USH1429H - Silver halide photographic light-sensitive material - Google Patents
Silver halide photographic light-sensitive material Download PDFInfo
- Publication number
- USH1429H USH1429H US07/901,089 US90108992A USH1429H US H1429 H USH1429 H US H1429H US 90108992 A US90108992 A US 90108992A US H1429 H USH1429 H US H1429H
- Authority
- US
- United States
- Prior art keywords
- sub
- group
- coupler
- silver halide
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- -1 Silver halide Chemical class 0.000 title claims abstract description 111
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 87
- 239000004332 silver Substances 0.000 title claims abstract description 87
- 239000000463 material Substances 0.000 title claims abstract description 42
- 150000001875 compounds Chemical class 0.000 claims abstract description 127
- 239000000839 emulsion Substances 0.000 claims abstract description 38
- 230000003647 oxidation Effects 0.000 claims abstract description 29
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 29
- 125000000217 alkyl group Chemical group 0.000 claims description 60
- 125000003118 aryl group Chemical group 0.000 claims description 28
- 239000003795 chemical substances by application Substances 0.000 claims description 26
- 125000001424 substituent group Chemical group 0.000 claims description 26
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 15
- 125000000623 heterocyclic group Chemical group 0.000 claims description 13
- 125000003545 alkoxy group Chemical group 0.000 claims description 12
- 238000005859 coupling reaction Methods 0.000 claims description 10
- 125000002947 alkylene group Chemical group 0.000 claims description 9
- 230000008878 coupling Effects 0.000 claims description 9
- 238000010168 coupling process Methods 0.000 claims description 9
- 125000004429 atom Chemical group 0.000 claims description 6
- 125000000962 organic group Chemical group 0.000 claims description 6
- 125000002252 acyl group Chemical group 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims 8
- 239000001257 hydrogen Substances 0.000 claims 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 6
- 150000002431 hydrogen Chemical class 0.000 claims 2
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims 1
- 238000012545 processing Methods 0.000 abstract description 18
- 125000004185 ester group Chemical group 0.000 abstract description 9
- 238000003860 storage Methods 0.000 abstract description 8
- 230000000977 initiatory effect Effects 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 64
- 230000000052 comparative effect Effects 0.000 description 60
- 239000000460 chlorine Substances 0.000 description 41
- 238000000034 method Methods 0.000 description 40
- 239000000975 dye Substances 0.000 description 37
- 108010010803 Gelatin Proteins 0.000 description 29
- 229920000159 gelatin Polymers 0.000 description 29
- 239000008273 gelatin Substances 0.000 description 29
- 235000019322 gelatine Nutrition 0.000 description 29
- 235000011852 gelatine desserts Nutrition 0.000 description 29
- 230000035945 sensitivity Effects 0.000 description 26
- 239000003381 stabilizer Substances 0.000 description 20
- 239000000243 solution Substances 0.000 description 19
- 239000004848 polyfunctional curative Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 238000009835 boiling Methods 0.000 description 12
- 239000003960 organic solvent Substances 0.000 description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 10
- 125000005843 halogen group Chemical group 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 229910021607 Silver chloride Inorganic materials 0.000 description 9
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 9
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 8
- 239000002250 absorbent Substances 0.000 description 8
- 230000002745 absorbent Effects 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- 230000006641 stabilisation Effects 0.000 description 8
- 238000011105 stabilization Methods 0.000 description 8
- 206010070834 Sensitisation Diseases 0.000 description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 230000008313 sensitization Effects 0.000 description 7
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 125000003342 alkenyl group Chemical group 0.000 description 6
- 125000004104 aryloxy group Chemical group 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 238000011161 development Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 230000001235 sensitizing effect Effects 0.000 description 5
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 4
- 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 4
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000004442 acylamino group Chemical group 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229940100484 5-chloro-2-methyl-4-isothiazolin-3-one Drugs 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 229920001174 Diethylhydroxylamine Polymers 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 3
- 238000005282 brightening Methods 0.000 description 3
- CODNYICXDISAEA-UHFFFAOYSA-N bromine monochloride Chemical compound BrCl CODNYICXDISAEA-UHFFFAOYSA-N 0.000 description 3
- DHNRXBZYEKSXIM-UHFFFAOYSA-N chloromethylisothiazolinone Chemical compound CN1SC(Cl)=CC1=O DHNRXBZYEKSXIM-UHFFFAOYSA-N 0.000 description 3
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 3
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012362 glacial acetic acid Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 3
- 239000001103 potassium chloride Substances 0.000 description 3
- 235000011164 potassium chloride Nutrition 0.000 description 3
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 3
- 235000019252 potassium sulphite Nutrition 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 3
- BKUSIKGSPSFQAC-RRKCRQDMSA-N 2'-deoxyinosine-5'-diphosphate Chemical compound O1[C@H](CO[P@@](O)(=O)OP(O)(O)=O)[C@@H](O)C[C@@H]1N1C(NC=NC2=O)=C2N=C1 BKUSIKGSPSFQAC-RRKCRQDMSA-N 0.000 description 2
- 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 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical group CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229910021612 Silver iodide Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 125000004423 acyloxy group Chemical group 0.000 description 2
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 2
- 125000004656 alkyl sulfonylamino group Chemical group 0.000 description 2
- 125000004414 alkyl thio group Chemical group 0.000 description 2
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 description 2
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004657 aryl sulfonyl amino group Chemical group 0.000 description 2
- 125000005110 aryl thio group Chemical group 0.000 description 2
- XNSQZBOCSSMHSZ-UHFFFAOYSA-K azane;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxymethyl)amino]acetate;iron(3+) Chemical compound [NH4+].[Fe+3].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O XNSQZBOCSSMHSZ-UHFFFAOYSA-K 0.000 description 2
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 2
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000005462 imide group Chemical group 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 2
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 125000005498 phthalate group Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003141 primary amines Chemical group 0.000 description 2
- 229940045105 silver iodide Drugs 0.000 description 2
- NHQVTOYJPBRYNG-UHFFFAOYSA-M sodium;2,4,7-tri(propan-2-yl)naphthalene-1-sulfonate Chemical compound [Na+].CC(C)C1=CC(C(C)C)=C(S([O-])(=O)=O)C2=CC(C(C)C)=CC=C21 NHQVTOYJPBRYNG-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- VNRMBUOLDUITOV-UHFFFAOYSA-N (2,3-dihydroxy-5-phosphonophenyl)phosphonic acid Chemical compound OC1=CC(P(O)(O)=O)=CC(P(O)(O)=O)=C1O VNRMBUOLDUITOV-UHFFFAOYSA-N 0.000 description 1
- UFPKLWVNKAMAPE-UHFFFAOYSA-N (4-aminophenyl)azanium;hydrogen sulfate Chemical compound OS(O)(=O)=O.NC1=CC=C(N)C=C1 UFPKLWVNKAMAPE-UHFFFAOYSA-N 0.000 description 1
- ZRHUHDUEXWHZMA-UHFFFAOYSA-N 1,4-dihydropyrazol-5-one Chemical compound O=C1CC=NN1 ZRHUHDUEXWHZMA-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- AXCGIKGRPLMUDF-UHFFFAOYSA-N 2,6-dichloro-1h-1,3,5-triazin-4-one;sodium Chemical compound [Na].OC1=NC(Cl)=NC(Cl)=N1 AXCGIKGRPLMUDF-UHFFFAOYSA-N 0.000 description 1
- PBKADZMAZVCJMR-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid;dihydrate Chemical compound O.O.OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O PBKADZMAZVCJMR-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 101100177155 Arabidopsis thaliana HAC1 gene Proteins 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- ZVFDTKUVRCTHQE-UHFFFAOYSA-N Diisodecyl phthalate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC(C)C ZVFDTKUVRCTHQE-UHFFFAOYSA-N 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- 101100434170 Oryza sativa subsp. japonica ACR2.1 gene Proteins 0.000 description 1
- 101100434171 Oryza sativa subsp. japonica ACR2.2 gene Proteins 0.000 description 1
- 101150108015 STR6 gene Proteins 0.000 description 1
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- HOLVRJRSWZOAJU-UHFFFAOYSA-N [Ag].ICl Chemical compound [Ag].ICl HOLVRJRSWZOAJU-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 125000005194 alkoxycarbonyloxy group Chemical group 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 125000003806 alkyl carbonyl amino group Chemical group 0.000 description 1
- 125000004448 alkyl carbonyl group Chemical group 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 150000003931 anilides Chemical group 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000004658 aryl carbonyl amino group Chemical group 0.000 description 1
- 125000005129 aryl carbonyl group Chemical group 0.000 description 1
- 125000004391 aryl sulfonyl group Chemical group 0.000 description 1
- 125000005200 aryloxy carbonyloxy group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- PJAOJNOBFQOBGE-UHFFFAOYSA-L azanium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxymethyl)amino]acetate;iron(2+) Chemical compound [NH4+].[Fe+2].OC(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O PJAOJNOBFQOBGE-UHFFFAOYSA-L 0.000 description 1
- 125000002511 behenyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- KHBQMWCZKVMBLN-IDEBNGHGSA-N benzenesulfonamide Chemical group NS(=O)(=O)[13C]1=[13CH][13CH]=[13CH][13CH]=[13CH]1 KHBQMWCZKVMBLN-IDEBNGHGSA-N 0.000 description 1
- 125000001231 benzoyloxy group Chemical group C(C1=CC=CC=C1)(=O)O* 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 description 1
- RNSLCHIAOHUARI-UHFFFAOYSA-N butane-1,4-diol;hexanedioic acid Chemical compound OCCCCO.OC(=O)CCCCC(O)=O RNSLCHIAOHUARI-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004063 butyryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001661 cadmium Chemical class 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 125000003901 ceryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- LBJNMUFDOHXDFG-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu].[Cu] LBJNMUFDOHXDFG-UHFFFAOYSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 238000000326 densiometry Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- DROMNWUQASBTFM-UHFFFAOYSA-N dinonyl benzene-1,2-dicarboxylate Chemical compound CCCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCCC DROMNWUQASBTFM-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000004705 ethylthio group Chemical group C(C)S* 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000003104 hexanoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- PTFYQSWHBLOXRZ-UHFFFAOYSA-N imidazo[4,5-e]indazole Chemical compound C1=CC2=NC=NC2=C2C=NN=C21 PTFYQSWHBLOXRZ-UHFFFAOYSA-N 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002503 iridium Chemical class 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- CTAPFRYPJLPFDF-UHFFFAOYSA-N isoxazole Chemical compound C=1C=NOC=1 CTAPFRYPJLPFDF-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 125000002463 lignoceryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000007764 o/w emulsion Substances 0.000 description 1
- 125000005064 octadecenyl group Chemical group C(=CCCCCCCCCCCCCCCCC)* 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000004989 p-phenylenediamines Chemical class 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000003170 phenylsulfonyl group Chemical group C1(=CC=CC=C1)S(=O)(=O)* 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- KNCYXPMJDCCGSJ-UHFFFAOYSA-N piperidine-2,6-dione Chemical group O=C1CCCC(=O)N1 KNCYXPMJDCCGSJ-UHFFFAOYSA-N 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 125000005936 piperidyl group Chemical group 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001490 poly(butyl methacrylate) polymer Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- MCSKRVKAXABJLX-UHFFFAOYSA-N pyrazolo[3,4-d]triazole Chemical compound N1=NN=C2N=NC=C21 MCSKRVKAXABJLX-UHFFFAOYSA-N 0.000 description 1
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003283 rhodium Chemical class 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229940065287 selenium compound Drugs 0.000 description 1
- 150000003343 selenium compounds Chemical class 0.000 description 1
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 239000007962 solid dispersion Substances 0.000 description 1
- 150000003413 spiro compounds Chemical class 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 101150035983 str1 gene Proteins 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical group O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 125000000565 sulfonamide group Chemical group 0.000 description 1
- 125000006296 sulfonyl amino group Chemical group [H]N(*)S(*)(=O)=O 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- KBLZDCFTQSIIOH-UHFFFAOYSA-M tetrabutylazanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC KBLZDCFTQSIIOH-UHFFFAOYSA-M 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 150000003475 thallium Chemical class 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920006163 vinyl copolymer Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 150000003751 zinc Chemical class 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
- G03C7/392—Additives
- G03C7/39208—Organic compounds
- G03C7/39212—Carbocyclic
- G03C7/39216—Carbocyclic with OH groups
-
- 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
- G03C7/392—Additives
- G03C7/39208—Organic compounds
- G03C7/3924—Heterocyclic
Definitions
- the present invention relates to a silver halide photographic light-sensitive material, more specifically a silver halide photographic light-sensitive material which is good in image storage stability and excellent in color developability and color reproducibility and which undergoes little change in the photographic performance thereof in continuous processing.
- a silver halide photographic light-sensitive material having at least one silver halide emulsion layer containing a dye-forming coupler on the support, wherein said silver halide emulsion layer contains at least one compound having an ester group and an oxidation potential of not more than 1800 mV.
- a silver halide photographic light-sensitive material as described in (1) above, wherein said compound having an ester group and an oxidation potential of not more than 1800 mV is a compound represented by the following formula II: ##STR2## (wherein R 21 and R 22 independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; J represents an alkylene group or a simple bond; R 23 represents a heterocyclic residue.)
- a silver halide photographic light-sensitive material having photographic structural layers including a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on the support, wherein at least one of said blue-sensitive silver halide emulsion layers contains at least one kind of the yellow coupler represented by formula Y-I, described in (5) above, and one kind of the compound represented by formula II, described in (3) above.
- the compound relating to the present invention which has an ester group and an oxidation potential of not more than 1800 mV, is described below.
- Oxidation potential is defined to be obtained by cyclic voltammetry. Oxidation potential can be determined by taking a cyclic voltamogram at a sweeping speed of 50 mV/second in acetonitrile solvent at 20° C., using platinum for a working electrode, an indicator electrode and saturated calomel for a reference electrode and tetra-n-butyl-ammonium perchlorate as a supporting electrolyte.
- a compound represented by the following formula I or II is desirable.
- R 11 and R 12 independently represent an alkyl group;
- R 13 represents a divalent binding group;
- R 14 represents a hydrogen atom or a substituent.
- R 21 and R 22 independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms;
- J represents an alkylene group or a simple bond;
- R 23 represents a heterocyclic residue.
- R 11 and R 12 independently represent an alkyl group.
- examples of preferable alkyl groups for R 11 and R 12 include linear or branched alkyl groups having 1 to 24 carbon atoms, such as a methyl group, an ethyl group, an isopropyl group, a t-butyl group, an octyl group, a 2-ethylhexyl group, a dodecyl group, a tetradecyl group, an eicosyl group and a benzyl group, with preference given to branched alkyl groups.
- R 13 represents a divalent binding group.
- groups for R 13 include an alkylene group and a phenylene group, which groups may have a substituent.
- the group for R 13 is preferably a linear alkylene group.
- the number of carbons contained in R 13 preferably ranges from 1 to 10, more preferably from 2 to 6.
- R 14 represents a hydrogen atom or a substituent.
- substituents represented by R 14 include alkyl groups, cycloalkyl groups, alkenyl groups, aryl groups, alkylamino groups, alkylthio groups, arylthio groups, alkoxycarbonyl groups and acyloxycarbonyl groups.
- R 14 preferably has at least one branching point in the molecular structure thereof.
- alkyl groups for R 21 and R 22 in formula II include a methyl group, an ethyl group, a propyl group, a butyl group and an amyl group, which alkyl groups may be branched.
