Claims
- 1. A planographic printing plate material comprising a support and a binderless light-sensitive layer provided on said support, said light-sensitive layer being composed of:
- (A) an inorganic material selected from the group consisting of
- (1) a sulfur group element selected from the group consisting of S, Te, Se and a mixture therof,
- (2) a chalcogenide composition represented by the formula
- M-Sulfur Group Element,
- M-Sulfur Group Element-X or
- M-Sulfur Group Element-X-Y,
- wherein the amount of said sulfur group element present in said chalcogenide composition is more than that of said sulfur group element stoichiometrically corresponding to the lowest valency of the atom represented by M with exception of a valency of zero; and M represents an atom of Group Ib, IIb, IIIb, IVa, IVb, Vb, VIa or VIII of the Period Table; and X and Y, which are not the same as M, each represents an atom selected from the group consisting of Al, Sb, Si, Mg, Ti, V, Mn, Co, Ni, Ta, Mo, W, Sn, Zn, Pb, Bi, Ag, Pd, In, O, P, Cl, Br and I and
- (3) a halide of an element selected from the group consisting of Pb, Sn and Ge, wherein the amount of the halogen present therein is more than that of said halogen stoichiometrically corresponding to a lowest valency of said element other than a valency of zero;
- (B) Ag or Cu
- (C) an organic compound selected from the group consisting of benzotriazole; carboxylic acids; phenols; amines, hydrazines; alkylene oxide polymers; --CO--NH group-containing compounds; sulfur-containing organic compounds having at least one of an --SH group, a >C.dbd.S group, an --(S).sub.n -group wherein n=1 to 6, an --SO.sub.2 H group or an --SO.sub.3 H group; selenic acids; a dye selected from the group consisting of an azo dye, an anthraquinone dye, an indigoid dye, a soluble vat dyeing dye, a sulfur dye, a carbonium dye, a quinoneimine dye, a phthalocyanine dye, a cyanine dye, a quinoline dye, a nitro dye and a nitroso dye; and spiropyrans, wherein said inorganic material (A) and said Ag or Cu (B) are capable of reacting with each other upon the application of electromagnetic radiation, said organic compound (C) is capable of affecting the reaction between said inorganic material (A) and said Ag or Cu (B), and said inorganic material (A), said Ag or Cu (B), and said organic compound (C) are all in contact with each other, at least one of said inorganic material (A), said Ag or Cu (B) and said organic compound (C) having been deposited in the form of discontinuous island-like particles, whereby upon the imagewise application of electromagnetic radiation, a difference in hydrophilic or olephilic nature is produced between the irradiated areas and the unirradiated areas of said light-sensitive layer.
- 2. The planographic printing plate material according to claim 1, wherein the support is selected from the group consisting of a metal plate, a plastic sheet whose surface has been rendered hydrophilic, and a sheet in which a metal plate or metal foil is laminated onto a plastic sheet or paper.
- 3. The planographic printing plate material according to claim 1, wherein the support is an aluminum plate or a zinc plate.
- 4. The planographic printing plate material according to claim 1, wherein M of said chalcogenide composition is an element of Group Ib, IVa, IVb or VIII of the Periodic Table.
- 5. The planographic printing plate material according to claim 4, wherein M is ge, Sn Pb, Si, Ag, Ti or Fe.
- 6. The planographic printing plate material according to claim 4 wherein said sulfur group element of said chalcogenide composition is sulfur.
- 7. The planographic printing plate material according to claim 1, wherein said halide of said element of Group IVb is PbI.sub.2, SnI.sub.4 or GeI.sub.4.
- 8. The planographic printing plate material according to claim 1, wherein said inorganic material (A) is a composition containing germanium and sulfur.
- 9. The planographic printing plate material according to claim 1, wherein said organic compound (C) is benzotriazole.
- 10. The planographic printing plate material according to claim 1, wherein said organic compound (C) is sulfur-containing organic compound.
