JPH01217454A - Silver halide photographic sensitive material - Google Patents
Silver halide photographic sensitive materialInfo
- Publication number
- JPH01217454A JPH01217454A JP4475788A JP4475788A JPH01217454A JP H01217454 A JPH01217454 A JP H01217454A JP 4475788 A JP4475788 A JP 4475788A JP 4475788 A JP4475788 A JP 4475788A JP H01217454 A JPH01217454 A JP H01217454A
- Authority
- JP
- Japan
- Prior art keywords
- dye
- group
- silver
- silver halide
- layer
- 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
- 239000000463 material Substances 0.000 title claims abstract description 33
- -1 Silver halide Chemical class 0.000 title claims description 40
- 229910052709 silver Inorganic materials 0.000 title claims description 31
- 239000004332 silver Substances 0.000 title claims description 31
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 239000000084 colloidal system Substances 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 claims abstract description 7
- 150000001450 anions Chemical class 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 3
- 125000001424 substituent group Chemical group 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 4
- 239000000975 dye Substances 0.000 abstract description 83
- 238000012545 processing Methods 0.000 abstract description 13
- 229910052755 nonmetal Inorganic materials 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 39
- 239000000839 emulsion Substances 0.000 description 37
- 108010010803 Gelatin Proteins 0.000 description 18
- 229920000159 gelatin Polymers 0.000 description 18
- 239000008273 gelatin Substances 0.000 description 18
- 235000019322 gelatine Nutrition 0.000 description 18
- 235000011852 gelatine desserts Nutrition 0.000 description 18
- 239000000203 mixture Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 239000007864 aqueous solution Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000001397 quillaja saponaria molina bark Substances 0.000 description 9
- 229930182490 saponin Natural products 0.000 description 9
- 150000007949 saponins Chemical class 0.000 description 9
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 8
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000011161 development Methods 0.000 description 6
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 6
- 239000011241 protective layer Substances 0.000 description 6
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 230000001235 sensitizing effect Effects 0.000 description 5
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 206010070834 Sensitisation Diseases 0.000 description 4
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000011109 contamination Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000004848 polyfunctional curative Substances 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- 230000008313 sensitization Effects 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- IHDBZCJYSHDCKF-UHFFFAOYSA-N 4,6-dichlorotriazine Chemical compound ClC1=CC(Cl)=NN=N1 IHDBZCJYSHDCKF-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 229940101006 anhydrous sodium sulfite Drugs 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 238000010186 staining Methods 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical group FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- FZERHIULMFGESH-UHFFFAOYSA-N N-phenylacetamide Chemical compound CC(=O)NC1=CC=CC=C1 FZERHIULMFGESH-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- XCFIVNQHHFZRNR-UHFFFAOYSA-N [Ag].Cl[IH]Br Chemical compound [Ag].Cl[IH]Br XCFIVNQHHFZRNR-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 239000000460 chlorine Chemical group 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000000586 desensitisation Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine group Chemical group N1=CCC2=CC=CC=C12 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 2
- 125000005647 linker group Chemical group 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000002245 particle Substances 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
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 229940001482 sodium sulfite Drugs 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- GVEYRUKUJCHJSR-UHFFFAOYSA-N (4-azaniumyl-3-methylphenyl)-ethyl-(2-hydroxyethyl)azanium;sulfate Chemical compound OS(O)(=O)=O.OCCN(CC)C1=CC=C(N)C(C)=C1 GVEYRUKUJCHJSR-UHFFFAOYSA-N 0.000 description 1
- ZRHUHDUEXWHZMA-UHFFFAOYSA-N 1,4-dihydropyrazol-5-one Chemical compound O=C1CC=NN1 ZRHUHDUEXWHZMA-UHFFFAOYSA-N 0.000 description 1
- GGZHVNZHFYCSEV-UHFFFAOYSA-N 1-Phenyl-5-mercaptotetrazole Chemical compound SC1=NN=NN1C1=CC=CC=C1 GGZHVNZHFYCSEV-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 125000001340 2-chloroethyl group Chemical group [H]C([H])(Cl)C([H])([H])* 0.000 description 1
- KRTDQDCPEZRVGC-UHFFFAOYSA-N 2-nitro-1h-benzimidazole Chemical compound C1=CC=C2NC([N+](=O)[O-])=NC2=C1 KRTDQDCPEZRVGC-UHFFFAOYSA-N 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- DRORSPJLYCDESA-UHFFFAOYSA-N 4,4-dimethylcyclohexene Chemical group CC1(C)CCC=CC1 DRORSPJLYCDESA-UHFFFAOYSA-N 0.000 description 1
- JBHOMBPISICFGB-UHFFFAOYSA-N 6-chloro-1h-1,3,5-triazin-2-one;sodium Chemical compound [Na].ClC1=NC=NC(=O)N1 JBHOMBPISICFGB-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- DFQVGTFDFGVTGK-KVVVOXFISA-M ClC(C(=O)[O-])CCCCCC\C=C/CCCCCCCC.[K+] Chemical compound ClC(C(=O)[O-])CCCCCC\C=C/CCCCCCCC.[K+] DFQVGTFDFGVTGK-KVVVOXFISA-M 0.000 description 1
- 229940090898 Desensitizer Drugs 0.000 description 1
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- NVXLIZQNSVLKPO-UHFFFAOYSA-N Glucosereductone Chemical compound O=CC(O)C=O NVXLIZQNSVLKPO-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- LEVWYRKDKASIDU-IMJSIDKUSA-N L-cystine Chemical compound [O-]C(=O)[C@@H]([NH3+])CSSC[C@H]([NH3+])C([O-])=O LEVWYRKDKASIDU-IMJSIDKUSA-N 0.000 description 1
- 206010067482 No adverse event Diseases 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910021612 Silver iodide Inorganic materials 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- SMEGJBVQLJJKKX-HOTMZDKISA-N [(2R,3S,4S,5R,6R)-5-acetyloxy-3,4,6-trihydroxyoxan-2-yl]methyl acetate Chemical compound CC(=O)OC[C@@H]1[C@H]([C@@H]([C@H]([C@@H](O1)O)OC(=O)C)O)O SMEGJBVQLJJKKX-HOTMZDKISA-N 0.000 description 1
- HOLVRJRSWZOAJU-UHFFFAOYSA-N [Ag].ICl Chemical compound [Ag].ICl HOLVRJRSWZOAJU-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229960001413 acetanilide Drugs 0.000 description 1
- 229940081735 acetylcellulose Drugs 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- HTKFORQRBXIQHD-UHFFFAOYSA-N allylthiourea Chemical compound NC(=S)NCC=C HTKFORQRBXIQHD-UHFFFAOYSA-N 0.000 description 1
- 235000011126 aluminium potassium sulphate Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- CODNYICXDISAEA-UHFFFAOYSA-N bromine monochloride Chemical compound BrCl CODNYICXDISAEA-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- DNSISZSEWVHGLH-UHFFFAOYSA-N butanamide Chemical compound CCCC(N)=O DNSISZSEWVHGLH-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- WBLIXGSTEMXDSM-UHFFFAOYSA-N chloromethane Chemical compound Cl[CH2] WBLIXGSTEMXDSM-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- JEVCWSUVFOYBFI-UHFFFAOYSA-N cyanyl Chemical group N#[C] JEVCWSUVFOYBFI-UHFFFAOYSA-N 0.000 description 1
- 229960003067 cystine Drugs 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- WFSXUTWNNVIIIG-ZPUQHVIOSA-N glutaconaldehyde Chemical compound O\C=C\C=C\C=O WFSXUTWNNVIIIG-ZPUQHVIOSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910001389 inorganic alkali salt Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 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 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Chemical class 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 1
- 229940067157 phenylhydrazine Drugs 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- GRLPQNLYRHEGIJ-UHFFFAOYSA-J potassium aluminium sulfate Chemical compound [Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRLPQNLYRHEGIJ-UHFFFAOYSA-J 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 1
- 229940100890 silver compound Drugs 0.000 description 1
- 150000003379 silver compounds Chemical class 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- UOULCEYHQNCFFH-UHFFFAOYSA-M sodium;hydroxymethanesulfonate Chemical compound [Na+].OCS([O-])(=O)=O UOULCEYHQNCFFH-UHFFFAOYSA-M 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 238000001429 visible spectrum Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- G03C1/00—Photosensitive materials
- G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
- G03C1/825—Photosensitive materials characterised by the base or auxiliary layers characterised by antireflection means or visible-light filtering means, e.g. antihalation
- G03C1/83—Organic dyestuffs therefor
- G03C1/832—Methine or polymethine dyes
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は染料を含有するハロゲン化銀写真感光材料に関
し、特に光吸収染料として有用な染料によって着色され
た親水性コロイド層を含有する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 light-sensitive material containing a dye, and particularly to a silver halide photographic material containing a hydrophilic colloid layer colored with a dye useful as a light-absorbing dye. Related to silver photographic materials.
