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EP0930536B1 - Silver halide photosensitive color photographic material, image forming method, image information forming method - Google Patents

️Wed Apr 20 2005

Silver halide photosensitive color photographic material, image forming method, image information forming method Download PDF

Info

Publication number

EP0930536B1

EP0930536B1 EP99300311A EP99300311A EP0930536B1 EP 0930536 B1 EP0930536 B1 EP 0930536B1 EP 99300311 A EP99300311 A EP 99300311A EP 99300311 A EP99300311 A EP 99300311A EP 0930536 B1 EP0930536 B1 EP 0930536B1 Authority

European Patent Office

Prior art keywords

silver

image information

sample

silver halide

forming method

Prior art date

1998-01-21

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.)

Expired - Lifetime

Application number

EP99300311A

Other languages

German (de)

French (fr)

Other versions

EP0930536A1 (en

Inventor

Shinri Tanaka

Tawara Komamura

Motoaki Sugino

Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)

Konica Minolta Inc

Original Assignee

Konica Minolta Inc

Priority date (The priority date 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 date listed.)

1998-01-21

Filing date

1999-01-18

Publication date

2005-04-20

1999-01-18 Application filed by Konica Minolta Inc filed Critical Konica Minolta Inc

1999-07-21 Publication of EP0930536A1 publication Critical patent/EP0930536A1/en

2005-04-20 Application granted granted Critical

2005-04-20 Publication of EP0930536B1 publication Critical patent/EP0930536B1/en

2019-01-18 Anticipated expiration legal-status Critical

Status Expired - Lifetime legal-status Critical Current

Links

239000000463 material Substances 0.000 title claims description 58
229910052709 silver Inorganic materials 0.000 title claims description 54
239000004332 silver Substances 0.000 title claims description 54
-1 Silver halide Chemical class 0.000 title claims description 44
238000000034 method Methods 0.000 title claims description 40
238000012545 processing Methods 0.000 claims description 31
BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 25
238000004061 bleaching Methods 0.000 claims description 15
238000002791 soaking Methods 0.000 claims description 5
238000006243 chemical reaction Methods 0.000 claims description 3
239000007787 solid Substances 0.000 claims description 2
239000010410 layer Substances 0.000 description 42
239000000975 dye Substances 0.000 description 30
238000011161 development Methods 0.000 description 29
238000007689 inspection Methods 0.000 description 22
108010010803 Gelatin Proteins 0.000 description 20
229910021612 Silver iodide Inorganic materials 0.000 description 20
239000000839 emulsion Substances 0.000 description 20
229920000159 gelatin Polymers 0.000 description 20
239000008273 gelatin Substances 0.000 description 20
235000019322 gelatine Nutrition 0.000 description 20
235000011852 gelatine desserts Nutrition 0.000 description 20
JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 19
229940045105 silver iodide Drugs 0.000 description 19
NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 18
230000000052 comparative effect Effects 0.000 description 17
ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 17
238000000354 decomposition reaction Methods 0.000 description 16
230000003287 optical effect Effects 0.000 description 16
0 Cc1cc(*C=C(C(*=O)=*N2c3ccccc3)C2=O)c(C)[n]1-c1cc(C(O)=O)cc(C(O)=O)c1 Chemical compound Cc1cc(*C=C(C(*=O)=*N2c3ccccc3)C2=O)c(C)[n]1-c1cc(C(O)=O)cc(C(O)=O)c1 0.000 description 14
SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 12
206010070834 Sensitisation Diseases 0.000 description 10
150000001875 compounds Chemical class 0.000 description 10
IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 10
230000008313 sensitization Effects 0.000 description 10
239000000126 substance Substances 0.000 description 9
WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 8
230000015572 biosynthetic process Effects 0.000 description 7
239000003795 chemical substances by application Substances 0.000 description 7
238000002360 preparation method Methods 0.000 description 7
230000008569 process Effects 0.000 description 7
230000005070 ripening Effects 0.000 description 7
238000005406 washing Methods 0.000 description 7
QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
239000000203 mixture Substances 0.000 description 6
229910001961 silver nitrate Inorganic materials 0.000 description 6
229910052717 sulfur Inorganic materials 0.000 description 6
239000011593 sulfur Substances 0.000 description 6
239000000654 additive Substances 0.000 description 5
238000011156 evaluation Methods 0.000 description 5
239000007921 spray Substances 0.000 description 5
101000633434 Arabidopsis thaliana Structural maintenance of chromosomes protein 1 Proteins 0.000 description 4
LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
239000011248 coating agent Substances 0.000 description 4
238000000576 coating method Methods 0.000 description 4
150000002344 gold compounds Chemical class 0.000 description 4
239000011229 interlayer Substances 0.000 description 4
150000002894 organic compounds Chemical class 0.000 description 4
238000011160 research Methods 0.000 description 4
238000005507 spraying Methods 0.000 description 4
FUOSTELFLYZQCW-UHFFFAOYSA-N 1,2-oxazol-3-one Chemical class OC=1C=CON=1 FUOSTELFLYZQCW-UHFFFAOYSA-N 0.000 description 3
229920002284 Cellulose triacetate Polymers 0.000 description 3
BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 3
NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 3
238000009835 boiling Methods 0.000 description 3
239000002738 chelating agent Substances 0.000 description 3
238000004040 coloring Methods 0.000 description 3
238000001035 drying Methods 0.000 description 3
PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
229910052737 gold Inorganic materials 0.000 description 3
239000010931 gold Substances 0.000 description 3
150000004820 halides Chemical class 0.000 description 3
239000004816 latex Substances 0.000 description 3
229920000126 latex Polymers 0.000 description 3
229910000510 noble metal Inorganic materials 0.000 description 3
229920000120 polyethyl acrylate Polymers 0.000 description 3
239000004848 polyfunctional curative Substances 0.000 description 3
CYMJPJKHCSDSRG-UHFFFAOYSA-N pyrazolidine-3,4-dione Chemical class O=C1CNNC1=O CYMJPJKHCSDSRG-UHFFFAOYSA-N 0.000 description 3
238000011084 recovery Methods 0.000 description 3
230000009467 reduction Effects 0.000 description 3
229910052711 selenium Inorganic materials 0.000 description 3
239000011669 selenium Substances 0.000 description 3
230000003595 spectral effect Effects 0.000 description 3
239000003381 stabilizer Substances 0.000 description 3
238000003756 stirring Methods 0.000 description 3
239000002699 waste material Substances 0.000 description 3
XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
WFFZGYRTVIPBFN-UHFFFAOYSA-N 3h-indene-1,2-dione Chemical class C1=CC=C2C(=O)C(=O)CC2=C1 WFFZGYRTVIPBFN-UHFFFAOYSA-N 0.000 description 2
OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 2
239000002253 acid Substances 0.000 description 2
230000002411 adverse Effects 0.000 description 2
ZOJBYZNEUISWFT-UHFFFAOYSA-N allyl isothiocyanate Chemical compound C=CCN=C=S ZOJBYZNEUISWFT-UHFFFAOYSA-N 0.000 description 2
229940051880 analgesics and antipyretics pyrazolones Drugs 0.000 description 2
238000000149 argon plasma sintering Methods 0.000 description 2
150000007656 barbituric acids Chemical class 0.000 description 2
238000011109 contamination Methods 0.000 description 2
239000013078 crystal Substances 0.000 description 2
230000006866 deterioration Effects 0.000 description 2
239000006185 dispersion Substances 0.000 description 2
238000009826 distribution Methods 0.000 description 2
239000010946 fine silver Substances 0.000 description 2
238000005189 flocculation Methods 0.000 description 2
230000016615 flocculation Effects 0.000 description 2
ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 2
230000006872 improvement Effects 0.000 description 2
150000002484 inorganic compounds Chemical class 0.000 description 2
229910010272 inorganic material Inorganic materials 0.000 description 2
238000005259 measurement Methods 0.000 description 2
125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
229910017604 nitric acid Inorganic materials 0.000 description 2
229910052700 potassium Inorganic materials 0.000 description 2
239000011591 potassium Substances 0.000 description 2
239000011241 protective layer Substances 0.000 description 2
JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical class O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 2
TUPZMLLDXCWVKH-UHFFFAOYSA-N pyrazolo[4,3-b]pyridin-3-one Chemical class C1=CN=C2C(=O)N=NC2=C1 TUPZMLLDXCWVKH-UHFFFAOYSA-N 0.000 description 2
UBQKCCHYAOITMY-UHFFFAOYSA-N pyridin-2-ol Chemical class OC1=CC=CC=N1 UBQKCCHYAOITMY-UHFFFAOYSA-N 0.000 description 2
230000001105 regulatory effect Effects 0.000 description 2
230000035945 sensitivity Effects 0.000 description 2
230000001235 sensitizing effect Effects 0.000 description 2
ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 2
229910000029 sodium carbonate Inorganic materials 0.000 description 2
239000007962 solid dispersion Substances 0.000 description 2
239000002904 solvent Substances 0.000 description 2
UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
