by the general formula (5), a case where glycerin is used as a polyhydric alcohol will be described.
The compound represented by the following formula (7) in which the hydroxyl group of glycerol monoacrylate is Michael-added to the acryloyl group of glycerol diacrylate, and the following formula (Michael-added hydroxyl group of 2-methoxyethanol to the acryloyl group of 2-methoxyethyl acrylate) 8), a compound represented by the following formula (9) in which the hydroxyl group of acrylic acid is Michael-added to the acryloyl group of 2-methoxyethyl acrylate, and the like.

  As an example of the side reaction product having a Rauhut-Currier reaction type structure, for example, a compound represented by the following general formula (10) can be given.

In [Equation (10), R ¹⁹ and R ²⁰ represents an organic group having 1 to 50 carbon atoms. R ¹⁹ and R ²⁰ may be the same or different.

Specific examples of R ¹⁹ and R ²⁰ in formula (10) include a hydrogen atom, an organic group exemplified by R ² in (formula 1), an organic group represented by the above general formula (6), and the like. it can.

The case where glycerin is used as a polyhydric alcohol will be described as a specific example of the side reaction product having a Rauhut-Curier reaction type structure represented by the general formula (10).
A compound represented by the following formula (11) in which the acryloyl group α-position of glycerin diacrylate and the acryloyl group β-position of 2-methoxyethyl acrylate have caused Rauhut-Currier reaction, 2-methoxyethyl acrylate is dimerized by Rauhut-Currier reaction And a compound represented by the following formula (12).

  Examples of the side reaction product derived from the polymerization inhibitor include compounds represented by the following general formulas (13) to (15) when hydroquinone is used as the polymerization inhibitor.

[In the formulas (13) to (15), R ¹⁴ , R ¹⁵ and R ¹⁶ are the same groups as those shown in the formula (5).]

  Examples of the side reaction product derived from the polymerization inhibitor include compounds represented by the following general formulas (16) to (18) when hydroquinone monomethyl ether is used as the polymerization inhibitor.

[In the formulas (16) to (18), R ¹⁴ , R ¹⁵ and R ¹⁶ are the same groups as those shown in the formula (5).]

  Examples of the side reaction product derived from the polymerization inhibitor include compounds represented by the following general formulas (19) to (22) when phenothiazine is used as the polymerization inhibitor.

[In the formulas (19) to (22), R ¹⁴ , R ¹⁵ and R ¹⁶ are the same groups as those shown in the formula (5)].

  As an example of the side reaction product derived from the polymerization inhibitor, for example, when 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl is used as the polymerization inhibitor, the following general formula (23) The compound etc. which are represented by-(32) can be mentioned.

[In the formulas (23) to (32), R ¹⁴ , R ¹⁵ and R ¹⁶ are the same groups as those shown in the formula (5)].

Among impurities contained in the component (A), used as a side reaction product having the above-mentioned Michael addition type structure, a side reaction product having a Rauhut-Curier reaction type structure, a side reaction product derived from a polymerization inhibitor, and a raw material The total amount of the polyhydric alcohol (hereinafter referred to as “main impurities”) is preferably less than 30% by weight as measured by gas chromatography (hereinafter referred to as “GC”), more preferably 20% by weight. Less, more preferably less than 10% by weight.
By setting the content ratio of these main by-products to less than 30% by weight, the viscosity of the component (A) can be prevented from increasing, and the coating property can be excellent, and the curable composition containing the component (A) It can be excellent in the curing speed of the product and the hardness of the cured film.

In the present invention, the GC measured value means a value measured under the following conditions.
・ Detector: FID detector ・ Carrier gas: helium ・ Column: Inert Cap (film thickness 0.5 μm, 0.32 mm ID × 60 m) manufactured by GL Sciences Inc.
・ Injection temperature: 200 ℃
・ FID temperature: 250 ℃
Column temperature: held at 120 ° C. for 5 minutes, then heated to 240 ° C. at a rate of 10 ° C./min and then held for 25 minutes.
Prepare an acetone solution containing 35% by weight of component (A), add toluene as an internal standard substance, and inject 0.2 μL.
・ By internal standard method, the content of by-products is determined by weight%.

Component (A) is a value obtained by GPC measurement as an indicator of the weight average molecular weight (hereinafter referred to as “Mw”), and excludes detection peaks derived from monofunctional (meth) acrylates and solvents (A) component Mw is preferably less than 350, more preferably less than 340, and particularly preferably less than 330.
When the component (A) has an Mw of less than 350, it means that there are few high molecular weight bodies (hereinafter referred to as “side reaction high molecular weight bodies”) due to side reactions (Michael addition, etc.) other than (meth) acrylate formation. The component (A) is preferable because it has a low viscosity and is excellent in operability. On the other hand, the reaction product containing a polyfunctional (meth) acrylate obtained by dehydration esterification reaction or the like contains more side reaction high molecular weight compounds than the component (A) obtained by the transesterification reaction of the present invention. . These side-reaction high molecular weight substances not only cause high viscosity, but are also distributed to the aqueous layer in the extraction washing process using water or aqueous sodium hydroxide solution after the reaction is completed, so the yield is greatly increased. descend.

  The (meth) acrylate is preferably an acrylate from the viewpoint of reactivity during the transesterification reaction and quick curability of the component (A).

2. Curable composition TECHNICAL FIELD This invention relates to the curable composition containing the said (A) component.
The production method of the composition includes a step of producing a mixture of a polyfunctional (meth) acrylate by subjecting a polyhydric alcohol and a monofunctional (meth) acrylate to a transesterification reaction in the presence of the catalysts X and Y. The method is preferred.
According to the production method, since the raw material polyhydric alcohol can produce dipentaerythritol, pentaerythritol, diglycerin and glycerin (A) component in high yield, and the obtained high molecular weight component (A) is small. It is preferable in that it has a low viscosity and few impurities, and thus the resulting composition can be excellent in various physical properties.
According to the said manufacturing method, since (A) component can be obtained with a high yield, it is excellent in cost and productivity. In addition, the component (A) obtained by the production method is preferable because it has a low side-reaction high molecular weight and is low in viscosity and easy to handle, and further, is excellent in fast curability and hardness of a cured product.
What is necessary is just to follow the manufacturing method of above-described (A) component as the said process.
Furthermore, when blending other components described later, the component (A) and other components may be stirred and mixed.

What is necessary is just to set suitably as a viscosity of a composition according to the objective.
When the component (A) is used for a preferred application such as coating agent, ink and pattern formation, it may be appropriately set according to the purpose, preferably 1 to 100,000 mPa · s, more preferably 5 to 50, 000 mPa · s. By setting it as the said viscosity range, it is excellent in the leveling property at the time of the coating of a composition, and shall be excellent in the external appearance of hardened | cured material.
The viscosity in the present invention means a value measured at 25 ° C. using an E-type viscometer.

The content ratio of the component (A) in the composition is preferably 20 to 100% by weight with respect to 100% by weight of the total amount of the curable components in terms of fast curability and hardness, and preferably 30 to 100% by weight. It is more preferable that
In the present invention, the “curable component” is “a component that is cured by heat or active energy rays”, means the component (A), and when blending the component (D) described later, ) And (D) components.
Furthermore, compounds having polymerizable functional groups other than the components (A) and (D) such as cationic curable compounds (for example, epoxy compounds and oxetane compounds) and reactive surfactants (hereinafter “other polymerizable components”). In the case of blending, the “curable component” means “(A) component and other polymerizable component” and “(A) component, (D) component and other polymerizable component”.

Although the composition of this invention can be used for both an active energy ray hardening-type composition and a thermosetting type composition, an active energy ray hardening-type composition is preferable.
The composition of the present invention contains (A) as an essential component, but various components can be blended depending on the purpose.
Other preferred components include a photopolymerization initiator (hereinafter referred to as “component (B)”), a thermal polymerization initiator (hereinafter referred to as “component (C)”), and an ethylenic polymer other than the component (A). Compound having saturated group [hereinafter referred to as “component (D)”], pigment or dye [hereinafter referred to as “component (E)”], organic solvent or water (hereinafter referred to as “component (F)”), colloidal Inorganic fine particles (hereinafter referred to as “component (G)”), polymers (hereinafter referred to as “component (H)”), reactive surfactants (hereinafter referred to as “component (I)”), and the like.
Hereinafter, these components will be described.
In addition, the other component mentioned later may use only 1 type of the illustrated compound, and may use 2 or more types together.

2-1. (B) Component When the composition of the present invention is used as an active energy ray curable composition and further used as an electron beam curable composition, it does not contain the component (B) (photopolymerization initiator) and is an electron. It can also be cured by a wire.
When the composition of the present invention is used as an active energy ray-curable composition, particularly when ultraviolet rays or visible rays are used as active energy rays, it is necessary to further contain the component (B).
When an electron beam is used as the active energy ray, it is not always necessary to add it, but a small amount can be added as necessary in order to improve curability.