ハロゲン化銀写真感光材料（以下、感光材料と称す）に
おいて、フィルター、ハレーション防止、イラジェーシ
ョン防止あるいは写真乳剤の感度調節のため、特定の波
長の光を吸収させる目的で、写真材料中に染料を含有さ
せることは、よく知られており、染料によって親水性コ
ロイド層を着色させることがよく行われている。In silver halide photographic materials (hereinafter referred to as "photosensitive materials"), dyes are added to the photographic material for the purpose of absorbing light of specific wavelengths for filters, anti-halation, anti-irradiation, or to adjust the sensitivity of photographic emulsions. It is well known that the hydrophilic colloid layer is colored with a dye.
フィルター層は、通常、感光性乳剤層の上層あるいは乳
剤層と乳剤層の間に位置し、乳剤層に到達する入射光を
好ましい分光組成の光とする役割を果たす。また、写真
画像の鮮鋭度を向上させ８目的で、乳剤層と支持体との
間あるいは支持体裏面にハレーション防止層を設けて、
乳剤層と支持体との界面や、支持体背面等での有害な反
射光を吸収させて、ハレーション防止をしたり、乳剤層
を着色してハロゲン化銀粒子等による有害な反射光や散
乱光等を吸収させて、イラジェーション防止をすること
がよく行われている。A filter layer is usually located above a photosensitive emulsion layer or between two emulsion layers, and serves to convert incident light that reaches the emulsion layer into light having a preferable spectral composition. In addition, for the purpose of improving the sharpness of photographic images, an antihalation layer is provided between the emulsion layer and the support or on the back side of the support.
Harmful reflected light from the interface between the emulsion layer and the support, the back surface of the support, etc. is absorbed to prevent halation, and the emulsion layer is colored to absorb harmful reflected light and scattered light from silver halide grains, etc. It is common practice to prevent irradiation by absorbing
このような目的で用いられる染料は、使用目的に応じた
良好な吸収スペクトル特性を有すること、写真現像処理
中に完全に脱色され、写真材料中から容易に溶出して、
現像処理後に染料による残色汚染がないこと、写真乳剤
に対してカブリ、減感等の悪影響を及ぼさないこと、染
着された層から他の層へ拡散しないこと、更に、溶液中
、あるいは写真材料中での経時安定性に優れ、変褪色し
ないこと等の諸条件を満足しなければならない。Dyes used for such purposes must have good absorption spectrum characteristics depending on the purpose of use, be completely decolorized during photographic processing, be easily eluted from the photographic material,
There should be no residual color staining caused by the dye after the development process, there should be no adverse effects such as fogging or desensitization on the photographic emulsion, there should be no diffusion from the dyed layer to other layers, and there should be no residual color contamination caused by the dye in the solution or in the photograph. It must satisfy various conditions such as having excellent stability over time in the material and not changing color or fading.
今日までに、前記の条件を満足する染料を見い出すこと
を目的として、多くの努力がなされ多数の染料が提案さ
れてきた。例えば、英国特許５０６゜３８５号、米国特
許３，２４７．１２７号、特公昭３９−２２０６９号、
同４３−１３１６８号等に記載されたオキソノール染料
、米国特許１，８４５，４０４号に代表されるスチリル
染料、米国特許２，４９３，７４７号に代表されるメロ
シアニン染料、米国特許２，８４３．４８６号に代表さ
れるシアニン染料等がある。しかし、前記の諸条件を全
て満足し、写真材料に使用し得る良好な染料は非常に少
ないのが実情である。To date, many efforts have been made and a large number of dyes have been proposed with the aim of finding dyes that satisfy the above conditions. For example, British Patent No. 506°385, U.S. Patent No. 3,247.127, Japanese Patent Publication No. 39-22069,
oxonol dyes described in U.S. Pat. No. 43-13168, styryl dyes as typified by U.S. Pat. No. 1,845,404, merocyanine dyes as typified by U.S. Pat. No. 2,493,747, and U.S. Pat. No. 2,843.486. There are cyanine dyes represented by No. However, the reality is that there are very few good dyes that satisfy all of the above conditions and can be used in photographic materials.
従って本発明の目的は、良好な吸収スペクトル特性を有
し、写真現像処理中に脱色し、かつ写真材料中から溶出
して処理後の残色汚染が極めて少なく、写真乳剤に対し
て不活性である染料を含有するハロゲン化懇写真感光材
料を提供することにある。Therefore, the object of the present invention is to have good absorption spectrum characteristics, be decolorized during photographic processing, have extremely little residual color staining after processing due to elution from photographic materials, and be inert to photographic emulsions. An object of the present invention is to provide a halogenated photosensitive material containing a certain dye.
本発明の上記目的は、′下記一般式（Ｉ）で表される染
料の少なくとも１種を含有する親水性コロイド層を有す
るハロゲン化銀写真感光材料によって達成された。The above objects of the present invention have been achieved by a silver halide photographic material having a hydrophilic colloid layer containing at least one dye represented by the following general formula (I).
一般式（Ｉ）
式中、Ｒ１，Ｒ２，Ｒ３，Ｒ４，Ｒ５およびＲ６は各々
、アルキル基を表し、ＺｌおよびＺ２は各々、ベンゾ縮
合環またはナフト縮合環を形成するに必要な非金属原子
群を表す。ただし、Ｒ、、Ｒ２，Ｒ、、Ｒ４＋Ｒ、、Ｒ
、、Ｚ 、およびＺ２は、染料分子が少なくとも２個の
酸基を有することを可能にし、かつ、ｚｌおよびＺ２は
染料分子が一〇８２ＣＨ２０Ｒ７基を１個以上有する置
換基を少なくとも２個有することを可能にする基を表す
。Ｒ２は水素原子またはアルキル基を表す。Ｌはメチン
基を表し、ｘｅはアニオンを表す。ｍは１〜５の整数を
表し、ｎは１または２の整数を表す。染料が分子内塩を
形成する場合ｎはｌである。General formula (I) In the formula, R1, R2, R3, R4, R5 and R6 each represent an alkyl group, and Zl and Z2 each represent a nonmetallic atomic group necessary to form a benzo condensed ring or a naphtho condensed ring. represents. However, R,,R2,R,,R4+R,,R
, , Z and Z2 allow the dye molecule to have at least two acid groups, and zl and Z2 allow the dye molecule to have at least two substituents with one or more 1082CH20R7 groups. represents a group that allows R2 represents a hydrogen atom or an alkyl group. L represents a methine group, and xe represents an anion. m represents an integer of 1 to 5, and n represents an integer of 1 or 2. When the dye forms an inner salt, n is l.
