Claims
- 1. A photopolymerizable composition comprising a polymerizable compound having at least one ethylenically unsaturated bond which is photopolymerizable with active light and a photopolymerization initiator, wherein said photopolymerization initiator comprises:
- (a) at least one salt of an organic boron anionic compound with an organic and cationic dye, and at least one compound represented by formula (I), (II), (III), (IV), (V) or (VI), or
- (b) a combination of at least one organic and cationic dye with a salt of an organic boron anionic compound, and at least one compound represented by the following general formula (I), (II), (III), (IV), (V) or (VI): ##STR28## wherein R.sub.1 represents an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an allyl group, a substituted allyl group, an aryl group, a substituted aryl group, a halogen atom, an alkoxy group, a substituted alkoxy group, a nitro group or a cyano group,
- X represents a halogen atom, and
- n represents an integer of 1 to 3;
- R.sup.2 --Z--CH.sub.m-- 1X.sub.m-- R.sup.3 (II)
- wherein
- R.sup.2 represents an aryl group or a substituted aryl group,
- R.sup.3 represents ##STR29## Z represents ##STR30## R.sup.4 and R.sup.5 each represents an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an allyl, group, a substituted allyl group, an aryl group or a substituted aryl group,
- R.sup.6 is the same as R.sup.1 of the general formula (I),
- X represents a halogen atom, and
- m represents 1 or 2; ##STR31## wherein R.sub.7 represents a substituted or unsubstituted aryl group or heterocyclic group,
- R.sub.8 represents a trihaloalkyl or trihaloalkenyl group having 1 to 3 carbon atoms, and
- p represents 1, 2 or 3; ##STR32## wherein: L represents a hydrogen atom or a substituent of the formula:
- CO--(R.sup.9)n(CX.sub.3)m,
- M represents a substituted or unsubstituted alkylene group,
- Q represents a sulfur, selenium or oxygen atom, dialkylmethylene group, an alken-1,2-ylene group, 1,2-phenylene group or a N--R group,
- M and Q together form a three-membered or four-membered ring,
- R.sup.9 represents a carbocyclic or heterocyclic aromatic group,
- R.sup.10 represents an alkyl group, an aralkyl group or an alkoxyalkyl group,
- X represents a halogen atom, and
- q is 0 and r is 1 or, alternatively, q is 1 and r is 1 or 2; ##STR33## wherein X represents a halogen atom,
- t represents an integer of 1 to 3,
- s represents an integer of 1 to 4,
- R.sup.11 represents a hydrogen atom or a CH.sub.3 --.sub.t X.sub.t group, and
- R.sup.12 represents a substituted or unsubstituted S-valent unsaturated organic group; and ##STR34## wherein X represents a halogen atom,
- v represents an integer of 1 to 3, u represents an integer of 1 to 4,
- R.sup.13 represents a hydrogen atom or a CH.sub.3 --.sub.v X.sub.v group,
- R.sup.14 represents a u-valent, substituted or unsubstituted unsaturated organic group.
- 2. The photopolymerizable composition of claim 1, wherein said photopolymerization initiator is used in an amount of 0.01 to 60 wt. % based on the total amount of said polymerizable compound and said linear organic polymer.
- 3. The photopolymerizable composition of claim 2, wherein said photopolymerization initiator is used in an amount of 1 to 30 wt. % based on the total amount of said polymerizable compound and said linear organic polymer.
- 4. The photopolymerizable composition of claim 1, further comprising a linear organic polymer.
- 5. The photopolymerizable composition of claim 4, wherein said linear organic polymer is soluble or swellable in water or an alkaline aqueous solution.
- 6. The photopolymerizable composition of claim 5, wherein said linear organic polymer is selected from the group consisting of acrylic acid copolymer or methacrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, and partially esterified maleic acid copolymer.
- 7. The photopolymerizable composition of claim 6, comprising said linear organic polymer in an amount of 5-50% by weight based on the total weight of the composition.