- 11. The planographic printing plate material according to claim 10, wherein said sulfur-containing organic compound is selected from the group consisting of:
- (1) a thiourea represented by the following formula: ##STR108## wherein R.sup.1 to R.sup.4 each represents a hydrogen atom, an alkyl group, an hydroxyalkyl group having 1 to 5 carbon atoms, or a phenyl group; and wherein either R.sup.1 and R.sup.2 or R.sup.3 and R.sup.4 may combine and form a 5-membered heterocyclic ring;
- (2) a thiosemicarbazide or a thiocarbazide represented by the following formulae and derivatives thereof: ##STR109## wherein R.sup.1 to R.sup.4 each represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group;
- (3) a dithiocarbamic acid represented by the following formula: ##STR110## wherein R.sup.1 and R.sup.2 each represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aralkyl group having 7 to 9 carbon atoms, or a phenyl group; wherein M.sub.1 represents a hydrogen atom or a metal ion having a valency represented by n; and wherein n represents 1 to 2;
- (4) a thiobenzophenone represented by the following formula: ##STR111## wherein R.sup.1 and R.sup.2 each represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an amino group substituted with 2 alkyl groups which each may have 1 to 5 carbon atoms, a chlorine atom, a bromine atom or an iodine atom;
- (5) a 5-membered ring or a derivative thereof containing a sulfur atom as one member of the ring;
- (6) an imidazole or benzimidazole each of which is substituted with any of an --SH group, an .dbd.S group or an --S--R group, wherein R represents an alkyl group having up to 20 carbon atoms, an alkenyl group having up to 20 carbon atoms or a phenyl group, and each of which can be further substituted with at least one of an alkyl group having 1 to 20 carbon atoms, an alkylamido group having 2 to 21 carbon atoms, and a phenyl group;
- (7) an imidazoline substituted with any of an --SH group, an .dbd.S group or an --S--R group, wherein R represents an alkyl group having up to 20 carbon atoms, an alkenyl group having up to 20 carbon atoms or a phenyl group;
- (8) a trizole or benzotriazole, each of which is substituted with any of an --SH group, an .dbd.S group or an --S--R group, wherein R represents an alkyl group having up to 20 carbon atoms, an alkenyl group having up to 20 carbon atoms or a phenyl group, and each of which can be further substituted with at least one of 1 or 2 alkyl groups having 1 to 20 carbon atoms, a phenyl group and a phenyl group substituted with an alkylamido group having 2 to 20 carbon atoms;
- (9) a tetrazole substituted with any of an --SH group, an .dbd.S group or an --S--R group, wherein R represents an alkyl group having up to 20 carbon atoms, an alkenyl group having up to 20 carbon atoms or a phenyl group, and which can be further substituted with 1 or 2 alkyl groups having 1 to 5 carbon atoms, a phenyl group, or a phenyl group substituted with at least one of a benzamido group and an alkylamido group having 2 to 21 carbon atoms;
- (10) a pyrimidine substituted with any one of an --SH group, an .dbd.S group or an --S--R group, wherein R represents an alkyl group having up to 20 carbon atoms, an alkenyl group having up to 20 carbon atoms or a phenyl group, and which can be further substituted with 1 or more alkyl groups having 1 to 5 carbon atoms or with an oxo group; and
- (11) a tetrazaindene substituted with any of an --SH group, an .dbd.S group or an --S--R group, wherein R represents an alkyl group having up to 20 carbon atoms, an alkenyl group having up to 20 carbon atoms or a phenyl group, and which can be further substituted with an alkyl group having 1 to 3 carbon atoms or a hydroxyl group.
- 12. The planographic printing plate material according to claim 11, wherein said 5-membered ring or said derivative thereof containing a sulfur atom as one member of the ring is selected from the group consisting of a dithiolan; a thiazole or benzothiazole, each of which can be substituted with at least one of an alkyl group having 1 to 5 carbon atoms, an acetylthioacetamido group, an --NH.sub.2 group and an --SH group; a thiazoline; a rhodanine, an isorhodanine; a thiazolidine; and a thiadiazole.
- 13. The planographic printing plate material according to claim 1, wherein said organic compound (C) is a dye.
- 14. The planographic printing plate material according to claim 13, wherein said dye is selected from the group consisting of Methylene Blue, Crystal Violet or Rhodamine B.
- 15. The planographic printing plate material according to claim 1, wherein said organic compound (C) is a spiropyran.