239000001043 yellow dye Substances 0.000 description 2
TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
AOSZTAHDEDLTLQ-AZKQZHLXSA-N (1S,2S,4R,8S,9S,11S,12R,13S,19S)-6-[(3-chlorophenyl)methyl]-12,19-difluoro-11-hydroxy-8-(2-hydroxyacetyl)-9,13-dimethyl-6-azapentacyclo[10.8.0.02,9.04,8.013,18]icosa-14,17-dien-16-one Chemical compound C([C@@H]1C[C@H]2[C@H]3[C@]([C@]4(C=CC(=O)C=C4[C@@H](F)C3)C)(F)[C@@H](O)C[C@@]2([C@@]1(C1)C(=O)CO)C)N1CC1=CC=CC(Cl)=C1 AOSZTAHDEDLTLQ-AZKQZHLXSA-N 0.000 description 1
ZRHUHDUEXWHZMA-UHFFFAOYSA-N 1,4-dihydropyrazol-5-one Chemical class O=C1CC=NN1 ZRHUHDUEXWHZMA-UHFFFAOYSA-N 0.000 description 1
XNCSCQSQSGDGES-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]propyl-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)C(C)CN(CC(O)=O)CC(O)=O XNCSCQSQSGDGES-UHFFFAOYSA-N 0.000 description 1
TVTJUIAKQFIXCE-HUKYDQBMSA-N 2-amino-9-[(2R,3S,4S,5R)-4-fluoro-3-hydroxy-5-(hydroxymethyl)oxolan-2-yl]-7-prop-2-ynyl-1H-purine-6,8-dione Chemical compound NC=1NC(C=2N(C(N(C=2N=1)[C@@H]1O[C@@H]([C@H]([C@H]1O)F)CO)=O)CC#C)=O TVTJUIAKQFIXCE-HUKYDQBMSA-N 0.000 description 1
RYYXDZDBXNUPOG-UHFFFAOYSA-N 4,5,6,7-tetrahydro-1,3-benzothiazole-2,6-diamine;dihydrochloride Chemical compound Cl.Cl.C1C(N)CCC2=C1SC(N)=N2 RYYXDZDBXNUPOG-UHFFFAOYSA-N 0.000 description 1
LHYQAEFVHIZFLR-UHFFFAOYSA-L 4-(4-diazonio-3-methoxyphenyl)-2-methoxybenzenediazonium;dichloride Chemical compound [Cl-].[Cl-].C1=C([N+]#N)C(OC)=CC(C=2C=C(OC)C([N+]#N)=CC=2)=C1 LHYQAEFVHIZFLR-UHFFFAOYSA-L 0.000 description 1
QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
MNHWYEGAZDMSQR-YVLHZVERSA-N CC(/C(/C1=O)=C/c(ccc(OC)c2)c2OC)=NN1c(cc1)ccc1C(O)=O Chemical compound CC(/C(/C1=O)=C/c(ccc(OC)c2)c2OC)=NN1c(cc1)ccc1C(O)=O MNHWYEGAZDMSQR-YVLHZVERSA-N 0.000 description 1
229940126657 Compound 17 Drugs 0.000 description 1
KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
RZSYLLSAWYUBPE-UHFFFAOYSA-L Fast green FCF Chemical compound [Na+].[Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C(=CC(O)=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 RZSYLLSAWYUBPE-UHFFFAOYSA-L 0.000 description 1
LEVWYRKDKASIDU-IMJSIDKUSA-N L-cystine Chemical compound [O-]C(=O)[C@@H]([NH3+])CSSC[C@H]([NH3+])C([O-])=O LEVWYRKDKASIDU-IMJSIDKUSA-N 0.000 description 1
238000001016 Ostwald ripening Methods 0.000 description 1
FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
239000005708 Sodium hypochlorite Substances 0.000 description 1
229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
XEIPQVVAVOUIOP-UHFFFAOYSA-N [Au]=S Chemical compound [Au]=S XEIPQVVAVOUIOP-UHFFFAOYSA-N 0.000 description 1
KWEGYAQDWBZXMX-UHFFFAOYSA-N [Au]=[Se] Chemical compound [Au]=[Se] KWEGYAQDWBZXMX-UHFFFAOYSA-N 0.000 description 1
238000002835 absorbance Methods 0.000 description 1
239000006096 absorbing agent Substances 0.000 description 1
238000010521 absorption reaction Methods 0.000 description 1
239000013543 active substance Substances 0.000 description 1
125000001931 aliphatic group Chemical group 0.000 description 1
235000016720 allyl isothiocyanate Nutrition 0.000 description 1
WLDHEUZGFKACJH-UHFFFAOYSA-K amaranth Chemical compound [Na+].[Na+].[Na+].C12=CC=C(S([O-])(=O)=O)C=C2C=C(S([O-])(=O)=O)C(O)=C1N=NC1=CC=C(S([O-])(=O)=O)C2=CC=CC=C12 WLDHEUZGFKACJH-UHFFFAOYSA-K 0.000 description 1
150000001408 amides Chemical class 0.000 description 1
239000002216 antistatic agent Substances 0.000 description 1
239000011230 binding agent Substances 0.000 description 1
239000007844 bleaching agent Substances 0.000 description 1
238000005282 brightening Methods 0.000 description 1
230000015556 catabolic process Effects 0.000 description 1
229910052798 chalcogen Inorganic materials 0.000 description 1
150000001787 chalcogens Chemical class 0.000 description 1
239000013522 chelant Substances 0.000 description 1
239000003638 chemical reducing agent Substances 0.000 description 1
GTKRFUAGOKINCA-UHFFFAOYSA-M chlorosilver;silver Chemical class [Ag].[Ag]Cl GTKRFUAGOKINCA-UHFFFAOYSA-M 0.000 description 1
230000001427 coherent effect Effects 0.000 description 1
239000003086 colorant Substances 0.000 description 1
229940125851 compound 27 Drugs 0.000 description 1
230000001276 controlling effect Effects 0.000 description 1
238000007796 conventional method Methods 0.000 description 1
230000008878 coupling Effects 0.000 description 1
238000010168 coupling process Methods 0.000 description 1
238000005859 coupling reaction Methods 0.000 description 1
229960003067 cystine Drugs 0.000 description 1
230000003247 decreasing effect Effects 0.000 description 1
238000006731 degradation reaction Methods 0.000 description 1
238000000586 desensitisation Methods 0.000 description 1
238000009792 diffusion process Methods 0.000 description 1
230000000694 effects Effects 0.000 description 1
239000003344 environmental pollutant Substances 0.000 description 1
ALCDAWARCQFJBA-UHFFFAOYSA-N ethylselanylethane Chemical compound CC[Se]CC ALCDAWARCQFJBA-UHFFFAOYSA-N 0.000 description 1
239000004744 fabric Substances 0.000 description 1
239000007850 fluorescent dye Substances 0.000 description 1
239000007789 gas Substances 0.000 description 1
RJHLTVSLYWWTEF-UHFFFAOYSA-K gold trichloride Chemical compound Cl[Au](Cl)Cl RJHLTVSLYWWTEF-UHFFFAOYSA-K 0.000 description 1
229910052736 halogen Inorganic materials 0.000 description 1
150000002367 halogens Chemical class 0.000 description 1
150000002429 hydrazines Chemical class 0.000 description 1
229910052739 hydrogen Inorganic materials 0.000 description 1
XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
238000010348 incorporation Methods 0.000 description 1
239000003112 inhibitor Substances 0.000 description 1
238000011835 investigation Methods 0.000 description 1
239000003446 ligand Substances 0.000 description 1
230000031700 light absorption Effects 0.000 description 1
239000010687 lubricating oil Substances 0.000 description 1
239000006224 matting agent Substances 0.000 description 1
229910052751 metal Inorganic materials 0.000 description 1
239000002184 metal Substances 0.000 description 1
150000002736 metal compounds Chemical class 0.000 description 1
AJDUTMFFZHIJEM-UHFFFAOYSA-N n-(9,10-dioxoanthracen-1-yl)-4-[4-[[4-[4-[(9,10-dioxoanthracen-1-yl)carbamoyl]phenyl]phenyl]diazenyl]phenyl]benzamide Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2NC(=O)C(C=C1)=CC=C1C(C=C1)=CC=C1N=NC(C=C1)=CC=C1C(C=C1)=CC=C1C(=O)NC1=CC=CC2=C1C(=O)C1=CC=CC=C1C2=O AJDUTMFFZHIJEM-UHFFFAOYSA-N 0.000 description 1
150000004780 naphthols Chemical class 0.000 description 1
239000002667 nucleating agent Substances 0.000 description 1
230000003647 oxidation Effects 0.000 description 1
238000007254 oxidation reaction Methods 0.000 description 1
150000002941 palladium compounds Chemical class 0.000 description 1
150000002989 phenols Chemical class 0.000 description 1
150000003014 phosphoric acid esters Chemical class 0.000 description 1
150000003021 phthalic acid derivatives Chemical class 0.000 description 1
239000004014 plasticizer Substances 0.000 description 1
231100000719 pollutant Toxicity 0.000 description 1
229920000768 polyamine Polymers 0.000 description 1
229920000139 polyethylene terephthalate Polymers 0.000 description 1
239000005020 polyethylene terephthalate Substances 0.000 description 1
239000001267 polyvinylpyrrolidone Substances 0.000 description 1
229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 1
229940116357 potassium thiocyanate Drugs 0.000 description 1
ZHHGTDYVCLDHHV-UHFFFAOYSA-J potassium;gold(3+);tetraiodide Chemical compound [K+].[I-].[I-].[I-].[I-].[Au+3] ZHHGTDYVCLDHHV-UHFFFAOYSA-J 0.000 description 1
239000002243 precursor Substances 0.000 description 1
238000004064 recycling Methods 0.000 description 1
KIWUVOGUEXMXSV-UHFFFAOYSA-N rhodanine Chemical compound O=C1CSC(=S)N1 KIWUVOGUEXMXSV-UHFFFAOYSA-N 0.000 description 1
150000003839 salts Chemical class 0.000 description 1
229940065287 selenium compound Drugs 0.000 description 1
150000003343 selenium compounds Chemical class 0.000 description 1
150000003346 selenoethers Chemical class 0.000 description 1
SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 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
235000011150 stannous chloride Nutrition 0.000 description 1
239000001119 stannous chloride Substances 0.000 description 1
238000000859 sublimation Methods 0.000 description 1
230000008022 sublimation Effects 0.000 description 1
150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 1
238000012546 transfer Methods 0.000 description 1

Classifications

- 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
- G03C7/3017—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials with intensification of the image by oxido-reduction
- 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
- G03C1/00—Photosensitive materials
- G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
- G03C1/825—Photosensitive materials characterised by the base or auxiliary layers characterised by antireflection means or visible-light filtering means, e.g. antihalation
- G03C1/83—Organic dyestuffs therefor
- 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
- G03C7/3022—Materials with specific emulsion characteristics, e.g. thickness of the layers, silver content, shape of AgX grains
- G03C2007/3025—Silver content
- 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
- G03C7/3022—Materials with specific emulsion characteristics, e.g. thickness of the layers, silver content, shape of AgX grains

