Claims
- 1. A process for forming images, which comprises
- (1) exposing imagewise a photographic material comprising:
- (a) a support,
- (b) a layer containing a salt or complex of monovalent or divalent copper and a hydrophilic binder formed on the support, and
- (c) a silver halide layer formed on layer (b);
- (2) developing the silver halide layer using a chemical developer solution for silver halide; and
- (3) developing the layer (b) using an aqueous developing solution for layer (b) containing at least one reducing agent thereby to form a black non-silver image derived from layer (b) and containing copper at the site of the silver image formed in step (2).
- 2. The process of claim 1, wherein the developer for layer (b) has a pH of 4 to 14.
- 3. The process of claim 1, wherein the developing step (2) is carried out at a temperature of about 20.degree. to about 80.degree. C. for a period of about 30 seconds to about 20 minutes.
- 4. The process of claim 1, wherein the silver halide layer is a vacuum-deposited or sputtered silver halide layer.
- 5. The process of claim 1, wherein the silver halide layer is a silver halide emulsion layer.
- 6. The process of claim 1, wherein the copper salt or complex is at least one compound selected from compounds of the following formulae (1) to (3)
- Cu.sub.n X.sub.m Y.sub.l.gCu.sub.n.spsb.' Z.sub.m.spsb.' ( 1)
- [Cu.sub.n A.sub.m B.sub.l ]X.sub.l.spsb.' ( 2)
- M.sub.r M'.sub.s [Cu.sub.n A.sub.m B.sub.2 X.sub.m.spsb.' Y.sub.l.spsb.' ](3)
- wherein n is an integer of 1 to 5; n' is an integer of 0 to 5, m, m', l, q, r and s each is an integer of 0 to 7 with the proviso that m and l are not 0 at the same time; l' is an integer of 1 to 10; X and Y each is an anion with a valence of 1 to 3; A and B each is a neutral molecule having the ability to coordinate as a Lewis base; Z is an anion with a valence of 1 to 3, a neutral molecule having the ability to coordinate as a Lewis base, or an element of Group VIa; and M and M' each is a cation with a valence of 1 to 3.
- 7. The process of claim 1, wherein in the general formulae (1) to (3),
- X and Y each is selected from the group consisting an anion, including an anion with one or more remaining hydrogens, with a valence of 1 to 3 derived from sulfuric acid, nitric acid, hydrochloric acid, hydrofluoric acid, hydroiodic acid, hydrobromic acid, phosphoric acid, phosphorous acid, nitrous acid, sulfurous acid, thiosulfuric acid, carbonic acid, arsenic acid, boric acid, hydrogen cyanide, perchloric acid, perbromic acid, periodic acid, chromic acid, molybdic acid, hydrogen azide, hydrogen sulfide, selenic acid, telluric acid, tungstic acid, hypochlorous acid, hydrobroic acid and hydrogen thiocyanide; a hydroxyl ion; a boron tetrahydride ion; a boron cyanohydride ion; a tetraaryl boron ion in which the aryl group is a phenyl group or a phenyl group substituted with an alkyl group containing 1 to 5 carbon atoms; and an anion derived from a carboxylic acid of the formula
- R.sup.1 (COOH).sub.p
- a sulfonic acid of the formula
- R.sup.2 (SO.sub.3 H).sub.p '
- a .beta.-diketone of the formula
- R.sup.3 COCHR.sup.4 COR.sup.5,
- a phenol of the following formula ##STR8## and a naphthol of the following formula ##STR9## wherein R.sup.1 represents a hydrogen atom or a straight-chain, branched-chain or cyclic alkyl group containing 1 to 25 carbon atoms or an aryl group with 1 to 3 rings; p is an integer of 1 to 6; R.sup.2 represents a straight-chain, branched-chain, or cyclic alkyl group containing 11 to 18 carbon atoms, or an aryl group containing 1 to 3 rings; p' is an integer of 1 to 6; R.sup.3 and R.sup.5 each represents a straight-chain, branched chain or cyclic alkyl group containing 1 to 5 carbon atoms, an aryl group containing 1 to 3 rings, a furyl group, a thienyl group, an alkoxy group, or a hydrogen atom; R.sup.4 represents a hydrogen atom, a straight-chain, branched