以下、本発明をより具体的に説明する。The present invention will be explained in more detail below.
前記一般式（Ｉ）において、Ｒ、、Ｒ２，Ｒ、、Ｒ４゜
Ｒｓ、Ｒａ、Ｚ ｒおよびＺ、で表される基の中、少な
くとも２個は酸置換基（例えばスルホ基、カルボキシル
基）を有し、特に好ましくは染料分子が少なくとも２個
のスルホ基を有することを可能にする基を表す。スルホ
基およびカルボキシル基は、各々、その塩を包含する。In the general formula (I), at least two of the groups represented by R, R2, R, R4゜Rs, Ra, Zr and Z are acid substituents (e.g. sulfo group, carboxyl group). and particularly preferably represents a group which allows the dye molecule to have at least two sulfo groups. A sulfo group and a carboxyl group each include their salts.
塩としては、ナトリウム、カリウム等のアルカリ金属塩
、アンモニウム、トリエチルアミン、ピリジン等の有機
アンモニウム塩を挙げることができる。Examples of the salt include alkali metal salts such as sodium and potassium salts, and organic ammonium salts such as ammonium, triethylamine, and pyridine.
Ｒｒ 、 Ｒ！ 、Ｒｓ 、Ｒ４、ＲｓおよびＲ，で表
されるアルキル基は、好ましくは炭素数１〜８の低級ア
ルキル基（例えば、メチル、エチル、プロピル、ｉ−プ
ロピル、ブチル基等）を表し、前記の酸置換基以外の置
換基を有してもよい。特に好ましくは、Ｒ１およびＲ１
がスルホ基を有する炭素数１〜５の低級アルキル基（例
えば、２−スルホエチル、３−スルホプロピル、４−ス
ルホブチル基等）である。Rr, R! , Rs, R4, Rs and R, preferably represent a lower alkyl group having 1 to 8 carbon atoms (e.g., methyl, ethyl, propyl, i-propyl, butyl group, etc.), It may have substituents other than acid substituents. Particularly preferably R1 and R1
is a lower alkyl group having 1 to 5 carbon atoms (for example, 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl group, etc.) having a sulfo group.
ＺｌおよびＺ２で表されるベンゼン環またはナフタレン
環は、直接または２価の連結基を介して−Ｃ）１２ＣＪ
ＯＲｙ基を含む置換基を少なくとも２個以上有すること
が必須である。２価の連結基としては、−Ｏ−、−ＮＨ
ＣＯ−、−ＮＨＳＯ，−、−ＮＨＣＯＯ−、−ＮＨＣＯ
ＮＨ−、−ＣＯＯ−、−ＣＯ−、−ＳＯ，−、−Ｎ＝等
が挙げられ、Ｒ２で表されるアルキル基は炭素数４以下
の低級アルキル基が好ましい。The benzene ring or naphthalene ring represented by Zl and Z2 is directly or via a divalent linking group -C)12CJ
It is essential to have at least two or more substituents containing an ORy group. As the divalent linking group, -O-, -NH
CO-, -NHSO,-, -NHCOO-, -NHCO
Examples include NH-, -COO-, -CO-, -SO,-, -N=, etc., and the alkyl group represented by R2 is preferably a lower alkyl group having 4 or less carbon atoms.
ＣＨ２Ｃｌ（２０Ｒ７基を含む置換基としては、例えば
ヒドロキシエチル基、ヒドロキシエトキシエチル基、メ
トキシエトキシエチル基、ヒドロキシエチルカルバモイ
ルメチル基、ヒドロキシエトキシエチルカルバモイルメ
チル基、Ｎ、Ｎ−ジヒドロキシエチルカルバモイルメチ
ル基、ヒドロキシエチルスルファモイルエチル基、メト
キシエトキシエトキシカルボニルメチル基等を挙げるこ
とができる。CH2Cl (substituents containing 20R7 groups include, for example, hydroxyethyl group, hydroxyethoxyethyl group, methoxyethoxyethyl group, hydroxyethylcarbamoylmethyl group, hydroxyethoxyethylcarbamoylmethyl group, N,N-dihydroxyethylcarbamoylmethyl group, hydroxy Examples include an ethylsulfamoylethyl group and a methoxyethoxyethoxycarbonylmethyl group.
ＺｌおよびＺ２が有してもよい、その他の置換基として
は、スルホ基（塩を含む）、カルボキシル基（塩を含む
）、ヒドロキシル基、シアノ基、ハロゲン原子（例えば
、弗素、塩素、臭素原子等）等が挙げられる。Other substituents that Zl and Z2 may have include sulfo groups (including salts), carboxyl groups (including salts), hydroxyl groups, cyano groups, halogen atoms (for example, fluorine, chlorine, bromine atoms) etc.) etc.
Ｌで表されるメチン基も置換基を有してもよく、置換基
としては炭素数１〜５の置換または無置換の低級アルキ
ル基（例えば、メチル、エチル、３−ヒドロキシプロピ
ル、２−クロロエチル基等）、ハロゲン原子（例えば、
弗素、塩素、臭素原子等）、アリール基（例えばフェニ
ル基）、アルコキシ基（例えば、メトキシ、エトキシ基
等）などが挙げられる。また、メチン基の置換基同士が
結合して３つのメチン基を含む６員環（例えば４．４−
ジメチルシクロヘキセン環）を形成してもよい。The methine group represented by L may also have a substituent, and examples of the substituent include substituted or unsubstituted lower alkyl groups having 1 to 5 carbon atoms (for example, methyl, ethyl, 3-hydroxypropyl, 2-chloroethyl groups), halogen atoms (e.g.
Examples include fluorine, chlorine, bromine atoms, etc.), aryl groups (eg, phenyl groups), and alkoxy groups (eg, methoxy, ethoxy groups, etc.). In addition, the substituents of the methine group are bonded to each other to form a 6-membered ring containing three methine groups (for example, 4,4-
dimethylcyclohexene ring).
Ｘｅで表されるアニオンは、特に制約されないが、具体
例としてハロゲンイオン、ｐ−トルエンスルホン酸イオ
ン、エチル硫酸イオン等が挙げられる。The anion represented by Xe is not particularly limited, but specific examples include a halogen ion, p-toluenesulfonate ion, and ethylsulfate ion.
