JP5698393B2 - Active energy ray-curable composition - Google Patents

Description

  The present invention relates to an active energy ray-curable composition.

  In recent years, studies on radical polymerization type active energy ray-curable materials using acrylate materials that can be used in a solvent-free manner have been underway and are usefully used for coating agents, adhesives, inks, and the like. This acrylate-based material generally has a short curing time, can be cured at low temperature, and can be made one-solvent and solvent-free, thus saving resources and reducing environmental pollution. doing.

  However, since radical polymerization is inhibited by dissolved oxygen in the polymerization reaction composition, oxygen in the air, etc., curing may be delayed and there may be a problem in productivity. Although this problem can be solved if polymerization is performed in an inert atmosphere such as nitrogen, there is a strong demand for shortening and simplification of work steps aimed at saving space and labor, and such a method is not practical. Absent.

For the purpose of suppressing polymerization inhibition by oxygen, a radical addition reaction type material combining an olefin compound and a thiol compound has been proposed (for example, Patent Document 1).
However, the olefin compound and the thiol compound have problems such as low storage stability because the reaction proceeds even in the dark due to Michael addition or the like.

JP 2004-285113 A

  The object of the present invention is applicable to various fields such as hard coats (hard coats of resin molded products or hard coats of displays), resists, UV curable inks, etc. An object of the present invention is to provide an active energy ray-curable composition that can be cured and can be cured even in a thin film that has a large oxygen inhibition, and has high storage stability.

As a result of intensive studies to achieve the above object, the present inventors have reached the present invention. That is, this invention contains the compound (A) which generate | occur | produces thiol by at least 1 sort (s) chosen from the group which consists of an active energy ray, an acid, and a base, a polymeric compound (B), and an active energy ray polymerization initiator (C). An active energy ray-curable composition, wherein (A) is at least one selected from a compound (A2) that generates thiol with an acid and a compound (A3) that generates thiol with a base, and (A) is an acid In the case of the compound (A2) that generates a thiol due to, further containing an acid generator (D) that generates an acid by active energy rays, and (A) is a compound (A3) that generates a thiol by a base Is an active energy ray-curable composition further containing a base generator (E) that generates a base by active energy rays.
Other than the above are reference inventions.

The active energy ray-curable composition of the present invention has the following effects.
(1) The active energy ray-curable composition of the present invention can be cured with a low exposure amount.
(2) The active energy ray-curable composition of the present invention can be cured even in a thin film.
(3) The active energy ray-curable composition of the present invention has high storage stability.

The active energy ray-curable composition of the present invention includes a compound (A) that generates thiol by at least one selected from the group consisting of an active energy ray, an acid, and a base, a polymerizable compound (B), and active energy ray polymerization initiation. An active energy ray-curable composition containing an agent (C), and when (A) is a compound (A2) that generates a thiol by an acid, an acid generator (D) that generates an acid by an active energy ray And (A) is a compound (A3) that generates a thiol with a base, an active energy ray-curable composition that further contains a base generator (E) that generates a base with active energy rays. is there.
Since the active energy ray-curable composition of the present invention does not contain thiols in the composition before irradiation with active energy rays, the composition has high storage stability.

The compound (A) in the present invention is a compound that generates thiol by at least one selected from active energy rays, acids, and bases. The compound (A1) that generates thiols by active energy rays, generates thiols by acids. The compound (A2) and the compound (A3) that generates thiol with a base are included.
In (A1), a thiol group is protected by a protecting group having an absorption region at a wavelength of 200 nm to 800 nm, or a methyl group in which at least one hydrogen atom is substituted with an organic group having an absorption region at a wavelength of 300 nm to 800 nm. The compound is included. Examples thereof include tris {S- (9-methylfluorenyl)} thiocyanuric acid and S-benzyl-3-mercapto-1,2,4-triazole.
(A2) includes compounds in which the thiol group is protected by a protecting group that is decomposed by an acid. For example, S-acetylthiourea, S-benzoyl-2-mercaptobenzimidazole, S- (2-pyridinylethyl-2-mercaptopyrimidine, S- (t-butoxycarbonyl) -4,6-dimethyl-2-mercaptopyrimidine, etc. Can be mentioned.
(A3) includes compounds in which the thiol group is protected by a protecting group that is decomposed by a base. Examples include 2-mercaptobenzimidazole disulfide, thiocyanuric acid disulfide, and S- (9-fluorenylmethyl) -5-mercapto-1-methyltetrazole.

Of the compounds (A) that generate thiol by at least one selected from active energy rays, acids and bases in the present invention, from the viewpoint of thiol generation efficiency, the following general formulas (1) to ( It is a compound represented by 4). (A) may be used individually by 1 type, and may use 2 or more types together.
The compounds represented by the general formulas (1) to (4) have a common skeleton (-S-C = (N) -N), and by having this skeleton, oxygen inhibition is suppressed. And the curability (low exposure and / or thin film can be cured) is improved.

In the formula, R ^{1 to} R ³ and R ^{5 to} R ⁸ are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms, and R ⁴ is a divalent carbon group having 2 to 30 carbon atoms. A hydrogen group, and X ^{1 to} X ⁶ are monovalent substituents in which a bond with a sulfur atom bonded thereto is cut by at least one selected from the group consisting of an active energy ray, an acid and a base .

Of X ^{1 to} X ⁶ in the general formulas (1) to (4), from the viewpoint of thiol generation efficiency, (A1) is preferably a fluorenylmethyl group and a benzyl group, A2) is a pyridylethylene group, t-butoxycarbonyl group, acetyl group and benzoyl group, and (A3) is represented by a fluorenylmethoxycarbonyl group and the following general formulas (5) to (8). It is a substituent.

In the formula, R ^{9 to} R ¹¹ and R ^{13 to} R ¹⁶ are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms, and R ¹² is a divalent carbon group having 2 to 30 carbon atoms. * Represents a hydrogen group, and * represents a substituent represented by the general formulas (5) to (8) by a bond to which X ^{1 to} X ⁶ in the general formulas (1) to (4) are bonded. It is bonded to the sulfur atom.

As the compound (A), from the viewpoint of thiol generation efficiency, more preferably, the compounds represented by the following general formulas (9) to (17) and two structural units represented by the following chemical formula (18) are used. It is 1 or more types chosen from the compound which has it above.

In the formula, X ^{7 to} X ¹³ each independently represents a monovalent substituent selected from the group consisting of a pyridylethylene group, a t-butoxycarbonyl group, a fluorenylmethyl group, a fluorenylmethoxycarbonyl group, an acetyl group, and a benzoyl group. It is a group.

  The content of the compound (A) in the active energy ray-curable composition of the present invention is based on the weight of the active energy ray-curable composition from the viewpoint of the suppression effect of oxygen inhibition and the surface hardness of the cured product. The content is preferably 0.001 to 30% by weight, more preferably 0.01 to 20% by weight.

  The compound (A) used in the present invention is, for example, a reaction between a thiol compound such as thiouric acid and a compound that reacts with a thiol group such as a halide in an organic solvent in the presence of a catalyst (such as triethylamine) as necessary. Then, the organic solvent can be obtained by distilling off under reduced pressure.

As the polymerizable compound (B) in the present invention, known compounds such as radically polymerizable compounds and ionic polymerizable compounds can be used. (B) may be used alone or in combination of two or more. Of these, radically polymerizable compounds are preferred from the viewpoint of curing speed. Further, if necessary, a polymerization inhibitor such as hydroquinone or methyl ether hydroquinone may be used in combination.
Among the polymerizable compounds (B), from the viewpoint of curability (which can be cured even with a low exposure amount and / or a thin film), preferable examples thereof include the following ester compound (B1) and (meth) having 3 to 35 carbon atoms. Acrylamide compound (B2), (meth) acrylate compound (B3) having 4 to 100 carbon atoms other than (B1), aromatic vinyl compound (B4) having 6 to 35 carbon atoms, vinyl ether having 3 to 20 carbon atoms (B5) More preferable are the following ester compound (B1) and the following (meth) acrylate compound (B31). (B1) is preferable from the viewpoint of the surface hardness and adhesion of the cured product of the active energy ray-curable composition, and (B31) is preferable from the viewpoint of the effect of suppressing oxygen inhibition.
Ester compound (B1): an ester having an ethylenically unsaturated bond-containing group (x) and not having a urethane group or a urea group, the group consisting of phthalic acid ester, trimellitic acid ester and pyromellitic acid ester At least one ester compound selected from the group consisting of:
Methacrylate compound (B31): A compound having a urethane group and / or a urea group in the (meth) acrylate compound (B3) having 4 to 100 carbon atoms other than the ester compound (B1).
In the above and the following, when referring to both and / or “acrylate” and “methacrylate”, when referring to “(meth) acrylate” and “acryl” and / or “methacryl”, “(meth) acryl” May be described respectively.

  An ester having the above-mentioned ethylenically unsaturated bond-containing group (x) and not having a urethane group or a urea group, at least selected from the group consisting of phthalic acid ester, trimellitic acid ester and pyromellitic acid ester One ester compound (B1) is composed of, for example, a compound having an ethylenically unsaturated bond-containing group (x) and a hydroxyl group, phthalic acid (including isophthalic acid and terephthalic acid), trimellitic acid and pyromellitic acid. It can be obtained by reacting with at least one acid selected from the group.

The ethylenically unsaturated bond-containing group (x) of the ester compound (B1) has a (meth) acryloyl group, a vinyl group, and 1-propenyl from the viewpoint of curability (low exposure and / or even a thin film can be cured). Group and allyl group are preferred, and more preferred is an allyl group.
When the ester (B1) has a plurality of (x), the plurality of (x) may be the same or different.

  Among the ester compounds (B1), from the viewpoint of curability (which can be cured even with a low exposure amount and / or a thin film), compounds represented by the following general formulas (19) to (21) are preferable. (B1) may be used individually by 1 type, and may use 2 or more types together.

In the formula, R ^{14 to} R ²² are each independently a substituent represented by any one of the following general formulas (22) to (26).

In the formula, R ²³ , R ²⁵ and R ²⁷ are each independently a divalent aliphatic hydrocarbon group having 2 to 12 carbon atoms, and R ²⁴ , R ²⁶ and R ²⁸ are each independently a hydrogen atom or a methyl group. * Indicates that the substituent represented by the general formulas (22) to (26) is bonded to the oxygen atom of the oxycarbonyl group in the above general formulas (19) to (21) by the bond to which it is attached. Represents that.

Of the compounds represented by the general formulas (19) to (21), from the viewpoint of surface hardness and adhesion, a compound represented by the general formula (20) or (21) is preferable, and more preferable. It is a compound represented by General formula (20). Of the substituents represented by the general formulas (22) to (26), the substituent represented by the general formula (22), (25) or (26) is preferable from the viewpoint of surface hardness and adhesion. And more preferred is a substituent represented by formula (26).
Among these, from the viewpoint of the suppression effect of oxygen inhibition, and particularly preferred are a substituent in the compound represented by the general formula (20) R ¹⁶ ~R ¹⁸ is represented by the general formula (22) R ²³ In which R ²⁴ is a hydrogen atom, a compound represented by the general formula (20), wherein R ^{16 to} R ¹⁸ are substituents represented by the general formula (25), and R ²⁸ is a hydrogen atom. Compound, a compound represented by the general formula (20), wherein R ^{16 to} R ¹⁸ are substituents represented by the general formula (26), and a compound represented by the general formula (21), R ^{19 to} R ²² Is a substituent represented by the general formula (22), R ²³ is an ethylene group and R ²⁴ is a hydrogen atom, and in the compound represented by the general formula (21), R ^{19 to} R ²² are represented by the general formula ( a compound R ²⁸ is a substituent represented is a hydrogen atom in 25), most Mashiino is the compound represented by the general formula (20) R ¹⁶ to R ¹⁸ is a substituent represented by the general formula (26) compounds.

  The ester compound (B1) is, for example, an acid such as trimellitic acid in an organic solvent and a compound having an ethylenically unsaturated bond-containing group (x) and a hydroxyl group, if necessary, an acid catalyst (paratoluenesulfonic acid or the like). After the reaction in the presence of the organic solvent, the organic solvent can be distilled off under reduced pressure.

  Examples of (meth) acrylamide (B2) having 3 to 35 carbon atoms include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, and N-n. -Butyl (meth) acrylamide, Nt-butyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) Other than (meth) acryloylmorpholine such as acrylamide and N, N-diethyl (meth) acrylamide.