Specific examples of the component (B) include benzyldimethyl ketal, 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] propanone, 2-hydroxy-1- [ 4- [4- (2-hydroxy-2-methyl-propionyl) benzyl] phenyl] -2-methylpropan-1-one, 2-methyl-1- [4- (methylthio)] phenyl] -2-morpholinopro Pan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-dimethylamino-2- 4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) butan-1-one, 3,6-bis (2-methyl-2-morpholinopropionyl) -9-n-octylcarbazole and the like Acetophenone compounds of
Benzoin compounds such as benzoin, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether;
Benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, methyl-2-benzophenone, 1- [4- (4-benzoylphenylsulfanyl) phenyl ] -2-Methyl-2- (4-methylphenylsulfonyl) propan-1-one, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone and 4-methoxy-4 ′ -Benzophenone compounds such as dimethylaminobenzophenone;
Such as bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide. Acylphosphine oxide compounds; and thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 1-chloro-4-propylthioxanthone, 3- [3,4-dimethyl-9-oxo-9H-thioxanthone-2 -Yl-oxy] -2-hydroxypropyl-N, N, N-trimethylammonium chloride and thioxanthone compounds such as fluorothioxanthone.
Examples of the compound other than the above include benzyl, ethyl (2,4,6-trimethylbenzoyl) phenyl phosphinate, methyl phenylglyoxylate, ethyl anthraquinone, phenanthrenequinone, and camphorquinone.

(B) As a content rate of a component, 10 weight part or less is preferable with respect to 100 weight part of sclerosing | hardenable component total amount, and 0.1-10 weight part is preferable.
When the component (B) is used singly, it may be carried out in accordance with a conventional means of radical thermal polymerization. In some cases, the reaction rate is further increased after photocuring in combination with the component (C) (thermal polymerization initiator). For the purpose of improving the temperature, thermosetting can also be performed.

2-2. (C) component When using the composition of this invention as a thermosetting type composition, (C) component (thermal polymerization initiator) can be mix | blended.
As the component (C), various compounds can be used, and organic peroxides and azo initiators are preferable.
Specific examples of the organic peroxide include 1,1-bis (t-butylperoxy) 2-methylcyclohexane, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, , 1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, , 2-bis (4,4-di-butylperoxycyclohexyl) propane, 1,1-bis (t-butylperoxy) cyclododecane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl- , 5-di (m-toluoylperoxy) hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy 2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5 -Di (benzoylperoxy) hexane, t-butylperoxyacetate, 2,2-bis (t-butylperoxy) butane, t-butylperoxybenzoate, n-butyl-4,4-bis (t-butyl) Peroxy) valerate, di-t-butylperoxyisophthalate, α, α′-bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-di (t- Butylperoxy) hexane, t-butylcumyl peroxide, di-t-butylperoxide P-menthane hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, diisopropylbenzene hydroperoxide, t-butyltrimethylsilyl peroxide, 1,1,3 Examples include 3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, and t-butyl hydroperoxide.
Specific examples of the azo compound include 1,1′-azobis (cyclohexane-1-carbonitrile), 2- (carbamoylazo) isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile. Azodi-t-octane, azodi-t-butane and the like.
These may be used alone or in combination of two or more. Moreover, an organic peroxide can also be made into a redox reaction by combining with a reducing agent.

As a content rate of (C) component, 10 weight part or less is preferable with respect to 100 weight part of sclerosing | hardenable component total amount.
When the component (C) is used alone, it may be carried out in accordance with conventional means for radical thermal polymerization. In some cases, the reaction rate is further used after being combined with the component (B) (photopolymerization initiator) and photocured. Thermosetting can also be performed for the purpose of improving the resistance.

2-3. Component (D) The component (D) is a compound having an ethylenically unsaturated group other than the component (A), and is blended for the purpose of imparting various physical properties to the cured product of the composition.
Examples of the ethylenically unsaturated group in component (D) include a (meth) acryloyl group, a (meth) acrylamide group, a maleimide group, a vinyl group, and a (meth) allyl group, with a (meth) acryloyl group being preferred.
In the following, “monofunctional” means a compound having one ethylenically unsaturated group, “◯ functional” means a compound having ○ ethylenically unsaturated groups, and “polyfunctional”. Means a compound having two or more ethylenically unsaturated groups.
Specific examples of the component (D) include (meth) acrylate, (meth) acrylamide, vinyl ether, maleimide and the like, and (meth) acrylate is preferable. Among these compounds, acrylate, acrylamide, and vinyl ether are preferable from the viewpoint of curability, and acrylate is more preferable.

In the component (D), the polyfunctional ethylenically unsaturated compound is a compound having two ethylenically unsaturated groups (D-1) [hereinafter referred to as “component (D-1)”], 3 or more Examples thereof include compounds having an ethylenically unsaturated group (D-2) [hereinafter referred to as “component (D-2)”] and monofunctional ethylenically unsaturated compounds (hereinafter referred to as “component (D-3)”). .
Hereinafter, the components (D-1) to (D-3) 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 solvent-free and low-viscosity composition can be obtained. Moreover, when a high molecular weight urethane (meth) acrylate oligomer is blended, it is possible to impart elongation to the cured film and improve adhesion to the adherend.

Specific examples of the component (D-1) include, for example, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hexanediol di Di (meta) of aliphatic diols such as (meth) acrylate and nonanediol di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, norbornane dimethylol di (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate ) Acrylate;
Polyalkylene glycol di (meth) acrylates such as polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate;
Di (meth) acrylate of an alkylene oxide adduct of a compound having two phenolic hydroxyl groups in one molecule such as di (meth) acrylate of an alkylene oxide adduct of bisphenol A, an alkylene oxide adduct of bisphenol F;
So-called epoxy (meth) acrylates such as compounds in which (meth) acrylic acid is added to bisphenol A type epoxy resin;
So-called polyester (meth) acrylates, such as compounds esterified with ethylene glycol, phthalic anhydride and (meth) acrylic acid; and
Examples include so-called urethane (meth) acrylates such as compounds obtained by urethanization of isophorone diisocyanate, polymer diol, and hydroxyalkyl (meth) acrylate.
Here, examples of the polymer diol include polyether diol, polyester diol, polycarbonate diol, or diol having a plurality of these skeletons.

  Specific examples of the component (D-1) include 2-vinyloxyethyl (meth) acrylate, 2-vinyloxyethoxyethyl (meth) acrylate, 1,4-butanediol divinyl ether, neopentyl glycol divinyl ether, cyclohexane di Bifunctional monomers including functional groups other than (meth) acrylates such as methanol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, and dipropylene glycol divinyl ether are also included.

When the component (D-1) is blended, the preferable content varies depending on the use of the composition of the present invention. In the coating varnish application for paper and plastic film, the content ratio of the component (D-1) is preferably 0 to 80 parts by weight and preferably 0 to 70 parts by weight with respect to 100 parts by weight of the curable component. More preferred.
On the other hand, in the hard coat application, the content ratio of the component (D-1) is preferably 0 to 40 parts by weight and more preferably 0 to 20 parts by weight with respect to 100 parts by weight of the curable component.

2-3-2. (D-2) component
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, for example, glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri- or tetra (meth) acrylate, ditrimethylolpropane tri- or tetra- (meta) ) Acrylate, diglycerin tri or tetra (meth) acrylate, dipentaerythritol tri, tetra, penta or hexa (meth) acrylate, tripentaerythritol tri, tetra, penta, hexa, hepta and octa (meth) acrylate Polyol poly (meth) acrylates such as polypentaerythritol poly (meth) acrylate and polyglycerin poly (meth) acrylate;
Tri (meth) acrylate of glycerin alkylene oxide adduct, tri (meth) acrylate of trimethylolpropane alkylene oxide adduct, tri or tetra (meth) acrylate of pentaerythritol alkylene oxide adduct, tri of diglycerin alkylene oxide adduct or Tetra (meth) acrylate, poly (meth) acrylate of polyglycerol alkylene oxide adduct, tri- or tetra (meth) acrylate of ditrimethylolpropane alkylene oxide adduct, tri-, tetra-, penta- or hexa- of dipentaerythritol alkylene oxide adduct (Meth) acrylate, tripentaerythritol alkylene oxide adduct tri, tetra, penta, hexa, hepta, and octa (meth) Acrylate, poly poly pentaerythritol alkylene oxide adduct (meth) acrylates, poly (meth) acrylate polyglycerol alkylene oxide adduct, poly (meth) acrylates of a polyol alkylene oxide adduct;
Tri (meth) acrylates of isocyanuric acid alkylene oxide adducts;
Michael addition-type multimers of hydroxyl-containing polyfunctional acrylates, such as polyfunctional acrylates in which the hydroxyl groups of pentaerythritol triacrylate are polymerized by Michael addition to the acrylate;
Polyfunctional urethane (meth), which is a reaction product of a compound having a hydroxyl group and three or more (meth) acryloyl groups, such as pentaerythritol tri (meth) acrylate and dipentaerythritol penta (meth) acrylate, and an organic polyisocyanate Acrylate;
Polyfunctional epoxy (meth) acrylates such as phenolic novolac epoxy resin and acrylic acid added trifunctional or higher functional (meth) acrylates; and polyols having 3 or more hydroxyl groups in one molecule such as trimethylolpropane and anhydrous Polyfunctional polyester (meth) acrylates, such as polyester (meth) acrylate which consists of acid anhydrides, such as phthalic acid, and (meth) acrylic acid are mentioned.
Examples of the alkylene oxide adduct include ethylene oxide adduct, propylene oxide adduct, ethylene oxide and propylene oxide adduct, and the like.
Examples of the organic polyisocyanate include hexamethylene diisocyanate, tetramethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, norbornane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated 4,4′-diphenylmethane diisocyanate, hydrogenated xylylene. Examples include diisocyanate, trimer of 4,4′-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and the like.