- 16. The planographic printing plate material according to claim 15, wherein said spiropyran is selected from the group consisting of
- 1,3,3-trimethyl-6'-nitro-spiro(indoline-2,2'-benzo-.alpha.-pyran),
- 3-(3-sulfopropyl)-5-chloro-6'-nitrospiro(benzothiazoline-2,2'-benzo-.alpha.-pyran),
- 1,3,3,-trimethyl-6',8'-dibromo-7'-nitrospiro(indoline-2,2'-benzo-.alpha.-pyran),
- 1,3,3-trimetyl-6'-nitro-8'-methoxyspiro(indoline-2,2'-benzo-.alpha.-pyran),
- 3-ethyl-6'-nitrospiro(benzothiazoline-2,2'-benzo-.alpha.-pyran),
- 1. 3,3-trimethyl-6'-bromospiro(indoline-2,2'-benzo-.alpha.-pyran),
- 1,3,3-trimethyl-6',8'-dibromospiro(indoline-2,2'-benzo-.alpha.-pyran),
- 3-ethyl-6'-nitrospiro(naphtho[2,1,d]thiazoline-2,2'-benzo-.alpha.-pyran),
- 1,3,3-trimethyl-6',8'-dichlorospiro(indoline-2,2'-benzo-.alpha.-pyran),
- 1,3-dimethyl-3-benzyl-6'-nitrospiro(indoline-2,2'-benzo-.alpha.-pyran),
- 3-ethyl-5-methoxy-6'-nitrospiro(benzoselenazoline-2,2'-benzo-.alpha.-pyran)
- 1,3,3-trimethyl-6'-bromo-8'-nitrospiro(indoline-2,2'-benzo-.alpha.-pyran),
- 3-ethyl-6'-bromospiro(naphtho[2,1,d]thiazoline-2,2'-benzo-.alpha.-pyran),
- 3-(4-sulfobutyl)-5-methoxy-6'-nitrospiro(benzoselenazoline-2,2'-benzo-.alpha.-pyran),
- 1,3,3-trimethyl-6'-nitro-8'-bromospiro(indoline-2,2'-benzo-.alpha.-pyran),
- 3-(4-sulfobutyl)-5-methoxy-6',8'-dibromo-7'-nitrospiro(benzoselenazoline-2,2'-benzo-.alpha.-pyran),
- 3-(3-sulfopropyl)-5-methoxy-6'-nitrospiro(benzoselenazoline-2,2'-benzo-.alpha.-pyran),
- 3-(3-sulfopropyl)-6'-nitrospiro(naphtho[1,2,d]-thiazoline-2,2-benzo-.alpha.-pyran), and
- 3-ethyl-6'-nitrospiro(benzoselenazoline-2,2'-benzo-.alpha.-pyran).
- 17. The planographic printing plate material according to claim 1, wherein said Ag or Cu (B) and said organic compound (C) are deposited in amounts of 1 to 300 parts by weight and 0.3 to 30 parts by weight, respectively, based on 100 parts by weight of said inorganic material (A).
- 18. The planographic printing plate material according to claim 1, wherein said inorganic material (A), said Ag or Cu (B) and said organic compound (C) are each deposited as discontinuous particles having an average particles size of about 10 A to about 0.5 micron.
- 19. The planographic printing plate material according to claim 1, wherein two of said inorganic material (A), said Ag or Cu (B) and said inorganic compound (C) are deposited in the form of discontinuous particles, and the remaining one of said inorganic material (A), said Ag or Cu (B) or said organic compound (C) is in the form of a layer.
- 20. The planographic printing plate material according to claim 1, wherein one of said inorganic material (A), said Ag or Cu (B) and said organic compound (C) is deposited in the form of discontinuous particles, and the other two of said inorganic material (A), said Ag or Cu (B) or said organic compound (C) are deposited in the form of a layer.
- 21. The planographic printing plate material according to claim 1, wherein said inorganic material (A) is deposited in an amount of 0.1 .mu.g to 10 .mu.g/cm.sup.2, said Ag or Cu (B) is deposited in an amount of 0.1 .mu.g to 30 .mu.g/cm.sup.2 and said organic compound (C) is deposited in an amount of 0.1 .mu.g to 3 .mu.g/cm.sup.2.
- 22. The planographic printing plate material according to claim 19, wherein said inorganic material (A) is deposited in an amount of 0.1 .mu.g/cm.sup.2 to 10 .mu.g/cm.sup.2, said Ag or Cu (B) is deposited in an amount of 0.1 .mu.g/cm.sup.2 to 30 .mu.g/cm.sup.2, and said organic compound (C) is deposited at a thickness of 300 A to 10.mu..