Examples of the (meth) acrylate (B3) having 4 to 100 carbon atoms other than the ester compound (B1) include, for example, the following monofunctional to hexafunctional (meth) acrylate having no urethane group and urea group, and urethane. And (meth) acrylate (B31) having a group and / or a urea group.
Monofunctional (meth) acrylates include ethyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, tert-octyl (meth) acrylate, isoamyl (meth) acrylate, decyl (meth) acrylate, isodecyl (Meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, cyclohexyl (meth) acrylate, 4-n-butylcyclohexyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, benzyl ( (Meth) acrylate, 2-ethylhexyl diglycol (meth) acrylate, butoxyethyl (meth) acrylate, 2-chloroethyl (meth) acrylate, 4-bromobutyl (meth) acrylate Relate, cyanoethyl (meth) acrylate, benzyl (meth) acrylate, butoxymethyl (meth) acrylate, methoxypropylene monoacrylate, 3-methoxybutyl (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, alkoxyethyl ( (Meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 2- (2-butoxyethoxy) ethyl (meth) acrylate, 2,2,2-tetrafluoroethyl (meth) acrylate, 1H, 1H, 2H, 2H-perfluorodecyl (meth) acrylate, 4-butylphenyl (meth) acrylate, phenyl (meth) acrylate, 2,4,5-tetramethylphenyl (meth) acrylate, 4-chlorophenyl (meth) acrylate Phenoxymethyl (meth) acrylate, phenoxyethyl (meth) acrylate, glycidyl (meth) acrylate, glycidyloxybutyl (meth) acrylate, glycidyloxyethyl (meth) acrylate, glycidyloxypropyl (meth) acrylate, diethylene glycol Monovinyl ether monoacrylate, tetrahydrofurfuryl (meth) acrylate, hydroxyalkyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy Butyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate Acrylate, dimethylaminopropyl (meth) acrylate, diethylaminopropyl (meth) acrylate, trimethoxysilylpropyl (meth) acrylate, trimethoxysilylpropyl (meth) acrylate, trimethylsilylpropyl (meth) acrylate, polyethylene oxide monomethyl ether (meth) acrylate , Oligoethylene oxide monomethyl ether (meth) acrylate, polyethylene oxide (meth) acrylate, oligoethylene oxide (meth) acrylate, oligoethylene oxide monoalkyl ether (meth) acrylate, polyethylene oxide monoalkyl ether (meth) acrylate, dipropylene glycol (Meth) acrylate, polypropylene oxide monoalkyl Ether (meth) acrylate, oligopropylene oxide monoalkyl ether (meth) acrylate, 2-methacryloyloxyethyl succinic acid, butoxydiethylene glycol (meth) acrylate, trifluoroethyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, EO modified phenol (meth) acrylate, EO modified cresol (meth) acrylate, EO modified nonylphenol (meth) acrylate, PO modified nonylphenol (meth) acrylate and EO modified-2- Examples include ethylhexyl (meth) acrylate.

Examples of the bifunctional (meth) acrylate include 1,4-butanedi (meth) acrylate, 1,6-hexanedi (meth) acrylate, polypropylene di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate, neopentyl di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2,4-dimethyl-1,5-pentanediol di (meth) acrylate, butylethylpropanediol (meth) Acrylate, ethoxylated cyclohexanemethanol di (meth) acrylate, polyethylene glycol di (meth) acrylate, oligoethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, 2-ethyl-2-butyl-butyl Diol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, EO-modified bisphenol A di (meth) acrylate, bisphenol F polyethoxydi (meth) acrylate, polypropylene glycol di (meth) acrylate, oligopropylene glycol di (meth) ) Acrylate, 1,4-butanediol di (meth) acrylate, 2-ethyl-2-butyl-propanediol di (meth) acrylate, 1,9-nonanedi (meth) acrylate, propoxylated ethoxylated bisphenol A di (meth) ) Acrylate and tricyclodecane di (meth) acrylate.

  Trifunctional (meth) acrylates include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane alkylene oxide modified tri (meth) acrylate, pentaerythritol tri (meth) acrylate, di Pentaerythritol tri (meth) acrylate, trimethylolpropane tri ((meth) acryloyloxypropyl) ether, isocyanuric acid alkylene oxide modified tri (meth) acrylate, dipentaerythritol tri (meth) acrylate propionate, tri ((meta ) Acryloyloxyethyl) isocyanurate, hydroxypivalaldehyde-modified dimethylolpropane tri (meth) acrylate, sorbitol tri (meth) acrylate , Propoxylated trimethylolpropane tri (meth) acrylate and ethoxylated glycerol triacrylate, and the like.

  Tetrafunctional (meth) acrylates include pentaerythritol tetra (meth) acrylate, sorbitol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate propionate and pentaerythritol EO addition. And tetra (meth) acrylate of the product.

  Examples of pentafunctional (meth) acrylates include sorbitol penta (meth) acrylate and dipentaerythritol penta (meth) acrylate.

  Examples of hexafunctional (meth) acrylates include dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate, phosphazene alkylene oxide modified hexa (meth) acrylate, and caprolactone modified dipentaerythritol hexa (meth) acrylate. It is done.

  As the (meth) acrylate (B31) having a urethane group and / or a urea group, the above monofunctional to hexafunctional (meth) acrylate contains a (meth) acrylate having a hydroxyl group and a (meth) acryloyl group in the molecule. (Meth) acrylates obtained by reacting the active hydrogen component (H) with the organic polyisocyanate component (I) are included.

  Examples of the (meth) acrylate having a hydroxyl group and a (meth) acryloyl group in the molecule of the active hydrogen component (H) include a hydroxyalkyl (meth) acrylate having 5 to 8 carbon atoms [for example, hydroxyethyl (meth) acrylate, hydroxypropyl ( Meth) acrylate], pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and the like.

  Of these, from the viewpoint of curability (low exposure and / or curing even in a thin film), hydroxyethyl (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate and dipenta are preferred. Erythritol penta (meth) acrylate.

Examples of the component other than the above {(meth) acrylate having a hydroxyl group and a (meth) acryloyl group in the molecule} in the active hydrogen component (H) include a polyol and a chain extender.

  Examples of the polyol include a high molecular polyol having a hydroxyl group equivalent (average molecular weight per hydroxyl group calculated from a hydroxyl value) of 150 or more and a low molecular polyol having a hydroxyl group equivalent of less than 150.

  Examples of the polymer polyol having a hydroxyl group equivalent of 150 or more include polyether polyol and polyester polyol.

  Examples of polyether polyols include aliphatic polyether polyols and aromatic ring-containing polyether polyols.

  Examples of the aliphatic polyether polyol include polyoxyethylene polyol (polyethylene glycol and the like), polyoxypropylene polyol (polypropylene glycol and the like), polyoxyethylene / propylene polyol and polytetramethylene ether glycol.

  As the aromatic polyether polyol, a polyol having a bisphenol skeleton, for example, an ethylene oxide (hereinafter abbreviated as EO) adduct of bisphenol A [EO2 mol adduct of bisphenol A, EO4 mol adduct of bisphenol A, EO6 of bisphenol A, Mole adduct, EO 8 mol adduct of bisphenol A, EO 10 mol adduct of bisphenol A and EO 20 mol adduct of bisphenol A] and propylene oxide (hereinafter abbreviated as PO) adduct of bisphenol A [PO2 mol of bisphenol A] Adduct, PO3 mol adduct of bisphenol A and PO5 mol adduct of bisphenol A, etc.] and EO or PO adduct of resorcin.

  Polyether polyol is obtained by subjecting an aliphatic or aromatic low molecular weight active hydrogen atom-containing compound to ring-opening addition reaction of EO or PO in the presence of an addition catalyst (a known catalyst such as alkali metal hydroxide and Lewis acid). It is obtained by.

  The number average molecular weight (hereinafter abbreviated as Mn) of the polyether polyol is usually 300 or more, preferably from 300 to 10,000 from the viewpoints of curability (low exposure and / or thin film can be cured) and viscosity (workability). More preferably, it is 300-6,000. The number average molecular weight of the polyol in the present invention is measured by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent and polyethylene glycol as a standard. However, Mn of the low molecular polyol is a calculated value from the chemical formula.

  Examples of the polyester polyol include condensed polyester, polylactone polyol, polycarbonate polyol, and castor oil-based polyol.

Condensation type polyesters are low molecular weight (Mn 300 or less) polyhydric alcohol and polyvalent carboxylic acid or ester-forming derivatives thereof [acid anhydride, acid halide, or low molecular weight alkyl (alkyl group having 1 to 4 carbon atoms) ester] And polyester.
Examples of the low molecular weight polyhydric alcohol include dihydric to octavalent or higher aliphatic polyhydric alcohol having a hydroxyl group equivalent of 30 to less than 150 and dihydric to octavalent or higher phenol having a hydroxyl group equivalent of 30 to less than 150. Alkylene oxide low molar adducts can be used.
Among the low molecular weight polyhydric alcohols that can be used in the condensation type polyester, ethylene glycol, propylene glycol, 1,4-butanediol from the viewpoints of curability (low exposure and / or curing even in a thin film) and viscosity (workability). Neopentyl glycol, 1,6-hexane glycol, EO or PO low molar adducts of bisphenol A and combinations thereof are preferred.

  Examples of polyvalent carboxylic acids or ester-forming derivatives thereof that can be used in the condensed polyester include aliphatic dicarboxylic acids (succinic acid, adipic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, etc.), alicyclic dicarboxylic acids ( Dimer acids, etc.), aromatic dicarboxylic acids (terephthalic acid, isophthalic acid, phthalic acid, etc.) and trivalent or higher polycarboxylic acids (trimellitic acid, pyromellitic acid, etc.), and their anhydrides (succinic anhydride, Maleic anhydride, phthalic anhydride, trimellitic anhydride, etc.), their acid halides (such as adipic acid dichloride), their low molecular weight alkyl esters (such as dimethyl succinate and dimethyl phthalate), and combinations thereof. .

  Examples of the condensed polyester include polyethylene adipate diol, polybutylene adipate diol, polyhexamethylene adipate diol, polyhexamethylene isophthalate diol, polyneopentyl adipate diol, polyethylene propylene adipate diol, polyethylene butylene adipate diol, polybutylene hexamethylene adipate Diol, polydiethylene adipate diol, poly (polytetramethylene ether) adipate diol, poly (3-methylpentylene adipate) diol, polyethylene azelate diol, polyethylene sebacate diol, polybutylene azelate diol, polybutylene sebacate diol and Examples include polyneopentyl terephthalate diol.

The polylactone polyol is a polyadduct of lactone to the low molecular weight polyhydric alcohol. As the lactone, a lactone having 4 to 12 carbon atoms can be used, for example, γ-butyrolactone, γ-valerolactone, ε-caprolactone, etc. Is mentioned.
Examples of the polylactone polyol include polycaprolactone diol, polyvalerolactone diol, and polycaprolactone triol.

The polycarbonate polyol is a polyaddition product of an alkylene carbonate to a low molecular weight polyhydric alcohol. As the alkylene carbonate, an alkylene carbonate having 2 to 8 carbon atoms can be used, and examples thereof include ethylene carbonate and propylene carbonate.
Examples of the polycarbonate polyol include polyhexamethylene carbonate diol.
Examples of commercially available polycarbonate polyols include NIPPOLAN 980R [Mn = 2,000, manufactured by Nippon Polyurethane Industry Co., Ltd.], T5652 [Mn = 2,000, manufactured by Asahi Kasei Co., Ltd.] and T4672 [Mn = 2,000, Asahi Kasei. Made by Co., Ltd.].

  The castor oil-based polyol includes castor oil and castor oil modified with polyol or alkylene oxide. Modified castor oil can be produced by transesterification of castor oil and polyol and / or addition of alkylene oxide. Castor oil-based polyols include castor oil, trimethylolpropane-modified castor oil, pentaerythritol-modified castor oil, and EO (4 to 30 mol) adduct of castor oil.

Low molecular polyols having a hydroxyl equivalent weight of less than 150 include aliphatic dihydric alcohols (ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, etc.) and aliphatic trihydric alcohols (triglycerides). Methylolpropane and glycerin).
A polyol may be used individually by 1 type and may use 2 or more types together.