Definitions

the present invention relates to an image information forming method.
photosensitive material silver halide photosensitive photographic materials
processing consisting of color development, bleaching, and fixing each employing a specific processing solution, and it has long been desired to develop a method in which image information is obtained using simple and convenient processing.
Conventional photosensitive materials comprise a yellow filter layer which prevents the deterioration of color reproduction due to the fact that green-sensitive layers and red-sensitive layers are sensitive to blue light on account of blue light absorption properties of silver halides. Furthermore, in order to minimize halation, generally, a layer comprising dyes has been provided. In the present invention, these layers are hereinafter referred to as a yellow filter layer and an antihalation layer, respectively.
Conventional photosensitive materials are generally subjected to bleaching and fixing after development. Though colloidal silver is incorporated into the yellow filter and the antihalation layer, it is removed during the bleaching and fixing processes. Therefore, there has been no problem with remaining colors after processing.
chelating agents such as EDTA, PDTA, etc. are employed.
these chelating agents are not readily biodegradable and cause an increase in treatment cost of solution waste. Accordingly, countermeasures have been sought.
JP09152700 A discloses color developing agents comprising specific hydrazine derivatives which significantly improve coloring and hue, light fastness and image stability.
EP-A-0730198 discloses a process for the formation of a color image which comprises the steps of exposing to light a silver halide light-sensitive material comprising a support having thereon at least one light-sensitive emulsion layer, and developing said light-sensitive material to form a color image, wherein said light-sensitive material comprises at least one dye-forming coupler and at least one specific coloring reducing agent, and is intensified with a solution containing hydrogen peroxide or a compound releasing hydrogen peroxide to form an intensified image.
the dyes which can be decomposed by a color developer denote dyes which are decomposed at a decomposition ratio of at least 50 percent during color development reaction employing the color developer.
the decomposition ratio is preferably at least 70 percent and is more preferably at least 90 percent.
Dyes as described in the present invention may include organic compounds or inorganic compounds, irrespective of their structure.
Organic compounds are preferred because they result in relatively rapid decomposition reaction in a color developer.
organic compounds such as organic dyes and inorganic compounds may be employed in combination.
processing solutions employed in the present invention it is preferred that processing in which almost all the supplied processing solution is absorbed by photosensitive material, is carried out because no solution waste is generated.
methods to supply the processing solution to the photosensitive material, spray development or coating development is preferable.
the spray development as described herein denotes a development in which a developer is supplied onto a photosensitive material as a spray in an amount substantially capable of soaking the photosensitive material.
the number of nozzles, shapes of nozzles, spraying may be carried out during movement of a single movable nozzle or employing a plurality of fixed nozzles.
the spraying may also be carried out by moving a nozzle while stopping a photosensitive material or may be carried out by moving a photosensitive material, or in a combination thereof.
the coating development as described herein denotes a development in which a developer is supplied onto a photosensitive material in an amount substantially capable of soaking the photosensitive material via a means of carrying the developer.
a means of carrying the developer felt, fabrics, metal sheets with holes or slits, etc. are preferably employed. While spraying a developer onto a photosensitive material or a medium, a method is preferred in which the developer is coated onto the photosensitive material employing the medium.
the present invention is preferably applied to a photosensitive material having a silver amount of not more than 2 g/m 2 .
a photosensitive material having a silver amount of not more than 2 g/m 2 yellow coloration and light scattering due to silver halides themselves are minor.
colloidal silver and non-decomposable dyes are incorporated into a yellow filter layer and an antihalation layer, coloration after processing is excessive and causes major problems. Accordingly, the embodiments of the present invention are preferably applied.
the dyes employed in the present invention exhibit decomposable properties.
Preferred examples include pyrazolidinediones, isoxazolones, pyrazolopyridones, barbituric acid series, pyrazolones, indandiones, pyridones, closed chain methylenes, etc.
Particularly preferred examples include pyrazolidinediones and isoxazolones.
Pyrazolidinediones are described in Japanese Patent Publication Open to Public Inspection Nos. 3-208046, 3-167546, and 9-106041; isoxazolones are described in Japanese Patent Publication Open to Public Inspection Nos.
Dyes for use in the present invention may be incorporated into a photosensitive material, employing conventional methods. Namely, other than addition as a solid dispersion, dyes may be dissolved in a high boiling point solvent and then added.
High boiling point solvents for use in the present invention are most preferably organic compounds having a boiling point of not less than 100 °C at one atmospheric pressure, and for example, phosphoric acid esters, phthalic acid esters, alkyl phenols, and amides are preferably employed.
a device when image information is converted to electrical image information, a device, generally referred to as a scanner, may be employed.
a scanner scans a photosensitive material
the photosensitive material is fixed and the optical portion of the scanner may only be moved, or the photosensitive material may only be moved, while the optical portion of the scanner is fixed.
Light sources which are employed to read image information include tungsten-filament lamps, fluorescent lamps, light emitting diodes, laser light, etc.
the tungsten-filament lamps are preferred in terms of low cost, while laser light (coherent light source) is preferred in terms of stability, high intensity, and minimum influence from scattering. Reading methods are not particularly specified, however, reading is preferably carried out employing transmitted light in terms of color reproduction and sharpness.
Thermal development is preferably applied to the color development of the present invention in terms of a decrease in processing time and less adverse impact on the environment.
the grain diameter, aspect ratio, silver halide composition (types and amounts of halogens in silver halide), halide distribution (distribution of each silver halide in silver halide grains), presence of dislocation lines, etc are selected for the characteristics of the recording material.
the grain diameter (converted to the one edge length of a cube having the same volume) of silver halide grains is preferably between 0.05 and 2 microns.
the aspect ratio is preferably 4 or more in terms of sharpness; is more preferably 8 or more, and is most preferably 12 or more.
the dominant component of halides is preferably silver bromide. Of the total silver halide, silver bromide is preferably between 80 and 99 mole percent, and silver iodide is preferably between 1 and 20 mole percent.
the presence of dislocation lines is preferred in terms of sensitivity.
a silver halide emulsion subjected to physical ripening, chemical sensitization, and spectral sensitization is generally employed.
Additives employed in these processes are described in Research Disclosure Nos. 17643, 18716, and 308119 (hereinafter, each is referred to respectively as RD 17643, RD 18716, and RD 308119).
employed can be, individually or in combination, sulfur-containing compounds capable of reacting with silver ions, a sulfur sensitization method using active gelatin, a selenium sensitization method using selenium compounds, a reduction sensitization method using reducing compounds, a noble metal sensitization method using gold and other noble metals, etc.
chalcogen sensitizers may be employed, and of these, sulfur sensitizers and selenium sensitizers are preferred.
Cited as the sulfur sensitizers are, for example, thiosulfates, allythiocarbamide, thiourea, allylisothiocyanate, cystine, p-trienthiosulfonate salts, rhodanine, etc.
sulfur sensitizers described in U.S. Pat. Nos. 1,574,944, 2,410,689, 2,278,947, 2,728,668, 3,501,313, and 3,656,955; West German OLS Patent No. 1,422,869; Japanese Patent Publication Open to Public Inspection Nos. 56-24937 and 55-45016; etc.
the added amount of the sulfur sensitizer varies in a fairly large range, depending on various conditions such as pH, temperature, silver halide size, etc., but as the standard, it preferably is between about 1 ⁇ 10 -7 and about 1 ⁇ 10 -1 mole per mole of silver halide.
selenium sensitizers employed can be aliphatic isoselenocyantes such as allylisoselenocyanates, selenoureas, selenides such as selenoselenide, and diethylselenide, etc. Specific examples of these are described in U.S. Pat. Nos. 1,574,944, 1,602,592, and 1,623,499. Furthermore, reduction sensitizers may also be employed in combination.
reduction sensitizers can be stannous chloride, thiourea dioxide, hydrazine, polyamine, etc.
noble metal compounds other than gold for example, palladium compounds, etc. can be employed together with these previously listed.
Silver halide grains of the emulsion employed in the present invention preferably undergo chemical sensitization employing gold compounds.
gold compounds preferably employed in the present invention are those in which the gold oxidation number may have a valence of +1 or +3, and many types of gold compounds may be employed.
potassium chloroaurate As representative examples, listed are potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanoauric acid, ammonium aurous thiocyanate, pyridyltrichlorogold, gold sulfide, gold selenide, etc.
the added amount of the gold compound varies depending on ambient conditions, but as the standard, it is usually between 1 ⁇ 10 -8 and 1 ⁇ 10 -1 mole per mole of silver halide, and is preferably between 1 ⁇ 10 -7 and 1 ⁇ 10 -2 mole.
these compounds may be added during formation of silver halide grains, physical ripening, chemical ripening and during any process after chemical ripening.
Photographic additives which can be employed in the present invention, are also described in the above-mentioned Research Disclosures.
5-pyrazolone series and pyrazoloazole series compounds those are particularly preferred which are described in U.S. Pat. Nos. 4,310,619 and 4,351,897; European Patent No. 73,636; U.S. Pat. Nos. 3,061,432 and 3,725,067; Research Disclosure Item No. 24230 (June 1984); Japanese Patent Publication Open to Public Inspection Nos. 60-43659, 61-72238, 60-35730, 55-118034, 60-185951; U.S. Pat. Nos. 4,500,630, 4,540,654, 4,556,630; International Patent Publication Open to Public Inspection WO 88/04795; etc.
Couplers which release a photographically useful residual group upon coupling are also preferably employed.
DIR couplers which release a development inhibitor those which are preferred are described in patents in the above-mentioned RD 17643, VII-F; Japanese Patent Publication Open to Public Inspection Nos. 57-151944, 57-154234, 60-184248, and 63-37346; U.S. Pat. Nos. 4,248,962, and 4,782,012; etc.
couplers which release imagewise nucleation agents or development accelerators preferred which are those described in U.K. Patent Nos. 2,097,140 and 2,131,188; Japanese Patent Publication Open to Public Inspection Nos. 59-157638 and 59-170840.
couplers which can be employed in the present invention include competing couplers described in U.S. Pat. No. 4,130,427; polyequivalent couplers described in U.S. Pat. Nos. 4,283,427, 4,338,393, and 4,310,618; DIR redox compound releasing couplers, DIR coupler releasing couplers, DIR coupler releasing redox compounds or DIR redox compound releasing redox compounds described in Japanese Patent Publication Open to Public Inspection Nos. 60-185950 and 62-24252, etc.; couplers which form no leuco dye after being released, described in European Patent No. 173,302A; bleach accelerator releasing couplers described in RD Nos.
Couplers can be employed in the present invention. The specific examples are described in the RDs described below. The related pages are listed below. (Item) (Page of RD 308119) (RD 17643) Yellow Couplers 1001 Section VII-D Section VII C to G Magenta Couplers 1001 Section VII-D Section VII C to G Cyan Couplers 1001 Section VII-D Section VII C to G Colored Couplers 1002 Section VII-G Section VII G DIR Couplers 1001 Section VII-F Section VII F BAR Couplers 1002 Section VII-F Couplers releasing other useful residual groups 1001 Section VII-F
