JPS62278552A - Silver halide color photosensitive material - Google Patents
Silver halide color photosensitive materialInfo
- Publication number
- JPS62278552A JPS62278552A JP12147786A JP12147786A JPS62278552A JP S62278552 A JPS62278552 A JP S62278552A JP 12147786 A JP12147786 A JP 12147786A JP 12147786 A JP12147786 A JP 12147786A JP S62278552 A JPS62278552 A JP S62278552A
- Authority
- JP
- Japan
- Prior art keywords
- silver
- coupler
- color
- group
- silver halide
- 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.)
- Pending
Links
- -1 Silver halide Chemical class 0.000 title claims abstract description 138
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 114
- 239000004332 silver Substances 0.000 title claims abstract description 114
- 239000000463 material Substances 0.000 title claims abstract description 52
- 239000000839 emulsion Substances 0.000 claims abstract description 120
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 44
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 238000005691 oxidative coupling reaction Methods 0.000 claims description 2
- 150000004989 p-phenylenediamines Chemical class 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 abstract description 10
- 239000003381 stabilizer Substances 0.000 abstract description 10
- 238000010521 absorption reaction Methods 0.000 abstract description 9
- 239000004014 plasticizer Substances 0.000 abstract description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 120
- 239000000975 dye Substances 0.000 description 91
- 238000000034 method Methods 0.000 description 74
- 150000001875 compounds Chemical class 0.000 description 68
- 239000000243 solution Substances 0.000 description 56
- 230000001235 sensitizing effect Effects 0.000 description 53
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 45
- 230000008569 process Effects 0.000 description 44
- 108010010803 Gelatin Proteins 0.000 description 43
- 239000008273 gelatin Substances 0.000 description 43
- 229920000159 gelatin Polymers 0.000 description 43
- 235000019322 gelatine Nutrition 0.000 description 43
- 235000011852 gelatine desserts Nutrition 0.000 description 43
- 239000002253 acid Substances 0.000 description 38
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 33
- 238000011282 treatment Methods 0.000 description 29
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 27
- 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 25
- 229910021612 Silver iodide Inorganic materials 0.000 description 25
- 239000002245 particle Substances 0.000 description 25
- 229940045105 silver iodide Drugs 0.000 description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 21
- 238000011161 development Methods 0.000 description 21
- 238000012545 processing Methods 0.000 description 20
- 150000003839 salts Chemical class 0.000 description 20
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 18
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 15
- 238000009835 boiling Methods 0.000 description 15
- 239000000084 colloidal system Substances 0.000 description 14
- 239000003960 organic solvent Substances 0.000 description 14
- 239000012190 activator Substances 0.000 description 13
- 238000004061 bleaching Methods 0.000 description 13
- 239000007844 bleaching agent Substances 0.000 description 13
- 239000003112 inhibitor Substances 0.000 description 13
- 238000000576 coating method Methods 0.000 description 9
- 239000006185 dispersion Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 150000004820 halides Chemical class 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- 229910001961 silver nitrate Inorganic materials 0.000 description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 150000007513 acids Chemical class 0.000 description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000006096 absorbing agent Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000000049 pigment Substances 0.000 description 6
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 6
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 6
- 108010002352 Interleukin-1 Proteins 0.000 description 5
- 206010070834 Sensitisation Diseases 0.000 description 5
- 235000011054 acetic acid Nutrition 0.000 description 5
- 229940125904 compound 1 Drugs 0.000 description 5
- 230000008878 coupling Effects 0.000 description 5
- 238000010168 coupling process Methods 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 150000007524 organic acids Chemical class 0.000 description 5
- 239000004848 polyfunctional curative Substances 0.000 description 5
- 235000011118 potassium hydroxide Nutrition 0.000 description 5
- 230000008313 sensitization Effects 0.000 description 5
- 230000000087 stabilizing effect Effects 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 5
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 108010002386 Interleukin-3 Proteins 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 4
- 239000000908 ammonium hydroxide Substances 0.000 description 4
- CJPQIRJHIZUAQP-MRXNPFEDSA-N benalaxyl-M Chemical compound CC=1C=CC=C(C)C=1N([C@H](C)C(=O)OC)C(=O)CC1=CC=CC=C1 CJPQIRJHIZUAQP-MRXNPFEDSA-N 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 4
- 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 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 235000011181 potassium carbonates Nutrition 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000003755 preservative agent Substances 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000011241 protective layer Substances 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- CNGYZEMWVAWWOB-VAWYXSNFSA-N 5-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-[(e)-2-[4-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-sulfophenyl]ethenyl]benzenesulfonic acid Chemical compound N=1C(NC=2C=C(C(\C=C\C=3C(=CC(NC=4N=C(N=C(NC=5C=CC=CC=5)N=4)N(CCO)CCO)=CC=3)S(O)(=O)=O)=CC=2)S(O)(=O)=O)=NC(N(CCO)CCO)=NC=1NC1=CC=CC=C1 CNGYZEMWVAWWOB-VAWYXSNFSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 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 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 3
- 108010002350 Interleukin-2 Proteins 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical class O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 101150004094 PRO2 gene Proteins 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000002738 chelating agent Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 235000005985 organic acids Nutrition 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 2
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 description 2
- XNCSCQSQSGDGES-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]propyl-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)C(C)CN(CC(O)=O)CC(O)=O XNCSCQSQSGDGES-UHFFFAOYSA-N 0.000 description 2
- DETXZQGDWUJKMO-UHFFFAOYSA-N 2-hydroxymethanesulfonic acid Chemical compound OCS(O)(=O)=O DETXZQGDWUJKMO-UHFFFAOYSA-N 0.000 description 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound 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
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- ONIBWKKTOPOVIA-BYPYZUCNSA-N L-Proline Chemical compound OC(=O)[C@@H]1CCCN1 ONIBWKKTOPOVIA-BYPYZUCNSA-N 0.000 description 2
- FZERHIULMFGESH-UHFFFAOYSA-N N-phenylacetamide Chemical compound CC(=O)NC1=CC=CC=C1 FZERHIULMFGESH-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 description 2
- 229940107816 ammonium iodide Drugs 0.000 description 2
- 229940101006 anhydrous sodium sulfite Drugs 0.000 description 2
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000006224 matting agent Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 235000013336 milk Nutrition 0.000 description 2
- 239000008267 milk Substances 0.000 description 2
- 210000004080 milk Anatomy 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 2
- 239000007764 o/w emulsion Substances 0.000 description 2
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 230000002335 preservative effect Effects 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 235000009518 sodium iodide Nutrition 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 125000005504 styryl group Chemical group 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 2
- 229920001059 synthetic polymer Polymers 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- ZRHUHDUEXWHZMA-UHFFFAOYSA-N 1,4-dihydropyrazol-5-one Chemical compound O=C1CC=NN1 ZRHUHDUEXWHZMA-UHFFFAOYSA-N 0.000 description 1
- QIVYTYXBBRAXNG-UHFFFAOYSA-N 2-(2-hydroxyethylimino)acetic acid Chemical class OCCN=CC(O)=O QIVYTYXBBRAXNG-UHFFFAOYSA-N 0.000 description 1
- MWGATWIBSKHFMR-UHFFFAOYSA-N 2-anilinoethanol Chemical compound OCCNC1=CC=CC=C1 MWGATWIBSKHFMR-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- NEAQRZUHTPSBBM-UHFFFAOYSA-N 2-hydroxy-3,3-dimethyl-7-nitro-4h-isoquinolin-1-one Chemical compound C1=C([N+]([O-])=O)C=C2C(=O)N(O)C(C)(C)CC2=C1 NEAQRZUHTPSBBM-UHFFFAOYSA-N 0.000 description 1
- YCMLQMDWSXFTIF-UHFFFAOYSA-N 2-methylbenzenesulfonimidic acid Chemical group CC1=CC=CC=C1S(N)(=O)=O YCMLQMDWSXFTIF-UHFFFAOYSA-N 0.000 description 1
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- 239000002344 surface layer Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000003831 tetrazolyl group Chemical group 0.000 description 1
- 150000003475 thallium Chemical class 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 150000003567 thiocyanates Chemical class 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- HERBOKBJKVUALN-UHFFFAOYSA-K trisodium;2-[bis(carboxylatomethyl)amino]acetate;hydrate Chemical compound O.[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CC([O-])=O HERBOKBJKVUALN-UHFFFAOYSA-K 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 239000004711 α-olefin Substances 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
- G03C7/32—Colour coupling substances
- G03C7/36—Couplers containing compounds with active methylene groups
- G03C7/38—Couplers containing compounds with active methylene groups in rings
- G03C7/381—Heterocyclic compounds
- G03C7/382—Heterocyclic compounds with two heterocyclic rings
- G03C7/3825—Heterocyclic compounds with two heterocyclic rings the nuclei containing only nitrogen as hetero atoms
Abstract
Description
【発明の詳細な説明】
１、技術分野
本発明は、色再現性の改良されたハロゲン化銀カラー感
光材料に関する。特に新規なマゼンタカプラーを用いる
事により、色再現性が改良されたハロゲン化銀カラー感
光材料に関する。DETAILED DESCRIPTION OF THE INVENTION 1. Technical Field The present invention relates to a silver halide color photosensitive material with improved color reproducibility. In particular, the present invention relates to a silver halide color photosensitive material with improved color reproducibility by using a new magenta coupler.
■、従米技術
従来から、ハロゲン化銀カラー写真感光材料を画像露光
し、発色現像することにより芳香族第１級アミン系発色
現像主薬の酸化体と発色剤とがカップリング反応を行っ
て、例えばインド７エ／−ル、インドアニリン、イング
ミン、アゾメチン、７エ／キサノン、７エナノンおよび
それらに類似する色素が生成し、色画像が形成されるこ
とは良く知られているところである。このような写真方
式においては通常減色法による色再現方法が採られ、青
感性、緑感性ならびに赤感性の感光性ハロゲン化銀乳剤
層に、それぞれ余色関係にある発色剤、すなわちイエロ
ー、マゼンタおよびシアン１こ発色するカプラーを含有
せしめたハロゲン化銀カラー写真感光材料が使用される
。(2) Conventional technology Conventionally, by imagewise exposing a silver halide color photographic light-sensitive material and performing color development, the oxidized product of an aromatic primary amine color developing agent and a color forming agent undergo a coupling reaction, for example. It is well known that indo7er/-el, indoaniline, ingmin, azomethine, 7er/xanone, 7enanone, and pigments similar to these are produced and color images are formed. In such photographic systems, a subtractive color reproduction method is usually adopted, and color forming agents having additional colors, namely yellow, magenta and A silver halide color photographic material containing a coupler that develops a cyan color is used.
上記のイエａ−色画像を形成させるために用いられるカ
プラーとしでは、例えばアシルアセト７二リド系カプラ
ーがあり、又マゼンタ色画像形成用のカプラーとしては
例えばピッゾロン、ビラゾロベンズイミグゾール、ピッ
ゾロトリフゾールまたはイングゾロン系カプラーが知ら
れており、さらにシアン色画像形成用のカプラーとして
は、例えばフェノールまたはす７トール系カプラーが一
般的に用いられる。Couplers used to form the above-mentioned yellow-a color image include, for example, acylaceto-7 dilide couplers, and couplers for forming magenta color images include, for example, pizzolone, birazolobenzimigsol, and pizzolone. Trifusol or ingzolone couplers are known, and as couplers for forming cyan images, for example, phenol or 7-thol couplers are generally used.
マゼンタ色素を形成するために広く使用されているカプ
ラーは、１，２−ピラゾロ−５−オン類である。この１
．２−ピラゾロ−５−オン類のマゼンタカプラーから形
成される色素は５５０ｎｍ付近の主吸収以外に、４３０
ｎｍ付近の副吸収を有していることが大きな問題であり
、これを解決するために種々の研究がなされてきた。Couplers commonly used to form magenta dyes are 1,2-pyrazolo-5-ones. This one
．． In addition to the main absorption near 550 nm, the dye formed from magenta couplers of 2-pyrazolo-5-ones has an absorption wavelength of 430 nm.
Having sub-absorption in the vicinity of nm is a major problem, and various studies have been conducted to solve this problem.
１．２−ピラゾロ−５−オン類の３位にアニリノ基を有
するマゼンタカプラーが上記副吸収が小さく、特にプリ
ント用カラー画像を得るために有用であることが、例え
ば米国特許第２，３４３，７０３号、英国特許第１，０
５９，９９４号等公報に記載されている。It has been reported, for example, in U.S. Pat. No. 2,343, that magenta couplers having an anilino group at the 3-position of 1.2-pyrazolo-5-ones have small side absorption and are particularly useful for obtaining color images for printing. No. 703, British Patent No. 1,0
It is described in publications such as No. 59,994.
しかしながら、４３０ｎ−付近の吸収を完全になくせた
わけではなく、更に改善が望まれている。However, absorption near 430n- has not been completely eliminated, and further improvement is desired.
上記マゼンタカプラーの４３０ｎ−付近の副吸収を減少
させるための別の手段として、英国特許第１．０４７，
６１２号に記載されているビラゾロベンズイミダゾール
類、米国特許第３，７７０，４４７号に記載のイングゾ
ロン類、また同第３，７２５，０６７号、英国特許第１
，２５２，４１８号、同第１，３３４，５１５号に記載
のピラゾロｌＪ７ゾール顕等のマゼンタカプラーが提案
されている。これらの内、米国特許第３，７２５．０６
７号、英国特許第１，２５２，４１８号、同第１，３３
４，５１５号に記載されたＩＨ−ピラゾロ−［３，２−
Ｃｌ−５−トリアゾール型カプラーから形成される色素
は、４３０ｎ−付近の副吸収が、前記の３位にアニリノ
基を有する１、２−ピラゾロ−５−オン類から形成され
る色素に比べて者しく小さく色再現上好ましく、さらに
、光、熱、湿度に対する未発色部のＹ−ステインの発生
も極めて小さく好ましい利点を有するものである。As another means for reducing the side absorption near 430n of the magenta coupler, British Patent No. 1.047,
3,770,447, as well as U.S. Pat. No. 3,725,067 and British Patent No. 1.
Magenta couplers such as the pyrazolo IJ7 sol microscope described in , 252,418 and 1,334,515 have been proposed. Among these, U.S. Patent No. 3,725.06
7, British Patent No. 1,252,418, British Patent No. 1,33
IH-pyrazolo-[3,2-
The dye formed from the Cl-5-triazole type coupler has a sub-absorption near 430n-, compared to the dye formed from the 1,2-pyrazol-5-one having an anilino group at the 3-position. It has the advantage of being very small and favorable in terms of color reproduction, and also has the advantage that the occurrence of Y-stain in uncolored areas is very small when exposed to light, heat, and humidity.
しかしながら、ＩＨ−ピラゾロ−［３，２−Ｃｌ−ｓ
）リアゾール型カプラーから形成され゛るアゾメチン
色素の光に対する堅牢性は着しく低く、その上、前記色
素は光により変色し易く、カラー写真材料、特にプリン
ト系カラー写真材料の性能を着しく損なうものであり、
プリント系カラー写真材料には実用化されていない。However, IH-pyrazolo-[3,2-Cl-s
) The light fastness of azomethine dyes formed from lyazole couplers is rather low, and in addition, the dyes are easily discolored by light, which seriously impairs the performance of color photographic materials, especially printed color photographic materials. and
It has not been put to practical use in printed color photographic materials.
■１発明の目的
本発明は上記の問題点に鑑みなされたものであり、本発
明の第１の目的は、副吸収の少ない色素を形成する新規
カプラーを提供する事にある。(1) Purpose of the Invention The present invention has been made in view of the above-mentioned problems, and the first object of the present invention is to provide a new coupler that forms a dye with little side absorption.
本発明の第２の目的は色再現性にすぐれたハロゲン化銀
カラー感光材料を提供する事にある。A second object of the present invention is to provide a silver halide color photosensitive material with excellent color reproducibility.
■０発明のｌ１１ｅ。■0 invention l11e.
本発明の目的は、支持体上に、下記一般式［Ｉ］で示さ
れるマゼンタカプラーを含有するハロゲン化銀乳剤層を
少なくとも１層有することを特徴とするハロゲン化銀カ
ラー感光材料により達成できる。The object of the present invention can be achieved by a silver halide color light-sensitive material having on a support at least one silver halide emulsion layer containing a magenta coupler represented by the following general formula [I].
一般式［１Ｆ
式中、Ｚｂ 、Ｚｂ 、Ｚｅ 、Ｚｄ 、Ｚｅは、メチ
ン基、置換メチン基又は、窒素原子を表わすが、Ｚｂ、
Ｚｃ、Ｚｅのいずれか１つは、ｐ−７ヱニレンノアミン
系力ラー発色現像主薬の酸化体と酸化カップリング反応
を行う、メチン基又は置換メチン基（以後、活性メチン
基と略称する）である。General formula [1F In the formula, Zb , Zb , Ze , Zd , and Ze represent a methine group, a substituted methine group, or a nitrogen atom, but Zb,
Either one of Zc and Ze is a methine group or a substituted methine group (hereinafter abbreviated as an active methine group) that performs an oxidative coupling reaction with an oxidized product of a p-7enylenenoamine type color developing agent.
但し、以下の（１）〜 （６）の場合を除く一般式［１
］で表わされるアゾール糸化合物の中で好ましいものは
以下の一般式［Ｉ［］ 〜［Ｘ Ｘ Ｘ Ｖ ］で表わ
される。However, except for the following cases (1) to (6), general formula [1
] Preferred azole thread compounds are represented by the following general formulas [I[] to [XXXV].
一般式［Ｔ［］ 一般式［ＨＩ
］一般式［１’Ｖ］ 一般式［Ｖ］一
般式［■ｌ 一般式【■ｌ一般
式［■］ 一般式［ＸＸｌ一般式［Ｘ
］ 一般式［ＸＸｌ−ｆｆ式［Ｘｌ
ｌ］ 一般式［ＸＩＩＩ］一般式［
：ｌ’ｌ 一般式［ＸＶ］一般式［Ｘ
■］ 一般式［ＸＸｌ［］一般式［Ｘ■
ｊ 一般式［Ｘｆｆ］一般式［ＸＸｌ
一般式［ＸＸＩ］一般式［ＸＸ［］
一般ＸＸＸＸＩ］一般式［ＸＸＩＶｌ
一般式［ＸＸＶ］−ｆｆ式［ＸＸＷ］
一般式［ＸＸ’／ｌ１ｌ一般式［ＸＸＷ］
一般式［ＸＸＩＸ］一般式［×Ｘχ］
−ｆｆ式［ＸＸＸＩ］一般式［ＸＸＸＨ
］ 一般式［ＸＸＸＩ］−を式［ＸＸ
ＸＩＩ／］ 一般式［ＸＸＸＶ］式中、
Ｒ，、Ｒ，は水素原子、ハロゲン原子Ｒ”、 Ｋ＝″
に
二で、Ｒ’ 、、Ｒ“ＩＩＲ＃′ｌは同一でも異なって
いてもよく、各々水素原子、置換基を有してもよいアル
キル基、置換基を有してもよいアリール基を表わす。General formula [T[] General formula [HI
] General formula [1'V] General formula [V] General formula [■l General formula [■l General formula [■] General formula [XXl General formula [X
] General formula [XXl-ff formula [Xl
l] General formula [XIII] General formula [
:l'l General formula [XV] General formula [X
■] General formula [XXl[] General formula [X■
j General formula [Xff] General formula [XXl
General formula [XXI] General formula [XX[]
General XXXXI] General formula [XXIVl
General formula [XXV]-ff formula [XXW]
General formula [XX'/l1l General formula [XXW]
General formula [XXIX] General formula [×Xχ]
-ff formula [XXXI] General formula [XXXH
] The general formula [XXXI]- is replaced with the formula [XX
XII/] In the general formula [XXXV],
R,, R, are hydrogen atoms, halogen atoms R", K="
2, R', , R'IIR#'l may be the same or different and each represents a hydrogen atom, an alkyl group which may have a substituent, and an aryl group which may have a substituent. .
以下に、Ｒ，、Ｒ３で示される置換基の具体的な例を挙
げる。Specific examples of the substituents represented by R, and R3 are listed below.
ハロゲン原子：塩素、臭素、７７素
アルキル基：メチル基、エチル基、１ｓｏ−プロピル基
、ブチル基、ｔ−ブチル基、し−ペンチル基
アルコキシ基：メトキシ基、エトキシ基、ブトキシ基、
５ｅｃ−ブトキシ基、１ｓｏ−ペンチルオキシ基
・
アリールオキシ基：７二／キシ基、β−す７トキシ基等
であるが、このアリール部分には更に置換基を有しても
よい。Halogen atom: chlorine, bromine, 77 alkyl group: methyl group, ethyl group, 1so-propyl group, butyl group, t-butyl group, pentyl group Alkoxy group: methoxy group, ethoxy group, butoxy group,
5ec-butoxy group, 1so-pentyloxy group
- Aryloxy group: 72/xy group, β-su7toxy group, etc., but this aryl moiety may further have a substituent.
アルフキジカルボニル基：上述したアルコキシ基の付い
たカルボニル基を言いメトキシカルボニル基、ペンチル
オキシカルボニル基
カルバモイル基：力ルバモイル基、ジメチルカルバモイ
ル基等のフルキルカルバモイル基スルファモイル基：ス
ル７アモイル基、メチルスル７７モイル基、ツメチルス
ル７７モイル基、エチルスル７７モイル基等のフルキル
スルファモイル基
スルホニル基：メタンスルホニル基、エタンスルホニル
基、ブタンスルホニル基等のフルキルスルホニル基
スルホンアミド基：メタンスルホンアミド基、トルエン
スルホンアミド基等のフルキルスルホンアミド基、アリ
ールスルホンアミド基
アシルアミ７基：アセトアミ７基、ピパロイルアミ７基
、ベンズアミド基等
アリール基：フェニル基、ナフチル基で上述の置換基を
有していてもよい。Alfkidicarbonyl group: Refers to the above-mentioned carbonyl group with an alkoxy group attached. Methoxycarbonyl group, pentyloxycarbonyl group Carbamoyl group: Furkylcarbamoyl group such as rubamoyl group and dimethylcarbamoyl group Sulfamoyl group: Sulfamoyl group, methylsulfo7moyl group Sulfonyl group: Furkylsulfonyl group such as methanesulfonyl group, ethanesulfonyl group, butanesulfonyl group Sulfonamide group: methanesulfonamide group, toluenesulfonamide group Furkylsulfonamide group, arylsulfonamide group etc. Acylamide 7 group: Acetamide 7 group, Piparoylamide group 7 group, Benzamide group etc. Aryl group: Phenyl group, naphthyl group may have the above-mentioned substituents.