- alkylene groups for J include alkylene groups having 1 to 20 carbon atoms, such as a methylene group, an ethylene group, a propylene group and a butylene group, which alkylene groups may be branched.
- heterocyclic residues for R 23 include 5- or 6-membered ring residues containing a heteto atom such as of oxygen, sulfur or nitrogen, e.g., a thienyl group, a furyl group, a pyrrolyl group, a pyrrolidinyl group, a piperidyl group, a piperazinyl group, a morpholino group, a thiacyclohexyl group, a dithiacyclohexyl group, an oxacyclohexyl group and a dioxacyclohexyl group, which heterocyclic residues may have been condensed with another heterocyclic ring or a hydrocarbon ring and may have formed a spiro compound.
- a heteto atom such as of oxygen, sulfur or nitrogen
- the oxidation potential of the compound of the present invention is preferably in the range from 800 to 1800 mV, more preferably from 1200 to 1500 mV.
- the amount of their addition is preferably 5 to 300 mol %, more preferably 10 to 200 mol % relative to the amount of couplers.
- a yellow coupler represented by formula Y-I is preferred.
- R 1 represents an alkyl group or a cycloalkyl group
- R 2 represents an alkyl group, a cycloalkyl group, an aryl group or an acyl group
- R 3 represents a group capable of substituting a benzene ring
- n represents 0 or 1
- X 1 represents a group capable of splitting off upon coupling with the oxidation product of a developing agent
- y 1 represents an organic group.
- Examples of the alkyl group for R 1 in formula Y-I include a methyl group, an ethyl group, an isopropyl group, a t-butyl group and a dodecyl group. These alkyl groups for R 1 may have a substituent. Examples of the substituent include a halogen atom, an aryl group, an alkoxy group, an aryloxy group, an alkylsulfonyl group, an acylamino group and a hydroxyl group.
- Examples of the cycloalkyl group for R 1 include a cyclopropyl group, a cyclohexyl group and an adamantyl group, with preference given to a branched alkyl group, more specifically a t-butyl group.
- Examples of the alkyl group or cycloalkyl group for R 2 in formula Y-I include the groups specified for R 1 .
- Examples of the aryl group for R 2 include a phenyl group. These alkyl groups, cycloalkyl groups and aryl groups for R 2 include those having the same substituent as specified for R 1 .
- Examples of the acyl group for R 2 include an acetyl group, a propionyl group, a butyryl group, a hexanoyl group and a benzoyl group.
- the group for R 2 is preferably an alkyl group or an aryl group, more preferably an alkyl group, and still more preferably a lower alkyl group having not more than 5 carbon atoms.
- Examples of the group capable of substituting a benzene ring, represented by R 3 in formula y-I, include halogen atoms such as a chlorine atom, alkyl groups such as an ethyl group, an isopropyl group and a t-butyl group, alkoxy groups such as a methoxy group, aryloxy groups such as a phenyloxy group, acyloxy groups such as a methylcarbonyloxy group and a benzoyloxy group, acylamino groups such as an acetamide group and a phenylcarbonylamino group, carbamoyl groups such as an N-methylcarbamoyl group and an N-phenylcarbamoyl group, alkylsulfonylamino groups such as an ethylsulfonylamino group, arylsulfonylamino groups such as a phenylsulfonylmaino group, s
- y 1 represents an organic group without limitation, but it is preferably a group represented by the following formula Y-II:
- R 4 and R 5 independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.
- alkyl groups for R 4 and R 5 include a methyl group, an ethyl group, an isopropyl group, a t-butyl group and a dodecyl group.
- aryl groups for R 4 and R 5 include a phenyl group and a naphthyl group. These alkyl groups or aryl groups for R 4 and R 5 include those having a substituent.
- the substituent is not subject to limitation; typical examples thereof include halogen atoms such as a chlorine atom, alkyl groups such as an ethyl group and a t-butyl group, aryl groups such as a phenyl group, a p-methoxyphenyl group and a naphthyl group, alkoxy groups such as an ethoxy group and a benzyloxy group, aryloxy groups such as a phenoxy group, alkylthio groups such as an ethylthio group, arylthio groups such as a phenylthio group, alkylsulfonyl groups such as a ⁇ -hydroxyethylsulfonyl group and arylsulfonyl groups such as a phenylsulfonyl group.
- halogen atoms such as a chlorine atom
- alkyl groups such as an ethyl group and a t-butyl
- Examples also include acylamino groups such as an alkylcarbonylamino group, specifically an acetamide group, and arylcarbonylamino groups, specifically a phenylcarbonylamino group, carbamoyl groups, including those substituted by an alkyl group, an aryl group (preferably a phenyl group) or another substituent, such as an N-methylcarbamoyl group and an N-phenylcarbamoyl group, acyl groups such as an alkylcarbonyl group, specifically an acetyl group and an arylcarbonyl group, specifically a benzoyl group, sulfonamide groups such as an alkylsulfonylamino group and an arylsulfonylamino group, specifically a methylsulfonylamino group and a benzenesulfonamide group, sulfamoyl groups, including those substituted by an alkyl group, an aryl group
- R' 4 represents an organic group, preferably a linear or branched alkyl group having 1 to 30 carbon atoms, such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a t-butyl group, a n-pentyl group, a n-hexyl group, a 2-ethylhexyl group, a n-octyl group, a n-decyl group, a linear or branched dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an eicosyl group, a do
- X 1 represents a group splitting off upon coupling reaction with the oxidation product of a developing agent.
- groups include the group represented by the following formula Y-III or Y-IV, with preference given to the group represented by formula Y-IV.
- R 6 represents an aryl group which may have a substituent or a heterocyclic group.
- Z 1 represents a group of non-metallic atoms necessary to form a 5- or 6-membered ring in cooperation with the nitrogen atom.
- Examples of the group of non-metallic atoms necessary to form the 5- or 6-membered ring include a methylene group, a methine group, a substituted methine group, >C ⁇ O, >NR 7 (R 7 has the same definition as R 5 above), --N ⁇ , --O--, --S-- and --SO 2 --.)
- the yellow coupler represented by formula Y-I may bind at the R 1 , R 3 or y 1 moiety to form a bis configuration.
- the yellow couplers represented by formula Y-I relating to the present invention may be used singly or in combination, and may be used in combination with other kinds of yellow couplers.
- the yellow coupler can be used in the content ratio of about 1 ⁇ 10 -3 to about 1 mol, preferably 1 ⁇ 10 -2 mol to 8 ⁇ 10 -1 mol per mol of silver halide.
- the cyan couplers used for the present invention are described below.
- the cyan coupler for the present invention is preferably a naphthol cyan coupler, a phenol cyan coupler or an imidazole cyan coupler.
- More preferable cyan couplers are those represented by the following formulas C-I and C-II: ##STR89## (wherein R C1 represents an alkyl group having 2 to 6 carbon atoms; RC 2 represents a ballast group; Z C represents a hydrogen atom or a group capable of splitting off upon coupling with the oxidation product of a developing agent.) ##STR90## (wherein R C1 represents an alkyl group or an aryl group; R C2 represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group; R C3 represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group; R C1 and R C3 may cooperate to form a ring; Z C represents a hydrogen atom or an atom or group capable of splitting off upon coupling with the oxidation product of a developing agent.)
- the alkyl group represented by R C1 includes those having a substituent.
- the ballast group represented by R C2 is an organic group having a size and shape which provides the coupler molecule with sufficient bulkiness to make the coupler substantially incapable of diffusing from the layer to which it is applied to another layer.
- Said ballast group is preferably represented by the following formula: ##STR91## (wherein R C3 represents an alkyl group having 1 to 12 carbon atoms; Ar C represents an aryl group such as a phenyl group, which aryl group includes those having a substituent.)
- Examples of cyan couplers represented by formula C-I include example compounds PC-1 through PC-19 given in the upper right column, page 30, through upper left column, page 31, Japanese Patent O.P.I. Publication No. 156748/1989, example compounds C-1 through C-28 given in Japanese Patent O.P.I. Publication No. 249151/1987, the cyan couplers described in Japanese Patent Examined Publication No. 11572/1974 and Japanese Patent O.P.I. Publication No. 3142/1986, 9652/1986, 9653/1986, 39045/1986, 50136/1986, 99141/1986 and 105545/1986 and the cyan couplers described below, which are not to be construed as limitative.
- the alkyl group represented by R C1 preferably has 1 to 32 carbon atoms, which alkyl group may be linear or branched and includes those having a substituent.
- the aryl group represented by R C1 is preferably a phenyl group, including those having a substituent.
- the alkyl group represented by R C2 preferably has 1 to 32 carbon atoms, which alkyl group may be linear or branched and includes those having a substituent.
- the cycloalkyl group represented by R C2 preferably has 3 to 12 carbon atoms, which cycloalkyl group may be linear or branched and includes those having a substituent.
- the aryl group represented by R C2 is preferably a phenyl group, including those having a substituent.
- the heterocyclic group represented by R C2 preferably has 5 to 7 members, including those having a substituent, and may have been condensed.
- R C3 represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, which alkyl group and alkoxy group include those having a substituent, but R C3 is preferably a hydrogen atom.
- the ring formed by R C1 and R C3 in cooperation is preferably a 5- or 6-membered ring.
- Examples of such rings include the following: ##STR92##
- examples of the group capable of splitting off upon reaction with the oxidation product of a color developing agent, represented by Z C include halogen atoms, alkoxy groups, aryloxy groups, acyloxy groups, sulfonyloxy groups, acylamino groups, sulfonylamino groups, alkoxycarbonyloxy groups, aryloxycarbonyloxy groups and imide groups, with preference given to halogen atoms, aryloxy groups and alkoxy groups.
- cyan couplers represented by formula C-II those represented by the following formula C-II-A are preferred.
- R A1 represents a phenyl group substituted by at least one halogen atom; such phenyl groups include those having a non-halogen substituent.
- R A2 has the same definition as R C1 in formula C-II.
- X A represents a halogen atom, an aryloxy group or an alkoxy group, including those having a substituent.
- Examples of the cyan coupler represented by formula C-II include example compounds C-1 through C-25 given in Japanese Patent O.P.I. Publication No. 96656/1988, example compounds PC-II-1 through PC-II-31 given in lower left column, page 32, through upper left column, page 34, Japanese Patent O.P.I. Publication No. 156748/1989, the 2,5-diacylamino cyan couplers described in lower right column, page 7, through lower left column, page 9, Japanese Patent O.P.I. Publication No. 178962/1987, lower left column, page 7, through lower right column, page 10, Japanese Patent O.P.I. Publication No. 225155/1985, upper left column, page 6, through lower right column, page 8, Japanese Patent O.P.I.
- the cyan couplers can be used in the content range from 1 ⁇ 10 -3 to 1 mol, preferably from 1 ⁇ 10 -2 to 8 ⁇ 10 -1 mol per mol of silver halide.
- cyan couplers may be used in combination with other kinds of cyan coupler.
- magenta couplers including 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolotriazole couplers and chain-opened acylacetonitrile couplers.
- the compound of the present invention and couplers are used in the same layer, but the compound may be used in a layer adjacent to a coupler-containing layer.
- the compound of the present invention and couplers and other hydrophobic compounds can be added to the light-sensitive material by various methods, including solid dispersion, latex dispersion and oil-in-water emulsion dispersion.
- the compound of the present invention, couplers and other substances are dissolved in a high boiling organic solvent having a boiling point of over about 150° C.
- the resulting solution is emulsified and dispersed in a hydrophilic binder such as an aqueous solution of gelatin using a means of dispersion such as a mechanical stirrer, a homogenizer, a colloid mill, a flow jet mixer or an ultrasonicator in the presence of a surfactant, and the resulting emulsion is added to the target hydrophilic colloid layer.
- a hydrophilic binder such as an aqueous solution of gelatin using a means of dispersion such as a mechanical stirrer, a homogenizer, a colloid mill, a flow jet mixer or an ultrasonicator in the presence of a surfactant
- a means of dispersion such as a mechanical stirrer, a homogenizer, a colloid mill, a flow jet mixer or an ultrasonicator in the presence of a surfactant
- Another process may be added wherein the low boiling organic solvent is removed after or simultaneously with dispersion.
- the high boiling organic solvent preferably has a dielectric constant of less than 6.0.
- the lower limit of dielectric constant is not subject to limitation, it is preferably not less than 1.9.
- examples of such high boiling organic solvents include esters such as phthalates and phosphates, organic acid amides, ketones and hydrocarbon compounds, provided that they have a dielectric constant of less than 6.0.
- high boiling organic solvents having a vapor pressure at 100° C. of not more than 0.5 mmHg are preferred.
- the high boiling organic solvent may be a mixture of two or more kinds.
- the dielectric constant of the mixture is less than 6.0.
- dielectric constant is as determined at 30° C.
- the high boiling organic solvent is a phthalate or phosphate.
- phthalate advantageously used for the present invention is represented by the following formula HA: ##STR182##
- Formula HA ##STR182##
- R H1 and R H2 independently represent an alkyl group, an alkenyl group or an aryl group, provided that the total number of carbon atoms in the groups represented by R H1 and R H2 is 9 to 32, more preferably 16 to 24.
- the alkyl groups for R H1 and R H2 in formula HA may be linear or branched.
- Examples of aryl groups for R H1 and R H2 include a phenyl group and a naphthyl group;
- examples of alkenyl groups for R H1 and R H2 include a hexenyl group, a heptenyl group and an octadecenyl group.
- These alkyl groups, alkenyl groups and aryl groups may have a substituent.
- the phosphate advantageously used for the present invention is represented by the following formula HB: ##STR183## wherein R H3 , R H4 and R H5 independently represent an alkyl group, an alkenyl group or an aryl group, provided that the total number of carbon atoms in the groups represented by R H3 , R H4 and R H5 is 24 to 54. These alkyl groups, alkenyl groups and aryl groups may have one or more substituents.
- R H3 , R H4 and R H5 is an alkyl group, specifically a nonyl group, a n-decyl group, a sec-decyl group, a sec-dodecyl group and a t-octyl group.
- Examples of the high boiling organic solvent described above include example organic solvents 1 through 22 given in page 41 of Japanese Patent O.P.I. Publication No. 166331/1987.
- water-insoluble organic-solvent-soluble polymers used to disperse couplers etc. include the following:
- the number-average molecular weight of these polymers is not subject to limitation, it is preferably not more than 200,000, more preferably 5000 to 100,000.
- the ratio by weight of the polymer to the hydrophobic compounds is preferably 1:20 to 20:1, more preferably 1:10 to 10:1.
- polymers which are preferably used for the present invention are given below.
- ratio of monomer is given by weight.
- the light-sensitive material of the present invention is applicable to color negative films, color positive films, color printing paper, etc., with the effect of the invention enhanced when the light-sensitive material is used for color printing paper undergoing direct viewing.
- the silver halide for the present invention may be any silver halide, including silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide and silver chloroiodide.
- the silver halide grains preferably used for the present invention have a silver chloride content of not less than 90 mol % a silver bromide content of not more than 10 mol % and a silver iodide content of not more than 0.5 mol %, with more preference given to a silver chlorobromide having a silver bromide content of 0.1 to 2 mol %.
- Said silver halide grains may be used singly or in combination with other kinds of silver halide grains with different composition, and may also be used in combination with silver halide grains having a silver chloride content of not more than 90 mol %.
- the silver halide emulsion layers containing silver halide grains having a silver chloride content of not less than 90 mol % the silver halide grains having a silver chloride content of not less than 90 mol % account for not less than 60% by weight, preferably not less than 80% by weight of the total silver halide grain content of said emulsion layers.
