Photopolymerizable composition

Claim 2

A photopolymerizable composition comprising, as essential components, (1) an addition polymerizable compound having at least one ethylenically unsaturated double bond, and (2) a photopolymerization initiator, said photopolymerization initiator comprising a combination of: (a) at least one aromatic carbonyl compound selected from the group consisting of benzanthrone, 1,2-benzanthraquinone, fluorenone and mixtures thereof, and (b) at least one p-dialkylamino aromatic carbonyl compound selected from the group consisting of compounds represented by the general formulae (I) through (V): ##STR34## wherein R 1 and R 2 , which may be the same or different, each represents an alkyl group; R 3 represents an alkyl group, an aryl group selected from the class consisting of a residue of a benzene ring, a residue of a condensed system of a benzene ring and a 5-membered unsaturated ring, and a residue formed by substituting on the ring forming carbon atoms of these residues one or more substituents selected from the class consisting of a halogen atom, a nitro group, an amino group, a substituted amino group, a cyano group, an alkyl group, a haloalkyl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, and acyloxy group and an alkoxysulfonyl group, an aralkyl group, an alkoxy group, an aryloxy group, or a monovalent residue of a 5-membered or 6 membered heterocyclic aromatic ring containing one or more of a nitrogen atom, an oxygen atom and a sulfur atom as heteroatoms; n represents a positive integer of 3 to 8; and X represents a substituent having a Hammett sigma constant in the range of -0.9 to +0.7.

Claim 3

The photopolymerizable composition of claim 1, wherein said p-dialkylamino aromatic carbonyl compound (b) is at least one compound selected from the group consisting of compounds represented by the general formulae (I) and (II).

Claim 4

The photopolymerizable composition of claim 1, wherein said aromatic carbonyl compound (a) is benzanthrone, 1,2-benzanthraquinone or a mixture thereof.

Claim 5

The photopolymerizable composition of claim 1, wherein said aromatic carbonyl compound (a) is benzanthrone, 1,2-benzanthraquinone or a mixture thereof; and said p-dialkylaminoaromatic carbonyl compound (b) is p-dimethylaminostyryl methyl ketone, p-dimethylaminostyryl ethyl ketone, p-dimethylaminostyryl propyl ketone, p-dimethylaminostyryl isopropyl ketone, ethyl p-dimethylaminocinnamate, p-dimethylaminostyryl 4-pyridyl ketone, p-dimethylamino-m'-chlorochalcone, p-dimethylamino-p'-bromochalcone, p-dimethylamino-p'-cyanochalcone, p-dimethylamino-p'-methoxychaclone, p-dimethylamino-p'-methylchalcone, p-dimethylamino-m'-methylchalcone, p-dimethylaminostyryl p-methylstyryl ketone, p-dimethylaminostyryl p-methoxystyryl ketone, p-dimethylaminostyryl p-cyanostyryl ketone, p-dimethylaminostyryl m-methylstyryl ketone or bis(p-dimethylaminostyryl) ketone.

