JPS63143545A - Silver halide photographic sensitive material with improved shelf stability of dye image - Google Patents
Silver halide photographic sensitive material with improved shelf stability of dye imageInfo
- Publication number
- JPS63143545A JPS63143545A JP29127786A JP29127786A JPS63143545A JP S63143545 A JPS63143545 A JP S63143545A JP 29127786 A JP29127786 A JP 29127786A JP 29127786 A JP29127786 A JP 29127786A JP S63143545 A JPS63143545 A JP S63143545A
- Authority
- JP
- Japan
- Prior art keywords
- group
- silver halide
- layer
- emulsion layer
- present
- 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 63
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 41
- 239000004332 silver Substances 0.000 title claims abstract description 41
- 239000000463 material Substances 0.000 title claims abstract description 23
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 38
- 239000000839 emulsion Substances 0.000 claims abstract description 27
- 125000003118 aryl group Chemical group 0.000 claims abstract description 16
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 36
- 239000007788 liquid Substances 0.000 claims description 28
- 238000009835 boiling Methods 0.000 claims description 24
- 239000003960 organic solvent Substances 0.000 claims description 18
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 11
- 125000005843 halogen group Chemical group 0.000 claims description 9
- 125000000623 heterocyclic group Chemical group 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 2
- 238000005562 fading Methods 0.000 abstract description 22
- 239000002904 solvent Substances 0.000 abstract description 12
- 238000002845 discoloration Methods 0.000 abstract description 11
- 239000006096 absorbing agent Substances 0.000 abstract description 7
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 46
- 239000000975 dye Substances 0.000 description 16
- 125000003342 alkenyl group Chemical group 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 125000001424 substituent group Chemical group 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 108010010803 Gelatin Proteins 0.000 description 5
- 125000004104 aryloxy group Chemical group 0.000 description 5
- 239000000470 constituent Substances 0.000 description 5
- 229920000159 gelatin Polymers 0.000 description 5
- 239000008273 gelatin Substances 0.000 description 5
- 235000019322 gelatine Nutrition 0.000 description 5
- 235000011852 gelatine desserts Nutrition 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 206010070834 Sensitisation Diseases 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 230000008313 sensitization Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Natural products CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- 125000004442 acylamino group Chemical group 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- ZRHUHDUEXWHZMA-UHFFFAOYSA-N 1,4-dihydropyrazol-5-one Chemical compound O=C1CC=NN1 ZRHUHDUEXWHZMA-UHFFFAOYSA-N 0.000 description 1
- FJGQBLRYBUAASW-UHFFFAOYSA-N 2-(benzotriazol-2-yl)phenol Chemical class OC1=CC=CC=C1N1N=C2C=CC=CC2=N1 FJGQBLRYBUAASW-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- ZNBNBTIDJSKEAM-UHFFFAOYSA-N 4-[7-hydroxy-2-[5-[5-[6-hydroxy-6-(hydroxymethyl)-3,5-dimethyloxan-2-yl]-3-methyloxolan-2-yl]-5-methyloxolan-2-yl]-2,8-dimethyl-1,10-dioxaspiro[4.5]decan-9-yl]-2-methyl-3-propanoyloxypentanoic acid Chemical compound C1C(O)C(C)C(C(C)C(OC(=O)CC)C(C)C(O)=O)OC11OC(C)(C2OC(C)(CC2)C2C(CC(O2)C2C(CC(C)C(O)(CO)O2)C)C)CC1 ZNBNBTIDJSKEAM-UHFFFAOYSA-N 0.000 description 1
- YOVXRIACERVBAG-UHFFFAOYSA-N 6-hydroxy-2-oxo-6-phenylhexa-3,5-dienoic acid Chemical compound OC(=O)C(=O)C=CC=C(O)C1=CC=CC=C1 YOVXRIACERVBAG-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- AZFNGPAYDKGCRB-XCPIVNJJSA-M [(1s,2s)-2-amino-1,2-diphenylethyl]-(4-methylphenyl)sulfonylazanide;chlororuthenium(1+);1-methyl-4-propan-2-ylbenzene Chemical compound [Ru+]Cl.CC(C)C1=CC=C(C)C=C1.C1=CC(C)=CC=C1S(=O)(=O)[N-][C@@H](C=1C=CC=CC=1)[C@@H](N)C1=CC=CC=C1 AZFNGPAYDKGCRB-XCPIVNJJSA-M 0.000 description 1
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 1
- HOLVRJRSWZOAJU-UHFFFAOYSA-N [Ag].ICl Chemical compound [Ag].ICl HOLVRJRSWZOAJU-UHFFFAOYSA-N 0.000 description 1
- YOPJXCVPYNWFEM-UHFFFAOYSA-M [Cl-].[Th+] Chemical compound [Cl-].[Th+] YOPJXCVPYNWFEM-UHFFFAOYSA-M 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000005194 alkoxycarbonyloxy group Chemical group 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- DKBWAMSZIHBXME-UHFFFAOYSA-N azanium;acetate;dihydrate Chemical compound [NH4+].O.O.CC([O-])=O DKBWAMSZIHBXME-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid group Chemical group C(C1=CC=CC=C1)(=O)O WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- PBHVCRIXMXQXPD-UHFFFAOYSA-N chembl2369102 Chemical compound C1=CC(S(=O)(=O)O)=CC=C1C(C1=CC=C(N1)C(C=1C=CC(=CC=1)S(O)(=O)=O)=C1C=CC(=N1)C(C=1C=CC(=CC=1)S(O)(=O)=O)=C1C=CC(N1)=C1C=2C=CC(=CC=2)S(O)(=O)=O)=C2N=C1C=C2 PBHVCRIXMXQXPD-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- AJDUTMFFZHIJEM-UHFFFAOYSA-N n-(9,10-dioxoanthracen-1-yl)-4-[4-[[4-[4-[(9,10-dioxoanthracen-1-yl)carbamoyl]phenyl]phenyl]diazenyl]phenyl]benzamide Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2NC(=O)C(C=C1)=CC=C1C(C=C1)=CC=C1N=NC(C=C1)=CC=C1C(C=C1)=CC=C1C(=O)NC1=CC=CC2=C1C(=O)C1=CC=CC=C1C2=O AJDUTMFFZHIJEM-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005064 octadecenyl group Chemical group C(=CCCCCCCCCCCCCCCCC)* 0.000 description 1
- 125000005447 octyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 150000003021 phthalic acid derivatives Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 239000004304 potassium nitrite Substances 0.000 description 1
- 235000010289 potassium nitrite Nutrition 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- MCSKRVKAXABJLX-UHFFFAOYSA-N pyrazolo[3,4-d]triazole Chemical compound N1=NN=C2N=NC=C21 MCSKRVKAXABJLX-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 125000006296 sulfonyl amino group Chemical group [H]N(*)S(*)(=O)=O 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000000725 suspension 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
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000001043 yellow dye Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/392—Additives
- G03C7/39296—Combination of additives
-
- 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
- G03C7/3003—Materials characterised by the use of combinations of photographic compounds known as such, or by a particular location in the photographic element
- G03C7/3005—Combinations of couplers and photographic additives
- G03C7/3006—Combinations of phenolic or naphtholic couplers and photographic additives
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
- G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
- G03C1/815—Photosensitive materials characterised by the base or auxiliary layers characterised by means for filtering or absorbing ultraviolet light, e.g. optical bleaching
- G03C1/8155—Organic compounds therefor
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/32—Colour coupling substances
- G03C7/34—Couplers containing phenols
- G03C7/346—Phenolic couplers
-
- 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
- G03C7/388—Processes for the incorporation in the emulsion of substances liberating photographically active agents or colour-coupling substances; Solvents therefor
- G03C7/3885—Processes for the incorporation in the emulsion of substances liberating photographically active agents or colour-coupling substances; Solvents therefor characterised by the use of a specific solvent
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/392—Additives
- G03C7/39208—Organic compounds
- G03C7/39232—Organic compounds with an oxygen-containing function
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/392—Additives
- G03C7/39208—Organic compounds
- G03C7/3924—Heterocyclic
- G03C7/39244—Heterocyclic the nucleus containing only nitrogen as hetero atoms
- G03C7/39256—Heterocyclic the nucleus containing only nitrogen as hetero atoms three nitrogen atoms
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は形成される色素画像の保存性が良好なハロゲン
化銀写真感光材料に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic material in which the formed dye image has good storage stability.