- the composition of the silver halide grains may be uniform from inside to outside, or may be different between inside and outside. In cases where there is a difference between inside and outside, the composition change may be continuous or not.
- the grain size of silver halide grains is not subject to limitation, it is preferable in view of other photographic performance requirements such as rapid processing and sensitivity that the grain size be in the range from 0.2 to 1.6 ⁇ m, more preferably from 0.25 to 1.2 ⁇ m.
- the grain size can be determined by various methods in common use in the relevant field. Typical methods are described in "Particle-Size Measurement", ASTM Symposium on Light Microscopy, R. P. Loveland, pp. 94-122 (1955), or Chapter 2 of "The Theory of the Photographic Process", edited by Meath and James, 3rd edition, MacMillan (1966).
- the grain size can be determined on the basis of either the projected area of the grain or an approximated diameter.
- the grain size distribution of silver halide grains may be polydispersed or monodispersed.
- Preferred silver halide grains are monodispersed silver halide grains having a coefficient of variance of silver halide grain distribution of not more than 0.22, more preferably not more than 0.15.
- the coefficient of variance is a coefficient indicating grain size distribution, as defined by the following equation: ##EQU1##
- ri represents the diameter of each grain
- ni represents the number of grains.
- Grain size means the diameter of a grain, provided that the grain is a spherical silver halide grain, or the diameter of the circle with the same area converted from the projected area, provided that the grain is a cubic or otherwise nonspherical grain.
- the silver halide grains used for the present invention may be prepared by any of the acidic method, the neutral method and the ammoniacal method. These grains may be grown at once or grown after seed grain formation.
- the method of preparing the seed grains and the method of growing them may be identical or not.
- any of the normal precipitation method, the reverse precipitation method, the double jet precipitation method and combinations thereof may be used, but the grains obtained by the simultaneous precipitation method are preferred.
- the pAg controlled double jet method which is described in Japanese Patent O.P.I. Publication No. 48521/1979, can also be used.
- a silver halide solvent such as thioether may be used.
- a compound containing a mercapto group, a nitrogen-containing heterocyclic compound or a sensitizing dye compound may be added at the time of silver halide emulsion formation or after completion of said grains.
- the shape of the silver halide grains for the present invention may be any one.
- a preferred shape is a cube having ⁇ 100 ⁇ planes to form the crystal surface. It is also possible to use octahedral, tetradecahedral, dodecahedral or other forms of grains prepared by the methods described in U.S. Pat. Nos. 4,183,756 and 4,225,666, Japanese Patent O.P.I. Publication No. 26589/1980, Japanese Patent Examined Publication No. 42737/1980 and the Journal of Photographic Science, 21, 39 (1973). Grains having twin crystal planes may also be used.
- the silver halide grains for the present invention may be of a single shape or a combination of various shapes.
- the silver halide grains used for the present invention may be supplemented with metal ions using a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof or an iron salt or a complex salt thereof to contain such metal elements in and/or on the grains during formation and/or growth of silver halide grains.
- metal ions using a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof or an iron salt or a complex salt thereof to contain such metal elements in and/or on the grains during formation and/or growth of silver halide grains.
- reduction sensitization specks can be provided in and/or on the grains by bringing the grains in an appropriate reducing atmosphere.
- the emulsion containing silver halide grains may be treated to remove the undesirable soluble salts after completion of growth of silver halide grains or may retain said soluble salts. Removal of said salts can be achieved in accordance with the method described in Research Disclosure No. 17643.
- the silver halide grains used in the emulsion for the present invention may be grains wherein latent images are formed mainly on the surface thereof or grains wherein latent images are formed mainly therein, with preference given to grains wherein latent images are formed mainly on the surface thereof.
- the emulsion is chemically sensitized by a conventional method.
- sulfur sensitization which uses either a compound containing sulfur capable of reacting with silver ion or active gelatin, selenium sensitization, which uses a selenium compound, reduction sensitization, which uses a reducing substance, noble metal sensitization, which uses gold or another noble metal, and other sensitizing methods can be used singly or in combination.
- the emulsion can also be optically sensitized in the desired wavelength band using a sensitizing dye.
- Sensitizing dyes which can be used for the present invention include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxanol dyes.
- gelatin as a binder (or protective colloid) for the silver halide photographic light-sensitive material of the present invention
- gelatin derivatives, graft polymers of gelatin and another polymer and other hydrophilic colloids such as proteins, sugar derivatives, cellulose derivatives and synthetic hydrophilic polymer substances in the form of homo- or copolymer.
- the silver halide photographic light-sensitive material of the present invention may optionally incorporate other additives such as hardeners, antistaining agents, image stabilizer, UV absorbents, plasticizers, latices, surfactants, matting agents, lubricants and antistatic agents.
- additives such as hardeners, antistaining agents, image stabilizer, UV absorbents, plasticizers, latices, surfactants, matting agents, lubricants and antistatic agents.
- the total amount of gelatin coated on the support of the silver halide photographic light-sensitive material of the present invention is preferably less than 7 g/m 2 .
- the lower limit is not subject to limitation, the total amount is generally preferably not less than 3 g/m 2 from the viewpoint of physical properties or photographic performance.
- the amount of gelatin is determined as the weight of gelatin containing 11.0% water as determined by the PAGI method.
- the gelatin contained in the silver halide photographic light-sensitive material of the present invention is hardened with a hardener.
- a hardener can be used without limitation, including hardeners known in the photographic industry, such as aldehyde hardeners, active vinyl hardeners, active halogen hardeners, epoxy hardeners, ethyleneimine hardeners, methanesulfonate hardeners, carbodiimide hardeners, isoxazole hardeners and high molecular hardeners.
- the effect of the present invention is enhanced when the silver halide photographic light-sensitive material of the invention is a light-sensitive material undergoing direct viewing, such as color printing paper or a light-sensitive material for color copying, which are open to strict requirements for image storage stability.
- the light-sensitive material of the present invention permits image formation by a color developing process known in the relevant field.
- the color developing agent used in the color developer is a primary amine based color developing agent in wide use in various color photographic processes, such as an aminophenol or p-phenylenediamine derivative.
- known developer component compounds may be added to the color developer used to process the light-sensitive material of the present invention.
- the pH level of the color developer is normally not less than 9, preferably about 10 to 13.
- Color developing temperature is normally over 15° C., specifically in the range from 20° to 50° C. For rapid processing, it is preferable to carry out the color developing process at a temperature of over 30° C.
- developing time is normally 10 seconds to 4 minutes, it is preferable to carry out development in the range from 10 to 30 seconds when rapid processing is desired. When more speed-up is required, it is preferable to carry out development in the range from 10 to 30 seconds.
- the amount of color developer replenisher is preferably 20 to 150 ml, more preferably 20 to 120 ml, and more preferably 20 to 100 ml per m 2 of light-sensitive material.
- the effect of the present invention is enhanced when the running processing is carried out using such a low level of replenishment.
- the light-sensitive material of the present invention is subjected to bleach-fixation after color development.
- Bleach-fixation is normally followed by washing or stabilization or a combination thereof.
- the three kinds of silver halide emulsion listed in Table 1 were prepared by a combination of the neutral method and the double jet precipitation method.
- Each silver halide emulsion was supplemented with the following emulsion stabilizer STB-1 in an amount of 5 ⁇ 10 -4 mol per mol of silver halide after completion of chemical sensitization.
- This dispersion was mixed with a blue-sensitive silver chlorobromide emulsion Em-1 (containing 8.71 g of silver) and a gelatin solution for coating to yield a first layer coating solution.
- Second through seventh layer coating solutions were prepared in the same manner as with the first layer coating solution.
- the hardeners added were H-1 for layers 2 and 4 and H-2 for layer 7.
- Surfactants SU-2 and SU-3, as coating aids, were added to adjust surface tension.
- sample Nos. 102 through 132 were prepared in the same manner as above except that yellow coupler Y-51 for layer 1 was replaced as shown in Tables 4 and 5 and 0.1 mmol/m 2 of each of the dye image stabilizer shown in Tables 4 and 5 were added to layer 1.
- the samples thus obtained were subjected to blue light exposure through an optical wedge using the sensitometer KS-7 (produced by Konica Corporation) and then processed in the following procedures.
- the samples thus processed were subjected to densitometry using a densitometer (PDA-65 model, produced by Konica Corporation) to determine their sensitivity.
- Sensitivity was obtained as the reciprocal of the exposure amount corresponding to a density of 0.5.
- Figures for sensitivity are expressed as percent ratio relative to the sensitivity of sample No. 101.
- Light fastness was also evaluated by determining the residual rate of density in a dye image with an initial density of 1.0 after 10 weeks of storage of each processed sample under direct sunlight (exposure table). Color reproducibility was evaluated by visual observation of the print samples. The results are shown in Tables 4 and 5.
- Sample Nos. 101 through 132 prepared in Example 1, were each subjected to exposure through an optical wedge and then continuously processed using a paper processor in the following procedures until the amount of replenisher became 2 times the capacity of the color developer tank.
- the finished samples thus obtained are referred to as sample Nos. 201 through 232.
- Stabilization was conducted while supplying the replenisher in the direction from stabilization step 3 to 1 by the counter-current method.
- the processing solutions used in the respective processes had the following compositions.
- the silver halide photographic light-sensitive material of the present invention undergoes little change in the sensitivity thereof between initiation and completion of continuous processing and has excellent light fastness.
- Sample No. 301 was prepared in the same manner as with sample No. 102 of Example 1 except that layer 5 (red-sensitive layer) was replaced as described in Table 8 below.
- a cyan coupler (comparative coupler C-1), 0.33 g of an antistaining agent HQ-1, 6.7 g of a high boiling organic solvent DOP and 6.7 g of HBS-1 were dissolved in 60 ml of ethyl acetate. This solution was emulsified and dispersed in 215 ml of a 10% aqueous solution of gelatin containing 10 ml of 10% sodium triisopropylnaphthalenesulfonate SU-1 using a homogenizer to yield a cyan coupler dispersion.
- This dispersion was mixed with a red-sensitive silver chlorobromide emulsion Em-3 (containing 7.0 g of silver) and a gelatin solution for coating to yield a fifth layer coating solution.
- sample Nos. 302 through 315 were prepared in the same manner as above except that the cyan coupler C-1 for layer 5 was replaced as shown in Tables 9 and 10 and 0.1 mmol/m 2 of each of the dye image stabilizers shown in Tables 9 and 10 was added to layer 5.
- the resulting samples were each subjected to red light exposure through an optical wedge using the sensitometer KS-7 (produced by Konica Corporation) and processed in accordance with the procedures described in Example 2, after which they were evaluated in the same manner as in Example 1.
- Figures for sensitivity are expressed as percent sensitivity relative to the sensitivity of sample No. 301. The results are shown in Tables 9 and 10.
- Silver halide color photographic light-sensitive material sample No. 401 was prepared by coating the following layers from the support side on a polyethylene-laminated paper support (titanium oxide content 2.7 g/m 2 ).
- Layer 1 A layer containing 1.2 g/m 2 of gelatin, 0.32 g/m 2 (as silver; the same applies below) of a blue-sensitive silver chlorobromide emulsion (silver chloride content 99.3 mol %) and 0.80 g/m 2 of a yellow coupler Y-51 dissolved in 0.3 g/m 2 of dioctyl phthalate (hereinafter referred to as DOP).
- DOP dioctyl phthalate
- Layer 2 An interlayer comprising 0.7 g/m 2 of gelatin, 30 g/m 2 of an anti-irradiation dye AI-1 and 20 g/m 2 of another anti-irradiation dye M-2.
- Layer 3 A layer containing 1.25 g/m 2 of gelatin, 0.20 g/m 2 of a green-sensitive silver chlorobromide emulsion (silver chloride content 99.5 mol %) and 0.26 g/m 2 of a magenta coupler M-2 dissolved in 0.30 g/m 2 of DOP.
- Layer 4 An interlayer comprising 1.2 g/m 2 of gelatin.
- Layer 5 A layer containing 1.4 g/m 2 of gelatin, 0.20 g/m 2 of a red-sensitive silver chlorobromide emulsion (silver chloride content 99.7 mol %) and 0.40 g/m 2 of a cyan coupler C-4 dissolved in 0.20 g/m 2 of dibutyl phthalate (hereinafter referred to as DBP).
- DBP dibutyl phthalate
- Layer 6 An interlayer comprising 1.0 g/m 2 of gelatin and 0.3 g/m 2 of a UV absorbent UV-1 dissolved in 0.2 g/m 2 of DOP.
- Layer 7 A layer containing 0.5 g/m 2 of gelatin.
- Sample Nos. 402 through 422 were prepared in the same manner as with sample No. 401 except that yellow coupler Y-51 in layer 1 was replaced by each of the yellow couplers shown in Table 11 and each of the compounds of the present invention shown in Table 11 was added at 0.6 g/m 2 .
- the yellow coupler was added in an amount equal to that of yellow coupler Y-51 in sample No. 401.
- Samples Nos. 401 through 422 thus prepared were each subjected to blue light exposure through an optical wedge and then developed as follows.
- the processing solutions used in the respective processes had the following compositions.
- the maximum density (D max ) of the blue-sensitive emulsion layer was determined. Also, light fastness was evaluated by calculating the dye image residual rate (%) at an initial density of 1.0 in a 10-day fading test using a fade-O-meter. Also, a negative film was obtained by photographing a color checker (produced by Macbeth Company) using the Konica Color GX-100 (produced by Konica Corporation) and developed. Then, after tone adjustment in the gray portion, this negative film was printed on the above sample Nos. 401 through 422 and processed in the same procedures as above, after which color reproduction for each hue was evaluated. The results are shown in Table 11.
- sample Nos. 401 and 402 which incorporated a yellow coupler not represented by formula Y-I, had a high maximum density but poor color reproducibility.
- sample No. 403 which incorporated a yellow coupler represented by formula Y-I, cannot be said to be satisfactory as to maximum density and light fastness, though the color reproducibility improved.
- sample Nos. 404 through 422 of the present invention all had a high maximum density, excellent light fastness and a sufficient level of color reproducibility.
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Abstract
The present invention offers a silver halide photographic light-sensitive material which is excellent in dye image storage stability, which undergoes little change in the photographic performance thereof between initiation and completion of continuous processing, which has excellent color reproducibility and sufficient color developability. The present invention comprises a silver halide photographic light-sensitive material having at least one silver halide emulsion layer containing a dye-forming coupler on the support, wherein said silver halide emulsion layer contains at least one compound having an ester group and an oxidation potential of not more than 1800 mV.
Description
The present invention relates to a silver halide photographic light-sensitive material, more specifically a silver halide photographic light-sensitive material which is good in image storage stability and excellent in color developability and color reproducibility and which undergoes little change in the photographic performance thereof in continuous processing.
In silver halide photographic light-sensitive materials undergoing direct viewing, such as color printing paper, it is a common practice to use a yellow coupler, a magenta coupler and a cyan coupler in combination as dye-forming couplers. These couplers are required to offer the desired level of basic performance, including the color reproducibility, color developability and image storage stability in the dye image obtained. In recent years, there has been increasing demand from users for improved dye image storage stability and improved color reproducibility leading to exact reproduction of the original color of the subject.