Ｒ２，Ｒ，はＲ，、Ｒ，で述べたＲ’１１等を表わす。R2, R, represents R'11 etc. mentioned in R, , R,.
Ｘは：水素原子又は芳香族第１級アミン発色現像生薬の
酸化体とカップリングして色素が形成されるときに離脱
する基を表わす。X represents a hydrogen atom or a group that leaves when a dye is formed by coupling with an oxidized product of an aromatic primary amine color developing crude drug.
具体的には例えばハロゲン原子、アルコキシ基、７１７
−ルオキシ基、７シルオキシ基、７リールチ子と共に炭
素原子、酸素原子、窒素原子、イオウ原子の中から選ば
れた原子と５ないし６貝環を形成するに要する原子群を
表わす、）へテロ環オキシ基を表わす。Specifically, for example, a halogen atom, an alkoxy group, 717
-Heterocycle, which represents a group of atoms necessary to form a 5- or 6-shell ring with an atom selected from carbon, oxygen, nitrogen, and sulfur atoms together with a -ruoxy group, a 7-syloxy group, and a 7-aryl group. Represents an oxy group.
以下に具体的な例を挙げる。Specific examples are given below.
ハロゲン原子：塩素、臭素、７７素
アルフキシ基：エトキシ基、ベンノルオキシ基、メトキ
シエチルカルバモイルメトキシ基、テトラデシルカルバ
モイルメトキシ基等
アリールオキシ基：７ヱノキシ基、４−／トキシ７工／
キシ基、４−二トロフェノキシ基等アシルオキシ基：ア
セトキシ基、ミリストイルオキシ基、ベンゾイルオキシ
基等
アリールチオ基：フェニルチオ基、２−プトキシー５−
オクチルフェニルチオ基、２．５−ジヘキシルオキシフ
ェニルチオ基等
アルキルチオ基：メチルチオ基、オクチルチオ基、ヘキ
サデシルチオ基、ベンノルチオ基、２−（ノエチルアミ
ノ）エチルチオ基、エトキシカルボニルメチルチオ基、
ニドキシエチルチオ基、７１ツキジエチルチオ基等
−Ｎ Ｚ： ピラゾリル基、イミダゾリル基、トリ
アゾリル基、テトラゾリル基
またへテロ環オキシ基としては、例えば１−７ヱニルー
５−テトラゾリルオキシ基、インオキサシリルオキシ基
、４−ビリノニルオキシ基などがある。Halogen atoms: chlorine, bromine, 77 alkoxy group: ethoxy group, benoloxy group, methoxyethylcarbamoylmethoxy group, tetradecylcarbamoylmethoxy group, etc. Aryloxy group: 7enoxy group, 4-/toxy7-en/
Acyloxy groups such as xy group, 4-nitrophenoxy group: acetoxy group, myristoyloxy group, benzoyloxy group, etc. Arylthio group: phenylthio group, 2-ptoxy 5-
Alkylthio groups such as octylphenylthio group, 2.5-dihexyloxyphenylthio group: methylthio group, octylthio group, hexadecylthio group, bennorthio group, 2-(noethylamino)ethylthio group, ethoxycarbonylmethylthio group,
Nidoxyethylthio group, 71-diethylthio group, etc.-NZ: pyrazolyl group, imidazolyl group, triazolyl group, tetrazolyl group, and heterocyclic oxy group, such as 1-7enyl-5-tetrazolyloxy group, indoxyethylthio group, etc. Examples include oxacylyloxy group and 4-bilinonyloxy group.
以下に本発明の化合物の具体例を記すが、本発明はこれ
らにより限定されるものではない。Specific examples of the compounds of the present invention are shown below, but the present invention is not limited thereto.
しｉコ
５９ Ｃｌ２８２Ｓ
本発明の感光材料に用いるハロゲン化銀乳剤には、ハロ
ゲン化銀として臭化銀、沃臭化銀、沃塩化銀、塩臭化銀
、および塩化銀等の通常のハロゲン化銀乳剤に使用され
る任意のものを用いることができる。Shiiko59 Cl282S The silver halide emulsion used in the light-sensitive material of the present invention includes conventional halides such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. Any used in silver emulsions can be used.
ハロゲン化銀乳劉に用いられるハロゲン化銀粒子は、酸
性法、中性法及びアンモニア法のいずれで得られたもの
でもよい、該粒子は一時に成＆させてもよいし、種粒子
をつくった後成長させてもよい０種粒子をつくる方法と
成長させる方法は同じであっても、異なってもよい。The silver halide grains used in the silver halide emulsion may be obtained by any of the acidic method, neutral method, and ammonia method.The grains may be formed all at once, or by forming seed grains. The method for producing and growing the zero-type particles may be the same or different.
ハロゲン化銀乳剤はハロゲン化物イオンと銀イオンを同
時に混合しても、いずれか一方が存在する液中に、他方
を混合してもよい、また、ハロゲン化銀結晶の臨界成長
速度を考慮しつつ、ハロゲン化物イオンと銀イオンを混
合釜内のｐＨ＋ｐＡｆｆをコントロールしつつ逐次同時
に添加することにより生成させてもよい、この方法によ
り、結晶形がｍｉｑ的で粒子サイズが均一に近いハロゲ
ン化ｆｆｉ粒子が得られる。成長後にコンパーツシン法
を用いて、粒子のハロゲン組成を変化させてもよい。Silver halide emulsions can be prepared by mixing halide ions and silver ions at the same time, or by mixing one in a solution where the other is present. , it may be generated by sequentially and simultaneously adding halide ions and silver ions while controlling the pH+pAff in a mixing pot. By this method, halogenated ffi particles with a miq-like crystal shape and a nearly uniform particle size can be produced. can get. After growth, the halogen composition of the particles may be changed using the componentsyn method.
へロデン化ｉ粒子は、粒子を形成する過程及び／又は成
長させる過程で、カドミウム塩、亜鉛塩、鉛塩、タリウ
ム塩、イリノウム塩（錯塩を含む）、ロノクム塩（錯塩
を含む）及び鉄塩（錯塩を含む）から選ばれる少なくと
も１種を用いて金属イオンを添加し、粒子内部に及び／
又は粒子表面にこれらの金属元素を含有させることがで
き、また適当な還元的雰囲気におくことにより、粒子内
部及び／又は粒子表面に還元増感核を付与できる。In the process of particle formation and/or growth, the helodenated i particles contain cadmium salts, zinc salts, lead salts, thallium salts, ilinium salts (including complex salts), lonocum salts (including complex salts), and iron salts. (including complex salts) to add metal ions to the inside of the particles and/or
Alternatively, these metal elements can be contained on the particle surface, and reduction sensitizing nuclei can be provided inside the particle and/or on the particle surface by placing the particle in an appropriate reducing atmosphere.
ハロゲン化銀乳剤は、ハロゲン化銀粒子の成長の終了後
に不要な可溶性塩類を除去してもよいし、あるいは含有
させたままでもよい。Unnecessary soluble salts may be removed from the silver halide emulsion after the growth of silver halide grains is completed, or they may be left contained.
ハロゲン化銀粒子は′、粒子内において均一なノーロデ
ン化銀組成分布を有するものでも、粒子の内部と表面層
とでハロゲン化ｉ岨戊が異なるコア／シェル粒子であっ
てもよい。The silver halide grains may have a uniform silver norodide composition distribution within the grain, or may be core/shell grains in which the halide content differs between the interior and surface layer of the grain.
ハロゲン化銀粒子は、潜像が主として表面に形成される
ような粒子であってもよく、また主として粒子内部に形
成されるような粒子でらよい。The silver halide grains may be such that a latent image is mainly formed on the surface, or may be such that a latent image is mainly formed inside the grain.
へロデン化銀粒子は、里方体、八面体、十四面体のよう
な規則的な結晶形を持つものでもよいし、球状や板状の
ような変則的な結晶形をもつものでもよい、これらの粒
子において、（１１０１面と（１１１１面の比率は任意
のものが使用できる。又、これら結晶形の複合形を持つ
ものでよく、様々な結晶形の粒子が混合されてもよい。Silver herodenide grains may have regular crystal shapes such as cubes, octahedrons, and tetradecahedrons, or irregular crystal shapes such as spherical or plate shapes. In these particles, any ratio of the (1101 plane and (1111 plane) can be used. Also, they may have a composite form of these crystal forms, and particles of various crystal forms may be mixed.
ハロゲン化銀乳剤は、いかなる粒子サイズ分布を持つも
のを用いても構わない１粒子サイズ分布の広い乳剤（多
分散乳剤と称する）を用いてもよいし、粒子サイズ分布
の狭い乳剤（単分散乳剤と称する。ここでいう単分散乳
剤とは、粒径の分布の標準偏差を平均粒径で割ったとき
に、その値が０．２０以下のものをいう、ここで粒径は
球状のハロゲン化銀の場合はその直径を、球状以外の形
状の粒子の場合は、その投影像を同面積の円像に換算し
たときの直径を示す、）を単独又は数種類混合してもよ
い。又、多分散乳剤と単分散乳剤を混合して用いてもよ
い。Silver halide emulsions may have any grain size distribution. Emulsions with a wide grain size distribution (referred to as polydisperse emulsions) may be used, or emulsions with a narrow grain size distribution (monodisperse emulsions) may be used. The monodisperse emulsion referred to here refers to one in which the standard deviation of the grain size distribution divided by the average grain size is 0.20 or less, where the grain size is spherical halogenated emulsion. In the case of silver, the diameter is shown, and in the case of particles having a shape other than spherical, the diameter is shown when the projected image is converted into a circular image of the same area.) may be used alone or in combination. Further, a mixture of a polydisperse emulsion and a monodisperse emulsion may be used.
ハロゲン化銀乳剤は、別々に形成した２種以上のハロゲ
ン化銀乳剤を混合して用いてもよい。The silver halide emulsion may be a mixture of two or more separately formed silver halide emulsions.
ハロゲン化銀乳剤は、常法により化学増感することがで
きる。即ち、硫黄増感法、セレン増感法、還元増感法、
金その他の！金属化合物を用いる貴金属増感法などを単
独で又は組み合わせて用いることができる。Silver halide emulsions can be chemically sensitized by conventional methods. That is, sulfur sensitization method, selenium sensitization method, reduction sensitization method,
Money and more! Noble metal sensitization methods using metal compounds can be used alone or in combination.
ハロゲン化銀乳剤は、写真業界において増感色素として
知られている色素を用いて、所望の波長域に光学的に増
感できる。増感色素は単独で用いてもよいが、２種以上
を組み合わせて用いてもよい、増感色素とともにそれ自
身分光増感作用を持たない色素、あるいは可視光を実質
的に吸収しない化合物であって、増感色素の増感作用を
強める強色増感剤を乳剤中に含有させてもよい。Silver halide emulsions can be optically sensitized to a desired wavelength range using dyes known in the photographic industry as sensitizing dyes. The sensitizing dye may be used alone or in combination of two or more, and together with the sensitizing dye, it may be a dye that itself does not have a spectral sensitizing effect, or a compound that does not substantially absorb visible light. In addition, a supersensitizer that enhances the sensitizing action of the sensitizing dye may be included in the emulsion.
増感色素としては、シアニン色素、メロシアニン色素、
複合シアニン色素、複合メロシアニン色素、ホロポーラ
−シアニン色素、ヘミシアニン色素、スチリル色素およ
びヘミオキサノール色素が用いられる。Sensitizing dyes include cyanine dyes, merocyanine dyes,
Complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxanol dyes are used.
特に有用な色素は、シアニン色素、メロンアニン色素、
および複合メロシアニン色素である。Particularly useful pigments include cyanine pigments, melonanine pigments,
and a complex merocyanine pigment.
ハロゲン化銀乳剤には、感光材料の製造工程、保存中、
あるいは写真処理中のカプリの防止、又は写真性能を安
定に保つことを目的として化学熟成中、化学熟成の終了
時、及び／又は化学熟成の終了後、ハロゲン化銀乳剤を
塗布するまでに、写真業界においてカプリ防止剤又は安
定剤として知られている化合物を加えることができる。Silver halide emulsions are used during the manufacturing process of photosensitive materials, during storage,
Alternatively, for the purpose of preventing capri during photographic processing or maintaining stable photographic performance, photographic Compounds known in the art as anti-capri agents or stabilizers can be added.
ハロゲン化銀乳剤のバインダー（又は保護コロイド）と
しては、ゼラチンを用いるのが有利であるが、ゼラチン
誘導体、ゼラチンと他の高分子のグラフトポリマー、そ
れ以外の蛋白質、ｗ！誘導体、セルロース誘導体、単一
あるいは共重合体の如き合成親水性高分子物質等の親水
性コロイドも用いることができる。It is advantageous to use gelatin as a binder (or protective colloid) for silver halide emulsions, but gelatin derivatives, graft polymers of gelatin and other polymers, other proteins, etc. Hydrophilic colloids such as derivatives, cellulose derivatives, synthetic hydrophilic polymeric materials such as single or copolymers can also be used.
ハロゲン化銀乳剤を用いた感光材料の写真乳剤層、その
他親水性コロイド層は、バインダー （又は保護コロイ
ド）分子を架橋させ、膜強度を高める硬膜剤を１種又は
２種以上用いることにより硬膜することができる。硬膜
剤は、処理液中に硬膜剤を加える必要がない程度に感光
材料を硬膜できる量添加することができるが、処理液中
に硬膜剤を加えることも可能である。Photographic emulsion layers and other hydrophilic colloid layers of light-sensitive materials using silver halide emulsions are hardened by using one or more hardeners that crosslink binder (or protective colloid) molecules and increase film strength. It can be membraned. The hardening agent can be added in an amount capable of hardening the photosensitive material to such an extent that it is not necessary to add the hardening agent to the processing solution, but it is also possible to add the hardening agent to the processing solution.
感光材料のハロゲン化銀乳剤層及び／又は他の親水性コ
ロイド層には柔軟性を高める目的で可塑剤を添加できる
。A plasticizer can be added to the silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material for the purpose of increasing flexibility.
感光材料の写真乳剤層その他の親水性コロイド層には寸
度安定性の改良などを目的として、水不溶性又は難溶性
合成ポリマーの分散物（ラテックス）を含有させること
ができる。The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material may contain a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability.
感光材料の乳剤層には、発色現像処理において、芳香族
第１級アミン現像剤（例えばｐ−フェニレンジアミン誘
導体や、アミノ７エ／−ル誘導体など）の酸化体とカッ
プリング反応を行い色素を形成する色素形成カプラーが
用いられろ、該色素形成カプラーは各々の乳剤層に対し
て乳剤層の感光スペクトル光を吸収する色素が形成され
るように選択されるのが普通であり、青感性乳剤層には
イエロー色素形成カプラーが、緑感性乳剤層にはマゼン
タ色素形成カプラーが、赤感性乳剤層にはシアン色素形
成カプラーが用いられる。しかしながら、目的に応じて
上記組み合わせと異なった用い方でハロゲン化銀カラー
写真患光材料をつくってもよい。In the emulsion layer of a light-sensitive material, a dye is produced by a coupling reaction with an oxidized form of an aromatic primary amine developer (for example, a p-phenylenediamine derivative or an amino 7-ether derivative) during color development processing. If a forming dye-forming coupler is used, the dye-forming coupler is typically selected for each emulsion layer so that a dye is formed that absorbs light in the light-sensitive spectrum of the emulsion layer; A yellow dye-forming coupler is used in the layer, a magenta dye-forming coupler is used in the green-sensitive emulsion layer, and a cyan dye-forming coupler is used in the red-sensitive emulsion layer. However, depending on the purpose, the silver halide color photographic material may be produced using a method different from the above combination.
これら色素形成カプラーは分子中にバラスト基と呼ばれ
るカプラーを非拡散化する、炭素数８以上の基を有する
ことが望ましい、又、これら色素形成カプラーは１分子
の色素が形成されるために４個の銀イオンが還元される
必要がある４当量性であっても、２個の銀イオンが還元
されるだけでよい２当量性のどちらでもよい０色素形成
力プラーには色補正の効果を有しているカラードカプラ
ー及び現像主薬の酸化体とのカップリングによって現像
抑制剤、現像促進剤、漂白促進剤、現像剤、ハロゲン化
銀溶剤、調色剤、硬膜剤、カプリ剤、カブリ防止剤、化
学増感剤、分光増感剤、及び減感剤の上うな写真的に有
用な７ラグメントを放出する化合物が包含される。これ
らの中、現像に伴って現像抑制剤を放出し、画像の鮮鋭
性や画像の粒状性を改良するカプラーはＤＩＲカプラー
と呼ぼれる。ＤＩＲカプラーに代えて、現像主薬の酸化
体とカップリング反応し無色の化合物を生成すると同時
に現像抑制剤を放出するＤＩＲ化合物を用いてもよい。It is desirable that these dye-forming couplers have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. A 0-pigment forming power puller has a color-correcting effect, whether it is a 4-equivalent type in which 100 silver ions need to be reduced or a 2-equivalent type in which only two silver ions need to be reduced. Development inhibitors, development accelerators, bleach accelerators, developing agents, silver halide solvents, toning agents, hardeners, capri agents, antifoggants are produced by coupling with oxidized forms of colored couplers and developing agents. Included are compounds that release photographically useful 7-ragments, such as chemical sensitizers, spectral sensitizers, and desensitizers. Among these, couplers that release a development inhibitor during development and improve image sharpness and image graininess are called DIR couplers. In place of the DIR coupler, a DIR compound which undergoes a coupling reaction with the oxidized form of the developing agent to produce a colorless compound and at the same time releases a development inhibitor may be used.
用いられるＤＩＲカプラー及びＤＩＲ化合物には、カッ
プリング位に直接抑制剤が結合したものと、抑制剤が２
価基を介してカップリング位に結合しており、力γブリ
２フ反応により離脱した基内での分子内求核反応や、分
子内電子移動反応等により抑制剤が放出されるように結
合したもの（タイミングＤＩＲカプラー、及びタイミン
グＤＩＲ化合物と称する）が含まれる。又、抑制剤も離
脱後板散性のものとそれほど拡散性を有していないもの
を、用途により単独で又は併用して用いることができる
。芳昏族第１級アミン現像剤の酸化体とカップリング反
応を行うが、色素を形成しない無色カプラー （競合カ
プラーとも言う）を色素形成カプラーと併用して用いる
こともできる。The DIR couplers and DIR compounds used include those with an inhibitor directly attached to the coupling position and those with an inhibitor attached to the coupling position.
It is bonded to the coupling position via a valence group, and is bonded in such a way that the inhibitor is released by an intramolecular nucleophilic reaction or an intramolecular electron transfer reaction within the group that is released by a force gamma-brief reaction. (referred to as timing DIR couplers and timing DIR compounds). Also, depending on the purpose, inhibitors that are dispersible after release and those that are not so dispersible can be used alone or in combination. A colorless coupler (also called a competitive coupler) which undergoes a coupling reaction with an oxidized form of an aromatic primary amine developer but does not form a dye can also be used in combination with a dye-forming coupler.
イエロー色素形成カプラーとしては、公知の７シルアセ
トアニリド系カプラーを好ましく用いることができる。As the yellow dye-forming coupler, known 7-syl acetanilide couplers can be preferably used.
これらのうち、ベンゾイルアセトアニリド系及びピバロ
イルアセトアニリド系化合物は有利である。Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous.
マゼンタ色素形成カプラーとしては、公知の５−ピラゾ
ロン系カプラー、ビラゾロベンライミグゾール系カプラ
ー、ピラゾロトリアゾール系カプラー、開鎖アシルアセ
トニトリル系カプラー、イングゾロン系カプラー等を本
発明に係るカプラーと共に用いることができる。As magenta dye-forming couplers, known 5-pyrazolone couplers, virazolobenlimigzole couplers, pyrazolotriazole couplers, open-chain acylacetonitrile couplers, ingzolone couplers, etc. can be used together with the couplers of the present invention. can.
シアン色素形成カプラーとしては、７１７−ルまたはす
７）−ル系カプラーが一般的に用いられる。As the cyan dye-forming coupler, a 717-l or 7)-l coupler is generally used.
ハロゲン化銀結晶表面に吸着させる必要のない色素形成
カプラー、カラードカプラー、ＤＩＲカプラー、ＤＩＲ
化合物、画像安定剤、色カプリ防止剤、紫外線吸収剤、
蛍光増白剤等のうち、疎水性化合物は固体分散法、ラテ
ックス分散法、水中油滴型乳化分散法等、種々の方法を
用いることができ、これはカプラー等の疎水性化合物の
化学構造等に応じて適宜選択することができる。水中油
滴型乳化分散法は、カプラー等の疎水性添加物を分散さ
せる従来公知の方法が適用でき、通常、沸点約１５０℃
以上の高沸点有機溶媒に必要に応じて低沸点、及び又は
水溶性有機溶媒を併用して溶解し、ゼラチン水溶液など
の親水性バイングー中に界面活性側を用いで攪はん器、
ホモジナイザー、コロイドミル、７０−ノットミキサー
、超音波装置等の分散手段を用いて、乳化分散した後、
目的とする親水性コロイド液中に添加すればよい６分散
液又は分散と同時に低沸、克有機溶媒を除去する工程を
入れてもよい。Dye-forming couplers, colored couplers, DIR couplers, DIR that do not need to be adsorbed on the silver halide crystal surface
Compounds, image stabilizers, color capri inhibitors, ultraviolet absorbers,
Among fluorescent brighteners, hydrophobic compounds can be prepared using various methods such as solid dispersion method, latex dispersion method, and oil-in-water emulsion dispersion method. It can be selected as appropriate. For the oil-in-water emulsion dispersion method, conventionally known methods for dispersing hydrophobic additives such as couplers can be applied, and the boiling point is usually about 150°C.