［発明の背景］
一般にハロゲン化銀カラー写真感光材料は支持体上に青
色光・緑色光および赤色光に感光性を右するように選択
的に増感された３種のハロゲン化銀カラー写真用乳剤層
が塗設されている。[Background of the Invention] In general, silver halide color photographic light-sensitive materials consist of three kinds of silver halide color photographic materials that are selectively sensitized on a support to have sensitivity to blue light, green light, and red light. An emulsion layer is coated.
一般に色素画像は様々な保存条件の下で変退色すること
が知られている。例えばカラープリントを写真館でのシ
ョーウィンドーでのディスプレイの如く、長時間光に曝
されて保存さ場合の変退色があり、可変退色と呼んでい
る。更にカラープリントのアルバムでの保存の突如く、
光に曝される時間は短かいものの長時間高温多湿の暗所
に保存される場合の変退色もあり、暗度退色と呼んでい
る。前記カラープリントの如く色素画像を有する写真製
品を記録材料として見た場合、担持される色素画像の保
存性が半永久的であるためには、いかなる保存条件にお
いても前記の変退色が極力小さいことが望まれ、近年こ
の要望は高まるばかりである。とりわけシアンカプラー
においては、耐熱湿性（暗退色性）の改良が近年になっ
て重要な課題となっている。It is generally known that dye images change color and fade under various storage conditions. For example, when a color print is exposed to light for a long time and stored, such as when displayed in a show window at a photo studio, the color changes and fades, which is called variable fading. Furthermore, suddenly the color prints are saved in an album,
Although the time of exposure to light is short, there is also discoloration and fading when stored in a dark place with high temperature and humidity for a long period of time, which is called dark fading. When a photographic product having a dye image such as a color print is viewed as a recording material, in order for the dye image carried to be preserved semi-permanently, the above-mentioned discoloration and fading must be as small as possible under any storage conditions. This demand has only increased in recent years. Especially for cyan couplers, improvement of heat and humidity resistance (dark fading resistance) has become an important issue in recent years.
従来知られているシアンカプラーとしては、フェノール
の２位および５位がアシルアミノ基で置換された２、５
−ジアシルアミノフェノール系シアンカプラーが挙げら
れ、例えば米国特許第２，８９５．８２６号明ｉｌｌ書
、特開昭５０−１１２０３８号、同５３−１０９６３０
号、ならびに同５５−１６３５３７号各公報に記載され
ている。Conventionally known cyan couplers include 2 and 5, in which the 2- and 5-positions of the phenol are substituted with acylamino groups.
- diacylaminophenol cyan couplers, such as U.S. Patent Nos. 2,895.826 and 1989, JP 50-112038, JP 53-109630;
No. 55-163537.
これら２．５−ジアシルアミノフェノール系シアンカプ
ラーは、暗退色性の良好なシアン色素両画像が得られる
ことから多用されているが、一般に発色色素画像の光退
色性および未反応シアンカプラーの光による黄変（Ｙス
ティンと称す。）が著るしく劣るという欠点があった。These 2,5-diacylaminophenol-based cyan couplers are widely used because they can provide both cyan dye images with good dark fading resistance, but they are generally used due to the photobleaching of chromogenic dye images and the unreacted cyan coupler being affected by light. There was a drawback that yellowing (referred to as Y stain) was significantly inferior.
この光退色性については特に低濃度部がピンクに変色す
るという現象もみられ、視感上の退色が増幅されるとい
う問題をひき越こしかねない。Regarding photobleaching, there is a phenomenon in which the color changes to pink, especially in low-density areas, which may lead to the problem of amplified visual fading.
そこで２．５−ジアシルアミノ系シアンカプラーの光退
色性を改良する手段としては、例えば特開昭５０−１５
１１４９号にベンゾトリアゾール化合物を併用すること
が提案されている。ところがこの化合物は析出性が大き
く実用的でない。Therefore, as a means to improve the photobleaching property of 2,5-diacylamino cyan couplers, for example, JP-A No. 50-15
No. 1149 proposes the combined use of a benzotriazole compound. However, this compound has a high precipitation property and is not practical.
また、従来用いられてきたフタル酸ジブチルの如き高沸
点有機溶媒を壜台して用いることも知られており、これ
によれば光退色性が僅かながら改良されるものの、色調
等の写真特性に悪影響を及ぼしたり、暗退色性を劣化さ
せるなどの問題が生じた。また光Ｙスティンの抑Ｉｌ（
効果もほとんどない。It is also known to use a conventionally used high-boiling organic solvent such as dibutyl phthalate in a bottle, and although this slightly improves photobleaching, it does not affect photographic properties such as color tone. Problems such as adverse effects and deterioration of dark fading properties arose. Also, light Y stain suppression Il (
It has almost no effect.
また、特開昭５７−１７３８３５号公報には、フェノー
ルの２位がオルトスルホンアミドフェニルアシルアミノ
基で置換された２、５−ジアシルアミノフェノールシア
ンカプラーを特定の誘電率を有する高沸点有機溶媒を用
いて分散することにより、色調および色素の堅牢性を改
良する方法が提案されているが、この方法によっては、
シアン色素画像の光退色性が著しく損なわれることが確
認された。Furthermore, JP-A-57-173835 discloses that a 2,5-diacylaminophenol cyan coupler in which the 2-position of the phenol is substituted with an orthosulfonamidophenylacylamino group is treated with a high-boiling organic solvent having a specific dielectric constant. A method has been proposed to improve the color tone and fastness of pigments by dispersing them using
It was confirmed that the photobleachability of the cyan dye image was significantly impaired.
さらに、特開昭６０−２２２８５２号には液体状と固体
状の紫外線吸収剤を用いる方法、さらには米国特許第４
．５８７．３４６号には液体状紫外線吸収剤を用いる方
法等が提案されている。Furthermore, Japanese Patent Application Laid-Open No. 60-222852 describes a method using liquid and solid ultraviolet absorbers, and US Pat.
．． No. 587.346 proposes a method using a liquid ultraviolet absorber.
しかしながら、光退色性にある程度の効果はあるものの
特に低濃度部の変色については、はとんど効果がない。However, although it has some effect on photobleaching, it has little effect on discoloration, especially in low-density areas.
以上述べたように暗退色性、明退色性および低濃度部の
変色に優れたシアン色素画像を得る方法は見い出せてい
ないのが唄状であり、改良が大いに望まれていた。As mentioned above, no method has been found for obtaining cyan dye images that are excellent in dark fading, light fading, and discoloration in low density areas, and improvements have been highly desired.
［発明の目的］
本発明の第１の目的は、シアン色素画像の明退色性にお
いて、特に低濃度部の変色が解消されたハロゲン化銀写
真感光材料を提供することにある。[Object of the Invention] A first object of the present invention is to provide a silver halide photographic material in which discoloration of cyan dye images, particularly in low density areas, is eliminated.
本発明の第２の目的は、優れた暗退色性を有し、明退色
性の改良されたハロゲン化銀写真感光材料を提供するこ
とにある。A second object of the present invention is to provide a silver halide photographic material having excellent dark fading properties and improved light fading properties.
本発明の他の目的は以下の記載から明らかとなろう。Other objects of the invention will become apparent from the description below.
［発明の構成］
本発明の上記目的は、支持体上に少なくとも１層ハロゲ
ン化銀乳剤層および少なくとも１層の非感光性層を有す
るハロゲン化銀写真感光材料において、前記ハロゲン化
銀乳剤層の少なくとも１層は下記一般式［Ｉ］で示され
るシアンカプラーを含有し、該シアンカプラー含有ハロ
ゲン化銀乳剤層およびこの層に隣接する非感光性層から
選ばれる少なくとも１層には、常温にて液体の紫外線吸
収剤を含有し、かつ該紫外線吸収剤を含有する層に誘電
率６．０以下の高沸点有別溶媒を該紫外線吸収剤総量に
対して重量で０．６５〜０の範囲で含有するハロゲン化
銀写真感光材料により速成された。[Structure of the Invention] The above-mentioned object of the present invention is to provide a silver halide photographic material having at least one silver halide emulsion layer and at least one non-photosensitive layer on a support. At least one layer contains a cyan coupler represented by the following general formula [I], and at least one layer selected from the cyan coupler-containing silver halide emulsion layer and a non-photosensitive layer adjacent to this layer contains a cyan coupler represented by the following general formula [I]. Containing a liquid ultraviolet absorber, and adding a high boiling point specific solvent with a dielectric constant of 6.0 or less to the layer containing the ultraviolet absorber in an amount of 0.65 to 0 by weight based on the total amount of the ultraviolet absorber. It was rapidly produced using a silver halide photographic material containing
一般式［エコ ［式中、Ｒ１はアルキル基またはアリール基を表わす。General formula [Eco [In the formula, R1 represents an alkyl group or an aryl group.