- 8. The photopolymerizable composition of claim 1, wherein said salt of an organic boron anionic compound with an organic and cationic dye is defined by the general formula: ##STR35## wherein D.sup.+ represents an organic and cationic dye,
- R.sup.15, R.sup.16, R.sup.17 and R.sup.18 may be the same or different and each represents an alkyl group, an aryl group, an aralkyl group, an alkaryl group, an alkenyl group, an alkynyl group, an alicyclic group, a heterocyclic group, an allyl group, or a group derived from such a group, or two or more of R.sup.15, R.sup.16, R.sup.17 and R.sup.18 may be bonded together to form a cyclic structure.
- 9. The photopolymerizable composition of claim 8, wherein said organic and cationic dye is selected from the group consisting of polymethine dyes, cyanine dyes, azomethine dyes, triarylmethane dyes, xanthene dyes, acridine dyes, azine dyes, oxazine dyes, thiazine dyes, quinoline dyes, thiazole dyes, pyrylium dyes and thiapyrylium dyes.
- 10. The photopolymerizable composition of claim 8, wherein said salt of an organic boron anionic compound with an organic and cationic dye is defined by formula I or formula XI: ##STR36## wherein, Z.sub.1 and Z.sub.2 each represents an atomic group necessary for forming a usual heterocyclic nucleus of a cyanine dye such as thiazole, thiazoline, benzothiazole, naphthothiazole, oxazole, oxazoline, benzoxazole, naphthoxazole, tetrazole, pyridine, quinoline, imidazoline, imidazole, benzimidazole, naphthoimidazole, selenazoline, selenazole, benzoselenazole, naphthoselenazole or indolenine nucleus which may be substituted with a lower alkyl group such as a methyl group, a halogen atom, a phenyl group, a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, a carboxyl group, an alkoxycarbonyl group, an alkylsulfamoyl group, an alkylcarbamoyl group, an acetyl group, an acetoxy group, a cyano group, a trichloromethyl group, a trifluoromethyl group or a nitro group,
- L.sub.1, L.sub.2 and L.sub.3 represents a methine group which may be substituted with a lower alkyl group such as a methyl or ethyl group, a phenyl group, a substituted phenyl group, a methoxy group, an ethoxy group or an aralkyl group such as a phenethyl group,
- L.sub.1 and R.sub.19, L.sub.3 and R.sub.20, or L.sub.2 and L.sub.2 (in case .omega. is 3) may form an alkylene crosslinkage to form a five-membered or six-membered ring,
- R.sub.19 and R.sub.20 each represents a lower alkyl group (preferably an alkyl group having 1 to 8 carbon atoms), a carboxyl group, a sulfo group, a hydroxyl group, a halogen atom, an alkoxy group having 1 to 4 carbon atoms, a phenyl group or an alkyl group having a substituent such as a substituted phenyl group (preferably the alkylene moiety thereof having 1 to 5 carbon atoms) such as a .beta.-sulfoethyl, .gamma.-sulfopropyl, .gamma.-sulfobutyl, .delta.-sulfobutyl, 2- [2-(3-sulfopropoxy)ethoxy]ethyl, 2-hydroxysulfopropyl, 2-chlorosulfopropyl, 2-methoxyethyl, 2-hydroxyethyl, carboxymethyl, 2-carboxyethyl, 2,2,3,3'-tetrafluoropropyl or 3,3,3-trifluoroethyl group, an allyl group or a substituted alkyl group usually contained in cyanine dyes as an N-substituent,
- .omega. represents a number of 1, 2 or 3, and
- X.sup.- represents said boron anionic compound, and ##STR37## wherein R.sub.21, R.sub.22, R.sub.23 and R.sub.24 each represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group; R.sub.26 and R.sub.27 each represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group or, a substituted or unsubstituted aryl group;
- Y represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or ##STR38## (wherein R.sup.25 represents the same group as R.sup.26 or an alkaline metal); and
- X represents the boron anionic compound of the above formula (VII).
- 11. The photopolymerizable composition of claim 10, comprising said linear organic polymer in an amount of 30-85% by weight based on the total weight of the composition.