When the composition of the present invention is used as a hard coat, it preferably contains dipentaerythritol poly (meth) acrylate as the component (D-2), and can improve the curability and hardness of the cured composition. it can. The component (D-2) preferably contains a urethane (meth) acrylate having 3 or more (meth) acryloyl groups, and the curability and flexibility of the cured composition can be improved.
As component (D-2), dipentaerythritol poly (meth) acrylate, component (D-2-1) and urethane (meth) acrylate having three or more (meth) acryloyl groups may be used in combination. The scratch resistance of the cured product can be improved.

When component (D-2) is blended, the preferred content varies depending on the use of the composition of the present invention.
In the hard coat application, the amount is preferably 0 to 80 parts by weight, more preferably 0 to 70 parts by weight with respect to 100 parts by weight of the curable component.
On the other hand, in the active energy ray-curable coating varnish application for paper and plastic films, the amount is preferably 0 to 40 parts by weight, more preferably 0 to 20 parts by weight with respect to 100 parts by weight of the curable component.

2-3-3. (D-3) component
Component (D-3) is a compound having one ethylenically unsaturated group per molecule, and may be a low molecular weight compound or an oligomer.
By blending the component (D-3), it is possible to impart elongation to the cured film or improve the adhesion to the adherend.

Specific examples of the component (D-3) include the same compounds as the monofunctional (meth) acrylate described above.
As compounds other than the monofunctional (meth) acrylate described above, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1,4-cyclohexane Dimethylol mono (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, (meth) acrylate of phenol alkylene oxide adduct, (meth) acrylate of p-cumylphenol alkylene oxide adduct, o-phenylphenol alkylene oxide (Meth) acrylate of adduct, (meth) acrylate of nonylphenol alkylene oxide adduct, (meth) acrylate of alkylene oxide adduct of 2-ethylhexyl alcohol, pentanediol mono ( Acrylate), hexanediol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, di Propylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxy-3-butoxypropyl ( (Meth) acrylate, tetrahydrofurfuryl (meth) acrylate, caprolactone-modified tetrahydrofurfuryl (meth) acrylate, (2-ethyl-2-methyl- , 3-Dioxolan-4-yl) methyl (meth) acrylate, (2-isobutyl-2-methyl-1,3-dioxolan-4-yl) methyl (meth) acrylate, (1,4-dioxaspiro [4,5 ] Decan-2-yl) methyl (meth) acrylate, 2-oxotetrahydrofuran-3-yl (meth) acrylate, (5-ethyl-1,3-dioxane-5-yl) methyl (meth) acrylate, glycidyl (meth) ) Acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, (3-ethyloxetan-3-yl) methyl (meth) acrylate, 2- (meth) acryloyloxyethyl isocyanate, N- (meth) acryloyloxyethylhexa Hydrophthalimide, N- (meth) acryloyloxyethyl tet Lahydrophthalimide, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl succinic acid, ω-carboxy-polycaprolactone mono (meth) acrylate, 3- (meth) acryloyloxypropyltrimethoxy Examples thereof include silane, 3- (meth) acryloyloxypropyldimethoxymethylsilane, 3- (meth) acryloyloxypropyltriethoxysilane, and 2- (meth) acryloyloxyethyl acid phosphate.
A compound having both an ethylenically unsaturated group and an alkoxysilyl group is also called a silane coupling agent. A silane coupling agent or a compound having both an ethylenically unsaturated group and a phosphoric acid group is preferable for improving the adhesion to an inorganic substrate.

  (D-3) components other than monofunctional (meth) acrylates include N-vinylpyrrolidone, N-vinylcaprolactam, (meth) acrylamide, (meth) acryloylmorpholine, N, N-dimethyl (meth) acrylamide, N , N-diethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, maleic anhydride, N-phenylmaleimide, N-hydroxyethylmaleimide, N-hydroxyethylcitracimide, cyclohexyl Vinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 1,4-cyclohexanedimethanol monovinyl ether, diethylene glycol monovinyl ether, dipropylene glycol monovinyl ether, Seto carboxyethyl vinyl ether, acetoxy butyl ether, acetyl cyclohexanedimethanol monovinyl ether, acetyl diethylene glycol ether, glycidyl Giro carboxyethyl vinyl ether, glycidyl Giro carboxybutyl ether, etc. glycidyl cyclohexanedimethanol monovinyl ether and glycidyl diethylene glycol vinyl ether.

When the component (D-3) is blended, the preferred content varies depending on the use of the composition of the present invention, the type of adherend, the light source, the curing atmosphere, and the like.
In the case of a hard coat cured under air, a UV-LED curable clear coating agent and an ink, the content ratio of the component (D-3) is, in terms of rapid curing, in 100% by weight of the curable component. The content is preferably 0 to 30% by weight, and more preferably 0 to 15% by weight.
On the other hand, when it is applied to an adherend that is difficult to adhere to, or when ultra-low viscosity is required such as inkjet ink, the component (D-3) is 80% by weight in 100% by weight of the curable component. May be included.

2-4. Component (E) The component (E) is a coloring component selected from pigments or dyes, and is necessary when the composition of the present invention is used as an ink composition.
Examples of the pigment include organic pigments and inorganic pigments.
Specific examples of organic pigments include insoluble azo pigments such as toluidine red, toluidine maroon, Hansa Yellow, benzidine yellow and pyrazolone red; soluble azo pigments such as Ritol Red, Helio Bordeaux, Pigment Scarlet and Permanent Red 2B; Alizarin, Indantron And derivatives from vat dyes such as thioindigo maroon; phthalocyanine organic pigments such as phthalocyanine blue and phthalocyanine green; quinacridone organic pigments such as quinacridone red and quinacridone magenta; perylene organic pigments such as perylene red and perylene scarlet; Isoindolinone organic pigments such as indolinone yellow and isoindolinone orange; pyranthrone organic pigments such as pyranthrone red and pyranthrone orange Thioindigo organic pigments; condensed azo organic pigments; benzimidazolone organic pigments; quinophthalone organic pigments such as quinophthalone yellow; isoindoline organic pigments such as isoindoline yellow; and other pigments such as flavanthrone yellow and acylamide Examples include yellow, nickel azo yellow, copper azomethine yellow, perinone orange, anthrone orange, dianthraquinonyl red, and dioxazine violet.
Specific examples of the inorganic pigment include carbon black, titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red rose (red iron oxide (III)), cadmium red, ultramarine blue, Examples include bitumen, chromium oxide green, cobalt green, amber, titanium black, and synthetic iron black.
Examples of the dye include azo dyes and plant extracts.
The content ratio of the component (E) may be appropriately adjusted according to the application and film thickness, but in the case of the ink composition, it is preferably 5 to 200 parts by weight with respect to 100 parts by weight of the curable components. 10 to 100 parts by weight is more preferable.

2-5. Component (F) The composition of the present invention may contain an organic solvent or water as the component (F) for the purpose of reducing the viscosity.
Specific examples of the organic solvent include, for example, 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; acetone alcohols such as diacetone 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; ether compounds such as dibutyl ether; and N-methyl Examples include pyrrolidone and the like.
Among these, an alkylene glycol monoether compound and a low molecular weight alcohol compound are preferable.

The component (A), which is an essential component of the composition of the present invention, dissolves water to some extent when the proportion of hydroxyl groups in one molecule is large. For this reason, water can be mix | blended with the composition of this invention as (F) component.
Water has a very high viscosity dilution efficiency and is safe. For this reason, it can be set as a solvent-free, low-viscosity, low-odor, quick-hardening composition by using water.

  Although the preferable content rate of (F) component changes with uses of the composition of this invention, it is preferable that it is 0-1,000 weight part with respect to 100 weight part of total amounts of a sclerosing | hardenable component, 0 More preferably, it is -500 weight part, and it is further more preferable that it is 0-300 weight part.

2-6. Component (G) The composition of the present invention may contain colloidal inorganic fine particles as the component (G). Examples of inorganic fine particles include metal oxides such as silica, alumina, titania, zinc oxide, tin oxide and indium oxide, metals such as gold, silver, platinum and palladium, metal chalcogenide compounds such as zinc sulfide and zinc selenide. It is done.
Of these, colorless metal oxides are preferred for applications where scratch resistance and colorless transparency are required, such as hard coats. Specifically, silica, titania, zinc oxide, tin oxide, and indium oxide are preferred. Particularly preferred is silica. At this time, an average particle diameter is a particle diameter calculated | required from the specific surface area measurement by BET method, It is preferable that it is 1-200 nm, More preferably, it is 5-150 nm, More preferably, it is 10-100 nm.

As the component (G), there are colloidal inorganic fine particles (hereinafter referred to as “component (G-1)”) having radical polymerizable unsaturated groups or photoreactive groups bonded to the surface, radical polymerizable unsaturated groups or light. And colloidal inorganic fine particles having no reactive group (hereinafter referred to as “component (G-2)”).
As the component (G), the component (G-1) is preferably used when importance is attached to the scratch resistance, and when the curling suppression when coating on a thin substrate such as a film is important ( It is preferable to use the component G-2).
Specific examples of the component (G-1) include a reaction product of (meth) acryloyloxypropyltrimethoxysilane and colloidal silica.

When the component (G-1) is blended, the content ratio of the component (G-1) is preferably 0 to 60 parts by weight, and 0 to 30 parts by weight with respect to 100 parts by weight of the curable component. Is more preferable. On the other hand, when the component (G-2) is blended, the blending amount of the component (G-2) is preferably 0 to 100 parts by weight with respect to 100 parts by weight of the curable component, and 0 to 50 parts by weight. More preferably.
The component (G-1) is included in the curable component, and the component (G-2) is not included in the curable component.

