US20030054298A1 - Photographic processing composition containing heterocycle combination and method of forming image - Google Patents
Photographic processing composition containing heterocycle combination and method of forming image Download PDFInfo
- Publication number
- US20030054298A1 US20030054298A1 US10/108,900 US10890002A US2003054298A1 US 20030054298 A1 US20030054298 A1 US 20030054298A1 US 10890002 A US10890002 A US 10890002A US 2003054298 A1 US2003054298 A1 US 2003054298A1
- Authority
- US
- United States
- Prior art keywords
- photographic
- processing composition
- composition
- processing
- photographic processing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
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- 239000000203 mixture Substances 0.000 title claims abstract description 167
- 238000012545 processing Methods 0.000 title claims abstract description 128
- 238000000034 method Methods 0.000 title claims description 32
- 125000000623 heterocyclic group Chemical group 0.000 title description 4
- -1 silver halide Chemical class 0.000 claims abstract description 77
- 239000000463 material Substances 0.000 claims abstract description 61
- 150000001875 compounds Chemical class 0.000 claims abstract description 52
- 229910052709 silver Inorganic materials 0.000 claims abstract description 42
- 239000004332 silver Substances 0.000 claims abstract description 42
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 9
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims abstract description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 7
- 125000003118 aryl group Chemical group 0.000 claims abstract description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 5
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 5
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 5
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 claims abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 claims abstract description 4
- 125000001424 substituent group Chemical group 0.000 claims abstract description 4
- 238000011161 development Methods 0.000 claims description 43
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 5
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- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 4
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 4
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
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- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 238000005282 brightening Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
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- 230000002401 inhibitory effect Effects 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
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- 229910052700 potassium Inorganic materials 0.000 description 3
- 235000011181 potassium carbonates Nutrition 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
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- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 description 2
- YSEBWPQBEDKBBV-UHFFFAOYSA-N 4-aminobenzenesulfinic acid Chemical compound NC1=CC=C(S(O)=O)C=C1 YSEBWPQBEDKBBV-UHFFFAOYSA-N 0.000 description 2
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- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 2
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- RNMCCPMYXUKHAZ-UHFFFAOYSA-N 2-[3,3-diamino-1,2,2-tris(carboxymethyl)cyclohexyl]acetic acid Chemical compound NC1(N)CCCC(CC(O)=O)(CC(O)=O)C1(CC(O)=O)CC(O)=O RNMCCPMYXUKHAZ-UHFFFAOYSA-N 0.000 description 1
- DMQQXDPCRUGSQB-UHFFFAOYSA-N 2-[3-[bis(carboxymethyl)amino]propyl-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)CCCN(CC(O)=O)CC(O)=O DMQQXDPCRUGSQB-UHFFFAOYSA-N 0.000 description 1
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- KDWGEPODFRBACT-UHFFFAOYSA-N 2-[hydroxy(2-sulfoethyl)amino]ethanesulfonic acid Chemical class OS(=O)(=O)CCN(O)CCS(O)(=O)=O KDWGEPODFRBACT-UHFFFAOYSA-N 0.000 description 1
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- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 229960005261 aspartic acid Drugs 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 229940000635 beta-alanine Drugs 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- ZUIVNYGZFPOXFW-UHFFFAOYSA-N chembl1717603 Chemical compound N1=C(C)C=C(O)N2N=CN=C21 ZUIVNYGZFPOXFW-UHFFFAOYSA-N 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000012611 container material Substances 0.000 description 1
- 150000003950 cyclic amides Chemical class 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- WTNULKDCIHSVKN-UHFFFAOYSA-N imidazo[1,2-a]pyridin-2-ol Chemical compound C1=CC=CC2=NC(O)=CN21 WTNULKDCIHSVKN-UHFFFAOYSA-N 0.000 description 1
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- IUELRVAIJCOPFL-UHFFFAOYSA-N n-(4-amino-3-methylphenyl)pyrrolidine-3-carboxamide Chemical compound C1=C(N)C(C)=CC(NC(=O)C2CNCC2)=C1 IUELRVAIJCOPFL-UHFFFAOYSA-N 0.000 description 1
- HFWWEMPLBCKNNM-UHFFFAOYSA-N n-[bis(hydroxyamino)methyl]hydroxylamine Chemical compound ONC(NO)NO HFWWEMPLBCKNNM-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- YZMHQCWXYHARLS-UHFFFAOYSA-N naphthalene-1,2-disulfonic acid Chemical compound C1=CC=CC2=C(S(O)(=O)=O)C(S(=O)(=O)O)=CC=C21 YZMHQCWXYHARLS-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- CMCWWLVWPDLCRM-UHFFFAOYSA-N phenidone Chemical class N1C(=O)CCN1C1=CC=CC=C1 CMCWWLVWPDLCRM-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229940068886 polyethylene glycol 300 Drugs 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- RWPGFSMJFRPDDP-UHFFFAOYSA-L potassium metabisulfite Chemical compound [K+].[K+].[O-]S(=O)S([O-])(=O)=O RWPGFSMJFRPDDP-UHFFFAOYSA-L 0.000 description 1
- 229940043349 potassium metabisulfite Drugs 0.000 description 1
- 235000010263 potassium metabisulphite Nutrition 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 125000000246 pyrimidin-2-yl group Chemical group [H]C1=NC(*)=NC([H])=C1[H] 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- AYNUCZFIHUUAIZ-UHFFFAOYSA-N s-(2h-triazol-4-yl)thiohydroxylamine Chemical compound NSC1=CNN=N1 AYNUCZFIHUUAIZ-UHFFFAOYSA-N 0.000 description 1
- 150000003870 salicylic acids Chemical class 0.000 description 1
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 235000011182 sodium carbonates Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 150000003460 sulfonic acids Chemical group 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 239000003826 tablet Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 229960003080 taurine Drugs 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- 150000003567 thiocyanates Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/69—Two or more oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/72—Nitrogen atoms
- C07D213/73—Unsubstituted amino or imino radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D237/00—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings
- C07D237/02—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings
- C07D237/06—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D237/10—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D237/22—Nitrogen and oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D237/00—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings
- C07D237/26—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings condensed with carbocyclic rings or ring systems
- C07D237/30—Phthalazines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
- C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
- C07D239/48—Two nitrogen atoms
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/407—Development processes or agents therefor
- G03C7/413—Developers
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/42—Bleach-fixing or agents therefor ; Desilvering processes
- G03C7/421—Additives other than bleaching or fixing agents
Definitions
- the present invention relates to a processing composition for silver halide color photographic lightsensitive material. More particularly, the present invention relates to a processing composition which is excellent in the capability of reducing stain attributed to sensitizing dyes remaining in the lightsensitive material after the processing thereof and which is free of any precipitation deposits during the low-temperature storage thereof.
- JP-A- 6-329936 discloses a bistriazinylaminostilbenedisulfonic acid compound which has high solubility and is capable of reducing the residual color even in the expedited processing.
- U.S. Pat. Nos. 6,153,364 and 6,153,365 proposed methods of reducing the residual color with the use of highly stable compounds of novel structure.
- a photographic processing composition for silver halide color photographic lightsensitive material comprising at least one compound represented by the formula (I):
- each of A 1 and A 2 independently represents an aryl group or an aromatic heterocyclic group; L represents an aromatic heterocyclic group, with the proviso that a triazine ring is not represented thereby; and each of X and Y independently represents O, S or NR 1 , wherein R 1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, with the proviso that the molecule of the formula (I) has a substituent containing at least one of —OH, —CO 2 M and —SO 3 M groups, wherein M represents a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium or a pyridinium, and provided that the molecule of the formula (I) has no azo group.
- L is a pyridinediyl group, a pyrazinediyl group, a pyrimidinediyl group, a pyridazinediyl group or a phthalazinediyl group.
- a method of forming an image comprising using the photographic processing composition for silver halide color photographic lightsensitive material according to any of items (1) to (6) above.
- Each of A 1 and A 2 independently represents an aryl group or an aromatic heterocyclic group.
- the aryl group is preferably a substituted aryl group having 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms, and most preferably 6 to 8 carbon atoms, which is, for example, 3-carboxyphenyl, 4-carboxyphenyl, 3,5-dicarboxyphenyl, 4-methoxyphenyl, 2-sulfophenyl, 4-sulfophenyl or 5,7-disulfo-2-naphthyl.
- the heterocyclic group is preferably a substituted or unsubstituted 5- or 6-membered heterocyclic group having 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, and most preferably 2 to 8 carbon atoms, which is, for example, 2-furyl, 2-pyrimidinyl or 2-benzothiazolyl.
- the aromatic heterocyclic group represented by L is preferably a substituted or unsubstituted heterocyclic group having 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, and most preferably 2 to 8 carbon atoms, which is, for example, 3,5-(1,2,4-triazole)diyl, 3,5-isothiazolediyl, 2,6-pyridinediyl, 2,6-pyrazinediyl, 2,6-pyrimidinediyl, 3,6-pyridazinediyl or 1,4-phthalazinediyl.
- a triazine ring is not represented by L.
- Each of X and Y independently represents NR 1 , O or S.
- the substituent represented by R 1 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (for example, methyl, ethyl, i-propyl or n-propyl).
- the compound represented by the general formula (I) (hereinafter also referred to as “compound of the present invention”) has a carboxyl, sulfo or hydroxyl group.
- This carboxyl, sulfo or hydroxyl group may be in free form or in the form of a salt.
- the counter ion may be selected from among an alkali metal, an alkaline earth metal, ammonium and pyridinium. Of these, an alkali metal and an alkaline earth metal are preferred. Na and K are especially preferred.
- the above ammonium can be, for example, any of ammonium, triethylammonium and tetrabutylammonium. Of these, ammonium is preferred.
- the compound represented by the above general formula (I) has no azo group within its molecule.
- the processing composition of the present invention refers to a processing composition characterized by comprising at least one compound represented by the above general formula (I), which processing composition is needed in the processing of silver halide color photographic lightsensitive material for image formation.
- the processing composition of the present invention can be a color development composition, a bleach composition, a bleach-fix composition, a fixing composition, a washing composition or a stabilization composition.
- the processing composition of the present invention may be a black and white development composition, a reversal composition or a prebleach composition. These processing compositions comprehend preparation compositions.
- the processing composition of the present invention is preferably a color development composition or a black and white development composition, more preferably a color development composition.
- these processing compositions may be provided at concentrations of solutions fed as a tank solution or replenisher, or may be provided in the form of a concentrate.
- the processing composition of the present invention is in the form of a concentrate, it is mixed with water at a given ratio before use as a replenisher or tank solution.
- the compound of the present invention is characterized in that it is excellent in the precipitation stability in solution-form composition. Therefore, the effects of the present invention are striking in a single liquid or preparation composition in concentrate form.
- the compound of the present invention may be used in various processing compositions having the form of granules, tablets, powder or slurry.
- the photographic processing composition of the present invention may be an additive composition.
- the additive composition refers to a composition which is added, before or during the processing, to a tank solution or replenisher needed for the processing of silver halide color photographic lightsensitive material for image formation to thereby function for controlling of photographic performance.
- the concentration of compound of the general formula (I) in a use solution is preferably in the range of 0.05 to 20 mmol/L, more preferably 0.15 to 15 mmol/L, and most preferably 0.2 to 10 mmol/L.
- the concentration in the processing composition refers to a value as obtained by multiplying the concentration in use solution by a concentrating ratio.
- the processing composition of the present invention is used in at least one processing step.
- the processing composition of the present invention may be used in a plurality of processing steps or all the processing steps.
- Method A In this method, a small amount of water is introduced in a mixing vessel in advance, and constituent chemicals are sequentially placed therein under agitation.