Dissolve the above-mentioned high-boiling point organic solvent in combination with a low-boiling point and/or water-soluble organic solvent if necessary, and stir in a hydrophilic binder such as an aqueous gelatin solution using a surfactant.
After emulsifying and dispersing using a dispersion means such as a homogenizer, colloid mill, 70-knot mixer, or ultrasonic device,
The dispersion may be added to the desired hydrophilic colloid liquid, or a step of removing the low-boiling organic solvent simultaneously with the dispersion may be included.
高沸、く溶媒としては現像主薬の酸化体と反応しないフ
ェノール誘導体、７タール酸アルキルエステル、リン酸
エステル、クエン酸エステル、安息昏酸エステル、アル
キルアミド、脂肪酸エステル、トリノシン酸エステル等
の沸点１５０ ’Ｃ以上の有機溶媒が用いられる。Examples of high-boiling solvents include phenol derivatives that do not react with the oxidized form of the developing agent, alkyl 7-tar acids, phosphoric esters, citric esters, benzoic acid esters, alkylamides, fatty acid esters, trinosic acid esters, etc. with a boiling point of 150. An organic solvent of 'C or higher is used.
高沸点溶媒と共に、又その代わりに低沸点又は水溶性有
機溶媒を使用できる。低沸点の実質的に水に不溶の有機
溶媒としてはエチルアセテート、プロピルアセテート、
ブチルアセテート、ブタ／−ル、クロロホルム、四塩化
炭素、ニトロメタン、ニトロエタン、ベンゼン等があり
、又水溶性有機溶媒としては、アセシン、メチルイソブ
チルケトン、β−エトキシエチルアセテート、メトキシ
グリコールアセテート、メタ／−ル、エタノール、アセ
トニトリル、ノオキサン、ジメチルホルムアミド、ジメ
チルスルホキサイド、ヘキサメチルホスホニルアミド、
ジエチレングリコールモ／７エ二ルエーテル、７エ／キ
シエタ／−ル等が例として挙げられる。Low boiling or water-soluble organic solvents can be used in conjunction with or in place of high boiling solvents. Examples of organic solvents with low boiling points that are substantially insoluble in water include ethyl acetate, propyl acetate,
Examples include butyl acetate, butyl, chloroform, carbon tetrachloride, nitromethane, nitroethane, benzene, etc. Water-soluble organic solvents include acecin, methyl isobutyl ketone, β-ethoxyethyl acetate, methoxyglycol acetate, meta/ ethanol, acetonitrile, nooxane, dimethylformamide, dimethyl sulfoxide, hexamethylphosphonylamide,
Examples include diethylene glycol mole/7-enyl ether, 7-ethyl/xyethyl ether, and the like.
色素形成カプラー、ＤＩＲカプラー、カラードカプラー
、ＤＩＲ化合物、画像安定剤、色カプリ防止剤、紫外線
吸収剤、蛍光増白剤等がカルボン酸、スルフォン酸のご
とき酸基を有する場合には、アルカリ性水溶液として親
水性コロイド中に導入することもできる。When the dye-forming coupler, DIR coupler, colored coupler, DIR compound, image stabilizer, color capri-preventing agent, ultraviolet absorber, optical brightener, etc. has an acid group such as carboxylic acid or sulfonic acid, it can be used as an alkaline aqueous solution. They can also be incorporated into hydrophilic colloids.
疎水性化合物を低沸点溶媒単独又は高沸点溶媒と併用し
た溶媒に溶かし、機械的又は超音波を用いて水中に分散
するときの分散助剤として、アニオン性界面活性剤、ノ
ニオン性界面活性剤、カチオン性界面活性剤及び両性界
面活性剤を朋いることができる。Anionic surfactants, nonionic surfactants, Cationic surfactants and amphoteric surfactants can be used.
感光材料の乳剤層間（同−感色性層間及び／又は異なっ
た感色性Ｍ間）で、現像主薬の酸化体又は電子移動剤が
移動して色濁りが生じたり、鮮鋭性が劣化したり、粒状
性が目立つのを防止するために色カブリ防止剤を用いる
ことができる。The oxidized form of the developing agent or the electron transfer agent may migrate between the emulsion layers of the light-sensitive material (between the same color-sensitive layers and/or between different color-sensitive layers), causing color turbidity or deterioration of sharpness. A color antifoggant can be used to prevent graininess from becoming noticeable.
該色カプリ防止剤は乳剤層自身に含有させてもよいし、
中間層を隣接乳剤層間に設けて、該中間層に含有させて
もよい。The color anti-capri agent may be contained in the emulsion layer itself, or
An interlayer may be provided between adjacent emulsion layers and contained in the interlayer.
感光材料に１よ、色素画像の劣化を防止する画像安定剤
を用いることができる。Image stabilizers can be used in photosensitive materials to prevent deterioration of dye images.
感光材料の保護層、中間層等の親水性コロイド層は感光
材料が摩擦等で帯電することに起因する放電によるカプ
リ防止及び画像の紫外線による劣化を防止するために紫
外線吸収剤を含んでいてもよい。Hydrophilic colloid layers such as protective layers and intermediate layers of photosensitive materials may contain an ultraviolet absorber to prevent capri from discharge caused by charging of the photosensitive material due to friction, etc., and to prevent image deterioration due to ultraviolet rays. good.
感光材料の保存中のホルマリンによるマゼンタ色素形成
カプラー等の劣化を防止するために、感光材料にホルマ
リンスカベンジャ−を用いることができる。In order to prevent deterioration of magenta dye-forming couplers and the like due to formalin during storage of the light-sensitive material, a formalin scavenger can be used in the light-sensitive material.
感光材料の親水性コロイド層に染料や紫外線吸収剤等を
含有させる場合に、七へらはカチオン性ポリマー等の媒
染剤によって媒染されてもよい。When the hydrophilic colloid layer of the photosensitive material contains dyes, ultraviolet absorbers, etc., the seven spatulas may be mordanted with a mordant such as a cationic polymer.
感光材料のハロゲン化銀乳剤層及び／又はその池の親水
性コロイド層に現像促進剤、現（を遅延剤等の現像性を
変化させる化合物や漂白促進剤を添加できる。A development accelerator, a compound that changes the developability such as a retardant, and a bleach accelerator can be added to the silver halide emulsion layer and/or the hydrophilic colloid layer of the photosensitive material.
写真感光材料の乳剤層は、感度上昇、コントラスト上昇
、又は現像促進の目的でポリアルキレンオキシド又はそ
のエーテル、エステル、アミン等の誘導体、千オニーチ
ル化合物、チオモル７オリン類、４級アンモニウム化合
物、ウレタン誘導体、尿素誘導体、イミグゾール誘導体
等を含んでもよ（１゜
感光材料には、白地の白さを強調するとともに白地部の
着色を目立たせない目的で蛍光増白剤を用いることがで
きる。The emulsion layer of photographic light-sensitive materials is made of polyalkylene oxide or its derivatives such as ethers, esters, and amines, 1,000-onythyl compounds, thiomol-7-olins, quaternary ammonium compounds, and urethane derivatives for the purpose of increasing sensitivity, increasing contrast, or accelerating development. , urea derivatives, imiguzole derivatives, etc. (1°) A fluorescent whitening agent may be used in the photosensitive material for the purpose of emphasizing the whiteness of the white background and making the coloring of the white background less noticeable.
感光材料には、フィルタ一層、ハレーシタン防止層、イ
ラノエーシ３ン防止層等の補助層を設けることがでさる
。これらの層中及び／又は乳剤層中には現像処理中に感
光材料から流出するか、もしくは漂白される染料が含有
させられてもよい。The photosensitive material may be provided with auxiliary layers such as a filter layer, a halide prevention layer, an ylanacin prevention layer, and the like. These layers and/or the emulsion layer may contain dyes that are washed out of the light-sensitive material or bleached during the development process.
このような染料には、オキソノール染料、ヘミオキソノ
ール染料、スチリル染料、メロシアニン染料、シアニン
染料、アゾ染料等を挙げることができる。 感光材料の
ハロゲン化銀乳剤層及び／又はその他の親水性コロイド
層に感光材料の光沢の低減、加筆性の改良、感光材料相
互のくっつき防止等を目的としてマット剤を添加できる
。Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, azo dyes, and the like. A matting agent can be added to the silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material for the purpose of reducing the gloss of the light-sensitive material, improving the ease of writing, and preventing the light-sensitive materials from sticking together.
感光材料には滑り摩擦を低減させるために滑剤を添加で
きる。A lubricant can be added to the photosensitive material to reduce sliding friction.
感光材料に、帯電防止を目的とした：Ｔ？電防止剤を添
加できる。帯電防止剤は支持体の乳剤を積層してない側
の帯電防止層に用いてもよく、乳剤層及び／又は支持体
に対して乳剤層が８Ｉ層されている側の乳剤層以外の保
護コロイド層に用いられてもよい。For the purpose of preventing static electricity in photosensitive materials: T? Antistatic agents can be added. The antistatic agent may be used in the antistatic layer on the side of the support on which the emulsion is not laminated, and may be used as a protective colloid in the emulsion layer and/or the emulsion layer on the side where the emulsion layer is layered with respect to the support. It may be used in layers.
感光材料の写真乳剤層及び／又は他の現水性〕ロイド層
には、塗布性改良、帯電防止、滑り性改良、乳化分散、
接着防止、写真特性（現像促進、硬膜化、増感等）改良
等を目的として、種々の界面活性剤を用いることができ
る。The photographic emulsion layer and/or other water-based [lodoid] layer of the light-sensitive material may contain coating properties, antistatic properties, slipperiness properties, emulsification dispersion,
Various surfactants can be used for the purpose of preventing adhesion and improving photographic properties (development acceleration, film hardening, sensitization, etc.).
本発明の感光材料に用いられる支持体には、α−オレフ
インボリマー （例えばポリエチレン、ポリプロピレン
、エチレン／ブテン共重合体）等をラミネートした紙、
合成紙等の可撓性反射支持体、酢酸セルロース、硝酸セ
ルロース、ポリスチレン、ポリ塩化ビニル、ポリエチレ
ンテレフタレート、ポリカーボネート、ポリアミド等の
半合成又は合成高分子からなるフィルムや、これらのフ
ィルムに反射層を設けた可撓性支持体、ガラス、金属、
陶器などが含まれる。The support used in the photosensitive material of the present invention includes paper laminated with an α-olefin polymer (e.g., polyethylene, polypropylene, ethylene/butene copolymer), etc.
Flexible reflective supports such as synthetic paper, films made of semi-synthetic or synthetic polymers such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, and polyamide, and reflective layers provided on these films. flexible support, glass, metal,
Includes pottery etc.
感光材料は必要に応じて支持体表面にコロナ放電、紫外
線照射、火焔処理等を施した後、直接に又は支持体表面
の接着性、帯電防止性、寸法安定性、耐摩耗性、硬さ、
ツル−ジョン防止性、摩擦特性、及び／又はその池の特
性を向上するための１／！以上の下塗層を介して塗布さ
れてもより１゜感光材料の塗布に際して、塗布性を向上
させる為に増粘剤を用いてもよい、又、例えば硬膜剤の
如く、反応性が早いために予め塗布液中に添加すると塗
布する前にデル化を起こすようなものについては、スタ
チックミキサー等を用いて塗布直前に混合するのが好ま
しい。After subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc. as necessary, the photosensitive material can be used directly or to improve the adhesion, antistatic properties, dimensional stability, abrasion resistance, hardness, etc. of the support surface.
1/! to improve anti-tension properties, friction properties, and/or its pond properties! Even if it is coated through the above-mentioned undercoat layer, a thickener may be used to improve the coatability when coating the photosensitive material. Therefore, it is preferable to mix ingredients using a static mixer or the like just before coating if they are added to the coating solution in advance and cause delification before coating.
塗布法としては、２！１１以上の層を同時に塗布するこ
とのできるエクストル−ツａンコーティング及びカーテ
ンコーティングが特に有用であるが、目的によってはパ
ケット塗布も用いられる。又、塗布速度は任意に選ぶこ
とができる。As a coating method, Extru-Tsun coating and curtain coating, which can simultaneously coat 2 to 11 or more layers, are particularly useful, but packet coating may also be used depending on the purpose. Further, the coating speed can be arbitrarily selected.
本発明の感光材料を用いて色素画像を得るには露光後、
カラー写真処理を行う、カラー処理は、発色現像処理工
程、漂白処理工程、定着処理工程、水洗処理工程及び必
要に応じて安定化処理工程を行うが、漂白液を用いた処
理工程と定着液を用いた処理工程の代わりに、１浴漂白
定ＮｗＬを用いて、漂白定着処理工程を行うこともでき
るし、発色現像、漂白、定着を１浴中で行うことができ
る１浴現像漂白定着処理液を用いた七／バス処理工程を
行うことらできる。To obtain a dye image using the photosensitive material of the present invention, after exposure,
Color photographic processing is performed, and color processing includes a color development process, a bleaching process, a fixing process, a water washing process, and, if necessary, a stabilizing process. Instead of the processing step used above, the bleach-fixing processing step can be carried out using a one-bath bleach-fixing solution, or a one-bath developing bleach-fixing processing solution that can carry out color development, bleaching, and fixing in one bath. A 7/bath treatment process can be carried out using
これらの処理工程に組み合わせて前硬膜処哩工程、その
中和工程、停止定着処理工程、後硬膜処理工程等を行っ
てもよい、これら処理において発色現像処理工程の代わ
りに発色現像主薬、またはそのプレカーサーを材料中に
含有させておき現像処理を７クチベーター液で行うアク
チベーター処理工程を行ってもよいし、そのモノバス処
理に７クチベーター処理を適用することができる。これ
らの処理中、代表的な処理を次に示す、 （これらの処
理は最終工程として、水洗処理工程、水洗処理工程及ブ
安定化処理工程のいずれかを行つ、）・発色現像処理工
程−漂白処理工程一定着処理工程
・発色現像処理工程−漂白定着処理工程・前硬膜処理工
程−発色現像処理工程−停止定着処理工程−水洗処理工
程−漂白処理工程一定着処理工程−水洗処理工程−後硬
膜処理工程・発色現像処理工程−水洗処理工程−補足発
色現像処理工程−停止処理工程−漂白処理工程一定着処
理工程
・アクチベーター処理工程−漂白定着処理工程・アクチ
ベーター処理工程−漂白処理工程一定着処理工程
・モ／バ入処理工程
処理温度は通常、１０ ’Ｃ〜６５°Ｃの範囲に選ばれ
るが、６５°Ｃをこえる温度としてもよい、好ましくは
２５°Ｃ〜４５℃で処理される。In combination with these processing steps, a pre-hardening process, its neutralization process, a stop-fixing process, a post-hardening process, etc. may be performed.In these processes, a color developing agent, a color developing agent, Alternatively, an activator treatment step may be performed in which the precursor is contained in the material and development is performed using a 7 activator solution, or a 7 activator treatment may be applied to the monobath treatment. Typical treatments during these treatments are shown below. Bleaching process Fixed fixing process/Color development process - Bleach-fixing process/Pre-hardening process - Color developing process - Stop fixing process - Water washing process - Bleaching process Constant fixing process - Washing process - Post-hardening treatment process/Color development treatment process - Water washing treatment process - Supplementary color development treatment process - Stop treatment process - Bleaching treatment process Constant fixation treatment process/Activator treatment process - Bleach-fixing treatment process/Activator treatment process - Bleaching treatment Process: Fixed treatment process/mo/ba input treatment process The treatment temperature is usually selected in the range of 10'C to 65°C, but it may also be at a temperature exceeding 65°C, preferably between 25°C and 45°C. It is processed.
発色現像液は、一般に発色現像主薬を含むアルカリ性水
溶液からなる０発色現像主薬は芳昏族第１級アミン発色
現像主薬であり、７ミ／フエノール系及びｐ−フェニレ
ノンアミン系誘導体が含まれる。これらの発色現像主薬
は有機酸及び無機酸の塩として用いることができ、例え
ば塩へ酸、硫酸塩、９−トルエンスルホン酸塩、亜硫酸
塩、シェ’７１１１２ｍ、ベンゼンスルホン酸塩等を用
いることができる。The color developing solution is generally an alkaline aqueous solution containing a color developing agent.The color developing agent is an aromatic primary amine color developing agent, and includes 7mi/phenol derivatives and p-phenylenone amine derivatives. These color developing agents can be used as salts of organic acids and inorganic acids; for example, acid salts, sulfates, 9-toluenesulfonates, sulfites, Che'71112m, benzenesulfonates, etc. can be used. can.
これらの化合物は一般に発色現像は１ｒについて約０．
１〜３０ｇの濃度、更に好ましくは、発色現偉液１１に
ついて約１〜１５ｇの濃度で使用する。These compounds generally have a color development rate of about 0.0.
A concentration of 1 to 30 g, more preferably about 1 to 15 g per color developing solution 11 is used.
上記アミノ７エ／−ル系現像剤としては例えば、０−７
ミノ７エノール、 ｐ−７ミノ７エ／−ル、５−７ミノ
ー２−オキシ−トルエン、２−７ミノー３−オキ°シー
Ｆルエン、２−オキシ−３−アミ／−１，４−ツメチル
−ベンゼン等が含まれる。Examples of the above-mentioned amino 7-el/-based developer include 0-7
Mino-7enol, p-7mino-7-enol, 5-7-mino-2-oxy-toluene, 2-7-mino-3-oxy-F-toluene, 2-oxy-3-ami/-1,4-methyl -Includes benzene, etc.
特に有用な第１級芳香族アミン系発色現像剤はＮ、Ｎ−
ジアルキル−１１−フェニレンクアミン系化合物であり
、アルキル基及びフェニル基は置換されていても、ある
いは置換されていなくてもよい、その中でも特に有用な
化合物例としてはＮ。Particularly useful primary aromatic amine color developers include N, N-
A particularly useful example of the compound is N, which is a dialkyl-11-phenylenequamine compound, and the alkyl group and phenyl group may be substituted or unsubstituted.
Ｎ−ツメチル−ｐ−フェニレンジアミン＠酸塩、Ｎ−メ
チル−ｐ−フェニレンジアミン塩酸塩、Ｎ、Ｎ−ツメチ
ル−、−フェニレンジアミン塩酸塩、２−アミｙ−５−
（Ｎ−エチル−Ｎ−ドデシルアミノ）−）ルエン、Ｎ−
エチル−Ｎ−β−ノタンスルホンアミドエチルー３−メ
チル−４−７ミノアニリン硫酸塩、Ｎ−エチル−Ｎ−β
−ヒドロキシエチルアミノ７ニリン、４−７ミノー３−
メチル−Ｎ、Ｎ−ノエチル７ニリン、４−アミノ−Ｎ−
（２−７トキシエチル）−Ｎ−エチル−３−メチルアニ
リン−ｐ−）ルエンスルホネート等を挙げることができ
る。N-methyl-p-phenylenediamine@acid salt, N-methyl-p-phenylenediamine hydrochloride, N,N-methyl-,-phenylenediamine hydrochloride, 2-amy-5-
(N-ethyl-N-dodecylamino)-)luene, N-
Ethyl-N-β-notanesulfonamide ethyl-3-methyl-4-7minoaniline sulfate, N-ethyl-N-β
-Hydroxyethylamino 7niline, 4-7 minnow 3-
Methyl-N, N-noethyl 7-niline, 4-amino-N-
(2-7toxyethyl)-N-ethyl-3-methylaniline-p-)luenesulfonate and the like can be mentioned.
また、上記発色現像主薬は単独であるいは２種以上併用
して用いてもよい、更に又、上記発色現像主薬はカラー
写真材料中に内ｉＩＬされてもよい。Further, the above color developing agents may be used alone or in combination of two or more kinds.Furthermore, the above color developing agents may be incorporated into the color photographic material.
この場合、ハロゲン化銀カラー写真感光材料を発色現像
液のかわりにアルカリｗＬ（アクチベーター液）で処理
することも可能であり、アルカリ液処理の後、直ちに漂
白定着処理される。In this case, it is also possible to process the silver halide color photographic light-sensitive material with an alkali wL (activator liquid) instead of a color developing solution, and the bleach-fixing process is carried out immediately after the alkali solution treatment.
発色現像液は、現像液に通常用いられるアルカリ肩、例
えば水酸化ナトリウム、水酸化カリウム、水酸化アンモ
ニクム、炭酸ナトリウム、炭酸カリウム、硫酸ナトリウ
ム、メタホウ酸ナトリツムまたは硼砂等を含むことがで
き、更に種々の添加剤、例エバベンノルアルフール
金属、例えば、臭化カリウム、又は塩化カリツム等、あ
るいは現像調節剤として例えばシトラノン漿等、保恒剤
としてヒドロキシルアミンまたは亜硫酸塩等を含有して
ち゛よい．さらに各種消泡剤や界面活性剤を、またメタ
ノール、ジメチルホルムアミドまたはツメチルスルホキ
シド等の有機溶剤等を適宜含有せしめることができる。The color developing solution may contain alkaline carriers commonly used in developing solutions, such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate, or borax, and various other additives. It may contain additives such as evabennoralfur metals, such as potassium bromide or potassium chloride, development regulators such as citranone serum, and preservatives such as hydroxylamine or sulfites. Furthermore, various antifoaming agents and surfactants, as well as organic solvents such as methanol, dimethylformamide, and trimethylsulfoxide, can be appropriately contained.