2-7. (H) Component In the composition of the present invention, a polymer may be blended as the (H) component. When a polymer is blended as the component (H), curling when the substrate thickness is thin can be improved, and adhesion to plastics and metals can be improved.
Suitable polymers include (meth) acrylic polymers, and suitable constituent monomers include methyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylic acid, glycidyl (meth) acrylate, N- ( 2- (meth) acryloxyethyl) tetrahydrophthalimide and the like. In the case of a polymer copolymerized with (meth) acrylic acid, glycidyl (meth) acrylate may be added to introduce a (meth) acryloyl group into the polymer chain.
In addition to (meth) acrylic polymers, various polymers such as polyester, polyurethane, polycarbonate, polyvinyl pyrrolidone, polyvinyl acetate, vinyl pyrrolidone and vinyl acetate copolymer, polyvinyl alcohol, cellulose alkylate, diallyl phthalate resin are blended. can do.

As the component (H), a polymer having a radical polymerizable unsaturated group or photoreactive group bonded thereto (hereinafter referred to as “(H-1) component”) and a radical polymerizable unsaturated group or photoreactive group are included. Polymer [hereinafter referred to as “component (H-2)”].
As the component (H), when the composition of the present invention is used as a hard coat, the component (H-1) is preferable.

When the component (H-1) is blended, the content ratio of the component (H-1) is preferably 0 to 60 parts by weight, and 0 to 30 parts by weight with respect to 100 parts by weight of the curable component. Is more preferable. 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, and 0 to 25 parts by weight with respect to 100 parts by weight of the curable component. More preferably.
The component (H-1) is included in the curable component, and the component (H-2) is not included in the curable component.

2-8. (I) Component In the composition of this invention, you may mix | blend a reactive surfactant as (I) component. When a reactive surfactant is added as the component (I), durability can be imparted to the antifogging property of the cured film.
As reactive surfactants, reactive surfactants having propenyl groups (I-1) (hereinafter referred to as “component (I-1)”), reactive surfactants having (meth) allyl groups (I- 2) [hereinafter referred to as “component (I-2)”] and the like.

  Specific examples of the component (I-1) include the following compounds.

However, in the formula (33), R ²¹ , R ²² , R ²³ , A ¹ , a, and X ¹ are as shown below.
· R ^21: having 6 to 30 carbon atoms, an alkyl group, an alkenyl group, an alkylaryl group and aralkyl aryl group · R ^22: a hydrogen atom, having 6 to 30 carbon atoms, an alkyl group, an alkenyl group, an alkylaryl group and aralkyl aryl group · R ^23: a hydrogen atom or a propenyl group · a: 0 to 100 integer · a ^1: alkylene group · X ¹ C2-4: hydrogen atoms or sulfate [-SO ₃ L, as the L , Alkali metal, NH4 and alkanolamine residues, etc.)

In R ²¹ , examples of the alkyl group include hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, Nonadecyl group, eicosyl group, etc. are mentioned.
Examples of the alkenyl group include a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, an undecenyl group, a dodecenyl group, a tridecenyl group, a tetradecenyl group, a pentadecenyl group, a hexadecenyl group, a heptadecenyl group, and an octadecenyl group.
As the alkylaryl group, monobutylphenyl group, dibutylphenyl group, sec-butylphenyl group, disec-butylphenyl group, tert-butylphenyl group, octylphenyl group, nonylphenyl group, dinonylphenyl group, dodecylphenyl group And a didecylphenyl group.
Examples of the aralkylaryl group include a styrenated phenyl group, a benzylphenyl group, and a cumylphenyl group, and may be a di- or tri-form of an aralkyl group, and further may be substituted with an alkyl group.

Specific examples of the alkyl group, alkenyl group, and alkylaryl group aralkylaryl group having 6 to 30 carbon atoms in R ²² include the same groups as those described above for R ¹⁴ .

  The preferable range of a is 1-50, More preferably, it is 1-20.

Alkylene group having 2 to 4 carbon atoms of A ¹ is specifically an ethylene group, a propylene group, butylene group and isobutylene group, which alkylene group different in one molecule is bonded in a block form or at random But you can. A ¹ is preferably an ethylene group.

X ¹ is preferably a hydrogen atom because the cured film has excellent anti-fogging durability.

  In the formula (33), the propenyl group includes trans and cis stereoisomers. In the present invention, any of the isomers can be used alone or as a mixture.

  Preferable examples of the compound represented by the formula (33) include a compound represented by the following formula (34).

The compound represented by the formula (34) is a compound in which R ²¹ is a nonylphenyl group, R ²² , R ²³ and X ¹ are hydrogen atoms, and A ¹ is an ethylene group in the formula (33). ) Aqualon RN-20, Aqualon RN-2025, Aqualon RN-30, Aqualon RN-50, Aqualon HS-5, Aqualon HS-10 and the like from Daiichi Kogyo Seiyaku.

  Specific examples of the component (I-2) include the following compounds.

However, in the formula (35), R ²⁴ , R ²⁵ , b, c, A ² , A ³ and X ² are as shown below.
R ²⁴ : alkyl group, alkenyl group, alkylaryl group and aralkylaryl group having 6 to 30 carbon atoms R ²⁵ : hydrogen atom or methyl group b: integer of 0-100 c: integer of 0-100 · a ² represents an alkylene group · a ³ having 2 to 4 carbon atoms: an alkylene group · X ² C2-4: hydrogen atoms or sulfate [-SO ₃ L, as the L, alkali metals, NH4 and alkanolamines Residue etc.)

Specific examples of the alkyl group, alkenyl group, alkylaryl group, and aralkylphenyl group having 6 to 30 carbon atoms in R ²⁴ include the same groups as those described above for R ²¹ in formula (33). .

  The preferable range of b and c is 1-50, respectively, More preferably, it is 1-20.

Specific examples of A ² and A ³ include the same examples as those described for A ¹ in formula (33).
As A ² and A ³ , an ethylene group is preferable.

X ² is preferably a hydrogen atom because the cured film is excellent in anti-fogging durability.

  Preferable examples of the compound represented by the formula (35) include a compound represented by the following formula (36).

The compound represented by the formula (36) is a compound in which R ²⁴ is a nonylphenyl group, R ²⁵ is a hydrogen atom and b is 0 in the formula (35). For example, ADEKA Corp. ADEKA rear soap NE- 5, ADEKA rear soap NE-10, ADEKA rear soap NE-40P, ADEKA rear soap SE-10, etc. are mentioned.

  When the component (I) is blended, the content ratio of the component (I) is preferably 0.1 to 40 parts by weight and more preferably 1 to 30 parts by weight with respect to 100 parts by weight of the curable component. preferable. When the component (I) is less than 0.1 part, the antifogging sustainability of the cured film may be insufficient, and when it is more than 30 parts by weight, the hardness of the cured coating film may be insufficient.

2-9. Various additives In addition to the above-described components, various additives may be added to the composition of the present invention depending on the purpose. Various additives include surface modifiers, antioxidants, ultraviolet absorbers, light stabilizers, silane coupling agents, fine particles, polymerization inhibitors, conductivity imparting agents, pigment dispersants, antifoaming agents, antibacterial agents, Examples include photoacid generators, photobase generators, and thermal radical polymerization initiators. Some of these will be briefly explained below.

2-9-1. Surface modifier A surface modifier may be added to the composition of the present invention for the purpose of increasing the leveling property at the time of coating, the purpose of increasing the slipping property of the cured film and improving the scratch resistance, and the like. .
Examples of the surface modifier include a surface modifier, a surfactant, a leveling agent, an antifoaming agent, a slipperiness imparting agent, and an antifouling imparting agent, and these known surface modifiers can be used. .
Of these, silicone-based surface modifiers and fluorine-based surface modifiers are preferred. Specific examples include silicone polymers and oligomers having a silicone chain and a polyalkylene oxide chain, silicone polymers and oligomers having a silicone chain and a polyester chain, and fluorine polymers having a perfluoroalkyl group and a polyalkylene oxide chain. And a fluorine-based polymer and an oligomer having a perfluoroalkyl ether chain and a polyalkylene oxide chain.
Further, for the purpose of increasing the slidability, a surface modifier having an ethylenically unsaturated group, preferably a (meth) acryloyl group, in the molecule may be used.
It is preferable that the content rate of a surface modifier is 0.01-1.0 weight part with respect to 100 weight part of total amounts of a sclerosing | hardenable component. It is excellent in the surface smoothness of a cured film as it is the said range.