- Method B In this method, constituent chemicals are mixed in a mixing vessel in advance, and thereafter a small amount of water is poured once into the mixture.
- the color development composition of the present invention contains a color developing agent.
- Known aromatic primary amine color developing agents are preferred.
- p-Phenylenediamine derivatives are especially preferred. Representative examples thereof will be listed below, to which, however, the present invention is in no way limited.
- black and white lightsensitive materials loaded with a coupler which is colored black and developed with common color developer so as to form black and white images are available.
- the processing composition of the present invention is applicable to these types of lightsensitive materials as well.
- p-phenylenediamine derivatives include:
- p-phenylenediamine derivatives compound examples 5), 6), 7), 8) and 12) are preferred.
- Compound examples 5) and 8) are especially preferred.
- These p-phenylenediamine derivatives, in the solid state are generally in the form of, for example, a sulfate, a hydrochloride, a p-toluenesulfonate, a naphthalenedisulfonate or an N,N-bis(sulfonatoethyl)hydroxylamine salt.
- These p-phenylenediamine derivatives may also be added in free form without having any counter ion.
- the concentration of aromatic primary amine developing agent mentioned above in each use solution is preferably in the range of 4 to 100 mmol/L, more preferably 6 to 50 mmol/L, and most preferably 8 to 25 mmol/L.
- a compound capable of preventing the precipitation of color developing agent may be added to the color development composition of the present invention.
- a compound there can be mentioned polyethylene glycols, arylsulfonic acids, alkylsulfonic acids, or urea compounds described in JP-A-11-174643.
- diethylene glycol, polyethylene glycol 300, p-toluenesulfonic acid and its salts, sulfonic acid substituted with a linear alkyl having 5 to 9 carbon atoms and salts thereof, and ethyleneurea are especially preferred.
- the color development composition of the present invention preferably contains a compound capable of preventing the deterioration of color developing agent by air oxidation, namely, a preservative.
- a preservative a compound capable of preventing the deterioration of color developing agent by air oxidation.
- Sulfites and hydroxylamine are preferably used as an inorganic preservative. These exert conspicuous preserving actions and are preferably used in combination with organic preservatives. Sulfites and hydroxylamine may adversely affect photographic characteristics in the color development step, depending on the lightsensitive material processed. Therefore, there are occasions wherein only either of a sulfite and hydroxylamine is contained, or wherein both are substantially not contained and only an organic preservative is employed.
- organic preservative there can preferably be employed hydroxylamine derivatives, hydroxamic acids, hydrazides, phenols, monoamines, diamines, polyamines, alcohols, condensed-ring amines, cyclic amides, salicylic acids, polyethyleneimines, alkanolamines, aromatic polyhydroxy compounds, hydroxylamine derivatives described in JP-A's 3-56456 and 3-33845, and compounds described in JP-A's 3-33846 and 6-148841.
- hydroxylamine derivatives in combination with alkanolamines is preferred from the viewpoint that the stability of color developer in a continuous processing is enhanced.
- Triisopanolamine or triethanolamine can be mentioned as a compound especially preferred for use in combination with hydroxylamines.
- use in combination with cyclic amide compounds is preferred.
- ⁇ -caprolactam is especially preferred.
- the pH value of the color development composition of the present invention is preferably in the range of 9.5 to 13.5.
- the pH value of the color developer prepared therefrom is preferably in the range of 9.0 to 12.2, more preferably 9.9 to 11.2.
- a buffer there can preferably be employed inorganic salts such as sodium and potassium carbonates, bicarbonates, phosphates, borates and tetraborates.
- organic compounds such as 5-sulfosalicylic acid, ⁇ -alanine, proline and trishydroxyaminomethane are preferably used.
- the buffer for use in the present invention is not limited to these compounds. These buffers are contained in a concentration of 0.1 mol/L or more, preferably in the range of 0.1 to 0.4 mol/L, in terms of concentration of color development replenisher.
- chelating agents as a suspending agent for potassium, magnesium, etc. can be added to the color development composition of the present invention.
- a single or a plurality of chelating agents can be used.
- preferred chelating agent compounds include nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N′,N′-tetramethylenesulfonic acid, ethylenediaminesuccinic acid (s, s form), 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid and 1,2-dihydroxybenzene-4,6-disulfonic acid.
- the addition amount of chelating agents is satisfactory as long as it is sufficient to cover the metal ions of the color developer.
- the chelating agents are generally added in an amount of about 0.1 to 10 g
- an arbitrary development accelerator can be added to the color development composition of the present invention.
- the development accelerator there can be mentioned, for example, polyalkylene oxides, 1-phenyl-3-pyrazolidones, alcohols and carboxylic acids.
- an arbitrary antifoggant can be added to the color development composition of the present invention.
- the antifoggant there can be mentioned not only metal halides such as sodium chloride, potassium bromide and potassium iodide but also organic antifoggants whose representative compounds are nitrogenous heterocyclic compounds.
- the organic antifoggants include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chlorobenzotriazole, 2-thiazolylbenzimidazole, 2-thiazolylmethylbenzimidazole, indazole, hydroxyazaindolizine and adenine.
- other alkylcarboxylic acids, arylcarboxylic acids and saccharides may be added according to necessity.
- the processing temperature is preferably in the range of 30 to 55° C., more preferably 35 to 50° C., and most preferably 38 to 45° C.
- the development time is preferably in the range of 5 to 90 sec, more preferably 8 to 60 sec, and most preferably 10 to 45 sec.
- the quantity of replenisher is preferably in the range of 20 to 120 mL, more preferably 30 to 60 mL.
- the processing temperature is preferably in the range of 30 to 55° C., more preferably 35 to 50° C., and most preferably 38 to 45° C.
- the development time is in the range of 45 sec to 5 min, preferably 60 sec to 4 min, and more preferably 90 sec to 3 min 15 sec.
- the quantity of replenisher is preferably in the range of 12 to 60 mL, more preferably 15 to 30 mL.
- the processing temperature is preferably in the range of 32 to 45° C., more preferably 35 to 40° C., and most preferably 36.5 to 39.5° C.
- the development time is preferably in the range of 4 to 8 min, more preferably 5 to 7 min, and most preferably 5 min 30 sec to 6 min 30 sec.
- the quantity of replenisher is preferably in the range of 1500 to 2800 mL, more preferably 2000 to 2400 mL.
- the bleaching agent for use in the bleach composition and bleach-fix composition according to the present invention is preferably selected from among, for example, organic complex salts of iron (III) (for example, complex salts of aminopolycarboxylic acids or other organic acids such as citric acid, tartaric acid and malic acid), persulfates and hydrogen peroxide. Two or more bleaching agents may be used in combination.
- organic complex salts of iron (III) are especially preferred from the viewpoint of speediness and environmental pollution prevention.
- aminopolycarboxylic acids or salts thereof which are useful for forming organic complex salts of iron (III) there can be enumerated not only biodegradable ethylenediaminesuccinic acid (s, s-form), N-(2-carboxylatoethyl)-L-aspartic acid, ⁇ -alaninediacetic acid and methyliminodiacetic acid but also compounds such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid and iminodiacetic acid.
- These compounds may be in the form of any of sodium, potassium, lithium and ammonium salts. Further, a chelating agent may be used in excess of the amount needed for formation of a ferric complex salt.
- concentration of bleaching agent in the bleach solution or bleach-fix solution is in the range of 0.01 to 1.0 mol/L, preferably 0.05 to 0.5 mol/L, and more preferably 0.1 to 0.5 mol/L, based on the solution used.
- a buffer is preferably added to the bleach composition or bleach-fix composition.
- the buffer is selected depending on an intended pH value.
- organic acids such as succinic acid, maleic acid, glycolic acid, malonic acid, fumaric acid, sulfosuccinic acid and acetic acid
- organic bases such as imidazole and dimethylimidazole
- compounds represented by the general formulae (A-a) and (B-b) in JP-A-9-211819 are preferably in the range of 0.005 to 3.0 mol/L, more preferably 0.05 to 1.5 mol/L, based on the solution used.
- the pH value preferably ranges from 2 to 7, more preferably from 3 to 6.
- the pH value preferably ranges from 3 to 8, more preferably from 4 to 7.
- the processing temperature is preferably in the range of 30 to 55° C., more preferably 35 to 50° C., and most preferably 38 to 45° C.
- the bleach-fix time is preferably in the range of 5 to 90 sec, more preferably 8 to 60 sec, and most preferably 10 to 45 sec.
- the quantity of replenisher is preferably in the range of 25 to 120 mL, more preferably 30 to 50 mL.
- the processing temperature is preferably in the range of 30 to 55° C., more preferably 35 to 50° C., and most preferably 38 to 45° C.
- the bleach time is preferably in the range of 12 sec to 2 min, more preferably 15 sec to 1 min 15 sec, and most preferably 18 to 60 sec.
- the quantity of replenisher is preferably in the range of 3 to 25 mL, more preferably 4 to 12 mL.
- the processing temperature is in the range of 30 to 45° C., preferably 33 to 40° C., and more preferably 37 to 39° C.
- the bleach time is in the range of 4 to 8 min, preferably 5 to 7 min, and more preferably 5 min 30 sec to 6 min 30 sec.
- the quantity of replenisher is preferably in the range of 180 to 300 mL, more preferably 200 to 250 mL.
- fixing agent for use in the bleach-fix composition or fixing composition of the present invention there can be mentioned known fixing agents, for example, thiosulfates such as sodium thiosulfate and ammonium thiosulfate, thiocyanates such as sodium thiocyanate and ammonium thiocyanate, ethylenebisglycolic acid, 3,6-dithia-1,8-octanediol, thioether compounds and thioureas described in JP-A-4-317055, and water soluble silver halide dissolving agents such as mesoion compounds described in JP-A's 4-143757 and 4-230749. These can be used individually or in combination.
- thiosulfates such as sodium thiosulfate and ammonium thiosulfate
- thiocyanates such as sodium thiocyanate and ammonium thiocyanate
- ethylenebisglycolic acid 3,6-dithia-1,8
- the concentration of fixing agent in the fixing solution or bleach-fix solution is preferably in the range of 0.3 to 2 mol/L, more preferably 0.5 to 1.5 mol/L.
- a buffer is preferably added to the fixing composition.
- a buffer is preferred to add a buffer to the bleach-fix composition.
- heterocyclic organic bases such as imidazole and dimethylimidazole, aminoalkylenesulfonic acids such as taurine, and dibasic acids such as succinic acid, maleic acid and malonic acid.
- the pH value thereof is preferably in the range of 3 to 8, more preferably 4 to 7.
- the bleach-fix composition and fixing composition according to the present invention preferably contain, as a preservative, a compound capable of releasing sulfite ions, namely, a sulfite, a bisulfite, a metabisulfite, etc. These are preferably added in the form of a potassium salt, a sodium salt or an ammonium salt. Also, an arylsulfinic acid such as p-toluenesulfinic acid, m-carboxybenzenesulfinic acid or p-aminobenzenesulfinic acid is preferably contained therein. These compounds are preferably contained in a concentration of 0.02 to 1.0 mol/L based on the solution used. Also, other compounds such as ascorbic acid, a carbonyl bisulfuric acid adduct and a carbonyl compound may be added as the preservative.
- a compound capable of releasing sulfite ions namely, a sulfite, a bisul
- the bleach-fix composition and fixing composition according to the present invention may be dosed with a mercapto nitrogenous heterocyclic compound, such as mercaptotriazole, aminomercaptotriazole or N-methylmercaptoimidazole, capable of forming stable silver ions in order to improve image storage, and may be dosed with a bisamidine, bisguanidine or monoamidine compound capable of accelerating the washing away of developing agents as described in JP-A-5-303185.