- 12. The photopolymerizable composition of claim 8, wherein said salt of an organic boron anionic compound with an organic and cationic dye is selected from the group consisting of the following compounds: ##STR39##
- 13. The photopolymerizable composition of claim 1, wherein said organic boron anionic compound is selected from the group consisting of the following compounds: ##STR40##
- 14. The photopolymerizable composition of claim 1, wherein said organic and cationic dye is defined by formula I or formula XI: ##STR41## wherein, Z.sub.1 and Z.sub.2 each represents an atomic group necessary for forming a usual heterocyclic nucleus of a cyanine dye such as thiazole, thiazoline, benzothiazole, naphthothiazole, oxazole, oxazoline, benzoxazole, naphthoxazole, tetrazole, pyridine, quinoline, imidazoline, imidazole, benzimidazole, naphthoimidazole, selenazoline, selenazole, benzoselenazole, naphthoselenazole or indolenine nucleus which may be substituted with a lower alkyl group such as a methyl group, a halogen atom, a phenyl group, a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, a carboxyl group, an alkoxycarbonyl group, an alkylsulfamoyl group, an alkylcarbamoyl group, an acetyl group, an acetoxy group, a cyano group, a trichloromethyl group, a trifluoromethyl group or a nitro group,
- L.sub.1, L.sub.2 and L.sub.3 each represents a methine group which may be substituted with a lower alkyl group such as a methyl or ethyl group, a phenyl group, a substituted phenyl group, a methoxy group, an ethoxy group or an aralkyl group such as a phenethyl group,
- L.sub.1 and R.sub.19, L.sub.3 and R.sub.20, or L.sub.2 and L.sub.2 (in case .omega. is 3) may form an alkylene crosslinkage to form a five-membered or six-membered ring,
- R.sub.19 and R.sub.20 each represents a lower alkyl group (preferably an alkyl group having 1 to 8 carbon atoms), a carboxyl group, a sulfo group, a hydroxyl group, a halogen atom, an alkoxy group having 1 to 4 carbon atoms, a phenyl group or an alkyl group having a substituent such as a substituted phenyl group (preferably the alkylene moiety thereof having 1 to 5 carbon atoms) such as a .beta.-sulfoethyl, .gamma.-sulfopropyl, .gamma.-sulfobutyl, .delta.-sulfobutyl, 2-[2-(3-sulfopropoxy)ethoxy]ethyl, 2-hydroxysulfopropyl, 2-chlorosulfopropyl, 2-methoxyethyl, 2-hydroxyethyl, carboxymethyl, 2-carboxyethyl, 2,2,3,3'-tetrafluoropropyl or 3,3,3-trifluoroethyl group, an allyl group or a substituted alkyl group usually contained in cyanine dyes as an N-substituent,
- .omega. represents a number of 1, 2 or 3, and
- X.sup.- represents Cl.sup.-, Br.sup.-, F.sup.-, BF.sub.4.sup.-, ClO.sub.4.sup.- or PF.sub.6.sup.-, and tetrafluoropropyl or 3,3,3-trifluoroethyl group, an allyl group or a substituted alkyl group usually contained in cyanine dyes as an N-substituent,
- .omega. represents a number of 1, 2 or 3, and
- X.sup.- represents said boron anionic compound, and ##STR42## wherein R.sub.21, R.sub.22, R.sub.23 and R.sub.24 each represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group; R.sub.26 and R.sub.27 each represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group or, a substituted or unsubstituted aryl group;
- Y represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or ##STR43## (wherein R.sup.25 represents the same group as R.sup.26 or an alkaline metal); and
- X represents the boron anionic compound of the above formula (VII).
Priority Claims (1)
| Number |
Date |
Country |
Kind |
| 63-55857 |
Mar 1988 |
JPX |
|
Parent Case Info
This is a continuation-in-part application of Ser. No. 320,535 filed Mar. 8, 1989, now abandoned.
US Referenced Citations (12)
Continuation in Parts (1)
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Number |
Date |
Country |
| Parent |
320535 |
Mar 1989 |
|
Patent Grant
5168032