2-9-2. Antioxidant Antioxidant is mix | blended in order to improve durability, such as the heat resistance of a cured film, and a weather resistance.
Examples of the antioxidant include phenol-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants.
Examples of phenolic antioxidants include hindered phenols such as di-t-butylhydroxytoluene. As what is marketed, Ade-20 Co., Ltd. AO-20, AO-30, AO-40, AO-50, AO-60, AO-70, AO-80 etc. are mentioned.
Examples of the phosphorus-based antioxidant include phosphines such as trialkylphosphine and triarylphosphine, and trialkyl phosphites and triaryl phosphites. Examples of commercially available products of these derivatives include Adeka Co., Ltd., ADK STAB PEP-4C, PEP-8, PEP-24G, PEP-36, HP-10, 260, 522A, 329K, 1178, 1500, 135A, 3010. Etc.
Examples of the sulfur-based antioxidant include thioether compounds, and examples of commercially available products include AO-23, AO-412S, and AO-503A manufactured by Adeka Corporation.
These may be used alone or in combination of two or more. Preferred combinations of these antioxidants include the combined use of phenolic antioxidants and phosphorus antioxidants, and the combined use of phenolic antioxidants and sulfurous antioxidants.
What is necessary is just to set suitably as content rate of antioxidant according to the objective, 0.01-5 weight part is preferable with respect to 100 weight part of sclerosing | hardenable component total amount, More preferably, it is 0.1-1 weight part. It is. When the content ratio is 0.1 parts by weight or more, the durability of the composition can be improved. On the other hand, when the content ratio is 5 parts by weight or less, curability and adhesion can be improved.

2-9-3. Ultraviolet absorber An ultraviolet absorber can be mix | blended in order to improve the light resistance of a cured film.
Examples of the UV absorber include triazine UV absorbers such as TINUVIN400, TINUVIN405, TINUVIN460, and TINUVIN479 manufactured by BASF, and benzotriazole UV absorbers such as TINUVIN900, TINUVIN928, and TINUVIN1130.
What is necessary is just to set suitably as a content rate of a ultraviolet absorber according to the objective, 0.01-5 weight part is preferable with respect to 100 weight part of sclerosing | hardenable component total amount, More preferably, it is 0.1-1 weight part. It is. When the content ratio is 0.01% by weight or more, the light resistance of the cured film can be improved, and when it is 5% by weight or less, the curability of the composition is excellent. be able to.

2-9-4. Light stabilizer A light stabilizer can be mix | blended in order to improve the light resistance of a cured film.
As the light stabilizer, a hindered amine light stabilizer (so-called HALS) is preferable. Examples of HALS include TINUVIN123, TINUVIN144, TINUVIN111FDL, TINUVIN152, TINUVIN292, and TINUVIN5100 manufactured by BASF.

2-9-5. Silane coupling agent not belonging to component (D-3) The silane coupling agent can be blended for the purpose of improving the interfacial adhesive strength between the cured film and the substrate. The silane coupling agent is not particularly limited as long as it can contribute to improvement in adhesion to the substrate.
The silane coupling agent mentioned here is a compound having no radically polymerizable unsaturated group, and is a compound different from the component (D-3). Adhesion may be improved without having a radically polymerizable unsaturated group.
Specific examples of the silane coupling agent different from the component (D-3) include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidide. Xylpropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene ) Propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercapto Examples include propylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane.
The blending ratio of the silane coupling agent may be appropriately set according to the purpose, and is preferably 0.1 to 10 parts by weight, more preferably 1 to 5 parts by weight with respect to 100 parts by weight of the total amount of the curable component. . When the blending ratio is 0.1 parts by weight or more, the adhesive strength of the composition can be improved. On the other hand, when the blending ratio is 10 parts by weight or less, it is possible to prevent the adhesive force from changing over time.

2-9-6. Fine particles not belonging to component (G) For the purpose of imparting anti-glare properties to the cured film or providing slip properties when the substrates with the cured film are superimposed on the composition of the present invention. Fine particles other than the component (G) may be blended. The particle diameter of the fine particles varies depending on the application, but generally 0.2 to 100 μm can be preferably used.
The fine particles may be inorganic or organic. Examples of the inorganic fine particles include metal oxides such as silica, alumina, and titania that are not colloidal. Examples of the organic substance include fine particles obtained by crosslinking a polymer of a monomer such as alkyl (meth) acrylate or styrene.

2-9-7. Polymerization inhibitor In addition to the polymerization inhibitor contained in the component (A), a polymerization inhibitor can be further added to the composition of the present invention. As the polymerization inhibitor, the same compounds as those added in the synthesis of the component (A) are suitable.

2-9-8. Conductivity-imparting agent A conductivity-imparting agent such as an antistatic agent can be added to the composition of the present invention.
Examples of the antistatic agent include nonionic surfactants such as glycerin fatty acid ester, polyoxyalkylene alkyl ether, and alkyldiethanolamine;
Anionic surfactants such as alkyl sulfonates, alkyl benzene sulfonates, and alkyl phosphates;
Cationic surfactants such as tetraalkylammonium salts and trialkylbenzylammonium salts;
Amphoteric surfactants such as alkylbetaines and alkylimidazolium betaines;
Polymer type antistatic agents such as polyether esters, polyether ester amides, polystyrene sulfonates, (meth) acrylate polymers containing four-ball ammonium salts, polyether polyethers;
Monomers having acidic groups such as phosphoric acid (meth) acrylate;
Metal salts of bis (fluoroalkylsulfonyl) imide such as bis (trifluoromethanesulfonyl) imide lithium;
Alkali metal salts of tris (fluoroalkylsulfonyl) methides such as tris (trifluoromethanesulfonyl) methide lithium;
An alkali metal salt of a trifluoromethanesulfonate ion such as lithium trifluoromethanesulfonate; and
Examples thereof include ionic liquids such as imidazolium ionic liquid and pyridinium ionic liquid.
Imidolithium salts and ionic liquids have the effect of reducing volume resistivity as well as surface resistance.

2-10. Urethane (meth) acrylate The present invention relates to a curable composition containing the component (A). After the component (A) is reacted with an organic polyvalent isocyanate to form a urethane (meth) acrylate, The effect of this invention can also be expressed as a curable composition by mix | blending with B)-(I) component and the above-mentioned various additives. In particular, a cured product having excellent bending resistance can be obtained.

2-10-1. The organic polyvalent isocyanate compound to be reacted with the organic polyvalent isocyanate (A) component is preferably a divalent isocyanate compound, and is preferably an aliphatic polyvalent isocyanate compound.
Specific examples of preferable organic polyvalent isocyanate compounds include aliphatic divalent isocyanates such as isophorone diisocyanate, hexamethylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate and norbornane diisocyanate, and 2,4-tolylene diisocyanate and naphthalene. Examples thereof include aromatic divalent isocyanates such as diisocyanate, xylene diisocyanate and diphenylmethane diisocyanate, and nurate type trimers of these compounds. These may be used individually by 1 type, or may use 2 or more types together, but it is preferable to use individually by 1 type.

2-10-2. Production Method of Urethane (Meth) acrylate Urethane (meth) acrylate is produced by reacting the hydroxyl group in component (A) with the isocyanate group in the organic polyvalent isocyanate compound to form a urethane bond.
There is no restriction | limiting in particular as a manufacturing method of urethane (meth) acrylate, A well-known method can be used.
For example, the component (A) and the organic polyvalent isocyanate compound may be heated and stirred.

  The reaction ratio (molar ratio) between the hydroxyl group in component (A) and the isocyanate group of the organic polyvalent isocyanate compound is preferably hydroxyl group: isocyanate group = 1: 0.6 to 1: 1.3. : Isocyanate group = 1: 0.8-1: 1.2 is more preferable, and hydroxyl group: isocyanate group = 1: 0.9-1: 1 is more preferable. The hardness of the obtained cured film is more excellent as it is the said aspect.

The reaction between the hydroxyl group and the isocyanate group in the production of urethane (meth) acrylate can be performed without a catalyst, but a catalyst may be added in order to advance the reaction efficiently.
Examples of catalysts include organotin compounds such as dibutyltin dilaurate; acetylacetonate metal complexes such as iron acetylacetonate, zinc acetylacetonate and ruthenium acetylacetonate; weak metal organic acid salts such as lead naphthenate and potassium acetate; and , Triethylamine, triethanolamine, dimethylbenzylamine, trioctylamine, 1,4-diazabicyclo [2.2.2] octane, 1,8-diazabicyclo [5.4.0] undecene-7, 1,5-diazabicyclo [4.3.0] tertiary amine compounds such as nonene-5; and trialkylphosphine compounds such as triethylphosphine.
The ratio of the catalyst may be appropriately set according to the organic polyvalent isocyanate compound and the catalyst to be used, but is preferably 0.01 to 1,000 wtppm, more preferably 0.1 to 1 with respect to the reaction solution. , 000 wtppm.

  What is necessary is just to set suitably as reaction temperature according to the kind and ratio, etc. of the organic polyvalent isocyanate compound and catalyst to be used, and 60-130 degreeC is preferable, More preferably, it is 70-90 degreeC.

Moreover, a chain extender can also be mix | blended a small quantity for the purpose of adjusting the molecular weight of the urethane (meth) acrylate obtained by reaction of (A) component and an organic polyvalent isocyanate compound.
As the chain extender, those usually used in a urethanization reaction can be used.
Specific examples of the chain extender include low molecular weight polyols, polyether polyols, polycarbonate polyols and polyester polyols.
Examples of the low molecular weight polyol include ethylene glycol, polyethylene glycol, cyclohexanedimethanol, 3-methyl-1,5-pentanediol, propylene glycol, polypropylene glycol, 1,6-hexanediol, trimethylolpropane glycerin, and diglycerin. And polyols such as these alkylene oxide adducts.
Examples of the polyether polyol include polyalkylene glycol having 3 or more oxyalkylene units, and specific examples thereof include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.
Examples of the polycarbonate polyol include a reaction product of carbonate and diol. Specific examples of the carbonate include diaryl carbonates such as diphenyl carbonate, and dialkyl carbonates such as dimethyl carbonate and diethyl carbonate. Examples of the diol include the low molecular weight polyol described above.
Examples of the polyester polyol include a reaction product of an acid component with at least one selected from the group consisting of the low molecular weight polyol, the polyether polyol, and the polycarbonate polyol. Examples of the acid component include dibasic acids such as adipic acid, sebacic acid, succinic acid, maleic acid, phthalic acid, hexahydrophthalic acid and terephthalic acid, or anhydrides thereof. Moreover, the ring-opening reaction product of polycarbonate diol and caprolactone is also mentioned.
The proportion of the chain extender used is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, with respect to 100 parts by weight of the urethane (meth) acrylate finally obtained.