本発明に用いられる前記一般式ＣＩ）で表される染料（
以下、本発明の染料と称す）の具体例を以下に示すが、
本発明はこれ等に限定されるものしｔｌｌＬＬｌυ１１
Ｌ、ｔｌ、Ｌ、υυｉ
（Ｃｌｈ）ｚｓＯｉｅ（ＣＨｚ）ｘｓＯＪ（ＣＨｘ）＊
ＳＯ＋ｅ（ＣＨｔ）＊５ＯＪ（ＣＨｚ）ｔｓＯ＋”’
（ＣＨｔ）ｘｓＯＪ（ＣＨｘ）ｚｓ（ｈｅ（Ｃ
Ｈｔ）ｚｓＯＪ（しＨ２）、＞Ｃ１３９（Ｌ；１１２）
２）Ｕ、ｔｌ−Ｎ（Ｌ；２ｔ１５）３（Ｃ１１２）３ｓ
０１ｅ（Ｃ）１２）３ｓＯｓＨ’Ｎ（Ｃ２Ｈ５）３ＣＨ
，Ｃ０ＯＨＣＨ，Ｃ００Ｈ
（ＣＨ，）２ＳＯ，” （ＣＩ−１２）２ＳＯ
，Ｉｔ（ＣＩｌ、）：！５Ｏｔ（Ｃ８，）、Ｓｏ、Ｋ（
ＣＨｘ）ＩＳＯ＋ｅ（ＣＨＪｉＳＯＪ（（Ｊｌ＋ｈＳＯ
ｓｅ（ＣＨｘｈＳＯＪ（し■、）４ＳＯ１”
１．ＣＨｚノＪＳＯＩＫ一般式ＣＩ）で表される染
料は、ジャーナル・オブ曇ザφケミカル・ソサイエティ
（Ｊ 、Ｃｈｅｍ、Ｓｏｃ 、 ）１８９頁（１９３３
年）、米国特許２，８９５，９５５号および以下の合成
例等を参考にして合成することができる。The dye represented by the general formula CI) used in the present invention (
Specific examples of dyes (hereinafter referred to as dyes of the present invention) are shown below.
The present invention is not limited to these.tllLLlυ11
L, tl, L, υυi
(Clh)zsOie(CHz)xsOJ(CHx)*
SO+e(CHt)*5OJ(CHz)tsO+"'
(CHt)xsOJ(CHx)zs(he(C
Ht)zsOJ(shiH2),>C139(L;112)
2) U, tl-N(L;2t15)3(C112)3s
01e(C)12)3sOsH'N(C2H5)3CH
,C0OHCH,C00H (CH,)2SO,” (CI-12)2SO
,It(CIl,):! 5Ot(C8,), So,K(
CHx)ISO+e(CHJiSOJ((Jl+hSO
se(CHxhSOJ(し■、)4SO1"
1. The dye represented by the general formula CI) is described in the Journal of the Chemical Society (J, Chem, Soc, ) p. 189 (1933).
The compound can be synthesized with reference to U.S. Pat.
合成例１（染料（１）の合成）
■−（２−スルホエチル）−２，３，３−トリメチル−
５−（２−ヒドロキシエトキシ）−インドレニン６．５
ｇとメタノールｌＯＯｍ（２の混合液にトリエチルアミ
ン６．０ｇ、グルタコンアルデヒドシアニル塩酸塩２．
８ｇを加え、無水酢酸２ｍＱを滴下した。室温で３時間
撹拌後、濾過して濾液に酢酸カリウム３．９ｇをメタノ
ール５０ｒＡＱに溶かした溶液を加え、更に室温で２時
間撹拌した。生成した沈澱を濾取し、メタノールで再結
晶して染料（１）の結晶３．０ｇを得た。Synthesis Example 1 (Synthesis of dye (1)) ■-(2-sulfoethyl)-2,3,3-trimethyl-
5-(2-hydroxyethoxy)-indolenine 6.5
g and methanol 1OOm (2.6 g, triethylamine 6.0 g, glutaconaldehyde cyanyl hydrochloride 2.
8 g was added thereto, and 2 mQ of acetic anhydride was added dropwise. After stirring at room temperature for 3 hours, the mixture was filtered, and a solution of 3.9 g of potassium acetate dissolved in 50 rAQ of methanol was added to the filtrate, followed by further stirring at room temperature for 2 hours. The generated precipitate was collected by filtration and recrystallized with methanol to obtain 3.0 g of crystals of dye (1).
合成例２（染料（１９）の合成）
合成例１で使用したグルタコンアルデヒドシアニル塩酸
塩の代りにプロベンジアニル塩酸塩を使用して同様の方
法で合成した。Synthesis Example 2 (Synthesis of Dye (19)) Synthesis was carried out in the same manner as in Synthesis Example 1, except that glutaconaldehyde cyanyl hydrochloride was replaced with propendianil hydrochloride.
トリメチン染料、ノナメチン染料の場合も、それぞれ対
応するメチン鎖供給体を使用すれば同様に合成できる。Trimethine dyes and nonamethine dyes can be synthesized in the same manner by using the corresponding methine chain suppliers.
モノメチン染料の場合は、常法に従って２位にアルキル
チオ基を有するインドレニン母核化合物を使用すれば同
様に合成できる。In the case of a monomethine dye, it can be synthesized in the same manner by using an indolenine core compound having an alkylthio group at the 2-position according to a conventional method.
本発明に感光材料において、前記一般式（Ｉ）で表され
る染料は、ハロゲン化銀乳剤中に含有させて、イラジェ
ーション防止染料として用いることもできるし、また非
感光性の親水性コロイド層中に含有させて、フィルター
染料あるいは、ハレーション防止染料として用いること
もできる。また、使用目的により２種以上の染料を組合
わせて用いてもよいし、他の染料と組合わせて用いても
よい。本発明の染料をハロゲン化銀乳剤層中あるいは、
その他の親水性コロイド層中に含有させるためには、通
常の方法により容易に行なうことができる。一般には、
染料または、染料の有機・無機アルカリ塩を水に溶解し
、適当な濃度の染料水溶液とし、塗布液に添加して、公
知の方法で塗布を行ない感光材料中に染料を含有させる
ことができる。これらの染料の含有量としては、使用目
的によって異なるが、一般には写真材料上の面積１ｍ２
当り１〜８００ｍｇになるように塗布して用いる。In the light-sensitive material of the present invention, the dye represented by the general formula (I) can be incorporated into a silver halide emulsion and used as an irradiation-preventing dye, or can be used as a non-photosensitive hydrophilic colloid. It can also be incorporated into a layer and used as a filter dye or an antihalation dye. Furthermore, depending on the purpose of use, two or more types of dyes may be used in combination, or in combination with other dyes. The dye of the present invention is contained in a silver halide emulsion layer or
Incorporation into other hydrophilic colloid layers can be easily carried out by conventional methods. In general,
The dye or the organic/inorganic alkali salt of the dye is dissolved in water to form an aqueous dye solution of an appropriate concentration, which is added to a coating solution and coated by a known method to incorporate the dye into the photosensitive material. The content of these dyes varies depending on the purpose of use, but in general, the content of these dyes is
It is applied and used in an amount of 1 to 800 mg per serving.
本発明が適用される感光材料としては、黒白写真感光材
料の他、カラー写真感光材料も挙げることができる。前
者の例としては印刷用感光材料などを挙げることができ
る。このときハロゲン化銀乳剤層は２層以上設けること
もできる。塗布銀量は１〜８ ｇ／Ｉｌ＋２の範囲が望
ましい。The light-sensitive materials to which the present invention is applied include not only black-and-white photographic materials but also color photographic materials. Examples of the former include photosensitive materials for printing. At this time, two or more silver halide emulsion layers may be provided. The amount of coated silver is preferably in the range of 1 to 8 g/Il+2.