発色現像液の９８は通常７以上であり、好ましくは約９
〜１３である。98 of the color developer is usually 7 or more, preferably about 9
~13.
また、本発明に用いられる発色現像液には必要に応じて
酸化防止剤としてジエチルヒドロキシアミン、テトロン
酸、テトロンイミド、２−アニリノエタノール、ノヒド
ロキシアセトン、芳香族第２アルコール、ヒドロキサム
酸、ペントースまたはヘキソース、ピロガロール−１．
３ーツメチルエーテル等が含有されていてもよい。In addition, the color developing solution used in the present invention may contain antioxidants such as diethylhydroxyamine, tetronic acid, tetronimide, 2-anilinoethanol, nohydroxyacetone, aromatic secondary alcohol, hydroxamic acid, and pentose, if necessary. or hexose, pyrogallol-1.
It may also contain 3-methyl ether or the like.
発色現像液中には、金属イオン封鎖剤として、種々のキ
レート剤を併用することができる．例えば、該キレート
剤としてエチレンジアミン四酢酸、ノエチレントリ７ミ
／五酢酸等のアミンポリカルボン酸、１−ヒドロキシエ
チリデン−１．１″−ノホスホン酸等の有機ホスホン酸
、アミ／トリ（メチレンホスホン酸）もしくはエチレン
ノアミンチトラリン酸等のアミ／ポリホスホン酸、りエ
ン酸もしくはグルコン酸等のオキシカルボン酸、２−ホ
スホノブタン１，２．４−）リカルボン酸等のホスホノ
カルボン酸、トリポリリン酸もしくはヘキサメタリン酸
等のポリリン酸等、ゴリヒドロキシ化合物等が挙げられ
る。Various chelating agents can be used in combination as metal ion sequestering agents in the color developing solution. For example, as the chelating agent, amine polycarboxylic acids such as ethylenediaminetetraacetic acid, noethylenetri7mi/pentaacetic acid, organic phosphonic acids such as 1-hydroxyethylidene-1.1''-nophosphonic acid, ami/tri(methylenephosphonic acid) or Amino/polyphosphonic acids such as ethylenenoamine titraphosphoric acid, oxycarboxylic acids such as phosphoric acid or gluconic acid, phosphonocarboxylic acids such as 2-phosphonobutane 1,2,4-)licarboxylic acid, tripolyphosphoric acid or hexametaphosphoric acid, etc. Examples include polyphosphoric acid, golihydroxy compounds, and the like.
漂白処理工程は、前述したように定着処理工程と同時に
行われてもよく、個別に行われてもよい。The bleaching process may be performed simultaneously with the fixing process as described above, or may be performed separately.
漂白剤としては有機酸の金属錯塩が用いられ、例えばポ
リカルボン酸、アミ／ビリ力ｌレボン酸又は蓚酸、クエ
ン酸等の有機酸で、鉄、コバルト、銅等の金属イオンを
配位したものが用いられる．上記の有機酸のうちで最も
好ましい有機酸としては、ポリカルボン酸又はアミノポ
リカルボン酸が挙げられる，２粍らの具体例としてはエ
チレンジ７ミンテトラ酢酸、ノエチレントリアミンベン
タ酢酸、エチレンジアミンーＮ−（β−オキシエチル）
−Ｎ，Ｎ’ 、Ｎ′ ）り酢酸、プロピレンジアミンテ
トラ酢酸、ニトリロトリ酢酸、ンクロヘキサンノアミン
テトラ酢酸、イミ７ノ酢酸、ノヒロキシエチルグリシン
クエン酸（又は酒石Ｗｌ） 、エチルエ−チルジアミン
テトラ酢酸、グリコールエーテルノアミンチトラ酢酸、
エチレンノ７ミンテトラプロビオン酸、フェニレンジア
ミンテトラ酢酸等を挙げることができる。これらのポリ
カルボン酸はアルカリ金属塩、アンモニウム塩もしくは
水溶性アミン塩でありでもよい。As a bleaching agent, a metal complex salt of an organic acid is used, for example, an organic acid such as polycarboxylic acid, amino/bilylic acid, oxalic acid, citric acid, etc., coordinated with metal ions such as iron, cobalt, copper, etc. is used. Among the above organic acids, the most preferable organic acids include polycarboxylic acids and aminopolycarboxylic acids. Specific examples include ethylenedi7minetetraacetic acid, noethylenetriaminebentaacetic acid, and ethylenediamine-N-( β-oxyethyl)
-N, N', N') diacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, nclohexannoaminetetraacetic acid, imi7noacetic acid, nohyroxyethylglycinecitric acid (or tartar Wl), ethyl ethyldiaminetetra Acetic acid, glycol ethernoamine chitraacetic acid,
Examples include ethylene-7minetetraprobionic acid and phenylenediaminetetraacetic acid. These polycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.
これらの漂白剤は好ましくは５〜４５０ ｇ／ｌ、より
好ましくはＺＯ〜２５０ ｇ／ｌで使用する。These bleaching agents are preferably used at between 5 and 450 g/l, more preferably between ZO and 250 g/l.
漂白液には前記の如き漂白剤以外に、必要に応じて保恒
剤として亜硫酸塩を含有するＭＬｆ！ｔの液が適用され
る。又、エチレンノアミンチトラ酢酸鉄（Ｉ［ｌ）錯塩
漂白剤を含み、臭化アンモニウムの如きハロゲン化物を
多量に添加した組成からなる漂白液であってもよい、前
記ハロゲン化物としては、臭化アンモニウムの他に塩化
水素酸、臭化水素酸、臭化リチウム、臭化ナトリフム、
臭化カリワム、沃化ナトリウム、沃化カリワム、沃化ア
ンモニウム等も使用することができる。In addition to the above-mentioned bleaching agent, the bleaching solution may contain MLf! sulfite as a preservative if necessary. t solution is applied. Alternatively, it may be a bleaching solution containing an ethylenenoaminetitraacetate iron (I[l) complex salt bleaching agent and containing a large amount of a halide such as ammonium bromide. In addition to ammonium, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide,
Potassium bromide, sodium iodide, potassium iodide, ammonium iodide, and the like can also be used.
漂白液には種々の漂白促進珊を添加することができる。Various bleach-accelerating corals can be added to the bleach solution.
漂白液のｐＨは２．０以上で用いられるが、一般には４
．０〜９．５で使用さ沈、望ましくは４．５〜８．０で
使用され、最も好ましくは５．θ〜７．０である。The pH of the bleaching solution used is 2.0 or higher, but generally it is 4.
．． 0 to 9.5, preferably 4.5 to 8.0, most preferably 5. θ~7.0.
定着液は一般に用いられる組成のものを使用することが
できる。定着剤としては通常の定着処理に用いられるよ
うなハロゲン化銀と反応して水溶性の錯塩を形成する化
合物、例えば、チオ硫酸カリウム、千オ硫酸ナトリワム
、千オ硫酸アンモニウムの如きチオ硫酸塩、千オシ７ン
酸カリウム、チオシアン酸ナトリヴム、千オシアン酸ア
ンモニウムの如きチオシアン酸塩、千オ尿稟、千オニー
チル等がその代表的なものである。これらの定着剤は５
ｇ／１以上、溶解できる範囲の１で使用するが、一般に
は７０〜２５０ｇ／ １）で使用する。尚、定着剤はそ
の一部を漂白槽中に含有することができるし、逆に漂白
剤の一部を定着槽中に含有することもできる。A fixer having a commonly used composition can be used. The fixing agent may be a compound that reacts with silver halide to form a water-soluble complex salt, such as potassium thiosulfate, sodium periosulfate, ammonium periosulfate, etc., which is used in ordinary fixing processing. Typical examples thereof include potassium ocyanate, sodium thiocyanate, ammonium thiocyanate, thiocyanate salts, thiocyanate, thiocyanate, and thiocyanate. These fixatives are 5
It is used in a range of 1 g/1 or more, within the range that it can be dissolved, but it is generally used in a range of 70 to 250 g/1). Incidentally, a part of the fixing agent can be contained in the bleaching tank, or conversely, a part of the bleaching agent can also be contained in the fixing tank.
尚、漂白液及び／又は定５１１液にはｍｅ、ｒＭ砂、水
酸化ナトリクム、水酸化カリワム、炭酸ナトリウム、炭
酸カリツム、重炭酸ナトリウム、重炭酸カリウム、酢酸
、酢酸ナトリワム、水酸化アンモ二７ム等の各種ｐＨ級
衝剤を単独であるいは２種以上組み合わせて含有せしめ
ることができる。さらに又、各種の蛍光増白剤や消泡剤
あるいは界面活性剤を含有せしめることもでさる。又、
ヒドロキシルアミン、ヒドラノン、アルデヒド化合物の
重亜硫酸付加物等の保恒剤、アミ／ポリカルボン酸等の
有機キレート化剤あるいはニトロアルコール、硝酸塩等
の安定剤、水溶性アルミニツム塩の如き硬膜剤、メタ／
−ル、ツメチルスルホ７ミド、ツメチルスルホキシド等
の有機溶媒等を適宜含有せしめることができる。In addition, the bleach solution and/or the standard 511 solution contains me, rM sand, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide. It is possible to contain various pH-class buffering agents such as these alone or in combination of two or more. Furthermore, various optical brighteners, antifoaming agents, or surfactants may be contained. or,
Preservatives such as hydroxylamine, hydranone, bisulfite adducts of aldehyde compounds, organic chelating agents such as amide/polycarboxylic acids, stabilizers such as nitroalcohols and nitrates, hardeners such as water-soluble aluminum salts, meth /
An organic solvent such as -ol, trimethylsulfonamide, trimethylsulfoxide, etc. can be appropriately contained.
定着液のｐＨは３．０以上で坩いられるが、一般には４
．５〜１０で使用され、望ましくは５〜９．５で使用さ
れ、最も好ましくは６〜９である。The pH of the fixer can be fixed at 3.0 or higher, but generally it is 4.
．． 5 to 10, preferably 5 to 9.5, most preferably 6 to 9.
漂白定着液に使用される漂白剤として上記漂白処理工程
に記載した有機酵の金属錯塩を挙げることができ、好ま
しい化合物及び処理液における濃度も上記漂白処理工程
におけると同じである。Examples of the bleaching agent used in the bleach-fixing solution include the metal complex salts of organic enzymes described in the above bleaching process, and preferred compounds and concentrations in the processing solution are also the same as in the above bleaching process.
漂白定着液には前記の如き漂白剤以外にハｉ：７デン化
銀定着剤を含有し、必要に応じて保恒剤として亜硫酸塩
を含有するｍ成の液が適用される。また、エチレンノア
ミン四酢酸鉄（１）錯塩漂白剤と前記のハロゲン化銀定
ＩＦ剤の池の臭化アンモニウムの如きハロゲン化物を少
量添加した組成からなる）７白定着液、あるいは逆に臭
化７ンモニフムの如きハロゲン化物を多量に添加した組
成からなる漂白定着液、さらにエチレンノアミン四＃酸
鉄（Ｉ［Ｉ）錯塩ｉ！白剤と多量の臭化アンモニウムの
如きハロゲン化物との組み合わせからなるｍｅ、のｖｆ
殊なｉ７白定着液等ら用いる事ができる。ｔＪ記ハロゲ
ン化物としては、臭化アンモニフムの池に塩化水素酸、
臭化水素酸、臭化リチウム、臭化ナトリフム、臭化カリ
ウム、沃化ナトリ９ム、沃化カリウム、沃化アンモニウ
ム等ら使用することができる。The bleach-fix solution contains, in addition to the above-mentioned bleaching agent, a high-i:7 silver denride fixer and, if necessary, a sulfite salt as a preservative. In addition, a white fixer (composed of an ethylenenoaminetetraacetate iron (1) complex salt bleach and a small amount of a halide such as ammonium bromide of the above-mentioned silver halide constant IF agent) or, conversely, an odor A bleach-fixing solution consisting of a composition containing a large amount of a halide such as 7-ammonium chloride, and an ethylenenoamine tetraacid iron (I[I) complex salt i! vf of me, consisting of a combination of a whitening agent and a large amount of a halide such as ammonium bromide.
A special i7 white fixer can be used. The halides listed in tJ include hydrochloric acid,
Hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, and the like can be used.
）７白定着液に含有させることができるハロゲン化銀定
着剤として上記定着処理工程に記載した定着剤を挙げる
ことかでさる。定着剤の濃度及び漂白定着液に含有させ
ることができる ｐＨ緩ｌ！ｊ１削その他の添加剤につ
いては上記定着処理工程におけると同じである。) 7 Examples of the silver halide fixing agent that can be contained in the white fixing solution include the fixing agents described in the above fixing process. The concentration of the fixing agent and the pH level that can be included in the bleach-fixing solution! j1 cutting and other additives are the same as in the above fixing process.
漂白定着液の９８は４．０以上で用いられるが、一般に
は５．０〜９．５で使用され、望ましくは６．０〜８．
５で使用され、最も好ましくは６．５〜８．５である。98 of the bleach-fix solution is used at 4.0 or higher, but generally it is used at 5.0 to 9.5, preferably 6.0 to 8.
5, most preferably 6.5 to 8.5.
以下、実施例を示すが本発明は、これらにより限定され
るものではない。Examples will be shown below, but the present invention is not limited thereto.
実施例 １
１７０１／ｍ”の紙基体の片面にポリエチレンを、別の
面に、アナ７−ゼ型二酸化チタンを１１重量パーセント
含有するポリエチレンをラミネートした紙支持体の二酸
化チタン含有ポリエチレン側にコロナ放電を施し、次い
で、下記の層を順次塗設し、試料１〜１６を作成した。Example 1 Corona discharge on the titanium dioxide-containing polyethylene side of a paper support laminated with polyethylene on one side of a 1701/m" paper substrate and polyethylene containing 11% by weight of anan-7-ze titanium dioxide on the other side. Then, the following layers were sequentially applied to prepare samples 1 to 16.
なお、添加量は特に記載しない限り１■２あたりの量で
示した。Incidentally, the amount added is expressed as an amount per 1/2 unless otherwise specified.
層１： Ｌ、４ｇのゼラチン、０１２８ｇ （ｌＬ’ｌ
として、以下同じ）の！！−１に示す青感光性へロデン
化銀乳ｍ、１．３Ｘ１０”モルの表−１に示すイエロー
カプラー、０．０２ｇの色汚染防止剤ＨＱ−１、０，３
ｇのジノニル７タレー） （以下ＤＮＰと略称する）、
表−１に示す色素画像安定剤、０．０４ｇの表１に示す
活性剤、及びハロゲン化銀１モルあたり ０．０３゜の
表−１に示すカプリ防止剤を含有する層層２ ； ０，
９ｇのゼラチン、０．０４ｇの色汚染防止剤ＨＱ−１、
０，１ｇのノー２−エチルへキシル７タレート（以下Ｄ
ＯＰと略称する）、０．０５ｇのノアミノスチルベン系
水溶性蛍光増白剤、表−１に示すカプリ防止剤、および
！！−１に示す０，０１．の活性剤を含有する層
層３ ； １．４ｇのゼラチン、表−２に示す緑感光性
ハロゲン化銀乳剤、０．８Ｘ １０”モルの表−２に示
すマゼンカプラー、表２に示す色素ａＩ像安定イじ絢、
０、Ｏｌ［Ｆの色素汚染防止剤ＨＱ−１、表−２に示す
高沸点有機溶媒、０．０２ｇの表−２に示す活性剤、ハ
ロゲン化銀１モル当り０．０１ｇのカプリ防止剤（ＡＦ
−１）、および０．０５ｇのイラジエーシ１ン防止染料
（Ａ Ｉ −１）を含有する層
層４；１．４ｇのゼラチン、ｏ、ｏｅｇの色汚染防止剤
ＨＱ −１＋ Ｏ，Ｉｇの高沸点有機溶媒Ｄ Ｎ Ｐ
、 Ｏ，００１ｇのカプリ防止剤ＡＩ’−１，０，４ｇ
の紫外線吸収剤ＵＶ−１，０，２ｇの紫外線吸収剤Ｕ
Ｖ −２、０，００５゜のフィルター染料Ａ Ｉ−２，
０，０２ｇの表−２に示す活性剤、及び表−２に示す硬
膜剤を含有する層ｌ ５ ； １．４．のゼラチン、０
．２０ｇの表−３に示す赤感光性ハロゲン化銀乳剤、ｒ
Ｌ−３に示すシアンカプラー、衰３に示す色素画像安定
剤、０．０１ｇの色汚染防止剤ＨＱ−１．０．２ｇノ高
沸点油ｑＤＯＰ。Layer 1: L, 4g gelatin, 0128g (lL'l
(the same applies hereafter)! ! -1 Blue-sensitive silver helodenide milk m, 1.3 x 10" mole Yellow coupler shown in Table-1, 0.02 g Color stain inhibitor HQ-1, 0.3
g dinonyl 7-thale) (hereinafter abbreviated as DNP),
Layer 2 containing the dye image stabilizer shown in Table 1, 0.04 g of the activator shown in Table 1, and the anticapri agent shown in Table 1 at 0.03° per mole of silver halide; 0,
9g gelatin, 0.04g color stain inhibitor HQ-1,
0.1 g of no-2-ethylhexyl 7-talate (hereinafter referred to as D
(abbreviated as OP), 0.05 g of a noaminostilbene water-soluble optical brightener, an anti-capri agent shown in Table 1, and! ! 0,01 shown in -1. Layer 3 containing activator: 1.4 g of gelatin, green-sensitive silver halide emulsion as shown in Table 2, 0.8 x 10" moles of mazen coupler as shown in Table 2, dye al as shown in Table 2 The image is stable,
0, Ol [F dye stain inhibitor HQ-1, high boiling point organic solvent shown in Table 2, 0.02 g of the activator shown in Table 2, 0.01 g of anti-capri agent per mole of silver halide ( AF
-1), and layer 4 containing 0.05 g of anti-irradiation dye (A I-1); 1.4 g of gelatin, color stain inhibitor HQ of O, Oeg -1+ high boiling point of O, Ig Organic solvent DNP
, O,001 g of anti-capri agent AI' - 1,0,4 g
UV absorber UV-1, 0, 2g of UV absorber U
V-2, 0,005° filter dye A I-2,
Layer l 5 containing 0.02 g of the activator shown in Table-2 and the hardener shown in Table-2; 1.4. gelatin, 0
．． 20g of red-sensitive silver halide emulsion shown in Table-3, r
Cyan coupler shown in L-3, dye image stabilizer shown in Dec. 3, 0.01 g of color stain inhibitor HQ-1, 0.2 g of high boiling point oil qDOP.
０、Ｏｌｇのフィルター染料Ａｌ−２，０，５ｍｇのカ
プリ防止剤ＡＦ−１、および表−３に示す活性剤を含有
する層
層６；１．４．のゼラチン、ｏ、 Ｚｇの紫外線吸収剤
ＵＶ −１ｖ Ｑ、１ｇノ紫外線吸収削Ｕ Ｖ −２、
０，０１ｇ ノポリビニルピロリドン及Ｖ０．０６ｇの
表−３に示す活性剤を含有する層
層７ ； ０．８．のゼラチン、０．００５．のポリビ
ニルピロリドン、０．０４ｇの表−３に示す活性剤、Ｏ
，ｏｔｇの平均粒径約２μ鴫の二酸化ケイ素マット剤及
１表−３に示す硬膜剤を含有する層
別に、同様にして以下の試料を作成した。Layer 6 containing 0.0, Olg of filter dye Al-2, 0.5 mg of anticapri agent AF-1, and the activators shown in Table 3; 1.4. gelatin, o, Zg ultraviolet absorber UV-1v Q, 1g ultraviolet absorber UV-2,
Layer 7 containing 0.01 g of nopolyvinylpyrrolidone and 0.06 g of the activator shown in Table 3; 0.8. gelatin, 0.005. of polyvinylpyrrolidone, 0.04g of the activator shown in Table 3, O
, otg, a silicon dioxide matting agent having an average particle diameter of about 2 μm, and a hardening agent shown in Table 1-3, the following samples were prepared in the same manner.
試料１７〜３２
試料１〜１６において、層１に用いた青感光性ハロゲン
化銀乳剤の増感色素ＢＳＤ−１をＢＳＤ−２に変え、層
３に用いたｋｋｆ！！光性ハロゲン化乳乳剤の増感色素
をＧＳＤ−１からＧＳＤ−２に変えた試料
試料３３〜４８
試料１７〜３２において、層３、層４、層５に用いたＨ
Ｑ−１をＨＱ−２に変えた試料。Samples 17 to 32 In samples 1 to 16, the sensitizing dye BSD-1 in the blue-sensitive silver halide emulsion used in layer 1 was changed to BSD-2, and the kkf! ! Samples 33 to 48 in which the sensitizing dye of the photosensitive halogenated emulsion was changed from GSD-1 to GSD-2 In samples 17 to 32, H used in layer 3, layer 4, and layer 5
A sample in which Q-1 was changed to HQ-2.