Additives employed in the present invention can be added using a dispersion method described in RD 308119 XIV, and the like.
supports can be employed which are described on page 28 of the above-mentioned RD 17643, on pages 647 and 648 of RD 18716, and in XIX of RD 308119.
filter layers and supplementary interlayers can be provided which are described in Section VII-K of the above-mentioned RD 308119.
the pH of the topmost surface of the photographic constituting layers of the photosensitive material for use in the present invention is preferably between 5.0 and 7.0, and is more preferably between 5.5 and 6.5.
the pH can be measured by a method described in Japanese Patent Publication Open to Public Inspection No. 61-245153.
supports employed preferably are polyethylene terephthalate film, cellulose triacetate film, etc.
a support with a thickness of 50 to 200 ⁇ m is generally employed.
cartridge techniques may be referred to those which are disclosed in Japanese Patent Publication Open to Public Inspection Nos. 58-67329, 58-181035, 58-182634, and 58-195236; U.S. Pat. No. 4,221,479; Japanese Patent Application Nos.
the decomposition ratio of Sample 101 of the present invention was 0.96, while the decomposition ratios of Comparative Sample 102 and Comparative Sample 103 were 0.03 and 0.01, respectively.
Sample 101, Sample 102, and Sample 103 were washed in 25 °C water for 30 seconds and dried.
the optical density of the washed Sample was measured and the nondiffusion ratio of a dye was obtained upon comparing it to the optical density of the Sample previously measured, prior to washing.
Nondiffusion ratio optical density after washing/optical density prior to washing
the green-sensitive layer of Sample 101 comprised of the dye for use in the present invention was preferable because it exhibited less fog, compared to Comparative Sample 103.
Sample 201 On a cellulose triacetate support previously subjected to subbing treatment, the photographic constitution layers having compositions described below were provided and was designated Sample 201.
the addition amount is expressed in the number of grams per m 2 .
the amounts of silver halide and colloidal silver are expressed in terms of silver amount and the amount of the sensitizing dye (hereinafter referred to as SD) is expressed in the number of moles per mole of silver.
Second layer Polyethyl acrylate latex 0.20 Gelatin 1.40 AS-1 0.05 Third layer (slow red-sensitive layer) Silver iodide "a" 0.04 Silver iodide "b” 0.12 SD-1 3.0 ⁇ 10 -5 SD-4 1.5 ⁇ 10 -4 SD-3 3.0 ⁇ 10 -4 SD-6 3.0 ⁇ 10 -6 C-1 0.51 OIL-2 0.45 Gelatin 1.40 Fourth layer (intermediate red-sensitive layer) Silver iodide "c” 0.18 SD-1 3.0 ⁇ 10 -5 SD-2 1.5 ⁇ 10 -4 SD-3 3.0 ⁇ 10 -4 C-2 0.22 OIL-2 0.21 Gelatin 0.84 Fifth layer (fast red-sensitive layer) Silver iodide "c” 0.10 Silver iodide "d” 0.33 SD-1 3.0 ⁇ 10 -5 SD-2 1.5 ⁇ 10 -4 SD-3 3.0 ⁇ 10 -4 C-1 0.085 C-2 0.0
compositions added were coating aids SU-1, SU-2, and SU-3, dispersing aid SU-4, viscosity controlling agent V-1, stabilizers ST-1 and ST-2, antifoggant two types of polyvinylpyrrolidone with a weight average molecular weight of 10,000 (AF-1) and a weight average molecular weight of 1,100,000 (AF-2), retarders AF-3, AF-4, and AF-5, and hardeners H-1 and H-2.
coating aids SU-1, SU-2, and SU-3 dispersing aid SU-4
viscosity controlling agent V-1 stabilizers ST-1 and ST-2
retarders AF-3, AF-4, and AF-5 and hardeners H-1 and H-2.
Table 1 shows advantages of the above-mentioned silver iodide.
Silver Iodobromide "g” 0.40 2.0 Silver Iodobromide "h” 0.65 8.0 1.4
preparation examples of preferred silver halide grains for use in the present invention preparation examples of silver iodobromide "d", "f”, etc. are described below.
a seed crystal emulsion was prepared as described below.
nuclei were formed by adding during 2 minutes an aqueous silver nitrate solution (1.161 moles) and an aqueous potassium bromide and potassium iodide solution (2 mole percent of potassium iodide) to the following solution A1 regulated at 35 °C employing a double-jet method, while maintaining the silver potential at 0 mV (measured by a silver ion selection electrode employing a saturated silver-silver chloride electrode as the reference electrode). Subsequently, the resulting mixture was warmed to 60 °C over 60 minutes and the pH was adjusted to 5.0 employing an aqueous sodium carbonate solution.
an aqueous silver nitrate solution (5.902 moles) and an aqueous potassium bromide and potassium iodide solution (2 mole percent of potassium iodide) were added over 42 minutes, while maintaining the silver potential at 9 mV.
an aqueous silver nitrate solution (5.902 moles) and an aqueous potassium bromide and potassium iodide solution (2 mole percent of potassium iodide) were added over 42 minutes, while maintaining the silver potential at 9 mV.
the resulting mixture was immediately desalted and washed employing an ordinary flocculation method.
the resulting seed crystal emulsion was an emulsion comprised of hexagonal tabular grains having an average spherical converted diameter of 0.24 ⁇ m, an average aspect ratio of 4.8, and a maximum edge length ratio of the total projection area of not less than 90 percent of 1.0 to 2.0.
Ossein gelatin 24.2 g Potassium bromide 10.8 g HO(CH 2 CH 2 O) m (CH(CH 3 )CH 2 O) 19.8 (CH 2 CH 2 O) n H ( m + n 9.77 ) (10% ethanol solution) 6.78 ml 10% nitric acid 114 ml H 2 O 9657 ml
each solution was added at an optimum rate so that neither new nuclei formation nor Ostwald ripening among grains was carried out.
a washing treatment was carried out at 40 °C employing an ordinary flocculation method. After that, dispersion was repeated by the addition of gelatin and the pAg and pH were adjusted to 8.1 and 5.8, respectively.
the resulting emulsion was an emulsion comprised of tabular grains having a grain diameter (one edge length of a cube having the same volume) and an average aspect ratio of 5.0. Electron microscopic observation of the emulsion revealed the formation of at least 5 dislocation lines in both the fringe portion (external portion of not less than 50 percent from the center of a grain in terms of a silver halide amount) of grains of not less than 60 percent of the total projection area of grains in the emulsion, and also in the grain interior. The surface silver iodide content ratio was 6.7 mole percent.
Silver Iodobromide "f” was prepared in the entirely same manner as in Silver Iodobromide "d", except that in the preparation of Silver Iodobromide "d", in 1) step, pAg was adjusted to 8.8 and in step 3), the amount of silver nitrate was adjusted to 0.92 and the amount of SMC-10 was adjusted to 0.069 mole.
the resulting emulsion was comprised of tabular grains having a grain diameter (one edge length of a cube having the same volume) of 0.65 ⁇ m and an average aspect ratio of 6.5. Electron microscopic observation of the emulsion revealed the formation of at least 5 dislocation lines in both the fringe portion (external portion of not less than 60 percent from the center of a grain in terms of a silver halide amount) of grains of not less than 60 percent of the total projection area of grains in the emulsion, and also in the grain interior. The surface silver iodide content ratio was 11.9 mole percent.
silver iodobromides "a”, “b”, “c”, “en”, “g”, “h”, and “i” underwent spectral sensitization and chemical sensitization in the same manner as the above-mentioned "d” and "f” so as to have the properties described in the above Table 1.
Image information was subjected to subjective evaluation by 10 judges.
the image information was printed using a post chelate type sublimation thermal transfer printer CHC-S845-5C manufactured by Konica Corp.
Each of the resulting prints was subjectively evaluated by 10 judges. Unless otherwise specified, evaluation was carried out using a method in which two samples were compared to make a discrimination. Furthermore, the reasons for rating a better image quality were listed by the judges.
Sample 202 was prepared in the same manner as Sample 201, except that yellow colloidal silver contained in the tenth layer of Sample 201 was replaced with exemplified Compound 17 so that the absorbance became the same at 440 nm.
Sample 201 and Sample 202 were subjected to exposure of a Macbeth color chart and a human subject; after that, were subjected to color development employing a C-41 process; to washing at 25 °C for 10 seconds using an aqueous 1 percent acetic acid solution; to washing using water at 25 °C for 30 seconds, and to drying.
the resulting Samples were designated Sample 211 and Sample 212.
the image information on Sample 211 and Sample 212 was read employing a film scanner Q-Scan manufactured by Konica Corp.
the image data obtained from Sample 211 comprising the dyes for use in the present invention, were preferred due to excellent color reproduction. According to the subjective evaluation results, nine of ten judges responded that Sample 211 exhibited better color reproduction than Sample 212. The other judge responded that there was no difference in image quality between them. The image data obtained from Comparative Sample 212 using the colloidal silver exhibited poor color reproduction and satisfactory image data were not obtained from the Comparative Sample.
the time necessary for processing the Sample of the present invention was shortened up to 270 seconds while the conventional negative processing took 510 seconds until drying was finished.
the processing solution for use in the present invention contains no chelating agent, to minimize pollution of the environment.
Sample 101 prepared in Example 1 was treated with a 1% sodium hypochlorite solution and the emulsion layers were removed from the support.
the obtained support exhibited quality sufficient for recycling upon remelting. According to the constitution of the present invention, recovery of the resources employed for the support are now possible.
Sample 101 and Sample 102 were subjected to development by spraying only enough developer to completely soaking the Sample.
the resulting Samples were designated Sample 401 and Sample 402.
the image information of each of these Samples was read employing a scanner Q-Scan manufactured by Konica Corp.
the image information obtained from Sample 401 of the present invention exhibited high and satisfactory image quality.
the image information obtained from Comparative Sample 402 was unsatisfactory due to the deterioration in color reproduction, sharpness and graininess. According to the subjective evaluation results, all 10 judges responded that the color reproduction of Sample 401 was better than Sample 402. This processing generated absolutely no solution waste to result in minimum pollution to the environment, and was therefore the preferred one.
Samples were prepared in the same manner as in Sample 201 and Sample 202, except that the silver amount of each of Sample 201 and Sample 202 was decreased to 1/4.
the resulting samples were designated Sample 501 and Sample 502.
Sample 501 and Sample 502 were subjected to the same processing as Example 2 and the resulting samples were designated Sample 511 and Sample 512.
the image information of each of these Samples was read employing a scanner Q-Scan manufactured by Konica Corp.
the image information obtained from Sample 511 exhibited preferred excellent sharpness compared to the image information obtained from Sample 512, which only resulted in dark image information, being inferior in color reproduction and sharpness.
9 of the 10 judges responded that the image quality of Sample 511 was better than Sample 512.
the other judge responded that there was no difference in image quality.
Example 5 Based on Example 5, it is found that according to the constitution of the present invention, preferred characteristics are obtained for the variation of the silver amount and the image information with particularly preferred image quality is obtained in the case of the lower silver amount. On the contrary, it is found that in the Comparative Sample, image information with satisfactory image quality is not obtained, irrespective of the silver amount.
Color negative film JX-100 manufactured by Konica Corp. was subjected to exposure of a human subject and a Macbeth color chart.
the resulting film was subjected to development under the specified conditions employing a color negative photosensitive material process C-41 developer; then, to stop processing, 1% acetic acid solution was employed, followed by washing and drying.
the processed film was designated Comparative Sample-1. When trying to read the image of Comparative Sample-1, it was found to be absolutely impossible to read the image information using blue light.
a silver halide photosensitive color photographic material which can be applied to simple and convenient processing; and which generates minimum pollutants to the environment, and further allows for easy and efficient resource recovery, an image forming method, and provides an image information forming method, and a silver recovery method.