本発明に用いられるハロゲン化銀は、例えば塩化銀、臭
化銀、沃化銀、塩臭化銀、塩沃化銀、沃臭化銀、塩沃臭
化銀のいずれでもよい。The silver halide used in the present invention may be, for example, silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, or silver chloroiodobromide.
写真乳剤中のハロゲン化銀粒子は、立方体、八面体、十
四面体のような規則的な結晶体を有するいわゆるレギュ
ラー粒子でもよく、また球状などのような変則的な結晶
形を持つもつ、双晶面などの結晶欠陥を持つものあるい
はそれらの複合形でもよい。The silver halide grains in the photographic emulsion may be so-called regular grains having a regular crystal structure such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical shape. It may be one with crystal defects such as twin planes or a composite form thereof.
ハロゲン化銀の粒径は、狭い分布を有する単分散乳剤で
も、あるいは広い分布を有する多分散乳剤でもよい。The grain size of the silver halide may be a monodisperse emulsion with a narrow distribution or a polydisperse emulsion with a wide distribution.
本発明に使用できるハロゲン化銀写真乳剤は、公知の方
法で製造でき、例えばリサーチ・ディスクロージャー（
ＲＤ） 、 １７６巻、 Ｎｏ、１７６４３（１９７８
年１２月）。The silver halide photographic emulsion that can be used in the present invention can be produced by a known method, for example, as described in Research Disclosure (
RD), Volume 176, No. 17643 (1978
(December).
２２−２３頁、同Ｎｏ、１８７１６（１９７８年１１月
）６４８頁に記載の方法に従うことができる。The method described on pages 22-23, No. 18716 (November 1978), page 648 can be followed.
本発明の方法で用いるハロゲン化銀乳剤は化学増感して
いても、していなくてもよい。The silver halide emulsion used in the method of the present invention may or may not be chemically sensitized.
化学増感する場合は、通常の硫黄増感、還元増感、貴金
属増感及びそれらの組合せが用いられる。In the case of chemical sensitization, ordinary sulfur sensitization, reduction sensitization, noble metal sensitization, and combinations thereof are used.
さらに具体的な化学増感剤としては、アリルチオカルバ
ミド、チオ尿素、チオサルフェート、チオエーテルやシ
スチンなどの硫黄増感剤；ポタシウムクロロオーレイト
、オーラスチオサルフェートやポタシウムクロロパラデ
ートなどの貴金属増感剤；塩化錫、フェニルヒドラジン
やレダクトンなどの還元増感剤などを挙げることができ
る。More specific chemical sensitizers include sulfur sensitizers such as allylthiocarbamide, thiourea, thiosulfate, thioether and cystine; noble metal sensitizers such as potassium chlorooleate, aurous thiosulfate and potassium chloroparadate. ; Examples include reduction sensitizers such as tin chloride, phenylhydrazine, and reductone.
本発明に用いられるハロゲン化銀乳剤は、公知の分光増
感色素によって必要に応じて分光増感される。用いられ
る分光増感色素としてはリサーチ・ディスクロージャー
（前出） Ｎｏ、１７６４３．第■項に記載されたもの
を用いることができる。The silver halide emulsion used in the present invention is spectrally sensitized with a known spectral sensitizing dye, if necessary. The spectral sensitizing dye used is Research Disclosure (cited above) No. 17643. Those described in Section (2) can be used.
本発明の写真乳剤には感光材料の製造工程、保存中ある
いは処理中の感度低下やカブリの発生を防ぐために種々
の化合物を添加することができる。Various compounds can be added to the photographic emulsion of the present invention in order to prevent a decrease in sensitivity and the occurrence of fog during the manufacturing process, storage, or processing of the light-sensitive material.
それらの化合物はニトロベンズイミダゾール、アンモニ
ウムクロロプラチネート、４−ヒドロキシ−６−メチル
−１，３，３ａ、７−テトラアザイデン、１−フェニル
−５−メルカプトテトラゾールをはじめ多くの複素環化
合物、含水銀化合物、メルカプト化合物、金属塩類など
極めて多くの化合物が古くから知られている。These compounds include nitrobenzimidazole, ammonium chloroplatinate, 4-hydroxy-6-methyl-1,3,3a, 7-tetraazidene, 1-phenyl-5-mercaptotetrazole, and many other heterocyclic compounds and hydrated silver compounds. , mercapto compounds, metal salts, and many other compounds have been known for a long time.
感光材料に用いる結合剤また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、それ以外に親水性
合成高分子なども用いることができる。ゼラチンとして
は、石灰処理ゼラチン、酸処理ゼラチン、誘導体ゼラチ
ンなどを用いることもできる。Binders or protective colloids used in photosensitive materials include:
It is advantageous to use gelatin, but other hydrophilic synthetic polymers can also be used. As the gelatin, lime-treated gelatin, acid-treated gelatin, derivative gelatin, etc. can also be used.
本発明の感光材料には、前述のもの以外に、減感剤、増
白剤、カプラー、硬膜剤、塗布助剤、可塑剤、スベリ剤
、マット剤、高沸点有機溶剤、安定則、現像促進剤、帯
電防止剤、スティン防止剤など′を用いることができる
。これらの添加剤については、リサーチ・ディスクロー
ジャー（前出）Ｎｏ、１７６４３． Ｉ −Ｘ Ｖ１
項に記載されたものを用いることができる。In addition to the above-mentioned materials, the photosensitive material of the present invention includes desensitizers, brighteners, couplers, hardeners, coating aids, plasticizers, slipping agents, matting agents, high-boiling organic solvents, stability rules, and developing agents. Accelerators, antistatic agents, anti-stinting agents, etc. can be used. Regarding these additives, see Research Disclosure (supra) No. 17643. I-X V1
You can use those listed in the section.
本発明の感光材料の写真処理には、公知の方法のいずれ
をも用いることができるし処理液には公知のものを用い
ることができる。また、処理温度は通常１８°Ｃ〜５０
°Ｃの間に選ばれるが、１８°Ｃより低い温度または５
０°Ｃを越える温度としてもよい。目的に応し、銀画像
を形成する現像処理（黒白写真処理）、あるいは、色素
像を形成すべき現像処理から成るカラー写真地理のいず
れをも適用することができる。For photographic processing of the light-sensitive material of the present invention, any known method can be used, and known processing solutions can be used. In addition, the processing temperature is usually 18°C to 50°C.
temperature chosen between 18 °C or 5 °C
The temperature may exceed 0°C. Depending on the purpose, either a development process that forms a silver image (black and white photographic process) or a color photogeography process that consists of a development process that forms a dye image can be applied.
本発明のハロゲン化銀写真感光材料は、良好な画質を有
し感度を損なうことなく、現像処理後の残色が少ない。The silver halide photographic material of the present invention has good image quality, does not impair sensitivity, and has little residual color after development.
しかも、本発明のノ・ロゲン化銀写真感光材料の親水性
コロイド層は、水溶性染料によって着色されており写真
乳剤の写真特性に悪影響を与えることなく保存による安
定性が良く、かつ写真処理によって容易に脱色されると
いう点で極めて優れるものである。In addition, the hydrophilic colloid layer of the silver halide photographic light-sensitive material of the present invention is colored with a water-soluble dye and has good storage stability without adversely affecting the photographic properties of the photographic emulsion. It is extremely superior in that it can be easily decolored.
次に実施例を掲げ本発明を更に詳しく説明するが、本発
明はこれらに限定されるものではない。EXAMPLES Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.