- a mercapto nitrogenous heterocyclic compound such as mercaptotriazole, aminomercaptotriazole or N-methylmercaptoimidazole, capable of forming stable silver ions in order to improve image storage
- a bisamidine, bisguanidine or monoamidine compound capable of accelerating the washing away of developing agents as described in JP-A-5-303185.
- the bleach-fix composition and fixing composition according to the present invention may be dosed with a polymer such as polyethylene glycol or polyvinylpyrrolidone, a chelating agent, an antifoaming agent, a mildewproofing agent, etc.
- the processing temperature, bleach-fix time and quantity of replenisher are as aforementioned.
- the processing temperature is preferably in the range of 30 to 55° C., more preferably 35 to 50° C., and most preferably 38 to 45° C.
- the bleach time is preferably in the range of 20 sec to 2 min, more preferably 30 sec to 1 min 40 sec, and most preferably 35 sec to 1 min 20 sec.
- the quantity of replenisher is preferably in the range of 5 to 40 mL, more preferably 6 to 30 mL.
- the processing temperature is preferably in the range of 30 to 45° C., more preferably 33 to 40° C., and most preferably 37 to 39° C.
- the fixing time is preferably in the range of 2 to 6 min, more preferably 3 to 5 min, and most preferably 3 min 30 sec to 4 min 30 sec.
- the quantity of replenisher is preferably in the range of 900 to 1500 mL, more preferably 1000 to 1250 mL.
- the washing composition and stabilization composition according to the present invention may be dosed with formalin, acetaldehyde, pyruvinaldehyde, a formaldehyde bisulfuric acid adduct described in U.S. Pat. No. 4,921,779, or an N-methylol compound described in JP-A-5-34889, the disclosures of which are incorporated herein by reference, in order to prevent stain formation or dye discoloration attributed to residual magenta couplers.
- an arylsulfinic acid such as p-toluenesulfinic acid, m-carboxybenzenesulfinic acid or p-aminobenzenesulfinic acid is preferably contained therein.
- the washing composition and stabilization composition may be dosed with a surfactant as a dewatering agent, a chelating agent as a hard water softener, a buffer for pH adjustment, an antifoaming agent, a mildewproofing agent, an antibacterial agent, etc.
- the pH value thereof is preferably in the range of 4 to 10, more preferably 5 to 8.
- the temperature thereof although set for various values depending on the intended use, properties, etc. of lightsensitive material, is generally in the range of 20 to 50° C., preferably 25 to 45° C.
- Photographic elements to be processed by the use of the processing composition of the present invention can comprise any of common silver halides such as silver chloride, silver bromide, silver bromoiodide, silver chlorobromide, silver chloroiodide and mixtures thereof as a lightsensitive material.
- the photographic element is one of high silver chloride content containing at least 50 mol % of chlorides, preferably at least 90 mol % of silver chloride, and is often used in, for example, a color print lightsensitive material.
- At least one emulsion consists principally of silver bromide (at least 50 mol % silver bromide).
- this photographic element has at least one color recording, and each color recording comprises at least one emulsion principally of silver bromide as used in color negative films and color reversal films.
- the photographic element to be processed according to the present invention can be a monocolor element or multicolor element. Further, this element can include a magnetic recording layer known in the art to which the present invention pertains.
- RD Research Disclosures
- the processing composition of the present invention is a preparation composition
- a configuration wherein all the components to be contained in a use solution are incorporated in a single composition, namely, a one-pack configuration is advantageous.
- the color development composition or bleach-fix composition it is not desirable to bring constituent components into contact with each other for a prolonged period of time, it may be appropriate to produce a processing composition of two-pack or three-pack configuration wherein constituent components are separated into two or more liquid agents, or solid agents, or liquid and solid agents.
- These configurations of preparations are generally designated 1-part, 2-part, 3-part, . . . configurations under the nomenclature of international standards ISO 5989.
- the processing composition of the present invention is in no way deteriorated, with respect to the invention's effects and characteristics, by being divided into parts. In particular with respect to the color development composition, however, the 1-part configuration is preferred.
- the container for the processing composition of the present invention can be constituted of known materials according to the contents intended.
- the container may be prepared from a single material, or a composite material, for example, a composite material composed of a material of high gas permeability and a material of high alkali resistance. From the viewpoint of reuse and recycle, it is preferred that the container be constituted of a single material.
- the materials used for preparing the container include polyester resins, polyolefin resins, acrylic resins, ABS resins, epoxy resins, polyamide resins (such as nylons), polyurethane resins, polystyrene resins, polycarbonate resins, PVA, polyvinyl chloride, polyvinylidene chloride and polyethylene resins.
- containers constituted of a single material selected from among polyester resins (such as polyethylene terephthalate and polyethylene naphthalate) and polyolefin resins (such as polyethylene and polypropylene) are preferred.
- polyester resins such as polyethylene terephthalate and polyethylene naphthalate
- polyolefin resins such as polyethylene and polypropylene
- Polyethylene resins are more preferred, and a high-density polyethylene resin (HDPE) is most preferred as the container material.
- HDPE high-density polyethylene resin
- the material for preparing the container for use in the present invention can be loaded with carbon black, titanium white, a pigment, calcium carbonate, a plasticizer compatible with the material, etc., unless the loading is detrimental to the processing composition.
- the material for preparing the container is preferably one of 85% or more polyethylene content containing none of plasticizers, more preferably one of 95% or more polyethylene content containing none of plasticizers.
- the shape and structure of containers for accommodating the processing composition of the present invention can be arbitrarily designed in conformity with the object. Use can be made of not only bottles of regular shape but also expandable containers described in JP-A-1-235950, containers with flexible partition walls described in JP-A-62-134626, etc. Containers of JP-A-11-282148 are especially preferred as the container for accommodating the processing composition of the present invention from the viewpoint of capacity, space efficiency, self-supporting capability, shape retention, reuse and recycle.
- a kit comprising a single cartridge and, assembled therein, containers of the same shape and volume constituted of a single material wherein a plurality of compositions according to the present invention are accommodated presents a preferred form.
- the cartridge of JP-A-2000-3014 can be mentioned as an example thereof.
- the combination of processing compositions can be arbitrarily selected.
- the cartridges of JP-A'S 11-295858 and 11-288068 present preferred forms wherein the development composition, bleach composition and fixing composition are incorporated.
- One side of a support comprising a paper having its both major surfaces covered with a polyethylene resin was treated by corona discharge, furnished with a gelatin substratum layer containing sodium dodecylbenzenesulfonate, and further sequentially coated to provide the 1st to 7th layers.
- silver halide color photographic lightsensitive material P-1 of the following layer arrangement was obtained.
- the coating liquid for each photographic constituting element layer was prepared in the following manner.
- silver chlorobromide emulsion C (cubic form; 5:5 (silver molar ratio) mixture of large-size emulsion C of 0.40 ⁇ m average grain size and small-size emulsion C of 0.30 ⁇ m average grain size, the variation coefficients of grain size distribution thereof being 0.09 and 0.11, respectively; and with respect to both the large-size and small-size emulsions, 0.5 mol % of silver bromide localized on part of the surface of grains based on silver chloride emulsion).
- each of the following red-sensitive sensitizing dyes G and H was added to the large-size emulsion C in an amount of, per mol of silver, 9.0 ⁇ 10 ⁇ 5 mol, and added to the small-size emulsion C in an amount of 12.0 ⁇ 10 ⁇ 5 mol.
- the optimum chemical ripening of this emulsion was performed by adding a sulfur sensitizer and a gold sensitizer.
- the coating liquids for the 1st to 4th layers, the 6th layer and the 7th layer were prepared in the same manner as the coating liquid for the 5th layer.
- 1-Oxy-3,5-dichloro-s-triazine sodium salt was used as a gelatin hardener of each of the layers, and, to each of the layers, Ab-1, A-2, Ab-3 and Ab-4 were added in a total amount of 15.0 mg/m 2 , 60.0 mg/m 2 , 5.0 mg/m 2 and 10.0 mg/m2 , respectively.
- each of the sensitizing dyes A and C was added in an amount of, per mol of silver halides, 0.42 ⁇ 10 ⁇ 4 mol to the large-size emulsion and 0.50 ⁇ 10 ⁇ 4 mol to the small-size emulsion.
- the sensitizing dye B was added in an amount of, per mol of silver halides, 3.4 ⁇ 10 ⁇ 4 mol to the large-size emulsion and 4.1 ⁇ 10 ⁇ 4 mol to the small-size emulsion.
- the sensitizing dye D was added in an amount of, per mol of silver halides, 3.0 ⁇ 10 ⁇ 4 mol to the large-size emulsion and 3.6 ⁇ 10 ⁇ 4 mol to the small-size emulsion.
- the sensitizing dye E was added in an amount of, per mol of silver halides, 4.0 ⁇ 10 ⁇ 4 mol to the large-size emulsion and 7.0 ⁇ 10 ⁇ 5 mol to the small-size emulsion.
- the sensitizing dye F was added in an amount of, per mol of silver halides, 2.0 ⁇ 10 ⁇ 4 mol to the large-size emulsion and 2.8 ⁇ 10 ⁇ 4 mol to the small-size emulsion.
- each of the sensitizing dyes G and H was added in an amount of, per mol of silver halides, 8.0 ⁇ 10 ⁇ 5 mol to the large-size emulsion and 10.7 ⁇ 10 ⁇ 4 mol to the small-size emulsion. Further, the following compound I was added to the red-sensitive emulsion layer in an amount of 3.0 (ml 10 ⁇ 3 mol per mol of silver halides.)
- the blue-sensitive emulsion layer (1st layer), green-sensitive emulsion layer (3rd layer) and red-sensitive emulsion layer (5th layer) were loaded with 1-(3-methylureidophenyl)-5-mercaptotetrazole in an amount of 3.3 ⁇ 10 ⁇ 4 mol, 1.0 ⁇ 10 ⁇ 3 mol and 5.9 ⁇ 10 ⁇ 4 mol, respectively, per mol of silver halides.
- the 2nd layer, 4th layer, 6th layer and 7th layer were loaded with the above compound in an amount of 0.2 mg/m 2 , 0.2 mg/m 2 , 0.6 mg/m 2 and 0.1 mg/m2, respectively.
- the blue-sensitive emulsion layer and green-sensitive emulsion layer were loaded with 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene in an amount of 1 ⁇ 10 ⁇ 4 mol and 2 ⁇ 10 ⁇ 4 mol, respectively, per mol of silver halides.
- the red-sensitive emulsion layer was loaded with a latex of methacrylic acid/butyl acrylate copolymer (weight ratio 1:1, average molecular weight 200,000 to 400,000) in an amount of 0.05 g/m 2 .
- the 2nd layer, 4th layer and 6th layer were loaded with disodium catechol-3,5-disulfonate in an amount of 6 mg/m 2 , 6 mg/m 2 and 18 mg/m 2 , respectively.
- each layer is specified below.
- the numerals indicate the coating amount (g/m 2 ). With respect to the silver halide emulsions, the coating amount is in terms of silver.
- polyethylene resin on the 1st layer side contains white pigment (TiO 2 : 16% by weight content and ZnO: 4% by weight content), brightening agent (4,4′-bis(5-methylbenzoxazolyl)stilbene: 0.03% by weight content) and bluish dye (ultramarine)).
- composition of each processing solution was as follows. (Color developer) (Tank soln.) Water 800 mL Compound of the invention 2 mmol Brightening agent (FL-1) 0.35 g Triisopropanolamine 8.8 g Polyethylene glycol (av.
- Each prepared color development composition was placed in glass bottles, and stored at ⁇ 5° C. and at room temperature for 4 weeks. A 5-grade estimation of test results was made by visually inspecting the condition of liquid after storage. Level of conspicuous deposit precipitation was judged as x x; level of clear deposit precipitation as x; level of slight deposition recognized as ⁇ ; level of clouding but no deposit precipitation as o; and level of thorough transparency without any clouding and deposition recognized as @.