For improving image storage stability, the use of a phenol or piperidine derivative with a particular structure is proposed in Japanese Patent Examined Publication Nos. 1420/1976 and 6623/1977 and Japanese Patent Publication Open to Public Inspection (hereinafter referred to as Japanese Patent O.P.I. Publication) Nos. 87456/1984 and 96944/1991. However, these methods often result in reduction in coloring density.
Also, since the absorption characteristic of the obtained dye image is very important in color reproduction; couplers with good absorption characteristic have recently been studied actively. For example, the pivaloylacetanilide yellow couplers described in Japanese Patent O.P.I. Publication No. 123047/1988, 9051/1992 and Japanese Patent Application No. 245949/1990, which have an alkoxy group in the anilide moiety thereof, were found useful for color printing paper because they form a dye with sharp absorption. However, various investigations of these yellow couplers revealed a drawback of insufficient stability to light, i.e., light fastness, of the dye image formed.
Also, in color photographic light-sensitive materials and light-sensitive materials for printing, there recently has been increasing demand for high sensitivity and stable processing with the trend toward time reduction in the printing and developing processes. Particularly the photographic performance change with change in processing solution component concentration in continuous processing has posed an increasingly difficult problem in rapid processing.
It is an object of the present invention to provide a silver halide photographic light-sensitive material excellent in storage stability to heat and light. It is another object of the present invention to provide a silver halide photographic light-sensitive material excellent in color developability. It is still another object of the present invention to provide a silver halide photographic light-sensitive material undergoing little change in the photographic performance thereof in continuous processing. It is yet another object of the present invention to provide a silver halide photographic light-sensitive material excellent in color reproduction.
The objects of the present invention described above are accomplished by the following constituents:
(1) A silver halide photographic light-sensitive material having at least one silver halide emulsion layer containing a dye-forming coupler on the support, wherein said silver halide emulsion layer contains at least one compound having an ester group and an oxidation potential of not more than 1800 mV.
(2) A silver halide photographic light-sensitive material as described in (1) above, wherein said compound having an ester group and an oxidation potential of not more than 1800 mV is a compound represented by the following formula I: ##STR1## (wherein R11 and R12 independently represent an alkyl group; R13 represents a divalent binding group; R14 represents a hydrogen atom or a substituent.)
(3) A silver halide photographic light-sensitive material as described in (1) above, wherein said compound having an ester group and an oxidation potential of not more than 1800 mV is a compound represented by the following formula II: ##STR2## (wherein R21 and R22 independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; J represents an alkylene group or a simple bond; R23 represents a heterocyclic residue.)
(4) A silver halide photographic light-sensitive material as described in (1), (2) or (3) above, wherein said dye-forming coupler is a yellow coupler.
(5) A silver halide photographic light-sensitive material as described in (1), (2), (3) or (4) above, wherein said dye-forming coupler is a yellow coupler represented by the following formula Y-I: ##STR3## (wherein R1 represents an alkyl group or a cycloalkyl group; R2 represents an alkyl group, a cycloalkyl group, an aryl group or an acyl group; R3 represents a group capable of substituting a benzene ring; n represents 0 or 1; X1 represents a group capable of splitting off upon coupling with the oxidation product of a developing agent; y1 represents an organic group.)
(6) A silver halide photographic light-sensitive material as described in (1), (2), (3), (4) or (5) above, wherein said dye-forming coupler is a cyan coupler.
(7) A silver halide photographic light-sensitive material having photographic structural layers including a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on the support, wherein at least one of said blue-sensitive silver halide emulsion layers contains at least one kind of the yellow coupler represented by formula Y-I, described in (5) above, and one kind of the compound represented by formula II, described in (3) above.
First, the compound relating to the present invention (hereinafter referred to as the compound of the present invention), which has an ester group and an oxidation potential of not more than 1800 mV, is described below.
In the present invention, oxidation potential is defined to be obtained by cyclic voltammetry. Oxidation potential can be determined by taking a cyclic voltamogram at a sweeping speed of 50 mV/second in acetonitrile solvent at 20° C., using platinum for a working electrode, an indicator electrode and saturated calomel for a reference electrode and tetra-n-butyl-ammonium perchlorate as a supporting electrolyte.
For the present invention, a compound represented by the following formula I or II is desirable. ##STR4## (wherein R11 and R12 independently represent an alkyl group; R13 represents a divalent binding group; R14 represents a hydrogen atom or a substituent.) ##STR5## wherein R21 and R22 independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; J represents an alkylene group or a simple bond; R23 represents a heterocyclic residue.
Next, the compounds represented by formulas I and II are described below.
In formula I, R11 and R12 independently represent an alkyl group. Examples of preferable alkyl groups for R11 and R12 include linear or branched alkyl groups having 1 to 24 carbon atoms, such as a methyl group, an ethyl group, an isopropyl group, a t-butyl group, an octyl group, a 2-ethylhexyl group, a dodecyl group, a tetradecyl group, an eicosyl group and a benzyl group, with preference given to branched alkyl groups.
R13 represents a divalent binding group. Examples of groups for R13 include an alkylene group and a phenylene group, which groups may have a substituent. The group for R13 is preferably a linear alkylene group. Also, the number of carbons contained in R13 preferably ranges from 1 to 10, more preferably from 2 to 6.
R14 represents a hydrogen atom or a substituent. Examples of preferable substituents represented by R14 include alkyl groups, cycloalkyl groups, alkenyl groups, aryl groups, alkylamino groups, alkylthio groups, arylthio groups, alkoxycarbonyl groups and acyloxycarbonyl groups. R14 preferably has at least one branching point in the molecular structure thereof.
Examples of alkyl groups for R21 and R22 in formula II include a methyl group, an ethyl group, a propyl group, a butyl group and an amyl group, which alkyl groups may be branched. Examples of alkylene groups for J include alkylene groups having 1 to 20 carbon atoms, such as a methylene group, an ethylene group, a propylene group and a butylene group, which alkylene groups may be branched. Examples of heterocyclic residues for R23 include 5- or 6-membered ring residues containing a heteto atom such as of oxygen, sulfur or nitrogen, e.g., a thienyl group, a furyl group, a pyrrolyl group, a pyrrolidinyl group, a piperidyl group, a piperazinyl group, a morpholino group, a thiacyclohexyl group, a dithiacyclohexyl group, an oxacyclohexyl group and a dioxacyclohexyl group, which heterocyclic residues may have been condensed with another heterocyclic ring or a hydrocarbon ring and may have formed a spiro compound.
Also, the oxidation potential of the compound of the present invention is preferably in the range from 800 to 1800 mV, more preferably from 1200 to 1500 mV.
Examples of the compound of the present invention are given below, which are not to be construed as limitative on the invention. ##STR6##
These compounds can easily be synthesized by the method described in European Patent No. 310,552.
These compounds may be used singly or in combination. The amount of their addition is preferably 5 to 300 mol %, more preferably 10 to 200 mol % relative to the amount of couplers.
Next, the yellow couplers used for the present invention are described below. Although any yellow coupler can be used without limitation in the present invention, a yellow coupler represented by formula Y-I is preferred. ##STR7## (wherein R1 represents an alkyl group or a cycloalkyl group; R2 represents an alkyl group, a cycloalkyl group, an aryl group or an acyl group; R3 represents a group capable of substituting a benzene ring; n represents 0 or 1; X1 represents a group capable of splitting off upon coupling with the oxidation product of a developing agent; y1 represents an organic group.)
Examples of the alkyl group for R1 in formula Y-I include a methyl group, an ethyl group, an isopropyl group, a t-butyl group and a dodecyl group. These alkyl groups for R1 may have a substituent. Examples of the substituent include a halogen atom, an aryl group, an alkoxy group, an aryloxy group, an alkylsulfonyl group, an acylamino group and a hydroxyl group.
Examples of the cycloalkyl group for R1 include a cyclopropyl group, a cyclohexyl group and an adamantyl group, with preference given to a branched alkyl group, more specifically a t-butyl group.
Examples of the alkyl group or cycloalkyl group for R2 in formula Y-I include the groups specified for R1. Examples of the aryl group for R2 include a phenyl group. These alkyl groups, cycloalkyl groups and aryl groups for R2 include those having the same substituent as specified for R1. Examples of the acyl group for R2 include an acetyl group, a propionyl group, a butyryl group, a hexanoyl group and a benzoyl group. The group for R2 is preferably an alkyl group or an aryl group, more preferably an alkyl group, and still more preferably a lower alkyl group having not more than 5 carbon atoms.
Examples of the group capable of substituting a benzene ring, represented by R3 in formula y-I, include halogen atoms such as a chlorine atom, alkyl groups such as an ethyl group, an isopropyl group and a t-butyl group, alkoxy groups such as a methoxy group, aryloxy groups such as a phenyloxy group, acyloxy groups such as a methylcarbonyloxy group and a benzoyloxy group, acylamino groups such as an acetamide group and a phenylcarbonylamino group, carbamoyl groups such as an N-methylcarbamoyl group and an N-phenylcarbamoyl group, alkylsulfonylamino groups such as an ethylsulfonylamino group, arylsulfonylamino groups such as a phenylsulfonylmaino group, sulfamoyl groups such as an N-propylsulfamoyl group and an N-phenylsulfamoyl group and imide groups such as a succinimide group and glutarimide group. n represents 0 or 1.
In formula Y-I, y1 represents an organic group without limitation, but it is preferably a group represented by the following formula Y-II:
Formula Y--II--J--R.sup.4
(wherein J represents --N (R5) --CO--, --CON (R5) --, --COO--, --N (R5) --SO2 -- or --SO2 --N (R5) --; R4 and R5 independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.)
Examples of alkyl groups for R4 and R5 include a methyl group, an ethyl group, an isopropyl group, a t-butyl group and a dodecyl group. Examples of aryl groups for R4 and R5 include a phenyl group and a naphthyl group. These alkyl groups or aryl groups for R4 and R5 include those having a substituent. The substituent is not subject to limitation; typical examples thereof include halogen atoms such as a chlorine atom, alkyl groups such as an ethyl group and a t-butyl group, aryl groups such as a phenyl group, a p-methoxyphenyl group and a naphthyl group, alkoxy groups such as an ethoxy group and a benzyloxy group, aryloxy groups such as a phenoxy group, alkylthio groups such as an ethylthio group, arylthio groups such as a phenylthio group, alkylsulfonyl groups such as a β-hydroxyethylsulfonyl group and arylsulfonyl groups such as a phenylsulfonyl group. Examples also include acylamino groups such as an alkylcarbonylamino group, specifically an acetamide group, and arylcarbonylamino groups, specifically a phenylcarbonylamino group, carbamoyl groups, including those substituted by an alkyl group, an aryl group (preferably a phenyl group) or another substituent, such as an N-methylcarbamoyl group and an N-phenylcarbamoyl group, acyl groups such as an alkylcarbonyl group, specifically an acetyl group and an arylcarbonyl group, specifically a benzoyl group, sulfonamide groups such as an alkylsulfonylamino group and an arylsulfonylamino group, specifically a methylsulfonylamino group and a benzenesulfonamide group, sulfamoyl groups, including those substituted by an alkyl group, an aryl group (preferably a phenyl group) or another substituent, specifically an N-propylsulfamoyl group and an N-phenylsulfamoyl group, a hydroxy group and a nitrile group.
The preferable group represented by --J--R4 is --NHCOR'4 wherein R'4 represents an organic group, preferably a linear or branched alkyl group having 1 to 30 carbon atoms, such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a t-butyl group, a n-pentyl group, a n-hexyl group, a 2-ethylhexyl group, a n-octyl group, a n-decyl group, a linear or branched dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an eicosyl group, a docosyl group, a tetracosyl group and a hexacosyl group. Of these alkyl groups, those having 8 to 20 carbon atoms are particularly preferable.
In formula Y--I, X1 represents a group splitting off upon coupling reaction with the oxidation product of a developing agent. Examples of such groups include the group represented by the following formula Y-III or Y-IV, with preference given to the group represented by formula Y-IV.
Formula Y-III--OR.sup.6
(wherein R6 represents an aryl group which may have a substituent or a heterocyclic group.) ##STR8## (wherein Z1 represents a group of non-metallic atoms necessary to form a 5- or 6-membered ring in cooperation with the nitrogen atom. Examples of the group of non-metallic atoms necessary to form the 5- or 6-membered ring include a methylene group, a methine group, a substituted methine group, >C═O, >NR7 (R7 has the same definition as R5 above), --N═, --O--, --S-- and --SO2 --.)
The yellow coupler represented by formula Y-I may bind at the R1, R3 or y1 moiety to form a bis configuration.
Next, examples of yellow couplers represented by formula Y-I are given below.