Examples of chain extenders include water, diamines having 2 to 10 carbon atoms (for example, ethylenediamine, propylenediamine, hexamethylenediamine, isophoronediamine, toluenediamine and piperazine), polyalkylene polyamines (for example, diethylenetriamine and triethylenetetramine), hydrazine or hydrazine. Compounds having a skeleton (acid hydrazide and the like) (for example, dibasic acid dihydrazide such as adipic acid dihydrazide) and amino alcohols having 2 to 10 carbon atoms (for example, ethanolamine, diethanolamine, 2-amino-2-methylpropanol and triethanolamine) ) And the like.
A chain extender may be used individually by 1 type, and may use 2 or more types together.

  The organic polyisocyanate component (I) is an aromatic polyisocyanate having 2 to 3 or more isocyanate groups and having 6 to 20 carbon atoms (excluding carbon in the isocyanate group, the same shall apply hereinafter), and 2 to 18 carbon atoms. Aliphatic polyisocyanates, alicyclic polyisocyanates having 4 to 15 carbon atoms, and araliphatic polyisocyanates having 8 to 15 carbon atoms.

  Examples of the aromatic polyisocyanate include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate, 4,4′- or 2,4′-diphenylmethane diisocyanate, 1,5. Naphthylene diisocyanate, 4,4 ′, 4 ″ -triphenylmethane triisocyanate, m- or p-isocyanatophenylsulfonyl isocyanate.

  Examples of the aliphatic polyisocyanate include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, and 2-isocyanatoethyl-2,6-diisocyanate. Hexanoate is mentioned.

  Examples of the alicyclic polyisocyanate include isophorone diisocyanate, 4,4-dicyclohexylmethane diisocyanate, cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, bis (2-isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate and 2,5- or 2,6-norbornane diisocyanate is mentioned.

  Examples of the araliphatic polyisocyanate include m- or p-xylylene diisocyanate and α, α, α ′, α′-tetramethylxylylene diisocyanate.

Among the polyisocyanates, preferred are isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, from the viewpoint of surface hardness and adhesion. 4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate and 1,5-naphthalene diisocyanate.
The organic polyisocyanate component (I) may be used alone or in combination of two or more.

The (meth) acrylate (B31) having a urethane group and / or a urea group in the present invention can be produced by a usual method, for example, a (meth) acrylate having a hydroxyl group and a (meth) acryloyl group in the molecule. The active hydrogen component (H), which is contained as an essential component, and the organic polyisocyanate component (I) may be reacted together, or a (meth) acrylate having a hydroxyl group and a (meth) acryloyl group in the molecule is not contained. A urethane / urea prepolymer having an isocyanate group at the end obtained by reacting the active hydrogen component (H) with the organic polyisocyanate component (I), a (meth) acrylate having a hydroxyl group and a (meth) acryloyl group in the molecule; May be reacted.

  The ratio of the active hydrogen equivalent of the active hydrogen component (H) to the equivalent of the isocyanate group of the organic polyisocyanate component (I) (active hydrogen equivalent / isocyanate group equivalent) is preferably from 0.1 to 10, -1.2 is particularly preferred. The reaction temperature is preferably 30 to 150 ° C, more preferably 50 to 100 ° C. The end point of the reaction can be confirmed by, for example, disappearance of the isocyanate group absorption (2250 cm −1) in the infrared absorption spectrum or obtaining the isocyanate group content by the method described in JIS K 7301-1995.

  The content of the (meth) acrylate (B31) having a urethane group and / or a urea group in the polymerizable compound (B) is in view of the suppression effect of oxygen inhibition and curability (low exposure and / or thin film is also cured. ) Is preferably 0.1 to 100% by weight, more preferably 5 to 90% by weight, based on the weight of the polymerizable compound (B).

  Examples of the aromatic vinyl compound (B4) having 6 to 35 carbon atoms include vinyl thiophene, vinyl furan, vinyl pyridine, styrene, methyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, chloromethyl styrene, methoxy styrene, acetoxy styrene, chloro. Styrene, dichlorostyrene, bromostyrene, vinyl benzoic acid methyl ester, 3-methylstyrene, 4-methylstyrene, 3-ethylstyrene, 4-ethylstyrene, 3-propylstyrene, 4-propylstyrene, 3-butylstyrene, 4-butylstyrene, 3-hexylstyrene, 4-hexylstyrene, 3-octylstyrene, 4-octylstyrene, 3- (2-ethylhexyl) styrene, 4- (2-ethylhexyl) styrene, allylstyrene, Propenyl styrene, butenylstyrene, octenyl styrene, 4-t-butoxycarbonyl styrene, 4-methoxystyrene and 4-t-butoxystyrene, and the like.

As a C3-C35 vinyl ether (B5), the following monofunctional or polyfunctional vinyl ether is mentioned, for example.
Examples of the monofunctional vinyl ether include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, n-butyl vinyl ether, t-butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, cyclohexyl methyl vinyl ether, 4-methyl Cyclohexylmethyl vinyl ether, benzyl vinyl ether, dicyclopentenyl vinyl ether, 2-dicyclopentenoxyethyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, butoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, ethoxyethoxyethyl vinyl ether, methoxypolyethylene glycol vinyl ether , Tetrahydrofurfuryl vinyl ether, 2-hydroxyethyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxymethylcyclohexyl methyl vinyl ether, diethylene glycol monovinyl ether, polyethylene glycol vinyl ether, chloroethyl vinyl ether, chlorobutyl vinyl ether, chloroethoxy Examples include ethyl vinyl ether, phenyl ethyl vinyl ether, and phenoxy polyethylene glycol vinyl ether.

Examples of the polyfunctional vinyl ether include ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide divinyl ether. Divinyl ethers such as: trimethylolethane trivinyl ether, trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl Ether, ethylene oxide-added trimethylolpropane trivinyl ether, propylene oxide-added trimethylolpropane trivinyl ether, ethylene oxide-added ditrimethylolpropane tetravinyl ether, propylene oxide-added ditrimethylolpropane tetravinyl ether, ethylene oxide-added pentaerythritol tetravinyl ether, propylene oxide-added penta Examples include erythritol tetravinyl ether, ethylene oxide-added dipentaerythritol hexavinyl ether, and propylene oxide-added dipentaerythritol hexavinyl ether.

  Other polymerizable compounds (B6) other than (B1) to (B5) include acrylonitrile, vinyl esters (such as vinyl acetate, vinyl propionate and vinyl versatate), allyl esters (such as allyl acetate), and halogen-containing single quantities. And the like (vinylidene chloride, vinyl chloride, etc.) and olefins (ethylene, propylene, etc.).

The content of the polymerizable compound (B) in the active energy ray-curable composition of the present invention is such that the active energy ray-curable composition is a composition containing (A), (B) and (C). Is preferably 40 to 99.949% by weight, based on the weight of the active energy ray-curable composition, from the viewpoint of the inhibitory effect of oxygen inhibition and from the viewpoint of curability (can be cured even by a low exposure amount and / or a thin film). More preferably, it is 60 to 99.89% by weight.
Moreover, an active energy ray hardening-type composition contains the composition containing (A), (B), (C) and (D), or (A), (B), (C) and (E). In the case of a composition, from the viewpoint of the inhibitory effect on oxygen inhibition and the curability (it can be cured even with a low exposure amount and / or a thin film), preferably 10 to 10 based on the weight of the active energy ray-curable composition. 99.948% by weight, more preferably 35 to 99.88% by weight.

  Further, the content of the ester compound (B1) in the active energy ray-curable composition of the present invention is preferably 0 based on the weight of the active energy ray-curable composition from the viewpoint of surface hardness and adhesion. -80 wt%, more preferably 1-60 wt%, particularly preferably 5-40 wt%.

Examples of the active energy ray polymerization initiator (C) in the present invention include a polymerization initiator (C1) having an acylphosphine oxide skeleton, a polymerization initiator (C2) having an α-aminoacetophenone skeleton, and a polymerization initiation having a benzyl ketal skeleton. Agent (C3), polymerization initiator (C4) having an α-hydroxyacetophenone skeleton, polymerization initiator (C5) having a benzoin skeleton, polymerization initiator (C6) having an oxime ester skeleton, polymerization initiator having a titanocene skeleton ( C7), organic peroxide polymerization initiator (C8), azo compound polymerization initiator (C9) and other polymerization initiators (C10). (C) may be used individually by 1 type, and may use 2 or more types together.
Here, the polymerization initiator (C1) having an acylphosphine oxide skeleton means a polymerization initiator that is a compound in which a part of the acylphosphine oxide is substituted with another group. The polymerization initiator (C2) having an α-aminoacetophenone skeleton means a polymerization initiator which is a compound in which a part of α-aminoacetophenone is substituted with another group. The polymerization initiator (C3) having a benzyl ketal skeleton means a polymerization initiator that is a compound in which a part of α-dihydroxyacetophenone is substituted with another group. The polymerization initiator (C4) having an α-hydroxyacetophenone skeleton means a polymerization initiator which is a compound in which a part other than the hydroxyl group of α-monohydroxyacetophenone is substituted with another group. The polymerization initiator (C5) having a benzoin skeleton means a polymerization initiator that is a compound in which a part of benzoin is substituted with another group. The polymerization initiator (C6) having an oxime ester skeleton means a polymerization initiator that is a compound in which a part of N-acetyldimethyloxime is substituted with another group. The polymerization initiator (C7) having a titanocene skeleton means a polymerization initiator which is a compound in which a part of titanocene is substituted with another group. The organic peroxide polymerization initiator (C8) means a polymerization initiator that is a compound having a peroxy group. The azo compound polymerization initiator (C9) means a polymerization initiator that is a compound having an azo group.

  As the polymerization initiator (C1) having an acylphosphine oxide skeleton, 2,4,6-trimethylbenzoyldiphenylphosphine oxide [manufactured by BASF Japan (LUCILIN TPO)] and bis (2,4,6-trimethylbenzoyl) phenylphosphine Oxide [made by BASF Japan Ltd. (IRGACURE 819)] and the like.

  As a polymerization initiator (C2) having an α-aminoacetophenone skeleton, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one [manufactured by BASF Japan (IRGACURE 907)], 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone [manufactured by BASF Japan (IRGACURE 369)] and 1,2- (dimethylamino) -2-[(4-methylphenyl) methyl]- 1- [4- (4-morpholinyl) phenyl] -1-butanone [manufactured by BASF Japan (IRGACURE 379)] and the like.

  Examples of the polymerization initiator (C3) having a benzyl ketal skeleton include 2,2-dimethoxy-1,2-diphenylethane-1-one [manufactured by BASF Japan (IRGACURE 651)].

  As the polymerization initiator (C4) having an α-hydroxyacetophenone skeleton, 1-hydroxy-cyclohexyl-phenyl-ketone [manufactured by BASF Japan Ltd. (IRGACURE 184)], 2-hydroxy-2-methyl-1-phenyl-propane- 1-one [made by BASF Japan (DAROCUR 1173)], 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one [made by BASF Japan ( IRGACURE 2959)] and 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one [manufactured by BASF Japan Ltd. (IRGACURE) 127)] and the like.

  Examples of the polymerization initiator (C5) having a benzoin skeleton include benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.

  As a polymerization initiator (C6) having an oxime ester skeleton, 1,2-octanedione-1- (4- [phenylthio) -2- (O-benzoyloxime)] [manufactured by BASF Japan (IRGACURE OXE 01)] And ethanone-1- (9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (0-acetyloxime) [manufactured by BASF Japan Ltd. (IRGACURE OXE 02)] and the like. It is done.

  As a polymerization initiator (C7) having a titanocene skeleton, bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl ) Titanium [manufactured by BASF Japan Ltd. (IRGACURE 784)].

Examples of the organic peroxide polymerization initiator (C8) include benzoyl peroxide, t-butyl peroxyacetate, 2,2-di- (t-butylperoxy) butane, t-butyl peroxybenzoate, and n-butyl 4 , 4-Di- (t-butylperoxy) valerate, di-
(2-t-butylperoxyisopropyl) benzene, dicumyl peroxide, di-t-hexyl peroxide, 2,5, -dimethyl-2,5, -di (t-butylperoxy) hexane, t-butyl Cumyl peroxide, di-t-butyl peroxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-butyl hydro Examples thereof include peroxide and t-butyltrimethylsilyl peroxide.