- ⁇ D B was calculated by the following formula, whereby the degree of stain attributed to residual sensitizing dyes was estimated.
- sample 1-2 (comparative example) produced with the use of compound FL-2
- the degree of stain attributed to residual sensitizing dyes was similar to or on the level close to those of the samples produced with the use of compounds of the present invention, but deposit precipitation occurred upon storage of the processing composition.
- sample 1-1 comparative example
- the lightsensitive material having undergone the development processing wherein use was made of the processing composition of the present invention exhibited a low value with respect to the stain ⁇ D B attributed to residual sensitizing dyes, namely, only a slight coloring of white ground.
- the processing composition of the present invention even after storage for 4 weeks, was thoroughly transparent at room temperature, and was thoroughly transparent or in the state of slight clouding recognized at low temperature ( ⁇ 5° C.). Irrespective of the temperature, no deposit precipitation occurred. Therefore, it has become apparent that the present invention is excellent in the capability of reducing the stain attributed to sensitizing dyes remaining in the lightsensitive material after the processing, and that the processing composition of the present invention is a composition free of precipitation deposits during the low temperature storage of the processing composition.
- each processing composition of the present invention even after storage for 4 weeks, was thoroughly transparent at room temperature, and was thoroughly transparent or in the state of slight clouding recognized at low temperature ( ⁇ 5° C.). Irrespective of the temperature, no deposit precipitation occurred.
- the lightsensitive material having undergone the development processing wherein use was made of the processing composition of the present invention exhibited a low value with respect to the stain ⁇ D B attributed to residual sensitizing dyes, namely, only a slight coloring of white ground.
- the present invention is excellent in the capability of reducing the stain attributed to sensitizing dyes remaining in the lightsensitive material after the processing, and that the processing composition of the present invention is a composition free of precipitation deposits during the low temperature storage of the processing composition.
- the processing composition for silver halide photographic lightsensitive material wherein the heterocycle combination of the general formula (I) is contained according to the present invention and the method of forming an image with the use of the processing composition enable exerting the advantageous effects of not only reducing stain attributed to sensitizing dyes remaining in the lightsensitive material after the processing thereof but also being free of any precipitation deposits during the low-temperature storage of the processing composition.
Abstract
A photographic processing composition for silver halide color photographic lightsensitive material, comprising at least one compound represented by the formula (I):
A1—X—L—Y—A2 (I)
wherein each of A1 and A2 independently represents an aryl group or an aromatic heterocyclic group, L represents an aromatic heterocyclic group, with the proviso that a triazine ring is not represented thereby, and each of X and Y independently represents O, S or NR1, wherein R1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, with the proviso that the molecule of the formula (I) has a substituent containing at least one of —OH, —CO2M and —SO3M groups, wherein M represents a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium or a pyridinium, and provided that the molecule of the formula (I) has no azo group.
Description
- This application is based upon and claims the benefit of priority from the prior Japanese Patent Application No. 2001-102469, filed Mar. 30, 2001, the entire contents of which are incorporated herein by reference.
- 1. Field of the Invention
- The present invention relates to a processing composition for silver halide color photographic lightsensitive material. More particularly, the present invention relates to a processing composition which is excellent in the capability of reducing stain attributed to sensitizing dyes remaining in the lightsensitive material after the processing thereof and which is free of any precipitation deposits during the low-temperature storage thereof.
- 2. Description of the Related Art
- Under the circumstances wherein digital cameras and color printers are making striking progress, in the processing of silver halide color photographic lightsensitive materials, it is desired to speedily supply images of high quality to customers. However, simple time reduction in the conventional processing procedure would cause termination of processing before satisfactory washing away of sensitizing dyes from the lightsensitive material with the result that, on a white ground of color print, images would be colored by a large amount of residual sensitizing dyes to thereby become unbearable for appreciation. Further, with respect to color negative films, there have occurred such occasions that the density of minimum density portions is increased with the result that a color balance is deteriorated to thereby disenable providing appropriate prints.
- Moreover, in recent years, the use of tabular silver halide grains, presenting an important fundamental technology for highly sensitive photographic lightsensitive materials, increases the amount of sensitizing dyes remaining in the lightsensitive material after the processing thereof, although it enables increasing the amount of sensitizing dyes used per volume so as to exert the effect of enhancing the photographic speed and the ratio of photographic speed to graininess. An increase of the amount of residual sensitizing dyes cannot be ignored depending on processing conditions, and would result in occurrence of phenomena such as a density increase at minimum density portions of color negative films and coloring of highlight portions of color reversal films.
- Research Disclosure 20733 discloses the method of using a bistriazinylaminostilbenedisulfonic acid compound as an example of means for removing any residual color attributed to sensitizing dyes. This method has widely been employed in the processing of color photographic lightsensitive materials. Jpn. Pat. Appln. KOKAI Publication No. (hereinafter referred to as JP-A-) 6-329936 discloses a bistriazinylaminostilbenedisulfonic acid compound which has high solubility and is capable of reducing the residual color even in the expedited processing. Further, U.S. Pat. Nos. 6,153,364 and 6,153,365 proposed methods of reducing the residual color with the use of highly stable compounds of novel structure.
- However, there is a demand for further concentrating of the processing composition from the viewpoint of reduction of waste containers, recycling facilitation, reduction of transport and storage costs, etc. Any compound which is stably dissolved under a condition of high salt concentration after concentrating and exerts satisfactory effects even in the expedited processing when used below solubility, and which is excellent in the compound stability during storage has not yet been found.
- Accordingly, it is an object of the present invention to provide a processing composition for silver halide color photographic lightsensitive material, which enables reducing stain attributed to sensitizing dyes remaining in the lightsensitive material after the processing thereof and which is free of any precipitation deposits during the low-temperature storage thereof.
- This object has been attained by the following invention.
- (1) A photographic processing composition for silver halide color photographic lightsensitive material, comprising at least one compound represented by the formula (I):
- A1—X—L—Y—A2 (I)
- wherein each of A1 and A2 independently represents an aryl group or an aromatic heterocyclic group; L represents an aromatic heterocyclic group, with the proviso that a triazine ring is not represented thereby; and each of X and Y independently represents O, S or NR1, wherein R1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, with the proviso that the molecule of the formula (I) has a substituent containing at least one of —OH, —CO2M and —SO3M groups, wherein M represents a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium or a pyridinium, and provided that the molecule of the formula (I) has no azo group.
- (2) The photographic processing composition according to item (1) above, wherein, in the formula (I), L is a pyridinediyl group, a pyrazinediyl group, a pyrimidinediyl group, a pyridazinediyl group or a phthalazinediyl group.
- (3) The photographic processing composition according to item (1) or (2) above, for use in color development processing.
- (4) The photographic processing composition according to item (1) or (2) above, for use in bleach processing or bleach-fix processing.
- (5) The photographic processing composition according to item (1) or (2) above, for use in fixing processing.
- (6) The photographic processing composition according to item (1) above, for use in a use solution in which the concentration of compound represented by the formula (I) is in a range of 0.05 to 20 mmol/L.
- (7) A method of forming an image, comprising using the photographic processing composition for silver halide color photographic lightsensitive material according to any of items (1) to (6) above.
- Additional objects and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objects and advantages of the invention may be realized and obtained by means of the instrumentalities and combinations particularly pointed out hereinafter.
- The general formula (1) will be described in detail below.
- Each of A1 and A2 independently represents an aryl group or an aromatic heterocyclic group. The aryl group is preferably a substituted aryl group having 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms, and most preferably 6 to 8 carbon atoms, which is, for example, 3-carboxyphenyl, 4-carboxyphenyl, 3,5-dicarboxyphenyl, 4-methoxyphenyl, 2-sulfophenyl, 4-sulfophenyl or 5,7-disulfo-2-naphthyl. The heterocyclic group is preferably a substituted or unsubstituted 5- or 6-membered heterocyclic group having 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, and most preferably 2 to 8 carbon atoms, which is, for example, 2-furyl, 2-pyrimidinyl or 2-benzothiazolyl.
- The aromatic heterocyclic group represented by L is preferably a substituted or unsubstituted heterocyclic group having 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, and most preferably 2 to 8 carbon atoms, which is, for example, 3,5-(1,2,4-triazole)diyl, 3,5-isothiazolediyl, 2,6-pyridinediyl, 2,6-pyrazinediyl, 2,6-pyrimidinediyl, 3,6-pyridazinediyl or 1,4-phthalazinediyl. Provided that a triazine ring is not represented by L.
- Each of X and Y independently represents NR1, O or S. The substituent represented by R1 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (for example, methyl, ethyl, i-propyl or n-propyl).
- The compound represented by the general formula (I) (hereinafter also referred to as “compound of the present invention”) has a carboxyl, sulfo or hydroxyl group. This carboxyl, sulfo or hydroxyl group may be in free form or in the form of a salt. In the form of a salt, the counter ion may be selected from among an alkali metal, an alkaline earth metal, ammonium and pyridinium. Of these, an alkali metal and an alkaline earth metal are preferred. Na and K are especially preferred. The above ammonium can be, for example, any of ammonium, triethylammonium and tetrabutylammonium. Of these, ammonium is preferred.
- The compound represented by the above general formula (I) has no azo group within its molecule.
-
- When compounds represented by the general formula (I) of the present invention have a plurality of asymmetric carbon atoms within each molecule thereof, a plurality of stereoisomers exist with respect to each specific structure. The present invention comprehends all the possible stereoisomers. Among a plurality of stereoisomers, only one can be selected and used, or some can be selected and used in the form of a mixture.
- Among the compounds represented by the general formula (I) of the present invention, only one can be selected and used, or a plurality thereof can be selected and used in combination. The number of compounds used and the type of processing composition contained can be arbitrarily selected.
- The processing composition of the present invention will be described in detail below. The processing composition of the present invention refers to a processing composition characterized by comprising at least one compound represented by the above general formula (I), which processing composition is needed in the processing of silver halide color photographic lightsensitive material for image formation. Specifically, the processing composition of the present invention can be a color development composition, a bleach composition, a bleach-fix composition, a fixing composition, a washing composition or a stabilization composition. Further, the processing composition of the present invention may be a black and white development composition, a reversal composition or a prebleach composition. These processing compositions comprehend preparation compositions. The processing composition of the present invention is preferably a color development composition or a black and white development composition, more preferably a color development composition. In particular, in the application to a color development composition for color print material, the effects of the present invention are especially striking. These processing compositions may be provided at concentrations of solutions fed as a tank solution or replenisher, or may be provided in the form of a concentrate. When the processing composition of the present invention is in the form of a concentrate, it is mixed with water at a given ratio before use as a replenisher or tank solution. The compound of the present invention is characterized in that it is excellent in the precipitation stability in solution-form composition. Therefore, the effects of the present invention are striking in a single liquid or preparation composition in concentrate form. However, the compound of the present invention may be used in various processing compositions having the form of granules, tablets, powder or slurry.
- Moreover, the photographic processing composition of the present invention may be an additive composition. The additive composition refers to a composition which is added, before or during the processing, to a tank solution or replenisher needed for the processing of silver halide color photographic lightsensitive material for image formation to thereby function for controlling of photographic performance.
- With respect to the processing composition of the present invention, the concentration of compound of the general formula (I) in a use solution is preferably in the range of 0.05 to 20 mmol/L, more preferably 0.15 to 15 mmol/L, and most preferably 0.2 to 10 mmol/L. When the processing composition of the present invention is diluted with water or another processing composition before use, the concentration in the processing composition refers to a value as obtained by multiplying the concentration in use solution by a concentrating ratio.