Ｒ２はアルキル基、シクロアルキル基、アリール基また
は複素環基を表わす。Ｒ３は水素原子、ハロゲン原子、
アルキル基またはアルコキシ基を表わす。またＲ３はＲ
１と結合して環を形成しても良い。２は水素原子または
発色現像主薬の酸化体との反応により離脱可能な基を表
わす。］［発明の具体的構成］
本発明に用いられるシアンカプラーについて説明する。R2 represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. R3 is a hydrogen atom, a halogen atom,
Represents an alkyl group or an alkoxy group. Also, R3 is R
It may be combined with 1 to form a ring. 2 represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of a color developing agent. ] [Specific structure of the invention] The cyan coupler used in the invention will be explained.
一般式［Ｉ］で表わされるシアンカプラー（以下、本発
明のシアンカプラーという。）において、Ｒ１で表わさ
れるアルキル基としては、炭素数１〜３２のものが好ま
しく、これらは直鎖でも分岐でもよく、置換基を有する
ものも含む。In the cyan coupler represented by the general formula [I] (hereinafter referred to as the cyan coupler of the present invention), the alkyl group represented by R1 preferably has 1 to 32 carbon atoms, and these may be linear or branched. , including those having substituents.
Ｒ１で表わされるアリール基としてはフェニル基が好ま
しく、置換基を有するものも含む。The aryl group represented by R1 is preferably a phenyl group, including those having substituents.
Ｒ２で表わされるアルキル基としては炭素数１〜３２の
ものが好ましく、これらのアルキル基は直鎖でも分岐で
もよく、また置換基を有するものも含む。The alkyl group represented by R2 preferably has 1 to 32 carbon atoms, and these alkyl groups may be linear or branched, and include those having substituents.
Ｒ２で表わされるシクロアルキル基としては炭素数３〜
１２のものが好ましく、これらのシクロアルキル基は置
換基を有するものも含む。The cycloalkyl group represented by R2 has 3 to 3 carbon atoms.
12 are preferred, and these cycloalkyl groups also include those having substituents.
Ｒ２で表わされるアリール基としてフェニル基が好まし
く、置換基を有するものも含む。The aryl group represented by R2 is preferably a phenyl group, including those having substituents.
Ｒ２で表わされる複素環基としては５〜７ｍのものが好
ましく、置換されていてもよく、又縮合していてもよい
。The heterocyclic group represented by R2 is preferably a 5-7m heterocyclic group, which may be substituted or fused.
Ｒ３は水素原子、ハロゲン原子、アルキル基またはアル
コキシ基を表わすが、好ましくは水素原子である。R3 represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, preferably a hydrogen atom.
また、Ｒ１とＲ３が共同して形成する環としては５〜６
員環が好ましく、形成される５〜６員環られる。Furthermore, the ring formed jointly by R1 and R3 is 5 to 6
Preferably, a 5- to 6-membered ring is formed.
一般式ＣＩ］においてＺで表わされる発色現像主薬の酸
化体との反応により離脱可能な基としては、ハロゲン原
子、アルコキシ基、アリールオキシ基、アシルオキシ基
、スルホニルオキシ基、アシルアミノ基、スルホニルア
ミノ基、アルコキシカルボニルオキシ
シ
ましくは、ハロゲン原子、アリールオキシ基、アルコキ
シ基である。Examples of groups that can be separated by reaction with the oxidized product of the color developing agent represented by Z in the general formula CI] include a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, a sulfonyloxy group, an acylamino group, a sulfonylamino group, Alkoxycarbonyloxy is preferably a halogen atom, an aryloxy group, or an alkoxy group.
本発明のシアンカプラーのうち特に好ましいものは、下
記一般式’Ｉ−ＡＩで示されるものである。Particularly preferred among the cyan couplers of the present invention are those represented by the following general formula 'I-AI.
一般式［Ｉ−Ａ］
Ｘ＾
式中、Ｒ＾１は少なくとも１個のハロゲン原子で置換さ
れたフェニル基を表わし、これらのフェニル基は、さら
にハロゲン原子以外の置換基を有してもよい。Ｒ＾２は
前記一般式［Ｉ］のＲ１と同義である。Ｘ八はハロゲン
原子、アリールオキシ基またはアルコキシ基を表わす。General formula [I-A] . R^2 has the same meaning as R1 in the general formula [I]. X8 represents a halogen atom, an aryloxy group or an alkoxy group.
以下に一般式Ｍ］で表わされるシアンカプラーの代表的
具体例を示す。Typical specific examples of the cyan coupler represented by the general formula M are shown below.
本発明のシアンカプラーは例えば、特願昭６１−２１８
５３号明細書第２６頁〜３５頁、特開昭６０−２２５１
５５号公報第７頁左下の１ＩＩｌｌ〜１０頁右下の欄、
特開昭６０−２２２８５３号公報第６頁左上の欄〜８頁
右下の欄及び特開昭５９−１８５３３５号公報第６頁左
下の欄〜９頁左上の欄に記載された２、５−ジアシルア
ミノ系シアンカプラーを含み、これらの明細書及び公報
に記載されている方法に従って合成することができる。The cyan coupler of the present invention is disclosed in Japanese Patent Application No. 61-218, for example.
Specification No. 53, pages 26 to 35, JP-A-60-2251
Publication No. 55, page 7, lower left column 1IIll to page 10, lower right column,
2, 5- described in JP-A-60-222853, page 6, upper left column to page 8, lower right column, and JP-A-59-185335, page 6, lower left column to page 9, upper left column. It contains a diacylamino cyan coupler and can be synthesized according to the methods described in these specifications and publications.
一般式［Ｉ］で表わされるシアンカプラーは、本発明の
目的に反しない範囲において、池のシアンカプラーと組
合せて用いることができる。The cyan coupler represented by the general formula [I] can be used in combination with the Ike's cyan coupler to the extent that it does not contradict the purpose of the present invention.
本発明に係るシアンカプラーは、通常、ハロゲン化銀１
モル当り約０．０５〜２モル、好ましくは０．１〜１モ
ルの範囲で用いられる。The cyan coupler according to the present invention is usually silver halide 1
It is used in a range of about 0.05 to 2 mol, preferably 0.1 to 1 mol per mol.
本発明に係るシアンカプラーは、通常赤感光性ハロゲン
化銀乳剤層に含有させるが、非増感乳剤または赤色以外
のスペクトルの三原色領域に感光性を有する乳剤層中に
含有させても良い。The cyan coupler according to the present invention is usually contained in a red-sensitive silver halide emulsion layer, but it may also be contained in a non-sensitized emulsion or an emulsion layer sensitive to the three primary color regions of the spectrum other than red.
本発明には、常温にて液体の紫外線吸収剤（以下、本発
明の液状紫外線吸収剤という）が用いられる。In the present invention, an ultraviolet absorber that is liquid at room temperature (hereinafter referred to as the liquid ultraviolet absorber of the present invention) is used.
本発明において「常温で液体」とは、２５℃において、
「化学大辞典（１９６３）共立出版」等に定義される如
く、一定の形をもたず、流動性があり、はぼ一定の体積
を有するものを示す。従って、上記性質を有するもので
あれば、融点は限定されないが、融点３０℃以下、特に
好ましくは１５℃以下である化合物が好ましい。In the present invention, "liquid at room temperature" means at 25°C,
As defined in ``Chemistry Dictionary (1963) Kyoritsu Shuppan,'' etc., it refers to something that does not have a fixed shape, is fluid, and has a nearly constant volume. Therefore, as long as it has the above-mentioned properties, the melting point is not limited, but compounds with a melting point of 30°C or less, particularly preferably 15°C or less, are preferred.