試料４９〜６４
試料３３〜４８において、層３のＡｌ−１をＡｌ−３に
、層４に用いたＡｌ−２をＡｌ−４に変えた試料
試料６５〜８０
ｉ（ｌｉ１４９−６４１： オイ１：、Ｍｌ）ＵＶ−１
及（／ＵＶ−２をＵＶ−４、ＵＶ−５、ＵＶ−６の１：
２：４（重量比）の混合物に、また層６のｔＪＶ−１及
びＵＶ−２を、ＵＶ−４、ＵＶ−５、ＵＶ−６（ｎｌ：
３：６（重量比）の混合物に変えた試料試料８１〜９６
試料６５〜８０の層６のＵＶ−４、Ｕ Ｖ −５、ＵＶ
−６の１：３：６ （重量比）の混合物をＵＶ−３に
変えた試料
試料９７〜１１２
試料１〜１６において、層５の色素画像安定化剤を５Ｔ
Ｂ−７に変えた試料
試料１１３〜１２８
試料１〜１６において、／１５の色素画像安定化剤を５
ＴＢ−８に変えた試料
試料１２９〜１４４
試料１〜１６において層７の硬膜剤をＨＡ−３に変えた
試料
試料１４５〜１６０
試料１〜１６において、層１に用いた青感光性ハロゲン
化銀乳剤の増感色素ＢＳＤ−１をＢＳＤ−３に変えた試
料
試料１６１〜１７６
試料１７〜３２において、層５に用いた赤感光性ハロゲ
ン化銀乳剤の増感色素ＲＳＤ−１をＲＳＤ−２に変えた
試料
試料１７７〜１９２
試料１〜１６において、層１のＤＮＰ、層２の００２１
層３の高沸点有機溶媒、層４のＤＮＰ、層５のＤＯＰ、
層６のＤＮＰをＴＣＰに変えた試料試料１９３〜２０８
試料１〜１６において、層１のＤＮＰ、層２のＤＯＰ、
層３の高沸点有機溶媒、層４のＤＮＰ、層５のＤＯＰ％
Ｊ！６のＤＮＰをＴＩＮＰに変えた試料
試料２０９〜２２４
試料１〜１６において、層１のＤＮＰ、層２の００２１
層３の高沸点有機溶媒、層４のＤＮＰ、層５のＤＯＰ、
層６のＤＮＰをＴ Ｅ ＨＰ ｌ：変えた試料
ここで試料作成に用いた化合物を以下に示す。Samples 49 to 64 Samples 33 to 48, except that Al-1 in layer 3 was changed to Al-3 and Al-2 used in layer 4 was changed to Al-4 Samples 65 to 80 i (li149-641: Oi1 :, Ml) UV-1
and (/UV-2 to UV-4, UV-5, UV-6 1:
In a 2:4 (weight ratio) mixture, also tJV-1 and UV-2 of layer 6, UV-4, UV-5, UV-6 (nl:
Samples changed to a 3:6 (weight ratio) mixture Samples 81-96 UV-4, UV-5, UV of layer 6 of samples 65-80
Samples 97 to 112 in which a 1:3:6 (weight ratio) mixture of UV-6 was changed to UV-3 In samples 1 to 16, the dye image stabilizer in layer 5 was changed to 5T.
Samples 113 to 128 changed to B-7 In samples 1 to 16, /15 dye image stabilizer was added to 5
Samples 129 to 144 in which hardening agent in layer 7 was changed to TB-8 Samples 145 to 160 in samples 1 to 16 in which the hardener in layer 7 was changed to HA-3 Blue-sensitive halogenated material used in layer 1 in samples 1 to 16 Samples 161 to 176 in which the sensitizing dye BSD-1 in the silver emulsion was changed to BSD-3 In samples 17 to 32, the sensitizing dye RSD-1 in the red-sensitive silver halide emulsion used in layer 5 was changed to RSD-2. Samples 177 to 192 changed to Samples 1 to 16, DNP in layer 1, 0021 in layer 2
High boiling point organic solvent in layer 3, DNP in layer 4, DOP in layer 5,
Samples 193 to 208 in which DNP in layer 6 was changed to TCP In samples 1 to 16, DNP in layer 1, DOP in layer 2,
High boiling point organic solvent in layer 3, DNP in layer 4, DOP% in layer 5
J! Samples 209 to 224 in which DNP in layer 6 was changed to TINP In samples 1 to 16, DNP in layer 1 and 0021 in layer 2
High boiling point organic solvent in layer 3, DNP in layer 4, DOP in layer 5,
Sample in which DNP in layer 6 was changed to T E HP l: The compounds used to prepare the sample are shown below.
ＨＱ−Ｉ ＨＱ−２ Ｉ−Ｉ Ａ［−２ Ａｌ−３ ＵＶ−Ｉ ＵＶ−２ ＵＶ−３ ＵＶ−４ ＵＶ−５ ＵＶ−６ Ｃ４Ｆｌ ｓ （Ｌ １ （θ ｒσ ／′σ Ｙ−８ ／′〃 ＣＨ。HQ-I HQ-2 I-I A[-2 Al-3 UV-I UV-2 UV-3 UV-4 UV-5 UV-6 C4Fl s (L 1 (θ rσ /′σ Y-8 ／′〃 CH.
−Ｍ二２
しｌ
Ｃ−６
Ｓ’Ｔ Ｂ − ２
し？ｈ にＩ−ｈ
ＴＢ−５
ＴＢ−６
ＴＢ−７
ＴＢ−８
ＨＡ−１
ＨＡ−２
（ＣＨ２” ＣＨＳ Ｏ！ ＣＨｈＣとＮａ０ｒＳＣ８
２ＮＨ２（Ｆ）３：１（モル比）の反応生成物
ＨＡ−３
ＣＨ、＝ＣＨ−Ｓ Ｏ、ＣＨ２ＣＯＮＨ（ＣＨ２）「Ｎ
ＨＣＯＣＨ２Ｓｏ、ＣＨ＝ＣＨ。-M22 Shil C-6 S'T B-2 Shi? h to I-h TB-5 TB-6 TB-7 TB-8 HA-1 HA-2 (CH2” CHS O! CHhC and Na0rSC8
2NH2(F) 3:1 (molar ratio) reaction product HA-3 CH,=CH-S O, CH2CONH(CH2) "N
HCOCH2So, CH=CH.
５Ｄ−１
５Ｄ−２
３，３′−ノー（γ−スルホプロピル）−七しナシアニ
ンナトリウム塩
５Ｄ−３
５Ｄ−１
５Ｄ−２
３，３′−ノー（γ−スルホプロピル）−５゜５ ’
−９７ｚ 二ｋ ９−エチルオキサカルポジ７ニンナ
トリウム塩
５Ｄ−３
（ＣＨｉ）ｓｓＯｓＨ
５Ｄ−２
３，３′−クー（アニスルホプロビル）−９−メチルー
チアノカルポシアニンナトリウム塩Ｆ−１
ＣＨ，Ｃ００ＣＨ２（ＣＦ２ＣＦ、）、ＨＮａ０ｓＳ−
ＣＨＣＯＯＣＨｚ（ＣＦｚＣＦｚ）ｚＨＦ−２
Ｆ−３
ＣＨ２ＣＯＯＣｓ Ｈｌｔ
Ｎ ＊ ０３Ｓ ＣＨＣＯＯＣ＊ Ｈ＋ ｔＦ−Ｉ
Ｆ−２
ＣＰ
ＩＮＰ
ＥＨＰ
Ｑ
ＣＨ。5D-1 5D-2 3,3'-no(γ-sulfopropyl)-hanacyanine sodium salt 5D-3 5D-1 5D-2 3,3'-no(γ-sulfopropyl)-5゜5 '
-97z Nik 9-ethyloxacarposi7ine sodium salt 5D-3 (CHi)ssOsH 5D-2 3,3'-ku(anisulfoprovir)-9-methyl-thianocarpocyanine sodium salt F-1 CH , C00CH2 (CF2CF, ), HNa0sS-
CHCOOCHz (CFzCFz)zHF-2 F-3 CH2COOCs Hlt N * 03S CHCOOC* H+ tF-I F-2 CP INP EHP Q CH.
ＣＨ−ＣｘＨｓ
Ｃ４Ｈｓ
Ａ−１
試料１〜２２４において、層３のマゼンタカプラーを本
発明の例示カプラー１にかえた試料１−１〜２２４−１
を作成した。同様に試料１〜２２４において７１３のマ
ゼンタカプラーを本発明の例示化カプラーｎｌ：変えた
試料１−ｎ＝ ２２４ ｎを作成した（ｎ＝２〜７０
）、得られた試料の各々に対して、マクベスカラーチェ
ッカー （マクベス社！りを適正な光源下でサクラ−５
Ｒ１００（小西六写真工業（株）９１）で撮影し、ＣＮ
Ｋ−４（小西六写真工業（抹））処理したカラーネがを
通じて、露光、現像処理を行った。ｉ光量は、各々の試
料でマクベスカラーチェッカーの色が忠実に再現される
よう試行錯誤をくり返し、最良の条件を選択した。CH-CxHs C4Hs A-1 Samples 1-1 to 224-1 in which the magenta coupler in layer 3 was changed to exemplary coupler 1 of the present invention in samples 1 to 224
It was created. Similarly, in Samples 1 to 224, 713 magenta couplers were changed to the exemplified coupler of the present invention nl: Samples 1-n = 224 n were created (n = 2 to 70
), each of the obtained samples was tested using a Macbeth color checker (Macbeth Co., Ltd.) under an appropriate light source.
Photographed with R100 (Konishi Roku Photo Industry Co., Ltd. 91), CN
Exposure and development were carried out through a K-4 (Konishi Roku Photo Industry (M)) processed colorant. The best conditions for the amount of light were selected through repeated trial and error so that the colors of the Macbeth Color Checker could be faithfully reproduced for each sample.
表−５に示した各々の処理をほどこした試料を、各々の
試料について作成した。処理が同じであり、マゼンタカ
プラーのみ異なる試料についてマクベスカラーチェッカ
ーの色の再現の程度を総合的に判断したところマゼンタ
カプラーのみが異なる試料間で、本発明外のマゼンタカ
プラーを用いた試料に比べて本発明のマゼンタカプラー
を用いた試料の方が色再現性がすべて良好であった。Samples subjected to each treatment shown in Table 5 were prepared for each sample. Comprehensive judgment of the degree of color reproduction by Macbeth Color Checker was made for samples that were processed the same way but differed only in the magenta coupler. All samples using the magenta coupler of the present invention had better color reproducibility.
表−５
発色現像ａ−Ｓ
発色現像液−３のトリエタノールアミンのかわりにジェ
タノールアミンを用いた発色現像液
発色現像液−６
発色現像液−３のエチレンノアミン四酢酸のかわりにニ
トリロ三酢酸を用いた発色現像液発色現像液−７
発色現像液−３の７デニン０．００２ｇのかわりに発色
現像液−８
ベンノルアルコール １５ｍ１エチレ
ングリコール １５論ｌ亜硫酸カリウ
ム ２．ｏ、。Table-5 Color developer a-S Color developer using jetanolamine instead of triethanolamine in color developer-3 Color developer-6 Color developer-6 using nitrilotriacetic acid instead of ethylenenoaminetetraacetic acid in color developer-3 Color developer using acetic acid Color developer-7 Color developer-8 in place of 0.002 g of 7-denine in Color developer-3 Bennol alcohol 15 ml Ethylene glycol 15 mol Potassium sulfite 2. o.
臭化カリウム ０．７ｇ塩化ナ
トナトリツム ０．２ｇ炭酸カリウム
３０．０ｇヒドロキシルアミ
ン硫酸塩 ３．０゜ゴリリン酸 （ＴＰＰＳ
） ２．５ｇ３−メチル−４−７
ミ／−Ｎ−
（β−メタンスルホン７ミドエチ
ル）−アニリン硫酸塩 ５．５ｇ蛍光増白剤
（４，４’−ジアミノ
スチルベンズスルホン酸誘導体） １．０ｇ水酸
化カリウム Ｚ、 ｏｇ水を加え
て全量を１１とし、 ｐＨ１０，２０に調製する。Potassium bromide 0.7g Sodium chloride 0.2g Potassium carbonate 30.0g Hydroxylamine sulfate 3.0° Goliphosphoric acid (TPPS
) 2.5g3-methyl-4-7
Mi/-N- (β-methanesulfone 7midoethyl)-aniline sulfate 5.5g Fluorescent brightener (4,4'-diaminostilbenzsulfonic acid derivative) 1.0g Potassium hydroxide Z, og Add water Adjust the total volume to 11 and adjust the pH to 10.20.
安定化液−１
注１；発色現像液−１に用いた蛍光増白剤安定化液−２
安定化液−１の蛍光増白剤を発色現像液−３に用いた化
合物にかえた安定化液
ψＡ仁ｒ
処理工程
実施例２以降に用いるハロゲン化銀カラー感光材料試料
は、以下の層を岨合わせて作成した。Stabilizing solution-1 Note 1: Fluorescent brightener used in color developer-1 Stabilizing solution-2 Stabilization in which the fluorescent brightener in stabilizing solution-1 was replaced with the compound used in color developer-3 Liquid ψAnir Processing Steps The silver halide color light-sensitive material samples used in Example 2 and thereafter were prepared by combining the following layers.
ＢＳ；下引きをほどこしであるポリエチレンテレフタレ
ートフィルム支持体
ＨＬ−１；ハレーション防止層
０．１８ｇ／Ｉ＋＋”の黒色コロイド銀を含むゼラチン
層ＨＬ−２；ハレーシ３ン防止層
０．１８ｇ／ｍ”の黒色コロイド銀、０．１２ｇ／ｗ’
の紫外線吸収剤ＵＶ’−１及び０．１７ｇ／ｍ２の紫外
線吸収剤ＵＶ’ −２を含むゼラチン層
ＩＬ−１；中間層
０．０７ｇ／醜２の２，５−ノー を−オクチルハイド
ロキノン及び０．０７ｇ／−”のノブチル７タレートを
含有するゼラチン層
ＩＬ−２；中間層
０、１８ｇ／倫２の２，５−ジーセヵングリーペンタデ
シルハイドロキノン及び０．１１ｇ／ｍ”カラードカプ
ラー３及び０．１５ｇ／ｓ”の平均粒子サイズ０．０６
μの沃臭化銀（沃化銀１モル％）を含むゼラチン層
ＩＬ−３；中間層
ゼラチン層
ＹＦ−１； イエローフィルタ一層
ゼラチン水溶液中に黄色コロイド銀と２，５−ノーター
シャリ−オクチルハイドロキノンの乳化分散物とを°含
むゼラチン層
Ｐｒｏｌ；保護層
沃化銀１．２モル％の平均粒径０．０７μの沃臭化銀及
び紫外線吸収剤ＵＶ−１の乳化物を含むゼラチン層
塗布銀量０．４ｇ／ｍ２Ｐｒ、ｏ−２；保
護層
直径約１．４５μのポリメチルメタアクリレート粒子を
含むゼラチン層
ＲＬ−１；低感度緑感光性ハロゲン化銀乳剤層乳剤Ａ
（各実験例の表記載の乳剤）
１．５５ｇ／■２
増感色素１ 銀１モルに対して
４．４Ｘ１０−’モル
増感色素■ 銀１モルに対して
１．６Ｘ １０−’モル
カプラー■ （各実施例の表記載の化合物）銀１モルに
対して ０．０３モル
カラードカプラー！
（各実施例の表記載の化合物）
銀１モルに対して ０．００３モル
ＤＩＲ化合物Ｉ （各実施例の表記載の化合物）銀１モ
ルに対して ０．００４モル
トリクレノルアオス７二−ト；カプラー１１カラードカ
プラー■、ＤＩＲ化合物Ｉの総重量の１．５倍重量の量
ＲＨ−１；高感度赤感光性ハロゲン化銀乳剤層乳剤Ｂ
（各実験例の表記載の乳剤）１．３ｇ／Ｉｌ”増感色素
■ 銀１モルに対して
２．９Ｘ １０−’モル
増感色素■ 銀１モルに対して
１、ｌＸ１０−’モル
カプラー■ （各実施例の表記載の化合物）銀１モルに
対して ０．０２５モル
カラードカプラー■
（各実施例の表記載の化合物）
銀１モルに対して ０．００１５モル
トリクレノルアオス７二−ト；カプラー■、カラードカ
プラー■の総重量の１．３倍ｉｔのＩＧＬ−１；低感度
緑感光性ハロゲン化銀乳剤層乳剤Ｃ（各実験例の表記載
の乳剤）１．７ｇ／Ｉｌｚ増感色素■ 銀１モルに対し
て
４．９Ｘ１０−’モル
増感色素■ 銀１モルに対して
１．９Ｘ１０−’モル
カプラー■ （各実施例の表記載の化合物）銀１モルに
対して ０．０５モル
カラードカプラー■
（各実施例の表記載の化合物）
銀１モルに対して ｏ、ｏｏｓモル
ＤＩＲ化合物■ （各実施例の表記載の化合物）銀１モ
ルに対して ０．００１５モル
トリクレジｌし７オス７エート；カプラー■、カラード
カプラー■、ＤＩＲ化合物■の総重量の１．５倍重量の
量
ＧＨ−１；高感度緑感光性ハロゲン化銀乳剤層乳剤Ｄ
（各実験例の表記載の乳剤）
１．２５ｇ／ｍ”
増感色素■ 銀１モルに対して
３、ｌＸ１０−’モル
増感色素■ 銀１モルに対して
１．３Ｘ １０−モル
カプラー■（各実施例の表記載の化合物）銀１モルに対
して ０．０Ｚモル
カラードカプラー■
（各実施例の表記載の化合ｖＩＪ）
銀１モルに対して ０．００３モル
トリクレジル７オス７二−ト；カプラー■、カラードカ
プラー■の総重量の１．４倍重量の量ＢＬ−１：低域度
青患光性ノ１０デン化銀乳剤層乳剤Ｅ （各実験例の表
記載の乳剤）
０．８９ｇ／噛２
カプラー■（各実施例の表記載の化合物）銀１モルに対
して ０．２５モル
ＤＩＲ化合物■ （各実施例の表記載の化合物）銀１モ
ルに対して ０．０１７モル
トリクレジル７オス７エート； カプラーＶ１ＤＩＲ化
合物■の総重量の１．３倍重量の量ＢＨ−１；高感度青
感光性ノ）ロデン化銀乳剤層乳剤Ｆ （各実験例の表記
載の乳剤）
０．６１ｇ／＠”
カプラー■（各実施例の表記載の化合物）銀１モルに対
して ０．０７モル
） リクレノル７才ス７ｚ−）； カフ゛ラー■の重量
の１．２倍重量の量
ＲＬ−２；低感度赤感光性ハロゲン化銀乳剤層乳剤Ｇ（
各実験例の表記載の乳￥Ａ）
０．７３ｇ／糟２
増感色素■ 銀１モルに対して
７．０Ｘ１０−’モル
増感色素■ 銀１モルに対して
２．０Ｘ１０−Ｓモル
増感色素Ｖ 銀１モルに対して
Ｚ、８Ｘ １０−’モル
増感色素ＶＩ ＩＬ１モルに対して
２．０Ｘ１０−’モル
カプラー■（各実施例の表記載の化合物）１．２４ｇ／
ｍ２
カラードカプラ−■
（各実施例の表記載の化合物） ０．１４／＠２Ｄ
ＩＲ化合物■（各実施例の表記載の化合＊）０．０１ｇ
／儂２
トリフェニル７オス７エート； カプラー■、カラード
カプラーＶ、ＤＩＲ化合物■の総！！量の１．４倍重量
の量を含むゼラチン層
ＲＭ−１；中感度赤感光性／Ｎ Ｏデン化銀乳剤層乳剤
Ｈ（各実験例の表記載の乳剤）Ｌ４ｇ／■２増感色素■
Ｗ１１モルに対して
５．５Ｘ１０−’モル
増感色素１’Ｖ ｉ１モルに対して
１．６Ｘ １０″″５モル
増感色素■ 銀１モルに対して
２．２Ｘ ｔｏ−’モル・
増感色素■ 銀１モルに対して
１．８Ｘ１０−’モル
カプラー■（各実施例の表記載の化合物）０．２５ｇ／
噛２
カラードカプラー■
（各実施例の表記載の化合物） ０．０２ｇ／ｎ２
ＤＩＲ化合物Ｖ（各実施例の表記載の化合物）０．００
５Ｈ／ｍ”
ジブチル７タレート；カプラー■、カラードカプラー■
、ＤＩＲ化合物Ｖの総重量の１．３倍重量の量を含むゼ
ラチン層
ＲＨ−２；高恐度赤患光性ハロゲン化銀？し削層乳削Ｉ
（各実験例の表記載の乳剤）
１．７５Ｈ／ｍ”
増感色素■ 銀１モルに対して
５．５Ｘ １０−’モル
増感色素ＩＶ ｉ１モルに対して
１．６Ｘ１０−Ｓモル
増感色素■ 銀１モルに対して
２、ＺＸＩＯづモル
増感色素■ 銀１モルに対して
１、ｆ！Ｘ １０−’モル
カプラー■（各実施例の表記載の化合物）０．２１４／
ｍ’
カラードカプラー■
（各実施例の表記載の化合物） ０．ＯＺｇ／＋ａ
２ＤＩＲ化合物■ （各実施例の表記載の化合物）０．
００４ｇ／ｍ２
ＦＲ化合物■ （各実施例の表記載の化合物）０、００
０５ｇ／ ｍ２
トリフレツルフォスフエート； カプラーＩＸ、カラ
ードカプラー■、ＤＩＲ化合物■、ＦＲ化合物ＩＬ：ｒ
）総重量の１．５倍重量の１を含むゼラチン層ＧＬ−２
；低感度緑感光性ハロゲン化銀乳剤層゛ 乳剤Ｊ （
各実験例の表記載の乳剤）０．８ｇ／ｍ２増感色素■
銀１モルに対して
３．８Ｘ １０−’モル
増感色素Ｘ 銀１モルに対して
３．０×１０−ｓモル
増感色素釘 銀１モルに対して
１．２Ｘ １０″″４モル
カプラーＸ（各実施例の表記載の化合物）０．３５ｇ／
ｍ”
カラードカプラー■
（各実施例の表記載の化合物） ０，０９ｇ／＠”
ＤＩＲ化合化合物線実施例の表記載の化合物）０．０６
ｇ／ａ＋２
ジブチル７タレート；カプラーＸ１カラードカプラー■
、ＤＩＲ化合化合物線重量の１．５倍重量の１を含むゼ
ラチン層
ＧＭ−１；中感度緑感光性ハロゲン化銀乳剤層乳剤Ｋ
（各実験例の表記載の乳剤）
１．２５ｇ／鋤２
増感色素■ 銀１モルに対して
２．７Ｘ １０−’モル
増感色素Ｘ 銀１モルに対して
２、Ｉ Ｘ １０−５モル
増感色素ＸＩ ＩＮ１モルに対して
８．５Ｘ１０−’モル
カプラー■（各実施例の表記載の化合物）０．２５ｇ／
ｍ”
カラードカプラー■
（各実施例の表記載の化合物） ０．０２ｇ／ｍ２
ＤＩＲ化合物■（各実施例の表記載の化合物）Ｑ、０１
ｇ／ｍ２
トリフェニル７オス７二−ト； カプラーＸＩ、カラー
ドカプラー■、ＤＩＲ化合物■の総重量の１．４倍重量
の量を含むゼラチン層
ＧＨ−２；高感度緑患光性ハロゲン化銀乳剤層乳剤Ｌ
（各実験例の表記載の乳剤）
１．７５ｇ／瀉２
増感色素■ 銀１モルに対して
３、ＯＸ １０−’モル
増感色ＺＸ 銀１モルに対して
Ｚ、４Ｘ１０−’モル
増感色素て 銀１モルに対して
９．５Ｘ １０−’モル
カプラーＸ［（各実施例の表記載の化合物）０．０７ｇ
／ｍ”
カラードカプラーχ
（各実施例の表記載の化合物） ０．Ｏ１ｇ／ａ＋
”ＤＩＲ化合物■（各実施例の表記載の化合物）０、Ｏ
ＯＺｇ／ ｍ”
ＦＲ化合物■ （各実施例の表記載の化合物）０．００
０５ｇ／■２
トリクレノルアオス７ヱート；カプラー■、カラードカ
プラーＸ５ＤＩＲ化合物■、ＦＲ化合物■の総重量の１
．４倍重量の量を含むゼラチン層ＢＬ−２；低感度青患
光性ハロゲン化銀乳剤層乳剤Ｍ（各実験例の表記載の乳
剤）
０．３２１／ａ＋”
カプラーχ■ （各実施例の表記載の化合物）０．８８
ｇ／ｍ”
ＤＩＲ化合物Ｘ（各実施例の表記載の化合物）０．０３
ｇ／ｍ”
トリクレジル７オス７二−ト； カプラーＸ■、ＤＩＲ
化合物Ｘの総重量の１．３倍重量の量を含むゼラチン層
ＢＭ−１；中感度青感光性ハロゲン化銀乳剤層乳剤Ｎ
（各実験例の表記載の乳剤）
０．３５ｇ／ｃＡ２
増感色素■ 銀１モルに対して
２．２Ｘ １０−’モル
カプラーＸＩＶ （各実施例の表記載の化合物）０．２
２１１／’＋６２
ジブチル７タレート；カプラーＸＨの総重量の１．３倍
重量の量を含むゼラチン層
ＢＨ−２：高感度肯恐光性ハロゲン化銀乳剤層乳剤Ｏ（
各実験例の表記載の乳剤）１．８ｇ／ｍ”増感色素ｎ
銀１モルに対して
２．３Ｘ１０−’モル
カプラーＸＶ （各実施例の表記載の化合物）０．２Ｈ
／ｍ”
ＦＲ化合物■ （各実施例の表記載の化合物）０．００
０５ｇ／ ｍ”
トリフェニル７すス７二−ト；カプラーＸＶ１ＦＲ化合
物■の総重量の１．３倍重量の量を含むゼラチン層
各層には上記組成物の他に、ゼラチン硬化剤Ｈ−１又は
Ｈ−２や界面活性剤を添加した。BS: Polyethylene terephthalate film support HL-1 with subbing; gelatin layer HL-2 containing black colloidal silver of antihalation layer 0.18 g/m''; antihalation layer 0.18 g/m'' Black colloidal silver, 0.12g/w'
Gelatin layer IL-1 containing UV absorbers UV'-1 and 0.17 g/m2 of UV absorbers UV'-2; intermediate layer 0.07 g/m2 of 2,5-octylhydroquinone and 0 gelatin layer IL-2 containing .07 g/m" of butyl 7-thale; interlayer 0, 18 g/m2 of 2,5-Gysecanglypentadecylhydroquinone and 0.11 g/m" colored coupler 3; 0.15g/s” average particle size 0.06
Gelatin layer IL-3 containing μ silver iodobromide (silver iodide 1 mol %); Intermediate gelatin layer YF-1; Yellow filter single layer gelatin aqueous solution containing yellow colloidal silver and 2,5-not-tertiary-octylhydroquinone Gelatin layer Prol containing an emulsified dispersion of protective layer Prol; protective layer gelatin layer containing an emulsion of silver iodobromide with an average grain size of 0.07μ containing 1.2 mol % of silver iodide and an ultraviolet absorber UV-1;
Coated silver amount 0.4 g/m2Pr, o-2; Protective layer Gelatin layer RL-1 containing polymethyl methacrylate particles with a diameter of approximately 1.45 μ; Low-sensitivity green-sensitive silver halide emulsion layer Emulsion A
(Emulsion listed in the table for each experimental example) 1.55 g/■2 Sensitizing dye 1 4.4X 10-' mol sensitizing dye ■ per 1 mol of silver 1.6 X 10-' mol coupler ■ per 1 mol silver (Compounds listed in the table of each example) 0.03 mol colored coupler per 1 mol of silver! (Compounds listed in the table of each example) 0.003 mol per mol of silver DIR Compound I (Compounds listed in the table of each example) 0.004 mol triclenol aos72- per 1 mol of silver G; Coupler 11 Colored coupler (■), amount of 1.5 times the total weight of DIR compound I RH-1; High-sensitivity red-sensitive silver halide emulsion layer Emulsion B