chain or cyclic alkyl group containing 1 to 5 carbon atoms, an aryl group containing 1 to 3 rings, a halogen atom, a nitro group, or a thiocyano group; R.sup.6 and R.sup.9 each represents a formyl group, a carboxy group, an acetyl group, an amino group, a hydroxyamino group, an aminomethyl group, an aminoethyl group, a carbamoyl group, an N-aryl carbamoyl group with the aryl moiety containing 1 to 3 rings, an N-hydroxyiminomethine group, an N-aryl iminomethine group with the aryl moiety containing 1 to 3 rings, a hydroxyl group, a cyano group, a pyridyl group, an alkylpyridyl group with the alkyl moiety containing 1 to 5 carbon atoms, an aminophenyl group, a furyl group, an alkylfuryl group with the alkyl moiety containing 1 to 5 carbon atoms, a pyrrolyl group, an alkylpyrrolyl group with the alkyl moiety containing 1 to 5 carbon atoms, an imidazolyl group, an alkylimidazolyl group with the alkyl moiety containing 1 to 5 carbon atoms, a pyrazinyl group, an alkylpyrazinyl group with the alkyl moiety containing 1 to 5 carbon atoms, a pyrimidinyl group, a quinolinyl group, an isoquinolinyl group, a morpholinyl group, or a mercapto group; R.sup.7 and R.sup.8 each represents a straight-chain, branched-chain or cyclic alkyl group containing 1 to 25 carbon atoms, an aryl group containing 1 to 3 rings, a nitro group, a sulfonic acid group, an alkoxycarbonyl group with the alkoxy moiety containing 1 to 10 carbon atoms, or a hydrogen atom; and p" and p"' each is an integer of 0 to 5;
- A and B each is selected from the group consisting of straight-chain, branched-chain or cyclic alkylamines containing 1 to 25 carbon atoms and 1 to 4 amino groups, ammonium groups, imidazole, substituted imidazoles, pyrazole, substituted pyrazoles, pyridine, substituted pyridines, pyrazine, substituted pyrazines, pyrimidine, substituted pyrimidines, pyridazine, substituted pyridazines, indole, substituted indoles, purine, substituted purines, quinoline, substituted quinolines, isoquinoline, substituted isoquinolines, naphthyridine, substituted naphthyridines, quinoxaline, substituted quinoxalines, acridine, substituted acridines, thiophene, substituted thiophenes, benzothiophene, substituted benzothiophenes, naphthothiophene, substituted naphthothiophenes, thianthrene, and substituted thianthrenes, thioethers of the formula
- R.sup.10 -S-R.sup.11
- wherein R.sup.10 and R.sup.11 each represents a straight-chain, branched-chain or cyclic alkyl group containing 1 to 15 carbon atoms, or an aryl group containing 1 to 3 rings, phosphine compounds of the formula ##STR10## wherein R.sup.12, R.sup.13 and R.sup.14 each represents a hydrogen atom, a straight-chain, branched-chain or cyclic alkyl group containing 1 to 15 carbon atoms, an aryl group containing 1 to 3 rings, an alkoxy group containing 1 to 15 carbon atoms, or an aryloxy group containing 1 to 3 rings, stibine compounds of the formula ##STR11## wherein R.sup.12, R.sup.13 and R.sup.14 are the same as defined above, and nitriles of the formula
- NC-R.sup.15 -CN
- wherein R.sup.15 represents a straight-chain, branched-chain or cyclic divalent alkylene group containing 1 to 6 carbon atoms;
- Z is selected from the group consisting of the members described above for X, Y, A and B, and oxygen, sulfur, selenium and tellurium atoms, and water; and
- M and M' each is selected from the group consisting of an ammonium ion, lithium, sodium, potassium, rubidium, magnesium (Mg.sup.2.sym.), calcium, strontium, barium, aluminum, thallium (Tl.sup.3.sym.), chromium (Cr.sup.3.sym.), iron (Fe.sup.2.sym. and Fe.sup.3.sym.), cobalt (Co.sup.2.sym. and Co.sup.3.sym.), nickel (Ni.sup.2.sym. and Ni.sup.3.sym.), palladium (Pd.sup.2.sym.), platinum (Pt.sup.2.sym.), silver, gold (Au.sup..sym. and Au.sup.3.sym.), zinc, cadmium and mercury (Hg.sup.2.sym.) cations, and diazonium ions of the formula ArN.sub.2.sup..sym. wherein Ar represents a phenyl group.