  Further, when the isocyanate group remains, the component (A) does not have an isocyanate group or a small amount of the isocyanate group is preferable from the viewpoint of hardness and stability. A compound having two or more (meth) acryloyl groups (hereinafter also referred to as “hydroxyl group-containing polyfunctional (meth) acrylate”) may be added.

As the hydroxyl group-containing polyfunctional (meth) acrylate, various compounds can be used, which are (meth) acrylates derived from a trihydric or higher polyhydric alcohol, having two or more (meth) acryloyl groups, It is preferable that it is (meth) acrylate which has 1 or more.
Specific examples of the hydroxyl group-containing polyfunctional (meth) acrylate include trimethylolpropane di (meth) acrylate, di (meth) acrylate of trimethylolpropane alkylene oxide adduct, and di (meth) acrylate of alkylene oxide adduct of glycerin. , Di- or tri (meth) acrylate of pentaerythritol, di- or tri (meth) acrylate of alkylene oxide adduct of pentaerythritol, di- or tri (meth) acrylate of ditrimethylolpropane, diene of alkylene oxide adduct of ditrimethylolpropane Or tri (meth) acrylate, diglycerin alkylene oxide adduct di (meth) acrylate, dipentaerythritol di, tri, tetra or penta (meth) acrylate, dipenta Di, tri, tetra or penta (meth) acrylates of alkylene oxide adducts of lithitol and di (meth) acrylates of alkylene oxide adducts of isocyanurates, di, tri, tetra, penta, hexa or hepta (tripentaerythritol) Examples thereof include di (meth) acrylate, dipentaerythritol alkylene oxide adduct di, tri, tetra, penta, hexa or hepta (meth) acrylate, and isocyanurate alkylene oxide adduct di (meth) acrylate.
In this case, examples of the alkylene oxide include ethylene oxide and propylene oxide.
Among them, trimethylolpropane di (meth) acrylate, di or tri (meth) acrylate of pentaerythritol, di or tri (meth) acrylate of ditrimethylolpropane and di, tri, tetra or penta (meth) acrylate of dipentaerythritol Preferably mentioned.

3. Method of Use As a method of using the composition of the present invention, a conventional method may be followed.
For example, after apply | coating a composition to a base material, the method of making it harden | cure by irradiating an active energy ray or heating, etc. are mentioned.
Specifically, after applying or printing the composition on the substrate to be applied by a usual coating method, in the case of an active energy ray-curable composition, the active energy ray is irradiated and cured, or In the case of a thermosetting composition, a method of heating and curing can be used. In the case of applications such as molding materials, the composition is injected into a predetermined mold and then cured in the case of an active energy ray curable composition by irradiation with active energy rays, or a thermosetting composition. In the case of a thing, the method of heating and hardening etc. is mentioned.
A general method known as a conventional curing method may be adopted as the active energy ray irradiation method and heating method.
In addition, the component (B) (photopolymerization initiator) and the component (C) (thermal polymerization initiator) are used in combination with the composition, irradiated with active energy rays, and then heat-cured, thereby adhering to the substrate. A method for improving the property can also be adopted.

Examples of the substrate include paper, plastic film, plastic plate, wood, metal, inorganic materials other than metal, nails, bones, leather, and the like.
In particular, since the composition of the present invention is excellent in the bending resistance of the cured product, it can be preferably applied to a thin substrate such as paper or plastic film.

Specific examples of plastics include cellulose acetate resins such as triacetyl cellulose and diacetyl cellulose, cyclic polyolefin resins having cyclic olefins such as polyvinyl alcohol, acrylic resins, polyethylene terephthalate, polycarbonate, polyarylate, polyethersulfone, norbornene as monomers. , Polyvinyl chloride, epoxy resin, polyurethane resin and the like.
Examples of the wood include natural wood and synthetic wood.
Examples of the inorganic material include metals such as steel plates, 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). It is done.
Examples of other inorganic materials include glass, mortar, concrete and stone.
As a nail | claw, a bone | frame, and leather, the thing of the animal used for an ornament etc., and the coating agent to a human nail | claw may be sufficient.

What is necessary is just to set suitably the film thickness of the cured film of the composition with respect to a base material according to the objectives, such as a use of the base material to be used or the manufactured cured film.
As a film thickness of the cured film of a composition, 0.5-100 micrometers is preferable and 1-20 micrometers is more preferable.

  As a method for coating the substrate of the composition of the present invention, it may be appropriately set according to the purpose, and brush, brush, bar coater, applicator, doctor blade, dip coater, roll coater, spin coater, flow coater, Examples of the method include coating or printing using a knife coater, comma coater, reverse roll coater, die coater, lip coater, gravure coater, micro gravure coater, and inkjet.

When the composition of the present invention contains an organic solvent or water as the component (F), it is preferably dried after coating. In the case of a production line, it is preferable to provide a hot air dryer. It is preferable to install a local exhaust device in the hot air dryer.
However, when only water is included as the component (F), the drying step is not necessarily required. When the water content is small, a cured film that is transparent and has no problem in performance may be formed even if it is cured while containing water. In addition, even when the water content is high (for example, when it contains 50% or more of the whole), when the film thickness is as thin as about 2 μm, most of the water volatilizes even at room temperature, and a cured film that is transparent and has no performance problems can be formed. There is a case.

Examples of the active energy ray for curing the composition of the present invention include ultraviolet rays, visible rays, and electron beams, and ultraviolet rays are preferred.
Examples of the light source in the ultraviolet irradiation 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 amount of irradiation energy may be set as appropriate depending on the light source, application, and type and amount of component (B). As an example, when using a high-pressure mercury lamp, the irradiation energy in the UV-A region is 100 to 5, preferably ^{000mJ / cm 2, 200~1,000mJ / cm} 2 is more preferable.

4). Use The curable composition of the present invention is preferably used as an active energy ray-curable composition, and exhibits the effects of the above-mentioned fast curability and the hardness of the cured product. Can be used.
Examples of preferred applications include coating agents such as clear coating agents and paints, inks such as offset inks and inkjet inks, adhesives, shaping resins, resin films, resists, pattern forming compositions, and molding materials. .

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
In the following, “parts” means parts by weight.

1. Production example
1-1) Production Example 1 [Production of component (A), dipentaerythritol acrylate]
In a liter flask equipped with a stirrer, a thermometer, a gas introduction tube, a rectifying column and a cooling tube, 353.93 parts (1.39 mol) of dipentaerythritol, 2-methoxyethyl acrylate (hereinafter referred to as “MEAc”) 195.6.30 parts (15.03 moles), 8.264 parts (0.074 moles) of DABCO as catalyst X, 27.038 parts (0.147 moles) of zinc acetate as catalyst Y, hydroquinone monomethyl ether (Hereinafter referred to as “MEHQ”) 1.603 parts (0.013 mol), 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (hereinafter referred to as “TEMPOL”) 015 parts (0.0001 mol) was charged, and oxygen-containing gas (5% by volume of oxygen and 95% by volume of nitrogen) was bubbled into the liquid.
While heating and stirring the reaction solution at a temperature of 110 to 145 ° C., the pressure in the reaction system is adjusted within the range of 130 to 760 mmHg, and a mixed solution of 2-methoxyethanol and MEAc by-produced as the transesterification proceeds. It extracted from the reaction system through the rectification column and the cooling pipe. In addition, MEAc of the same weight part as the extracted liquid was added to the reaction system as needed. 20 hours after the start of heating and stirring, the pressure in the reaction system was returned to normal pressure, and the extraction was completed.
As a result of obtaining the acrylated rate of the hydroxyl group of dipentaerythritol from the amount of 2-methoxyethanol produced, it was 81 mol%.
After cooling the reaction solution to room temperature and separating the precipitate by filtration, 20.2 parts of aluminum silicate [KYOWARD 700 (trade name) manufactured by Kyowa Chemical Industry Co., Ltd.] was added to the filtrate and stirred. The mixture was heated and stirred in the range of -100 ° C for 1 hour. Thereafter, the reaction solution was cooled to 40 ° C. or lower, 12.9 parts of calcium hydroxide was added and stirred, and further stirred in the range of 20 to 40 ° C. for 1 hour.
Thereafter, the insoluble matter in the reaction solution was separated by filtration, and the filtrate was put into a flask connected with a stirrer, a thermometer, a gas introduction tube, a distillation cooling tube, and a decompression tube, and the temperature was 70 to 100 ° C. Under a pressure of 0.001 to 100 mmHg, vacuum distillation was performed for 15 hours while bubbling dry air, and a distillate containing unreacted MEAc was separated. 5.5 parts of diatomaceous earth [Radiolite (trade name) manufactured by Showa Chemical Industry Co., Ltd.] was added to the kettle and subjected to pressure filtration, and the resulting filtrate was used as component (A). The yield of component (A) was 666 parts.
As a result of composition analysis of component (A) using a high performance liquid chromatograph (hereinafter referred to as “HPLC”) equipped with a UV detector, it contains dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate as main components. (Hereinafter referred to as “EX-DPHA”).
Moreover, when the content rate of the by-product contained in (A) component was calculated | required by GC measurement, the compound shown by said Formula (8) is 0.73 weight%, and the compound shown by said Formula (9) is 0.00. 07% by weight and 0.58% by weight of the compound represented by the formula (12) were contained.
As a result of obtaining the area% of impurities by GPC measurement according to the above definition, it was 12.3 area%.