実施例１
蒸留水３５ｍ（２にゼラチン３．５ｇを加えて溶解し、
これに、本発明の例示染料（１）、（３）および（２２
）をそれぞれ２．ＯＸ １０−’モル含む５ｍＱの水溶
液を加え、さらに１０％のサポニン水溶液１．２５ｍＱ
と１％ホルマリン溶液０−７５ｍＱを添加し、水を加え
て全量を５０ｍＱとした。この染料溶液をアセチルセル
ロースフィルム支持体上に塗布し、乾燥して、試料１．
２および３とした。また、本発明に係る染料にかえて、
下記の比較染料（Ａ）および（Ｂ）を用いて、同様の方
法で比較試料４および５を作成した。Example 1 35 m of distilled water (add and dissolve 3.5 g of gelatin in 2,
In addition, exemplary dyes (1), (3) and (22) of the present invention
) for each 2. Add 5 mQ of an aqueous solution containing 10-' moles of OX, and then add 1.25 mQ of a 10% saponin aqueous solution.
and 0-75 mQ of 1% formalin solution were added, and water was added to bring the total volume to 50 mQ. This dye solution was coated onto an acetyl cellulose film support and dried.
2 and 3. Moreover, instead of the dye according to the present invention,
Comparative samples 4 and 5 were prepared in the same manner using the following comparative dyes (A) and (B).
（ＣＨ２）、Ｓｏ、０（ＣＨ２）、ＳＯ３Ｎａ比較染料
（Ｂ）
これらの各試料を下記組成の現像液に２５°Ｃで１分間
浸漬し、２０秒間水洗した後、乾燥した。(CH2), So, 0 (CH2), SO3Na comparative dye (B) Each of these samples was immersed in a developer having the composition shown below at 25°C for 1 minute, washed with water for 20 seconds, and then dried.
（現像液の組成）
メ ト − ル
３．０ｇ
亜硫酸ナトリウム（無水） ４５．０ｇハイド
ロキノン １２．０９炭酸ナトリウ
ム（ｌ水塩） ８０．０９臭化カリウム
２．０ｇ水を加えてＩＣとする。(Composition of developer) Meter
3.0g
Sodium sulfite (anhydrous) 45.0g Hydroquinone 12.09 Sodium carbonate (l hydrate) 80.09 Potassium bromide
Add 2.0g water to make IC.
現像液浸漬前、浸漬後の各試料の可視スペクトルを測定
し、吸収極大波長における吸光度の差から脱色率を求め
た。その結果を下記第１表に示す。The visible spectrum of each sample was measured before and after immersion in the developer, and the decolorization rate was determined from the difference in absorbance at the maximum absorption wavelength. The results are shown in Table 1 below.
（Ｅ、は、現像液浸漬前の吸光度であり、Ｅ２は現像液
浸漬後の吸光度を表す。）
第１表
第１表から明らかなように本発明の染料は、比較染料に
比較して優れた脱色性を示すことがわかつｌ二 。(E is the absorbance before immersion in the developer, and E2 is the absorbance after immersion in the developer.) As is clear from Table 1, the dye of the present invention is superior to the comparative dyes. It was found that it exhibits decolorizing properties.
実施例２
塩化銀８０モル％と臭化銀１９．５モル％および沃化ｍ
０９５モル％から成り、粒子の平均粒径が０．３２μｍ
の塩沃臭化銀ゼラチン乳剤を調整した。このゼラチン乳
剤１ｋｇ（銀４８ｇ、ゼラチン７５ｇを含む。）当り、
２．４−′；クロロー６−ヒドロキシー１，３．５−ト
リアジンナトリウム塩（１％水溶液）３５ｍ（２とサポ
ニン（１０’！≦水溶液）５０ｍ＋２を添加した後、下
引き処理されたポリエチレンテレフタレートフィルム支
持体上に、１００ｃｍ２当り銀が５０ｍｇ含まれるよう
に塗布し乾燥した。Example 2 80 mol% silver chloride, 19.5 mol% silver bromide and m iodide
095 mol%, and the average particle size of the particles is 0.32 μm.
A silver chloroiodobromide gelatin emulsion was prepared. Per 1 kg of this gelatin emulsion (containing 48 g of silver and 75 g of gelatin),
2.4-'; Polyethylene terephthalate film subjected to subbing treatment after adding 35 m of chloro-6-hydroxy-1,3.5-triazine sodium salt (1% aqueous solution) (2 and 50 m+2 of saponin (10'!≦aqueous solution) It was coated onto a support so that 50 mg of silver was contained per 100 cm 2 and dried.
更にこの乳剤層の上に本発明の例示染料（２）を含む下
記の組成の保護層を乾燥膜厚が２μｍになるように塗布
しｊ；。（試料６とする）（保護層組成）
ゼラチン ４０ｇ水
８５０ｍＱ本発明の例示染料（２）
（２％水溶液） ｌ ＯＯｍ（
１２，４−ジクロロ−６−ヒドロキン−
１，３，５−トリアジンナトリウム塩
（１％水溶液）２０ｍα
サポニン（１０％水溶液） ３０ｍ（
１同様にして本発明の例示染料（２）に代えて、例示染
料（４）および（１７）ならびに実施例１で用いた比較
染料（Ａ）および（Ｂ）を、それぞれ含む試料を作成し
、それぞれ試料７．８．９および１０とした。Further, on this emulsion layer, a protective layer containing the exemplary dye (2) of the present invention and having the composition shown below was coated to a dry film thickness of 2 μm. (Sample 6) (Protective layer composition) Gelatin 40g Water
850mQ Exemplary dye of the present invention (2) (2% aqueous solution) l OOm(
12,4-dichloro-6-hydroquine-1,3,5-triazine sodium salt (1% aqueous solution) 20mα Saponin (10% aqueous solution) 30m(
In the same manner as in Example 1, samples were prepared containing exemplary dyes (4) and (17) and comparative dyes (A) and (B) used in Example 1 instead of exemplary dye (2) of the present invention, respectively. Samples were designated as 7.8.9 and 10, respectively.
これらの各試料を小片に断裁し、写真光楔を介して露光
し、下記組成の現像液および定着液を用いて処理した。Each of these samples was cut into small pieces, exposed through a photographic light wedge, and processed using developer and fixer solutions having the following compositions.
現像は２０°Ｃで１．５分間行ない、定着は２０’Ｏで
２分間行ない、水洗は２０°Ｃで５分間行なった後、乾
燥した。Development was carried out at 20°C for 1.5 minutes, fixation was carried out at 20'O for 2 minutes, water washing was carried out at 20°C for 5 minutes, and then dried.