##STR9##
No. R.sub.A R.sub.B X.sub.A 3-position 4-position 5-position 6-position
Y-1 (t)C.sub.4 H.sub.9
CH.sub.3
##STR10##
H H
##STR11##
H Y-2 (t)C.sub.4 H.sub.9
CH.sub.3
##STR12##
H H
##STR13##
H Y-3 (t)C.sub.4 H.sub.9
CH.sub.3
##STR14##
H H
##STR15##
H Y-4 (t)C.sub.4 H.sub.9
CH.sub.3
##STR16##
H H
##STR17##
H Y-5 (t)C.sub.4 H.sub.9
CH.sub.3
##STR18##
H H
##STR19##
H Y-6 (t)C.sub.4 H.sub.9
CH.sub.3
##STR20##
H H
##STR21##
H Y-7 (t)C.sub.4 H.sub.9
CH.sub.3
##STR22##
H H
##STR23##
H Y-8 (t)C.sub.4 H.sub.9 C.sub.3 H.sub.7
(iso)
##STR24##
H H
##STR25##
H Y-9 (t)C.sub.4 H.sub.9
CH.sub.3
##STR26##
H H
##STR27##
H Y-10 (t)C.sub.4 H.sub.9
CH.sub.3
##STR28##
H H
##STR29##
H Y-11 (t)C.sub.4 H.sub.9
CH.sub.3
##STR30##
H H CONH(CH.sub.2).sub.2 NHSO.sub.2 C.sub.12 H.sub.25 H
Y-12 (t)C.sub.4 H.sub.9
CH.sub.3
##STR31##
H H
##STR32##
H Y-13 (t)C.sub.4 H.sub.9
CH.sub.3
##STR33##
H H
##STR34##
H Y-14 (t)C.sub.4 H.sub.9 C.sub.12
H.sub.25
##STR35##
H H
##STR36##
H Y-15 (t)C.sub.4 H.sub.9 C.sub.2
H.sub.5
##STR37##
H H
##STR38##
H Y-16 (t)C.sub.4 H.sub.9
CH.sub.3
##STR39##
H H COOC.sub.12 H.sub.25 H
Y-17
##STR40##
C.sub.12
H.sub.25
##STR41##
H H
##STR42##
H Y-18 (t)C.sub.5 H.sub.11
CH.sub.3
##STR43##
H H
##STR44##
H Y-19 (t)C.sub.4 H.sub.9
CH.sub.3
##STR45##
H H
##STR46##
H Y-20 (t)C.sub.4 H.sub.9
CH.sub.3
##STR47##
H H NHCOC.sub.13 H.sub.27 (n) H Y-21 (t)C.sub.4 H.sub.9 CH.sub.3
##STR48##
H H CONHC.sub.14 H.sub.29 (n) H Y-22 (t)C.sub.4 H.sub.9 CH.sub.3
##STR49##
H H NHCOC.sub.13 H.sub.27 (n) H Y-23 (t)C.sub.4 H.sub.9 CH.sub.3
##STR50##
H H NHCOC.sub.15 H.sub.31 (n) H Y-24 (t)C.sub.4 H.sub.9 CH.sub.3
##STR51##
H H NHCOC.sub.13 H.sub.27 (n) H Y-25 (t)C.sub.4 H.sub.9 C.sub.3
H.sub.7
(iso)
##STR52##
H H CONHC.sub.14 H.sub.29 (n) H Y-26 (t)C.sub.4 H.sub.9 CH.sub.3
##STR53##
H H CONHC.sub.14 H.sub.29 (n) H Y-27 (t)C.sub.4 H.sub.9 C.sub.15
H.sub.37
(n)
##STR54##
H H
##STR55##
H Y-28 (t)C.sub.4 H.sub.9
CH.sub.3
##STR56##
H H NHCOC.sub.9 H.sub.19 (n) H Y-29 (t)C.sub.4 H.sub.9 C.sub.4
H.sub.9
##STR57##
H H NHCOC.sub.13 H.sub.27 (n) H Y-30 (t)C.sub.4 H.sub.9 CH.sub.3
##STR58##
H H CONHC.sub.14 H.sub.29 (n) H Y-31 (t)C.sub.4 H.sub.9 C.sub.12
H.sub.25
(n)
##STR59##
H H NHCOC.sub.13 H.sub.27 (n) H Y-32 (t)C.sub.4 H.sub.9 C.sub.2
H.sub.5
##STR60##
H H NHCOC.sub.19 H.sub.39 (n) H Y-33 (t)C.sub.4 H.sub.9 CH.sub.3
##STR61##
H H CONHC.sub.16 H.sub.33 (n) H Y-34 (t)C.sub.4 H.sub.9 CH.sub.3
##STR62##
H H CONHC.sub.14 H.sub.29 (n) H Y-35 (t)C.sub.4 H.sub.9 CH.sub.3
##STR63##
H Cl NHCOC.sub.16 H.sub.31 (i) H Y-36 (t)C.sub.4 H.sub.9 CH.sub.3
##STR64##
H H NHCOC.sub.15 H.sub.31 (n) H Y-37 (t)C.sub.4 H.sub.9 CH.sub.3
##STR65##
H H NHCOC.sub.17 H.sub.36 (n) H Y-38 (t)C.sub.4 H.sub.9 CH.sub.3
##STR66##
H H
##STR67##
H Y-39 (t)C.sub.4 H.sub.9
CH.sub.3
##STR68##
H H
##STR69##
H Y-40 (t)C.sub.4 H.sub.9
CH.sub.3
##STR70##
H H
##STR71##
H Y-41 (t)C.sub.4 H.sub.9
CH.sub.3
##STR72##
H H NHCOC.sub.16 H.sub.31 (i) H Y-42 (t)C.sub.4 H.sub.9 CH.sub.3
##STR73##
H H NHCOC.sub.16 H.sub.31 (i) H Y-43 (t)C.sub.4 H.sub.9 CH.sub.3
##STR74##
H H
##STR75##
H Y-44 (t)C.sub.4 H.sub.9
CH.sub.3
##STR76##
H H NHSO.sub.2 C.sub. 12 H.sub.25 H Y-45 (t)C.sub.4 H.sub.9 CH.sub.3
##STR77##
H Cl
##STR78##
H Y-46 (t)C.sub.4 H.sub.9
CH.sub.3
##STR79##
H H
##STR80##
H Y-47 (t)C.sub.4 H.sub.9
CH.sub.3
##STR81##
H H
##STR82##
H Y-48 (t)C.sub.4 H.sub.9
CH.sub.3
##STR83##
H H
##STR84##
H Y-49 (t)C.sub.4 H.sub.9
CH.sub.3
##STR85##
H H
##STR86##
H Y-50 (t)C.sub.4 H.sub.9
CH.sub.3
##STR87##
H H
##STR88##
H
These yellow couplers of the present invention, represented by formula Y-I, can easily be synthesized by the methods described in Japanese Patent O.P.I. Publication No. 123047/1988, Japanese Patent Application Nos. 245949/1990 and 96774/1990.
The yellow couplers represented by formula Y-I relating to the present invention may be used singly or in combination, and may be used in combination with other kinds of yellow couplers.
In the present invention, the yellow coupler can be used in the content ratio of about 1×10-3 to about 1 mol, preferably 1×10-2 mol to 8×10-1 mol per mol of silver halide.
Next, the cyan couplers used for the present invention are described below. Although any cyan coupler may be used without limitation in the present invention, the cyan coupler for the present invention is preferably a naphthol cyan coupler, a phenol cyan coupler or an imidazole cyan coupler. More preferable cyan couplers are those represented by the following formulas C-I and C-II: ##STR89## (wherein RC1 represents an alkyl group having 2 to 6 carbon atoms; RC2 represents a ballast group; ZC represents a hydrogen atom or a group capable of splitting off upon coupling with the oxidation product of a developing agent.) ##STR90## (wherein RC1 represents an alkyl group or an aryl group; RC2 represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group; RC3 represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group; RC1 and RC3 may cooperate to form a ring; ZC represents a hydrogen atom or an atom or group capable of splitting off upon coupling with the oxidation product of a developing agent.)
With respect to formula C-I, the alkyl group represented by RC1, whether linear or branched, includes those having a substituent.
The ballast group represented by RC2 is an organic group having a size and shape which provides the coupler molecule with sufficient bulkiness to make the coupler substantially incapable of diffusing from the layer to which it is applied to another layer. Said ballast group is preferably represented by the following formula: ##STR91## (wherein RC3 represents an alkyl group having 1 to 12 carbon atoms; ArC represents an aryl group such as a phenyl group, which aryl group includes those having a substituent.)
Examples of cyan couplers represented by formula C-I include example compounds PC-1 through PC-19 given in the upper right column, page 30, through upper left column, page 31, Japanese Patent O.P.I. Publication No. 156748/1989, example compounds C-1 through C-28 given in Japanese Patent O.P.I. Publication No. 249151/1987, the cyan couplers described in Japanese Patent Examined Publication No. 11572/1974 and Japanese Patent O.P.I. Publication No. 3142/1986, 9652/1986, 9653/1986, 39045/1986, 50136/1986, 99141/1986 and 105545/1986 and the cyan couplers described below, which are not to be construed as limitative.
With respect to formula C-II, the alkyl group represented by RC1 preferably has 1 to 32 carbon atoms, which alkyl group may be linear or branched and includes those having a substituent.
The aryl group represented by RC1 is preferably a phenyl group, including those having a substituent.
The alkyl group represented by RC2 preferably has 1 to 32 carbon atoms, which alkyl group may be linear or branched and includes those having a substituent.
The cycloalkyl group represented by RC2 preferably has 3 to 12 carbon atoms, which cycloalkyl group may be linear or branched and includes those having a substituent.
The aryl group represented by RC2 is preferably a phenyl group, including those having a substituent.
The heterocyclic group represented by RC2 preferably has 5 to 7 members, including those having a substituent, and may have been condensed.
RC3 represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, which alkyl group and alkoxy group include those having a substituent, but RC3 is preferably a hydrogen atom.
The ring formed by RC1 and RC3 in cooperation is preferably a 5- or 6-membered ring. Examples of such rings include the following: ##STR92##
With respect to formula C-II, examples of the group capable of splitting off upon reaction with the oxidation product of a color developing agent, represented by ZC, include halogen atoms, alkoxy groups, aryloxy groups, acyloxy groups, sulfonyloxy groups, acylamino groups, sulfonylamino groups, alkoxycarbonyloxy groups, aryloxycarbonyloxy groups and imide groups, with preference given to halogen atoms, aryloxy groups and alkoxy groups.
Of the cyan couplers represented by formula C-II, those represented by the following formula C-II-A are preferred. ##STR93## (wherein RA1 represents a phenyl group substituted by at least one halogen atom; such phenyl groups include those having a non-halogen substituent. RA2 has the same definition as RC1 in formula C-II. XA represents a halogen atom, an aryloxy group or an alkoxy group, including those having a substituent.)
Examples of the cyan coupler represented by formula C-II include example compounds C-1 through C-25 given in Japanese Patent O.P.I. Publication No. 96656/1988, example compounds PC-II-1 through PC-II-31 given in lower left column, page 32, through upper left column, page 34, Japanese Patent O.P.I. Publication No. 156748/1989, the 2,5-diacylamino cyan couplers described in lower right column, page 7, through lower left column, page 9, Japanese Patent O.P.I. Publication No. 178962/1987, lower left column, page 7, through lower right column, page 10, Japanese Patent O.P.I. Publication No. 225155/1985, upper left column, page 6, through lower right column, page 8, Japanese Patent O.P.I. Publication No. 222853/1985 and lower left column, page 6, through upper left column, page 9, Japanese Patent O.P.I. Publication No. 185335/1984 and the cyan couplers described below, which can be synthesized in accordance with the methods described in these publications.
Examples of the cyan couplers represented by formulas C-I and C-II are given below.
__________________________________________________________________________
##STR94##
Couplers
R.sub.1 Z R.sub.2
__________________________________________________________________________
C-1 C.sub.2 H.sub.5
Cl
##STR95##
C-2 C.sub.2 H.sub.5
##STR96##
##STR97##
C-3
##STR98##
Cl
##STR99##
C-4 C.sub.2 H.sub.5
Cl
##STR100##
C-5 C.sub.4 H.sub.9
F
##STR101##
C-6 C.sub.2 H.sub.5
F
##STR102##
C-7 C.sub.2 H.sub.5
Cl
##STR103##
C-8 C.sub.2 H.sub.5
Cl
##STR104##
C-9 C.sub.2 H.sub.5
Cl
##STR105##
C-10 CH(CH.sub.3).sub.2
Cl C.sub.18 H.sub.37
C-11 C.sub.6 H.sub.13
Cl
##STR106##
C-12 C.sub.3 H.sub.7
Cl
##STR107##
C-13
##STR108##
Cl
##STR109##
C-14 C.sub.2 H.sub.4 OCH.sub.3
Cl
##STR110##
C-15 C.sub.2 H.sub.5
Cl
##STR111##
C-16 C.sub. 4 H.sub.9 (t)
OCH.sub.2 CH.sub.2 SO.sub.2 CH.sub.3
##STR112##
C-17 C.sub.2 H.sub.5
Cl
##STR113##
C-18 C.sub.2 H.sub.5
Cl
##STR114##
C-19 C.sub.2 H.sub.5
Cl
##STR115##
C-20 C.sub.2 H.sub.5
Cl C.sub.15 H.sub.31 (n)
__________________________________________________________________________
##STR116##
Couplers R.sup.2 R.sup.1 R.sup.3 Z
PC-1 (CF.sub.2).sub.4
H
##STR117##
H Cl PC-2
##STR118##
##STR119##
H Cl PC-3
##STR120##
##STR121##
H Cl PC-4
##STR122##
C.sub.16 H.sub.33 Cl Cl PC-5
##STR123##
##STR124##
H
##STR125##
PC-6
##STR126##
##STR127##
H H PC-7
##STR128##
##STR129##
H Cl PC-8
##STR130##
##STR131##
H Cl PC-9
##STR132##
##STR133##
H
##STR134##
PC-10
##STR135##
##STR136##
H Cl
PC-11
##STR137##
##STR138##
H Cl
PC-12
##STR139##
##STR140##
H OCH.sub.2 CONHC.sub.3 H.sub.7
PC-13
##STR141##
##STR142##
H Cl
PC-14
##STR143##
##STR144##
H Cl
PC-15
##STR145##
##STR146##
Cl
PC-16
##STR147##
##STR148##
Cl
PC-17
##STR149##
##STR150##
H Cl
PC-18
##STR151##
##STR152##
H Cl
PC-19
##STR153##
##STR154##
H
##STR155##
PC-20
##STR156##
##STR157##
H Cl
PC-21
##STR158##
##STR159##
H Cl
PC-22
##STR160##
##STR161##
H Cl
PC-23
##STR162##
##STR163##
H
##STR164##
PC-24
##STR165##
##STR166##
H Cl
PC-25
##STR167##
##STR168##
H OCH.sub.2 CONH(CH.sub.2).sub.2 OCH.sub.3
PC-26
##STR169##
##STR170##
H Cl PC-27 C.sub.3
F.sub.7
##STR171##
H H PC-28 C.sub.3
F.sub.7
##STR172##
H H
PC-29
##STR173##
##STR174##
H Cl
PC-30
##STR175##
##STR176##
OCH.sub.3 Cl
PC-31
##STR177##
##STR178##
H Cl PC-32 C.sub.3
F.sub.7
##STR179##
H H
CA-1
##STR180##
CA-2
##STR181##
The cyan couplers can be used in the content range from 1×10-3 to 1 mol, preferably from 1×10-2 to 8×10-1 mol per mol of silver halide.
These cyan couplers may be used in combination with other kinds of cyan coupler.
In the present invention, known couplers can be used as magenta couplers, including 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolotriazole couplers and chain-opened acylacetonitrile couplers.
Preferably the compound of the present invention and couplers are used in the same layer, but the compound may be used in a layer adjacent to a coupler-containing layer.
The compound of the present invention and couplers and other hydrophobic compounds can be added to the light-sensitive material by various methods, including solid dispersion, latex dispersion and oil-in-water emulsion dispersion. For example, the compound of the present invention, couplers and other substances are dissolved in a high boiling organic solvent having a boiling point of over about 150° C. or in a water-insoluble organic-solvent-soluble high molecular compound in the presence of a low boiling and/or water-soluble organic solvent used as necessary, the resulting solution is emulsified and dispersed in a hydrophilic binder such as an aqueous solution of gelatin using a means of dispersion such as a mechanical stirrer, a homogenizer, a colloid mill, a flow jet mixer or an ultrasonicator in the presence of a surfactant, and the resulting emulsion is added to the target hydrophilic colloid layer. Another process may be added wherein the low boiling organic solvent is removed after or simultaneously with dispersion.
In the present invention, the high boiling organic solvent preferably has a dielectric constant of less than 6.0. Although the lower limit of dielectric constant is not subject to limitation, it is preferably not less than 1.9. Examples of such high boiling organic solvents include esters such as phthalates and phosphates, organic acid amides, ketones and hydrocarbon compounds, provided that they have a dielectric constant of less than 6.0. Also, in the present invention, high boiling organic solvents having a vapor pressure at 100° C. of not more than 0.5 mmHg are preferred.
The high boiling organic solvent may be a mixture of two or more kinds. In this case, the dielectric constant of the mixture is less than 6.0. Here, dielectric constant is as determined at 30° C.
Preferably, the high boiling organic solvent is a phthalate or phosphate.
The phthalate advantageously used for the present invention is represented by the following formula HA: ##STR182## Formula HA
wherein RH1 and RH2 independently represent an alkyl group, an alkenyl group or an aryl group, provided that the total number of carbon atoms in the groups represented by RH1 and RH2 is 9 to 32, more preferably 16 to 24.
The alkyl groups for RH1 and RH2 in formula HA may be linear or branched. Examples of aryl groups for RH1 and RH2 include a phenyl group and a naphthyl group; examples of alkenyl groups for RH1 and RH2 include a hexenyl group, a heptenyl group and an octadecenyl group. These alkyl groups, alkenyl groups and aryl groups may have a substituent.
The phosphate advantageously used for the present invention is represented by the following formula HB: ##STR183## wherein RH3, RH4 and RH5 independently represent an alkyl group, an alkenyl group or an aryl group, provided that the total number of carbon atoms in the groups represented by RH3, RH4 and RH5 is 24 to 54. These alkyl groups, alkenyl groups and aryl groups may have one or more substituents.