- In the method of forming an image according to the present invention, the processing composition of the present invention is used in at least one processing step. The processing composition of the present invention may be used in a plurality of processing steps or all the processing steps.
- With respect to the process for producing the processing composition of the present invention, although quite some methods are available, desirable results can be obtained by the following three methods. However, the process for carrying out the present invention is in no way limited to the following three methods.
- (Method A) In this method, a small amount of water is introduced in a mixing vessel in advance, and constituent chemicals are sequentially placed therein under agitation.
- (Method B) In this method, constituent chemicals are mixed in a mixing vessel in advance, and thereafter a small amount of water is poured once into the mixture.
- (Method C) In this method, constituent chemicals are first divided into appropriate groups, these groups are each dissolved in water or a hydrophilic organic solvent to thereby obtain solutions of high concentration, and the solutions of high concentration are mixed together.
- Moreover, processes wherein the above methods are partially utilized can be implemented.
- Each of the development composition, bleach composition, bleach-fix composition, fixing composition, washing composition, stabilization composition and additive composition as varied forms of the processing compositions of the present invention will be described below.
- The color development composition of the present invention contains a color developing agent. Known aromatic primary amine color developing agents are preferred. p-Phenylenediamine derivatives are especially preferred. Representative examples thereof will be listed below, to which, however, the present invention is in no way limited. In recent years, black and white lightsensitive materials loaded with a coupler which is colored black and developed with common color developer so as to form black and white images are available. The processing composition of the present invention is applicable to these types of lightsensitive materials as well.
- Representative examples of the p-phenylenediamine derivatives include:
- 1) N,N-diethyl-p-phenylenediamine,
- 2) 4-amino-N,N-diethyl-3-methylaniline,
- 3) 4-amino-N-(β-hydroxyethyl)-N-methylaniline,
- 4) 4-amino-N-ethyl-N-(β-hydroxyethyl)aniline,
- 5) 4-amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)aniline,
- 6) 4-amino-3-methyl-N-ethyl-N-(3-hydroxypropyl)aniline,
- 7) 4-amino-3-methyl-N-ethyl-N-(4-hydroxybutyl)aniline,
- 8) 4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)-3-methylaniline,
- 9) 4-amino-N,N-diethyl-3-(β-hydroxyethyl)aniline,
- 10) 4-amino-3-methyl-N-ethyl-N-(β-methoxyethyl)aniline,
- 11) 4-amino-3-methyl-N-(β-ethoxyethyl)-N-ethylaniline,
- 12) 4-amino-3-methyl-N-(3-carbamoylpropyl)-N-n-propylaniline,
- 13) 4-amino-3-methyl-N-(4-carbamoylbutyl)-N-n-propylaniline,
- 14) N-(4-amino-3-methylphenyl)-3-hydroxypyrrolidine,
- 15) N-(4-amino-3-methylphenyl)-3-hydroxymethylpyrrolidine, and
- 16) N-(4-amino-3-methylphenyl)-3-pyrrolidinecarboxamide.
- Among these p-phenylenediamine derivatives, compound examples 5), 6), 7), 8) and 12) are preferred. Compound examples 5) and 8) are especially preferred. These p-phenylenediamine derivatives, in the solid state, are generally in the form of, for example, a sulfate, a hydrochloride, a p-toluenesulfonate, a naphthalenedisulfonate or an N,N-bis(sulfonatoethyl)hydroxylamine salt. These p-phenylenediamine derivatives may also be added in free form without having any counter ion. The concentration of aromatic primary amine developing agent mentioned above in each use solution is preferably in the range of 4 to 100 mmol/L, more preferably 6 to 50 mmol/L, and most preferably 8 to 25 mmol/L.
- A compound capable of preventing the precipitation of color developing agent may be added to the color development composition of the present invention. As such a compound, there can be mentioned polyethylene glycols, arylsulfonic acids, alkylsulfonic acids, or urea compounds described in JP-A-11-174643. Among these, from the viewpoint of exerting excellent effects with the slightest influence on photographic performance, diethylene glycol, polyethylene glycol 300, p-toluenesulfonic acid and its salts, sulfonic acid substituted with a linear alkyl having 5 to 9 carbon atoms and salts thereof, and ethyleneurea are especially preferred.
- The color development composition of the present invention preferably contains a compound capable of preventing the deterioration of color developing agent by air oxidation, namely, a preservative. Sulfites and hydroxylamine are preferably used as an inorganic preservative. These exert conspicuous preserving actions and are preferably used in combination with organic preservatives. Sulfites and hydroxylamine may adversely affect photographic characteristics in the color development step, depending on the lightsensitive material processed. Therefore, there are occasions wherein only either of a sulfite and hydroxylamine is contained, or wherein both are substantially not contained and only an organic preservative is employed.
- As the organic preservative, there can preferably be employed hydroxylamine derivatives, hydroxamic acids, hydrazides, phenols, monoamines, diamines, polyamines, alcohols, condensed-ring amines, cyclic amides, salicylic acids, polyethyleneimines, alkanolamines, aromatic polyhydroxy compounds, hydroxylamine derivatives described in JP-A's 3-56456 and 3-33845, and compounds described in JP-A's 3-33846 and 6-148841.
- Use of hydroxylamine derivatives in combination with alkanolamines is preferred from the viewpoint that the stability of color developer in a continuous processing is enhanced. Triisopanolamine or triethanolamine can be mentioned as a compound especially preferred for use in combination with hydroxylamines. Also, use in combination with cyclic amide compounds is preferred. Among such compounds, ε-caprolactam is especially preferred.
- The pH value of the color development composition of the present invention is preferably in the range of 9.5 to 13.5. The pH value of the color developer prepared therefrom is preferably in the range of 9.0 to 12.2, more preferably 9.9 to 11.2. For maintaining an appropriate pH value, it is preferred to add a buffer. As such a buffer, there can preferably be employed inorganic salts such as sodium and potassium carbonates, bicarbonates, phosphates, borates and tetraborates. Also, organic compounds such as 5-sulfosalicylic acid, β-alanine, proline and trishydroxyaminomethane are preferably used. The buffer for use in the present invention is not limited to these compounds. These buffers are contained in a concentration of 0.1 mol/L or more, preferably in the range of 0.1 to 0.4 mol/L, in terms of concentration of color development replenisher.
- Various chelating agents as a suspending agent for potassium, magnesium, etc. can be added to the color development composition of the present invention. A single or a plurality of chelating agents can be used. Examples of preferred chelating agent compounds include nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N′,N′-tetramethylenesulfonic acid, ethylenediaminesuccinic acid (s, s form), 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid and 1,2-dihydroxybenzene-4,6-disulfonic acid. The addition amount of chelating agents is satisfactory as long as it is sufficient to cover the metal ions of the color developer. The chelating agents are generally added in an amount of about 0.1 to 10 g/L.
- If necessary, an arbitrary development accelerator can be added to the color development composition of the present invention. As the development accelerator, there can be mentioned, for example, polyalkylene oxides, 1-phenyl-3-pyrazolidones, alcohols and carboxylic acids.
- If necessary, an arbitrary antifoggant can be added to the color development composition of the present invention. As the antifoggant, there can be mentioned not only metal halides such as sodium chloride, potassium bromide and potassium iodide but also organic antifoggants whose representative compounds are nitrogenous heterocyclic compounds. Examples of the organic antifoggants include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chlorobenzotriazole, 2-thiazolylbenzimidazole, 2-thiazolylmethylbenzimidazole, indazole, hydroxyazaindolizine and adenine. Further, other alkylcarboxylic acids, arylcarboxylic acids and saccharides may be added according to necessity.
- In the color development to which the present invention applies, with respect to color print lightsensitive materials, the processing temperature is preferably in the range of 30 to 55° C., more preferably 35 to 50° C., and most preferably 38 to 45° C. The development time is preferably in the range of 5 to 90 sec, more preferably 8 to 60 sec, and most preferably 10 to 45 sec. Although the smaller the quantity of replenisher, the greater the preference, it is generally suitable to use 15 to 200 mL of replenisher per m2 of lightsensitive material. The quantity of replenisher is preferably in the range of 20 to 120 mL, more preferably 30 to 60 mL.
- With respect to color negative films, the processing temperature is preferably in the range of 30 to 55° C., more preferably 35 to 50° C., and most preferably 38 to 45° C. The development time is in the range of 45 sec to 5 min, preferably 60 sec to 4 min, and more preferably 90 sec to 3 min 15 sec. Although the smaller the quantity of replenisher, the greater the preference, it is generally suitable to use 10 to 200 mL of replenisher per 24 exp. The quantity of replenisher is preferably in the range of 12 to 60 mL, more preferably 15 to 30 mL.
- With respect to color reversal films, the processing temperature is preferably in the range of 32 to 45° C., more preferably 35 to 40° C., and most preferably 36.5 to 39.5° C. The development time is preferably in the range of 4 to 8 min, more preferably 5 to 7 min, and most preferably 5 min 30 sec to 6 min 30 sec. Although the smaller the quantity of replenisher, the greater the preference, it is generally suitable to use 1000 to 3000 mL of replenisher per m2 of lightsensitive material. The quantity of replenisher is preferably in the range of 1500 to 2800 mL, more preferably 2000 to 2400 mL.
- The color development composition obtained by concentrating replenishers as described in JP-A's 11-174643, 11-194461 and 11-194462, the disclosures of which are incorporated herein by reference, presents a preferred form of development composition.
- The bleaching agent for use in the bleach composition and bleach-fix composition according to the present invention, although known bleaching agents can be used as the same, is preferably selected from among, for example, organic complex salts of iron (III) (for example, complex salts of aminopolycarboxylic acids or other organic acids such as citric acid, tartaric acid and malic acid), persulfates and hydrogen peroxide. Two or more bleaching agents may be used in combination.
- Of these, organic complex salts of iron (III) are especially preferred from the viewpoint of speediness and environmental pollution prevention. As the aminopolycarboxylic acids or salts thereof which are useful for forming organic complex salts of iron (III), there can be enumerated not only biodegradable ethylenediaminesuccinic acid (s, s-form), N-(2-carboxylatoethyl)-L-aspartic acid, β-alaninediacetic acid and methyliminodiacetic acid but also compounds such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid and iminodiacetic acid. These compounds may be in the form of any of sodium, potassium, lithium and ammonium salts. Further, a chelating agent may be used in excess of the amount needed for formation of a ferric complex salt. The concentration of bleaching agent in the bleach solution or bleach-fix solution is in the range of 0.01 to 1.0 mol/L, preferably 0.05 to 0.5 mol/L, and more preferably 0.1 to 0.5 mol/L, based on the solution used.
- A buffer is preferably added to the bleach composition or bleach-fix composition. The buffer is selected depending on an intended pH value. As preferred buffers, there can be mentioned organic acids such as succinic acid, maleic acid, glycolic acid, malonic acid, fumaric acid, sulfosuccinic acid and acetic acid; organic bases such as imidazole and dimethylimidazole; and compounds represented by the general formulae (A-a) and (B-b) in JP-A-9-211819. The addition amount of these compounds is preferably in the range of 0.005 to 3.0 mol/L, more preferably 0.05 to 1.5 mol/L, based on the solution used. In the bleach solution, the pH value preferably ranges from 2 to 7, more preferably from 3 to 6. In the bleach-fix solution, the pH value preferably ranges from 3 to 8, more preferably from 4 to 7.
- In the bleach-fix of color print lightsensitive materials to which the present invention applies, the processing temperature is preferably in the range of 30 to 55° C., more preferably 35 to 50° C., and most preferably 38 to 45° C. The bleach-fix time is preferably in the range of 5 to 90 sec, more preferably 8 to 60 sec, and most preferably 10 to 45 sec. Although the smaller the quantity of replenisher, the greater the preference, it is generally suitable to use 20 to 200 mL of replenisher per m2 of lightsensitive material. The quantity of replenisher is preferably in the range of 25 to 120 mL, more preferably 30 to 50 mL.