（現像液組成）
ハイドロキノン １５ｇホルムア
ルデヒド亜硫酸
水素ナトリウム付加物 ５５９無水亜硫酸
ナトリウム ３ｇ炭酸ナトリウム（−
水塩）８０ｇ
硼酸 ５ｇ臭化カリ
ウム ２．５ｇエチレンジア
ミン四酢酸二
ナトリウム ２ｇ水を加えて
ｌ 、 ＯＯＯｍＱ（定着液組
成）
千オ硫酸ナトリウム １６（ｈ無水亜
硫酸ナトリウム １４ｇ氷酢酸
１２ｍ１２硼砂
１２９カリ明ばん
５ｇ水ヲ加えテ１．０００ｍ（２
現像処理した各試料を、それぞれ１０枚ずつ重ね合わせ
、試料上の着色汚染の有無を調べた。得られた結果を下
記第２表に示す。(Developer composition) Hydroquinone 15g Formaldehyde sodium bisulfite adduct 559 anhydrous sodium sulfite 3g Sodium carbonate (-
(water salt) 80g Boric acid 5g Potassium bromide 2.5g Disodium ethylenediaminetetraacetate 2g Add water
l, OOOmQ (fixer composition) Sodium 1,000 sulfate 16 (h Anhydrous sodium sulfite 14 g Glacial acetic acid
12m12 borax
129 potash alum
5 g of water was added and the sample was heated for 1,000 m (2) Ten sheets of each developed sample were stacked one on top of the other, and the presence or absence of colored contamination on the sample was examined. The obtained results are shown in Table 2 below.
比較染料を用いた試料では、試料に着色汚染がみられた
が、本発明の染料では、流出、脱色性に優れ全く着色汚
染がなかった。In the sample using the comparative dye, color staining was observed in the sample, but with the dye of the present invention, there was no color stain at all due to excellent run-off and decoloring properties.
実施例３
塩化銀７０モル％と臭化銀３０モル％から成り、粒子の
平均粒径が０．３μｍの塩臭化銀乳剤を調製した。Example 3 A silver chlorobromide emulsion containing 70 mol % of silver chloride and 30 mol % of silver bromide and having an average grain size of 0.3 μm was prepared.
この乳剤１ ｋｇ（銀４８９、ゼラチン７５ｇを含む）
当り、ホルマリン（１％水溶液） ２０ｍＱとサポニン
（１０％水溶液） ５０ｍ＆を添加した後、下引き処理
したポリエチレンテレフタレートフィルム支持体上に塗
布し、更にこの乳剤層の上に下記組成の保護層を塗布し
た。1 kg of this emulsion (contains 489 silver and 75 g gelatin)
After adding 20mQ of formalin (1% aqueous solution) and 50mQ of saponin (10% aqueous solution), it was coated on a subbed-treated polyethylene terephthalate film support, and then a protective layer with the following composition was coated on top of this emulsion layer. did.
（保護層組成）
ゼラチン ４０９水
９６０＋＋＋Ｑホルマリン（１％水溶液）
１２ｍＱサポニン（１０％水溶液）
３０ｍ１次に、乳剤層および保護層を塗布した支
持体の裏面に下記の組成の染料を含有するゼラチン層を
乾燥膜厚が３μｍになるように塗布した。（試料１１と
する）
（ゼラチン層組成）
ゼラチン ５０ｇ水
８３５ｍＱ本発明に係る例示染料（５）
（２％水溶液） １００ｍ１２
ホルマリン（１％水溶液） １５＋ｎ１
２サポニン（１０％水溶液）５０ｍρ
同様にして、本発明の例示染料（５）に代えて、例示染
料（１８）および下記の染料（Ｃ）を用いて試料を作成
し、試料１２および１３とした。 −８以・５、
下金１
−・
比較染料（Ｃ）
前記実施例２と同様の方法で現像処理をし、各試料１０
枚ずつを重ね合わせて着色汚染の評価をした。得られた
結果を下記第３表に示す。(Protective layer composition) Gelatin 409 water
960+++Q formalin (1% aqueous solution)
12mQ saponin (10% aqueous solution)
Next, on the back side of the support coated with the emulsion layer and the protective layer, a gelatin layer containing a dye having the composition shown below was coated to a dry film thickness of 3 μm. (Same as sample 11) (Gelatin layer composition) Gelatin 50g water
835mQ Exemplary dye according to the present invention (5) (2% aqueous solution) 100m12
Formalin (1% aqueous solution) 15+n1
2 saponin (10% aqueous solution) 50mρ In the same manner, samples were prepared using Exemplary Dye (18) and the following dye (C) in place of Exemplary Dye (5) of the present invention, and Samples 12 and 13 were prepared. . -8 or more・5,
Lower gold 1 - Comparative dye (C) Developed in the same manner as in Example 2, and each sample 10
The sheets were stacked one on top of the other and colored contamination was evaluated. The results obtained are shown in Table 3 below.
第３表
上記衣か示すように比較染料を用いた試料では試料に着
色汚染がみられたが、本発明の染料では全く着色汚染が
みられなかった。また、本発明の染料は写真乳剤に対し
てカブリ、減感等の悪影響を及ぼすことなく、優れたハ
レーション防止効果を有する感光材料を得ることができ
ることがわかっｌ二 。As shown in Table 3 above, colored stains were observed in the samples using the comparative dyes, but no colored stains were observed with the dyes of the present invention. Furthermore, it has been found that the dye of the present invention can provide a photographic material having an excellent antihalation effect without causing any adverse effects such as fogging or desensitization on photographic emulsions.
実施例４
ポリエチレン被覆紙からなる支持体上に、下記の各層を
支持体側より順次設層し、カラー写真材料を作成した（
試料１４）。Example 4 A color photographic material was prepared by sequentially depositing the following layers on a support made of polyethylene-coated paper from the support side (
Sample 14).
１１層・・・黄色カプラー；α−ピバリルーα−（１−
ベンジル−２−フェニル−３，５−ジオキソトリアシリ
ジン−４−イル）−２７−クロロ−５７−〔γ−（２，
４−ジ−ｔ−アミルフェノキシ）ブチルアミド〕アセト
アニリド、硬膜剤（ジクロロトリアジン）および界面活
性剤（サポニン）を含有する青感性ハロゲン化銀乳剤層
（９０モル％の臭化銀を含む塩臭化銀乳剤で、増感色素
を用いて増感したもの）を塗布銀量が３．５ｍ９／１０
０ｃｍ２となるように設けた。11 layer...Yellow coupler; α-pivalyl α-(1-
benzyl-2-phenyl-3,5-dioxotriasilidin-4-yl)-27-chloro-57-[γ-(2,
A blue-sensitive silver halide emulsion layer containing 4-di-t-amylphenoxy)butyramide]acetanilide, a hardener (dichlorotriazine) and a surfactant (saponin) (chlorobromide containing 90 mol% silver bromide) A silver emulsion sensitized using a sensitizing dye) was coated with a silver amount of 3.5 m9/10.
It was set so that the distance was 0 cm2.
ｖＪ２層・・・ゼラチン層（中間層）を設けた。vJ2 layer: A gelatin layer (intermediate layer) was provided.
第３層・・・マゼンタカプラー； １−（２，４，６−
１−ジクロロフェニル） −３−（３−（２，４−ジ−
ｔ−アミルフェノキシアセトアミド）ベンズアミド〕−
５−ピラゾロン、硬膜剤（ジクロロトリアジン）および
界面活性剤（サポニン）を含有する緑感性ハロゲン化銀
乳剤層（８０モル％の臭化銀を含む塩臭化銀乳剤で、増
感色素を用いて増感したもの。）を塗布銀量が４．５ｍ
ｇ／１００ｃｍ”となるように設けた。3rd layer...magenta coupler; 1-(2,4,6-
1-dichlorophenyl) -3-(3-(2,4-di-
t-amylphenoxyacetamide)benzamide]-
A green-sensitive silver halide emulsion layer containing 5-pyrazolone, a hardener (dichlorotriazine) and a surfactant (saponin) (a silver chlorobromide emulsion containing 80 mol% silver bromide, using a sensitizing dye) sensitized) with a coating silver amount of 4.5 m
g/100 cm".