  As the azo compound polymerization initiator (C9), 1-[(1-cyano-1-methylethyl) azo] formamide, 2,2′-azobis (N-butyl-2-methylpropionamide), 2,2 ′ -Azobis (N-cyclohexyl-2-methylpropionamide), 2,2'-azobis (2,4,4-trimethylpentane) and the like.

  Examples of the other polymerization initiator (C10) include 2,3-dimethyl-2,3-diphenylbutane.

  Among these, from the viewpoint of photocurability, a polymerization initiator (C1) having an acylphosphine oxide skeleton, a polymerization initiator (C2) having an α-aminoacetophenone skeleton, and a polymerization initiator having a benzyl ketal skeleton ( C3), a polymerization initiator having an α-hydroxyacetophenone skeleton (C4), a polymerization initiator having a benzoin skeleton (C5), a polymerization initiator having an oxime ester skeleton (C6), and a polymerization initiator having a titanocene skeleton (C7) More preferred is a polymerization initiator (C1) having an acylphosphine oxide skeleton.

  The content of the active energy ray polymerization initiator (C) in the active energy ray curable composition of the present invention is preferably 0.00 on the basis of the weight of the active energy ray curable composition from the viewpoint of photocurability. It is 05-30 weight%, More preferably, it is 0.1-20 weight%.

When the active energy ray-curable composition of the present invention contains (A2) as (A), it further contains (D). Moreover, when (A3) is contained as (A), (E) is further contained. When (A) contains (A2) and / or (A3), an acid generator (D) that generates an acid by active energy rays and / or a base generator that generates a base by active energy rays ( E).
When (A2) is contained, thiol is generated from (A2) by the acid generated from (D), oxygen inhibition in the curing reaction is suppressed, and curability is improved. Moreover, when (A3) is contained, the thiol is generated from (A3) by the base generated in (E), oxygen inhibition in the curing reaction is suppressed, and curability is improved. Moreover, also when (A1) is contained as (A), by containing (D) and / or (E) in the active energy ray-curable composition, only the active energy polymerization initiator (C) is contained. Is more preferable because the curability inside the composition is improved.

  Examples of the acid generator (D) that generates an acid by active energy rays include a sulfonium salt (D1) and an iodonium salt (D2). (D) may be used individually by 1 type, and may use 2 or more types together.

As the sulfonium salt (D1), triphenylsulfonium tetrafluoroborate, triphenylsulfonium bromide, tri-p-tolylsulfonium hexafluorophosphate, tri-p-tolylsulfonium trifluoromethanesulfonate, [p- (phenyl mercapto) Phenyl] diphenylsulfonium hexafluorophosphate [“CPI-100P” manufactured by San Apro Co., Ltd.] and [p- (phenylmercapto) phenyl] diphenylsulfonium [tri (perfluoroethyl)] trifluorophosphate.

  Examples of the iodonium salt (D2) include iodonium (4-methylphenyl) {4- (2-methylpropyl) phenyl} -hexafluorophosphate [manufactured by BASF Japan (DAROCUR 250)], iodonium [bis (4-t- Butylphenyl)] hexafluorophosphate, iodonium [bis (4-t-butylphenyl)] trifluoro [tris (perfluoroethyl)] phosphate, iodonium [bis (4-methoxyphenyl)] trifluoro [tris (per Fluoroethyl)] phosphate, iodonium [bis (4-methoxyphenyl)] [tetrakis (perfulphenyl)] borate, and a compound represented by the following chemical formula (27).

Of these, the compound represented by the chemical formula (27) is preferable from the viewpoint of photocurability.
Further, the acid generator is preferably one having a high strength of acid generated by decomposition by active energy rays from the viewpoint of photocurability. The acid strength increases in the order of BF4- <PF6- <AsF6- <SbF6-.
From the viewpoint of low toxicity and high photocurability, PF3 (C2F5) 3- is particularly preferable.
The combination of (C) and (D) contained in the active energy ray-curable composition is composed of a polymerization initiator (C1) having an acylphosphine oxide skeleton and an iodonium salt (D2) from the viewpoint of photocurability. A combination is preferred.

The content of the acid generator (D) in the active energy ray-curable composition of the present invention is preferably 0.001 to 30 based on the weight of the active energy ray-curable composition from the viewpoint of photocurability. % By weight, more preferably 0.05 to 25% by weight, particularly preferably 0.1 to 20% by weight.
The weight ratio {weight of (A) / weight of (D)} of compound (A) and acid generator (D) in the active energy ray-curable composition is 0.01 / 1-10 / 1 is preferable, More preferably, it is 0.1 / 1-5 / 1.

  The base generator (E) in the present invention is not particularly limited, but includes a compound having an oxime skeleton (E1), a compound having a quaternary ammonium salt skeleton (E2), and a compound having a quaternary amidine salt skeleton (E3). It is.

Examples of the compound (E1) having an oxime skeleton include O-acyloxime.
Examples of the compound (E2) having a quaternary ammonium salt skeleton and the compound (E3) having a quaternary amidine salt skeleton include compounds represented by the following general formulas (28) to (30), and more preferably The compound etc. which are represented with General formula (33) are mentioned.

In the formula, R ^{29 to} R ⁵⁶ are each independently a hydrogen atom, a halogen atom, an acyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or 1 to 1 carbon atom. 20 alkylthio groups, C1-C20 alkylsilyl groups, nitro groups, carboxyl groups, hydroxyl groups, mercapto groups, amino groups, cyano groups, phenyl groups, naphthyl groups, groups represented by the following general formula (31), and An atom or a substituent selected from the group consisting of groups represented by the following general formula (32), wherein any one of R ^{29 to} R ³⁸ is the following general formula (31) or the following general formula (32) Any one of R ^{39 to} R ⁴⁶ is a substituent represented by the following general formula (31) or the following general formula (32), and any one of R ^{47 to} R ⁵⁶ Is represented by the following general formula (31) or the following general formula (32). It is a substituent. ]

In the formula, R ^{57 to} R ⁶⁰ are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R ^{61 to} R ⁶³ are each independently independently substituted with a hydroxyl group. an alkyl group, (X ^{14) -} and (X ^{15) -} each represent an anion, a is an integer from 2 to 4, and * are each substituent by binding it is attached, the It represents bonding to the carbon atom in general formulas (28) to (30).

In the formula, (X ¹⁶ ) ⁻ represents an anion.

  Examples of the halogen atom include fluorine, chlorine, bromine and iodine, and fluorine and chlorine are preferable.

  Examples of the acyl group having 1 to 20 carbon atoms include formyl group, acetyl group, propionyl group, isobutyryl group, valeryl group, and cyclohexylcarbonyl group.

  Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n- or iso-propyl group, n-, sec- or tert-butyl group, n-, iso- or neo-pentyl group, hexyl group, A heptyl group, an octyl group, etc. are mentioned.

  Examples of the alkoxy group having 1 to 20 carbon atoms include methoxy group, ethoxy group, n- or iso-propoxy group, n-, sec- or tert-butoxy group, n-, iso- or neo-pentyloxy group, A hexyloxy group, a heptyloxy group, an octyloxy group, etc. are mentioned.

  Examples of the alkylthio group having 1 to 20 carbon atoms include a methylthio group, an ethylthio group, an n- or iso-propylthio group, an n-, sec- or tert-butylthio group, an n-, iso- or neo-pentylthio group, and a hexylthio group. , Heptylthio group, octylthio group and the like.

  Examples of the alkylsilyl group having 1 to 20 carbon atoms include trialkylsilyl groups such as trimethylsilyl group and triisopropylsilyl group. Here, the alkyl may be a linear structure or a branched structure.

The compound represented by the general formula (28) is an anthracene skeleton, the compound represented by the general formula (29) is a thioxanthone skeleton, and the compound represented by the general formula (30) is a compound having a benzophenone skeleton. It is an example of a compound having a maximum absorption wavelength in the vicinity of (365 nm). R ^{29 to} R ⁵⁶ are modified in consideration of adjustment of absorption wavelength, sensitivity adjustment, thermal stability, reactivity, decomposability, etc., and include hydrogen atom, halogen atom, C 1-20 alkoxy group, Nitro group, carboxyl group, hydroxyl group, mercapto group, alkyl silyl group having 1 to 20 carbon atoms, acyl group having 1 to 20 carbon atoms, amino group, cyano group, alkyl group having 1 to 20 carbon atoms, phenyl group, naphthyl group The atom or substituent selected from the group consisting of is modified according to the purpose. However, any one of R ²⁹ to R ⁵⁶ is a substituent represented by the general formula (31) or formula (32).

The substituent represented by the general formula (31) is a substituent having a cationized amidine skeleton, and a is an integer of 2 to 4. Examples of the substituent include a substituent having a structure in which 1,8-diazabicyclo [5.4.0] -7-undecene in which a is 4, and 1,5-diazabicyclo [4. 3.0] -5-Nonene is preferably a substituent having a cationized structure. R ⁵⁷ and R ⁵⁸ represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, preferably a hydrogen atom and an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom and an alkyl group having 1 to 5 carbon atoms. It is.

General formula (32) has a quaternary ammonium structure, R ⁹ and R ⁶⁰ represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, More preferably, they are a hydrogen atom or a C1-C5 alkyl group. R ^{61 to} R ⁶³ represent an alkyl group having 1 to 20 carbon atoms which may be substituted with a hydroxyl group, and may be linear, branched or cyclic. R ^{61 to} R ⁶³ are preferably an alkyl group having 1 to 10 carbon atoms, and particularly preferably an alkyl group having 1 to 5 carbon atoms.

The compound represented by the general formula (31) generates a basic compound having an amidine skeleton by cleaving the bond between carbon and nitrogen to which R ⁵⁷ and R ⁵⁸ are bonded by irradiation with active energy rays. In the compound represented by the general formula (32), the bond between carbon and nitrogen to which R ⁵⁹ and R ⁶⁰ are bonded is cleaved by irradiation with active energy rays to generate a tertiary amine. In the present invention, from the viewpoint of photocurability, those having a strong base generated by decomposition with active energy rays are preferred. Specifically, a compound having a substituent represented by the general formula (31) is provided. More preferred is a compound having a cationized 1,8-diazabicyclo [5.4.0] -7-undecene in which a is 4 in the general formula (31).

Examples of the anion represented by (X ¹⁴ ) ⁻ to (X ¹⁶ ) ⁻ in the general formulas (31) to (33) include a halide anion, a hydroxide anion, a thiocyanate anion, and those having 1 to 4 carbon atoms. Dialkyldithiocarbamate anion, carbonate anion, bicarbonate anion, aliphatic or aromatic carboxy anion optionally substituted with halogen (benzoate anion, trifluoroacetate anion, perfluoroalkylacetate anion, phenylglyoxylate anion, etc.) An aliphatic or aromatic sulfoxy anion (trifluoromethanesulfonic acid anion, etc.) optionally substituted with halogen, hexafluoroantimonate anion (SbF6-), phosphine anion [hexafluorophosphine anion (PF ₆ ⁻ ) And tris trifluoride (perfluoroethyl) Scan fins anion _{(PF 3 (C 2 F 5} ) 3 -) , etc.] and borate anion (tetraphenyl borate and butyl triphenyl borate anion), and the like, among these, from the viewpoint of light degradable, aliphatic or Aromatic carboxy ions and borate anions are preferred.

The addition amount of the base generator (E) in the active energy ray-curable composition of the present invention is preferably 0.001 based on the weight of the active energy ray-curable composition from the viewpoint of the effect of suppressing oxygen inhibition. -30% by weight, more preferably 0.05-25% by weight, particularly preferably 0.1-20% by weight.
The weight ratio {weight of (A) / weight of (E)} between the compound (A) and the base generator (E) in the active energy ray-curable composition is 0.01 / 1-10 / 1 is preferable, More preferably, it is 0.1 / 1-5 / 1.

  If necessary, an organic solvent, a sensitizer, an adhesion-imparting agent (such as a silane coupling agent), a leveling agent, and a polymerization inhibitor may be added to the active energy ray-curable composition of the present invention.

Organic solvents include glycol ethers (ethylene glycol monoalkyl ether and propylene glycol monoalkyl ether, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), esters (ethyl acetate, butyl acetate, ethylene glycol alkyl ether acetate, and the like). Propylene glycol alkyl ether acetate etc.), aromatic hydrocarbons (toluene, xylene, mesitylene and limonene etc.), alcohols (methanol, ethanol, normal propanol, isopropanol, butanol, geraniol, linalool and citronellol etc.) and ethers (tetrahydrofuran and 1, 8-cineole etc.). These may be used alone or in combination of two or more.
The addition amount of the organic solvent is preferably 0 to 400% by weight, more preferably 3 to 350% by weight, and particularly preferably 5 to 300% by weight with respect to the weight of the active energy ray-curable composition.