本発明の液状紫外線吸収剤は単一化合物であっても混合
物であってもよく、混合物としては構造異性体群から構
成されるものを好ましく用いることができる。（ｍ造異
性体については米国特許第４．５８７，３４６号等に記
載されている。）本発明の液状紫外線吸収剤は上記を満
足すればいかなる構造をとることができるが、紫外線吸
収剤自身の光堅牢性の点から下記一般式［ａ ］で示さ
れる２−（２’−ヒドロキシフェニル）ベンゾトリアゾ
ール系化合物が好ましい。The liquid ultraviolet absorber of the present invention may be a single compound or a mixture, and as a mixture, one composed of a group of structural isomers can be preferably used. (The m-configuration isomer is described in U.S. Pat. No. 4,587,346, etc.) The liquid ultraviolet absorber of the present invention can have any structure as long as it satisfies the above requirements, but the ultraviolet absorber itself From the viewpoint of light fastness, 2-(2'-hydroxyphenyl)benzotriazole compounds represented by the following general formula [a] are preferred.
一般式［ａ ］
Ｋ２
上記一般式［ａ ］において、Ｒ１、Ｒ２およびＲ３は
それぞれ水素原子、ハロゲン原子、アルキル基、アリー
ル基、アルコキシ基、アリールオキシ基、アルケニル基
、ニトロ基または水Ｍｌを表わす。General formula [a] K2 In the above general formula [a], R1, R2 and R3 each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkenyl group, a nitro group or water Ml .
Ｒ＋ 、Ｒ２およびＲ３で表わされるハロゲン原子とし
ては、例えば、弗素原子、塩素原子、臭素原子等が挙げ
られ、特に塩素原子が好ましい。Examples of the halogen atom represented by R+, R2, and R3 include a fluorine atom, a chlorine atom, a bromine atom, and the like, with a chlorine atom being particularly preferred.
Ｒ＋ 、Ｒ２およびＲ３で表わされるアルキル基、アル
コキシ基としては、炭素数１〜３０のものが好ましく、
またアルケニル基としては、炭素数２〜３ｏのものが好
ましく、これらの基は直鎖でも分岐で５よい。The alkyl group and alkoxy group represented by R+, R2 and R3 preferably have 1 to 30 carbon atoms,
The alkenyl group preferably has 2 to 3 carbon atoms, and these groups may be linear or branched.
また、これらアルキル基、アルケニル基、アルコキシ基
は、さらに置換基を有してもよい。Moreover, these alkyl groups, alkenyl groups, and alkoxy groups may further have a substituent.
アルキル基、アルケニル基、アルコキシ基の具体例とし
ては、例えばメチル基、エチル基、イソプロピル基、ｔ
−ブチル基、５ｅｃ−ブチル基、ｎ−ブチル基、ｎ−ア
ミル基、５ｅｃ−アミル基、【−アミル基、オクチル基
、ノニル基、ドデシル基、エイコシル基、α、α−ジメ
チルベンジル基、オクチルオキシカルボニルエチル基、
メトキシ基、エトキシ基、オクチルオキシ基、アリル基
等が挙げられる。Specific examples of alkyl groups, alkenyl groups, and alkoxy groups include methyl groups, ethyl groups, isopropyl groups, t
-butyl group, 5ec-butyl group, n-butyl group, n-amyl group, 5ec-amyl group, [-amyl group, octyl group, nonyl group, dodecyl group, eicosyl group, α,α-dimethylbenzyl group, octyl group oxycarbonylethyl group,
Examples include methoxy group, ethoxy group, octyloxy group, and allyl group.
Ｒ＋ 、Ｒ２およびＲ３で表わされるアリール基、アリ
ールオキシ基としては、例えばフェニル基、フェニルオ
キシ基が特に好ましく、置換基を有していてもよい。具
体的には、例えばフェニル基、４−ｔ−ブチルフェニル
基、２，４−ジ−ｔ−アミルフェニル基等が挙げられる
。The aryl group and aryloxy group represented by R+, R2 and R3 are particularly preferably, for example, a phenyl group or a phenyloxy group, which may have a substituent. Specific examples include phenyl group, 4-t-butylphenyl group, 2,4-di-t-amylphenyl group, and the like.
Ｒ１およびＲ２で表わされる基のうち、水素原子、アル
キル基、アルコキシ基およびアリール基が好ましく、特
に水素原子、アルキル基およびアルコキシ基が好ましい
。Among the groups represented by R1 and R2, a hydrogen atom, an alkyl group, an alkoxy group, and an aryl group are preferred, and a hydrogen atom, an alkyl group, and an alkoxy group are particularly preferred.
Ｒ３で表わされる基のうち、特に水素原子、ハロゲン原
子、アルキル基、アルコキシ基が好ましいが、明退色の
点からざらに水素原子、アルキル基、アルコキシ基が好
ましい。Among the groups represented by R3, a hydrogen atom, a halogen atom, an alkyl group, and an alkoxy group are particularly preferred, and a hydrogen atom, an alkyl group, and an alkoxy group are generally preferred from the viewpoint of light fading.
Ｒ＋ 、Ｒ２及びＲ３で表わされる基のうち、常温で液
体となるためには、少なくとも１つはアルキル基である
ことが好ましく、更に好ましくは少なくとも２つがアル
キル基であることが好ましい。Among the groups represented by R+, R2 and R3, at least one is preferably an alkyl group, and more preferably at least two are alkyl groups in order to become liquid at room temperature.
Ｒ＋ 、Ｒ２及びＲ３で表わされるアルキル基は、如
何なるアルキル基をとることもできるが、少なくとも一
つは第三級アルキル基又は第二級アルキル基であること
が好ましい。特にＲ１及びＲ２で表わされるアルキル基
の少なくとも一方が第三級アルキル基又は第三級アルキ
ル基であることが好ましい。The alkyl groups represented by R+, R2 and R3 can be any alkyl group, but preferably at least one is a tertiary alkyl group or a secondary alkyl group. In particular, it is preferred that at least one of the alkyl groups represented by R1 and R2 is a tertiary alkyl group or a tertiary alkyl group.
以下に本発明に係る液状紫外線吸収剤の代表的（続き）
前記本発明に係る液状紫外線吸収剤の添加ｍとしては、
如何なる吊で用いることもできるが紫外線吸収剤を含有
ゴる写真構成層のバインダーに対してｍｍで０１−、３
００％の範囲で用いることができ、好ましくは１−２０
０％、更に好ましくは５〜１００％の範囲で用いること
ができる。また塗布ｍとしては０．０１〜ｉｏｏｍｇ／
１００ｃ、２で好ましく用いルコとができ、更に：
ハ０．１〜５０ ｍ（］／ １１００Ｃ’ 、特に０，
５〜３０ ｍ（Ｊ／ｌｏｔ＋−で用いることが好ましい
。Representative examples of the liquid ultraviolet absorber according to the present invention (continued) The addition m of the liquid ultraviolet absorber according to the present invention includes:
Any suspension can be used, but it is 01-3 mm in mm with respect to the binder of the photographic constituent layer containing the ultraviolet absorber.
It can be used in the range of 00%, preferably 1-20%.
It can be used in a range of 0%, more preferably 5 to 100%. Also, the coating m is 0.01~ioomg/
100c, 2 is preferably used, and further:
Ha0.1~50 m(]/1100C', especially 0,
It is preferable to use 5 to 30 m (J/lot+-).
本発明において、前記本発明に係るシアンカプラーがハ
ロゲン化銀乳剤層に含有され、上記本発明に係る液状紫
外線吸収剤は、前記シアンカプラー含有ハロゲン化銀乳
剤層およびこの層に隣接する非感光性層から選ばれる少
なくとも１唐に含有されるが、本発明の係る液状紫外線
吸収剤は、好ましくは、少なくとも支持体から見て該ハ
ロゲン化銀乳剤層の支持体とは反対側に隣接する非感光
性に含有する場合であり、さらに好ましくは、上記ハに
１ゲン化銀乳剤層に隣接する両方の非感光性層に含有す
る場合である。In the present invention, the cyan coupler according to the present invention is contained in a silver halide emulsion layer, and the liquid ultraviolet absorber according to the present invention is contained in the cyan coupler-containing silver halide emulsion layer and the non-photosensitive layer adjacent to this layer. The liquid ultraviolet absorber according to the present invention is preferably contained in at least one layer selected from the layer, and is preferably contained in at least one non-photosensitive layer adjacent to the silver halide emulsion layer on the side opposite to the support when viewed from the support. More preferably, it is contained in both non-photosensitive layers adjacent to the silver 1-genide emulsion layer.