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Physics & Mathematics (AREA)
General Physics & Mathematics (AREA)
Silver Salt Photography Or Processing Solution Therefor (AREA)

Description

FIELD OF THE INVENTION

The present invention relates to an image information forming method.

BACKGROUND OF HE INVENTION

Conventionally, silver halide photosensitive photographic materials (hereinafter occasionally referred to as photosensitive material) have generally required processing consisting of color development, bleaching, and fixing each employing a specific processing solution, and it has long been desired to develop a method in which image information is obtained using simple and convenient processing.
Conventional photosensitive materials comprise a yellow filter layer which prevents the deterioration of color reproduction due to the fact that green-sensitive layers and red-sensitive layers are sensitive to blue light on account of blue light absorption properties of silver halides. Furthermore, in order to minimize halation, generally, a layer comprising dyes has been provided. In the present invention, these layers are hereinafter referred to as a yellow filter layer and an antihalation layer, respectively. Conventional photosensitive materials are generally subjected to bleaching and fixing after development. Though colloidal silver is incorporated into the yellow filter and the antihalation layer, it is removed during the bleaching and fixing processes. Therefore, there has been no problem with remaining colors after processing.
When conventional photosensitive materials are subjected to bleaching, so-called chelating agents such as EDTA, PDTA, etc. are employed. However, these chelating agents are not readily biodegradable and cause an increase in treatment cost of solution waste. Accordingly, countermeasures have been sought.
It is common knowledge that yellow dyes are incorporated into the yellow filter, which are described, for example, in Japanese Patent Publication Open to Public Inspection Nos. 2-1839, 3-72340, 4-362634, etc. However, photosensitive materials disclosed in these patent publications are premised on bleaching and fixing. Therefore, when these patents are applied to the photosensitive material of the present invention, which is not subjected to bleaching, there are problems in which decomposition properties are insufficient and undesired yellow coloring remains after processing. Further, in those patent publications, technical concept is not at all disclosed in which processing is accomplished without carrying out bleaching as described in the present invention, and image information of the photosensitive photographic material which has been subjected to such processing is converted to electrical image information. In addition, no technical problem is described nor suggested in which, when processing is terminated without carrying out bleaching, the dye decomposition is insufficient and improvement is required to overcome this disadvantage.
A method in which neither fixing nor bleaching is carried out after color development has been known as one applied to the product introduced by 3M Co. as Dry Silver. However, in this product, bleaching and fixing for the silver halide photosensitive material comprising no yellow filter only are eliminated. There has been no disclosure of technical concepts such that in accordance with it, it is desired to improve decomposition properties of the dyes and there has also been no description at all on the presence of such a problem.
JP09152700 A discloses color developing agents comprising specific hydrazine derivatives which significantly improve coloring and hue, light fastness and image stability.
EP-A-0730198 discloses a process for the formation of a color image which comprises the steps of exposing to light a silver halide light-sensitive material comprising a support having thereon at least one light-sensitive emulsion layer, and developing said light-sensitive material to form a color image, wherein said light-sensitive material comprises at least one dye-forming coupler and at least one specific coloring reducing agent, and is intensified with a solution containing hydrogen peroxide or a compound releasing hydrogen peroxide to form an intensified image.

SUMMARY OF THE INVENTION

The invention and embodiments are described below:
1. There is provided an image information forming method comprising the steps of exposing a silver halide photosensitive photographic material according to image information,
a) developing the exposed silver halide photosensitive photographic material by use of a color developer, and
followed by no bleaching, b) conversion of image information to electrical image information,
2. An image information forming method of item 1, wherein the processing is carried out by supplying a processing solution with an soaking amount on to the silver halide photosensitive photographic material comprising a dye which can be decomposed by the color developer.
3. An image information forming method of item 1, wherein the dye which can be decomposed by the color developer is dispersed in a solid state in the silver halide photosensitive photographic material.
4. An image information forming method of item 1 or item 2, wherein the silver halide photosensitive photographic material comprises silver in an amount of not more than 2 g/m².

DETAIL DESCRIPTION OF THE INVENTION

In the present invention, the dyes which can be decomposed by a color developer denote dyes which are decomposed at a decomposition ratio of at least 50 percent during color development reaction employing the color developer. In terms of color reproduction, the decomposition ratio is preferably at least 70 percent and is more preferably at least 90 percent. The dye decomposition ratio was obtained using the formula described below in comparison to the optical density of a sample prior to color development, which is prevented from interference due to dyes formed by color development.
Decomposition ratio = (optical density prior to color development - optical density after color development)/optical density prior to color development
Dyes as described in the present invention may include organic compounds or inorganic compounds, irrespective of their structure. Organic compounds are preferred because they result in relatively rapid decomposition reaction in a color developer. In the scope of the present invention, organic compounds such as organic dyes and inorganic compounds may be employed in combination.
Investigation performed by the inventors of the present invention revealed that when a photosensitive material, prepared by using dyes which were not decomposed by a developer, was subjected to color development followed by no bleaching and the resulting image was read, reading the image information was hindered due to the presence of the absorption of the dyes, colloidal silver, etc., due to insufficient decomposition of these dyes. It was found that, particularly, when the image information formed by a yellow dye forming coupler was read, the remaining yellow color caused major problem.
As for the processing solutions employed in the present invention, it is preferred that processing in which almost all the supplied processing solution is absorbed by photosensitive material, is carried out because no solution waste is generated. Examples of methods to supply the processing solution to the photosensitive material, spray development or coating development is preferable.
The spray development as described herein denotes a development in which a developer is supplied onto a photosensitive material as a spray in an amount substantially capable of soaking the photosensitive material. Irrespective of spray methods and types, the number of nozzles, shapes of nozzles, spraying may be carried out during movement of a single movable nozzle or employing a plurality of fixed nozzles. The spraying may also be carried out by moving a nozzle while stopping a photosensitive material or may be carried out by moving a photosensitive material, or in a combination thereof.
The coating development as described herein denotes a development in which a developer is supplied onto a photosensitive material in an amount substantially capable of soaking the photosensitive material via a means of carrying the developer. As for the means of carrying the developer, felt, fabrics, metal sheets with holes or slits, etc. are preferably employed. While spraying a developer onto a photosensitive material or a medium, a method is preferred in which the developer is coated onto the photosensitive material employing the medium.
The present invention is preferably applied to a photosensitive material having a silver amount of not more than 2 g/m². In the photosensitive material having a silver amount of not more than 2 g/m², yellow coloration and light scattering due to silver halides themselves are minor. As a result, when colloidal silver and non-decomposable dyes are incorporated into a yellow filter layer and an antihalation layer, coloration after processing is excessive and causes major problems. Accordingly, the embodiments of the present invention are preferably applied.
The dyes employed in the present invention exhibit decomposable properties. Preferred examples include pyrazolidinediones, isoxazolones, pyrazolopyridones, barbituric acid series, pyrazolones, indandiones, pyridones, closed chain methylenes, etc. Particularly preferred examples include pyrazolidinediones and isoxazolones. Pyrazolidinediones are described in Japanese Patent Publication Open to Public Inspection Nos. 3-208046, 3-167546, and 9-106041; isoxazolones are described in Japanese Patent Publication Open to Public Inspection Nos. 3-208044, 3-72340, 4-362634, 5-209133, 7-92613, and 8-6196; pyrazolopyridones are described in Japanese Patent Publication Open to Public Inspection Nos. 2-282244, 3-7931, 3-167546, 8-6196, and 9-106041; barbituric acid series are described in European Patent No. 274723, Japanese Patent Publication Open to Public Inspection Nos. 3-223747, 3-167546, 8-6196, and 9-106041; pyrazolones are described in U.S. Pat No. 4,092,168, and Japanese Patent Publication Open to Public Inspection Nos. 3-23441, 3-19544, 3-206441, 3-206442, 3-208043, 4-151651, 3-144438, 3-167546, 5-50345, 5-53241, 5-86056, 8-6196, and 8-50345, and Japanese Patent Publication No. 55-155351; indandiones are described in European Patent No. 524593, and Japanese Patent Publication Open to Public Inspection Nos. 5-289239 and 8-6190; pyridones are described in Japanese Patent Publication Open to Public Inspection Nos. 55-155351, 4-37841, 2-277044, and 8-6196; closed chain methylenes are described in Japanese Patent Publication Open to Public Inspection No. 3-182742 and European Patent No. 762198. However, in these specifications, technical concept are not at all disclosed in which processing is completed without carrying out bleaching as mentioned in the present invention and image information of a photosensitive material which has been subjected to such processing being converted to electrical image information. Furthermore, technical problems are neither described nor noted in which, when processing is completed without carrying out bleaching, the resulting insufficient dye decomposition requires improvement.
Dyes for use in the present invention may be incorporated into a photosensitive material, employing conventional methods. Namely, other than addition as a solid dispersion, dyes may be dissolved in a high boiling point solvent and then added.
High boiling point solvents for use in the present invention are most preferably organic compounds having a boiling point of not less than 100 °C at one atmospheric pressure, and for example, phosphoric acid esters, phthalic acid esters, alkyl phenols, and amides are preferably employed.
In the present invention, when image information is converted to electrical image information, a device, generally referred to as a scanner, may be employed. Generally, when such a scanner scans a photosensitive material, it is recommended that the necessary area of the photosensitive material is scanned by moving the optical portion of the scanner in a direction different from the motion of the photosensitive material. However, the photosensitive material is fixed and the optical portion of the scanner may only be moved, or the photosensitive material may only be moved, while the optical portion of the scanner is fixed.
Light sources, which are employed to read image information include tungsten-filament lamps, fluorescent lamps, light emitting diodes, laser light, etc. The tungsten-filament lamps are preferred in terms of low cost, while laser light (coherent light source) is preferred in terms of stability, high intensity, and minimum influence from scattering. Reading methods are not particularly specified, however, reading is preferably carried out employing transmitted light in terms of color reproduction and sharpness.
Thermal development is preferably applied to the color development of the present invention in terms of a decrease in processing time and less adverse impact on the environment.
Incorporation of a developing agent precursor into the photosensitive material for use in the present invention is preferred for easier management of the developer.
Materials employed in the present invention other than dyes mentioned above are described in publications, and referring to these, those skilled in the art can readily synthesize or purchase such materials. As the publications, cited can be, for example, Japanese Patent Publication Open to Public Inspection Nos. 8-166644, 8-202002, 8-286340, 8-292531, 8-227131, 8-292529, 8-234388, 8-234390, 9-34081, 9-76570, 9-114062, 9-152686, 9-152691, 9-152692, 9-152693, 9-152700, 9-152701, 9-159702, 9-159703, 9-150794, and 9-150795.
Various types of silver halide emulsions may be employed. Regarding the silver halide emulsion, the grain diameter, aspect ratio, silver halide composition (types and amounts of halogens in silver halide), halide distribution (distribution of each silver halide in silver halide grains), presence of dislocation lines, etc are selected for the characteristics of the recording material. The grain diameter (converted to the one edge length of a cube having the same volume) of silver halide grains is preferably between 0.05 and 2 microns. The aspect ratio is preferably 4 or more in terms of sharpness; is more preferably 8 or more, and is most preferably 12 or more. The dominant component of halides is preferably silver bromide. Of the total silver halide, silver bromide is preferably between 80 and 99 mole percent, and silver iodide is preferably between 1 and 20 mole percent. The presence of dislocation lines is preferred in terms of sensitivity.
When materials for use in the present invention are constituted, a silver halide emulsion subjected to physical ripening, chemical sensitization, and spectral sensitization is generally employed. Additives employed in these processes are described in Research Disclosure Nos. 17643, 18716, and 308119 (hereinafter, each is referred to respectively as RD 17643, RD 18716, and RD 308119).