第４層・・・ゼラチン層（中間層）を設けた。Fourth layer: A gelatin layer (intermediate layer) was provided.
第５層・・・ンアンカブラー；２，４−ジクロロ−３−
メチル−６−（２，４−ジ−ｔ−アミルフェノキシアセ
トアミド）フェノール、硬膜剤（ジクロロトリアジン）
および界面活性剤（サポニン）を含有する赤感性ハロゲ
ン化銀乳剤層（７５モル％の臭化銀を含む塩臭化銀乳剤
で、増感色素を用いて増感したもの。）を塗布銀量が２
．０ｍｇ７１００ｃｍ”となるように設けた。5th layer...uncoupler; 2,4-dichloro-3-
Methyl-6-(2,4-di-t-amylphenoxyacetamide)phenol, hardener (dichlorotriazine)
A red-sensitive silver halide emulsion layer (silver chlorobromide emulsion containing 75 mol% silver bromide, sensitized using a sensitizing dye) containing a surfactant (saponin) is applied to the coating amount of silver. is 2
．． 0mg7100cm''.
第６層・・・ゼラチン層（保護層）を設けた。Sixth layer: A gelatin layer (protective layer) was provided.
更に、本発明の例示染料（３２）あるいは比較染料（Ｄ
）の２％水溶液を乳剤１ｋｇ当り２００ｍα加えた緑感
性乳剤（第３層塗布液）を作り、それぞれ上記試料１４
と同様にして、試料１５および試料１６を作成し ｊこ
。Furthermore, the exemplary dye (32) of the present invention or the comparative dye (D
) was added to 200 mα per 1 kg of emulsion to prepare a green-sensitive emulsion (third layer coating solution).
Sample 15 and sample 16 were prepared in the same manner as above.
比較染料（Ｄ）
これらの試料１４．１５および１６を露光した後、下記
の処理工程に従って処理した。Comparative Dye (D) These samples 14, 15 and 16 were exposed and then processed according to the processing steps below.
〔処理工程（３１°Ｏ））
処理時間
１、発色現像 ３分
２、漂白定着 １分
３、水 洗 ２分
４、安定化 １分
５、水 洗 ２分
径処理工程において使用した処理液組成は、下記の通り
である。[Processing process (31°O)] Processing time 1, color development 3 minutes 2, bleach-fixing 1 minute 3, water washing 2 minutes 4, stabilization 1 minute 5, water washing 2 Composition of processing liquid used in the diameter processing step is as follows.
４−アミノ−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
４．８゜無水亜硫酸ナトリウム
４，０ｇヒドロキシアミン・ｌ／２硫酸
塩 ２・０ｇ無水炭酸カリウム
２８．０ｇ臭化カリウム
１．５ｇ水酸化カリウム １
．０ｇ水を加えて１１２とする。4-Amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)aniline sulfate 4.8゜Anhydrous sodium sulfite
4.0g hydroxyamine l/2 sulfate 2.0g anhydrous potassium carbonate
28.0g potassium bromide
1.5g potassium hydroxide 1
．． Add 0g water to make 112.
〔漂白定着液組成〕
エチレンジアミン四酢酸第二鉄塩 ６５．Ｏｇエチレ
ンジアミン四酢酸
２ナトリウム塩 ３．０ｇ無水亜
硫酸ナトリウム ９．５ｇチオ硫酸アン
モニウム ７７．５ｇ無水炭酸ナトリウ
ム ４．０９水を加えてｌＱとする。[Bleach-fix solution composition] Ethylenediaminetetraacetic acid ferric salt 65. Og Ethylenediaminetetraacetic acid disodium salt 3.0g Anhydrous sodium sulfite 9.5g Ammonium thiosulfate 77.5g Anhydrous sodium carbonate 4.09 Add water to make 1Q.
氷酢酸 ９ｍα酢酸ナト
リウム ３ｇ水を加えてｌＩ２と
する。Glacial acetic acid 9mα Sodium acetate 3g Add water to make lI2.
旭理後の各試料の未露光部の濃度を第４表に示す。Table 4 shows the density of the unexposed area of each sample after the washing.
第４表から明らかなように、本発明の染料を含有する試
料では、比較試料を含有する試料が示すような染料の残
色による着色汚染が認められなかった。また各試料の感
度を比較したところ、本発明の染料は、乳剤に対する悪
影響が極めて少ないことがわかった。As is clear from Table 4, in the samples containing the dye of the present invention, no color contamination due to residual color of the dye was observed, as was the case with the samples containing the comparative sample. Furthermore, when the sensitivity of each sample was compared, it was found that the dye of the present invention had extremely little adverse effect on the emulsion.
Claims (1)
含有する親水性コロイド層を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、Ｒ＿２、Ｒ＿３、Ｒ＿４、Ｒ＿５およ
びＲ＿６は各々、アルキル基を表し、Ｚ＿１およびＺ＿
２は各々、ベンゾ縮合環またはナフト縮合環を形成する
に必要な非金属原子群を表す。ただし、Ｒ＿１、Ｒ＿２
、Ｒ＿３、Ｒ＿４、Ｒ＿５、Ｒ＿６、Ｚ＿１およびＺ＿
２は、染料分子が少なくとも２個の酸基を有することを
可能にし、かつ、Ｚ＿１およびＺ＿２は染料分子が−Ｃ
Ｈ＿２ＣＨ＿２ＯＲ＿７基を１個以上有する置換基を少
なくとも２個有することを可能にする基を表す。Ｒ＿７
は水素原子またはアルキル基を表す。Ｌはメチン基を表
し、Ｘ＾■はアニオンを表す。ｍは１〜５の整数を表し
、ｎは１または２の整数を表す。染料が分子内塩を形成
する場合ｎは１である。〕[Scope of Claims] A silver halide photographic material characterized by having a hydrophilic colloid layer containing at least one dye represented by the following general formula (I). General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1, R_2, R_3, R_4, R_5 and R_6 each represent an alkyl group, and Z_1 and Z_
2 each represents a nonmetallic atomic group necessary to form a benzo-fused ring or a naphtho-fused ring. However, R_1, R_2
, R_3, R_4, R_5, R_6, Z_1 and Z_
2 allows the dye molecule to have at least two acid groups, and Z_1 and Z_2 allow the dye molecule to have -C
Represents a group capable of having at least two substituents having one or more H_2CH_2OR_7 groups. R_7
represents a hydrogen atom or an alkyl group. L represents a methine group, and X^■ represents an anion. m represents an integer of 1 to 5, and n represents an integer of 1 or 2. n is 1 if the dye forms an inner salt. ]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4475788A JPH01217454A (en) | 1988-02-26 | 1988-02-26 | Silver halide photographic sensitive material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4475788A JPH01217454A (en) | 1988-02-26 | 1988-02-26 | Silver halide photographic sensitive material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01217454A true JPH01217454A (en) | 1989-08-31 |
Family
ID=12700303
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4475788A Pending JPH01217454A (en) | 1988-02-26 | 1988-02-26 | Silver halide photographic sensitive material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01217454A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01233439A (en) * | 1988-03-14 | 1989-09-19 | Konica Corp | Silver halide photographic sensitive material |
-
1988
- 1988-02-26 JP JP4475788A patent/JPH01217454A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01233439A (en) * | 1988-03-14 | 1989-09-19 | Konica Corp | Silver halide photographic sensitive material |
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