前記本発明に係るシアンカプラー含有ハロゲン化銀乳剤
層に、本発明に係る液状紫外線吸収剤を含有する場合、
その添加方法としては、本発明に係る液状紫外線吸収剤
は常温で液体であり、本発明に係るシアンカプラーの溶
媒として用いることができるため、本発明に係る液状紫
外線吸収剤とシアンカプラーを単に混合しであるいは必
要に応じて酢酸エチル等の低沸点溶媒を用いてゼラチン
水溶液などの親水性バインダー中に界面活性剤を用いて
微分散することができる。When the cyan coupler-containing silver halide emulsion layer according to the present invention contains the liquid ultraviolet absorber according to the present invention,
As for the addition method, since the liquid ultraviolet absorber according to the present invention is liquid at room temperature and can be used as a solvent for the cyan coupler according to the present invention, the liquid ultraviolet absorber according to the present invention and the cyan coupler are simply mixed together. It can be finely dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant or, if necessary, a low boiling point solvent such as ethyl acetate.
また、必要に応じてフェノール誘導体、フタル酸エステ
ル、リン酸エステル、クエン酸エステル、安息香酸エス
テル、アルキルアミド、脂肪酸エステル、トリメシン酸
エステル等の高沸点溶媒を併用してもよい。In addition, high boiling point solvents such as phenol derivatives, phthalic esters, phosphoric esters, citric esters, benzoic esters, alkylamides, fatty acid esters, and trimesic esters may be used in combination, if necessary.
本発明に係る液状紫外線吸収剤をシアンカプラー含有ハ
ロゲン化銀乳剤に隣接する非感光性層に添加する場合、
本発明に係る液状紫外線吸収剤をそのままあるいは必要
に応じて酢酸エチル等の低沸点溶媒を用いてゼラチン水
溶液などの親水性バインダー中に界面活性剤を用いて微
分散することができる。When adding the liquid ultraviolet absorber according to the present invention to a non-photosensitive layer adjacent to a cyan coupler-containing silver halide emulsion,
The liquid ultraviolet absorber according to the present invention can be used as it is, or if necessary, it can be finely dispersed in a hydrophilic binder such as an aqueous gelatin solution using a low boiling point solvent such as ethyl acetate using a surfactant.
また、必要に応じて上記と同様の高沸点溶媒を併用して
もよい。Further, if necessary, a high boiling point solvent similar to the above may be used in combination.
更に、本発明に係る液状紫外線吸収剤は常温にて固体状
の紫外線吸収剤を併用してもよいが、この場においても
前記した添加方法が適用できる。Furthermore, the liquid ultraviolet absorber according to the present invention may be used in combination with a solid ultraviolet absorber at room temperature, and the above-described addition method can also be applied in this case.
本発明のハロゲン化銀写真感光材料が多色カラー感光材
料である場合、具体的な層構成としては、支持体上に、
支持体側より順次、イエローカプラー含有ハロゲン化銀
乳剤層、第１中間層、マゼンタカプラー含有ハロゲン化
銀乳剤層、第２中間層、本発明に係るシアンカプラー含
有ハロゲン化銀乳剤層、第３中間層、保護層と配列した
ものが特に好ましい。When the silver halide photographic light-sensitive material of the present invention is a multicolor light-sensitive material, the specific layer structure includes:
Sequentially from the support side: a yellow coupler-containing silver halide emulsion layer, a first intermediate layer, a magenta coupler-containing silver halide emulsion layer, a second intermediate layer, a cyan coupler-containing silver halide emulsion layer according to the present invention, and a third intermediate layer. , and those arranged with a protective layer are particularly preferred.
本発明のハロゲン化銀写真感光材料が特に上記の層構成
よりなる場合には、本発明の液状紫外線吸収剤は少なく
とも第３中間層に含有することが好ましく、さらに好ま
しくは第２中間層及び第３中間層に含有することが好ま
しい。In particular, when the silver halide photographic light-sensitive material of the present invention has the above layer structure, the liquid ultraviolet absorber of the present invention is preferably contained in at least the third intermediate layer, and more preferably in the second intermediate layer and the third intermediate layer. 3. It is preferable to contain it in the intermediate layer.
また、本発明においては、上記本発明に係る液状紫外線
吸収剤を含有する層には、誘電率６．０以下の高沸点有
機溶媒が、紫外線吸収剤総量に対して重量で０６５〜Ｏ
の範囲で含有され、好ましくは０．３０〜０で含有され
る。Further, in the present invention, in the layer containing the liquid ultraviolet absorber according to the present invention, a high boiling point organic solvent with a dielectric constant of 6.0 or less is added to the layer containing the liquid ultraviolet absorber according to the present invention.
It is contained in a range of 0.30 to 0, preferably 0.30 to 0.
本発明に係る上記高沸点有様溶媒は、誘電率６．０以下
の化合物であればいずれでもよい。下限については、特
に限定はしないが誘電率が１．９以上が好ましい。例え
ば誘電率６．０以下のフタル酸エステル、リン酸エステ
ル等のエステル類、有機酸アミド類、ケトン類、炭化水
素化合物等である。The high boiling point solvent according to the present invention may be any compound having a dielectric constant of 6.0 or less. The lower limit is not particularly limited, but the dielectric constant is preferably 1.9 or more. Examples include esters such as phthalic esters and phosphoric esters, organic acid amides, ketones, and hydrocarbon compounds having a dielectric constant of 6.0 or less.
より好ましくは、フタル酸エステル類、またはリン酸エ
ステル類である。More preferred are phthalic acid esters or phosphoric acid esters.
１００℃に於ける蒸気圧が０．５１１１ｆｆｌＨＩＪ以
下の高沸点有機溶媒が好ましい。有機溶媒は、２種以上
の混合物であってもよく、この場合は混合物の誘電率が
６．０以下であればよい。本発明における誘電率は、３
０℃におけるｙ、電率を示している。A high boiling point organic solvent having a vapor pressure of 0.5111 fflHIJ or less at 100°C is preferred. The organic solvent may be a mixture of two or more types, and in this case, the dielectric constant of the mixture may be 6.0 or less. The dielectric constant in the present invention is 3
y indicates electrical conductivity at 0°C.
フタル酸エステルとしては、一般式［１−ＩＡ］で示さ
れる。The phthalate ester is represented by the general formula [1-IA].
一般式［＋−Ｉ Ａコ
Ｒ１−１１およびＲ）４２は、それぞれアルキル基、ア
ルケニル基またはアリール基を表わす。但し、ＲＨＩお
よびＲＨ２で表わされる基の炭素原子数の総和は９乃至
３２であり、好ましくは炭素原子数の総和が１６乃至２
４である。The general formulas [+-IAcoR1-11 and R)42 each represent an alkyl group, an alkenyl group, or an aryl group. However, the total number of carbon atoms in the groups represented by RHI and RH2 is 9 to 32, preferably 16 to 2.
It is 4.
一般式［ＨＡ、］のＲＨ＋およびＲＨ２で表わされるア
ルキル基、直鎮もしくは分岐のものであり、例えばブチ
ル基、ヘキシル基、オクチル基、ノニル基、ドデシル基
、テトラデシル基、ヘキサデシル基、ヘプタデシル基等
、オクタデシル基等である。The alkyl group represented by RH+ and RH2 in the general formula [HA, ], straight or branched, such as butyl group, hexyl group, octyl group, nonyl group, dodecyl group, tetradecyl group, hexadecyl group, heptadecyl group, etc. , octadecyl group, etc.
ＲＨｌｅよびＲ）４２で表わされるアリール基はフェニ
ル基、ナフチル基等であり、またアルケニル基はへキセ
ニル基、ヘプテニル基、オクタデセニル基等である。こ
れらのアルキル基、アルケニル基およびアリール基は、
単一もしくは複数の置換基を有していても良い。The aryl group represented by RHle and R)42 is a phenyl group, naphthyl group, etc., and the alkenyl group is a hexenyl group, heptenyl group, octadecenyl group, etc. These alkyl groups, alkenyl groups and aryl groups are
It may have single or multiple substituents.