(Emulsion listed in the table for each experimental example) 1.3 g/Il" sensitizing dye ■ 2.9 x 10-' mol sensitizing dye per 1 mol of silver ■ 1, l x 10-' mol coupler per 1 mol of silver ■ (Compounds listed in the table of each example) 0.025 mol per mol of silver Colored coupler ■ (Compounds listed in the table of each example) 0.0015 mol triclenol aos72- per 1 mol of silver G; IGL-1 of 1.3 times the total weight of coupler ■ and colored coupler ■; low-sensitivity green-sensitive silver halide emulsion layer Emulsion C (emulsion listed in the table of each experimental example) 1.7 g/Ilz increase Sensitizing dye■ 4.9 x 10-' mol per mol of silver Sensitizing dye■ 1.9 x 10-' mol per mol of silver Coupler■ (Compounds listed in the table of each example) 0. 05 mol Colored coupler ■ (Compound listed in the table of each example) o, oos mol per 1 mol of silver DIR compound ■ (Compound listed in the table of each example) 0.0015 mol trichrome per 1 mol of silver 7 male 7 ate; 1.5 times the total weight of coupler ■, colored coupler ■, and DIR compound ■ GH-1; High-sensitivity green-sensitive silver halide emulsion layer Emulsion D
(Emulsion listed in the table for each experimental example) 1.25 g/m" Sensitizing dye ■ 3, l x 10-' mol coupler per mole of silver ■ 1.3 x 10-mol coupler per mole of silver ( Compound listed in the table of each example) 0.0 Z mol per mol of silver Colored coupler ■ (Compound vIJ listed in the table of each example) 0.003 mol tricresyl 7 male 7 di-to per mol of silver; Amount of 1.4 times the total weight of coupler ■ and colored coupler ■ BL-1: Low-frequency blue photosensitive 10 silver denide emulsion layer Emulsion E (emulsion listed in the table of each experimental example) 0.89 g /2 Coupler ■ (Compound listed in the table of each example) 0.25 mol per mol of silver DIR compound ■ (Compound listed in the table of each example) 0.017 mol tricresyl 7 male per mol of silver 7ate; 1.3 times the total weight of coupler V1 DIR compound BH-1; High-sensitivity blue-sensitive silver lodenide emulsion layer Emulsion F (emulsion listed in the table of each experimental example) 0.61 g/ ＠” Coupler ■ (compound listed in the table of each example) 0.07 mol per mol of silver) Liklenor 7 years old 7z-); Amount 1.2 times the weight of coupler ■ RL-2; Low Sensitivity Red-sensitive silver halide emulsion layer Emulsion G (
Milk ￥ A) 0.73 g/2 mols Sensitizing dye ■ 7.0 x 10-' mol Sensitizing dye ■ 2.0 x 10-S mol increase per 1 mol silver Sensitizing dye V Z, 8X 10-' mol per mole of silver Sensitizing dye VI 2.0X 10-' mol coupler (compound listed in the table of each example) 1.24 g/
m2 Colored coupler ■ (Compound listed in the table of each example) 0.14/@2D
IR compound ■ (compound listed in the table of each example *) 0.01 g
/I2 triphenyl 7mose 7ate; total of coupler ■, colored coupler V, and DIR compound ■! ! gelatin layer RM-1 containing 1.4 times the weight of the gelatin layer RM-1; medium red sensitivity/N O silver denide emulsion layer Emulsion H (emulsion listed in the table of each experimental example) L4g/■2 sensitizing dyes■
5.5X to 1 mole of W 1 mole Sensitizing dye 1'Vi 1.6X to 1 mole of 5 mole sensitizing dye ■ 2.2X to 1 mole of silver Sensitizing dye Dye ■ 1.8X10-' mol coupler ■ (compound listed in the table of each example) 0.25 g/mole of silver
2 Colored coupler ■ (Compound listed in the table of each example) 0.02g/n2
DIR compound V (compound listed in the table of each example) 0.00
5H/m” dibutyl 7 talate; coupler■, colored coupler■
, gelatin layer RH-2 containing an amount of 1.3 times the total weight of DIR compound V; high-performance red photosensitive silver halide? Layer milking I
(Emulsion listed in the table for each experimental example) 1.75H/m" Sensitizing dye ■ 5.5X 10-' mole sensitizing dye IV for 1 mole of silver 1.6X 10-S mole sensitizing for 1 mole of i Dye ■ 2, ZXIO mol per mole of silver Sensitizing dye ■ 1 per mole of silver, f!
m' Colored coupler ■ (Compound listed in the table of each example) 0. OZg/+a
2DIR compound ■ (Compound listed in the table of each example) 0.
004g/m2 FR compound ■ (Compound listed in the table of each example) 0,00
05g/m2 trifretulphosphate; coupler IX, colored coupler ■, DIR compound ■, FR compound IL:r
) Gelatin layer GL-2 containing 1.5 times the total weight of 1
; Low-sensitivity green-sensitive silver halide emulsion layer ゛ Emulsion J (
Emulsion in the table of each experimental example) 0.8 g/m2 sensitizing dye ■
3.8x 10-' mole sensitizing dye X per mole of silver 3.0x10-s mole sensitizing dye (Compound listed in the table of each example) 0.35g/
m" Colored coupler (compound listed in the table of each example) 0.09g/@"
DIR compound compound line Compounds listed in the table of Examples) 0.06
g/a+2 dibutyl 7 tallate; coupler X1 colored coupler ■
, gelatin layer GM-1 containing 1.5 times the linear weight of the DIR compound compound; medium-sensitivity green-sensitive silver halide emulsion layer emulsion K
(Emulsion listed in the table for each experimental example) 1.25 g/plow 2 Sensitizing dye ■ 2.7X per mole of silver 10-' mol Sensitizing dye X 2, I X 10-5 per mole of silver 8.5 x 10-' molar coupler ■ (compound listed in the table of each example) 0.25 g/mole of molar sensitizing dye XI IN
m” Colored coupler■ (Compound listed in the table of each example) 0.02g/m2
DIR compound ■ (compound listed in the table of each example) Q, 01
g/m2 Triphenyl 7-mose-7-2; gelatin layer GH-2 containing an amount 1.4 times the total weight of coupler XI, colored coupler ■, DIR compound ■; high sensitivity green photosensitive silver halide Emulsion layer emulsion L
(Emulsion listed in the table for each experimental example) 1.75 g/2 Sensitizing dye ■ 3, OX per mole of silver 10-' mole sensitizing color ZX Z, 4X10-' mole increase per mole of silver Sensitive dye: 9.5 x 10-' mol coupler X [(compound listed in the table of each example) 0.07 g
/m” Colored coupler χ (compounds listed in the table of each example) 0.O1g/a+
"DIR compound ■ (compound listed in the table of each example) 0, O
OZg/m” FR compound ■ (Compound listed in the table of each example) 0.00
05g/■2 Triclenol aos7et; 1 of the total weight of coupler ■, colored coupler X5DIR compound ■, FR compound ■
．． Gelatin layer BL-2 containing 4 times the amount by weight; low-sensitivity blue photosensitive silver halide emulsion layer Emulsion M (emulsion listed in the table of each experimental example) 0.321/a+" coupler χ■ (of each example Compounds listed in the table) 0.88
g/m” DIR Compound X (compound listed in the table of each example) 0.03
g/m” tricresyl 7 male 7 dual; coupler X, DIR
Gelatin layer BM-1 containing 1.3 times the total weight of compound X; medium-sensitivity blue-sensitive silver halide emulsion layer Emulsion N
(Emulsion listed in the table for each experimental example) 0.35 g/cA2 Sensitizing dye ■ 2.2X per mole of silver 10-' mol coupler XIV (Compound listed in the table for each example) 0.2
211/'+62 dibutyl 7 tallate; Gelatin layer BH-2 containing 1.3 times the total weight of coupler XH: High-sensitivity photosensitive silver halide emulsion layer Emulsion O (
Emulsion described in the table of each experimental example) 1.8 g/m" sensitizing dye n
2.3 x 10-' mol coupler XV (compound listed in the table of each example) 0.2H per mol of silver
/m” FR compound■ (Compounds listed in the table of each example) 0.00
05 g/m" Gelatin layer containing 1.3 times the total weight of the coupler XV1FR compound H-2 and a surfactant were added.
実施例２以降に用いた化合物を以下に示す。The compounds used in Example 2 and thereafter are shown below.
Ｙ′−１ Ｙ′−２ Ｃσ Ｙ′−３ Ｙ′−６ Ｃσ Ｙ′−７ Ｍ′−１ ユニに、（Ｌ）ＣｓＨ＋ｙは （ＣＨ、）、ＣＣＨｉｃ （ＣＨ、）２−を表わす。Y'-1 Y'-2 Cσ Y'-3 Y'-6 Cσ Y'-7 M'-1 Uni, (L)CsH+y is (CH,), CCHic (CH,)2-.
Ｍ′−４ Ｍ′ −６ しＺ Ｍ′−８ し１ Ｍ’−１１ Ｃ′−６ Ｃ′−８ Ｃ′−９ Ｃ’−１０ Ｃ’−１１ Ｃ’−１２ Ｃ’−１３ ＣＣ−Ｉ ＣＣ−２ ＣＣ−３ ＣＣ−４ ｃｏｏｃｉＨｓ ＩＲ−Ｉ ＩＲ−２ ＩＲ−４ ＣＣ ＩＲ−５ 脣 ＤＩＲ−７ ｒθ ＩＲ−９ Ｉ ＩＲ−１１ ＩＲ−１２ ＩＲ−１４ Ｎ＝Ｎ ＤＩＲ−１７ ＤＩＲ−１８ ＩＲ−１９ ＩＲ−２０ ＩＲ−２３ リレルコ 増感色素Ｉ 増感色素■ 増感色素■ （ＣＨ２）＋ＳＯ＋Ｎａ 増感色素■ 増感色素■ 増感色素■ Ｃ２Ｈｓ 増感色素■ 増感色素■ 増感色素■ 増感色素Ｘ 増感色素℃ 増感色素■ （ＣＨ２）＋Ｓ○コＫ ｘ／ｙ＝ ７ ／ ３ （重量比） ＵＶ’ −２ −一９ Ｒ−５ Ｒ−６ ＣＨ，＝ＣＨ−３Ｑ２−ＣＨ２−ＣＯＮＨ−ＣＨ。M'-4 M'-6 ShiZ M'-8 1 M'-11 C'-6 C'-8 C'-9 C'-10 C’-11 C’-12 C’-13 CC-I CC-2 CC-3 CC-4 coociHs IR-I IR-2 IR-4 C.C. IR-5 Shoulder DIR-7 rθ IR-9 I IR-11 IR-12 IR-14 N=N DIR-17 DIR-18 IR-19 IR-20 IR-23 Lilelco Sensitizing dye I Sensitizing dye■ Sensitizing dye■ (CH2)+SO+Na Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ C2Hs Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ Sensitizing dye X Sensitizing dye °C Sensitizing dye■ (CH2)+S○koK x/y=7/3 (weight ratio) UV’ -2 -19 R-5 R-6 CH,=CH-3Q2-CH2-CONH-CH.
ＣＨ２＝ＣＨ−８Ｑ、−ＣＨ，−ＣＯＮＨ−ＣＨ２）！
−２
以下の実施例で用いる乳剤は下記のものである。CH2=CH-8Q, -CH, -CONH-CH2)!
-2 The emulsions used in the following examples are as follows.
以下の記述において、範囲内粒子比とは、平均粒径下を
中心に±２０％の粒径範囲内に含まれるハロゲン化銀粒
子の重量の全ハロゲン化銀粒子の重量に対する比率をい
う。In the following description, the within-range grain ratio refers to the ratio of the weight of silver halide grains included within a grain size range of ±20% centered on the average grain size to the weight of all silver halide grains.
ここに平均粒径〒は、粒径ｒｉを有する粒子の頻度ｎｉ
と「ｉコ との積ｎｉＸ ｒｉ’が最大となるときの粒
径ｒｉ （有効数字３桁、最小桁数字は４捨５人）と定
義される。Here, the average particle size 〒 is the frequency ni of particles with particle size ri
is defined as the particle size ri (3 significant figures, minimum digit is 5 to the nearest 4) when the product niXri' of
ここでいう粒径ｒｉとは、球状のハロゲン化銀粒子の場
合はその直径、また球状以外の形状の粒子の場合は、そ
の投影像を同面積の円像に換算した時の直径である。こ
の粒径は、例えば、該粒子を、電子顕微鏡で１０，００
０倍から５０，０００倍に拡大して撮影し、そのプリン
ト上の粒子直径または、投影像の面積を有効数字３桁（
４桁目４捨５人）を実測することによって得ることがで
きる。（測定粒子個数は、無差別に１，０００個以上あ
る事とする。）。The grain size ri here means the diameter in the case of spherical silver halide grains, and in the case of grains having shapes other than spherical, the diameter when the projected image is converted into a circular image of the same area. This particle size is, for example, 10,000 by electron microscopy.
Take a photograph at magnification of 0 to 50,000 times, and calculate the particle diameter on the print or the area of the projected image to 3 significant digits (
It can be obtained by actually measuring the 4th digit (4 to 5 people). (The number of particles to be measured shall be 1,000 or more indiscriminately.)
ＥＭ−１；平均粒径０．６０μ、範囲内粒子比４０％の
沃 化銀６．０モル％の沃臭化銀？Ｌ剤、平均アスペク
ト比１．５：Ｉ
ＥＭ−２；平均粒径０．７４μ、範囲内粒子比４２％の
沃 化銀６．０モル％の沃臭化銀乳
剤、平均アスペクト比１．５：Ｉ
ＥＭ−３；平均粒径３μ論、平均アスペクト比１０：１
の沃臭化銀乳剤、範囲内粒子
比３８％
ＥＭ−４；平均粒径０．５０μ、範囲内粒子比７２％、
ファーの沃化銀含有率１２モル％、シ
ェルの沃化銀含有率Ｏ％、全粒子中
の沃化銀含有率８．７％、シェルの厚
み０．０２５μの沃臭化銀乳剤
ＥＭ−５；平均粒径１．０μ、範囲内粒子比４１％、沃
化ＩＩ ７．０モル％を含む沃臭化銀乳剤、平均アスペ
クト比１．５：Ｉ
ＥＭ−６；平均粒径２．８μ−１平均アスペクト比７：
１、内部沃化銀１０モル％、外
部沃化銀２モル％の沃臭化銀乳剤
ＥＭ−７；平均粒径０．３２μ、範囲内粒子比６５％、
ファーの沃化銀含有率８モル％、シ
ェルの沃化銀含有率０．５モル％、全
粒子の沃化銀含有率６．０％、シェル
の厚み０．０１６μの沃臭化銀乳剤
ＥＭ−８；平均粒径０．７μ、範囲内粒子比７５％、沃
化銀７モル％の沃臭化銀乳剤
ＥＭ−９：平均粒径Ｑ、８μ閣、範囲内粒子比７４％、
沃化銀モル％が粒子内部から順
次１５モル％、５モル％及び０．３モル％のファー／シ
ェル沃臭化銀乳剤
Ｅ Ｍ −１０；平均粒径２．６μ輪、平均アスペクト
比＝７：１、内部沃化銀２モル％、
外部沃化銀１０モル％の沃臭化銀乳剤
Ｅ Ｍ −１１；平均粒径１．７μｍ、範囲内粒子比３
２％、沃化銀１０モル％の沃臭化銀乳剤
Ｅ Ｍ −１２；平均粒径３．５μｍ、平均アスペクト
比６：１、内部沃化銀１０モル％、外
部沃化銀２モル％の沃臭化銀乳剤
次にこれら実施例で使用したハロゲン化銀乳剤の代表的
調製法を示す。EM-1: Silver iodobromide containing 6.0 mol% of silver iodide with an average grain size of 0.60μ and a grain ratio within the range of 40%? Agent L, average aspect ratio 1.5: I EM-2; silver iodobromide emulsion containing 6.0 mol% silver iodide with average grain size 0.74μ and range grain ratio 42%, average aspect ratio 1.5 :I EM-3; Average grain size 3 μ theory, average aspect ratio 10:1
Silver iodobromide emulsion, grain ratio within the range 38% EM-4; average grain size 0.50μ, grain ratio within the range 72%,
Silver iodobromide emulsion EM-5: silver iodide content in fur 12 mol%, silver iodide content in shell 0%, silver iodide content in all grains 8.7%, shell thickness 0.025μ Silver iodobromide emulsion containing 7.0 mol% of II iodide, average grain size 1.0μ, in-range grain ratio 41%, average aspect ratio 1.5:I EM-6; Average grain size 2.8μ- 1 average aspect ratio 7:
1. Silver iodobromide emulsion EM-7 with 10 mol% of internal silver iodide and 2 mol% of external silver iodide; average grain size 0.32μ, grain ratio within the range 65%,
Silver iodobromide emulsion EM with silver iodide content of fur 8 mol%, silver iodide content of shell 0.5 mol%, silver iodide content of all grains 6.0%, and shell thickness 0.016 μm. -8; Silver iodobromide emulsion EM-9: average grain size Q, 8μ, grain ratio within the range 74%, silver iodide 7 mol%;
Fur/shell silver iodobromide emulsion EM-10 with silver iodide mole % of 15 mol %, 5 mol % and 0.3 mol % sequentially from inside the grain; average grain size 2.6 μm, average aspect ratio = 7 :1, silver iodobromide emulsion EM-11 with 2 mol% internal silver iodide and 10 mol% external silver iodide; average grain size 1.7 μm, grain ratio within the range 3
Silver iodobromide emulsion EM-12 with 2% silver iodide and 10 mol% silver iodide; average grain size 3.5 μm, average aspect ratio 6:1, internal silver iodide 10 mol%, external silver iodide 2 mol%. Silver Iodobromide Emulsion Next, a typical method for preparing the silver halide emulsion used in these Examples will be described.