Specific pages which describe additives are listed below:

(Item)	(page in RD 308119)	(RD 17643)	(RD 18716)
Chemical Sensitizers	996	Section III-A	23	648
Spectral Sensitizers	996	IV-A, B Section C, D, H, I, J	23 and 24	648 and 649
Supersensitizers	996	Section IV-A to E, J	23 and 24	648 and 649
Antifoggants	998	VI	24 and 25	649
Stabilizers	998	VI	24 and 25	649

For the chemical sensitization of the silver halide emulsion employed in the present invention, more specifically, employed can be, individually or in combination, sulfur-containing compounds capable of reacting with silver ions, a sulfur sensitization method using active gelatin, a selenium sensitization method using selenium compounds, a reduction sensitization method using reducing compounds, a noble metal sensitization method using gold and other noble metals, etc.
In the present invention, as chemical sensitizers, for example, chalcogen sensitizers may be employed, and of these, sulfur sensitizers and selenium sensitizers are preferred.
Cited as the sulfur sensitizers, are, for example, thiosulfates, allythiocarbamide, thiourea, allylisothiocyanate, cystine, p-trienthiosulfonate salts, rhodanine, etc.
In addition to these, employed may be sulfur sensitizers described in U.S. Pat. Nos. 1,574,944, 2,410,689, 2,278,947, 2,728,668, 3,501,313, and 3,656,955; West German OLS Patent No. 1,422,869; Japanese Patent Publication Open to Public Inspection Nos. 56-24937 and 55-45016; etc.
The added amount of the sulfur sensitizer varies in a fairly large range, depending on various conditions such as pH, temperature, silver halide size, etc., but as the standard, it preferably is between about 1 × 10^-7 and about 1 × 10^-1 mole per mole of silver halide.
As the selenium sensitizers, employed can be aliphatic isoselenocyantes such as allylisoselenocyanates, selenoureas, selenides such as selenoselenide, and diethylselenide, etc. Specific examples of these are described in U.S. Pat. Nos. 1,574,944, 1,602,592, and 1,623,499. Furthermore, reduction sensitizers may also be employed in combination.
As reduction sensitizers, cited can be stannous chloride, thiourea dioxide, hydrazine, polyamine, etc. Furthermore, noble metal compounds other than gold, for example, palladium compounds, etc. can be employed together with these previously listed.
Silver halide grains of the emulsion employed in the present invention preferably undergo chemical sensitization employing gold compounds.
As gold compounds preferably employed in the present invention, are those in which the gold oxidation number may have a valence of +1 or +3, and many types of gold compounds may be employed.
As representative examples, listed are potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanoauric acid, ammonium aurous thiocyanate, pyridyltrichlorogold, gold sulfide, gold selenide, etc.
The added amount of the gold compound varies depending on ambient conditions, but as the standard, it is usually between 1 × 10^-8 and 1 × 10^-1 mole per mole of silver halide, and is preferably between 1 × 10^-7 and 1 × 10^-2 mole.
Furthermore, these compounds may be added during formation of silver halide grains, physical ripening, chemical ripening and during any process after chemical ripening.
Photographic additives, which can be employed in the present invention, are also described in the above-mentioned Research Disclosures.

Pages which describe related additives are shown below.

(Item)	(Page of RD 308119	(RD 17643)	(RD 18716)
Color Contamination Preventing Agents	1002	Section VII-I	25	650
Dye Image Stabilizing Agents	1001	Section VII J	25
Brightening Agents	998	V	24
UV Absorbers	1003	VIII-C, Section XIIIC	25 to 26
Light Scattering Agents	1003	VIII
Binders	1003	IX	26	651
Antistatic Agents	1006	XIII	27	650
Hardeners	1004	X	26	651
Plasticizers	1006	XII	27	650
Lubricating Oil	1006	XII	27	650
Active Agents and Coating Aids	1005	XI	26 to 27	650
Matting Agents	1007	XVI
Developing Agents	1011	Section XXB

Furthermore, in order to minimize the degradation of photographic properties due to formaldehyde gas, compounds which react with formaldehyde to result in fixation, described in U.S. Pat. Nos. 4,411,987 and 4,435,503, are preferably incorporated into the photosensitive material.
Various types of colored couplers may be employed in the present invention. Specific examples are described in patents described in the above-mentioned Research Disclosure (RD) Item No. 17643, Sections VII-C to G.
As examples of 5-pyrazolone series and pyrazoloazole series compounds, those are particularly preferred which are described in U.S. Pat. Nos. 4,310,619 and 4,351,897; European Patent No. 73,636; U.S. Pat. Nos. 3,061,432 and 3,725,067; Research Disclosure Item No. 24230 (June 1984); Japanese Patent Publication Open to Public Inspection Nos. 60-43659, 61-72238, 60-35730, 55-118034, 60-185951; U.S. Pat. Nos. 4,500,630, 4,540,654, 4,556,630; International Patent Publication Open to Public Inspection WO 88/04795; etc.
As phenol series and naphthol series couplers, those which are preferred are described in U.S. Pat. Nos. 4,052,212, 4,146,396, 4,228,233, 4,296,200, 2,369,929, 2,801,171, 2,772,162, 2,895,826, 2,772,002, 3,758,908, 4,334,011, and 4,327,173; West German Patent Publication Open to Public Inspection No. 3,329,729; European Patent Nos. 121,365A, 249,453A; U.S. Pat. Nos. 3,446,622, 4,333,999, 4,775,616, 4,451,559, 4,427,767, 4,690,889, 4,254,212, and 4,296,199; Japanese Patent Publication Open to Public Inspection Nos. 61-42658 and 63-88551; etc.
Typical examples of polymerized dye-forming couplers which can be employed in the present invention are described in U.S. Pat. Nos. 3,451,820, 4,080,211, 4,367,282, and 4,409,320, 4,576,910; U.K. Patent No. 2,102,173; etc.
Couplers which release a photographically useful residual group upon coupling are also preferably employed. As DIR couplers which release a development inhibitor, those which are preferred are described in patents in the above-mentioned RD 17643, VII-F; Japanese Patent Publication Open to Public Inspection Nos. 57-151944, 57-154234, 60-184248, and 63-37346; U.S. Pat. Nos. 4,248,962, and 4,782,012; etc.
As couplers which release imagewise nucleation agents or development accelerators, preferred which are those described in U.K. Patent Nos. 2,097,140 and 2,131,188; Japanese Patent Publication Open to Public Inspection Nos. 59-157638 and 59-170840.
In addition to those, couplers which can be employed in the present invention include competing couplers described in U.S. Pat. No. 4,130,427; polyequivalent couplers described in U.S. Pat. Nos. 4,283,427, 4,338,393, and 4,310,618; DIR redox compound releasing couplers, DIR coupler releasing couplers, DIR coupler releasing redox compounds or DIR redox compound releasing redox compounds described in Japanese Patent Publication Open to Public Inspection Nos. 60-185950 and 62-24252, etc.; couplers which form no leuco dye after being released, described in European Patent No. 173,302A; bleach accelerator releasing couplers described in RD Nos. 11440 and 24241, and Japanese Patent Publication Open to Public Inspection No. 61-201247, etc.; ligand releasing couplers described in U.S. Pat. No 4,553,477, etc.; leuco dye releasing couplers described in Japanese Patent Publication Open to Public Inspection No. 63-757747; fluorescent dye releasing couplers described in U.S. Pat. No. 4,774,181; etc.

Furthermore, various other couplers can be employed in the present invention. The specific examples are described in the RDs described below. The related pages are listed below.