HPLC and GC were measured under the following conditions.
◆ HPLC measurement conditions and equipment: ACQUITY UPLC manufactured by Waters Co., Ltd.
・ Detector: UV detector ・ Detection wavelength: 210 nm
Column: Waters Co., Ltd. ACQUITY UPLC BEH C18 (Part No. 186002350, column inner diameter 2.1 mm, column length 50 mm)
Column temperature: 40 ° C
-Composition of eluent: 0.03% by weight trifluoroacetic acid aqueous solution and methanol mixed solution-Eluent flow rate: 0.3 mL / min

◆ GC measurement conditions and equipment: GC-17A manufactured by Shimadzu Corporation
・ Detector: FID detector ・ Carrier gas: helium ・ Column: Inert Cap (film thickness 0.5 μm, 0.32 mm ID × 60 m) manufactured by GL Sciences Inc.
・ Injection temperature: 200 ℃
・ FID temperature: 250 ℃
Column temperature: held at 120 ° C. for 5 minutes, then heated to 240 ° C. at a rate of 10 ° C./min and then held for 25 minutes.
-An acetone solution containing 35% by weight of component (A) was prepared, and toluene was added as an internal standard substance, and 0.2 μL was injected.
-The content of by-products was determined in wt% by the internal standard method.

1-2) Production Example 2 [Production of component (A), pentaerythritol acrylate]
In a 1 liter flask equipped with a stirrer, thermometer, gas introduction tube, rectification column and cooling tube, 97.07 parts (0.71 mol) of pentaerythritol and 666.81 parts (5.14 mol) of MEAc ), 1.881 parts (0.017 mol) of DABCO as catalyst X, 6.155 parts (0.034 mol) of zinc acetate as catalyst Y, 0.038 parts (0.0003 mol) of MEHQ, phenothiazine ( Hereinafter, 0.006 part (0.00003 mol) of “PZ” was charged, and oxygen-containing gas (5% by volume of oxygen and 95% by volume of nitrogen) was bubbled into the liquid.
While stirring and heating in the reaction liquid temperature range of 105 to 120 ° C., the pressure in the reaction system is adjusted in the range of 130 to 760 mmHg, and a mixed liquid of 2-methoxyethanol and MEAc by-produced as the transesterification proceeds. It extracted from the reaction system through the rectification column and the cooling pipe. In addition, MEAc of the same weight part as the extracted liquid was added to the reaction system as needed. After 21 hours from the start of heating and stirring, the pressure in the reaction system was returned to normal pressure, and the extraction was completed.
It was 85 mol% as a result of calculating | requiring the acrylate-ized rate of the hydroxyl group of pentaerythritol from the production amount of 2-methoxyethanol.
After cooling the reaction solution to room temperature and separating the precipitate by filtration, 3.0 parts of aluminum silicate [KYOWARD 700 (trade name) manufactured by Kyowa Chemical Industry Co., Ltd.] was added to the filtrate and stirred. The mixture was heated and stirred in the range of -100 ° C for 1 hour. Thereafter, the reaction solution was cooled to room temperature and filtered to separate insoluble matters, and then the filtrate was placed in a flask connected with a stirrer, thermometer, gas introduction tube, distillation cooling tube, and decompression tube, and the temperature was 70. Distilled liquid containing unreacted MEAc was separated by performing vacuum distillation for 10 hours while bubbling dry air in a range of ˜100 ° C. and pressure of 0.001 to 100 mmHg. 2.0 parts of diatomaceous earth [Radiolite (trade name) manufactured by Showa Chemical Industry Co., Ltd.] was added to the kettle and subjected to pressure filtration, and the obtained filtrate was used as component (A). The yield of component (A) was 239 parts.
As a result of analyzing the composition of the component (A) using HPLC, it was confirmed that pentaerythritol triacrylate and pentaerythritol tetraacrylate were contained as main components (hereinafter referred to as “EX-PETTA”).
Moreover, when the content rate of the by-product contained in (A) component was calculated | required by GC measurement, the compound shown by said Formula (8) is 0.84 weight%, and the compound shown by said Formula (9) is 0.8. It contained 03% by weight and 0.15% by weight of the compound represented by the formula (12).
Table 1 shows the area percentage of impurities measured according to the same method as in Production Example 1.

1-3) Production Example 3 [Production of Component (A), Glycerol Acrylate]
302.71 parts (3.29 mol) of glycerin and 2312.76 parts (17.77 mol) of MEAc in a 3 liter flask equipped with a stirrer, thermometer, gas introduction tube, rectification column and cooling tube , 9.758 parts (0.087 mol) of DABCO as catalyst X, 36.103 parts (0.174 mol) of zinc acrylate as catalyst Y, 1.587 parts (0.013 mol) of MEHQ, and PZ 0.294 parts (0.003 mol) and 5.0 parts of pure water were charged, and oxygen-containing gas (5% by volume of oxygen and 95% by volume of nitrogen) was bubbled into the liquid.
While stirring the reaction liquid at a temperature of 110 to 130 ° C., the pressure in the reaction system is adjusted within the range of 130 to 760 mmHg, and a mixed liquid of 2-methoxyethanol and MEAc by-produced as the transesterification proceeds. It extracted from the reaction system through the rectification column and the cooling pipe. In addition, MEAc of the same weight part as the extracted liquid was added to the reaction system as needed. After 33 hours from the start of heating and stirring, the pressure in the reaction system was returned to normal pressure, and the extraction was completed.
It was 89 mol% as a result of calculating | requiring the acrylate-ized rate of the hydroxyl group of glycerol from the production amount of 2-methoxyethanol.
After cooling the reaction solution to room temperature and separating the precipitate by filtration, 15.0 parts of aluminum silicate [KYOWARD 700 (trade name) manufactured by Kyowa Chemical Industry Co., Ltd.] was added to the filtrate and stirred. The mixture was heated and stirred in the range of -100 ° C for 1 hour. Thereafter, the reaction solution was cooled to room temperature and filtered to separate insoluble matters, and then the filtrate was placed in a flask connected with a stirrer, thermometer, gas introduction tube, distillation cooling tube, and decompression tube, and the temperature was 70. Distilled liquid containing unreacted MEAc was separated by performing vacuum distillation for 15 hours while bubbling dry air in a range of ˜100 ° C. and pressure of 0.001 to 100 mmHg. 5.5 parts of diatomaceous earth [Radiolite (trade name) manufactured by Showa Chemical Industry Co., Ltd.] was added to the kettle and subjected to pressure filtration, and the resulting filtrate was used as component (A). The yield of component (A) was 819 parts.
As a result of composition analysis of the component (A) using HPLC, it was confirmed that glycerin diacrylate and glycerin triacrylate were included as main components (hereinafter referred to as “EX-GLYA”).
Moreover, when the content rate of the by-product contained in (A) component was calculated | required by GC measurement, the compound shown by said Formula (8) is 0.63 weight%, and the compound shown by said Formula (9) is 0.00. 20% by weight and 0.11% by weight of the compound represented by the formula (12) were contained.
Table 1 shows the area percentage of impurities measured according to the same method as in Production Example 1.

1-4) Comparative Production Example 1 (Production of DPHA by dehydrated ester method)
In a flask equipped with a stirrer, thermometer, gas introduction tube, rectifying column, cooling tube and water separator, 3,811 parts (15 moles) of dipentaerythritol and 8,425 parts (117 moles) of acrylic acid 11,111 parts of toluene, 500 parts of para-toluenesulfonic acid, 18.5 parts of cupric chloride (775 wtppm with respect to the total weight of the charged raw materials), oxygen-containing gas (oxygen 5% by volume, nitrogen Was volatilized into the liquid.
Stirring while heating and refluxing at a pressure of 600 mmHg in the reaction system, 1,506 parts (84 moles) of water produced as a by-product with the progress of the dehydration esterification reaction was withdrawn from the reaction system via a rectification column and a cooling tube. . After 7 hours from the start of heating and stirring, the heating of the reaction solution was completed, and the pressure in the reaction system was returned to normal pressure to complete the extraction.
After cooling the reaction solution to room temperature, 2,950 parts of water was added and stirred, and then allowed to stand to separate the lower layer (aqueous layer). Thereafter, 2,756 parts of a 20% aqueous sodium hydroxide solution was added to the upper layer (organic layer), stirred, and allowed to stand to separate the lower layer (aqueous layer). Thereafter, 2,950 parts of water was added to the upper layer (organic layer), stirred and allowed to stand, and the lower layer (aqueous layer) was separated. 3.6 parts of hydroquinone monomethyl ether is added to the upper layer (organic layer), and vacuum distillation is performed for 8 hours at a temperature of 60 to 90 ° C. and a pressure of 0.001 to 100 mmHg while bubbling dry air, and contains toluene. The distillate was separated.
As a result of analyzing the composition of the pot liquid after vacuum distillation using a high performance liquid chromatograph equipped with a UV detector, it was confirmed that dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate were included as main components (hereinafter, "DH-DPHA"). The purification yield calculated by regarding the kettle liquor as a purified product was 80%. As a result of measuring the hydroxyl value of the purified product obtained in the same manner as described above, it was 18 mgKOH / g.
Table 1 shows the area percentage of impurities measured according to the same method as in Production Example 1.