上記において、ＲＨＩおよびＲＨ２の好ましくはアルキ
ル基であり、例えば２−エチルヘキシル基、３．５．５
−トリメチルヘキシル基、ローオチクル基、ｎ−ノニル
基等である。In the above, RHI and RH2 are preferably alkyl groups, such as 2-ethylhexyl group, 3.5.5
-trimethylhexyl group, rhoticle group, n-nonyl group, etc.
リン酸エステルとしては、下記一般式［ＨＢ］で示され
る。The phosphoric acid ester is represented by the following general formula [HB].
一般式［ＨＢ］
ＲＨ３、Ｒ１−１４およびＲ）＋５は、それぞれ、アル
キル基、アルケニル基またはアリール基を表わす。但し
、ＲＨ３、ＲＨ４およびＲｈ６で表わされる炭素原子数
の総和は２４乃至５４である。General formula [HB] RH3, R1-14 and R)+5 each represent an alkyl group, an alkenyl group or an aryl group. However, the total number of carbon atoms represented by RH3, RH4 and Rh6 is 24 to 54.
一般式［トＩＢ］のＲＨ３、ＲＨ４およびＲ１，ｌぢで
表わされるアルキル基は、直鎖または分岐のものであり
、例えばブチル基、ペンチル基、ヘキシル基、オクチル
基、ノニル基、ドアシル基、ペンタデシル基、ヘキサデ
シル基、オクタデシル基、ノナデシル基等である。The alkyl groups represented by RH3, RH4 and R1,1 in the general formula [IB] are linear or branched, such as butyl, pentyl, hexyl, octyl, nonyl, doacyl, These include pentadecyl group, hexadecyl group, octadecyl group, nonadecyl group, etc.
これらのアルキル基、アルケニル基およびアリール基は
、単一もしくは複数の置換基を有していても良い。好ま
しくはＲ、ＲおよびＲはアルキル基であり、例えば、２
−エチルヘキシル基、ｎ−オクチル基、３．５．５−ト
リメチルヘキシル基、ｎ−ノニル基、ｎ−デシル基、５
ｅｃ−デシル基、５ｅｃ−ドデシル基、ｔ−オクチル基
等が挙げられる。These alkyl groups, alkenyl groups and aryl groups may have single or multiple substituents. Preferably R, R and R are alkyl groups, for example 2
-ethylhexyl group, n-octyl group, 3.5.5-trimethylhexyl group, n-nonyl group, n-decyl group, 5
Examples include ec-decyl group, 5ec-dodecyl group, t-octyl group, and the like.
有機溶媒の具体例を示すが本発明はこれらに限定される
ものではない。Although specific examples of organic solvents are shown, the present invention is not limited thereto.
一般式［）（Ａコ
一般式［）（Ｂ：１
本発明において用いられる誘電率６．０以下の高沸点有
機溶媒において、好ましくは前記一般式［ＨＡ］および
［ＨＢ］で示される高沸点有機♂媒であり、さらに好ま
しくは前記一般式［ＨＡ］で示されるフタル酸エステル
系高沸点有機溶媒である。General formula [) (A) General formula [) (B:1 In the high boiling point organic solvent with a dielectric constant of 6.0 or less used in the present invention, preferably the high boiling point represented by the above general formulas [HA] and [HB] It is an organic male medium, and more preferably a phthalate-based high boiling point organic solvent represented by the general formula [HA].
さらに本発明においては誘電率６，０を越える高沸点有
機溶媒を誘電率６６０以下の高沸点有機溶媒と同時に含
んでもよく、誘電率６．０以下の高沸点有機溶媒総量に
対する重量比で０．５以下、好ましくは０．２５以下、
さらに好ましくは０１以下である。Furthermore, in the present invention, a high boiling point organic solvent with a dielectric constant of over 6.0 may be included simultaneously with a high boiling point organic solvent with a dielectric constant of 660 or less, and the weight ratio to the total amount of high boiling point organic solvents with a dielectric constant of 6.0 or less is 0.0. 5 or less, preferably 0.25 or less,
More preferably, it is 01 or less.
上記の構成になる本発明のハロゲン化銀写真感光材料は
、例えばカラーネガのネガ及びポジフィルム、ならびに
カラー印画紙などであることができるが、とりわけ直接
鑑賞用に供されるカラー印画紙を用いた場合に本発明方
法の効果が有効に発揮される。The silver halide photographic light-sensitive material of the present invention having the above structure can be, for example, color negative and positive films, color photographic paper, etc., but in particular color photographic paper used for direct viewing can be used. In such cases, the effects of the method of the present invention are effectively exhibited.
本発明に用いられる色素画像形成カプラーは前記本発明
に係るシアンカプラー以外特に限定されるものではなく
、種々のカプラーを用いることができるが、下記特許に
記載の化合物が代表的なものとして包含される。The dye image-forming coupler used in the present invention is not particularly limited other than the cyan coupler according to the present invention, and various couplers can be used, but the compounds described in the following patents are included as representative examples. Ru.
イエロー色素両会形成カプラーとしてはアシルアセトア
ミド型、ベンゾイルメタン型カプラーである。The yellow dye conjugate-forming couplers include acylacetamide type and benzoylmethane type couplers.
マゼンタ色素画像形成カプラーとしては、５−ピラゾロ
ン系、ピラゾロトリアゾール系、ピラゾリノベンツイミ
ダゾール系、インダシロン系、シアノアセチル系マゼン
タ色素画像形成カプラーである。Examples of magenta dye image-forming couplers include 5-pyrazolone type, pyrazolotriazole type, pyrazolinobenzimidazole type, indasilone type, and cyanoacetyl type magenta dye image forming couplers.
本発明のハロゲン化銀写真感光材料に用いられるハロゲ
ン化銀としては臭化銀、沃臭化銀、沃塩化銀、塩臭化銀
、及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。The silver halide used in the silver halide photographic light-sensitive material of the present invention includes silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride, which are commonly used in silver halide emulsions. Any one can be used.
本発明に用いられるハロゲン化銀乳剤は、硫黄増感法、
セレン増感法、還元増感法、貴金属増感法などにより化
学増感される。The silver halide emulsion used in the present invention can be prepared by sulfur sensitization method,
Chemically sensitized by selenium sensitization, reduction sensitization, noble metal sensitization, etc.
本発明に用いられる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。The silver halide emulsion used in the present invention can be optically sensitized to a desired wavelength range using a dye known as a sensitizing dye in the photographic industry.
本発明のハロゲン化銀写真感光材料に用いられるバイン
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、それ以外にゼラチン誘導体、ゼラチ
ンと他の高分子のグラフトポリマー、蛋白質、糖誘導体
、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事が出来
る。As the binder (or protective colloid) used in the silver halide photographic material of the present invention, gelatin is advantageously used, but gelatin derivatives, graft polymers of gelatin and other polymers, proteins, sugars, etc. Hydrophilic colloids such as derivatives, cellulose derivatives, synthetic hydrophilic polymeric substances such as single or copolymers can also be used.
本発明のハロゲン化銀写真感光材料には、ざらに硬膜剤
、色濁り防止剤、画像安定化剤、可塑剤、ラテックス、
界面活性剤、マット剤、滑剤、帯電防止剤等の添加剤を
必要に応じて用いることができる。The silver halide photographic light-sensitive material of the present invention contains a hardening agent, a color clouding preventive agent, an image stabilizer, a plasticizer, latex,
Additives such as surfactants, matting agents, lubricants, and antistatic agents can be used as necessary.
本発明のハロゲン化銀写真感光材料は、当業界公知の発
色現像処理を行うことにより画像を形成することができ
る。An image can be formed on the silver halide photographic material of the present invention by subjecting it to color development treatment known in the art.
［発明の具体的効果］
以上説明した如く、本発明のハロゲン化銀写真感光材料
には、シアン色素画像の明退色性が改良され、特に低８
１度部の変色が解消され、長期間保る。[Specific Effects of the Invention] As explained above, the silver halide photographic light-sensitive material of the present invention has improved brightness fading resistance of cyan dye images, and particularly has a low 8
Discoloration of the 1st degree area is eliminated and it lasts for a long time.
