Stabilized infrared-sensitive polymerizable systems
View Patent ↗The use of certain mercapto compounds as shelf life improvers for infrared-sensitive lithographic printing plate precursors is disclosed. The compounds are five-membered heteroaromatic rings containing a nitrogen atom and at least one other heteroatom, which can be oxygen, sulfur, or another nitrogen atom, such that two ring heteroatoms are bonded to a ring carbon bearing a thiol group.
1. An infrared-sensitive composition comprising:
(i) an initiator system comprising:
(a) at least one compound capable of absorbing infrared radiation selected from the group consisting of triarylamine dyes, thiazolium dyes, indolium dyes, oxazolium dyes, cyanine dyes, polyaniline dyes, polypyrrole dyes, polythiophene dyes, and phthalocyanine pigments,
(b) at least one compound capable of producing free radicals, the compound selected from polyhaloalkyl-substituted compounds, and
(c) at least one carboxylic acid represented by formula (I):
R 4 —(CR 5 R 6 ) n —Y—CH 2 COOH (I)
in which:
Y is selected from the group consisting of O, S and NR 7 ;
R 7 is selected from the group consisting of hydrogen, C 1 -C 6 alkyl, —CH 2 CH 2 OH, and C 1 -C 5 alkyl substituted with —COOH;
R 4 , R 5 and R 6 are each independently selected from the group consisting of hydrogen, C 1 -C 4 alkyl, substituted or unsubstituted aryl, —COOH and —NR 8 CH 2 COOH;
R 8 is selected from the group consisting of —CH 2 COOH, —CH 2 OH, and —(CH 2 ) 2 N(CH 2 COOH) 2 ; and
n is 0, 1, 2 or 3;
(ii) at least one component selected from unsaturated free radical-polymerizable monomers, unsaturated oligomers which are free radical-polymerizable, polymers containing free radical-polymerizable carbon-carbon double bonds in one or both of the backbone and a side chain, and mixtures thereof;
(iii) at least one polymeric binder; and
(iv) a heterocyclic mercapto compound comprising an aromatic 5-membered heterocyclic ring with a thiol group substituted thereon, the ring comprising a nitrogen atom and at least one heteroatom selected from the group consisting of nitrogen, oxygen and sulfur, in which the heteroatom is separated in the ring from the nitrogen atom by one carbon atom, and in which the thiol group is bonded to the carbon atom;
in which:
ox a <red b +1.6 eV,
in which ox a is the oxidation potential of component (a) in eV, and red b is the reduction potential of component (b) in eV.
2. The composition of claim 1 in which the compound capable of absorbing infrared radiation is a cyanine dye of the formula (A):
in which:
X 1 and X 2 are each independently S, O, NR or C(alkyl) 2 ;
R 1a and R 1b are each independently an alkyl group, an alkylsulfonate group, an alkylcarboxylate group or an alkylammonium group;
R 2 is hydrogen, halogen, SR, SO 2 R, OR or NR 2 ;
R 3a and R 3b are each independently a hydrogen atom, an alkyl group, COOR, OR, SR, NR 2 , a halogen atom, or a substituted or unsubstituted benzofused ring;
R is an alkyl group or an aryl group;
C is a counterion present in sufficient amount to achieve charge neutrality for cyanine dye (A);
is either two hydrogen atoms or a two-carbon or three-carbon chain; and
n 1 and n 2 are each independently 0, 1, 2 or 3.
3. The composition of claim 1 in which the compound capable of producing radicals is 2-phenyl-4,6-bis(trichloromethyl)-1,3,5-triazine; 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine; tribromomethylphenylsulfone; 2,4,6-tris(trichloromethyl)- 1,3,5-triazine; or 1,2,3,4-tetrabromo-n-butane.
4. The composition of claim 1 in which the carboxylic acid is a compound of the formula (B)
in which Ar is a mono-, poly- or unsubstituted aryl group, p is an integer from 1 to 5, R 9 and R 10 are independently selected from the group consisting of hydrogen and C 1 -C 4 alkyl and q is 0 or an integer from 1 to 3; or
a compound of the formula (C)
in which R 11 is a hydrogen atom or a C 1 -C 6 alkyl group, k and m are each independently an integer from 1 to 5.