- 8. The process of claim 1, wherein the copper salt or complex is at least one member selected from the group consisting of CuCl, CuBr, CuOH, CuCN, CuSCN, Cu(NO.sub.3).sub.2, CuSO.sub.4, CuSO.sub.3, Cu(HCOO).sub.2, Cu(CH.sub.3 COO).sub.2, Cu[CH.sub.3 (CH.sub.2).sub.t COO].sub.2 wherein t is an integer of 1 to 16, Cu(C.sub.6 H.sub.5 COO).sub.2, Cu.sub.3 (C.sub.6 H.sub.5 O.sub.7).sub.2 (copper citrate), CuCl.sub.2, Cu(OH).sub.2, CuBr.sub.2, CuCl.sub.2.Cu(OH).sub.2, Cu(ClO).sub.2, Cu(BrO.sub.3).sub.2, Cu(ClO.sub.4).sub.2, Cu(ClO.sub.2).sub.2.3Cu(OH).sub.2, CuCO.sub.3, CuCO.sub.3.Cu(OH).sub.2, CuI, CuNO.sub.3, Cu(NO.sub.2).sub.3.3Cu(OH).sub.2, Cu.sub.3 (PO.sub.4).sub.2, Cu.sub.2 S, CuS.sub.4 O.sub.6, CuSO.sub.4.3Cu(OH).sub.2, Cu.sub.2 Se, CuTeO.sub.4, CuTeO.sub.4, Cu.sub.2 WO.sub.4.2CuWO.sub.4, K.sub.2 [CuCl.sub.2 (H.sub.2 O).sub.2 ]Cl.sub.2, K.sub.2 Cu(SO.sub.4).sub.2, KCa[Cu(NO.sub.2).sub.6 ], K[Cu(S.sub.2 O.sub.3)], Na.sub.3 [Cu(S.sub.2 O.sub.3).sub.2 ], (NH.sub.4).sub.2 Cu(SO.sub.4).sub.2, Cu(CH.sub.3 COO), Cu(CH.sub.3 COO).sub.2.3CH.sub.3 COOK, Cu(CH.sub.3 COO).sub.2.3Cu(AsO.sub.2).sub.2, (NH.sub.4).sub.2 [Cu(CH.sub.3 COO).sub.4 ], Cu(BrCH.sub.2 COO).sub.2, Cu(C.sub.6 H.sub.5 COO), Cu(C.sub.15 H.sub.31 COO).sub.2, Cu(C.sub.17 H.sub.35 COO).sub.2, Cu(C.sub.12 H.sub.25 COO).sub.2, Cu(C.sub.10 H.sub.21 COO).sub.2, Cu(C.sub.3 H.sub.7 COO).sub.2, Cu(C.sub.6 H.sub.5 C.sub.10 H.sub.20 COO).sub.2, Cu(C.sub.2 H.sub.5 C.sub.6 H.sub.4 COO).sub.2, Cu(OC.sub.6 H.sub.4 CHO).sub.2, Cu[CH.sub.3 CH(OH)COO].sub.2, Cu[CH.sub.3 CH(NH.sub.2)COO].sub.2, Cu[HOCH.sub.2 CH(OH)COO].sub.2, Cu[OOCCH.sub.2 CH(NH.sub.2)COO], Cu[OOC(CHOH).sub.2 COO], Cu[ONC(CH.sub.3)C(CH.sub.3)NOH].sub.2, Cu(CH.sub.3 COCHCHCHO).sub.2, Cu[OOCCH(NH.sub.2)CH.sub.2 CH.sub. 2 COO], Cu(CH.sub.3 COCHCOCH.sub.3).sub.2, Cu(CH.sub.3 COCHCOOCH.sub.3).sub.2, Cu(CF.sub.3 COCH.sub.2 COCH.sub.3).sub.2, Cu(C.sub.6 H.sub.5 COCHCOCH.sub.3).sub.2, Cu(C.sub.6 H.sub.5 COCHCOCF.sub.3).sub.2, Cu(CH.sub.3 COC(C.sub.6 H.sub.5)COCH.sub.3).sub.2, Cu(CH.sub.3 