Claim 6

The photopolymerizable composition of claim 1, wherein said at least one p-dialkylamino aromatic carbonyl compound is selected from the group consisting of p-dimethylaminostyryl methyl ketone, p-dimethylaminostyryl ethyl ketone, p-dimethylaminostyryl propyl ketone, p-dimethylaminostyryl butyl ketone, p-dimethylaminostyryl isobutyl ketone, p-dimethylaminostyryl tert-butyl ketone, p-dimethylaminostyryl cyclohexyl ketone, p-dimethylaminostyryl benzyl ketone, p-dimethylaminostyryl phenethyl ketone, methyl p-dimethylaminocinnamate ester, ethyl p-diamethylaminocinnamate, p-dimethylaminostyr-1 2-pyridyl ketone, p-dimethylaminostyryl 4-pyridyl ketone, p-dimethylaminostyryl 2-thienyl ketone, p-dimethylaminostyryl 9-anthryl ketone, p-diethylaminostyryl methyl ketone, p-diethylaminostyryl ethyl ketone, p-diethylaminostyryl butyl ketone, 2-(p-dimethylaminobenzylidene)cyclohexanone, 2-(p-dimethylaminobenzylidene)cyclopentanone, 2-(p-diethylaminobenzylidene)cyclohexanone, 2-(p-diethylaminobenzylidene)cyclopentanone, p-dimethylaminochalcone, p-dimethylamino-p'-cyanochalcone, p-dimethylamino-p'-chlorochalcone, p-dimethylamino-m'-chlorochalcone, p-dimethylamino-p'-bromochalcone, p-dimethylamino-m'-bromochalcone, p-dimethylamino-p'-methylchalcone, p-dimethylamino-m'-methylchalcone, p-dimethylamino-p'-ethylchalcone, p-dimethylamino-m'-ethylchalcone, p-dimethylamino-p'-methoxychalcone, p-dimethylamino-m'-methoxychalcone, p-dimethylamino-p'-ethoxychalcone, p-dimethylamino-m'-ethoxychalcone, p-dimethylamino-p'-dimethylaminochalcone, p-diethylaminochalcone, p-diethylamino-p'-cyanochalcone, p-diethylamino-m'-chlorochalcone, p-diethylamino-p'-chlorochalcone, p-diethylamino-m'-bromochalcone, p-diethylamino-p'-bromochalcone, p-diethylamino-m'-methylchalcone, p-diethylamino-p'methylchalcone, p-diethylamino-m'-ethylchalcone, p-diethylamino-p'-methylchalcone, p-diethylamino-p'-ethoxychalcone, p-diethylamino-m'-methoxychalcone, p-diethylamino-p'-diethylaminochalcone, p'-dimethylaminochalcone, p-cyano-p'-dimethylaminochalcone, p-chloro-p'-dimethylaminochalcone, m-chloro-p'-dimethylaminochalcone, m-bromo-p'-dimethylaminochalcone, p-bromo-p'-dimethylaminochalcone, m-methyl-p'-dimethylaminochalcone, p-methyl-p'-dimethylaminochalcone, m-ethyl-p'-dimethylaminochalcone, p-ethyl-p'-dimethylaminochalcone, m-methocy-p'-dimethylaminochalcone, p-methoxy-p'-dimethylaminochalcone, m-ethoxy-p'-dimethylaminochalcone, p-ethoxy-p'-dimethylaminochalcone, p,p'-bis(dimethylamino)chalcone, p,p' 40 -bis(diethylamino)chalcone, p'-diethylaminocalchone, p-cyano-p'-diethylaminochalcone, p-chloro-p'-diethylaminochalcone, m-bromo-p'-diethylaminochalcone, p-chloro-p'-diethylaminochalcone, p-ethyl-p'-diethylaminochalcone, m-ethyl-p'-diethylaminochalcone, p-methoxy-p'-diethylaminochalcone and m-ethoxy-p'-diethylaminochalcone, p-dimethylaminostyryl p-cyanostyryl ketone, p-dimethylaminostyryl p-chlorostyryl ketone, p-dimethylaminostyryl m-chlorostyryl ketone, p-dimethylaminostyryl p-bromostyryl ketone, p-dimethylaminostyryl m-bromostyryl ketone, p-dimethylaminostyryl ketone, p-dimethylaminostyryl m-methylstyryl ketone, p-dimethylaminostyryl p-methylstyryl ketone, p-dimethylaminostyryl p-ethylstyryl ketone, p-dimethylaminostyryl m-ethylstyryl ketone, p-dimethylaminostyryl p-methoxy styryl ketone, p-dimethylaminostyryl m-methoxystyryl ketone, p-dimethylaminostyryl p-ethoxystyryl ketone, bis(p-dimethylaminostyryl) ketone, p-diethylaminostyryl p-cyanostyryl ketone, p-diethylaminostyryl p-bromostyryl ketone, p-diethylaminostyryl m-chlorostyryl ketone, p-diethylaminostyryl styryl ketone, p-diethylaminostyryl p-methylstyryl ketone, p-diethylaminostyryl m-ethylstyryl ketone, p-diethylaminostyryl p-methoxystyryl ketone, p-diethylaminostyryl m-ethoxystyryl ketone and bis(p-diethylaminostyryl) ketone.