Examples of the sensitizer include ketocoumarin, fluorene, thioxanthone, anthraquinone, naphthiazoline, biacetyl, benzyl and derivatives thereof, perylene, and substituted anthracene. The addition amount of the sensitizer is preferably 0 to 100% by weight, more preferably 1 to 95% by weight, and particularly preferably 5 to 90% by weight with respect to the weight of the active energy ray-curable composition.

  Adhesion imparting agents include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, urea propyltri Examples include ethoxysilane, tris (acetylacetonate) aluminum, and acetylacetate aluminum diisopropylate. The addition amount of the adhesion-imparting agent is preferably 0 to 100% by weight, more preferably 1 to 95% by weight, and particularly preferably 5 to 90% by weight with respect to the weight of the active energy ray-curable composition.

  Examples of the leveling agent include fluorine-based leveling agents (perfluoroalkylethylene oxide adducts and the like) and silicone-based leveling agents (amino polyether-modified silicone, methoxy-modified silicone, polyether-modified silicone, and the like). The addition amount of the leveling agent is preferably 0 to 20% by weight, more preferably 0.05 to 10% by weight, particularly preferably from the viewpoint of the effect of addition and transparency with respect to the weight of the active energy ray-curable composition. 0.1 to 5% by weight.

  Examples of the polymerization inhibitor include hydroquinone and methyl ether hydroquinone. The addition amount of the polymerization inhibitor is preferably 0 to 2% by weight, more preferably 0 to 0.5% by weight, based on the weight of the active energy ray-curable composition.

  The active energy ray-curable composition of the present invention further comprises inorganic fine particles, a dispersant, an antifoaming agent, a thixotropy imparting agent, a slip agent, a flame retardant, an antistatic agent, an antioxidant, and an ultraviolet absorber according to the purpose of use. Known additives that can be added to active energy ray-curable compositions, photosensitive compositions, thermosetting compositions, paints, and the like can be added. Specific examples include those described in known literatures (JP 2010-132895, JP 2009-030047, JP 2010-222554, 2008-116493, etc.) and the like.

  The active energy ray-curable composition of the present invention includes a compound (A) that generates thiol by at least one selected from the group consisting of an active energy ray, an acid and a base, a polymerizable compound (B), and active energy ray polymerization initiation. Agent (C), if necessary, at least one of an acid generator (D) that generates an acid by active energy rays and a base generator (E) that generates a base by active energy rays, and, if necessary, an organic solvent or other components Is obtained by mixing and stirring with a disperser or the like. Mixing stirring temperature is 10 to 40 degreeC normally, Preferably it is 20 to 30 degreeC.

  The active energy ray-curable composition of the present invention can be used for forming a negative resist pattern by further adding a polymer having a carboxyl group.

  As the polymer having a carboxyl group in the present invention, a known compound such as a cresol novolac-type acid-modified epoxy acrylate resin can be used. For example, CCR-1218H, CCR-1159H, CCR-1222H, CCR-1314H, PCR- 1191H, TCR-1335H, ZAR-2001H, and ZCR-1569H [all are all manufactured by Nippon Kayaku Co., Ltd.]. The addition amount of the polymer having a carboxyl group is preferably 0 to 200% by weight, more preferably 0 to 100% by weight, from the viewpoint of developability, with respect to the weight of the active energy ray-curable composition.

  The active energy ray-curable composition of the present invention can be used in UV curable inks by adding pigments conventionally used in paints and inks. The addition amount of the pigment is preferably 0 to 300% by weight, more preferably 0 to 200% by weight, from the viewpoint of concealability and curability with respect to the weight of the active energy ray-curable composition.

  Examples of the pigment include yellow lead, zinc yellow, bitumen, barium sulfate, cadmium red, titanium oxide, zinc white, bengara, alumina, calcium carbonate, ultramarine blue, carbon black, graphite, and titanium black.

In the active energy ray-curable composition of the present invention, when a pigment is used, a pigment dispersant can be added in order to improve the dispersibility and the storage stability of the active energy ray-curable composition.
Examples of the pigment dispersant include pigment dispersants manufactured by Big Chemie (Anti-Terra-U, Disperbyk-101, 103, 106, 110, 161, 162, 164, 166, 167, 168, 170, 174, 182, 184 and 2020). Etc.), Ajinomoto Fine Techno Co., Ltd. pigment dispersants (Ajisper PB711, PB821, PB814, PN411, PA111, etc.), Lubrizol Corporation pigment dispersants (Solspers 5000, 12000, 32000, 33000, 39000, etc.). These pigment dispersants may be used alone or in combination of two or more. The addition amount of the pigment dispersant is preferably 0 to 20% by weight, more preferably 0 to 10% by weight, from the viewpoint of concealability and curability, with respect to the weight of the active energy ray-curable composition.

Examples of the method for applying the active energy ray-curable composition of the present invention to a substrate include known coating methods such as spin coating, roll coating, and spray coating, and lithographic printing, carton printing, metal printing, offset printing, screen printing, and the like. A known printing method such as gravure printing can be applied. In addition, ink-jet coating that continuously discharges fine droplets can also be applied.
The coating film thickness is preferably 0.5 to 300 μm as the film thickness after curing and drying, and from the viewpoint of drying property and curability, the more preferable upper limit is 250 μm, and wear resistance, solvent resistance, and stain resistance. In view of the above, a more preferable lower limit is 1 μm.

  When the active energy ray-curable composition of the present invention is used after being diluted with an organic solvent, it is preferably dried after coating. Examples of the drying method include hot air drying (such as a dryer). The drying temperature is preferably 10 to 200 ° C., more preferably 150 ° C. from the viewpoint of the smoothness and appearance of the coating film, and more preferably 30 ° C. from the viewpoint of the drying speed.

Examples of active energy rays in the present invention include actinic rays and electron beams.
As an energy source for curing the active energy ray-curable composition of the present invention by actinic ray irradiation, in addition to a commonly used high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a high-power metal halide lamp, and the like (UV・ Latest trends in EB curing technology, edited by Radtech Research Association, CM Publishing, 138 pages, 2006) can be used. Moreover, the irradiation apparatus using an LED light source can also be used conveniently.

As an energy source for curing the active energy ray-curable composition of the present invention by electron beam irradiation, a commonly used electron beam irradiation device can be used.
The irradiation amount (Mrad) of the electron beam is preferably 0.5 to 20, preferably 1 from the viewpoint of curability of the active energy ray-curable composition, flexibility of the cured product, and prevention of damage to the cured film and the substrate. ~ 15.

An active energy ray-curable composition for the purpose of diffusing the acid and / or base generated from the acid generator (D) and / or base generator (E) during and / or after irradiation with actinic rays or electron beams. The temperature may be 30 ° C to 200 ° C, more preferably 35 ° C to 150 ° C, and still more preferably 40 ° C to 120 ° C.

EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to these. Hereinafter, unless otherwise specified, “%” means “% by weight” and “part” means “part by weight”.
Examples 5 to 6, 17, 29 to 30, 40, and 44 are reference examples.

Production Example 1
[Synthesis of Compound (A1-1) {Compound Represented by Chemical Formula (34)} Generating Thiol]

  A flask equipped with a thermometer and a stirrer was charged with 177 parts of thiocyanuric acid, 100 parts of triethylamine, and 500 parts of acetone, and 644 parts of 9- (methyl chloride) fluorene was kept in an ice bath while keeping the liquid temperature at 20 ° C. After dropwise addition, the temperature was returned to room temperature (about 25 ° C.), and further stirred for 2 hours to obtain a reaction solution. After 500 parts of ethyl acetate and 500 parts of 5% NaOH aqueous solution were added to wash the organic layer, the aqueous layer was removed by a liquid separation operation, and the organic layer was washed with 130 parts of water three times. Then, the organic layer was dried over anhydrous sodium sulfate, and then ethyl acetate was distilled off under reduced pressure to obtain 604 parts of (A1-1) as a yellow solid (yield 85%).

Production Example 2
[Synthesis of Compound (A1-2) {Compound Represented by Chemical Formula (35)} Generating Thiol]

  Production Example 1 except that “177 parts of thiocyanuric acid” is changed to “101 parts of 3-mercapto-1,2,4-triazole” and “644 parts of 9- (methyl chloride) fluorene” is changed to “127 parts of benzyl chloride”. In the same manner, 182 parts of (A1-2) was obtained as a yellow solid (yield 95%).

Production Example 3
[Synthesis of Compound (A2-1) that Generates Thiol {Compound Represented by Chemical Formula (36)}]

  A light yellow solid was prepared in the same manner as in Production Example 1 except that “177 parts of thiocyanuric acid” was changed to “76 parts of thiourea” and “644 parts of 9- (methyl chloride) fluorene” was changed to “79 parts of acetyl chloride” ( A2-1) 109 parts were obtained (yield 92%).

Production Example 4
[Synthesis of Compound (A2-2) {Compound Represented by Chemical Formula (37)} Generating Thiol]

  A yellow solid in the same manner as in Production Example 1 except that “177 parts of thiocyanuric acid” is changed to “150 parts of 2-mercaptobenzimidazole” and “644 parts of 9- (methyl chloride) fluorene” is changed to “141 parts of benzoyl chloride”. As a result, 240 parts of (A2-2) were obtained (yield 95%).

Production Example 5
[Synthesis of Compound Generating Thiol (A2-3) {Compound Represented by Chemical Formula (38)}]

A yellow solid was prepared in the same manner as in Production Example 1 except that “177 parts of thiocyanuric acid” was changed to “112 parts of 2-mercaptopyrimidine” and “644 parts of 9- (methyl chloride) fluorene” was changed to “105 parts of vinylpyridine”. 213 parts of (A2-3) were obtained (yield 98%).

Production Example 6
[Synthesis of Compound (A2-4) {Compound Represented by Chemical Formula (39)} Generating Thiol]

  Other than changing “177 parts of thiocyanuric acid” to “140 parts of 4,6-dimethyl-2-mercaptopyrimidine” and “644 parts of 9- (methyl chloride) fluorene” to “218 parts of di-tert-butyl dicarbonate”. Produced 240 parts of (A2-4) as a yellow solid in the same manner as in Production Example 1 (yield 100%).

Production Example 7
[Synthesis of Compound (A3-1) {Compound Represented by Chemical Formula (15)} Generating Thiol]

  A flask equipped with a thermometer and a stirrer was charged with 150 parts of 2-mercaptobenzimidazole and 500 parts of hydrogen peroxide, and the reaction liquid was stirred for 2 hours while keeping the liquid temperature at 20 ° C. or lower in an ice bath. Obtained. After 500 parts of ethyl acetate and 500 parts of 5% NaOH aqueous solution were added to wash the organic layer, the aqueous layer was removed by a liquid separation operation, and the organic layer was washed with 130 parts of water three times. Next, after drying the organic layer with anhydrous sodium sulfate, ethyl acetate was distilled off under reduced pressure to obtain 268 parts of (A3-1) as a yellow solid (yield 90%).

Production Example 8
[Synthesis of Compound (A3-2) {Compound Having Two or More Structural Units Represented by Chemical Formula (18)} Having a Crosslinked Structure that Generates Thiol}

  170 parts of (A3-2) was obtained as a yellow solid in the same manner as in Production Example 7 except that “150 parts of 2-mercaptobenzimidazole” was changed to “177 parts of thiocyanuric acid” (yield 98%).

Production Example 9
[Synthesis of Compound (A3-3) {Compound Represented by Chemical Formula (40)} Generating Thiol]

  “177 parts of thiocyanuric acid” is changed to “116 parts of 5-mercapto-1-methyltetrazole”, “644 parts of 9- (methyl chloride) fluorene 214.69” is changed to “259 parts of chloroformic acid 9-fluorenylmethyl”. Except for changing, 311 parts of (A3-3) was obtained as a yellow solid in the same manner as in Production Example 1 (yield 92%).