COCBrCOCH.sub.3).sub.2, Cu(CH.sub.3 COCCH.sub.3 COCH.sub.3).sub.2, Cu(CH.sub.3 COCHCOOC.sub.2 H.sub.5).sub.2, Cu[(CH.sub.3 CO).sub.2 CCOOCH.sub.3 ].sub.2, Cu[(CH.sub.3 COCHCOOC.sub.2 H.sub.5).sub.2 (NH.sub.3).sub.2 ], Cu(C.sub.5 H.sub.4 NCOO).sub.2, Cu[C.sub.5 H.sub.3 N(COO).sub.2 ], Cu(NH.sub.2 C.sub.6 H.sub.4 SO.sub.3).sub.2, Cu(HOC.sub.6 H.sub.5 SO.sub.3).sub.2, Cu[(CH.sub.3).sub.2 CHCH.sub.2 CH(NH.sub.2)COO].sub.2, Cu(C.sub.6 H.sub.5 CONH.sub.2 COO).sub.2, Cu[OOC(CH.sub.2).sub.8 COO], Cu(OC.sub.6 H.sub.4 CH.dbd.NH).sub.2, Cu[OC.sub.6 H.sub.3 (NO.sub.2)CH.sub.2 NH.sub.2 ].sub.2, Cu[(CH.sub.3).sub.2 NCS.sub.2 ].sub.2, Cu(NH.sub.3).sub.2 Cl.sub.2, [Cu(NH.sub.3).sub.2 ](NCS).sub.2, [Cu(C.sub.5 H.sub.5 N).sub.6 ]Cl.sub.2, [Cu(C.sub.5 H.sub.5 N).sub.6 ](ClO.sub.4).sub.2, [Cu(C.sub.5 H.sub.5 N).sub.6 ](NO.sub.3).sub.2, {Cu[(C.sub.5 H.sub.4 N).sub.2 ].sub.3 }Cl.sub.2, {Cu[(C.sub.5 H.sub.4 N).sub.2 ].sub.2 }(NO.sub.3).sub.2, [Cu(H.sub.2 NCH.sub.2 CH.sub.2 NH.sub.2).sub.2 ]Cl.sub.2, [Cu(H.sub.2 NCH.sub.2 CH.sub.2 NH.sub.2).sub.3 ]Cl.sub.2, [Cu(H.sub.2 NCH.sub.2 CH.sub.2 NH.sub.2).sub.2 ](ClO.sub.4).sub.2, {Cu[H.sub.2 N(CH.sub.2).sub.4 NH.sub.2 ]}.sub.2 (ClO.sub.4).sub.2, [Cu(H.sub.2 NCH.sub.2 CH.sub.2 NH.sub.2).sub.2 ].[B(C.sub.6 H.sub.5).sub.4 ].sub.2, Cu[(H.sub.2 NCH.sub.2 COO).sub.2 (H.sub.2 NCH.sub.2 CH.sub.2 NH.sub.2).sub.2 ], [Cu(CH.sub.3 CSNH.sub.2).sub.4 ]Cl, [Cu(CH.sub.3 CSNH.sub.2).sub.4 ]NO.sub.3, [Cu(CH.sub.3 CSNH.sub.2).sub.4 ].sub.2 SO.sub.4, [Cu(CH.sub.3 CSNH.sub.2).sub.4 Br, [Cu(CH.sub.3 SCH.sub.2 CH.sub.2 SCH.sub.3)]Br, Cu(NO.sub.3).sub.2.Cu(N.sub.3).sub.2, Cu.sub.2 [OOC(CHOH).sub.2 COO], Cu(CH.sub.3 SCH.sub.2 CH.sub.2 SCH.sub.3)Cl.sub.2, ##STR12## Cu(C.sub.6 H.sub.5 CH.sub.2 SCH.sub.2 C.sub.6 H.sub.5).sub.2 Cl.sub.2, {Cu[HONC(CH.sub.3)C(CH.sub.3)NOH].sub.2 }Cl.sub.2, {Cu[HONC(CH.sub.3)C(CH.sub.3)NOH].sub.2 }SO.sub.4, [2CuCl.CH.sub.3 N.dbd.NCH.sub.3 ].CuC.sub.2 O.sub.4, {Cu[(C.sub.2 H.sub.5 O).sub.3 P].sub.3 NO.sub.3, {Cu[(C.sub.6 H.sub.5 O).sub.3 P].sub.3 }Cl, {Cu[(C.sub.6 H.sub.5 O).sub.3 P].sub.2 }BH.sub.4, {Cu[(C.sub.2 H.sub.5 O).sub.3 P].sub.2 }BH.sub.4, {Cu[(C.sub.2 H.sub.5 O).sub.2 P].sub.2 }BH.sub.3 CN, {Cu[(C.sub.6 H.sub.5).sub.3 P].sub.2 }BH.sub.4, {Cu[(C.sub.6 H.sub.5).sub.3 P].sub.2 }BH.sub.3 CN, {Cu[(CH.sub.3 C.sub.6 H.sub.4).sub.3 P].sub.3 }BH.sub.3 CN, {Cu[(C.sub.6 H.sub.5).sub.3 Sb].sub.3 }NO.sub.3, {Cu[(C.sub.6 H.sub.5).sub.3 Sb].sub.3 }BH.sub.3 CN, Cu(NCCH.sub.2 CN).sub.2 NO.sub.3, Cu[NC(CH.sub.2).sub.2 CN].sub.2 NO.sub.3, Cu[NC(CH.sub.2).sub.3 CN].sub.2 NO.sub.3, Cu[NC(CH.sub.2).sub.4 CN]NO.sub.3, Cu[NC(CH.sub.2).sub.5 CN].sub.2 NO.sub.3, Cu[C.sub.6 H.sub.4 (CN).sub.2 ].sub.2 NO.sub.3, ##STR13## Cu(HOC.sub.6 H.sub.4 COO).sub.2, Cu[C.sub.6 H.sub.13 (OH).sub.2 COO].sub.2, Cu(CH.sub.3 C.sub.6 H.sub.4 COO).sub.2, Cu(CH.sub.3 COCH.sub.3 COCH.sub.3).sub.2, Cu(CF.sub.3 COCHCOCH.sub.3).sub.2, ##STR14## Cu[OOC(CH.sub.2).sub.u COO] wherein u is an integer of 1 to 8, Cu(NH.sub.3).sub.2 Cl.sub.2, [Cu(NH.sub.3).sub.2 ](NCS).sub.2, [Cu(H.sub.2 NCH.sub.2 CH.sub.2 NH.sub.2).sub.2 ]Cl.sub.2, [Cu(H.sub.2 NCH.sub.2 CH.sub.2 NH.sub.2).sub.2 ]Br.sub.2, [Cu(H.sub.2 NCH.sub.2 CH.sub.2 NH.sub.2).sub.2 ][B(C.sub.6 H.sub.5).sub.4 ].sub.2, [Cu(H.sub.2 NCH.sub.2 CH.sub.2 NH.sub.2).sub.2 ](NO.sub.3).sub.2, [Cu(H.sub.2 NCH.sub.2 CH.sub.2 NH.sub.2).sub.2 ]SO.sub.4, [Cu(C.sub.5 H.sub.5 N).sub.2 ]Cl.sub.2, [Cu(C.sub.5 H.sub.5 N).sub.2 ]Br.sub.2, Cu[NC(CH.sub.2).sub.v CN].sub.2 NO.sub.3 wherein v is an integer of 1 to 8, Cu[C.sub.6 H.sub.4 (CN).sub.2 ].sub.2 NO.sub.3, Cu[P(C.sub.6 H.sub.5).sub.3 ].sub.2 BH.sub.4, Cu[P(C.sub.6 H.sub.4 CH.sub.3).sub.3 ].sub.2 BH.sub.4, Cu[P(C.sub.6 H.sub.5).sub.3 ].sub.3 BH.sub.3 CN, Cu[P(C.sub.6 H.sub.5).sub.3 ].sub.2 NO.sub.3, Cu[P(C.sub.6 H.sub.5).sub.3 ].sub.4 B(C.sub.6 H.sub.5).sub.4, Cu[P(C.sub.6 H.sub.5).sub.3 ].sub.2 Cl, Cu[Sb(C.sub.6 H.sub.5).sub.3 ].sub.3 BH.sub.3 CN, Cu[Sb(C.sub.6 H.sub.5).sub.3 ].sub.3 Cl, Cu[P(OCH.sub.3).sub.3 ].sub.4 B(C.sub.6 H.sub.5).sub.4, and Cu[P(OCH.sub.3).sub.3 ].sub.3 BH.sub.3 CN.