Claim 7

The photopolymerizable composition of claim 1, wherein said at least one p-dialkylamino aromatic carbonyl compound is selected from the group consisting of p-dimethylaminostyryl methyl ketone, p-dimethylaminostyryl ethyl ketone, p-dimethylaminostyryl propyl ketone, p-dimethylaminostyryl butyl ketone, p-dimethylaminostyryl isobutyl ketone, p-dimethylaminostyryl tert-butyl ketone, p-dimethylaminostyryl cyclohexyl ketone, p-dimethylaminostyryl benzyl ketone, p-dimethylaminostyryl phenethyl ketone, methyl p-dimethylamino cinnamate, ethyl p-dimethylaminocinnamate, p-dimethylaminostyryl 2-pyridyl ketone, p-dimethylaminostyryl 4-pyridyl ketone, p-dimethylaminostyryl 2-thienyl ketone, p-dimethylamino 9-anthryl ketone, 2-(p-dimethylaminobenzylidene)cyclohexanone, 2-(p-dimethylaminobenzylidene)cyclopentanone, p-dimethylaminochalcone, p-dimethylamino-m'-chlorochalcone, p-dimethylamino-p'-chlorochalcone, p-dimethylamino-m'-bromochalcone, p-dimethylamino-p'-bromochalcone, p-dimethylamino-p'-cyanochalcone, p-dimethylamino-p'-methoxychalcone, p-dimethylamino-p'-methylchalcone, p-dimethylamino-m'-methylchalcone, p-dimethylamino-p'-ethylchalcone, p-dimethylamino-m'-ethylchalcone, p-diethylamino-p'-bromochalcone, p-diethylamino-m'-bromochalcone, p'-diethylamino-p'-chlorochalcone, p-diethylamino-m'-chlorochalcone, p'-dimethylaminochalcone, p-cyano-p'-dimethylaminochalcone, m-chloro-p'-dimethylaminochalcone, p-chloro-p'-dimethylaminochalcone, m-bromo-p'-dimethylaminochalcone, p-bromo-p'-dimethylaminochalcone, m-methyl-p'-dimethylaminochalcone, p-methyl-p'-dimethylaminochalcone, p-methyl-p'-dimethylaminochalcone, m-ethyl-p'-dimethylaminochalcone, p-ethyl-p'-dimethylaminochalcone, p-methoxy-p'-dimethylaminochalcone, p,p'-bis(dimethylamino)chalcone, p-dimethylaminostyryl p-methylstyryl ketone, p-dimethylaminostyryl p-ethylstyryl ketone, p-dimethylaminostyryl p-chlorostyryl ketone, p-dimethylaminostyryl m-chlorostyryl ketone, p-dimethylaminostyryl p-bromostyryl ketone, p-dimethylaminostyryl m-bromostyryl ketone, p-dimethylaminostyryl p-methoxystyryl ketone, p-dimethylaminostyryl p-ethoxystyryl ketone, p-dimethylaminostyryl p-cyanostyryl ketone, p-dimethylaminostyryl m-methylstyryl ketone, p-dimethylaminostyryl m-ethylstyryl ketone, bis(p-dimethylaminostyryl) ketone and bis(p-diethylaminostyryl) ketone.

Claim 8

A composition as claimed in claim 1, wherein the addition-polymerizable compound (1) is selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid and maleic acid.

Claim 9

A composition as claimed in claim 1, wherein the addition-polymerizable compound (1) is an ester of an aliphatic polyhydric alcohol.

Claim 10

A composition as claimed in claim 1, wherein the addition-polymerizable compound (1) is selected from the group consisting of trimethylolpropane triacrylate, trimethylolethane triacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritol octaacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol tetramethacrylate, tripentaerythritol octamethacrylate, pentaerythritol diitaconate, dipentaerythritol trisitaconate, dipentaerythritol pentaitaconate, dipentaerythritol hexaitaconate, ethylene glycol dimethacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol diitaconate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol tetramethacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, 1,4-butylene modified diacrylate, trimethylolpropane modified triacrylate, pentaerythritol modified triacrylate and mixtures thereof.

Claim 11

A composition as claimed in claim 1, wherein the addition-polymerizable compound (1) is an oligoester acrylate or oligoester methacrylate.

Claim 12

A composition as claimed in claim 10, wherein said oligester is of the general formula ##STR35## wherein R 4 represents a member selected from the group consisting of a hydrogen atom and a methyl group, Q represents an ester group containing at least one ester bond which comprises one or more polyhydric alcohols and one or more polybasic acids, and p represents an integer of 1 to 6.

Claim 13

A composition as claimed in claim 11, wherein said oligoester is selected from the group consisting of: ##STR36##

Claim 14

A composition as claimed in claim 1, wherein the ratio by weight of the initiator to the addition-polymerizable compound is about 1:5 to about 1:1000.

Claim 15

A composition as claimed in claim 13, wherein said ratio is about 1:10 to about 1:100.

Claim 16

A composition as claimed in claim 1, wherein the ratio by weight of components (a) and (b) of the initiator is about 30:1 to about 1:30.

Claim 17

A composition as claimed in claim 15, wherein said ratio is about 10:1 to about 1:10.

Claim 18

A composition as claimed in claim 1, which also includes a film-forming organic polymer of high molecular weight as a binder.

Claim 19

The photopolymerizable composition of claim 1, wherein said photopolymerization initiator consists essentially of a combination of elements (a) and (b).

Claim 20

The photopolymerizable composition of claim 1, wherein said photopolymerization initiator comprises a combination of ##STR37##

Claim 21

The photopolymerizable composition of claim 1, wherein said photopolymerization initiator comprises a combination of ##STR38##

Claim 22

The photopolymerizable composition of claim 1, wherein said at aleast one p-dialkylamino aromatic carbonyl compound has general formula (I).

Claim 23

The photopolymerizable composition of claim 1, wherein said at least one p-dialkylamino aromatic carbonyl compound has general formula (II).

Claim 24

The photopolymerizable composition of claim 1, wherein said at least one p-dialkylamino aromatic carbonyl compound has general formula (IV).

Claim 25

The photopolymerizable composition of claim 1, wherein said at least one p-dialkylamino aromatic carbonyl compound has general formula (V).