5. The composition of claim 1 in which the carboxylic acid is (3,4-dimethoxyphenylthio)acetic acid, anilino diacetic acid, or N-(carboxymethyl)-N-benzylglycine.
6. The composition of claim 1 in which the mercapto compound is selected from the group consisting of 3-mercapto-1,2,4-triazole; 2-mercaptobenzimidazole; 2-mercaptobenzoxazole; 5-mercapto-3-methylthio-1,2,4-thiadiazole; and 2-mercapto-1-methylimidazole.
7. The composition of claim 1 in which the polymeric binder has an acid number of >70 mg KOH/g.
8. The composition of claim 1 in which component (ii) is selected from the group consisting of pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, di(trimethylol propane) tetraacrylate, diethyleneglycol diacrylate, prepolymers comprising allyl alcohol ester groups, oligomeric urethane (meth)acrylates, and mixtures thereof.
9. The composition of claim 1 in which:
the at least one compound capable of absorbing infrared radiation is a cyanine dye or a mixture of cyanine dyes;
the carboxylic acid is selected from the group consisting of (3,4-dimethoxyphenylthio)acetic acid, anilino diacetic acid, and N-(carboxymethyl)-N-benzylglycine;
the compound capable of producing radicals is selected from the group consisting of 2-phenyl-4,6-bis(trichloromethyl)-1,3,5-triazine; 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine; tribromomethylphenylsulfone; 2,4,6-tris(trichloromethyl)-1,3,5-triazine; 1,2,3,4-tetrabromo-n-butane, and mixtures thereof;
the mercapto compound is selected from the group consisting of 3-mercapto-1,2,4-triazole; 2-mercaptobenzimidazole; 2-mercaptobenzoxazole; 5-mercapto-3-methylthio-1,2,4-thiadiazole; 2-mercapto-1-methylimidazole, and mixture thereof; and
the polymeric binder has an acid number of >70 mg KOH/g.
10. A printing plate precursor comprising a printing plate substrate and a layer of an infrared-sensitive composition on the substrate,
the infrared-sensitive composition comprising:
(i) an initiator system comprising:
(a) at least one compound capable of absorbing infrared radiation selected from the group consisting of triarylamine dyes, thiazolium dyes, indolium dyes, oxazolium dyes, cyanine dyes, polyaniline dyes, polypyrrole dyes, polythiophene dyes, and phthalocyanine pigments,
(b) at least one compound capable of producing free radicals, the compound selected from polyhaloalkyl-substituted compounds, and
(c) at least one carboxylic acid represented by formula (I):
R 4 —(CR 5 R 6 ) n —Y—CH 2 COOH (I)
in which:
Y is selected from the group consisting of O, S and NR 7 ;
R 7 is selected from the group consisting of hydrogen, C 1 -C 6 alkyl, —CH 2 CH 2 OH, and C 1 -C 5 alkyl substituted with —COOH;
R 4 , R 5 and R 6 are each independently selected from the group consisting of hydrogen, C 1 -C 4 alkyl, substituted or unsubstituted aryl, —COOH and —NR 8 CH 2 COOH;
R 8 is selected from the group consisting of —CH 2 COOH, —CH 2 OH, and —(CH 2 ) 2 N(CH 2 COOH) 2 ; and
n is 0, 1, 2 or 3;
(ii) at least one component selected from unsaturated free radical-polymerizable monomers, unsaturated oligomers which are free radical-polymerizable, polymers containing free radical-polymerizable carbon-carbon double bonds in one or both of the backbone and a side chain, and mixtures thereof;
(iii) at least one polymeric binder; and
(iv) a heterocyclic mercapto compound comprising an aromatic 5-membered heterocyclic ring with a thiol group substituted thereon, the ring comprising a nitrogen atom and at least one heteroatom selected from the group consisting of nitrogen, oxygen and sulfur, in which the heteroatom is separated in the ring from the nitrogen atom by one carbon atom, and in which the thiol group is bonded to the carbon atom;
in which:
ox a <red b +1.6 eV,
in which ox a is the oxidation potential of component (a) in eV, and red b is the reduction potential of component (b) in eV.
11. The printing plate precursor of claim 10 additionally comprising a substantially oxygen-impermeable barrier layer over the layer of infrared-sensitive composition.
