Photocurable resin composition

Abstract

Disclosed is a photocurable composition comprising (a) a radical-polymerizable monomer, (b) an alpha -ketocarbonyl compound and (c) a derivative of mercaptobenzimidazole, mercaptobenzothiazole or mercaptobenzoxazole or an aromatic amine nucleus-substituted with an electron-attractive group. This composition has a high photocuring speed at a temperature close to normal temperature and gives a cured product excellent in various physical properties. This composition is valuable as a dental adhesive or resin.

We claim: .[.1. A photocurable composition comprising (a) a radical-polymerizable monomer, (b) an α-ketocarbonyl compound and (c) an amine, wherein the amine (c) is at least one member selected from the group consisting of compounds represented by the following general formula: ##STR11## wherein X stands for >NR 2 , an oxygen atom or a sulfur atom, Y stands for a hydrogen atom, --SR 3  or a monovalent, divalent or tnvalent metal, R 1  stands for an alkyl group, an aryl group, an aralkyl group or a halogen atom, n is an integer of from 0 to 4 with the proviso that when n is 2 or larger, a plurality of groups R 1  may be the same or different, R 2  stands for a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, and R 3   stands for an alkyl group or an aryl group, or a group represented by the following general formula: ##STR12## wherein X, R 1  and n are as defined above, and substituted amines represented by the following general formula: ##STR13## wherein R 4  stands for a hydrogen atom or an alkyl group, R 5  stands for a hydrogen atom, an alkyl group, a hydroxyalkyl group of an aryl group, R 6  stands for a monovalent, electron-attractive atom or 
     
        organic group, and n is an integer of from 0 to 4..]. .[.2.  A composition as set forth in claim 1, wherein the amine (c) is 2-mercaptobenzothiazole, 2-mercaptomethylbenzothiazole, zinc (II) 2-mercaptobenzothiazole or zinc (II) 2-mercaptomethylbenzothiazole..]. .[.3. A composition as set forth in claim 1, wherein the amine (C) is a substituted aromatic amine represented by the following general formula: ##STR14## wherein R 4  stands for a hydrogen atom or an alkyl group, R 5  stands for a hydrogen atom, an alkyl group,, a hydroxyalkyl group or an aryl group, R 7  stands for a hydrogen atom, an alkyl group, a hydroxyl group, an alkoxyl group, a hydroxyalkyl group, an aryl group or a group --NR 8  R 9  in which R 8  and R 9  stand for a hydrogen atom 
     
     
        or an alkyl group, and n is an integer of from 0 to 4..]. .[.4.  A composition as set forth in claim 3, wherein the substituted aromatic amine is 4-dimethylaminobenzaldehyde, 4-dimethylaminobenzoic acid or methyl 4-dimethylaminobenzoate..]. .[.5. A composition as set forth in claim 1, wherein the amine (c) is a substituted aromatic amine in which R 6  is a cyano group..]. .[.6. A composition as set forth in claim 5, wherein the substituted aromatic amine is N,N-dimethyl-p-cyanoaniline or N,N-diethyl-p-cyanoaniline..]. .[.7. A composition as set forth in claim 1, wherein the radical-polymerizable monomer is a monomer having at least one acryloyl or methacryloyl group..]. .[.8. A composition as set forth in claim 1, wherein the radical-polymerizable monomer is a combination of (i) an ester monomer of an aliphatic alcohol or aliphatic polyol with methacrylic acid and (ii) at least one monomer selected from the group consisting of an ester monomer of a polyol having a bisphenol skeleton or dihydric phenol skeleton with methacrylic acid and a methacryloyloxyl 
     
     
        group-containing aromatic polycarboxylic acid or its anhydride..]. .[.9. A composition as set forth in claim 8, wherein the monomers (i) and (ii) are present at a (i)/(ii) weight ratio of from 5/95 to 95/5..]. .[.10. A composition as set forth in claim 1, wherein the α-ketocarbonyl compound (b) is an α-diketone..]. .[.11. A composition as set forth in claim 1, wherein the α-ketocarbonyl compound (b) is benzil or 
     
     
        camphorquinone..]. .[.12.  A composition as set forth in claim 1, wherein the α-ketocarbonyl compound (b) is present in an amount of 0.01 to 15 parts by weight per 100 parts by weight of the radical-polymerizable monomer (a) and the amine (c) is present in an amount of 0.01 to 15 parts by weight per 100 parts by weight of the radical-polymerizable monomer (a)..]. .[.13. A dental treatment material comprising a composition as set 
     
     
        forth in claim 1..]. .Iadd.14.  A visible ray curable composition for dental treatment comprising: (a) a radical-polymerizable monomer,   (b) an α-ketocarbonyl compound which is camphorquinone or diacetyl and   (c) an amine represented by the formula ##STR15## wherein R 4  and R 5  represent ethyl, propyl, butyl, pentyl or hexyl, R 7  represents hydroxy or alkoxy having 1 to 6 carbon atoms,   (a), (b) and (c) forming a visible ray curable dental composition.   
     
     
        .Iaddend. .Iadd.15.  The composition as set forth in claim 14, wherein radical-polymerizable monomer is a monomer having at least one acryloyl or 
     
     
        methacryloyl qroup. .Iaddend. .Iadd.16.  The composition as set forth in claim 14, wherein the radical-polymerizable monomer is a combination of (i) an ester monomer of an aliphatic alcohol or aliphatic polyol with methacrylic acid and (ii) at least one monomer selected from the group consisting of an ester monomer of a polyol having a bisphenol skeleton or dihydric phenol skeleton with methacrylic acid and a methacryloyloxyl group-containing aromatic polycarboxylic acid or its anhydride. .Iaddend. .Iadd.17. The composition as set forth in claim 16, wherein the monomers (i) and (ii) are present at a (i)/(ii) weight ratio of from 5/95 to 95/5. .Iaddend. .Iadd.18. The composition of claim 14, wherein the α-ketocarbonyl compound (b) is camphorquinone. .Iaddend. .Iadd.19. The composition of claim 14, wherein the α-ketocarbonyl compound (b) is diacetyl. .Iaddend. .Iadd.20. The composition as set forth in claim 14, wherein the α-ketocarbonyl compound (b) is present in an amount of 0.01 to 15 parts by weight per 100 parts by weight of the radical-polymerizable monomer (a) and the amine (c) is present in an amount of 0.01 to 15 parts by weight per 100 parts by weight of the radical-polymerizable monomer (a). .Iaddend. .Iadd.21. The composition of claim 14, which is diethylaminobenzoic acid or alkyl ester thereof. .Iaddend. .Iadd.22. The composition of claim 14, which is dipropylaminobenzoic acid or alkyl ester thereof. .Iaddend. .Iadd.23. A dental material comprising a composition as set forth in claim 14. .Iaddend.