Photopolymerizable composition containing a sensitizing dye and a titanocene compound

Abstract

A photopolymerizable composition is disclosed, which comprises an addition-polymerizable compound having at least one ethylenically unsaturated double bond, a sensitizing dye represented by the following formula (I): wherein the all symbols are defined in the disclosure, and a titanocene compound.

What is claimed is:  
     
       1. A photopolymerizable composition comprising an addition-polymerizable compound having at least one ethylenically unsaturated double bond, a sensitizing dye represented by the following formula (1) and a titanocene compound:                    
       wherein Z 1  and Z 2  each represents a nonmetallic atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring used is cyanine dyes; R 1  and R 2  each represents an alkyl group; Q 1  and Q 2  represent in combination therewith an atomic group necessary for forming a 4-thiazolidinone ring, a 5-thiazolidinone ring, a 4-imidazolidinone ring, a 4-oxazolidinone ring, a 5-oxazolidinone ring a 5-imidazolidinone ring or a 4-dithiolanone ring; L 1 , L 2 , L 3 , L 4  and L 5  each represents a methine group; m represents 1 or 2; i and h each represents 0 or 1; 1 represents 1 as 2; j and k each represents 0, 1, 2 or 3; and X − represents a counter anion. 
     
     
       2. The photopolymerizable composition of  claim 1 , wherein said addition-polymerizable compound is present in an amount of 5 to 50% by weight based on the entire components. 
     
     
       3. The photopolymerizable composition of  claim 1 , wherein said sensitizing dye is present in an amount of from 0.05 to 30 parts by weight per 100 parts by weight of said addition-polymerizable compound. 
     
     
       4. The photopolymerizable composition of  claim 1 , wherein said titanocene compound is present in an amount of from 0.5 to 100 parts by weight per 100 parts by weight of said addition-polymerizable compound. 
     
     
       5. The photopolymerizable composition of  claim 1 , which further comprises at least one compound selected from the group consisting of the compounds 1) to 8): 
       1) a compound having a carbon-halogen bond;  
       2) a ketone compound represented by the following formula (II):                    
       wherein or represents an aromatic group selected from those represented by the following formulae:                    
       wherein R 5 , R 6 , R 7 , R 8 , and R 9 , which are the same or optionally are different, each represents a hydrogen atom, a halogen atom, an alkyl group, as alkenyl group, an aryl group, a substituted aryl group, a hydroxyl group, an alkoxy group, an —S—R 11  group, an —SO—R 11  group or an —SO 2 —R 11  group, provided that at least one of R 5 , R 6 , R 7 , R 8  and R 9  represents an —S—R 11  or —SO—R 11  group (wherein R 11  represents an alkyl group or an alkenyl group); R 10  represents a hydrogen atom, an alkyl group or an acyl group; and Y 1  represents a hydrogen atom or                    
       R 3  and R 4  each represents a hydrogen atom or an alkyl group and R 3  and R 4  optionally are combined with each other to represent an alkylene group; 
       3) a ketooxime compound represented by the following formula (III):                    
       wherein R 12  and R 13 , which are the same or optionally are different, each represents a hydrocarbon group which optionally has a substituent and optionally contains an unsaturated bond or a heterocyclic group; R 14  and R 15 , which are the same or optionally are different, each represents a hydrogen atom, a hydrocarbon group which optionally has a substituent and optionally contains an unsaturated bond, a heterocyclic group, a hydroxyl group, a substituted oxy group, a mercapto group or a substituted thio group, and R 14  and R 10  optionally are combined with each other to form a ring and represent an alkylene group having from 2 to 8 carbon atoms which optionally contains —O—, —NR— 16 —, —O—CO—, NH—CO—, —S— or —SO 2 — in the linking main chain of the ring; and R 16  and R 17  each represents a hydrogen atom, a hydrocarbon group which optionally has a substituent and optionally contains an unsaturated bond or a substituted carbonyl group; 
       4) an organic peroxide;  
       5) a thio compound represented by formula (IV):                    
       wherein R 18  represents an alkyl group, an aryl group or a substituted aryl group and R 19  represents a hydrogen atom or an alkyl group, or R 18  and R 19  optionally are combined with each other to represent a nonmetallic atom group necessary for forming a 5-, 6- or 7-membered ring which optionally contains a hetero atom selected from an oxygen atom, a sulfur atom and a nitrogen atom; 
       6) hexaarylbiimidazole;  
       7) an aromatic opium salt; and  
       8) a ketooxime ester.  
     
     
       6. The photopolymerizable composition of  claim 5 , wherein said compounds 1) to 8) are present in a total amount of 0.05 to 100 parts by weight per 100 parts by weight of said addition-polymerizable compound.