12. The printing plate precursor of claim 10 in which the compound capable of absorbing infrared radiation is a cyanine dye of the formula (A):
in which:
X 1 and X 2 are each independently S, O, NR or C(alkyl) 2 ;
R 1a and R 1b are each independently an alkyl group, an alkylsulfonate group, an alkylcarboxylate group or an alkylammonium group;
R 2 is hydrogen, halogen, SR, SO 2 R, OR or NR 2 ;
R 3a and R 3b are each independently a hydrogen atom, an alkyl group, COOR, OR, SR, NR 2 , a halogen atom, or a substituted or unsubstituted benzofused ring;
R is an alkyl group or an aryl group;
C is a counterion present in sufficient amount to achieve charge neutrality for cyanine dye (A);
is either two hydrogen atoms or a two-carbon or three-carbon chain; and
n 1 and n 2 are each independently 0, 1, 2 or 3.
13. The printing plate precursor of claim 10 in which the compound capable of producing radicals is 2-phenyl-4,6-bis(trichloromethyl)-1,3,5-triazine; 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine; tribromomethylphenylsulfone; 2,4,6-tris(trichloromethyl)-1,3,5-triazine; or 1,2,3,4-tetrabromo-n-butane.
14. The printing plate precursor of claim 10 in which the carboxylic acid is a compound of the formula (B)
in which Ar is a mono-, poly- or unsubstituted aryl group, p is an integer from 1 to 5, R 9 and R 10 are independently selected from the group consisting of hydrogen and C 1 -C 4 alkyl and q is 0 or an integer from 1 to 3; or of a compound of the formula (C)
in which R 11 is a hydrogen atom or a C 1 -C 6 alkyl group, k and m are each independently an integer from 1 to 5.
15. The printing plate precursor of claim 10 in which the carboxylic acid is (3,4-dimethoxyphenylthio)acetic acid, anilino diacetic acid, or N-(carboxymethyl)-N-benzylglycine.
16. The printing plate precursor of claim 10 in which the mercapto compound is selected from the group consisting of 3-mercapto-1,2,4-triazole; 2-mercaptobenzimidazole; 2-mercaptobenzoxazole; 5-mercapto-3-methylthio-1,2,4-thiadiazole; and 2-mercapto-1-methylimidazole.
17. The printing plate precursor of claim 10 in which the polymeric binder has an acid number of >70 mg KOH/g.
18. The printing plate precursor of claim 10 in which:
the at least one compound capable of absorbing infrared radiation is a cyanine dye or a mixture of cyanine dyes;
the carboxylic acid is selected from the group consisting of (3,4-dimethoxyphenylthio)acetic acid, anilino diacetic acid, and N-(carboxymethyl)-N-benzylglycine;
the compound capable of producing radicals is selected from the group consisting of 2-phenyl-4,6-bis(trichloromethyl)-1,3,5-triazine; 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine; tribromomethylphenylsulfone; 2,4,6-tris(trichloromethyl)-1,3,5-triazine; 1,2,3,4-tetrabromo-n-butane, and mixtures thereof;
the mercapto compound is selected from the group consisting of 3-mercapto-1,2,4-triazole; 2-mercaptobenzimidazole; 2-mercaptobenzoxazole; 5-mercapto-3-methylthio-1,2,4-thiadiazole; 2-mercapto-1-methylimidazole, and mixtures thereof; and
the polymeric binder has an acid number of >70 mg KOH/g.