(Item)	(Page of RD 308119)	(RD 17643)
Yellow Couplers	1001	Section VII-D	Section VII C to G
Magenta Couplers	1001	Section VII-D	Section VII C to G
Cyan Couplers	1001	Section VII-D	Section VII C to G
Colored Couplers	1002	Section VII-G	Section VII G
DIR Couplers	1001	Section VII-F	Section VII F
BAR Couplers	1002	Section VII-F
Couplers releasing other useful residual groups	1001	Section VII-F

Additives employed in the present invention can be added using a dispersion method described in RD 308119 XIV, and the like.
In the present invention, supports can be employed which are described on page 28 of the above-mentioned RD 17643, on pages 647 and 648 of RD 18716, and in XIX of RD 308119.
In the photosensitive material for use in the present invention, filter layers and supplementary interlayers can be provided which are described in Section VII-K of the above-mentioned RD 308119.
The pH of the topmost surface of the photographic constituting layers of the photosensitive material for use in the present invention is preferably between 5.0 and 7.0, and is more preferably between 5.5 and 6.5. The pH can be measured by a method described in Japanese Patent Publication Open to Public Inspection No. 61-245153.
As supports, employed preferably are polyethylene terephthalate film, cellulose triacetate film, etc. A support with a thickness of 50 to 200 µm is generally employed.
When rolled photosensitive material is used, it is preferred to be loaded in a cartridge. At present, the most common cartridge is a case in the 135 format. Other cartridges which are proposed in patent publications described below may be employed. Namely, cartridge techniques may be referred to those which are disclosed in Japanese Patent Publication Open to Public Inspection Nos. 58-67329, 58-181035, 58-182634, and 58-195236; U.S. Pat. No. 4,221,479; Japanese Patent Application Nos. 63-57785, 63-183344, 63-325638, 1-21862, 1-25362, 1-30246, 1-20222, 1-21863, 1-37181, 1-33108, 1-85198, 1-172595, 1-172594, and 1-172593; U.S. Pat. Nos. 4,846,418, 4,848,693, and 4,832,275; etc.

EXAMPLES

The present invention is described with reference to Examples below.
Exemplified Compound 27, Comparative Dye 1 solid dispersion, and colloidal silver were added to an aqueous gelatin solution, hardener H-1 was then added, and the resulting mixture was coated onto a cellulose triacetate support. The resulting samples were termed Sample 101, Sample 102, and Sample 103, respectively.
Sample 101, Sample 102, and Sample 103 were subjected to color development employing color negative photosensitive material process C-41 and dried. The optical density of each processed Sample was measured and the dye decomposition ratio was obtained by comparing it to the optical density of the Sample previously measured prior to processing.
Decomposition ratio = (optical density prior to color development - optical density after color development)/optical density prior to color development
The decomposition ratio of Sample 101 of the present invention was 0.96, while the decomposition ratios of Comparative Sample 102 and Comparative Sample 103 were 0.03 and 0.01, respectively.
Sample 101, Sample 102, and Sample 103 were washed in 25 °C water for 30 seconds and dried. The optical density of the washed Sample was measured and the nondiffusion ratio of a dye was obtained upon comparing it to the optical density of the Sample previously measured, prior to washing.
Nondiffusion ratio = optical density after washing/optical density prior to washing
The nondiffusion ratios of Sample 101 of the present invention and Comparative Sample 103 were 0.99, while that of Comparative Sample 102 was 0.03.
Based on these results, it is clear that the Sample of the present invention is quickly decomposed by a developer and can achieve the objects of the present invention, while in Comparative Sample 102, diffusion to the other layer results in adverse effects such as desensitization of the blue-sensitive layer and color contamination, while in Comparative Sample 103, decomposition is not sufficiently carried out and is not suitable for quick and simple processing.
Further, the green-sensitive layer of Sample 101 comprised of the dye for use in the present invention was preferable because it exhibited less fog, compared to Comparative Sample 103.

On a cellulose triacetate support previously subjected to subbing treatment, the photographic constitution layers having compositions described below were provided and was designated Sample 201. The addition amount is expressed in the number of grams per m². However, the amounts of silver halide and colloidal silver are expressed in terms of silver amount and the amount of the sensitizing dye (hereinafter referred to as SD) is expressed in the number of moles per mole of silver.

First layer (UV absorbing layer)
UV-1	0.3
OIL-1	0.044
Gelatin	1.33

Second layer (interlayer)
Polyethyl acrylate latex	0.20
Gelatin	1.40
AS-1	0.05

Third layer (slow red-sensitive layer)
Silver iodide "a"	0.04
Silver iodide "b"	0.12
SD-1	3.0 × 10^-5
SD-4	1.5 × 10^-4
SD-3	3.0 × 10^-4
SD-6	3.0 × 10^-6
C-1	0.51
OIL-2	0.45
Gelatin	1.40

Fourth layer (intermediate red-sensitive layer)
Silver iodide "c"	0.18
SD-1	3.0 × 10 ^-5
SD-2	1.5 × 10 ^-4
SD-3	3.0 × 10 ^-4
C-2	0.22
OIL-2	0.21
Gelatin	0.84

Fifth layer (fast red-sensitive layer)
Silver iodide "c"	0.10
Silver iodide "d"	0.33
SD-1	3.0 × 10^-5
SD-2	1.5 × 10^-4
SD-3	3.0 × 10^-4
C-1	0.085
C-2	0.084
OIL-2	0.23
Gelatin	1.23

Sixth layer (interlayer)
Polyethyl acrylate latex	0.23
Gelatin	1.00
AS-1	0.08

Seventh layer (slow green-sensitve layer)
Silver iodide "a"	0.08
Silver iodide "b"	0.02
SD-6	5.0 × 10 ^-4
SD-5	5.0 × 10 ^-4
M-1	0.21
OIL-1	0.25
Gelatin	0.98

Eighth layer (intermediate green-sensitive layer)
Silver iodide "e"	0.18
SD-7	3.0 × 10^-4
SD-8	6.0 × 10^-5
SD-9	4.0 × 10^-5
M-2	0.17
OIL-1	0.29
Gelatin	1.43

Ninth layer (fast green-sensitive layer)
Silver iodide "f"	0.40
SD-7	4.0 × 10^-4
SD-8	8.0 × 10^-5
SD-9	5.0 × 10^-5
M-1	0.09
OIL-1	0.11
Gelatin	0.78

Tenth layer (interlayer)
Yellow colloidal silver	0.02
Polyethyl acrylate latex	0.20
Gelatin	1.00
AS-1	0.08

Eleventh layer (slow blue-sensitive layer)
Silver iodide "g"	0.08
Silver iodide "h"	0.03
SD-10	8.0 × 10^-4
SD-11	3.0 × 10^-4
Y-1	0.91
OIL-1	0.37
Gelatin	1.29

Twelfth layer (fast blue-sensitive layer)
Silver iodide "h"	0.08
solver iodide "i"	0.30
SD-10	4.4 × 10^-4
SD-11	1.5 × 10^-4
Y-1	0.48
OIL-1	0.21
Gelatin	1.55

Thirteenth layer (first protective layer)
Silver iodide j	0.05
UV-1	0.055
UV-2	0.110
OIL-2	0.63
Gelatin	1.32

Fourteenth layer (second protective layer)
PM-1	0.15
PM-2	0.04
WAX-1	0.02
D-1	0.001
Gelatin	0.55

Further, other than the above-mentioned compositions, added were coating aids SU-1, SU-2, and SU-3, dispersing aid SU-4, viscosity controlling agent V-1, stabilizers ST-1 and ST-2, antifoggant two types of polyvinylpyrrolidone with a weight average molecular weight of 10,000 (AF-1) and a weight average molecular weight of 1,100,000 (AF-2), retarders AF-3, AF-4, and AF-5, and hardeners H-1 and H-2.
The structures of compounds employed in the above-mentioned Samples are illustrated below.

Table 1 shows advantages of the above-mentioned silver iodide.

Emulsion No.	Average Grain Diameter (µm)	Average AgI Amount (mole percent)	Diameter/Thickness Ratio
Silver Iodobromide "a"	0.30	2.0	1.0
Silver Iodobromide "b"	0.40	8.0	1.4
Silver Iodobromide "c"	0.60	7.0	3.1
Silver Iodobromide "d"	0.75	7.0	5.0
Silver Iodobromide "e"	0.60	7.0	4.1
Silver Iodobromide "f"	0.65	9.0	6.5
Silver Iodobromide "g"	0.40	2.0	4.0
Silver Iodobromide "h"	0.65	8.0	1.4
Silver Iodobromide "i"	1.00	8.0	2.0
Silver Iodobromide "j"	0.05	2.0	1.0

Further, as preparation examples of preferred silver halide grains for use in the present invention, preparation examples of silver iodobromide "d", "f", etc. are described below.
A seed crystal emulsion was prepared as described below.
Employing a mix-stirring machine described in Japanese Patent Publication Nos. 5-58288 and 58-58289, nuclei were formed by adding during 2 minutes an aqueous silver nitrate solution (1.161 moles) and an aqueous potassium bromide and potassium iodide solution (2 mole percent of potassium iodide) to the following solution A1 regulated at 35 °C employing a double-jet method, while maintaining the silver potential at 0 mV (measured by a silver ion selection electrode employing a saturated silver-silver chloride electrode as the reference electrode). Subsequently, the resulting mixture was warmed to 60 °C over 60 minutes and the pH was adjusted to 5.0 employing an aqueous sodium carbonate solution. Thereafter, an aqueous silver nitrate solution (5.902 moles) and an aqueous potassium bromide and potassium iodide solution (2 mole percent of potassium iodide) were added over 42 minutes, while maintaining the silver potential at 9 mV. After completing the addition, after lowering the temperature to 40 °C, the resulting mixture was immediately desalted and washed employing an ordinary flocculation method.
The resulting seed crystal emulsion was an emulsion comprised of hexagonal tabular grains having an average spherical converted diameter of 0.24 µm, an average aspect ratio of 4.8, and a maximum edge length ratio of the total projection area of not less than 90 percent of 1.0 to 2.0.