- 23. The planographic printing plate material according to claim 19, wherein said inorganic material (A) is deposited in an amount of 0.1 .mu.g/cm.sup.2 to 10 .mu.g/cm.sup.2, said Ag or Cu (B) is deposited at a thickness of 300 A to 10.mu., and said organic compound (C) is deposited in an amount of 0.1 .mu.g/cm.sup.2 to 3 .mu.g/cm.sup.2.
- 24. The planographic printing plate material according to claim 19, wherein said inorganic material (A) is deposited at a thickness of 300 A to 10.mu., said Ag or Cu (B) is deposited in an amount of 0.1 .mu.g/cm.sup.2 to 30 .mu.g/cm.sup.2, and said organic compound (C) is deposited in an amount of 0.1 .mu.g/cm.sup.2 to 3 .mu.g/cm.sup.2.
- 25. The planographic printing plate material according to claim 20, wherein said inorganic material (A) is deposited in an amount of 0.1 .mu.g/cm.sup.2 to 10 .mu.g/cm.sup.2 and said Ag or Cu (B) and said organic compound (C) are each deposited at a thickness of 300 A to 10.mu..
- 26. The planographic printing plate material according to claim 20, wherein said Ag or Cu (B) is deposited in an amount of 0.1 .mu.g/cm.sup.2 to 30 .mu.g/cm.sup.2, and said inorganic material (A) and said orgnaic compound (C) are each deposited at a thickness of 300 A to 10.mu..
- 27. The planographic printing plate material according to claim 20, wherein said organic compound (C) is deposited in an amount of 0.1 .mu.g/cm.sup.2 to 3 .mu.g/cm.sup.2 and said inorganic material (A) and said Ag or Cu (B) are each deposited at a thickness of 300 A to 10.mu..
- 28. A process for producing a non-treatment type planographic printing plate by image-wise exposing to electromagnetic radiation the planographic printing plate material according to claim 1.
- 29. The planographic printing plate material according to claim 1 wherein the chalcogenide composition is selected from the group consisting of: chalcogenide compositions represented by M-sulfur Group Element which satisfy the relationship 2n/km>1 when the quantitative relationship between each element contained therein is considered to be (M).sub.m.sup.k (Sulfur Group Element).sub.n [wherein k is the lowest valency which M can have, other than 0, m is the number of M] and n is the number of the Sulfur Group Element;
- (ii) Chalcogenide compositions represented by M-Sulfur Group Element-X which satisfy the following relationship. ##EQU3## when the quantitative relationship between each element present therein is considered to be (M).sub.m.sup.k (Sulfur Group Element).sub.n (X).sub.l.sup.h [wherein k, m and n each has the same meanings as defined above, h is the lowest valency which X can have, other than 0, and 1 is the number of X] and when X is an element which folls in the category defined as M, M in the above formula represents the element of the two elements, which is present in larger amount; and
- (iii) Chalcogenide compositions represented by M-Sulfur Group Element-X-Y which satisfy the following relationship; ##EQU4## when the quantitative relationship between each element present therein is considered to be (M).sub.m.sup.k (Sulfur Group Element).sub.n (X).sub.l.sup.h (Y).sub.p.sup.j [wherein k, m, n, h, l, each has the same meanings as defined above, j is the lowest valency which Y can have, other than 0, and p is the number of Y] and when X and/or Y are elements which fall in the category defined as M, M in the above formula represents the element of the two or three elements, which is present in largest amount; and wherein in the chalcogenide composition of M-Sulfur Group element-X, a content of X is not more than 30 atomic % based on the composition, and in the chalcogenide composition of M-Sulfur Group Element-X-Y, the total amount of X and Y is not more than 30 atomic % based on the total composition.
- 30. The planographic printing plate material according to claim 8 wherein the composition ratio of the germanium and sulfur-containing compositions is in the range of 1.5.ltoreq.S/Ge<16.
- 31. The planographic printing plate material according to claim 30 wherein the ratio is 1.7.ltoreq.S/Ge<9.
Priority Claims (1)
Number |
Date |
Country |
Kind |
50-92391 |
Jul 1975 |
JPX |
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CROSS REFERENCE TO RELATED APPLICATIONS
This application is a continuation-in-part application of copending application, Ser. No. 709,744, filed July 29, 1976, now abandoned.
US Referenced Citations (9)
Continuation in Parts (1)
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Number |
Date |
Country |
Parent |
709744 |
Jul 1976 |
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