Production Example 10
<Synthesis of ester (B1-1)>
In a flask equipped with a thermometer, an air / nitrogen mixed gas introduction tube, a stirrer, a water separator, and a reflux condenser, 210 parts of trimellitic acid, 365.4 parts of 2-hydroxyethyl acrylate, 70 parts of toluene, p- Charge 5 parts of toluenesulfonic acid and 2 parts of p-methoxyphenol, raise the temperature to 120 ° C while stirring under an air / nitrogen mixed gas stream, and continuously remove the generated water from the system using a water separator. The reaction was continued until the acid value of the reaction solution was 5 or less. After completion of the reaction, toluene was distilled off under reduced pressure to obtain trimellitic acid ester (B1-1) having an acryloyl group.

Production Example 11
<Synthesis of ester (B1-2)>
A flask equipped with a thermometer, air / nitrogen mixed gas introduction tube, stirrer, water separator and reflux condenser was charged with 254 parts pyromellitic acid, 344 parts vinyl acetate, 5 parts calcium hydroxide and 70 parts toluene. While stirring under an air / nitrogen mixed gas stream, the temperature is raised to 120 ° C., and the generated water is continuously removed from the system by a water separator, until the acid value of the reaction solution becomes 5 or less. Reacted. After cooling, it was washed with water three times, and toluene was distilled off under reduced pressure to obtain a pyromellitic acid ester (B1-2) having a vinyl group.

Production Example 12
<Synthesis of ester (B1-3)>
A flask equipped with a thermometer, an air / nitrogen mixed gas introduction tube, a stirrer, a water separator, and a reflux condenser was charged with 210 parts of trimellitic acid, 76.5 parts of allyl chloride, 70 parts of toluene and 101 parts of triethylamine. The mixture was stirred at 25 ° C. for 20 hours under an air / nitrogen mixed gas stream. After completion of the reaction, the precipitate was removed by filtration, and toluene was distilled off under reduced pressure to obtain trimellitic acid ester (B1-3) having an allyl group.

Production Example 13
<Synthesis of urethane acrylate (B31-1)>
In a flask equipped with a stirrer, an air / nitrogen mixed gas inlet tube, a condenser tube and a thermometer, 568 parts of butyl acetate, 168 parts of hexamethylene diisocyanate, 1.2 parts of p-methoxyphenol and 1.2 parts of dibutyltin diacetate The temperature was raised to 70 ° C. under a stream of air / nitrogen mixed gas, and while maintaining the temperature at 70 ± 10 ° C., “light acrylate PE3A” [manufactured by Kyoeisha Chemical Co., Ltd .: pentaerythritol diacrylate and pentane 795 parts of a mixture of erythritol triacrylate and pentaerythritol tetraacrylate (weight ratio is about 5:60:35)] was added dropwise over 1 hour. After completion of the dropping, the reaction was allowed to proceed at 70 ° C. for 3 hours under a stream of air / nitrogen mixed gas, and butyl acetate was distilled off under reduced pressure to obtain urethane acrylate (B31-1).

Production Example 14
<Synthesis of urethane acrylate (B31-2)>
Urethane acrylate (B31-2) was obtained in the same manner as in Production Example 11 except that “795 parts of“ light acrylate PE3A ”” was changed to “243.6 parts of 2-hydroxyethyl acrylate”.

Production Example 15
<Synthesis of urethane acrylate (B31-3)>
“Hexamethylene diisocyanate 168 parts” is changed to “4,4′-dicyclohexylmethane diisocyanate 262 parts”, “Light acrylate PE3A” 795 parts is changed to “Neomer DA-600” (manufactured by Sanyo Chemical Industries, Ltd .: Dipenta Urethane acrylate (B31-3) was obtained in the same manner as in Production Example 11, except that the mixture was changed to 831 parts). (Erithritol pentaacrylate and dipentaerythritol hexaacrylate mixture)

Production Example 16
<Synthesis of urethane acrylate (B31-4)>
The same purpose as in Production Example 11 except that “795 parts of“ light acrylate PE3A ”” is changed to “243.6 parts of 2-hydroxyethyl acrylate” and “168 parts of hexamethylene diisocyanate” is changed to “222 parts of isophorone diisocyanate”. A urethane acrylate (B31-4) was obtained.

Production Example 17
[Synthesis of Acid Generator (D-1) {Compound Represented by Chemical Formula (27)}]

  In a flask equipped with a thermometer and a stirrer, 6.5 parts of toluene, 8.1 parts of isopropylbenzene, 5.35 parts of potassium iodide and 20 parts of acetic anhydride were dissolved in 70 parts of acetic acid, and cooled to 10 ° C. While maintaining the temperature at 10 ± 2 ° C., a mixed solution of 12 parts of concentrated sulfuric acid and 15 parts of acetic acid was added dropwise over 1 hour. It heated up to 25 degreeC and stirred for 24 hours. Thereafter, 50 parts of diethyl ether was added to the reaction solution, washed with water three times, and diethyl ether was distilled off under reduced pressure. An aqueous solution in which 118 parts of potassium [trifluoro {tris (perfluoroethyl)} phosphate] was dissolved in 100 parts of water was added to the residue, followed by stirring at 25 ° C. for 20 hours. Thereafter, 500 parts of ethyl acetate was added to the reaction solution, washed three times with water, and ethyl acetate was distilled off under reduced pressure to obtain 5.0 parts of a light yellow solid acid generator (D-1).

Production Example 18
[Synthesis of base generator (E3-1) {compound represented by the following chemical formula (41)}]

(1) Synthesis of methylthioxanthone [intermediate (E3-1-1)]:
In a flask equipped with a thermometer and a stirrer, dithiosalicylic acid [manufactured by Wako Pure Chemical Industries, Ltd.] 10
A part was dissolved in 139 parts of sulfuric acid and stirred at room temperature (about 25 ° C.) for 1 hour, and then cooled in an ice bath to obtain a cooled solution. Next, 25 parts of toluene was dropped little by little while keeping the liquid temperature of this cooling solution at 20 ° C. or lower, and then returned to room temperature (about 25 ° C.) and further stirred for 2 hours to obtain a reaction solution. The reaction solution was added little by little to 815 parts of water, and the precipitated yellow solid was filtered off. This yellow solid is dissolved in 260 parts of dichloromethane, 150 parts of water is added, 6.7 parts of 24% KOH aqueous solution is further added to make the aqueous layer alkaline, and the mixture is stirred for 1 hour, and then the aqueous layer is removed by a liquid separation operation. The organic layer was washed 3 times with 130 parts of water. Then, the organic layer was dried over anhydrous sodium sulfate, and then the organic solvent was distilled off under reduced pressure to obtain 8.7 parts of intermediate (E3-1-1) (yellow solid). The intermediate (E3-1-1) is a mixture of 2-methylthioxanthone and 3-methylthioxanthone.

(2) Synthesis of 2-bromomethylthioxanthone [intermediate (E3-1-2)]:
In a flask equipped with a thermometer, a stirrer, a water separator, and a reflux condenser, 2.1 parts of the intermediate (E3-1-1) was dissolved in 120 parts of cyclohexane, and N-bromosuccinimide [Wako Pure Chemical Industries, Ltd.] [Industrial Co., Ltd.] 8.3 parts and benzoyl peroxide [Wako Pure Chemical Industries, Ltd.] 0.1 parts were added and reacted for 4 hours under reflux (3-methylthioxanthone does not react). The solvent (cyclohexane) was distilled off, 50 parts of chloroform was added thereto, and the residue was redissolved to obtain a chloroform solution. The chloroform solution was washed with 30 parts of water three times, and the aqueous layer was removed by a liquid separation operation. Then, the organic solvent was distilled off under reduced pressure to obtain 1.7 parts of a brown solid. This was recrystallized from ethyl acetate (3-methylthioxanthone was removed here) to obtain 1.5 parts of intermediate (E3-1-2) (yellow solid).

(3) 8- (9-oxo-9H-thioxanthen-2-yl) methyl-1,8-diazabicyclo [5.4.0] -7-undecenium bromide [intermediate (E3-1-3) ]:
In a flask equipped with a thermometer and a stirrer, 1.0 part of the intermediate (E3-1-2) (2-bromomethylthioxanthone) was dissolved in 85 g of dichloromethane, and 1,8-diazabicyclo [5.4. 0] -7-Undecene ["DBU" manufactured by San Apro Co., Ltd.] was added dropwise (heated after dropping), and stirred at room temperature (about 25 ° C) for 1 hour, and the organic solvent was distilled off under reduced pressure. As a result, 2.2 parts of a white solid was obtained. This white solid was recrystallized with a tetrahydrofuran / dichloromethane mixed solution to obtain 1.0 part of an intermediate (E3-1-3) (white solid).

(4) Synthesis of base generator (E3-1):
In a flask equipped with a thermometer and a stirrer, 0.8 parts of sodium tetraphenylborate salt [manufactured by Nacalai Tesque Co., Ltd.] was dissolved in 17 parts of water. -3) A solution in which 1.0 part was dissolved was added dropwise little by little, followed by stirring at room temperature (about 25 ° C.) for 1 hour, the aqueous layer was removed by a liquid separation operation, and the organic layer was removed 3 times with 30 parts of water. Washed. The organic solvent was distilled off under reduced pressure to obtain a yellow solid. This yellow solid was recrystallized with an acetonitrile / ether mixed solution to obtain 1.3 parts of a base generator (E3-1) (light yellowish white powder).

Example 1 [active energy ray-curable composition for hard coat; generation of thiol by acid generator]
1 part of compound (A2-4) generating thiol, 14 parts of ester (B1-3), 63 parts of urethane acrylate (B31-1), 15 parts of urethane acrylate (B31-2), 2,4,6-trimethylbenzoyl Diphenylphosphine oxide [BASF Japan Co., Ltd. “LUCILIN TPO”] (C-1) 5 parts, acid generator (D-1) 1 part, and aminopolyether-modified silicone [manufactured by Shin-Etsu Chemical Co., Ltd.] [KF-889]] 1 part was blended in a lump and uniformly mixed and stirred with a disperser to obtain an active energy ray-curable composition (Q-1) of the present invention.

Examples 2-24
Like Example 1, it mix | blends with the mixing | blending ratio of Table 1 and 2 at once, mixes and stirs uniformly with a disperser, and active energy ray hardening-type composition (Q-2)-(Q-24) for hard-coats. It was created.

Comparative Example 1 [active energy ray-curable composition for hard coat; when it does not contain compound (A) that generates thiol]
In the same manner as in Example 1, they were blended together at the blending ratios shown in Table 2, and uniformly mixed and stirred with a disperser to obtain an active energy ray-curable composition for hard coat (Q′-1) for comparison.

Comparative Example 2 [active energy ray-curable composition for hard coat; not containing compound (A) that generates thiol but containing thiol compound]
In the same manner as in Example 1, they were blended together at the blending ratios shown in Table 2, and uniformly mixed and stirred with a disperser to obtain an active energy ray-curable composition for hard coat (Q′-2) for comparison.

[Performance evaluation of composition before curing and coating film after curing]
Active energy ray-curable compositions for hard coats (Q-1) to (Q-24) and (Q'-1) to (Q'-2) obtained in Examples 1 to 24 and Comparative Examples 1 and 2 Is applied to a 100 μm-thick PET (polyethylene terephthalate) film [Cosmo Shine A4300 manufactured by Toyobo Co., Ltd.] using an applicator so that the film thickness is 20 μm or 1 μm. Or it exposed using the belt conveyor type | mold UV irradiation apparatus (Eye Graphics Co., Ltd. "ECS-151U") in nitrogen atmosphere.
Pencil hardness, adhesion, transmittance, and haze (transparency) were evaluated using a coating film exposed to 150 mJ / cm 2 in an air atmosphere.
Tables 1 and 2 show the results of performance evaluation of the cured coating film by the following method.

[Performance evaluation method]
(1) Storage stability About composition (Q-1)-(Q-24) and (Q'-1)-(Q'-2) before hardening, immediately after compounding and for 3 months (25 degreeC, humidity 65) %) The viscosity (25 ° C.) at the time of storage was measured and evaluated by applying the following equation. The viscosity was measured using a viscosity measuring apparatus [“Viscolite B type” manufactured by FUNGILAB Co., Ltd.]. In Table 1 and 2, it shows that storage stability is so high that the numerical value of the viscosity ratio immediately after a mixing | blending and after storage is close to 1.
Viscosity ratio immediately after compounding and after storage = (viscosity after three months storage / viscosity immediately after compounding)

(2) Curability The surface of the coating film is not tacky by scratching the surface of the coating film with fingers and nails against the coating film cured in the atmosphere and the coating film cured in a nitrogen atmosphere. The amount of exposure at a point where no damage was found was measured.