19. A method for producing a lithographic printing plate precursor, comprising applying a layer of an infrared-sensitive composition to a substrate, the infrared sensitive composition comprising:
(i) an initiator system comprising:
(a) at least one compound capable of absorbing infrared radiation selected from the group consisting of triarylamine dyes, thiazolium dyes, indolium dyes, oxazolium dyes, cyanine dyes, polyaniline dyes, polypyrrole dyes, polythiophene dyes, and phthalocyanine pigments,
(b) at least one compound capable of producing free radicals, the compound selected from polyhaloalkyl-substituted compounds, and
(c) at least one carboxylic acid represented by formula (I):
R 4 —(CR 5 R 6 ) n —Y—CH 2 COOH (I)
in which:
Y is selected from the group consisting of O, S and NR 7 ;
R 7 is selected from the group consisting of hydrogen, C 1 -C 6 alkyl, —CH 2 CH 2 OH, and C 1 -C 5 alkyl substituted with —COOH;
R 4 , R 5 and R 6 are each independently selected from the group consisting of hydrogen, C 1 -C 4 alkyl, substituted or unsubstituted aryl, —COOH and —NR 8 CH 2 COOH;
R 8 is selected from the group consisting of —CH 2 COOH, —CH 2 OH, and —(CH 2 ) 2 N(CH 2 COOH) 2 ; and
n is 0, 1, 2 or 3;
(ii) at least one component selected from unsaturated free radical-polymerizable monomers, unsaturated oligomers which are free radical-polymerizable, polymers containing free radical-polymerizable carbon-carbon double bonds in one or both of the backbone and a side chain, and mixtures thereof;
(iii) at least one polymeric binder; and
(iv) a heterocyclic mercapto compound comprising an aromatic 5-membered heterocyclic ring with a thiol group substituted thereon, the ring comprising a nitrogen atom and at least one heteroatom selected from the group consisting of nitrogen, oxygen and sulfur, in which the heteroatom is separated in the ring from the nitrogen atom by one carbon atom, and in which the thiol group is bonded to the carbon atom;
in which:
ox a <red b +1.6 eV,
in which ox a is the oxidation potential of component (a) in eV, and red b is the reduction potential of component (b) in eV.
20. The method of claim 19 additionally comprising applying a substantially oxygen-impermeable barrier layer over the layer of the infrared-sensitive composition.
21. A method for producing a lithographic printing plate, comprising:
(A) providing a lithographic printing plate precursor comprising a layer of an infrared-sensitive composition over a substrate, the infrared-sensitive composition comprising:
(i) an initiator system comprising:
(a) at least one compound capable of absorbing infrared radiation selected from the group consisting of triarylamine dyes, thiazolium dyes, indolium dyes, oxazolium dyes, cyanine dyes, polyaniline dyes, polypyrrole dyes, polythiophene dyes, and phthalocyanine pigments,
(b) at least one compound capable of producing free radicals, the compound selected from polyhaloalkyl-substituted compounds, and
(c) at least one carboxylic acid represented by formula (I):
R 4 —(CR 5 R 6 ) n —Y—CH 2 COOH (I)
in which:
Y is selected from the group consisting of O, S and NR 7 ;
R 7 is selected from the group consisting of hydrogen, C 1 -C 6 alkyl, —CH 2 CH 2 OH, and C 1 -C 5 alkyl substituted with —COOH;
R 4 , R 5 and R 6 are each independently selected from the group consisting of hydrogen, C 1 -C 4 alkyl, substituted or unsubstituted aryl, —COOH and —NR 8 CH 2 COOH;
R 8 is selected from the group consisting of —CH 2 COOH, —CH 2 OH, and —(CH 2 ) 2 N(CH 2 COOH) 2 ; and
n is 0, 1, 2 or 3;
(ii) at least one component selected from unsaturated free radical-polymerizable monomers, unsaturated oligomers which are free radical-polymerizable, polymers containing free radical-polymerizable carbon-carbon double bonds in one or both of the backbone and a side chain, and mixtures thereof;
(iii) at least one polymeric binder; and
(iv) a heterocyclic mercapto compound comprising an aromatic 5-membered heterocyclic ring with a thiol group substituted thereon, the ring comprising a nitrogen atom and at least one heteroatom selected from the group consisting of nitrogen, oxygen and sulfur, in which the heteroatom is separated in the ring from the nitrogen atom by one carbon atom, and in which the thiol group is bonded to the carbon atom;
in which:
ox a <red b +1.6 eV,
in which ox a is the oxidation potential of component (a) in eV, and red b is the reduction potential of component (b) in eV;
(B) imagewise exposing the precursor to infrared radiation to form an imagewise-exposed precursor comprising exposed and unexposed regions in the layer of infrared sensitive composition, and
(C) developing the imagewise-exposed precursor with a developer to remove said unexposed regions and leave said exposed regions.
22. The method of claim 21 in which the precursor additionally comprises a substantially oxygen-impermeable barrier layer over the layer of the infrared-sensitive composition.
23. The method of claim 21 additionally comprising heating the imagewise exposed precursor before step (C).
24. A printing plate obtained by the method of claim 21 .
25. The printing plate of claim 24 in which the precursor additionally comprises a substantially oxygen-impermeable barrier layer over the layer of the infrared-sensitive composition.
26. A printing plate obtained by the method of claim 23 .