The preferable group for RH3, RH4 and RH5 is an alkyl group, specifically a nonyl group, a n-decyl group, a sec-decyl group, a sec-dodecyl group and a t-octyl group.
Examples of the high boiling organic solvent described above include example organic solvents 1 through 22 given in page 41 of Japanese Patent O.P.I. Publication No. 166331/1987.
Examples of water-insoluble organic-solvent-soluble polymers used to disperse couplers etc. include the following:
(1) vinyl polymers and copolymers,
(2) condensation polymers of polyhydric alcohol and polybasic acid,
(3) polyesters obtained by ring-opening polymerization, and
(4) others, including polycarbonate resin, polyurethane resin and polyamide resin.
Although the number-average molecular weight of these polymers is not subject to limitation, it is preferably not more than 200,000, more preferably 5000 to 100,000. The ratio by weight of the polymer to the hydrophobic compounds is preferably 1:20 to 20:1, more preferably 1:10 to 10:1.
Examples of polymers which are preferably used for the present invention are given below. For copolymers, the ratio of monomer is given by weight.
PO-1: Poly(N-t-butyracrylamide)
PO-2: N-t-butyracrylamide-methyl methacrylate copolymer (60:40)
PO-3: Polybutyl methacrylate
PO-4: Methyl methacrylate-styrene copolymer (90:10)
PO-5: N-t-butyracrylamide-2-methoxyethyl acrylate copolymer (55:45)
PO-6: ω-methoxypolyethylene glycol acrylate (adduct molar number n=9)-N-t-butyracrylamide copolymer (25:75)
PO-7: 1,4-butanediol-adipic acid polyester
PO-8: Polypropiolactam
The light-sensitive material of the present invention is applicable to color negative films, color positive films, color printing paper, etc., with the effect of the invention enhanced when the light-sensitive material is used for color printing paper undergoing direct viewing.
The silver halide for the present invention may be any silver halide, including silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide and silver chloroiodide. The silver halide grains preferably used for the present invention have a silver chloride content of not less than 90 mol % a silver bromide content of not more than 10 mol % and a silver iodide content of not more than 0.5 mol %, with more preference given to a silver chlorobromide having a silver bromide content of 0.1 to 2 mol %. Said silver halide grains may be used singly or in combination with other kinds of silver halide grains with different composition, and may also be used in combination with silver halide grains having a silver chloride content of not more than 90 mol %. In the silver halide emulsion layers containing silver halide grains having a silver chloride content of not less than 90 mol %, the silver halide grains having a silver chloride content of not less than 90 mol % account for not less than 60% by weight, preferably not less than 80% by weight of the total silver halide grain content of said emulsion layers. The composition of the silver halide grains may be uniform from inside to outside, or may be different between inside and outside. In cases where there is a difference between inside and outside, the composition change may be continuous or not.
Although the grain size of silver halide grains is not subject to limitation, it is preferable in view of other photographic performance requirements such as rapid processing and sensitivity that the grain size be in the range from 0.2 to 1.6 μm, more preferably from 0.25 to 1.2 μm. The grain size can be determined by various methods in common use in the relevant field. Typical methods are described in "Particle-Size Measurement", ASTM Symposium on Light Microscopy, R. P. Loveland, pp. 94-122 (1955), or Chapter 2 of "The Theory of the Photographic Process", edited by Meath and James, 3rd edition, MacMillan (1966). The grain size can be determined on the basis of either the projected area of the grain or an approximated diameter.
When the grains have a substantially uniform shape, grain size distribution can be expressed with fair accuracy using the diameter or projected area. The grain size distribution of silver halide grains may be polydispersed or monodispersed. Preferred silver halide grains are monodispersed silver halide grains having a coefficient of variance of silver halide grain distribution of not more than 0.22, more preferably not more than 0.15. Here, the coefficient of variance is a coefficient indicating grain size distribution, as defined by the following equation: ##EQU1##
Here, ri represents the diameter of each grain; ni represents the number of grains. Grain size means the diameter of a grain, provided that the grain is a spherical silver halide grain, or the diameter of the circle with the same area converted from the projected area, provided that the grain is a cubic or otherwise nonspherical grain.
The silver halide grains used for the present invention may be prepared by any of the acidic method, the neutral method and the ammoniacal method. These grains may be grown at once or grown after seed grain formation. The method of preparing the seed grains and the method of growing them may be identical or not. As for the mode of reaction of a soluble silver salt and a soluble halide, any of the normal precipitation method, the reverse precipitation method, the double jet precipitation method and combinations thereof may be used, but the grains obtained by the simultaneous precipitation method are preferred. As a mode of the double jet precipitation method, the pAg controlled double jet method, which is described in Japanese Patent O.P.I. Publication No. 48521/1979, can also be used.
If necessary, a silver halide solvent such as thioether may be used. Also, a compound containing a mercapto group, a nitrogen-containing heterocyclic compound or a sensitizing dye compound may be added at the time of silver halide emulsion formation or after completion of said grains.
The shape of the silver halide grains for the present invention may be any one. A preferred shape is a cube having {100} planes to form the crystal surface. It is also possible to use octahedral, tetradecahedral, dodecahedral or other forms of grains prepared by the methods described in U.S. Pat. Nos. 4,183,756 and 4,225,666, Japanese Patent O.P.I. Publication No. 26589/1980, Japanese Patent Examined Publication No. 42737/1980 and the Journal of Photographic Science, 21, 39 (1973). Grains having twin crystal planes may also be used. The silver halide grains for the present invention may be of a single shape or a combination of various shapes.
The silver halide grains used for the present invention may be supplemented with metal ions using a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof or an iron salt or a complex salt thereof to contain such metal elements in and/or on the grains during formation and/or growth of silver halide grains. Also, reduction sensitization specks can be provided in and/or on the grains by bringing the grains in an appropriate reducing atmosphere.
The emulsion containing silver halide grains may be treated to remove the undesirable soluble salts after completion of growth of silver halide grains or may retain said soluble salts. Removal of said salts can be achieved in accordance with the method described in Research Disclosure No. 17643.
The silver halide grains used in the emulsion for the present invention may be grains wherein latent images are formed mainly on the surface thereof or grains wherein latent images are formed mainly therein, with preference given to grains wherein latent images are formed mainly on the surface thereof.
In the present invention, the emulsion is chemically sensitized by a conventional method. Specifically, sulfur sensitization, which uses either a compound containing sulfur capable of reacting with silver ion or active gelatin, selenium sensitization, which uses a selenium compound, reduction sensitization, which uses a reducing substance, noble metal sensitization, which uses gold or another noble metal, and other sensitizing methods can be used singly or in combination.
The emulsion can also be optically sensitized in the desired wavelength band using a sensitizing dye. Sensitizing dyes which can be used for the present invention include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxanol dyes.
It is the common practice to select dye-forming couplers for use in the silver halide photographic light-sensitive material of the present invention so that a dye absorbing the sensitization spectral light for each emulsion layer is formed; a yellow coupler, a magenta coupler and a cyan coupler are used in the blue-, green- and red-sensitive emulsion layers, respectively. However, the silver halide photographic light-sensitive material may be prepared using these couplers in different combinations according to the purpose.
Although it is advantageous to use gelatin as a binder (or protective colloid) for the silver halide photographic light-sensitive material of the present invention, it is possible to use gelatin derivatives, graft polymers of gelatin and another polymer and other hydrophilic colloids such as proteins, sugar derivatives, cellulose derivatives and synthetic hydrophilic polymer substances in the form of homo- or copolymer.
The silver halide photographic light-sensitive material of the present invention may optionally incorporate other additives such as hardeners, antistaining agents, image stabilizer, UV absorbents, plasticizers, latices, surfactants, matting agents, lubricants and antistatic agents.
The total amount of gelatin coated on the support of the silver halide photographic light-sensitive material of the present invention is preferably less than 7 g/m2. Although the lower limit is not subject to limitation, the total amount is generally preferably not less than 3 g/m2 from the viewpoint of physical properties or photographic performance. The amount of gelatin is determined as the weight of gelatin containing 11.0% water as determined by the PAGI method.
The gelatin contained in the silver halide photographic light-sensitive material of the present invention is hardened with a hardener. Any hardener can be used without limitation, including hardeners known in the photographic industry, such as aldehyde hardeners, active vinyl hardeners, active halogen hardeners, epoxy hardeners, ethyleneimine hardeners, methanesulfonate hardeners, carbodiimide hardeners, isoxazole hardeners and high molecular hardeners.
The effect of the present invention is enhanced when the silver halide photographic light-sensitive material of the invention is a light-sensitive material undergoing direct viewing, such as color printing paper or a light-sensitive material for color copying, which are open to strict requirements for image storage stability.
The light-sensitive material of the present invention permits image formation by a color developing process known in the relevant field.
The color developing agent used in the color developer is a primary amine based color developing agent in wide use in various color photographic processes, such as an aminophenol or p-phenylenediamine derivative.
In addition to the primary amine based color developing agent described above, known developer component compounds may be added to the color developer used to process the light-sensitive material of the present invention. The pH level of the color developer is normally not less than 9, preferably about 10 to 13. Color developing temperature is normally over 15° C., specifically in the range from 20° to 50° C. For rapid processing, it is preferable to carry out the color developing process at a temperature of over 30° C.
Although developing time is normally 10 seconds to 4 minutes, it is preferable to carry out development in the range from 10 to 30 seconds when rapid processing is desired. When more speed-up is required, it is preferable to carry out development in the range from 10 to 30 seconds.
When the light-sensitive material of the present invention is subjected to running processing while continuously supplying a color developer replenisher, the amount of color developer replenisher is preferably 20 to 150 ml, more preferably 20 to 120 ml, and more preferably 20 to 100 ml per m2 of light-sensitive material. The effect of the present invention is enhanced when the running processing is carried out using such a low level of replenishment.
The light-sensitive material of the present invention is subjected to bleach-fixation after color development.
Bleach-fixation is normally followed by washing or stabilization or a combination thereof.
The present invention is hereinafter described in more detail by means of the following examples, which are not to be construed as limitative on the embodiment of the invention.
The three kinds of silver halide emulsion listed in Table 1 were prepared by a combination of the neutral method and the double jet precipitation method.
TABLE 1
______________________________________
Average Spectral
Emulsion
AgCl AgBr grain Chemical sensitizing
No. (%) (%) size (μ)
sensitizers
dye
______________________________________
Em-1 99.5 0.5 0.67 Sodium SD-1*3
thiosulfate*1
Em-2 99.5 0.5 0.46 Chloroauric
SD-2*4
acid*2
Em-3 99.5 0.5 0.43 SD-3*5
______________________________________
*1: 2 mg added per mol of silver halide.
*2: 5 × 10.sup.-5 mol added per mol of silver halide.
*3: 0.9 mmol added per mol of silver halide
*4: 0.7 mmol added per mol of silver halide.
*5: 0.2 mmol added per mol of silver halide.
Each silver halide emulsion was supplemented with the following emulsion stabilizer STB-1 in an amount of 5×10-4 mol per mol of silver halide after completion of chemical sensitization.
Layers with the following compositions were coated on a paper support, laminated with polyethylene on one face and titanium oxide containing polyethylene on the first layer side of the other face, to yield multiple-layered photographic light-sensitive material No. 101. The coating solutions were prepared as follows.
26.7 g of a yellow coupler Y-51, 0.67 g of an antistaining agent HQ-1 and 6.7 g of a high boiling organic solvent DNP were dissolved in 60 ml of ethyl acetate. This solution was emulsified and dispersed in 200 ml of a 10% aqueous solution of gelatin containing 10 ml of 10% sodium triisopropylnaphthalenesulfonate SU-1 using a homogenizer to yield a yellow coupler dispersion.
This dispersion was mixed with a blue-sensitive silver chlorobromide emulsion Em-1 (containing 8.71 g of silver) and a gelatin solution for coating to yield a first layer coating solution.
Second through seventh layer coating solutions were prepared in the same manner as with the first layer coating solution. The hardeners added were H-1 for layers 2 and 4 and H-2 for layer 7. Surfactants SU-2 and SU-3, as coating aids, were added to adjust surface tension.
TABLE 2
______________________________________
Amount of
Layer Composition addition (g/m.sup.2)
______________________________________
Layer 7: Gelatin 1.00
Protective layer
Layer 6: Gelatin 0.40
Ultraviolet
UV absorbent UV-1
0.10
absorbing layer
UV absorbent UV-2
0.04
UV absorbent UV-3
0.16
Antistaining agent HQ-1
0.01
DNP 0.20
PVP 0.03
Layer 5: Red-
Gelatin 1.30
sensitive layer
Red-sensitive silver
0.21
chlorobromide emulsion
Em-3
Cyan coupler C-4 0.24
Cyan coupler CC-2
0.08
Dye image stabilizer ST-1
0.20
Antistaining agent HQ-1
0.01
HBS-1 0.20
DOP 0.20
Layer 4: Gelatin 0.94
Ultraviolet
UV absorbent UV-1
0.28
absorbing layer
UV absorbent UV-2
0.09
UV absorbent UV-3
0.38
Antistaining agent HQ-1
0.03
DNP 0.40
Layer 3: Green-
Gelatin 1.40
sensitive layer
Green-sensitive silver
0.17
chlorobromide emulsion
Em-2
Magenta coupler M-1
0.35
Dye image stabilizer ST-2
0.20
Dye image stabilizer ST-3
0.20
DNP 0.20
Layer 2: Gelatin 1.20
Interlayer Antistaining agent HQ-2
0.12
DIDP 0.15
______________________________________
TABLE 3
______________________________________
Layer 1: Blue-
Gelatin 1.20
sensitive layer
Blue-sensitive silver
0.26
chlorobromide emulsion
Em-1
Yellow coupler Y-51
0.80
Antistaining agent HQ-1
0.02
DNP 0.20
Support Polyethylene-laminated
paper
______________________________________
Figures for silver halide emulsions are expressed as silver.
DOP: Dioctyl phthalate DIDP: Diisodecyl phthalate
DNP: Dinonyl phthalate PVP: Polyvinylpyrrolidone
Next, sample Nos. 102 through 132 were prepared in the same manner as above except that yellow coupler Y-51 for layer 1 was replaced as shown in Tables 4 and 5 and 0.1 mmol/m2 of each of the dye image stabilizer shown in Tables 4 and 5 were added to layer 1.
The samples thus obtained were subjected to blue light exposure through an optical wedge using the sensitometer KS-7 (produced by Konica Corporation) and then processed in the following procedures.
______________________________________
Processing procedures
Temperature Time
______________________________________
Color development
35.0 ± 0.3° C.
45 seconds
Bleach-fixation 35.0 ± 0.5° C.
45 seconds
Stabilization 30 to 34° C.
90 seconds
Drying 60 to 80° C.
60 seconds
______________________________________
Color developer
______________________________________
Water 800 ml
Triethanolamine 10 g
N,N-diethylhydroxylamine 5 g
Potassium bromide 0.02 g
Potassium chloride 2 g
Potassium sulfite 0.3 g
1-hydroxyethylidene-1,1-diphosphonic acid
1.0 g
Ethylenediaminetetraacetic acid
1.0 g
Disodium catechol-3,5-diphosphonate
1.0 g
N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-
4.5 g
4-aminoaniline sulfate
Brightening agent (4,4'-diaminostylbenedisulfonic
1.0 g
acid derivative)
Potassium carbonate 27 g
______________________________________
Water was added to make a total quantity of 1 l, and the solution was adjusted to a pH of 10.10.