ＥＭ−３（沃化銀７モル％を含む、平均粒径３μ−１平
均アスペクト比１０：１のｊｋｒ化休、体剤）特開昭５
８−１１３９２８記載と同様な手法により調製した。即
ち、臭化カリウム５９，５．を含有する ０．８％ゼラ
チン溶ｆｉ ５，０ｆｆｉを８０℃に撹拌しなからダブ
ルジェット法により、臭化カリウム８．３３ｇを添加し
た水溶１５８．３＋ｆと硝酸銀１１．９ｇ添加した水溶
液５８．３ｍｌを同流量で加えた０次いで７タル化ゼラ
チン１７．６ｇを含有する溶液８００／！ ＠加えた０
次いで硝酸銀溶液をＰＢｒが１．４０に達するまで加え
た。EM-3 (JKR compound containing 7 mol% silver iodide, average grain size 3μ-1, average aspect ratio 10:1) JP-A-1988
8-113928. That is, potassium bromide 59,5. 58.3 ml of an aqueous solution containing 0.8% gelatin solution 158.3+f containing 8.33 g of potassium bromide and 11.9 g of silver nitrate was stirred at 80°C and then mixed using the double jet method. 800/! @Added 0
Silver nitrate solution was then added until the PBr reached 1.40.
次いで沃化カリウム３８．７． 、臭化カリウム３４０
ｇの水溶９２．６１をダブルジェット法により硝酸銀５
２５１ｇを含む水溶液２．６１を等流量で添加した。Then potassium iodide 38.7. , potassium bromide 340
92.61 g of aqueous solution was converted into silver nitrate by the double jet method.
2.61 g of an aqueous solution containing 251 g was added at equal flow rates.
この間、ＰＢｒを１．４０に維持した。温度を４０℃と
し、沈澱水洗した後、ゼラチンを加え、再分散させ、２
０℃で凝固させ、 ２．０ｋｇの乳剤を調整した。During this time, PBr was maintained at 1.40. After setting the temperature to 40°C and washing the precipitate with water, gelatin was added and redispersed.
It was coagulated at 0°C to prepare 2.0 kg of emulsion.
ジェット法にて等速で添加した。温度を４０℃にし、沈
澱水洗後、ゼラチンを加え、再分散させ、２０℃で凝固
させ、 ２．０ｋｇの乳剤をａ整した。It was added at a constant speed using a jet method. The temperature was raised to 40°C, and after washing the precipitate with water, gelatin was added, redispersed, and coagulated at 20°C to form a 2.0 kg emulsion.
ＥＭ−５（沃化銀７モル％、平均粒径１．０μ鴫、平均
７スベクト比１．５ ： １の沃臭化銀乳剤）臭化カ
リウム４１．６５ｇ 、沃化カリウム１３．９ｇ及びチ
オシアン酸カリウム３４．６３．を含む溶液７．０１（
７タル化ゼラチン１．２５％含有）を８０℃において撹
拌しつつ、これにダブルジェット法により沃化カリウム
２６．８．及び臭化力リ−ラム ３８７ｇを含む溶液２
．４５１と硝酸銀５９４．６ｇを含む溶ｆｉ２．４５１
を等流量で加えた０次いで、温度を４０℃に落とし、沈
澱水洗した後、ゼラチンを加え再分散し、その後２０℃
で凝固し、乳剤２．０に、を調整した。EM-5 (silver iodobromide emulsion with 7 mol % silver iodide, average grain size 1.0 μm, average 7 spectral ratio 1.5:1) 41.65 g of potassium bromide, 13.9 g of potassium iodide and thiocyanide potassium acid 34.63. Solution 7.01 containing (
While stirring 7-tal gelatin (containing 1.25%) at 80°C, 26.8% of potassium iodide was added to it by double jet method. and Solution 2 containing 387 g of Bromide Reelum
．． 451 and 594.6g of silver nitrate
Then, the temperature was lowered to 40°C, the precipitate was washed with water, gelatin was added and redispersed, and then the temperature was lowered to 40°C.
The emulsion was solidified and the emulsion was adjusted to 2.0.
ＥＭ−６（平均粒径２．８μ論、平均アスペクト比７：
１、内部沃化銀１０モル％、外部沃化銀２モル％の沃臭
化銀乳剤）
臭化カリウム１０．７ｇを含有する １．５％ゼラチン
水水溶ｌ：ｌ上ニア０、ｐＨ５，８１：オイて撹拌し、
臭化カリウム２．５４．を加えた水溶液１１．９ｍｊ！
と硝酸銀１３．９６ｇを加えた水溶ａ１１．９ｍｌをＰ
Ｂｒｏ、９に維持しなからダブルジェット法により等流
量で添加した０次に、硝酸銀３３．７ｇを加えた水溶液
２．８１と臭化カリウム２１４ｇ及び沃化カリウム３３
．２ｇを加えた水溶ａ ２．８１とをＰＢｒｌ、２に維
持しながらダブルジェット法により等流量で添加した。EM-6 (average particle size 2.8μ theory, average aspect ratio 7:
1. Silver iodobromide emulsion with 10 mol% of internal silver iodide and 2 mol% of external silver iodide) 1.5% gelatin in water containing 10.7 g of potassium bromide (1:1), pH 5.81 :Oy and stir.
Potassium bromide 2.54. 11.9 mj of aqueous solution added!
and 13.96 g of silver nitrate were added to P.
Next, 2.81 of an aqueous solution containing 33.7 g of silver nitrate, 214 g of potassium bromide, and 33 g of potassium iodide were added at equal flow rates by the double jet method while maintaining Bro, 9.
．． 2.81 g of aqueous a was added at equal flow rates by a double jet method while maintaining PBrl at 2.
犬に硝酸銀２２４．９ｇを加えた水溶ｆｉ １，９１７
と臭化カリウム１５５．５ｇ及び沃化カリウム４．４２
ｇを加えた水溶？［Ｉ １，９１とをＰＢｒｌ、２に維
持しながらダブルジェット法により等流量で添加し、直
径２．８μ気、厚さ０．４μ１１アスペクト比７；１の
平板状粒子を沈澱生成した。後に４０゛Ｃで脱塩処理を
行ない、ゼラチンを加え、再分散させた後、２０℃に冷
却凝固させ、 １．５ｋｇのハロゲン化銀乳剤ＥＭ−６
を得た。Water-soluble fi 1,917 with 224.9g of silver nitrate added to dogs
and potassium bromide 155.5g and potassium iodide 4.42g
Aqueous solution with added g? [I1,91] were added at equal flow rates by a double jet method while maintaining PBrl, 2, to precipitate tabular grains having a diameter of 2.8 μm, a thickness of 0.4 μm, and an aspect ratio of 7:1. Afterwards, it was desalted at 40°C, gelatin was added, and after redispersion, it was cooled to 20°C and solidified to form 1.5 kg of silver halide emulsion EM-6.
I got it.
ＥＭ−１０（平均粒径２．６μ脇、平均アスペクト比７
： １、内部沃化ｆ１１２モル％、外部沃化銀１０モル
％の沃臭化銀乳剤）
臭化カリウム５０．６ｇを含有する １．５％ゼラチン
水溶液Ｚ、５１を６５゛Ｃ″Ｃ″攪拌しながら、これに
ダブルジェット法により、ＰＢｒを０．８に維持しなが
ら硝酸４１５．７０ｇ ヲ含す水溶液（溶［Ａ）ｌｌｃ
ｃト臭化カリウム ４．０ｇを含む水＃液（溶液Ｂ）ｌ
ｌｃｃとを等流量で加えた後、硝酸銀を加え、ＰＢｒを
１．４に調整した。EM-10 (average grain size 2.6μ, average aspect ratio 7)
: 1. Silver iodobromide emulsion with 112 mol% of internal iodide and 10 mol% of external silver iodide) A 1.5% gelatin aqueous solution Z, 51 containing 50.6 g of potassium bromide was stirred at 65゛C''C'' Meanwhile, an aqueous solution (solution [A)] containing 415.70 g of nitric acid was added to this by a double jet method while maintaining PBr at 0.8.
c Water solution containing 4.0 g of potassium bromide (solution B) l
After adding lcc at equal flow rates, silver nitrate was added to adjust PBr to 1.4.
次いで、硝酸＠ ５９０ｇを含む溶液（溶液Ｃ）２．５
１と沃化カリウム１４．１ｇ及１臭化カリウム３３０ｇ
を含む溶液（溶液Ｄ）２１とをダブルジェット法でＰＢ
ｒを１．５に維持しながら等速″Ｃ添加し、溶ｉ（！Ｄ
が添加終了後、溶ｇｃと沃化カリウム１１．３ｇ及び臭
化カリウム７３．０ｇ を含む溶液５００ｍ１！とをＰ
Ｂｒを１．５に維持しながらダブルジェット法にて等速
で添加した。温度を４０℃にし、沈澱水洗後、ゼラチン
を加え、再分散させ、２０°ｃ’ｔ’凝固させ、２．０
ｋｇの乳剤をｌＮ製した。Next, a solution containing 590 g of nitric acid (solution C) 2.5
1 and potassium iodide 14.1g and potassium monobromide 330g
(solution D) 21 containing PB using the double jet method.
While maintaining r at 1.5, add ``C'' at a constant rate, and dissolve i(!D
After addition, 500ml of solution containing molten gc, 11.3g of potassium iodide and 73.0g of potassium bromide was added! and P
It was added at a constant speed by a double jet method while maintaining Br at 1.5. The temperature was set to 40°C, and after washing the precipitate with water, gelatin was added, redispersed, and solidified at 20°c't'.
kg of emulsion was prepared in IN.
ＥＭ−１２
５０℃において、特開昭５７−９２５２３号、同５７−
９２５２４号で示される混合撹拌器を用いて溶液Ａ−１
に溶ＲＥ−１とＢ−１とを同時混合法によって添加し、
Ｂ−１添加終了と同時にＧ−１を添加し、Ｃ−１の添加
終了と同時にＤ−１を添加した。同時混合中のｐＡｇ、
ｐＨ及び溶１Ｅ−１の添加速度は表−Ａに示すように制
御した。ｐＡｇ及Ｖ ｐＨの制御は流量可変のローラー
チニープポンプにより、溶？１ｌＦ−１と溶１Ｇ−１の
流量を変えることによって行った。EM-12 At 50°C, JP-A No. 57-92523, No. 57-
Solution A-1 using a mixing stirrer shown in No. 92524.
Adding dissolved RE-1 and B-1 to the solution by simultaneous mixing method,
G-1 was added at the same time as the addition of B-1 was completed, and D-1 was added at the same time as the addition of C-1 was completed. pAg during simultaneous mixing,
The pH and addition rate of Solution 1E-1 were controlled as shown in Table-A. pAg and V pH are controlled by a roller tinip pump with variable flow rate. This was done by changing the flow rates of 11F-1 and 1G-1.
溶液Ｅ−１の添加終了２分後に溶液Ｆ−１によってｐＡ
、を１０．４に、更に２分後に溶液Ｇ−１によって９８
を６．０に調節した。Two minutes after the addition of solution E-1 was completed, pA was adjusted by solution F-1.
, to 10.4 and after another 2 minutes to 98 with solution G-1.
was adjusted to 6.0.
（溶液Ａ−１）
・オセインゼラチン ２２．５ｇ、
蒸留水 ６７９９ａ＋ト
ポリインプロピレン一ポリエチレン
オキシージコハク酸エステルナトリ
フム塩１０％エタノール水溶液 ２０ｒａｌ・
４−ヒドロキシ−６−メチル−１゜
３．３ａ、７−チトラザインデン ２７７＋＊ｇ・
２８％アンモニア水 ４６９社・種
乳剤 ０．８８２８モル相当量（溶液
Ｂ−１）
・オセインゼラチン ６．０ｇ・Ｋ
Ｂ ｒ ２１２ｇ
・Ｋｌ ５２，３ｇ
・４−ヒドロキシ−６−メチル−１゜
３．３ａ 、７−チトラザインデン ４ＺＩａｇ・
蒸留水 ５０醜ｌ（溶液
Ｃ−１）
・オセインゼラチン ５．０ｇ・Ｋ
Ｂ ｒ １９ｋ・
Ｋ Ｉ １４，５ｇ
・４−ヒドロキシ−６−メチル−１゜
３．３ａ、７−チトラザインデン３５１ＩＦＩ・蒸留水
４２２ｖａｌ（溶液Ｄ−
１）
・オセインゼラチン ２０゜・Ｋ
Ｂｒ ８３０ｇ・Ｋ
ｒ ３，５ｇ・
４−ヒドロキシ−６−メチル−１゜
３．３ａ、７−チトラザインデン １３９ｗＦｌ・
蒸留水 １６７２／！（
溶液Ｅ−１）
・ＡｇＮ０１ １１０９ｇ・
２８％アンモニア水 ９０４＋１・
蒸留水で１８６６１１１１にする。(Solution A-1) - Ossein gelatin 22.5g,
Distilled water 6799a + topolyinpropylene - polyethylene oxydisuccinic acid ester sodium salt 10% ethanol aqueous solution 20ral.
4-Hydroxy-6-methyl-1゜3.3a,7-chitrazaindene 277+*g・
28% ammonia water 469 companies Seed emulsion 0.8828 mol equivalent (solution B-1) Ossein gelatin 6.0 g K
B r 212g
・Kl 52.3g
・4-hydroxy-6-methyl-1゜3.3a, 7-chitrazaindene 4ZIag・
Distilled water 50 liters (solution C-1) ・Ossein gelatin 5.0 g・K
B r 19k・
K I 14.5g
・4-hydroxy-6-methyl-1゜3.3a,7-chitrazaindene 351IFI ・Distilled water 422val (solution D-
1) ・Ossein gelatin 20°・K
Br 830g・K
r 3.5g・
4-Hydroxy-6-methyl-1゜3.3a,7-chitrazaindene 139wFl・
Distilled water 1672/! (
Solution E-1) ・AgN01 1109g・
28% ammonia water 904+1・
Make 18661111 with distilled water.
（溶ｔＦ−１）
・５０％ＫＢｒ水溶液 ｐＡｇ調整必要量（溶Ｒ
Ｇ−１）
・５６％酢酸水溶液 ｐＨｉｌ［必要１各々
の工程に用いた処理液を以下に示す。(Solution tF-1) ・50% KBr aqueous solution pAg adjustment required amount (Solution R
G-1) - 56% acetic acid aqueous solution pHil [Required 1 The treatment liquid used in each step is shown below.
発色現像ｇ、−１
４−７ミ／−３−メチル−Ｎ−エチ
ル−Ｎ−（β−ヒドロキシエチル）
−アニリン・硫酸塩 ４．７５ｇ無水
亜硫酸ナトリウム ４．２５ｇヒドロキ
シルアミン・１／２硫酸塩 ２．０ｇ無水炭酸カリウ
ム ３７．５ｇ臭化ナトリワム
１．３ｇニトリロトリ酢酸・３ナト
リウム塩
（１水塩） ２．５ｇ水
酸化カリウム １．０゜水を加え
て１１とする。Color development g, -1 4-7mi/-3-methyl-N-ethyl-N-(β-hydroxyethyl) -aniline sulfate 4.75g anhydrous sodium sulfite 4.25g hydroxylamine 1/2 sulfate 2.0g anhydrous potassium carbonate 37.5g sodium bromide worm
1.3g nitrilotriacetic acid trisodium salt (monohydrate) 2.5g potassium hydroxide 1.0° Add water to make 11.
１票白液−１
エチレンノアミン四酢酸鉄アンモニ
ウム塩 １００．０゜エチ
レンノアミン四酢酸２アンモニ
ウム塩 １０．０ｇ臭化
アンモニウム １５０．Ｑｇ水水酸酸
１０，０ｍＮ水を加えて１
１とし、アンモニア水を用いてｐＨ＝６．０にｌｌ！整
する。1 white liquor - 1 Ethylenenoaminetetraacetic acid iron ammonium salt 100.0° Ethylenenoaminetetraacetic acid diammonium salt 10.0g Ammonium bromide 150. Qg Hydroxylic acid Add 10.0mN water to 1
1 and then adjust the pH to 6.0 using aqueous ammonia! Arrange.
定着７１！−１
千オ硫酸アンモニウム １７５．０゜無水
亜硫酸ナトリウム ８．５ｇメタ亜硫酸
ナトリウム ２．３ｇ水を加えて１１と
し、酢酸を用いてｐＨ＝６．０に調整する。Fixation 71! -1 Ammonium 1,000 sulfate 175.0° Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Add water to make 11, and adjust to pH = 6.0 using acetic acid.
漂白定着液−１
エチレンジアミン四酢酸ノアンモニ
ウム塩 ７．５ｇエチレ
ンノアミン四酢酸鉄アンモニ
ウム塩
（以後ＥＤＴＡ−Ｆｅと略称する。）
０．３５モル
亜硫酸アンモニウム（５０％Ｉｆｆ） １０，０
ｇチオ硫酸アンモニウム （７０％溶［） Ｚｏｏ、
０ｇ水を加えて１１とし、水酸化アンモニウムにてｐＨ
７，５に調整した。Bleach-fix solution-1 Ethylenediaminetetraacetic acid noammonium salt 7.5g Ethylenediaminetetraacetic acid iron ammonium salt (hereinafter abbreviated as EDTA-Fe) 0.35 mol Ammonium sulfite (50% Iff) 10.0
gAmmonium thiosulfate (70% solution [) Zoo,
Add 0g of water to bring the pH to 11, and adjust the pH with ammonium hydroxide.
Adjusted to 7.5.
ｉ票白定着液−２
漂白定着液−１においてＥＤＴＡ Ｆｅの代わりに、
二）リロトリ酢酸第２鉄塩を使用。i-ballot white fixer-2 In place of EDTA Fe in bleach-fixer-1,
2) Using ferric salt of lilotriacetic acid.
漂白定着液−３
漂白定着液−１においてＥＤＴＡ−Ｆｅの代わりに、ヒ
ドロキシエチルイミノノ酢酸第２鉄塩を使用。Bleach-fix solution-3 In bleach-fix solution-1, ferric hydroxyethyliminoacetic acid salt was used instead of EDTA-Fe.
漂白定着８Ｉ−４
漂白定着液−１においてＥＤＴＡ−Ｆｅの代わりに、エ
チレンノアミン四酢酸第２鉄塩を使用。Bleach-fixing 8I-4 In place of EDTA-Fe in bleach-fixing solution-1, ferric salt of ethylenenoaminetetraacetic acid was used.
漂白定着１−５
漂白定着液−１においてＥＤＴＡ−Ｆｅの代わりに、１
，２−ジアミノプロパン四酢酸第２鉄塩を使用。Bleach-fixing solution 1-5 In place of EDTA-Fe in bleach-fixing solution-1, 1
, 2-diaminopropanetetraacetic acid ferric salt was used.
漂白定着液−６
漂白定着液−１においてＥＤＴＡ−Ｆｅの代わりに、ノ
エチレントリアミン五酢酸第２鉄塩を使用。Bleach-fix solution-6 In bleach-fix solution-1, ferric noethylenetriaminepentaacetic acid salt was used instead of EDTA-Fe.
ｊ７白定着液−７
漂白定着？ａ−１においてＥＤＴＡ−Ｆｅの代わりに、
シクロヘキサンノアミン四酢酸第２鉄塩を使用。j7 White fixer-7 Bleach fixing? In place of EDTA-Fe in a-1,
Uses ferric salt of cyclohexanenoaminetetraacetic acid.
安定液−１
１−ヒドロキシエチリデン１−１ノ
ホスホン酸 ３．０゜５−ク
ロロ−２−メチル−４−イソ
チアゾリン−３−オン １．０ｇエチレ
ングリコール １．０ｇ水を加えて１
ｒとし、水酸化カリウムでｐＨ７，１にｒ！４整した。Stabilizing solution-1 1-Hydroxyethylidene 1-1 nophosphonic acid 3.0° 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g Ethylene glycol 1.0 g Add water and 1
r, and adjust the pH to 7.1 with potassium hydroxide. I made 4 adjustments.
安定液−２
ホルマリン（３５％水溶液） ７．０ｍ１
１．０ｍｌ
水を加えて１１に仕上げる。Stabilizer-2 Formalin (35% aqueous solution) 7.0ml
Add 1.0ml water to make 11.