Ossein gelatin 24.2 g

Potassium bromide 10.8 g

HO(CH₂CH₂O)_m(CH(CH₃)CH₂O)_19.8(CH₂CH₂O)_nH (m + n = 9.77) (10% ethanol solution) 6.78 ml

10% nitric acid 114 ml

H₂O 9657 ml
To 5 liters of an aqueous 6.0 weight percent gelatin solution containing 0.06 mole of potassium iodide, 2 liters of an aqueous 7.06 mole silver nitrate solution and 2 liters of an aqueous 7.06 mole potassium iodide solution were added with vigorous stirring over 10 minutes. During the addition, the pH was adjusted to 2.0 using nitric acid and the temperature was regulated at 40 °C. After grain formation, the pH was adjusted to 5.0 using an aqueous sodium carbonate solution. The resulting fine silver iodide grains had an average grain diameter of 0.05 µm. The resulting emulsion was designated SMC-1.
The temperature of 700 ml of an aqueous 4.5 weight percent inert gelatin solution containing Seed Crystal Emulsion-1 equivalent to 0.178 mole and 0.5 ml of a 10 percent ethanol solution of HO(CH₂CH₂O)_m(CH(CH₃)CH₂O)_19.8(CH₂CH₂O)_nH (m + n = 9.77) was maintained at 75 °C, and the pAg and pH were adjusted to 8.4 and 5.0, respectively. After that, grains were formed under vigorous stirring employing a double-jet method according to the following steps:
1) an aqueous 2.1 mole silver nitrate solution, an 0.195 mole SMC-1 solution and an aqueous potassium bromide solution were added, while maintaining the pAg at 8.4 and the pH at 5.0.
2) subsequently, the solution was cooled to 60 °C, and the pAg was adjusted to 9.8. After that, 0.071 mole of SMC was added and ripening (introduction of dislocation lines) was carried out for 2 minutes
3) an aqueous 0.959 mole silver nitrate solution, an aqueous 0.03 mole SMC-1 solution, and an aqueous potassium bromide solution were added while maintaining the pAg at 9.8 and the pH at 5.0.
Further, during grain formation, each solution was added at an optimum rate so that neither new nuclei formation nor Ostwald ripening among grains was carried out. After the completion of the above addition, a washing treatment was carried out at 40 °C employing an ordinary flocculation method. After that, dispersion was repeated by the addition of gelatin and the pAg and pH were adjusted to 8.1 and 5.8, respectively.
The resulting emulsion was an emulsion comprised of tabular grains having a grain diameter (one edge length of a cube having the same volume) and an average aspect ratio of 5.0. Electron microscopic observation of the emulsion revealed the formation of at least 5 dislocation lines in both the fringe portion (external portion of not less than 50 percent from the center of a grain in terms of a silver halide amount) of grains of not less than 60 percent of the total projection area of grains in the emulsion, and also in the grain interior. The surface silver iodide content ratio was 6.7 mole percent. Preparation of Silver Iodobromide "f"
Silver Iodobromide "f" was prepared in the entirely same manner as in Silver Iodobromide "d", except that in the preparation of Silver Iodobromide "d", in 1) step, pAg was adjusted to 8.8 and in step 3), the amount of silver nitrate was adjusted to 0.92 and the amount of SMC-10 was adjusted to 0.069 mole.
The resulting emulsion was comprised of tabular grains having a grain diameter (one edge length of a cube having the same volume) of 0.65 µm and an average aspect ratio of 6.5. Electron microscopic observation of the emulsion revealed the formation of at least 5 dislocation lines in both the fringe portion (external portion of not less than 60 percent from the center of a grain in terms of a silver halide amount) of grains of not less than 60 percent of the total projection area of grains in the emulsion, and also in the grain interior. The surface silver iodide content ratio was 11.9 mole percent.
After adding the above-mentioned sensitizing dyes and carrying out ripening, added were triphosphine selenide, sodium thiosulfate, chloroauric acid, and potassium thiocyanate, and according to a common method, chemical ripening was carried out so that the relationship between the fog and the sensitivity became optimum.
Further, silver iodobromides "a", "b", "c", "en", "g", "h", and "i" underwent spectral sensitization and chemical sensitization in the same manner as the above-mentioned "d" and "f" so as to have the properties described in the above Table 1.
Image information was subjected to subjective evaluation by 10 judges. The image information was printed using a post chelate type sublimation thermal transfer printer CHC-S845-5C manufactured by Konica Corp. Each of the resulting prints was subjectively evaluated by 10 judges. Unless otherwise specified, evaluation was carried out using a method in which two samples were compared to make a discrimination. Furthermore, the reasons for rating a better image quality were listed by the judges.
Sample 202 was prepared in the same manner as Sample 201, except that yellow colloidal silver contained in the tenth layer of Sample 201 was replaced with exemplified Compound 17 so that the absorbance became the same at 440 nm.
Sample 201 and Sample 202 were subjected to exposure of a Macbeth color chart and a human subject; after that, were subjected to color development employing a C-41 process; to washing at 25 °C for 10 seconds using an aqueous 1 percent acetic acid solution; to washing using water at 25 °C for 30 seconds, and to drying. The resulting Samples were designated Sample 211 and Sample 212. The image information on Sample 211 and Sample 212 was read employing a film scanner Q-Scan manufactured by Konica Corp.
As compared to Sample 212 employing colloidal silver, the image data obtained from Sample 211, comprising the dyes for use in the present invention, were preferred due to excellent color reproduction. According to the subjective evaluation results, nine of ten judges responded that Sample 211 exhibited better color reproduction than Sample 212. The other judge responded that there was no difference in image quality between them. The image data obtained from Comparative Sample 212 using the colloidal silver exhibited poor color reproduction and satisfactory image data were not obtained from the Comparative Sample.
The time necessary for processing the Sample of the present invention was shortened up to 270 seconds while the conventional negative processing took 510 seconds until drying was finished. The processing solution for use in the present invention contains no chelating agent, to minimize pollution of the environment.
Sample 101 prepared in Example 1 was treated with a 1% sodium hypochlorite solution and the emulsion layers were removed from the support. The obtained support exhibited quality sufficient for recycling upon remelting. According to the constitution of the present invention, recovery of the resources employed for the support are now possible.
Sample 101 and Sample 102 were subjected to development by spraying only enough developer to completely soaking the Sample. The resulting Samples were designated Sample 401 and Sample 402. The image information of each of these Samples was read employing a scanner Q-Scan manufactured by Konica Corp. The image information obtained from Sample 401 of the present invention exhibited high and satisfactory image quality. On the other hand, the image information obtained from Comparative Sample 402 was unsatisfactory due to the deterioration in color reproduction, sharpness and graininess. According to the subjective evaluation results, all 10 judges responded that the color reproduction of Sample 401 was better than Sample 402. This processing generated absolutely no solution waste to result in minimum pollution to the environment, and was therefore the preferred one. The image quality difference between Sample 401 of the present invention obtained by this processing and Comparative Sample 402 was greater than that between Sample 211 of the present invention in Example 2 and Comparative Sample 212. It was confirmed that when spray development was carried out, the advantages of the present invention were obtained more effectively.
Samples were prepared in the same manner as in Sample 201 and Sample 202, except that the silver amount of each of Sample 201 and Sample 202 was decreased to 1/4. The resulting samples were designated Sample 501 and Sample 502. Sample 501 and Sample 502 were subjected to the same processing as Example 2 and the resulting samples were designated Sample 511 and Sample 512. The image information of each of these Samples was read employing a scanner Q-Scan manufactured by Konica Corp. The image information obtained from Sample 511 exhibited preferred excellent sharpness compared to the image information obtained from Sample 512, which only resulted in dark image information, being inferior in color reproduction and sharpness. According to the subjective evaluation results, 9 of the 10 judges responded that the image quality of Sample 511 was better than Sample 512. The other judge responded that there was no difference in image quality.
Based on Example 5, it is found that according to the constitution of the present invention, preferred characteristics are obtained for the variation of the silver amount and the image information with particularly preferred image quality is obtained in the case of the lower silver amount. On the contrary, it is found that in the Comparative Sample, image information with satisfactory image quality is not obtained, irrespective of the silver amount.
Color negative film JX-100 manufactured by Konica Corp. was subjected to exposure of a human subject and a Macbeth color chart. The resulting film was subjected to development under the specified conditions employing a color negative photosensitive material process C-41 developer; then, to stop processing, 1% acetic acid solution was employed, followed by washing and drying. The processed film was designated Comparative Sample-1. When trying to read the image of Comparative Sample-1, it was found to be absolutely impossible to read the image information using blue light.
Based on this, it was clarified that when conventional color negative film was employed and was subjected to development while retaining silver resources in the photosensitive material, only one part of the image information was readable.
According to the present invention, it is possible to provide a silver halide photosensitive color photographic material which can be applied to simple and convenient processing; and which generates minimum pollutants to the environment, and further allows for easy and efficient resource recovery, an image forming method, and provides an image information forming method, and a silver recovery method.

Claims (4)

An image information forming method comprising the steps of exposing a silver halide photosensitive photographic material according to image information,

a) developing the exposed silver halide photosensitive photographic material by use of a color developer, and
followed by no bleaching, b) conversion of image information to electrical image information,

wherein the silver halide photosensitive photographic material comprises a dye which can be decomposed by the color developer.
An image information forming method as claimed in claim 1, wherein the processing is carried out by supplying a processing solution with an soaking amount on to the silver halide photosensitive photographic material comprising a dye which can be decomposed by the color developer.
An image information forming method as claimed in claim 1, wherein the dye which can be decomposed by the color developer is dispersed in a solid state in the silver halide photosensitive photographic material.
An image information forming method as claimed in claim 1 or claim 2, wherein the silver halide photosensitive photographic material comprises silver in an amount of not more than 2 g/m².

EP99300311A 1998-01-21 1999-01-18 Silver halide photosensitive color photographic material, image forming method, image information forming method Expired - Lifetime EP0930536B1 (en)

Applications Claiming Priority (2)

Application Number	Priority Date	Filing Date	Title
JP10023958A JPH11209125A (en)	1998-01-21	1998-01-21	Silver halide color photographic sensitive material, image forming method, forming method of image information and recovering method of resource
JP2395898		1998-01-21

Publications (2)

Publication Number	Publication Date
EP0930536A1 EP0930536A1 (en)	1999-07-21
EP0930536B1 true EP0930536B1 (en)	2005-04-20

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Application Number	Title	Priority Date	Filing Date
EP99300311A Expired - Lifetime EP0930536B1 (en)	1998-01-21	1999-01-18	Silver halide photosensitive color photographic material, image forming method, image information forming method