- In the bleach of color negative films, the processing temperature is preferably in the range of 30 to 55° C., more preferably 35 to 50° C., and most preferably 38 to 45° C. The bleach time is preferably in the range of 12 sec to 2 min, more preferably 15 sec to 1 min 15 sec, and most preferably 18 to 60 sec. Although the smaller the quantity of replenisher, the greater the preference, it is generally suitable to use 2.5 to 50 mL of replenisher per 24 exp. The quantity of replenisher is preferably in the range of 3 to 25 mL, more preferably 4 to 12 mL.
- In the bleach of color reversal films, the processing temperature is in the range of 30 to 45° C., preferably 33 to 40° C., and more preferably 37 to 39° C. The bleach time is in the range of 4 to 8 min, preferably 5 to 7 min, and more preferably 5 min 30 sec to 6 min 30 sec. Although the smaller the quantity of replenisher, the greater the preference, it is generally suitable to use 160 to 400 mL of replenisher per m2 of lightsensitive material. The quantity of replenisher is preferably in the range of 180 to 300 mL, more preferably 200 to 250 mL.
- As the fixing agent for use in the bleach-fix composition or fixing composition of the present invention, there can be mentioned known fixing agents, for example, thiosulfates such as sodium thiosulfate and ammonium thiosulfate, thiocyanates such as sodium thiocyanate and ammonium thiocyanate, ethylenebisglycolic acid, 3,6-dithia-1,8-octanediol, thioether compounds and thioureas described in JP-A-4-317055, and water soluble silver halide dissolving agents such as mesoion compounds described in JP-A's 4-143757 and 4-230749. These can be used individually or in combination. It is preferred to use thiosulfates, especially ammonium thiosulfate, as the fixing agent. The concentration of fixing agent in the fixing solution or bleach-fix solution is preferably in the range of 0.3 to 2 mol/L, more preferably 0.5 to 1.5 mol/L.
- As aforementioned, a buffer is preferably added to the fixing composition. Likewise, it is preferred to add a buffer to the bleach-fix composition. As preferred buffers, there can be mentioned heterocyclic organic bases such as imidazole and dimethylimidazole, aminoalkylenesulfonic acids such as taurine, and dibasic acids such as succinic acid, maleic acid and malonic acid. The pH value thereof is preferably in the range of 3 to 8, more preferably 4 to 7.
- The bleach-fix composition and fixing composition according to the present invention preferably contain, as a preservative, a compound capable of releasing sulfite ions, namely, a sulfite, a bisulfite, a metabisulfite, etc. These are preferably added in the form of a potassium salt, a sodium salt or an ammonium salt. Also, an arylsulfinic acid such as p-toluenesulfinic acid, m-carboxybenzenesulfinic acid or p-aminobenzenesulfinic acid is preferably contained therein. These compounds are preferably contained in a concentration of 0.02 to 1.0 mol/L based on the solution used. Also, other compounds such as ascorbic acid, a carbonyl bisulfuric acid adduct and a carbonyl compound may be added as the preservative.
- The bleach-fix composition and fixing composition according to the present invention may be dosed with a mercapto nitrogenous heterocyclic compound, such as mercaptotriazole, aminomercaptotriazole or N-methylmercaptoimidazole, capable of forming stable silver ions in order to improve image storage, and may be dosed with a bisamidine, bisguanidine or monoamidine compound capable of accelerating the washing away of developing agents as described in JP-A-5-303185. Furthermore, if necessary, the bleach-fix composition and fixing composition according to the present invention may be dosed with a polymer such as polyethylene glycol or polyvinylpyrrolidone, a chelating agent, an antifoaming agent, a mildewproofing agent, etc.
- In the bleach-fix of color print lightsensitive materials to which the present invention applies, the processing temperature, bleach-fix time and quantity of replenisher are as aforementioned. In the fixing of color negative films, the processing temperature is preferably in the range of 30 to 55° C., more preferably 35 to 50° C., and most preferably 38 to 45° C. The bleach time is preferably in the range of 20 sec to 2 min, more preferably 30 sec to 1 min 40 sec, and most preferably 35 sec to 1 min 20 sec. Although the smaller the quantity of replenisher, the greater the preference, it is generally suitable to use 4 to 60 mL of replenisher per 24 exp. The quantity of replenisher is preferably in the range of 5 to 40 mL, more preferably 6 to 30 mL.
- In the fixing of color reversal films, the processing temperature is preferably in the range of 30 to 45° C., more preferably 33 to 40° C., and most preferably 37 to 39° C. The fixing time is preferably in the range of 2 to 6 min, more preferably 3 to 5 min, and most preferably 3 min 30 sec to 4 min 30 sec. Although the smaller the quantity of replenisher, the greater the preference, it is generally suitable to use 800 to 2000 mL of replenisher per m2 of lightsensitive material. The quantity of replenisher is preferably in the range of 900 to 1500 mL, more preferably 1000 to 1250 mL.
- The washing composition and stabilization composition according to the present invention may be dosed with formalin, acetaldehyde, pyruvinaldehyde, a formaldehyde bisulfuric acid adduct described in U.S. Pat. No. 4,921,779, or an N-methylol compound described in JP-A-5-34889, the disclosures of which are incorporated herein by reference, in order to prevent stain formation or dye discoloration attributed to residual magenta couplers. Also, an arylsulfinic acid such as p-toluenesulfinic acid, m-carboxybenzenesulfinic acid or p-aminobenzenesulfinic acid is preferably contained therein. Further, if necessary, the washing composition and stabilization composition may be dosed with a surfactant as a dewatering agent, a chelating agent as a hard water softener, a buffer for pH adjustment, an antifoaming agent, a mildewproofing agent, an antibacterial agent, etc. The pH value thereof is preferably in the range of 4 to 10, more preferably 5 to 8. The temperature thereof, although set for various values depending on the intended use, properties, etc. of lightsensitive material, is generally in the range of 20 to 50° C., preferably 25 to 45° C.
- Photographic elements to be processed by the use of the processing composition of the present invention can comprise any of common silver halides such as silver chloride, silver bromide, silver bromoiodide, silver chlorobromide, silver chloroiodide and mixtures thereof as a lightsensitive material. In one form, the photographic element is one of high silver chloride content containing at least 50 mol % of chlorides, preferably at least 90 mol % of silver chloride, and is often used in, for example, a color print lightsensitive material.
- In another form, at least one emulsion consists principally of silver bromide (at least 50 mol % silver bromide). Most preferably, this photographic element has at least one color recording, and each color recording comprises at least one emulsion principally of silver bromide as used in color negative films and color reversal films. The photographic element to be processed according to the present invention can be a monocolor element or multicolor element. Further, this element can include a magnetic recording layer known in the art to which the present invention pertains.
- The details of each individual photographic element are described in, for example, Research Disclosures (hereinafter referred to as “RD”). Reference can be made to RD 17643 pages 23 to 27, RD 18716 pages 647 to 650, RD 307105 pages 866 to 868 and pages 873 to 879, and RD 36544 pages 501 to 541. These relate to useful silver halide emulsions (negative type or positive type) and processes for preparing the same, various sensitizers, dye forming couplers, image dye stabilizers, dyes, ultraviolet absorbents, filters, binders, film hardeners, plasticizers, lubricants, coating aids, surfactants, antistatic agents, matting agents, paper and film supports, various image forming methods for negative or positive image forming color elements, etc.
- When the processing composition of the present invention is a preparation composition, a configuration wherein all the components to be contained in a use solution are incorporated in a single composition, namely, a one-pack configuration is advantageous. However, when, with respect to, for example, the color development composition or bleach-fix composition, it is not desirable to bring constituent components into contact with each other for a prolonged period of time, it may be appropriate to produce a processing composition of two-pack or three-pack configuration wherein constituent components are separated into two or more liquid agents, or solid agents, or liquid and solid agents. These configurations of preparations are generally designated 1-part, 2-part, 3-part, . . . configurations under the nomenclature of international standards ISO 5989. The processing composition of the present invention is in no way deteriorated, with respect to the invention's effects and characteristics, by being divided into parts. In particular with respect to the color development composition, however, the 1-part configuration is preferred.
- The container for the processing composition of the present invention can be constituted of known materials according to the contents intended. The container may be prepared from a single material, or a composite material, for example, a composite material composed of a material of high gas permeability and a material of high alkali resistance. From the viewpoint of reuse and recycle, it is preferred that the container be constituted of a single material. Examples of the materials used for preparing the container include polyester resins, polyolefin resins, acrylic resins, ABS resins, epoxy resins, polyamide resins (such as nylons), polyurethane resins, polystyrene resins, polycarbonate resins, PVA, polyvinyl chloride, polyvinylidene chloride and polyethylene resins. In particular, containers constituted of a single material selected from among polyester resins (such as polyethylene terephthalate and polyethylene naphthalate) and polyolefin resins (such as polyethylene and polypropylene) are preferred. Polyethylene resins are more preferred, and a high-density polyethylene resin (HDPE) is most preferred as the container material.
- The material for preparing the container for use in the present invention can be loaded with carbon black, titanium white, a pigment, calcium carbonate, a plasticizer compatible with the material, etc., unless the loading is detrimental to the processing composition. The material for preparing the container is preferably one of 85% or more polyethylene content containing none of plasticizers, more preferably one of 95% or more polyethylene content containing none of plasticizers.
- The shape and structure of containers for accommodating the processing composition of the present invention can be arbitrarily designed in conformity with the object. Use can be made of not only bottles of regular shape but also expandable containers described in JP-A-1-235950, containers with flexible partition walls described in JP-A-62-134626, etc. Containers of JP-A-11-282148 are especially preferred as the container for accommodating the processing composition of the present invention from the viewpoint of capacity, space efficiency, self-supporting capability, shape retention, reuse and recycle. A kit comprising a single cartridge and, assembled therein, containers of the same shape and volume constituted of a single material wherein a plurality of compositions according to the present invention are accommodated presents a preferred form. The cartridge of JP-A-2000-3014 can be mentioned as an example thereof. In the cartridge, the combination of processing compositions can be arbitrarily selected. The cartridges of JP-A'S 11-295858 and 11-288068 present preferred forms wherein the development composition, bleach composition and fixing composition are incorporated.
- The present invention will be described in greater detail below while indicating the stability against deposit precipitation and photographic properties of processing compositions with respect to the following Examples, to which, however, the present invention is in no way limited.
-
Compound of the invention see Table 1 Brightening agent (FL-1) 1.75 g Triisopropanolamine 34.0 g Ethylenediaminetetraacetic acid 15.0 g Sodium sulfite 0.80 g Polyethylene glycol (av. MW: 300) 40.0 g Sodium 4,5-dihydroxybenzene-1,3-disulfonate 2.0 g Disodium-N,N-bis(sulfonatoethyl)hydroxylamine 55.0 g 4-Amino-3-methyl-N-ethyl-N-(β-methanesulfonamidoethyl)aniline.3/2sulfate.monohydrate 55.0 g Potassium hydroxide 19.0 g Sodium hydroxide 24.0 g Potassium carbonate 100.0 g Water q.s. ad 1000 mL pH 13.2. - One side of a support comprising a paper having its both major surfaces covered with a polyethylene resin was treated by corona discharge, furnished with a gelatin substratum layer containing sodium dodecylbenzenesulfonate, and further sequentially coated to provide the 1st to 7th layers. Thus, silver halide color photographic lightsensitive material P-1 of the following layer arrangement was obtained. The coating liquid for each photographic constituting element layer was prepared in the following manner.