安定液−３
アルデヒド誘導体
（ホルムアルデヒド重亜硫酸付加物） ２．７ｇ５−
クロロ−２−メチル−４−イン
チアゾリン−３−オン ０．１ｇ水を加
えて１１！とじ、水酸化アンモニウム又は硫酸にてｐＨ
７，０に１３１整した。Stabilizer-3 Aldehyde derivative (formaldehyde bisulfite adduct) 2.7g5-
Add 0.1 g of chloro-2-methyl-4-inthiazolin-3-one water and 11! Bind, pH with ammonium hydroxide or sulfuric acid
131 was adjusted to 7.0.
処理工程の詳細を表−７に示す。Details of the treatment steps are shown in Table-7.
実施例２
ＢＳ上に順次、ＨＬ−１，ＲＬ−１，ＲＨ−１゜ＩＬ−
１，ＧＬ−１，ＧＨ−１，ＹＣ−１，ＢＬ−１，ＢＨ−
１，Ｐｒｏ−２を設けた試料２２５〜２３４を作成した
（表８に記載の素材を用いた）。Example 2 HL-1, RL-1, RH-1゜IL-
1, GL-1, GH-1, YC-1, BL-1, BH-
1. Samples 225 to 234 provided with Pro-2 were created (materials listed in Table 8 were used).
また、試料２２５〜２３４のＧＬ−１及びＧＨ−１のマ
ゼンタカプラーを本発明のマゼンタカプラー例示化合物
−１に代えた試料２２５−１〜２３４−１を作成した。In addition, samples 225-1 to 234-1 were prepared by replacing the magenta couplers of GL-1 and GH-1 in samples 225 to 234 with magenta coupler exemplified compound-1 of the present invention.
同様に試料２２５〜２３４のＧＬ−１及びＧＨ−１のマ
ゼンタカプラーを本発明のマゼンタカプラー例示化合物
−ｎ（ｎ＝２〜７０）に代えた試料２２５− ｎ −２
３４−ｎ （ｎ＝ ２−７０）を作成した。Sample 225-n-2 in which the magenta couplers of GL-1 and GH-1 of Samples 225-234 were similarly replaced with magenta coupler exemplified compounds-n (n=2-70) of the present invention.
34-n (n=2-70) were prepared.
各々の試料を用いて、マクベスカラーチェ７カー（マク
ベス社製）を適正な光源下で撮影し、処理１５〜５９の
各処理を行ったカラーネ〃を各々の試料につき４５種作
製し、それを用いてサクラ力う−ペーパータイプＳＲ１
ｍ露光した。露光済のサクラカラーペーパータイプＳＲ
はＣＰＫ−１８処理（小西六写真工業（抹）ｇｌ）を行
い、処理が同じであり、マゼンタカプラーのみ異なる試
料間でマクベスカラーチェッカーの色の再現の程度を総
合的に判断したところ、本発明外のマゼンタカプラーを
用いた試料に比べて本発明のマゼンタカプラーを用いた
試料の方が色再現性がすべて良好であった。Using each sample, a Macbeth color check 7 car (manufactured by Macbeth Co., Ltd.) was photographed under an appropriate light source, and 45 types of color nets were prepared for each sample using each of the treatments 15 to 59. Using Sakura Force - Paper Type SR1
m exposure. Exposed Sakura color paper type SR
was subjected to CPK-18 processing (Konishi Roku Photo Industry (Maku) GL), and the degree of color reproduction of the Macbeth color checker was comprehensively judged between samples that had been processed the same but differed only in magenta coupler. All samples using the magenta coupler of the present invention had better color reproducibility than samples using other magenta couplers.
実施例３
ＢＳ上に順次、ＨＬ−１，ＲＬ−１，ＧＬ−１゜ＩＬ−
１，ＲＨ−１，ＧＨ−１，ＹＦ−１，ＢＬ−１１ＢＨ−
１，Ｐｒｏ ２を設けた試料２３５−２４４を表９に
記載の素材を用いて作成した。Example 3 HL-1, RL-1, GL-1゜IL-
1, RH-1, GH-1, YF-1, BL-11BH-
1. Samples 235-244 provided with Pro 2 were prepared using the materials listed in Table 9.
また、試料２３５〜２４４のＧＬ−１及びＧＨ−１のマ
ゼンタカプラーを本発明のマゼンタカプラー例示化合物
−１に代えた試料２３５−１〜２４４−１を作成した。In addition, samples 235-1 to 244-1 were prepared by replacing the magenta couplers of GL-1 and GH-1 in samples 235 to 244 with magenta coupler exemplified compound-1 of the present invention.
同様に試料２３５〜２４４のＧＬ−１及びＧＨ−１のマ
ゼンタカプラーを本発明のマゼンタカプラー例示化合物
−ｎ（ｎ−２〜７０）に代えた試料２３５− ｎ−２４
４−ｎ （ｎ＝ ２−７０）を作成した。Similarly, samples 235-n-24 were obtained by replacing the magenta couplers of GL-1 and GH-1 in samples 235-244 with magenta coupler exemplified compounds-n (n-2 to 70) of the present invention.
4-n (n=2-70) were created.
各々の試料を用いて、マクベスカラーチェッカー （マ
クベス社製）を適正な光源下で撮影し、処３！！１５〜
５９の各処理を行ったカラーネがを各々の試料につ１１
４５種作製し、それを用いてサクラカラーペーパータイ
プＳＲＩ：ｉ光した。露光済のサクラ力う−ベーバータ
イプＳＲはＣＰＫ−１８処理（小西六写真工業（株）！
！りを行い、処理が同じであり、マゼンタカプラーのみ
異なる試料間でマクベスカラーチェッカーの色の再現の
程度を総合的に判断したところ、本発明外のマゼンタカ
プラーを用いた試料に比べて本発明のマゼンタカプラー
を用いた試料の方が色再現性がすべて良好であった。Using each sample, photograph the Macbeth Color Checker (manufactured by Macbeth) under an appropriate light source, and then take a photo of the sample. ! 15~
59 treatments were carried out for each sample.
45 types were prepared and used for Sakura Color Paper Type SRI: i light. Exposed Sakura Power-Baber Type SR is treated with CPK-18 (Konishiroku Photo Industry Co., Ltd.)!
! We conducted a comprehensive evaluation of the degree of color reproduction of Macbeth Color Checker between samples that had been processed the same but differed only in magenta coupler. The samples using the magenta coupler had better color reproducibility in all cases.
以Ａ食泊 ヅニＣ−１・。Meals and overnight stay Zuni C-1.
Φ扉士
実施例４
ＢＳＳ上覧類次、ＨＬ−１，ＲＬ−１，ＩＬ−１゜ＧＬ
−１，ＩＬ−１，ＢＬ−１，ＩＬ−１，ＲＨ−１，ＩＬ
−１，ＧＨ−１，ＩＬ−１，ＢＨ−１゜Ｐｒｏ−２を設
けた試料２４５〜２５４を表１０に記載の素材を用いて
作成した。Φ Doorman Example 4 BSS list following, HL-1, RL-1, IL-1゜GL
-1, IL-1, BL-1, IL-1, RH-1, IL
-1, GH-1, IL-1, BH-1° Samples 245 to 254 provided with Pro-2 were prepared using the materials listed in Table 10.
また、試料２４５〜２５４のＧＬ−１及びＧＨ−１のマ
ゼンタカプラーを本発明のマゼンタカプラー例示化合物
−１に代えた試料２４５−１〜２５４−１を作成した６
同様に試料２４５〜２５４のＧＬ−１及びＧＨ−１のマ
ゼンタカプラーを本発明のマゼンタカプラー例示化合物
−ｎ（ｎ”２〜７０）に代えた試料２４５− ｎ＝ ２
５４ ｎ（ｎ＝２〜７０）を作成した。In addition, samples 245-1 to 254-1 were prepared by replacing the magenta couplers of GL-1 and GH-1 in samples 245 to 254 with magenta coupler exemplified compound-1 of the present invention.
Similarly, sample 245-n=2 was obtained by replacing the magenta couplers of GL-1 and GH-1 of samples 245-254 with magenta coupler exemplified compounds-n (n''2-70) of the present invention.
54 n (n=2 to 70) were prepared.
各々の試料を用いて、マクベスカラーチェッカー（マク
ベス社製）を適正な光源下で撮影し、処Ｅ！１５〜５９
の各処理を行ったカラーネガを各々の試料につき４５種
作製し、それを用いてサクラ力う−ペーパータイプＳＲ
１，：露光した。露光済のサクラ力う−ペーパータイプ
ＳＲはＣＰＫ−１８処理（小四六写真工業（株）製）を
行い、処理が同じであり、マゼンタカプラーのみ異なる
試料間でマクベスカラーチェッカーの色の再現の程度を
総合的に判断したところ、本発明外のマゼンタカプラー
を用いた試料に比べて本発明のマゼンタカプラーを用い
た試料の方が色再現性がすべて良好であツｒこ。Each sample was photographed using a Macbeth color checker (manufactured by Macbeth) under an appropriate light source, and the treatment E! 15-59
We created 45 types of color negatives for each sample and used them to create Sakura Power-Paper Type SR.
1,: Exposed. The exposed Sakura Power Paper Type SR is processed with CPK-18 processing (manufactured by Koshiroku Photo Industry Co., Ltd.), and the color reproduction of Macbeth Color Checker is different between samples that have the same processing but differ only in magenta coupler. Comprehensive evaluation of the color reproducibility showed that the sample using the magenta coupler of the present invention had better color reproducibility than the sample using the magenta coupler other than the present invention.
’ｆ’４−
実施例５
ＢＳ上に順次、ＨＬ−２，ＩＬ−２，ＲＬ−２゜ＲＭ−
１，ＩＬ−３，ＧＬ−２，ＧＭ−１，ＧＨ−２，ＹＦ−
１，ＢＬ−２，ＢＭ−１，ＢＨ−２゜Ｐｒｏ −１＋
Ｐｒｏ −２を設けた試料２５５−２６４を作成した。'f'4- Example 5 HL-2, IL-2, RL-2°RM-
1, IL-3, GL-2, GM-1, GH-2, YF-
1, BL-2, BM-1, BH-2゜Pro -1+
Samples 255-264 with Pro-2 were created.
各々の層に用いた素材を表１１に示す。Table 11 shows the materials used for each layer.
また、試料２５５〜２６４のＧＬ−２，ＧＭ−１及［７
ＧＨ−２のマゼンタカプラーを本発明のマゼンタカプラ
ー例示化合物−１に代えた試料２５５−１〜２６４−１
を作成した。同様に試料２５５〜２６４のＧＬ−２，Ｇ
Ｍ−１及びＧＨ−２のマゼンタカプラーを本発明のマゼ
ンタカプラー例示化合物−ｎ（ｎ＝ ２−７０）に代え
た試料２５５− ｎ−２６４−ｎ（ｎ＝２〜７０）を作
成した。In addition, samples 255 to 264 of GL-2, GM-1 and [7
Samples 255-1 to 264-1 in which the magenta coupler of GH-2 was replaced with magenta coupler exemplified compound-1 of the present invention
It was created. Similarly, GL-2 and G of samples 255 to 264
Samples 255-n-264-n (n=2-70) were prepared by replacing the magenta couplers of M-1 and GH-2 with magenta coupler exemplified compounds-n (n=2-70) of the present invention.
各々の試料を用いて、マクベスカラーチェッカー （マ
クベス社製）を適正な光源下で撮影し、処理１５〜５９
の各処理を行ったカラーネガを各々の試料にっ慇４５Ｆ
１作製し、それを用いてサクラ力う−ベーバータイプＳ
Ｒに露光した。露光済のサクラ力う−ペーパータイプＳ
ＲはＣＰＫ−１８処理（小四六写真工業（株）Ｍ）を行
い、処理が同じであり、マゼンタカプラーのみ異なる試
料間でマクベスカラーチェッカーの色の再現の程度を総
合的に判断したところ、本発明外のマゼンタカプラーを
用いた試料に比べて本発明のマゼンタカプラーを用いた
試料の方が色再現性がすべて良好であった。Using each sample, photograph the Macbeth color checker (manufactured by Macbeth) under an appropriate light source, and process 15 to 59.
The color negatives subjected to each treatment were transferred to each sample at 45F.
1 and use it to power Sakura - Baber type S
Exposure to R. Exposed Sakura Power-Paper Type S
R was subjected to CPK-18 processing (Koshiroku Photo Industry Co., Ltd. M), and the degree of color reproduction of the Macbeth color checker was comprehensively judged between samples that had the same processing but differed only in magenta coupler. The color reproducibility of the samples using the magenta couplers of the present invention was better in all cases than the samples using magenta couplers other than those of the present invention.
４飄ｄム二
実施例６
ＢＳ上に順次、ＨＬ−２，ＩＬ−２，ＲＬ−２゜ＲＭ−
’１．ＩＬ−３．ＧＬ−２．ＧＭ−１，ＩＬ−３，ＲＨ
−２，ＧＨ−２，ＹＦ−１，ＢＬ−１゜ＢＨ１，Ｐｒｏ
−２を設けた試料２６５−２７４を表−１２のように作
成した。4-speed Muni Example 6 HL-2, IL-2, RL-2゜RM-
'1. IL-3. GL-2. GM-1, IL-3, RH
-2, GH-2, YF-1, BL-1゜BH1, Pro
Samples 265-274 provided with -2 were prepared as shown in Table-12.
また、試料２６５〜２７４のＧＬ−２，ＧＭ−１及びＧ
Ｈ−２のマゼンタカプラーを本発明のマゼンタカプラー
例示化合物−１に代えた試料２６５−１〜２７４−１を
作成した。同様に試料２６５〜２７４のＧＬ−２，ＧＭ
−１及びＧＨ−２のマゼンタカプラーを本発明のマゼン
タカプラー例示化合物−ｎ（ｎ＝２〜７０）に代えた試
料２６５− ｎ＝２７４− ｎ（ｎ＝２〜７０）を作成
した。In addition, GL-2, GM-1 and G of samples 265 to 274
Samples 265-1 to 274-1 were prepared by replacing the magenta coupler of H-2 with magenta coupler exemplified compound-1 of the present invention. Similarly, GL-2 and GM of samples 265 to 274
Sample 265-n=274-n (n=2-70) was prepared by replacing the magenta couplers of -1 and GH-2 with magenta coupler exemplified compounds-n (n=2-70) of the present invention.
各々の試料を用いて、マクベスカラーチェッカー （マ
クベス社製）を適正な光源下で撮影し、処理１５〜５９
の各処理を行ったカラーネガを各々の試料につき４５種
作製し、それを用いてサクラ力う−ペーパータイプＳＲ
に露光した。露光済のサクラカラーベーバータイブＳＲ
はＣＰＫ−１８処理（小西六写真工業（株）製）を行い
、処理が同じであり、マゼンタカプラーのみ異なる試料
間でマクベスカラーチェッカーの色の再現の程度を総合
的に判断したところ、本発明外のマゼンタカプラーを用
いた試料に比べて本発明のマゼンタカプラーを用いた試
料の方が色再現性がすべて良好であった。Using each sample, photograph the Macbeth color checker (manufactured by Macbeth) under an appropriate light source, and process 15 to 59.
We created 45 types of color negatives for each sample and used them to create Sakura Power-Paper Type SR.
exposed to light. Exposed Sakura Color Baber Type SR
was subjected to CPK-18 processing (manufactured by Konishiroku Photo Industry Co., Ltd.), and the degree of color reproduction of the Macbeth Color Checker was comprehensively judged between samples that had undergone the same processing but differed only in magenta coupler. All samples using the magenta coupler of the present invention had better color reproducibility than samples using other magenta couplers.
手続補正訓 （自制
昭和６１年０６月２４日
３、補正をする者
事件との関係 特許出願人
住所 東京都新宿区西新宿１丁目２６番２号名称
（１２７） 小西六写真工業株式会ネ１代表取締役
打手 恵生
４、代理人 〒１０２
住所 東京都千代田区九段北４丁目１番１号九段−ロ
坂ピル電話２６３−９５２４
ＩＪ ａ ｉ！全全文浄書（内容に変更なし）６、補正
の内容Instructions for amending procedures (Self-restraint June 24, 1985, Relationship with the case of the person making the amendment Patent applicant address: 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name
(127) Representative Director of Konishiroku Photo Industry Co., Ltd.
Hitter Keio 4, Agent 102 Address Kudan-Rosaka Pill, 4-1-1 Kudankita, Chiyoda-ku, Tokyo Telephone 263-9524 IJ a i! Full text engraving (no changes to the content) 6. Contents of amendments
Claims (1)
プラーを含有するハロゲン化銀乳剤層を少なくとも１層
有することを特徴とするハロゲン化銀カラー感光材料。 一般式［ I ］ ▲数式、化学式、表等があります▼ 式中、Ｚａ、Ｚｂ、Ｚｃ、Ｚｄ、Ｚｅは、メチン基、置
換メチン基又は、窒素原子を表わすが、Ｚｂ、Ｚｃ、Ｚ
ｅのいずれか１つは、ｐ−フェニレンジアミン系カラー
発色現像主薬の酸化体と酸化カップリング反応を行う、
メチン基又は置換メチン基である。 但し、以下の（１）〜（６）の場合を除く[Scope of Claims] A silver halide color light-sensitive material comprising, on a support, at least one silver halide emulsion layer containing a magenta coupler represented by the following general formula [I]. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, Za, Zb, Zc, Zd, and Ze represent a methine group, a substituted methine group, or a nitrogen atom, but Zb, Zc, and Z
Any one of e performs an oxidative coupling reaction with an oxidized form of a p-phenylenediamine color developing agent,
It is a methine group or a substituted methine group. However, cases (1) to (6) below are excluded.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12147786A JPS62278552A (en) | 1986-05-27 | 1986-05-27 | Silver halide color photosensitive material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12147786A JPS62278552A (en) | 1986-05-27 | 1986-05-27 | Silver halide color photosensitive material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62278552A true JPS62278552A (en) | 1987-12-03 |
Family
ID=14812122
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12147786A Pending JPS62278552A (en) | 1986-05-27 | 1986-05-27 | Silver halide color photosensitive material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62278552A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01288855A (en) * | 1988-05-17 | 1989-11-21 | Fuji Photo Film Co Ltd | Silver halide color photographic sensitive material |
| US5215871A (en) * | 1990-11-07 | 1993-06-01 | Fuji Photo Film Co., Ltd. | Method of forming cyan image with cyan dye forming coupler, and silver halide color photographic material containing the cyan dye forming coupler |
| EP0544322A1 (en) | 1991-11-27 | 1993-06-02 | Fuji Photo Film Co., Ltd. | Silver halide color photographic light-sensitive material |
| US5256526A (en) * | 1990-11-30 | 1993-10-26 | Fuji Photo Film Co., Ltd. | Cyan image forming method and silver halide color photographic material containing cyan coupler |
| US5270153A (en) * | 1990-11-28 | 1993-12-14 | Fuji Photo Film Co., Ltd. | Cyan image forming method and silver halide color photographic material containing cyan coupler |
| JPH0627612A (en) * | 1992-07-08 | 1994-02-04 | Fuji Photo Film Co Ltd | Silver halide color photographic sensitive material |
| US5292630A (en) * | 1992-02-17 | 1994-03-08 | Fuji Photo Film Co., Ltd. | Silver halide color photographic material containing an imidazotriazole cyan coupler |
| US5362882A (en) * | 1991-06-07 | 1994-11-08 | Fuji Photo Film Co., Ltd. | Pyrrolotriazole derivative and heat transfer dye providing material containing a pyrrolotriazole azomethine dye |
| EP0711804A2 (en) | 1994-11-14 | 1996-05-15 | Ciba-Geigy Ag | Latent light stabilizers |
-
1986
- 1986-05-27 JP JP12147786A patent/JPS62278552A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01288855A (en) * | 1988-05-17 | 1989-11-21 | Fuji Photo Film Co Ltd | Silver halide color photographic sensitive material |
| EP0342637A2 (en) * | 1988-05-17 | 1989-11-23 | Fuji Photo Film Co., Ltd. | Silver halide color photographic material |
| US5215871A (en) * | 1990-11-07 | 1993-06-01 | Fuji Photo Film Co., Ltd. | Method of forming cyan image with cyan dye forming coupler, and silver halide color photographic material containing the cyan dye forming coupler |
| US5270153A (en) * | 1990-11-28 | 1993-12-14 | Fuji Photo Film Co., Ltd. | Cyan image forming method and silver halide color photographic material containing cyan coupler |
| US5256526A (en) * | 1990-11-30 | 1993-10-26 | Fuji Photo Film Co., Ltd. | Cyan image forming method and silver halide color photographic material containing cyan coupler |
| US5362882A (en) * | 1991-06-07 | 1994-11-08 | Fuji Photo Film Co., Ltd. | Pyrrolotriazole derivative and heat transfer dye providing material containing a pyrrolotriazole azomethine dye |
| US5508421A (en) * | 1991-06-07 | 1996-04-16 | Fuji Photo Film Co., Ltd. | Pyrrolotriazole azomethine dye, and heat transfer dye providing material containing a pyrrolotriazole azomethine dye |
| EP0544322A1 (en) | 1991-11-27 | 1993-06-02 | Fuji Photo Film Co., Ltd. | Silver halide color photographic light-sensitive material |
| US5292630A (en) * | 1992-02-17 | 1994-03-08 | Fuji Photo Film Co., Ltd. | Silver halide color photographic material containing an imidazotriazole cyan coupler |
| JPH0627612A (en) * | 1992-07-08 | 1994-02-04 | Fuji Photo Film Co Ltd | Silver halide color photographic sensitive material |
| EP0711804A2 (en) | 1994-11-14 | 1996-05-15 | Ciba-Geigy Ag | Latent light stabilizers |
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