［発明の具体的実施例］
以下、本発明を実施例により具体的に説明するが、本発
明の実施の態様はこれらに限定されるものではない。[Specific Examples of the Invention] Hereinafter, the present invention will be specifically explained using Examples, but the embodiments of the present invention are not limited thereto.
以ｉ′ｂ
１：ｉ
［実施例−１１
表−１に示した層構成にて以下に訂述づる多層ハロゲン
化銀写真感光材料を作成した。i'b 1:i [Example 11 A multilayer silver halide photographic material as detailed below was prepared with the layer structure shown in Table 1.
表−１ （）内は塗布ｍまたは添加ｍを表わす。Table-1 The numbers in parentheses represent application m or addition m.
表−１（つづき） 傘は表−２に示す。Table-1 (continued) Umbrellas are shown in Table-2.
ここで用いた△５−１Ｄ、Ｓ−１、Ｙ−１、Ｍ−１６よ
びＵＶ−８１は下記に示す構造の化合物である。Δ5-1D, S-1, Y-1, M-16 and UV-81 used here are compounds having the structures shown below.
スティン防止剤ＡＳ−１
退色防止剤Ｄ Ｓ −’１
イエローカプラー Ｙ−１
マＵンタカブラー Ｍ−１
固体状紫外線吸収剤 ＵＶ−８１
これらの試料１乃至２２に感光ｉＩ（小西六写真工業株
式会社製Ｋ Ｓ −７型）を用いて白色光により光横露
光を行なった後、以Ｆの９ｊｌ ３＄を施した。Anti-stinting agent AS-1 Anti-fading agent D S-'1 Yellow coupler Y-1 Maunta coupler M-1 Solid ultraviolet absorber UV-81 These samples 1 to 22 were coated with photosensitive iI (manufactured by Konishiroku Photo Industry Co., Ltd.) After performing horizontal exposure with white light using a KS-7 model, the following 9jl 3$ was applied.
基準処理工程（９８理濡度と処理時間）［１］発色現像
３８℃ ３分３０秒［２］漂白定着 ３３℃
１分３０秒［３］水洗処理 ２５〜３０℃ ３分
［４１乾 燥 ７５〜８０℃ 約２分処理液組成
（発色現像液）
ベンジルアルコール １５Ｍ＋２エチ
レングリコール １５顧亜＠酸カリウム
２．０ （１臭化カリウム
０．７（１塩化すトリウム
０．２ｇ炭酸カリウム
３０．０ （］ヒドロキシルアミン硫Ｍ塩３．０（１
ポリリン酸（ＴＰＰＳ） ２．５σ３−
メチル−４アミリーＮ−
エチル−Ｎ−（β−メタンスルホン
アミド１デル）−アニリン＠酸塩 ５．５ ｇ蛍光
増白剤（４，／Ｉ’ −ジアミノ
スヂルベンジダレスルホン酸誘導体） １０ｇ水酸化
カリウム ２．０９水を加えて仝吊
１１とし、ｐｌｌ ＋０．２０に調整づる。Standard processing steps (98 degrees wetness and processing time) [1] Color development 38°C 3 minutes 30 seconds [2] Bleach fixing 33°C
1 minute 30 seconds [3] Washing process 25-30℃ 3 minutes [41 Drying 75-80℃ approx. 2 minutes Processing solution composition (color developer) Benzyl alcohol 15M + 2 ethylene glycol 15% Potassium nitrite 2.0 (1 potassium bromide
0.7 (thorium monochloride
0.2g potassium carbonate
30.0 (]Hydroxylamine sulfate M salt 3.0 (1 Polyphosphoric acid (TPPS) 2.5σ3-
Methyl-4amylyN-ethyl-N-(β-methanesulfonamide 1del)-aniline @acid 5.5 g Optical brightener (4,/I'-diaminosulfonamide derivative) 10 g water Potassium oxide 2.09 Add water to make the volume 11 and adjust to pll +0.20.
（漂白定着液）
■ヂレンジアミンテトラ酢酸第２鉄
アンモニウム２水Ｊ３３ ６０ｇエヂ
レンジアミンテトラ酢Ｍ ３（ＪヂＡ硫酸ア
ンモニウム（７０％溶液） １００．．１２亜硫酸
アンモニウム（４０％溶液） ２７．５＋ｇ炭酸カ
リウムまたは氷酢酸でＩ）Ｈ７，１に調整し水を加えて
全１１ｙとする。(Bleach-fix solution) ■ Dilene diamine tetraferric ammonium acetate diwater J33 60 g Dilene diamine tetra vinegar M3 (JjiA ammonium sulfate (70% solution) 100..12 Ammonium sulfite (40% solution) 27.5 + g Adjust to I)H7.1 with potassium carbonate or glacial acetic acid and add water to make a total of 11y.
［光退色試験］ 初濃度［）ｏ ＝ １．０の残存率で示した。[Photobleaching test] It is shown as a residual rate of initial concentration [)o=1.0.
残存率−（Ｄ／Ｄｏ）ｘ １００（１）＝退色後の濃
度）［明退色試験］
１０の残存率で示した。Residual rate - (D/Do) x 100 (1) = density after fading) [Bright fading test] Shown as a residual rate of 10.
残存率＝ （Ｄ／Ｄｏ）Ｘ １００（Ｄ＝退色後の濃
度）［イエロースティン］
明暗退色試験における各々の未発色部のイエロースティ
ン（以下ＹＳともいう）は次のようにして求めた。Remaining rate = (D/Do) x 100 (D = density after fading) [Yellow stain] The yellow stain (hereinafter also referred to as YS) of each uncolored area in the bright and dark fading test was determined as follows.
イエロースディンΔＯＢ＝ΔＤＢ−Ｄｏ８Ｄ８−保存後
の青色光濃度
ｏ ＯＢ・保存前の青色光濃度
なお、これらの試料は光学濃度８１（小西六写真工業（
株） ’ＨＰ Ｄ Ａ ＝ ６５型）を用いて測定した
。Yellow Sudin ΔOB = ΔDB - Do8D8 - Blue light density after storage o OB - Blue light density before storage These samples have an optical density of 81 (Konishiroku Photo Industry
It was measured using HPDA=65 type).
［変色試験］
また、シアン色素画１象の変色の程度を示すのに「Ｐ変
度」を下記の如く定義した。シアン初ｉｌ力度（ＤＲ）
０．５０が試験後に退色し、退色後の赤色８１度Ｄ
Ｒ′、緑色８１度Ｄｑの比率（％）で示す。[Discoloration Test] In addition, "P variation" was defined as follows to indicate the degree of discoloration of one cyan dye image. Cyan initial power level (DR)
0.50 faded after the test, red 81 degrees D after fading
It is expressed as a ratio (%) of R' and green color 81 degrees Dq.
ずなわち、 を用いｌ〔。Zunawachi, Use l[.
また、実施例で用いた本発明の高沸点有機溶媒の誘電率
を示ず。Further, the dielectric constant of the high boiling point organic solvent of the present invention used in the examples is not shown.
高沸点ｆｉｎ溶媒ＮＯ９誘電率
１−１−２ ５．１１−１
−６ 、 １１．６）−１−
８４，４
１−１−１２４，６
以上の結果をまとめて表−２に承り。High boiling point fin solvent NO9 dielectric constant 1-1-2 5.11-1
-6, 11.6) -1-
84,4 1-1-124,6 The above results are summarized in Table-2.
表−２の結果から、本発明のシアンカプラーのみを用い
た試料１に対して、本発明外の固体状紫外線吸収剤を用
いた試ｔｌ、また本発明の液状紫外線吸収剤を用いても
高沸点有機溶媒の種類、添加ｍ、また紫外線吸収剤の添
加位置が本発明外である試料２〜５および２２では、い
ずれにおいても光退色性、光イエロースティンにやや改
良効果が見られるものの、ピンク変色が大きく問題であ
る。From the results in Table 2, it can be seen that for Sample 1 using only the cyan coupler of the present invention, the test tl using a solid UV absorber other than the present invention and the liquid UV absorber of the present invention were also high. Samples 2 to 5 and 22, in which the type of boiling point organic solvent, the addition m, and the addition position of the ultraviolet absorber were outside the scope of the present invention, all showed a slight improvement effect on photobleaching and optical yellow stain. Discoloration is a major problem.