______________________________________
Bleach-fixer
______________________________________
Ferric ammonium ethylenediaminetetraacetate
60 g
dihydrate
Ethylenediaminetetraacetic acid
3 g
Ammonium thiosulfate (70% aqueous solution)
100 ml
Ammonium sulfite (40% aqueous solution)
27.5 ml
______________________________________
Water was added to make a total quantity of 1l, and potassium carbonate or glacial acetic acid was added to obtain a pH of 5.7.
______________________________________
Stabilizer
______________________________________
5-chloro-2-methyl--4-isothiazolin-3-one
1.0 g
Ethylene glycol 1.0 g
1-hydroxyethylidene-1,1-diphosphonic acid
2.0 g
Ethylenediaminetetraacetic acid
1.0 g
Ammonium hydroxide (20% aqueous solution)
3.0 g
Ammonium sulfite 3.0 g
Brightening agent (4,4'-diaminostylbenedisulfonic
1.5 g
acid derivative)
______________________________________
Water was added to make a total quantity of 1l, and sulfuric acid or potassium hydroxide was added to obtain a pH of 7.0.
The samples thus processed were subjected to densitometry using a densitometer (PDA-65 model, produced by Konica Corporation) to determine their sensitivity. Sensitivity was obtained as the reciprocal of the exposure amount corresponding to a density of 0.5. Figures for sensitivity are expressed as percent ratio relative to the sensitivity of sample No. 101. Light fastness was also evaluated by determining the residual rate of density in a dye image with an initial density of 1.0 after 10 weeks of storage of each processed sample under direct sunlight (exposure table). Color reproducibility was evaluated by visual observation of the print samples. The results are shown in Tables 4 and 5.
TABLE 4
__________________________________________________________________________
Dye image
Oxidation
Yellow Color Relative
Residual
Sample No
stabilizer
potential
coupler
reproduction
sensitivity
rate (%)
__________________________________________________________________________
101 Not added Example
C 100 60
(comparative) coupler Y-51
102 Comparative
2060 Example
C 89 85
(comparative)
compound YST-1
coupler Y-51
103 Comparative
1400 Example
C 102 70
(comparative)
compound YST-2
coupler Y-51
104 (inventive)
Example 1420 Example
C 97 80
compound I-1 coupler Y-51
105 (inventive)
Example 1540 Example
C 102 83
compound I-6 coupler Y-51
106 (inventive)
Example 1510 Example
C 102 81
compound I-8 coupler Y-51
107 (inventive)
Example 1590 Example
C 92 82
compound I-17 coupler Y-51
108 (inventive)
Example 1200 Example
C 97 83
compound I-21 coupler Y-51
109 (inventive)
Example 1600 Example
C 92 84
compound I-22 coupler Y-51
110 (inventive)
Example 1580 Example
C 102 83
compound I-25 coupler Y-51
111 Not added Example
B 111 52
(comparative) coupler Y-3
112 Comparative
2060 Example
B 68 82
(comparative)
compound YST-1
coupler Y-3
113 Comparative
1400 Example
B 102 60
(comparative)
compound YST-2
coupler Y-3
114 (inventive)
Example 1420 Example
A 102 88
compound I-1 coupler Y-3
115 (inventive)
Example 1540 Example
A 97 90
compound I-6 coupler Y-3
116 (inventive)
Example 1510 Example
B 106 86
compound I-8 coupler Y-3
117 (inventive)
Example 1590 Example
A 102 92
compound I-17 coupler Y-3
118 (inventive)
Example 1200 Example
B 87 82
compound I-21 coupler Y-3
119 (inventive)
Example 1600 Example
B 92 80
compound I-22 coupler Y-3
120 (inventive)
Example 1580 Example
B 97 85
compound I-25 coupler Y-3
121 Comparative
2060 Example
A 73 89
(comparative)
compound YST-1
coupler Y-20
__________________________________________________________________________
Note: Color reproducibility increases in the order of A > B > C.
TABLE 5
__________________________________________________________________________
Dye image
Oxidation
Yellow Color Relative
Residual
Sample No
stabilizer
potential
coupler
reproduction
sensitivity
rate (%)
__________________________________________________________________________
122 (inventive)
Example 1420 Example
B 106 91
compound I-1 coupler Y-20
123 (inventive)
Example 1540 Example
A 102 90
compound I-6 coupler Y-20
124 (inventive)
Example 1510 Example
A 106 88
compound I-8 coupler Y-20
125 Comparative
2060 Example
A 68 89
(comparative)
compound YST-1
coupler Y-36
126 (inventive)
Example 1420 Example
B 102 90
compound I-1 coupler Y-36
127 (inventive)
Example 1540 Example
A 102 91
compound I-6 coupler Y-36
128 (inventive)
Example 1510 Example
A 106 88
compound I-8 coupler Y-36
129 Comparative
2060 Example
B 73 90
(comparative)
compound YST-1
coupler Y-46
130 (inventive)
Example 1420 Example
A 106 89
compound I-1 coupler Y-46
131 (inventive)
Example 1540 Example
A 106 89
compound I-6 coupler Y-46
132 (inventive)
Example 1510 Example
A 102 90
compound I-8 coupler Y-46
__________________________________________________________________________
Note: Color reproducibility increases in the order of A > B > C.
From Tables 4 and 5, it is evident that the samples incorporating comparative compound YST-1 as a dye image stabilizer, which has an ester group in the molecular structure thereof and an oxidation potential of 2060 mV (sample Nos. 102, 112, 121, 125 and 129), had reduced sensitivity, though the light fastness improved. Also, sample Nos. 103 and 113, which incorporated comparative compound YST-2 as a dye image stabilizer, which had no ester group in the molecular structure thereof, though the oxidation potential was 1400 mV, falling in the range of the present invention, had no sufficient light fastness, though the sensitivity did not decrease. On the other hand, the use of a compound relating to the present invention offered sufficient sensitivity and excellent light fastness. ##STR184##
Sample Nos. 101 through 132, prepared in Example 1, were each subjected to exposure through an optical wedge and then continuously processed using a paper processor in the following procedures until the amount of replenisher became 2 times the capacity of the color developer tank. The finished samples thus obtained are referred to as sample Nos. 201 through 232.
______________________________________
Tank
Amount of capa-
Temperature
Time replenisher
city
______________________________________
Color 34.7 ± 0.3° C.
45 seconds
160 ml/m.sup.2
16 l
development
Bleach-fixation
34.7 ± 0.5° C.
45 seconds
215 ml/m.sup.2
16 l
Stabilization 1
30 to 34° C.
30 seconds 10 l
Stabilization 2
30 to 34° C.
30 seconds 10 l
Stabilization 3
30 to 34° C.
30 seconds
245 ml/m.sup.2
10 l
Drying 60 to 80° C.
60 seconds
______________________________________
Stabilization was conducted while supplying the replenisher in the direction from stabilization step 3 to 1 by the counter-current method. The processing solutions used in the respective processes had the following compositions.
______________________________________
Color developer
Tank solution
Replenisher
______________________________________
Pure water 800 ml 800 ml
Triethanolamine 8 g 10 g
N,N-diethylhydroxylamine
5 g 7 g
Potassium chloride 2 g 1.1 g
N-ethyl-N-(β-methanesulfonamido-
5 g 7.4 g
ethyl-3-methyl-4-aminoaniline sulfate
Sodium tetrapolyphosphate
2 g 2.8 g
Potassium carbonate 30 g 30 g
Potassium sulfite 0.2 g 0.3 g
Brightening agent 4,4'-diaminostyl-
1 g 1.2 g
benedisulfonic acid derivative
______________________________________
Water was added to make a total quantity of 1 l, and pH was adjusted to 10.2.
______________________________________
Bleach-fixer (tank solution and replenisher)
______________________________________
Water 800 ml
Iron (II) ammonium ethylenediaminetetraacetate
60 g
Ethylenediaminetetraacetic acid
3 g
Ammonium thiosulfate (70% aqueous solution)
100 ml
Ammonium sulfite (40% aqueous solution)
27.5 ml
______________________________________
Water was added to make a total quantity of 1 l, and potassium carbonate or glacial acetic acid was added to obtain a pH of 5.7.
______________________________________
Stabilizer (tank solution and replenisher)
______________________________________
Water 800 ml
5-chloro-2-methyl-4-isothiazolin-3-one
1 g
1-hydroxyethylidene-1,1-diphosphonic acid
2 g
______________________________________
Water was added to make a total quantity of 1l, and sulfuric acid or potassium hydroxide was added to obtain a pH of 7.0.
Light fastness and sensitivity were evaluated in the same manner as in Example 1. Figures for sensitivity are expressed as percent sensitivity relative to the sensitivity of each sample at initiation of continuous processing. The results are shown in Tables 6 and 7.
TABLE 6
__________________________________________________________________________
Dye image Oxidation Relative
Residual
Sample No.
stabilizer
potential (mV)
Yellow coupler
Sensitivity
rate (%)
__________________________________________________________________________
201 (comparative)
Not added Example coupler
89 53
Y-51
202 (comparative)
Comparative
2060 Example coupler
84 72
compound YST-1 Y-51
203 (comparative)
Comparative
1400 Example coupler
90 62
compound YST-2 Y-51
204 (inventive)
Example compound
1420 Example coupler
88 75
I-1 Y-51
205 (inventive)
Example Compound
1540 Example coupler
89 78
I-6 Y-51
206 (inventive)
Example Compound
1510 Example coupler
90 76
I-8 Y-51
207 (inventive)
Example Compound
1590 Example coupler
85 77
I-17 Y-51
208 (inventive)
Example compound
1200 Example coupler
88 78
I-21 Y-51
209 (inventive)
Example compound
1600 Example coupler
85 78
I-22 Y-51
210 (inventive)
Example Compound
1580 Example coupler
90 78
I-25 Y-51
211 (comparative)
Not added Example coupler
94 50
Y-3
212 (comparative)
Comparative
2060 Example coupler
76 74
compound YST-1 Y-3
213 (comparative)
Comparative
1400 Example coupler
92 57
compound YST-2 Y-3
214 (inventive)
Example compound
1420 Example coupler
93 84
I-1 Y-3
215 (inventive)
Example Compound
1540 Example coupler
90 86
I-6 Y-3
216 (inventive)
Example Compound
1510 Example coupler
94 82
I-8 Y-3
217 (inventive)
Example Compound
1590 Example coupler
92 88
I-17 Y-3
218 (inventive)
Example compound
1200 Example coupler
85 78
I-21 Y-3
219 (inventive)
Example compound
1600 Example coupler
88 76
I-22 Y-3
220 (inventive)
Example Compound
1580 Example coupler
90 81
I-25 Y-3
221 (comparative)
Comparative
2060 Example coupler
78 82
compound YST-1 Y-20
__________________________________________________________________________
TABLE 7
__________________________________________________________________________
Dye image
Oxidation Relative
Residual
Sample No.
stabilizer
potential (mV)
Yellow coupler
sensitivity
rate (%)
__________________________________________________________________________
222 (inventive)
Example 1420 Example coupler
94 87
compound I-1 Y-20
223 (inventive)
Example 1540 Example coupler
92 86
compound I-6 Y-20
224 (inventive)
Example 1510 Example coupler
94 84
compound I-8 Y-20
225 (comparative)
Comparative
2060 Example coupler
76 81
compound YST-1 Y-36
226 (inventive)
Example 1420 Example coupler
93 86
compound I-1 Y-36
227 (inventive)
Example 1540 Example coupler
92 87
compound I-6 Y-36
228 (inventive)
Example 1510 Example coupler
94 84
compound I-8 Y-36
229 (comparative)
Comparative
2060 Example coupler
78 82
compound YST-1 Y-46
230 (inventive)
Example 1420 Example coupler
94 85
compound I-1 Y-46
231 (inventive)
Example 1540 Example coupler
94 85
compound I-6 Y-46
232 (inventive)
Example 1510 Example coupler
92 86
compound I-8 Y-46
__________________________________________________________________________
As is evident from Tables 6 and 7, the silver halide photographic light-sensitive material of the present invention undergoes little change in the sensitivity thereof between initiation and completion of continuous processing and has excellent light fastness.
Sample No. 301 was prepared in the same manner as with sample No. 102 of Example 1 except that layer 5 (red-sensitive layer) was replaced as described in Table 8 below.
10.7 g of a cyan coupler (comparative coupler C-1), 0.33 g of an antistaining agent HQ-1, 6.7 g of a high boiling organic solvent DOP and 6.7 g of HBS-1 were dissolved in 60 ml of ethyl acetate. This solution was emulsified and dispersed in 215 ml of a 10% aqueous solution of gelatin containing 10 ml of 10% sodium triisopropylnaphthalenesulfonate SU-1 using a homogenizer to yield a cyan coupler dispersion.
This dispersion was mixed with a red-sensitive silver chlorobromide emulsion Em-3 (containing 7.0 g of silver) and a gelatin solution for coating to yield a fifth layer coating solution.
TABLE 8
______________________________________
Layer 5 (red-
Gelatin 1.30
sensitive layer)
Red-sensitive silver
chlorobromide 0.21
emulsion (Em-3)
Cyan coupler (C-1)
0.32
Antistaining agent (HQ-1)
0.01
HBS-1 0.20
DOP 0.20
______________________________________
Next, sample Nos. 302 through 315 were prepared in the same manner as above except that the cyan coupler C-1 for layer 5 was replaced as shown in Tables 9 and 10 and 0.1 mmol/m2 of each of the dye image stabilizers shown in Tables 9 and 10 was added to layer 5. The resulting samples were each subjected to red light exposure through an optical wedge using the sensitometer KS-7 (produced by Konica Corporation) and processed in accordance with the procedures described in Example 2, after which they were evaluated in the same manner as in Example 1. Figures for sensitivity are expressed as percent sensitivity relative to the sensitivity of sample No. 301. The results are shown in Tables 9 and 10.