(3) Pencil hardness Pencil hardness was measured based on JIS K-5400 with respect to the coating film cured in an air atmosphere.

(4) Adhesiveness The adhesiveness was evaluated by a cross cellophane tape peeling test based on JIS K-5400 with respect to the coating film cured in the air atmosphere.

(5) Transmittance and haze (transparency)
In accordance with JIS-K7105, the transmittance and haze are measured using a total light transmittance measuring device [trade name “haze-garddual” manufactured by BYK Gardner Co., Ltd.] in accordance with JIS-K7105. did. In both cases, the unit is%.

表１及び２中、各成分は下記の通りである。
Ａ１−１：製造例１で得た化学式（３４）で表される化合物であって、活性エネルギー線
によりチオールを発生する化合物
Ａ１−２：製造例２で得た化学式（３５）で表される化合物であって、活性エネルギー線によりチオールを発生する化合物
Ａ２−１：製造例３で得た化学式（３６）で表される化合物であって、酸によりチオールを発生する化合物
Ａ２−２：製造例４で得た化学式（３７）で表される化合物であって、酸によりチオールを発生する化合物
Ａ２−３：製造例５で得た化学式（３８）で表される化合物であって、酸によりチオールを発生する化合物
Ａ２−４：製造例６で得た化学式（３９）で表される化合物であって、酸によりチオールを発生する化合物
Ａ３−１：製造例７で得た化学式（１５）で表される化合物であって、塩基によりチオールを発生する化合物
Ａ３−２：製造例８で得た化学式（１８）で表される化合物であって、塩基によりチオールを発生する化合物
Ａ３−３：製造例９で得た化学式（４０）で表される化合物であって、塩基によりチオールを発生する化合物
Ｂ１−１：製造例１０で得たエステル化合物
Ｂ１−２：製造例１１で得たエステル化合物
Ｂ１−３：製造例１２で得たエステル化合物
Ｂ３１−１：製造例１３で得たウレタンアクリレート化合物
Ｂ３１−２：製造例１４で得たウレタンアクリレート化合物
Ｂ３１−３：製造例１５で得たウレタンアクリレート化合物
Ｂ３１−４：製造例１６で得たウレタンアクリレート化合物
Ｂ３−５：「ネオマーＤＡ−６００」（三洋化成工業（株）製：ジペンタエリスリトールペンタアクリレートとジペンタエリスリトールヘキサアクリレートの混合物）
開始剤（Ｃ−１）：２，４，６−トリメチルベンゾイルジフェニルホスフィンオキサイド［ＢＡＳＦジャパン（株）製「ＬＵＣＩＬＩＮ ＴＰＯ」］
Ｄ−１：製造例１７で得た化学式（２７）で表される酸発生剤
Ｅ３−１：製造例１８で得た化学式（４１）で表される塩基発生剤
レベリング剤：アミノポリエーテル変性シリコーン［信越化学（株）製「ＫＦ−８８９」］
チオール化合物：ペンタエリスリトールテトラキス（３−メルカプトブチレート）（昭和電工（株）製、「カレンズＭＴ ＰＥ１」）

In Tables 1 and 2, each component is as follows.
A1-1: Compound represented by the chemical formula (34) obtained in Production Example 1 and generating thiol by active energy rays A1-2: Represented by the chemical formula (35) obtained in Production Example 2 Compound A2-1 that generates thiol by active energy ray: Compound represented by chemical formula (36) obtained in Preparation Example 3, and compound A2-2 that generates thiol by acid: Preparation Example The compound represented by the chemical formula (37) obtained in 4 and generating a thiol by an acid A2-3: the compound represented by the chemical formula (38) obtained in Production Example 5 and a thiol by an acid A2-4: A compound represented by the chemical formula (39) obtained in Production Example 6 and a compound A3-1 that produces a thiol by an acid: represented by the chemical formula (15) obtained in Production Example 7. Is a compound Compound A3-2 that generates thiol with base: Compound represented by chemical formula (18) obtained in Production Example 8 and compound that generates thiol with base A3-3: Chemical formula obtained in Production Example 9 (40 Compound B1-1 that generates thiol with a base: ester compound B1-2 obtained in Production Example 10: ester compound B1-3 obtained in Production Example 11: obtained in Production Example 12 Ester compound B31-1: urethane acrylate compound B31-2 obtained in Production Example 13: urethane acrylate compound B31-3 obtained in Production Example 14: urethane acrylate compound B31-4 obtained in Production Example 15: in Production Example 16 Obtained urethane acrylate compound B3-5: “Neomer DA-600” (manufactured by Sanyo Chemical Industries, Ltd .: dipentaerythritol pentaacrylate) Mixture of dipentaerythritol hexaacrylate)
Initiator (C-1): 2,4,6-trimethylbenzoyldiphenylphosphine oxide [“LUCILIN TPO” manufactured by BASF Japan Ltd.]
D-1: Acid generator E3-1 represented by chemical formula (27) obtained in Production Example 17: Base generator leveling agent represented by chemical formula (41) obtained in Production Example 18: aminopolyether-modified silicone ["KF-889" manufactured by Shin-Etsu Chemical Co., Ltd.]
Thiol compound: Pentaerythritol tetrakis (3-mercaptobutyrate) (manufactured by Showa Denko KK, “Karenz MT PE1”)

  From Tables 1 and 2, the active energy ray-curable compositions (Q-1) to (Q-24) for hard coat of the present invention are comparative compositions (Q ′) with respect to curability at film thicknesses of 20 μm and 1 μm. -1) to (Q'-2) are hardened at a lower exposure amount, and it can be seen that the curability is high. In addition, (Q-1) to (Q-24) are hardly changed between the curability in the air atmosphere and the curability in the nitrogen atmosphere, and it is understood that the effect of suppressing oxygen inhibition is high. . Moreover, (Q-1)-(Q-24) are excellent in pencil hardness, adhesiveness, and transparency, and it turns out that it is excellent as an active energy ray hardening-type composition for hard-coats. Furthermore, (Q-1) to (Q-24) have a viscosity ratio of 1 immediately after compounding and after storage, and the viscosity hardly changes after storage and after storage, and are known oxygen inhibition inhibitors. It can be seen that the storage stability is superior to (Q′-2) using the thiol compound.

Examples 25-38 [active energy ray-curable composition for negative resist]
Like Example 1, it mix | blends with the mixing | blending ratio of Table 3 at once, mixes and stirs uniformly with a disperser, and active energy ray hardening-type composition (Q-25)-(Q-38) for negative resists. Created.

Comparative Example 3 [Active Energy Ray-Curable Composition for Negative Resist; When Compound (A) That Generates Thiol Generation is not Contained]
As in Example 1, the active energy ray-curable composition for negative resist (Q′-3) was prepared by batch blending at the blending ratio shown in Table 3 and uniformly mixing and stirring with a disperser.

Comparative Example 4 [Active Energy Ray-Curable Composition for Negative Resist; When Compound (A) That Generates Thiol Generation Is Not Contained, and Contains a Thiol Compound]
In the same manner as in Example 1, they were blended together at the blending ratios shown in Table 3, and uniformly mixed and stirred with a disperser to obtain an active energy ray-curable composition for hard coat (Q′-4) for comparison.
[Performance evaluation of composition before curing and coating film after curing]
The active energy ray-curable compositions for negative resists obtained in Examples 25 to 38 and Comparative Examples 3 to 4 were subjected to surface treatment and a PET (polyethylene terephthalate) film having a thickness of 100 [Cosmo manufactured by Toyobo Co., Ltd. It was apply | coated to Shine A4300] so that it might become a film thickness of 20 micrometers or 10 micrometers using an applicator. Subsequently, under reduced pressure (30 mmHg), pre-baking was performed at 80 ° C. for 3 minutes to dry the solvent. Next, after setting a linear mask having a width of 15 μm, exposure was performed in an air atmosphere or a nitrogen atmosphere. For the exposure, a belt conveyor type UV irradiation device (“Egraphics Co., Ltd.“ ECS-151U ”) was used.

[Performance evaluation method]
(1) Storage stability About composition (Q-25)-(Q-38) and (Q'-3)-(Q'-4) before hardening immediately after compounding and for 3 months (25 degreeC, humidity 65) %) The viscosity (25 ° C.) at the time of storage was measured and evaluated by applying the following equation. The viscosity was measured using a viscosity measuring apparatus [“Viscolite B type” manufactured by FUNGILAB Co., Ltd.]. In Table 3, it shows that storage stability is so high that the numerical value of the viscosity ratio immediately after a mixing | blending and after storage is close to 1.
Viscosity ratio immediately after compounding and after storage = (viscosity after three months storage / viscosity immediately after compounding)

(2) Curability The surface of the coating film is not tacky by scratching the surface of the coating film with fingers and nails against the coating film cured in the atmosphere and the coating film cured in a nitrogen atmosphere. The amount of exposure at a point where no damage was found was measured.

[Evaluation of coating film developability]
With respect to developability, after exposure to 150 mJ / cm 2 in an air atmosphere, the exposed specimen was immersed in a 1% NaCO 3 aqueous solution for 100 seconds and then subjected to alkali development by spraying with ion exchange water. Subsequently, post-baking was performed under reduced pressure (30 mmHg) at 80 ° C. for 3 minutes.
Table 3 shows the results obtained by visually observing the developability of the coating film after development with an optical microscope and evaluating the patterning area (%).

In Table 3, each component (A)-(E), a leveling agent, and a thiol compound (Karenz MTP)
E1) is the same as Tables 1 and 2. Moreover, the following were used as other components. Polymer having carboxyl group: CCR-1314H [Nippon Kayaku Co., Ltd.]
Organic solvent: ethylene glycol monomethyl ether [manufactured by Tokyo Chemical Industry Co., Ltd.]

  From Table 3, the active energy ray-curable compositions (Q-25) to (Q-38) for negative resists of the present invention are comparative compositions (Q′−) with respect to curability at film thicknesses of 20 μm and 10 μm. 3) to (Q′-4) are cured at a lower exposure amount, and it can be seen that the curability is high. In addition, (Q-25) to (Q-38) are hardly changed between the curability in the air atmosphere and the curability in the nitrogen atmosphere, and it is understood that the effect of suppressing oxygen inhibition is high. . Moreover, (Q-25)-(Q-38) is excellent also in developability, and it turns out that it is excellent as an active energy ray hardening-type composition for negative resists. Furthermore, it can be seen that (Q-25) to (Q-38) are superior in storage stability to (Q′-4) using a thiol compound which is a known oxygen inhibition inhibitor.

Examples 39 to 52 [active energy ray-curable composition for UV ink]
[Preparation of ink composition]
<Preparation of high concentration pigment dispersion>
42 parts of titanium oxide [Ishihara Sangyo "Typaque R-930"], pigment dispersant [Lubrisol "Solspers 32000"] 5 parts, N, N-diethylacrylamide [Kojin Co., Ltd. "DEAA"] A mixture of 31 parts of (B2-1) and 22 parts of the compound that generates thiol (A1-1) was kneaded for 3 hours using a ball mill to prepare a pigment dispersant solution having a pigment concentration of 42%.
<Preparation of ink composition containing pigment>
In the same manner as in Example 1, blended together at the blending ratios shown in Table 4 and uniformly mixed and stirred with a disperser to prepare active energy ray-curable compositions (Q-39) to (Q-52) for UV ink. did.

Comparative Example 5 [Active energy ray-curable composition for UV ink]
In the same manner as in Example 1, they were mixed at the mixing ratio shown in Table 4 and mixed and stirred uniformly with a disperser to prepare an active energy ray-curable composition for UV ink (Q′-5).

Comparative Example 6 [Active Energy Ray-Curable Composition for Negative Resist; When Compound (A) That Generates Thiol Generation Is Not Contained, and Contains a Thiol Compound]
In the same manner as in Example 1, they were blended together at the blending ratios shown in Table 4, and uniformly mixed and stirred with a disperser to obtain an active energy ray-curable composition for hard coat (Q′-6) for comparison.