これら比較試料に対して本発明の構成である試料６乃至
２１では、いずれの評価に対しても良好な結果を示して
おり、優れた画像保存性を有していることがわかる。さ
らに本発明の試料において、１りられた結果を詳細に検
討してみると、紫外線吸収剤総量に対する高沸点有機溶
媒の重量化が０．３以下である試ｆｉｔ ７乃至２１が
光ならびに暗イエロースティンの点でより好ましいこと
が分る。さらに一般式［ａ］で示される液体状紫外線吸
収剤のうらＲＲＩニハロゲン原子を含まない液体状紫外
線吸収剤を用いた試料６乃至１４．１６乃至１８、ｄ３
よび２０．２１がピンク変色の点でより好ましくまた、
本発明の高沸点有機溶媒のうちフタル酸エステル系高沸
点有機溶媒を用いた試お１６と７．９乃至１７Ｊ３よび
２１が暗イエロースティンの点で好ましいことが分る。Compared to these comparative samples, Samples 6 to 21 having the configuration of the present invention showed good results in all evaluations, and it can be seen that they have excellent image storage properties. Furthermore, when we examine the results obtained in detail for the samples of the present invention, we find that test fits 7 to 21, in which the weight of the high boiling point organic solvent relative to the total amount of ultraviolet absorber is 0.3 or less, are light and dark yellow. It turns out that it is more preferable in terms of stability. Further, samples 6 to 14, 16 to 18, d3 using a liquid ultraviolet absorber containing no RRI dihalogen atoms among the liquid ultraviolet absorbers represented by general formula [a]
and 20.21 are more preferable in terms of pink discoloration, and
It can be seen that among the high boiling point organic solvents of the present invention, Tests 16, 7.9 to 17J3 and 21 using phthalate ester high boiling point organic solvents are preferable in terms of dark yellow stain.
また、本発明の液体状紫外線吸収剤を本発明のシアンカ
プラー川の高沸点有は溶媒として用いた試料２０および
２１でも同様の効果が認られる。Further, similar effects were observed in Samples 20 and 21 in which the liquid ultraviolet absorber of the present invention was used as a solvent for the cyan coupler of the present invention.
［実施例−２１
実施例−１と同様にして、紫外線吸収剤の含有ｍと含有
層、ならびに第５層に含有させるシアンカプラーの種類
を表−３に承り如く変化させて試料３１乃至４４を作成
し、評価した。[Example 21 Samples 31 to 44 were prepared in the same manner as in Example 1 by changing the content m of the ultraviolet absorber, the containing layer, and the type of cyan coupler contained in the fifth layer as shown in Table 3. Created and evaluated.
なお、紫外線吸収剤、高沸点有機溶媒ならびに前記それ
ぞれの重量圧は実施例−１と同様で、その内容を実施例
−１の試料番号Ｃ示乃。The ultraviolet absorber, high boiling point organic solvent, and weight pressure of each of the above are the same as in Example-1, and the contents are shown in sample number C of Example-1.
１ｑられた評価結果を表−３に示す。Table 3 shows the evaluation results.
シアンカプラー
ｋＣＣ−・１
固体状紫外線吸収剤
固体状紫外線吸収剤
傘ＵＶ−３３
表−３の結果から、試料３２乃至３６、／ｌ３Ｊ３よび
／Ｉ／Ｉにおいて、本発明の４Ｍ成要Ｆ１を本発明の写
真構成層のうら少なくども１Ｆ１または２層以上いずれ
の膚に適用した場合でも、又試ＩＩ ４１と４２におい
て異なる構成数ｆ１がそれぞれの写真構成層に適用され
／、：ｉ’Ａ合でも、本発明の効果が十分に発揮されて
いることが分る。Cyan coupler kCC-・1 Solid ultraviolet absorber Solid ultraviolet absorber Umbrella UV-33 From the results in Table 3, in samples 32 to 36, /l3J3 and /I/I, the 4M component F1 of the present invention was applied to the present invention. Regardless of whether at least 1F1 or 2 or more layers of the photographic constituent layers of the invention are applied to the skin, different numbers of constituents f1 are applied to the respective photographic constituent layers in Tests II 41 and 42. However, it can be seen that the effects of the present invention are fully exhibited.
また、支持体側から見て本発明のシアンカプラーを含有
するハロゲン化銀乳剤層とは反対側の非感光性層（第６
層）に本発明の構成要件を含有する試料３２．３５乃至
４２Ｊ３よび４４は、光退色性ならびに光イエローステ
ィンの点で特に好ましい結果を示していることが分る。In addition, a non-photosensitive layer (sixth
It can be seen that Samples 32.35 to 42J3 and 44, which contain the constituent elements of the present invention in layer), show particularly favorable results in terms of photobleaching properties and photoyellow stain.
Claims (1)
なくとも１層の非感光性層を有するハロゲン化銀写真感
光材料において、前記ハロゲン化銀乳剤層の少なくとも
１層は下記一般式［ I ］で示されるシアンカプラーを
含有し、該シアンカプラー含有ハロゲン化銀乳剤層およ
びこの層に隣接する非感光性層から選ばれる少なくとも
１層には、常温にて液体の紫外線吸収剤を含有し、かつ
該紫外線吸収剤を含有する層に誘電率６．０以下の高沸
点有機溶媒を該紫外線吸収剤総量に対して重量で０．６
５〜０の範囲で含有することを特徴とするハロゲン化銀
写真感光材料。 一般式［ I ］ ▲数式、化学式、表等があります▼ ［式中、Ｒ＾１はアルキル基またはアリール基を表わす
。Ｒ＾２はアルキル基、シクロアルキル基、アリール基
または複素環基を表わす。Ｒ＾３は水素原子、ハロゲン
原子、アルキル基またはアルコキシ基を表わす。またＲ
＾３はＲ＾１と結合して環を形成しても良い。Ｚは水素
原子または発色現像主薬の酸化体との反応により離脱可
能な基を表わす。］[Scope of Claims] In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer and at least one non-light-sensitive layer on a support, at least one of the silver halide emulsion layers has the following general structure. At least one layer selected from the cyan coupler-containing silver halide emulsion layer and the non-photosensitive layer adjacent to this layer contains a cyan coupler represented by formula [I], and contains an ultraviolet absorber that is liquid at room temperature. and a high boiling point organic solvent with a dielectric constant of 6.0 or less in the layer containing the ultraviolet absorber by weight of 0.6 with respect to the total amount of the ultraviolet absorber.
A photographic material containing silver halide in the range of 5 to 0. General formula [I] ▲There are numerical formulas, chemical formulas, tables, etc.▼ [In the formula, R^1 represents an alkyl group or an aryl group. R^2 represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. R^3 represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. Also R
^3 may be combined with R^1 to form a ring. Z represents a hydrogen atom or a group capable of being separated by reaction with an oxidized product of a color developing agent. ]
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29127786A JPS63143545A (en) | 1986-12-06 | 1986-12-06 | Silver halide photographic sensitive material with improved shelf stability of dye image |
| EP19870117905 EP0271005B1 (en) | 1986-12-06 | 1987-12-03 | Silver halide photographic light-sensitive material excellent in dye-image preservability |
| DE19873751418 DE3751418T2 (en) | 1986-12-06 | 1987-12-03 | Silver halide photographic light-sensitive material excellent in dye image durability. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29127786A JPS63143545A (en) | 1986-12-06 | 1986-12-06 | Silver halide photographic sensitive material with improved shelf stability of dye image |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63143545A true JPS63143545A (en) | 1988-06-15 |
Family
ID=17766793
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29127786A Pending JPS63143545A (en) | 1986-12-06 | 1986-12-06 | Silver halide photographic sensitive material with improved shelf stability of dye image |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63143545A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60256142A (en) * | 1984-06-01 | 1985-12-17 | Fuji Photo Film Co Ltd | Color photographic sensitive material |
| JPS60260951A (en) * | 1984-06-07 | 1985-12-24 | Fuji Photo Film Co Ltd | Treatment of silver halide color photographic sensitive material |
-
1986
- 1986-12-06 JP JP29127786A patent/JPS63143545A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60256142A (en) * | 1984-06-01 | 1985-12-17 | Fuji Photo Film Co Ltd | Color photographic sensitive material |
| JPS60260951A (en) * | 1984-06-07 | 1985-12-24 | Fuji Photo Film Co Ltd | Treatment of silver halide color photographic sensitive material |
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