TABLE 9
__________________________________________________________________________
Dye image
Oxidation Relative
Residual
Sample No.
stabilizer
potential (mV)
Cyan coupler
sensitivity
rate (%)
__________________________________________________________________________
301 (comparative)
Not added Example coupler
100 72
C-1
302 (comparative)
Comparative
2060 Example coupler
82 80
compound YST-1 C-1
303 (comparative)
Comparative
1400 Example coupler
90 75
compound YST-2 C-1
304 (inventive)
Example 1420 Example coupler
96 90
compound I-1 C-1
305 (inventive)
Example 1540 Example coupler
101 83
compound I-6 C-1
306 (inventive)
Example 1510 Example coupler
102 83
compound I-8 C-1
307 (inventive)
Example 1590 Example coupler
94 85
compound I-17 C-1
308 (inventive)
Example 1200 Example coupler
95 83
compound I-21 C-1
309 (inventive)
Example 1600 Example coupler
93 84
compound I-22 C-1
310 (inventive)
Example 1580 Example coupler
92 80
compound I-25 C-1
311 (comparative)
Not added Example coupler
98 74
C-4
312 (comparative)
Comparative
2060 Example coupler
81 82
compound YST-1 C-4
313 (comparative)
Comparative
1400 Example coupler
88 75
compound YST-2 C-4
314 (inventive)
Example 1420 Example coupler
87 90
compound I-1 C-4
315 (inventive)
Example 1540 Example coupler
99 92
compound I-6 C-4
316 (inventive)
Example 1510 Example coupler
101 92
compound I-8 C-4
317 (inventive)
Example 1590 Example coupler
90 90
compound I-17 C-4
318 (inventive)
Example 1200 Example coupler
91 90
compound I-21 C-4
319 (inventive)
Example 1600 Example coupler
92 88
compound I-22 C-4
320 (inventive)
Example 1580 Example coupler
93 89
compound I-25 C-4
321 (comparative)
Not added Example coupler
94 42
PC-1
__________________________________________________________________________
TABLE 10
__________________________________________________________________________
Dye image
Oxidation Relative
Residual
Sample No.
stabilizer
potential (mV)
Cyan coupler
sensitivity
rate (%)
__________________________________________________________________________
322 (comparative)
Comparative
2060 Example coupler
75 60
compound YST-1 PC-1
323 (comparative)
Comparative
1400 Example coupler
90 45
compound YST-2 PC-1
324 (inventive)
Example 1420 Example coupler
91 84
compound I-1 PC-1
325 (inventive)
Example 1540 Example coupler
98 86
compound I-6 PC-1
326 (inventive)
Example 1510 Example coupler
99 82
compound I-8 PC-1
327 (comparative)
Not added Example coupler
102 74
CA-1
328 (comparative)
Comparative
2060 Example coupler
85 82
compound YST-1 CA-1
329 (comparative)
Comparative
1400 Example coupler
100 75
compound YST-2 CA-1
330 (inventive)
Example 1420 Example coupler
98 93
compound I-1 CA-1
331 (inventive)
Example 1540 Example coupler
103 85
compound I-6 CA-1
332 (inventive)
Example 1510 Example coupler
103 85
compound I-8 CA-1
__________________________________________________________________________
As is evident from Tables 9 and 10, the samples incorporating comparative compound YST-1 as a dye image stabilizer, which has an ester group in the molecular structure thereof and an oxidation potential of 2060 mV (sample Nos. 302, 312, 322 and 328), had reduced sensitivity, irrespective of which cyan coupler was used. Also, the samples incorporating comparative compound YST-2 as a dye image stabilizer, which had no ester group in the molecular structure thereof but had an oxidation potential of 1400 mV, falling in the range of the present invention (sample Nos. 303, 313, 323 and 329), had no sufficient light fastness, though the sensitivity did not decrease. On the other hand, the use of a compound relating to the present invention offered sufficient sensitivity and excellent light fastness.
Silver halide color photographic light-sensitive material sample No. 401 was prepared by coating the following layers from the support side on a polyethylene-laminated paper support (titanium oxide content 2.7 g/m2).
Layer 1: A layer containing 1.2 g/m2 of gelatin, 0.32 g/m2 (as silver; the same applies below) of a blue-sensitive silver chlorobromide emulsion (silver chloride content 99.3 mol %) and 0.80 g/m2 of a yellow coupler Y-51 dissolved in 0.3 g/m2 of dioctyl phthalate (hereinafter referred to as DOP).
Layer 2: An interlayer comprising 0.7 g/m2 of gelatin, 30 g/m2 of an anti-irradiation dye AI-1 and 20 g/m2 of another anti-irradiation dye M-2.
Layer 3: A layer containing 1.25 g/m2 of gelatin, 0.20 g/m2 of a green-sensitive silver chlorobromide emulsion (silver chloride content 99.5 mol %) and 0.26 g/m2 of a magenta coupler M-2 dissolved in 0.30 g/m2 of DOP.
Layer 4: An interlayer comprising 1.2 g/m2 of gelatin.
Layer 5: A layer containing 1.4 g/m2 of gelatin, 0.20 g/m2 of a red-sensitive silver chlorobromide emulsion (silver chloride content 99.7 mol %) and 0.40 g/m2 of a cyan coupler C-4 dissolved in 0.20 g/m2 of dibutyl phthalate (hereinafter referred to as DBP).
Layer 6: An interlayer comprising 1.0 g/m2 of gelatin and 0.3 g/m2 of a UV absorbent UV-1 dissolved in 0.2 g/m2 of DOP.
Layer 7: A layer containing 0.5 g/m2 of gelatin.
As a hardener, 2,4-dichloro-6-hydroxy-s-triazine sodium was added to layers 2, 4 and 7 to 0.017 g per gram of gelatin. ##STR185##
Sample Nos. 402 through 422 were prepared in the same manner as with sample No. 401 except that yellow coupler Y-51 in layer 1 was replaced by each of the yellow couplers shown in Table 11 and each of the compounds of the present invention shown in Table 11 was added at 0.6 g/m2.
For these samples, the yellow coupler was added in an amount equal to that of yellow coupler Y-51 in sample No. 401.
Samples Nos. 401 through 422 thus prepared were each subjected to blue light exposure through an optical wedge and then developed as follows.
______________________________________
Developing procedures
Temperature
Time
______________________________________
Color development
34.7 ± 0.3° C.
45 seconds
Bleach-fixation
34.7 ± 0.5° C.
45 seconds
Stabilization 30 to 34° C.
90 seconds
Drying 60 to 80° C.
60 seconds
______________________________________
The processing solutions used in the respective processes had the following compositions.
______________________________________
Color developer
______________________________________
Water 800 ml
Triethanolamine 8 g
N,N-diethylhydroxylamine 5 g
Potassium chloride 2 g
N-ethyl-N-(β-methanesulfonamidoethyl-3-methyl-
5 g
4-aminoaniline sulfate
Sodium tetrapolyphosphate 2 g
Potassium carbonate 30 g
Potassium sulfite 0.2 g
______________________________________
Water was added to make a total quantity of 1l, and pH was adjusted to 10.05.
______________________________________
Bleach-fixer
______________________________________
Iron (III) ammonium ethylenediaminetetraacetate
60 g
Ethylenediaminetetraacetic acid
3 g
Ammonium thiosulfate (70% aqueous solution)
100 ml
Ammonium sulfite (40% aqueous solution)
27.5 ml
______________________________________
Water was added to make a total quantity of 1l, and potassium carbonate or glacial acetic acid was added to obtain a pH of 5.7.
______________________________________
Stabilizer
______________________________________
5-chloro-2-methyl-4-isothiazolin-3-one
1 g
1-hydroxyethylidene-1,1-diphosphonic acid
2 g
______________________________________
Water was added to make a total quantity of 1l, and sulfuric acid or potassium hydroxide was added to obtain a pH of 7.0.
With respect to each sample after processing, the maximum density (Dmax) of the blue-sensitive emulsion layer was determined. Also, light fastness was evaluated by calculating the dye image residual rate (%) at an initial density of 1.0 in a 10-day fading test using a fade-O-meter. Also, a negative film was obtained by photographing a color checker (produced by Macbeth Company) using the Konica Color GX-100 (produced by Konica Corporation) and developed. Then, after tone adjustment in the gray portion, this negative film was printed on the above sample Nos. 401 through 422 and processed in the same procedures as above, after which color reproduction for each hue was evaluated. The results are shown in Table 11.
TABLE 11
__________________________________________________________________________
Yellow
Compound of Light
Color
Sample.
coupler in
the present
Maximum
fastness
reproduction*1
No layer 1
invention
density
(%) Red
Green
Yellow
Remark
__________________________________________________________________________
401 Y-51 -- 2.62 72 B C C Comparative
402 Y-51 II-10 2.65 91 B C C Comparative
403 Y-2 -- 2.41 53 A A A Comparative
404 Y-2 II-10 2.50 92 A A A Inventive
405 Y-2 II-1 2.51 89 A A A Inventive
406 Y-2 II-4 2.52 89 A A A Inventive
407 Y-2 II-17 2.50 91 A A A Inventive
408 Y-2 II-18 2.51 90 A A A Inventive
409 Y-3 II-1 2.49 90 A A A Inventive
410 Y-3 II-4 2.47 89 A A A Inventive
411 Y-3 II-10 2.51 91 A A A Inventive
412 Y-3 II-17 2.48 90 A A A Inventive
413 Y-3 II-18 2.50 88 A A A Inventive
414 Y-36 II-1 2.48 89 A A A Inventive
415 Y-36 II-4 2.51 91 A A A Inventive
416 Y-36 II-10 2.50 93 A A A Inventive
417 Y-36 II-17 2.53 91 A A A Inventive
418 Y-36 II-18 2.52 90 A A A Inventive
419 Y-46 II-4 2.49 85 A A A Inventive
420 Y-46 II-10 2.51 88 A A A Inventive
421 Y-46 II-17 2.51 86 A A A Inventive
422 Y-46 II-18 2.48 85 A A A Inventive
__________________________________________________________________________
*1: Color reproduction (hue, chromaticity) C = poor; B = slightly poor; A
= good.
As is evident from Table 11, sample Nos. 401 and 402, which incorporated a yellow coupler not represented by formula Y-I, had a high maximum density but poor color reproducibility.
On the other hand, sample No. 403, which incorporated a yellow coupler represented by formula Y-I, cannot be said to be satisfactory as to maximum density and light fastness, though the color reproducibility improved. In contrast, sample Nos. 404 through 422 of the present invention all had a high maximum density, excellent light fastness and a sufficient level of color reproducibility.
Claims (2)
1. A silver halide light-sensitive photographic material comprising a support having provided thereon, a silver halide emulsion layer containing a compound represented by Formula II, and a cyan coupler represented by Formula C-I or CII; ##STR186## wherein R21 and R22 independently represent hydrogen or alkyl having 1 to 5 carbon atoms; J represents alkylene or a simple bond; R23 represents a heterocyclic residue; ##STR187## wherein RC1 represents alkyl having 2 to 6 carbon atoms; Rc2 represents a ballast group; Zc represents hydrogen or a group capable of splitting off upon coupling with the oxidation product of a developing agent, ##STR188## wherein Rc1 represents alkyl, cycloalkyl, aryl or a heterocyclic group; Rc2 represents a ballast group; Rc3 represents hydrogen, halogen, alkyl or alkoxy; Rc1 and Rc3 may combine to form a ring; Zc represents hydrogen or an atom or group capable of splitting off upon coupling with the oxidation product of a developing agent.
2. A silver halide light-sensitive photographic material comprising a support having provided thereon, a plurality of silver halide emulsion layers including at least a first silver halide emulsion layer containing a compound represented by Formula II, and a yellow coupler represented by Formula Y-I; and a second silver halide emulsion layer containing a cyan coupler represented by Formula C-I or C-II, and a compound of Formula II; ##STR189## wherein R21 and R22 independently represent hydrogen or alkyl having 1 to 5 carbon atoms; J represents alkylene or a simple bond; R23 represents a heterocyclic residue; ##STR190## wherein R1 represents alkyl or cycloalkyl; R2 represents alkyl, cycloalkyl, aryl or acyl; R3 represents a group capable of being a substituent on a benzene ring; n represents 0 or 1; X1 represents a group capable of splitting off upon coupling with the oxidation product of a developing agent; Y1 represents an organic group; ##STR191## wherein Rc1 represents alkyl having 2 to 6 carbon atoms; Rc2 represents a ballast group; Zc represents hydrogen or a group capable of splitting off upon coupling with the oxidation product of a developing agent, ##STR192## wherein Rc1 represents alkyl, cycloalkyl, aryl or a heterocyclic group; Rc2 represents a ballast group; Rc3 represents hydrogen, halogen, alkyl or alkoxy; Rc1 and Rc3 may combine to form a ring; Zc represents hydrogen or an atom or group capable of splitting off upon coupling with the oxidation product of a developing agent.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3185114A JP2914790B2 (en) | 1991-06-28 | 1991-06-28 | Silver halide photographic material |
| JP3-185114 | 1991-06-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| USH1429H true USH1429H (en) | 1995-04-04 |
Family
ID=16165111
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US07/901,089 Abandoned USH1429H (en) | 1991-06-28 | 1992-06-19 | Silver halide photographic light-sensitive material |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | USH1429H (en) |
| EP (1) | EP0520412B1 (en) |
| JP (1) | JP2914790B2 (en) |
| DE (1) | DE69229848D1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0585679A1 (en) * | 1992-09-01 | 1994-03-09 | Konica Corporation | Method for forming a photographic color image |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0111448A2 (en) * | 1982-12-08 | 1984-06-20 | Ciba-Geigy Ag | Colour-photographic recording material |
| US4540658A (en) * | 1982-06-29 | 1985-09-10 | Konishiroku Photo Industry Co. Ltd. | Silver halide color photographic products |
| EP0159912A1 (en) * | 1984-04-20 | 1985-10-30 | Konica Corporation | Silver halide photographic light-sensitive material |
| US4840878A (en) * | 1986-01-23 | 1989-06-20 | Fuji Photo Film Co., Ltd. | Method of color image formation using a high chloride emulsion and a developer free of benzyl alcohol |
| US4923783A (en) * | 1987-10-14 | 1990-05-08 | Fuji Photo Film Co., Ltd. | Silver halide photographic materials and method of processing the same |
| EP0393718A2 (en) * | 1989-04-21 | 1990-10-24 | Konica Corporation | Silver halide color photographic material |
| US5009989A (en) * | 1987-09-17 | 1991-04-23 | Fuji Photo Film Co., Ltd. | Silver halide photographic material |
| US5059515A (en) * | 1987-09-28 | 1991-10-22 | Ciba-Geigy Ag | Stabilizers for color photographic recording materials |
| US5084375A (en) * | 1984-05-26 | 1992-01-28 | Fuji Photo Film Co., Ltd. | Color photographic light-sensitive material |
-
1991
- 1991-06-28 JP JP3185114A patent/JP2914790B2/en not_active Expired - Fee Related
-
1992
- 1992-06-19 US US07/901,089 patent/USH1429H/en not_active Abandoned
- 1992-06-24 DE DE69229848T patent/DE69229848D1/en not_active Expired - Lifetime
- 1992-06-24 EP EP92110647A patent/EP0520412B1/en not_active Expired - Lifetime
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4540658A (en) * | 1982-06-29 | 1985-09-10 | Konishiroku Photo Industry Co. Ltd. | Silver halide color photographic products |
| EP0111448A2 (en) * | 1982-12-08 | 1984-06-20 | Ciba-Geigy Ag | Colour-photographic recording material |
| US4629682A (en) * | 1982-12-08 | 1986-12-16 | Ciba-Geigy Ag | Recording material for color photography |
| EP0159912A1 (en) * | 1984-04-20 | 1985-10-30 | Konica Corporation | Silver halide photographic light-sensitive material |
| US5084375A (en) * | 1984-05-26 | 1992-01-28 | Fuji Photo Film Co., Ltd. | Color photographic light-sensitive material |
| US4840878A (en) * | 1986-01-23 | 1989-06-20 | Fuji Photo Film Co., Ltd. | Method of color image formation using a high chloride emulsion and a developer free of benzyl alcohol |
| US5009989A (en) * | 1987-09-17 | 1991-04-23 | Fuji Photo Film Co., Ltd. | Silver halide photographic material |
| US5059515A (en) * | 1987-09-28 | 1991-10-22 | Ciba-Geigy Ag | Stabilizers for color photographic recording materials |
| US4923783A (en) * | 1987-10-14 | 1990-05-08 | Fuji Photo Film Co., Ltd. | Silver halide photographic materials and method of processing the same |
| EP0393718A2 (en) * | 1989-04-21 | 1990-10-24 | Konica Corporation | Silver halide color photographic material |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0520412A1 (en) | 1992-12-30 |
| DE69229848D1 (en) | 1999-09-30 |
| EP0520412B1 (en) | 1999-08-25 |
| JP2914790B2 (en) | 1999-07-05 |
| JPH0627617A (en) | 1994-02-04 |
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