- 300 g of cyan coupler (ExC), 250 g of dye image stabilizer (Cpd-1), 30 g of dye image stabilizer (Cpd-14), 100 g of dye image stabilizer (Cpd-15), 80 g of dye image stabilizer (Cpd-16), 50 g of dye image stabilizer (Cpd-17) and 10 g of dye image stabilizer (Cpd-18) were dissolved in 230 g of solvent (Solv-6) and 350 mL of ethyl acetate, and emulsified in 6500 g of a 10% aqueous gelatin solution containing 25 g of sodium dodecylbenzenesulfonate. Thus, emulsified dispersion C was obtained.
- Separately, there was prepared silver chlorobromide emulsion C (cubic form; 5:5 (silver molar ratio) mixture of large-size emulsion C of 0.40 μm average grain size and small-size emulsion C of 0.30 μm average grain size, the variation coefficients of grain size distribution thereof being 0.09 and 0.11, respectively; and with respect to both the large-size and small-size emulsions, 0.5 mol % of silver bromide localized on part of the surface of grains based on silver chloride emulsion).
- In this emulsion, each of the following red-sensitive sensitizing dyes G and H was added to the large-size emulsion C in an amount of, per mol of silver, 9.0×10−5 mol, and added to the small-size emulsion C in an amount of 12.0×10−5 mol. The optimum chemical ripening of this emulsion was performed by adding a sulfur sensitizer and a gold sensitizer.
- Mixing and dissolution of the above emulsified dispersion C and silver chlorobromide emulsion C were effected to thereby obtain the 5th layer coating liquid of the following composition. The coating amount of emulsion is in terms of silver quantity.
- The coating liquids for the 1st to 4th layers, the 6th layer and the 7th layer were prepared in the same manner as the coating liquid for the 5th layer. 1-Oxy-3,5-dichloro-s-triazine sodium salt was used as a gelatin hardener of each of the layers, and, to each of the layers, Ab-1, A-2, Ab-3 and Ab-4 were added in a total amount of 15.0 mg/m2, 60.0 mg/m2, 5.0 mg/m2 and 10.0 mg/m2 , respectively.
(Ab-1) Antiseptics (Ab-2) Antiseptics (Ab-3) Antiseptics (Ab-4) Antiseptics R1 R2 a —CH3 —NHCH3 b —CH3 —NH2 c —H —NH2 d —H —NHCH3 - The silver chlorobromide emulsion of each lightsensitive emulsion layer was loaded with the following spectral sensitizing dyes.
-
- (Each of the sensitizing dyes A and C was added in an amount of, per mol of silver halides, 0.42×10−4 mol to the large-size emulsion and 0.50×10−4 mol to the small-size emulsion. The sensitizing dye B was added in an amount of, per mol of silver halides, 3.4×10−4 mol to the large-size emulsion and 4.1×10−4 mol to the small-size emulsion.)
-
- (The sensitizing dye D was added in an amount of, per mol of silver halides, 3.0×10−4 mol to the large-size emulsion and 3.6×10−4 mol to the small-size emulsion. The sensitizing dye E was added in an amount of, per mol of silver halides, 4.0×10−4 mol to the large-size emulsion and 7.0×10−5 mol to the small-size emulsion. The sensitizing dye F was added in an amount of, per mol of silver halides, 2.0×10−4 mol to the large-size emulsion and 2.8×10−4 mol to the small-size emulsion.)
-
-
- The blue-sensitive emulsion layer (1st layer), green-sensitive emulsion layer (3rd layer) and red-sensitive emulsion layer (5th layer) were loaded with 1-(3-methylureidophenyl)-5-mercaptotetrazole in an amount of 3.3×10−4 mol, 1.0×10−3 mol and 5.9×10−4 mol, respectively, per mol of silver halides.
- The 2nd layer, 4th layer, 6th layer and 7th layer were loaded with the above compound in an amount of 0.2 mg/m2, 0.2 mg/m2, 0.6 mg/m2 and 0.1 mg/m2, respectively.
- The blue-sensitive emulsion layer and green-sensitive emulsion layer were loaded with 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene in an amount of 1×10−4 mol and 2×10−4 mol, respectively, per mol of silver halides.
- The red-sensitive emulsion layer was loaded with a latex of methacrylic acid/butyl acrylate copolymer (weight ratio 1:1, average molecular weight 200,000 to 400,000) in an amount of 0.05 g/m2.
- The 2nd layer, 4th layer and 6th layer were loaded with disodium catechol-3,5-disulfonate in an amount of 6 mg/m2, 6 mg/m2 and 18 mg/m2, respectively.
-
- The constitution of each layer is specified below. The numerals indicate the coating amount (g/m2). With respect to the silver halide emulsions, the coating amount is in terms of silver.
- (polyethylene resin on the 1st layer side contains white pigment (TiO2: 16% by weight content and ZnO: 4% by weight content), brightening agent (4,4′-bis(5-methylbenzoxazolyl)stilbene: 0.03% by weight content) and bluish dye (ultramarine)).
1st layer (blue-sensitive emulsion layer) Silver chlorobromide emulsion A (cubic form; 0.24 5:5 (silver molar ratio) mixture of large-size emulsion A of 0.74 μm average grain size and small-size emulsion A of 0.65 μm average grain size, the variation coefficients of grain size distribution thereof being 0.08 and 0.10, respectively; and with respect to both the large-size and small-size emulsions, 0.3 mol % of silver bromide localized on part of the sur- face of grains based on silver chloride) Gelatin 1.25 Yellow coupler (ExY) 0.57 Dye image stabilizer (Cpd-1) 0.07 Dye image stabilizer (Cpd-2) 0.04 Dye image stabilizer (Cpd-3) 0.07 Solvent (Solv-1) 0.21 2nd layer (color mixing inhibiting layer) Gelatin 0.99 Color mixing inhibitor (Cpd-4) 0.09 Color mixing inhibitor (Cpd-5) 0.018 Stabilizer (Cpd-6) 0.13 Color mixing inhibitor (Cpd-7) 0.01 Solvent (Sov-1) 0.06 Solvent (Sov-2) 0.22 3rd layer (green-sensitive emulsion layer) Silver chlorobromide emulsion B (cubic form; 0.14 1:3 (silver molar ratio) mixture of large-size emulsion B of 0.45 μm average grain size and small-size emulsion B of 0.35 μm average grain size, the variation coefficients of grain size distribution thereof being 0.10 and 0.08, respectively; and with respect to both the large-size and small-size emulsions, 0.4 mol % of silver bromide localized on part of the sur- face of grains based on silver chloride) Gelatin 1.36 Magenta coupler (ExM) 0.15 Ultraviolet absorbent (UV-1) 0.05 Ultraviolet absorbent (UV-2) 0.03 Ultraviolet absorbent (UV-3) 0.02 Ultraviolet absorbent (UV-4) 0.04 Dye image stabilizer (Cpd-2) 0.02 Color mixing inhibitor (Cpd-4) 0.002 Stabilizer (Cpd-6) 0.09 Dye image stabilizer (Cpd-8) 0.02 Dye image stabilizer (Cpd-9) 0.03 Dye image stabilizer (Cpd-10) 0.01 Dye image stabilizer (Cpd-11) 0.0001 Solvent (Solv-3) 0.11 Solvent (Solv-4) 0.22 Solvent (Solv-5) 0.20 4th layer (color mixing inhibiting layer) Gelatin 0.71 Color mixing inhibitor (Cpd-4) 0.06 Color mixing inhibiting aid (Cpd-5) 0.013 Stabilizer (Cpd-6) 0.10 Color mixing inhibitor (Cpd-7) 0.007 Solvent (Solv-1) 0.04 Solvent (Solv-2) 0.16 5th layer (red-sensitive emulsion layer) Silver chlorobromide emulsion C (cubic form; 0.20 5:5 (silver molar ratio) mixture of large-size emulsion C of 0.40 μm average grain size and small-size emulsion C of 0.30 μm average grain size, the variation coefficients of grain size distribution thereof being 0.09 and 0.11, respectively; and with respect to both the large-size and small-size emulsions, 0.5 mol % of silver bromide localized on part of the sur- face of grains based on silver chloride) Gelatin 1.11 Cyan coupler (ExC-1) 0.15 Cyan coupler (ExC-2) 0.10 Dye image stabilizer (Cpd-1) 0.25 Dye image stabilizer (Cpd-14) 0.03 Dye image stabilizer (Cpd-15) 0.10 Dye image stabilizer (Cpd-16) 0.08 Dye image stabilizer (Cpd-17) 0.05 Dye image stabilizer (Cpd-18) 0.01 Solvent (Solv-5) 0.23 6th layer (ultraviolet absorbing layer) Gelatin 0.46 Ultraviolet absorbent (UV-1) 0.14 Ultraviolet absorbent (UV-2) 0.05 Ultraviolet absorbent (UV-3) 0.04 Ultraviolet absorbent (UV-4) 0.06 Solvent (Solv-7) 0.25 7th layer (protective layer) Gelatin 1.00 Acrylic denatured copolymer of poly (vinyl 0.04 alcohol) (degree of denaturation 17%) Liquid paraffin 0.02 Surfactant (Cpd-13) 0.01 -
-
-
- The thus obtained lightsensitive material sample was formed into 127 mm wide rolls and, with the use of Minilab Printer Processor PP350 manufactured by Fuji Photo Film Co., Ltd., the lightsensitive material sample was subjected to imagewise exposure through an average-density negative film and continuous processing (running test) until the volume of color development replenisher used in the following processing steps became half (0.5-fold) the volume of color development tank.
Qty. of Processing Step Temp. Time replenisher Color develop- 38.5° C. 45 sec 45 mL ment Bleach-fix 38.0° C. 45 sec 35 mL Rinse 1 38.0° C. 20 sec — Rinse 2 38.0° C. 20 sec — Rinse 3 38.0° C. 20 sec — Rinse 4 38.0° C. 20 sec 121 mL Drying 80° C. # the reverse osmosis module was effected at controlled temperature for 10 hr per day. Rinsing was performed by a 4-tank countercurrent system from Rinse (4) through Rinse (1). - The composition of each processing solution was as follows.
(Color developer) (Tank soln.) Water 800 mL Compound of the invention 2 mmol Brightening agent (FL-1) 0.35 g Triisopropanolamine 8.8 g Polyethylene glycol (av. MW: 300) 10.0 g Ethylenediaminetetraacetic acid 4.0 g Sodium sulfite 0.10 g Potassium chloride 10.0 g Sodium 4,5-dihydroxybenzene-1,3-disulfonate 0.50 g Disodium-N,N-bis (sulfonatoethyl) hydroxylamine 8.5 g 4-Amino-3-methyl-N-ethyl-N-(β- 4.8 g methanesulfonamidoethyl) aniline.3/2sul- fate.monohydrate Potassium carbonate 26.3 g Water q.s. ad 1000 mL pH (25° C., adjusted with sulfuric acid and KOH) 10.15 - A 3.8-fold aqueous dilution of color development composition prepared in item (1) above was used as the color development replenisher.