[Performance evaluation of composition before curing and coating film after curing]
The active energy ray-curable compositions for UV inks obtained in Examples 39 to 52 and Comparative Examples 5 to 6 were subjected to surface treatment and a 100 μm-thick PET (polyethylene terephthalate) film [Cosmo Shine manufactured by Toyobo Co., Ltd. A4300] was applied using an applicator to a film thickness of 20 μm or 10 μm. About exposure, it implemented in the air atmosphere or nitrogen atmosphere using the following irradiation apparatus. For the exposure, a belt conveyor type UV irradiation device (“Egraphics Co., Ltd.“ ECS-151U ”) was used. The exposure amount was 80 mJ / cm @ 2 at 365 nm.

[Performance evaluation method]
(1) Storage stability About composition (Q-39)-(Q-52) and (Q'-5)-(Q'-6) before hardening, immediately after compounding and for 3 months (25 degreeC, humidity 65) %) The viscosity (25 ° C.) at the time of storage was measured and evaluated by applying the following equation. The viscosity was measured using a viscosity measuring apparatus [“Viscolite B type” manufactured by FUNGILAB Co., Ltd.]. In Table 4, it shows that storage stability is so high that the numerical value of the viscosity ratio immediately after a mixing | blending and after storage is close to 1.
Viscosity ratio immediately after compounding and after storage = (viscosity after three months storage / viscosity immediately after compounding)

(2) Curability The curability immediately after light irradiation of the coating film cured in the air atmosphere and the coating film cured in the nitrogen atmosphere was evaluated according to the following evaluation criteria by scratching with finger touch and nails. The results are shown in Table 4.
A: There is no tack on the surface and the nail is not damaged.
○: There is no tack on the surface and the nail is not scratched, but a mark remains.
Δ: There is no tack on the surface, but the nail is damaged.
X: There is a tack on the surface, and the nail is damaged.

In Table 4, each component (A) to (E), a leveling agent and a thiol compound (Karenz MTP)
E1) is the same as Tables 1 and 2. Moreover, the following were used as other components. Pigment dispersion: Pigment dispersion obtained in “Preparation of high concentration pigment dispersion”

  From Table 4, the active energy ray-curable compositions (Q-39) to (Q-52) for UV inks according to the present invention have a curability at a film thickness of 20 μm and 10 μm, and a comparative composition (Q ′ -5) and (Q'-6) are hardened at a lower exposure amount, and it is understood that the curability is high and suitable for UV ink. In addition, (Q-39) to (Q-52) are hardly changed between the curability in the air atmosphere and the curability in the nitrogen atmosphere, and it can be seen that the effect of suppressing oxygen inhibition is high. . Furthermore, it can be seen that (Q-39) to (Q-52) are superior in storage stability to (Q'-6) using a known thiol compound.

  The active energy ray curable composition of the present invention can be applied to various fields such as hard coat (hard coat of resin molded product or hard coat of display), resist, UV curable ink, etc. Since it has excellent curability and high storage stability, it is useful for resin molded product hard coat applications and display hard coat applications (for cathode ray tubes, liquid crystal displays, plasma displays, electroluminescence displays, or touch panels). The cured film obtained by curing the active energy ray-curable composition of the present invention is also useful as a protective film for a polarizing plate. In addition, because it has excellent developability of the resist pattern of the cured film, it is also useful for resists, and can be cured with a thick film at a high colorant concentration even with a small amount of energy. Therefore, UV curable ink (UV printing ink and UV inkjet printing) Ink etc. are also useful.

Claims (20)

Active energy ray curable type containing active energy ray, compound (A) which generates thiol by at least one selected from the group consisting of acid and base, polymerizable compound (B) and active energy ray polymerization initiator (C) It is a composition, and (A) is at least one selected from a compound (A2) that generates a thiol with an acid and a compound (A3) that generates a thiol with a base,
When (A) is a compound (A2) that generates a thiol by an acid, it further contains an acid generator (D) that generates an acid by active energy rays,
When (A) is a compound (A3) that generates a thiol with a base, the active energy ray-curable composition further contains a base generator (E) that generates a base with active energy rays. The active energy ray-curable composition according to claim 1, wherein the compound (A) is at least one compound selected from the group consisting of compounds represented by the following general formulas (1) to (4).

[Wherein, R ^{1 to} R ³ and R ^{5 to} R ⁸ are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms, and R ⁴ is a divalent hydrocarbon group having 2 to 30 carbon atoms. It is a hydrocarbon group, X < ¹ > -X < ⁶ > is a monovalent substituent by which the coupling | bonding with the sulfur atom couple | bonded with these is cut | disconnected by at least 1 sort (s) chosen from the group which consists of an acid and a base. ] The substituents X ^{1 to} X ⁶ are each independently represented by a pyridylethylene group, a t-butoxycarbonyl group, a fluorenylmethoxycarbonyl group, an acetyl group, a benzoyl group, and the following general formulas (5) to (8). The active energy ray-curable composition according to claim 2, which is a substituent selected from the group consisting of:

[Wherein, R ^{9 to} R ¹¹ and R ^{13 to} R ¹⁶ are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms, and R ¹² is a divalent hydrocarbon group having 2 to 30 carbon atoms. * Is a hydrocarbon group, and * is a substituent represented by the general formulas (5) to (8) by at least one bond to which X ^{1 to} X ⁶ in the general formulas (1) to (4) is attached. Represents that it is bonded to the sulfur atom to which is bonded. ] The compound (A) is at least one selected from the group consisting of compounds represented by the following general formulas (9) to (17) and compounds having two or more structural units represented by the following chemical formula (18). The active energy ray hardening-type composition in any one of Claims 1-3.

[Wherein, X ^{7 to} X ¹³ are each independently a monovalent substituent selected from the group consisting of a pyridylethylene group, a t-butoxycarbonyl group, a fluorenylmethoxycarbonyl group, an acetyl group, and a benzoyl group. ] The polymerizable compound (B) is the following ester compound (B1), (meth) acrylamide compound (B2) having 3 to 35 carbon atoms, (meth) acrylate compound (B3) having 4 to 100 carbon atoms other than (B1), The active energy ray according to any one of claims 1 to 4, which is at least one selected from the group consisting of an aromatic vinyl compound (B4) having 6 to 35 carbon atoms and a vinyl ether compound (B5) having 3 to 20 carbon atoms. A curable composition.
Ester compound (B1): an ester having an ethylenically unsaturated bond-containing group (x) and not having a urethane group or a urea group, the group consisting of phthalic acid ester, trimellitic acid ester and pyromellitic acid ester At least one ester compound selected from the group consisting of: The active energy according to claim 5, wherein the polymerizable compound (B) contains an ester compound (B1), and (B1) is at least one compound represented by the following general formulas (19) to (21). Line curable composition.

[Wherein, R ^{14 to} R ²² are each independently a substituent represented by any one of the following general formulas (22) to (26). ]

[Wherein R ²³ , R ²⁵ and R ²⁷ are each independently a divalent aliphatic hydrocarbon group having 2 to 12 carbon atoms, and R ²⁴ , R ²⁶ and R ²⁸ are each independently a hydrogen atom or methyl. * Means that the substituent represented by the general formulas (22) to (26) is bonded to the oxygen atom of the oxycarbonyl group in the above general formulas (19) to (21) by the bond to which it is attached. Represents that ] The ethylenically unsaturated bond-containing group (x) of the ester compound (B1) is at least one substituent selected from the group consisting of a (meth) acryloyl group, a vinyl group, a 1-propenyl group, and an allyl group. Item 7. The active energy ray-curable composition according to Item 5 or 6. The polymerizable compound (B) contains the following (meth) acrylate compound (B31), and the content of (B31) in (B) is 0.1 to 100% by weight based on the weight of (B). Item 8. The active energy ray-curable composition according to any one of Items 5 to 7.
Methacrylate compound (B31): A (meth) acrylate compound (B3) having 4 to 100 carbon atoms other than the ester compound (B1), which has a urethane group and / or a urea group. The active hydrogen component (H) containing the (meth) acrylate (B31) having a urethane group and / or a urea group and a (meth) acrylate having a hydroxyl group and a (meth) acryloyl group in the molecule (I) And (I) are isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2 The active energy ray-curable composition according to claim 8, which is at least one isocyanate selected from the group consisting of 4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate and 1,5-naphthalene diisocyanate. Active energy ray polymerization initiator (C) is a polymerization initiator (C1) having an acylphosphine oxide skeleton, a polymerization initiator (C2) having an α-aminoacetophenone skeleton, a polymerization initiator (C3) having a benzyl ketal skeleton, A group consisting of a polymerization initiator (C4) having an α-hydroxyacetophenone skeleton, a polymerization initiator (C5) having a benzoin skeleton, a polymerization initiator (C6) having an oxime ester skeleton, and a polymerization initiator (C7) having a titanocene skeleton The active energy ray-curable composition according to any one of claims 1 to 9, which is at least one radical polymerization initiator selected from the above. The active energy ray-curable composition according to any one of claims 1 to 10, wherein the acid generator (D) that generates an acid by active energy rays is a sulfonium salt (D1) and / or an iodonium salt (D2). The active energy ray-curable composition according to claim 11, wherein the iodonium salt (D2) is a compound represented by the following chemical formula (27).

The base generator (E) that generates a base by active energy rays is at least one selected from the group consisting of a compound (E1) having an oxime skeleton, a quaternary ammonium salt (E2), and a quaternary amidine salt (E3). It is a base generator, The active energy ray hardening-type composition in any one of Claims 1-12. The base generator (E) which generates a base by active energy rays is a quaternary ammonium salt (E2) and a quaternary amidine salt (E3), which are compounds represented by the following general formulas (28) to (30). The active energy ray-curable composition according to claim 13.

[Wherein, R ^{29 to} R ⁵⁶ are each independently a hydrogen atom, a halogen atom, an acyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or 1 carbon atom. -20 alkylthio group, C1-C20 alkylsilyl group, nitro group, carboxyl group, hydroxyl group, mercapto group, amino group, cyano group, phenyl group, naphthyl group, group represented by the following general formula (31) And an atom or substituent selected from the group consisting of groups represented by the following general formula (32). Any one of R ^{29 to} R ³⁸ is a substituent represented by the following general formula (31) or the following general formula (32), and any one of R ^{39 to} R ⁴⁶ is the following general formula (31). or a substituent represented by the following general formula (32), one of R ⁴⁷ to R ⁵⁶ is a substituent represented by the following general formula (31) or the following general formula (32). ]

[Wherein, R ^{57 to} R ⁶⁰ are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R ^{61 to} R ⁶³ are each independently a group having 1 to 1 carbon atoms optionally substituted with a hydroxyl group. 20 is an alkyl group, (X ¹⁴ ) ⁻ and (X ¹⁵ ) ⁻ each represent an anion, a is an integer of 2 to 4, and * represents a compound represented by the general formula (31) depending on the bond to which it is attached. Or it represents that the substituent represented by (32) has couple | bonded with the carbon atom in the said general formula (28)-(30). ] The active energy ray-curable composition according to claim 13 or 14, wherein the quaternary amidine salt (E3) is a compound represented by the following general formula (33).

[Wherein (X ¹⁶ ) ⁻ represents an anion. ] Based on the weight of the active energy ray-curable composition, the content of the compound (A) is 0.001 to 30% by weight and the content of the polymerizable compound (B) is 10 to 99.948% by weight [however, The content of the ester compound (B1) is 0 to 80% by weight], the content of the active energy ray polymerization initiator (C) is 0.05 to 30% by weight, and an acid generator that generates an acid by active energy rays (D ) Is 0.001 to 30% by weight. The active energy ray-curable composition according to any one of claims 5 to 15. Based on the weight of the active energy ray-curable composition, the content of the compound (A) is 0.001 to 30% by weight and the content of the polymerizable compound (B) is 10 to 99.948% by weight [however, The content of the ester compound (B1) is 0 to 80% by weight], the content of the active energy ray polymerization initiator (C) is 0.05 to 30% by weight, and a base generator (E ) Is 0.001 to 30% by weight. The active energy ray-curable composition according to any one of claims 5 to 15. Based on the weight of the active energy ray-curable composition, the content of the compound (A) is 0.001 to 30% by weight and the content of the polymerizable compound (B) is 40 to 99.949% by weight [however, The activity according to any one of claims 5 to 15, wherein the content of the ester compound (B1) is 0 to 80% by weight] and the content of the active energy ray polymerization initiator (C) is 0.05 to 30% by weight. Energy ray curable composition. The active energy ray-curable composition according to claim 1, which is used for hard coating, resist, or UV curable ink. The active energy ray-curable composition according to any one of claims 1 to 19, which is used for a hard coat of a resin molded product or a hard coat of a display.