1-5) Comparative Production Example 2 (Production of polyfunctional acrylate by dehydration ester method)
A polyfunctional acrylate was produced in the same manner as in Comparative Production Example 1 except that pentaerythritol was used as the polyhydric alcohol.
As a result of analyzing the composition of the pot liquid after distillation under reduced pressure using a high performance liquid chromatograph equipped with a UV detector, it was confirmed that pentaerythritol triacrylate was contained as a main component (hereinafter referred to as “DH-PETA”). . The purification yield calculated by regarding the kettle liquor as a purified product was 72%. As a result of measuring the hydroxyl value of the purified product obtained in the same manner as described above, it was 18 mgKOH / g.
Table 1 shows the area percentage of impurities measured according to the same method as in Production Example 1.

1-6) Comparative Production Example 3 ( Production of GLY-TA by dehydrated ester method)
In a flask equipped with a stirrer, a thermometer, a gas introduction tube, a rectifying column, a cooling tube and a water separator, 55.9 parts (0.46 mol) of glycerin and 157.59 parts of acrylic acid (2.19) Mol), 118.30 parts of toluene, 5.85 parts of sulfuric acid, 0.34 parts of copper sulfate (1000 wtppm with respect to the total weight of the charged raw materials), oxygen-containing gas (oxygen 5% by volume, nitrogen 95% by volume) was bubbled into the liquid. The reaction system was stirred while being heated to reflux at a pressure of 370 mmHg, and water produced as a by-product with the progress of the dehydration esterification reaction was withdrawn from the reaction system via a rectification column and a cooling tube. During this time, the temperature of the reaction solution changed in the range of 80 to 90 ° C. After 5 hours from the start of heating and stirring, the heating of the reaction solution was completed, and the pressure in the reaction system was returned to normal pressure to complete the extraction.
After cooling the reaction solution to room temperature, 137 parts of toluene and 56 parts of water were added and stirred, and then allowed to stand to separate the lower layer (aqueous layer). Thereafter, 29 parts of 20% aqueous sodium hydroxide solution was added to the upper layer (organic layer), stirred and allowed to stand, and the lower layer (aqueous layer) was separated. Thereafter, 39 parts of water was added to the upper layer (organic layer), stirred, and allowed to stand to separate the lower layer (aqueous layer). 0.018 parts of hydroquinone monomethyl ether is added to the upper layer (organic layer), and vacuum distillation is performed for 8 hours at a temperature of 60 to 90 ° C. and a pressure of 0.001 to 100 mmHg while bubbling dry air and contains toluene. The distillate was separated. 2.0 parts of diatomaceous earth [Radiolite (trade name) manufactured by Showa Chemical Industry Co., Ltd.] was added to the kettle and subjected to pressure filtration, and the obtained filtrate was used as a purified product.
As a result of analyzing the composition of the purified product using a high performance liquid chromatograph equipped with a UV detector, it was confirmed that glycerin triacrylate was contained (hereinafter referred to as “DH-GLYA”). The yield of the purified product was 8%. As a result of measuring the hydroxyl value of the purified product obtained in the same manner as described above, it was 52 mgKOH / g.
The ratio of impurities was measured according to the same method as in Production Example 1. The results are shown in Table 1.
2) Production of active energy ray-curable composition The compounds shown in Table 2 below were stirred and mixed in the proportions shown in Table 2 to produce an active energy ray-curable composition.
The obtained composition was used and evaluated as described later. The results are shown in Table 2.

The numbers in Table 2 mean the number of copies.
Moreover, the symbol in Table 2 means the following.
IRG907: 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, IRGACURE907 manufactured by BASF

3) Evaluation method
(1) Curability The obtained composition was applied to a polyethylene terephthalate film [manufactured by Toyobo Co., Ltd., Cosmo Shine A4300 (thickness: 100 μm)] with a bar coater so as to have a film thickness of 5 μm.
The obtained test specimen was irradiated with an irradiation energy of 100 mJ / cm ² per pass at a UV region (UV-A) intensity of 800 mW / cm ² centered at 365 nm using a metal halide lamp manufactured by Eye Graphics Co., Ltd. The conveyor was adjusted so that it was conveyed in an air atmosphere and irradiated with ultraviolet rays.
In Examples 7 and 8 and Comparative Examples 7 and 8, the coating film was dried on a hot plate at 100 ° C. for 3 minutes to form a coating film having a dry film thickness of 5 μm.
As a method for evaluating curability, the number of passes until the surface tack was eliminated was determined.

(2) Universal hardness of cured film (evaluation as an active energy ray curable composition for coating agent)
The composition described in Table 5 below was applied to a 10 cm glass substrate with a bar coater so as to have a film thickness of 20 μm, and an ultraviolet region centered at 365 nm using a high-pressure mercury lamp manufactured by Eye Graphics Co., Ltd. (UV-A) The conveyor was adjusted to an irradiation energy of 800 mJ / cm ² per pass at an intensity of 500 mW / cm ² , and was conveyed in an air atmosphere and irradiated with ultraviolet rays.
When the hardness of the obtained cured film was measured using a micro hardness tester (manufactured by Fisher Instruments Co., Ltd., H-100C), the surface hardness was measured at room temperature under the condition that the maximum load of the Vickers indenter was 20 mN. The universal hardness was evaluated.

As is clear from the results of Examples 1 to 3, the composition of the present invention exhibits the same curability as the compositions of Comparative Examples 1 to 3 containing a polyfunctional acrylate produced by a conventional dehydrating ester method. Since the area% of the impurity of the component (A) is 30% or less, the cured film was excellent in hardness.
On the other hand, since the compositions of Comparative Examples 1 to 3 containing components produced by the conventional dehydrated ester method are compositions containing more than 30 area% of impurities, examples containing the corresponding compounds The hardness of the cured film was inferior to that of the composition.

  The curable composition of the present invention can be used for various applications such as a coating agent, an ink, an adhesive, a shaping resin, a resin film, and a pattern forming composition, preferably as an active energy ray hardening composition. Since it is fast-curing and the resulting cured film is excellent in hardness, it can be preferably used as a coating agent composition.

Claims (13)

A mixture of compounds having two or more (meth) acryloyl groups obtained by transesterification of a polyhydric alcohol and a compound having one (meth) acryloyl group in the presence of the following catalysts X and Y A curable composition comprising a mixture (A) in which impurities by gel permeation chromatography are 30 area% or less in the mixture.
Catalyst X: a kind selected from the group consisting of a cyclic tertiary amine having an azabicyclo structure or a salt or complex thereof, an amidine or a salt or complex thereof, a compound having a pyridine ring or a salt or complex thereof, and phosphine or a salt or complex thereof The above compound.
Catalyst Y: Compound containing zinc. The curable composition according to claim 1, wherein the polyhydric alcohol is a polyhydric alcohol having 3 or more alcoholic hydroxyl groups. The curable composition according to claim 2, wherein the compound having one (meth) acryloyl group is an alkoxyalkyl (meth) acrylate. The catalyst X is one or more compounds selected from the group consisting of a cyclic tertiary amine having an azabicyclo structure or a salt or complex thereof, an amidine or a salt or complex thereof, and a compound having a pyridine ring or a salt or complex thereof. The curable composition according to any one of claims 1 to 3. The curable composition according to any one of claims 1 to 4, wherein the catalyst Y is an organic acid zinc or / and a zinc diketone enolate. The active energy ray hardening-type composition containing the composition of any one of Claims 1-5. Furthermore, the active energy ray hardening-type composition of Claim 6 containing a photoinitiator (B). The active energy ray hardening-type composition for coating containing the composition of Claim 6 or Claim 7. A mixture of compounds having two or more (meth) acryloyl groups obtained by transesterification of a polyhydric alcohol and a compound having one (meth) acryloyl group in the presence of the following catalysts X and Y And the manufacturing method of the curable composition including the process of manufacturing the (A) whose impurity by a gel permeation chromatography measurement is 30 area% or less in a mixture.
Catalyst X: a kind selected from the group consisting of a cyclic tertiary amine having an azabicyclo structure or a salt or complex thereof, an amidine or a salt or complex thereof, a compound having a pyridine ring or a salt or complex thereof, and phosphine or a salt or complex thereof The above compound.
Catalyst Y: Compound containing zinc. The method for producing a curable composition according to claim 9, wherein the compound having one (meth) acryloyl group is an alkoxyalkyl (meth) acrylate. The catalyst X is one or more compounds selected from the group consisting of a cyclic tertiary amine having an azabicyclo structure or a salt or complex thereof, an amidine or a salt or complex thereof, and a compound having a pyridine ring or a salt or complex thereof. The manufacturing method of the curable composition of Claim 9 or Claim 10. The method for producing a curable composition according to any one of claims 9 to 11, wherein the catalyst Y is an organic acid zinc or / and a zinc diketone enolate. (A) The manufacturing method of the curable composition of any one of Claims 9-12 including the process of mixing a photoinitiator (B), after manufacturing a component.