- 9. The process of claim 1, wherein the copper salt or complex is present in an amount of about 5 to about 60 parts by weight per 100 parts by weight of the hydrophilic binder.
- 10. The process of claim 1, wherein the hydrophilic binder has a molecular weight of about 5,000 to about 300,000 and is selected from the group consisting of cellulose acetate having a degree of acetylation of 40 to 60%, gelatin, carboxymethyl cellulose, polyvinyl alcohol, polyvinyl pyrrolidone and polyacrylamide.
- 11. The process of claim 1, wherein the support has a thickness of about 10 .mu.m to about 2 mm and is at least one member selected from the group consisting of polyethylene terephthalate sheetlike materials, polyamide sheet-like materials, nylon sheet-like materials, triacetyl cellulose sheet-like materials, baryta paper, coated papers, resin-finished papers, synthetic paper-like sheets, wooden plates, metal plates and glass sheets.
- 12. The process of claim 1, wherein layer (b) has a thickness of about 1 .mu.m to about 100 .mu.m.
- 13. The process of claim 1, wherein the silver halide is at least one member selected from the group consisting of silver chloride, silver bromide, silver chlorobromide with a silver chloride content of about 2 to about 98 mole %, silver iodobromide with a silver iodide content of about 1 to about 10 mole %, and silver chloroiodide with a silver iodide content of about 1 to about 10 mole %.
- 14. The process of claim 1, wherein the silver halide emulsion layer contains a binder which is at least one member selected from the group consisting of gelatin, a gelatin derivative, carboxymethyl cellulose, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide and cellulose acetate with a degree of acetylation of 40 to 60%.
- 15. The process of claim 1, wherein the silver halide layer contains about 0.005 to 1 g of silver halide calculated as metallic silver per square meter of the photographic material.
- 16. The process of claim 5, wherein the silver halide emulsion layer has a thickness of about 0.1 .mu.m to about 20 .mu.m.
- 17. The process of claim 1, wherein the development of the silver halide layer and layer (b) is performed simultaneously in one developing solution.
- 18. The process of claim 1, wherein the development of the silver halide layer and layer (b) is performed successively by developing the silver halide layer in one chemical developing solution, fixing the developed silver halide layer, and then developing layer (b) in a different developing solution.
- 19. The process of claim 1, wherein the aqueous developer solution for the layer (b) has a concentration of said reducing agent from about 1 to about 15% by weight based on water.
- 20. The process of claim 1, wherein the reducing agent is paraformaldehyde, dimethylamineborane, sodium borohydride, L-asocorbic acid or sodium dithionite (Na.sub.2 S.sub.2 O.sub.4).
- 21. The process of claim 1 wherein the black non-silver image contains copper (II) oxide at the site of the silver image formed in step (2).
- 22. The process of claim 1, wherein said silver halide layer is a vacuum deposited or sputter etched layer and said black non-silver image contains copper II oxide.
Priority Claims (2)
Number |
Date |
Country |
Kind |
50-142077 |
Nov 1975 |
JPX |
|
51-13797 |
Feb 1976 |
JPX |
|
Parent Case Info
This is a continuation of application Ser. No. 745,908 filed Nov. 29, 1976, now abandoned.
US Referenced Citations (9)
Continuations (1)
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Number |
Date |
Country |
Parent |
745908 |
Nov 1976 |
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