(Tank soln.) (Replenisher) (Bleach-fix soln.) Water 800 mL 800 mL Ammonium thiosulfate (750 g/L) 107 mL 214 mL m-Carboxybenzenesulfinic acid 8.3 g 16.5 g Fe (III) ammonium ethylenediamine- 47.0 g 94.0 g tetraacetate Ethylenediaminetetraacetic acid 1.4 g 2.8 g Nitric acid (67%) 16.5 g 33.0 g Imidazole 14.6 g 29.2 g Ammonium sulfite 16.0 g 32.0 g Potassium metabisulfite 23.1 g 46.2 g Water q.s. ad 1000 mL pH (25° C., adjusted with nitric 6.5 6.5 acid and aqueous ammonia) (Rinse soln.) Sodium chloroisocyanurate 0.02 g 0.02 g Deionized water (permittivity: 1000 mL 1000 mL 5 μs/cm or less) pH (25° C.) 6.5 6.5 - (i) Stability against deposit precipitation
- Each prepared color development composition was placed in glass bottles, and stored at −5° C. and at room temperature for 4 weeks. A 5-grade estimation of test results was made by visually inspecting the condition of liquid after storage. Level of conspicuous deposit precipitation was judged as x x; level of clear deposit precipitation as x; level of slight deposition recognized as Δ; level of clouding but no deposit precipitation as o; and level of thorough transparency without any clouding and deposition recognized as @.
- (ii) Photographic characteristics in color paper processing
- With respect to an unexposed lightsensitive material sample after the development processing, a reflection spectrum thereof was produced with the use of spectrophotometer model U-3500 equipped with an integrating sphere of 150 mm diameter, manufactured by Hitachi, Ltd. Absorbance at 450 nm was measured on the reflection spectrum and designated DB. Each sample was washed with the use of 40° C. distilled water for 5 min, dried and subjected to the same measurement. The absorbance at 450 nm of the resultant sample was designated DBW.
- ΔDB was calculated by the following formula, whereby the degree of stain attributed to residual sensitizing dyes was estimated.
- ΔD B =D B −D BW
- (iii) Result
TABLE 1 Estimation of Addition Estimation of Estimation of photographic Added amount precipitation precipitation characteristics Sample compound (mmol) (−5° C.) (Room temp.) (ΔDB) Remark 1-1 Non — ⊚ ⊚ 0.020 Comp. 1-2 FL-2 15 XX X 0.005 Comp. 1-3 3 15 ⊚ ⊚ 0.007 Inv. 1-4 8 15 ◯ ⊚ 0.006 Inv. 1-5 15 15 ⊚ ⊚ 0.009 Inv. - With respect to sample 1-2 (comparative example) produced with the use of compound FL-2, the degree of stain attributed to residual sensitizing dyes was similar to or on the level close to those of the samples produced with the use of compounds of the present invention, but deposit precipitation occurred upon storage of the processing composition. With respect to sample 1-1 (comparative example), no deposit precipitation occurred. Therefore, the deposit precipitation is attributable to the added compound.
-
-
(1) Preparation of bleach composition Water 400 mL Compound of the invention Table 2 m-Carboxybenzenesulfinic acid 50.0 g Fe (III) ammonium ethylenediamine- 210 g tetraacetate Ethylenediaminetetraacetic acid 7.5 g Ammonium nitrate 24.0 g Water q.s. ad 1000 mL pH (25° C., adjusted with nitric 6.00. acid and aqueous ammonia) (2) Preparation of fixing composition Compound of the invention Table 3 Ammonium thiosulfate (750 g/mL) 575 mL Imidazole 7.5 g Ethylenediaminetetraacetic acid 9.0 g Ammonium sulfite 183 g Water q.s. ad 1000 mL pH (25° C., adjusted with nitric 6.00. acid and aqueous ammonia) - Development processing was carried out in the same manner as in Example 1. In the color development replenisher, use was made of a 3.8-fold aqueous dilution of the composition for sample 1-1 of Example 1. As the replenisher for bleach-fix solution, use was made of a 1.5-fold dilution of a 1:1 mixture of bleach composition prepared in item (1) above and fixing composition prepared in item (2) above. As the tank solution of bleach-fix solution, use was made of a 3-fold dilution of a 1:1 mixture of bleach composition prepared in item (1) above and fixing composition prepared in item (2) above. The combination of bleach composition and fixing composition was as indicated in Table 4.
- (i) Stability against deposit precipitation
- The same estimation as in Example 1 was effected.
- (ii) Photographic characteristics in color paper processing
- The same estimation as in Example 1 was effected.
- (iii) Result
TABLE 2 Added Addition Estimation of Estimation of com- amount precipitation precipitation Sample pound (mmol) (−5° C.) (Room temp.) Remark 2-1 Non — ⊚ ⊚ Comp. 2-2 3 6 ◯ ◯ Inv. 2-3 8 6 ◯ ⊚ Inv. 2-4 12 6 ◯ ⊚ Inv. 2-5 15 6 ◯ ⊚ Inv. -
TABLE 3 Added Addition Estimation of Estimation of com- amount precipitation precipitation Sample pound (mmol) (−5° C.) (Room temp.) Remark 3-1 Non — ⊚ ⊚ Comp. 3-2 3 6 ◯ ◯ Inv. 3-3 8 6 ◯ ⊚ Inv. 3-4 12 6 ◯ ⊚ Inv. 3-5 15 6 ◯ ⊚ Inv. -
TABLE 4 Bleach Fixing Estimation of photographic composition composition characteristics (ΔDB) Remark 2-1 3-1 0.020 Comp. 2-3 3-1 0.007 Inv. 2-3 3-3 0.005 Inv. 2-3 3-5 0.010 Inv. 2-5 3-5 0.007 Inv. - As apparent from Tables 2 and 3, each processing composition of the present invention, even after storage for 4 weeks, was thoroughly transparent at room temperature, and was thoroughly transparent or in the state of slight clouding recognized at low temperature (−5° C.). Irrespective of the temperature, no deposit precipitation occurred. As apparent from Table 4, the lightsensitive material having undergone the development processing wherein use was made of the processing composition of the present invention exhibited a low value with respect to the stain ΔDB attributed to residual sensitizing dyes, namely, only a slight coloring of white ground. Therefore, it has become apparent that the present invention is excellent in the capability of reducing the stain attributed to sensitizing dyes remaining in the lightsensitive material after the processing, and that the processing composition of the present invention is a composition free of precipitation deposits during the low temperature storage of the processing composition.
- As apparent from the foregoing detailed description, the processing composition for silver halide photographic lightsensitive material wherein the heterocycle combination of the general formula (I) is contained according to the present invention and the method of forming an image with the use of the processing composition enable exerting the advantageous effects of not only reducing stain attributed to sensitizing dyes remaining in the lightsensitive material after the processing thereof but also being free of any precipitation deposits during the low-temperature storage of the processing composition.
- Additional advantages and modifications will readily occur to those skilled in the art. Therefore, the invention in its broader aspects is not limited to the specific details and representative embodiments shown and described herein. Accordingly, various modifications may be made without departing from the spirit or scope of the general inventive concept as defined by the appended claims and their equivalents.
Claims (18)
1. A photographic processing composition for silver halide color photographic lightsensitive material, comprising at least one compound represented by the formula (I):
A1—X—L—Y—A2 (I)
wherein each of A1 and A2 independently represents an aryl group or an aromatic heterocyclic group; L represents an aromatic heterocyclic group, with the proviso that a triazine ring is not represented thereby; and each of X and Y independently represents O, S or NR1, wherein R1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, with the proviso that the molecule of the formula (I) has a substituent containing at least one of —OH, —CO2M and —SO3M groups, wherein M represents a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium or a pyridinium, and provided that the molecule of the formula (I) has no azo group.
2. The photographic processing composition according to claim 1 , wherein, in the formula (I), L is a pyridinediyl group, a pyrazinediyl group, a pyrimidinediyl group, a pyridazinediyl group or a phthalazinediyl group.
3. The photographic processing composition according to claim 1 , for use in color development processing.
4. The photographic processing composition according to claim 2 , for use in color development processing.
5. The photographic processing composition according to claim 1 , for use in bleach processing or bleach-fix processing.
6. The photographic processing composition according to claim 2 , for use in bleach processing or bleach-fix processing.
7. The photographic processing composition according to claim 1 , for use in fixing processing.
8. The photographic processing composition according to claim 2 , for use in fixing processing.
9. The photographic processing composition according to claim 1 , for use in a use solution in which the concentration of compound represented by the formula (I) is in a range of 0.05 to 20 mmol/L.
10. A method of forming an image, comprising using the photographic processing composition for silver halide color photographic lightsensitive material according to claim 1 .
11. A method of forming an image, comprising using the photographic processing composition for silver halide color photographic lightsensitive material according to claim 2 .
12. A method of forming an image, comprising using the photographic processing composition for silver halide color photographic lightsensitive material according to claim 3 .
13. A method of forming an image, comprising using the photographic processing composition for silver halide color photographic lightsensitive material according to claim 4 .
14. A method of forming an image, comprising using the photographic processing composition for silver halide color photographic lightsensitive material according to claim 5 .
15. A method of forming an image, comprising using the photographic processing composition for silver halide color photographic lightsensitive material according to claim 6 .
16. A method of forming an image, comprising using the photographic processing composition for silver halide color photographic lightsensitive material according to claim 7 .
17. A method of forming an image, comprising using the photographic processing composition for silver halide color photographic lightsensitive material according to claim 8 .
18. A method of forming an image, comprising using the photographic processing composition for silver halide color photographic lightsensitive material according to claim 9.
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US20050203146A1 (en) * | 2004-01-21 | 2005-09-15 | Herpin Timothy F. | Amino-benzazoles as P2Y1 receptor inhibitors |
GB2520633A (en) * | 2013-11-25 | 2015-05-27 | Crayola Llc | Marking system |
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US7108962B2 (en) * | 2002-01-25 | 2006-09-19 | Fuji Photo Film Co., Ltd. | Photographic processing composition and image-forming method using the same |
US7122299B2 (en) * | 2002-11-06 | 2006-10-17 | Fuji Photo Film Co., Ltd. | Silver halide photographic light-sensitive material |
JP2009226781A (en) | 2008-03-24 | 2009-10-08 | Fujifilm Corp | Method of forming inkjet image |
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US5994375A (en) | 1996-02-12 | 1999-11-30 | Berlex Laboratories, Inc. | Benzamidine derivatives substituted by amino acid and hydroxy acid derivatives and their use as anti-coagulants |
EP0905169B8 (en) | 1997-09-24 | 2008-07-16 | Infineon Technologies AG | Precursors of polybenzoxazoles and polybenzothiazoles |
US6262088B1 (en) | 1998-11-19 | 2001-07-17 | Berlex Laboratories, Inc. | Polyhydroxylated monocyclic N-heterocyclic derivatives as anti-coagulants |
US6153364A (en) | 1999-12-16 | 2000-11-28 | Eastman Kodak Company | Photographic processing methods using compositions containing stain reducing agent |
US6153365A (en) | 1999-12-16 | 2000-11-28 | Eastman Kodak Company | Photographic processing compositions containing stain reducing agent |
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Cited By (8)
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US20050203146A1 (en) * | 2004-01-21 | 2005-09-15 | Herpin Timothy F. | Amino-benzazoles as P2Y1 receptor inhibitors |
US20080275090A1 (en) * | 2004-01-21 | 2008-11-06 | Bristol-Myers Squibb Company | Amino-benzazoles as p2y1 receptor inhibitors with pyridine ring and heterocyclic components |
US7470712B2 (en) | 2004-01-21 | 2008-12-30 | Bristol-Myers Squibb Company | Amino-benzazoles as P2Y1 receptor inhibitors |
US8053450B2 (en) | 2004-01-21 | 2011-11-08 | Bristol-Myers Squibb Company | Amino-benzazoles as P2Y1 receptor inhibitors with pyridine ring and heterocyclic components |
GB2520633A (en) * | 2013-11-25 | 2015-05-27 | Crayola Llc | Marking system |
US9464185B2 (en) | 2013-11-25 | 2016-10-11 | Crayola Llc | Marking system |
US9790383B2 (en) | 2013-11-25 | 2017-10-17 | Crayola Llc | Marking system |
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US20030224300A1 (en) | 2003-12-04 |
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