JPH01179150A - Silver halide photographic sensitive material - Google Patents
Silver halide photographic sensitive materialInfo
- Publication number
- JPH01179150A JPH01179150A JP235388A JP235388A JPH01179150A JP H01179150 A JPH01179150 A JP H01179150A JP 235388 A JP235388 A JP 235388A JP 235388 A JP235388 A JP 235388A JP H01179150 A JPH01179150 A JP H01179150A
- Authority
- JP
- Japan
- Prior art keywords
- group
- acid
- layer
- color
- silver halide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- -1 Silver halide Chemical class 0.000 title claims abstract description 149
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 45
- 239000004332 silver Substances 0.000 title claims abstract description 45
- 239000000463 material Substances 0.000 title claims abstract description 36
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 24
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 18
- 125000003118 aryl group Chemical group 0.000 claims abstract description 18
- 125000000542 sulfonic acid group Chemical group 0.000 claims abstract description 17
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 11
- 150000001768 cations Chemical class 0.000 claims abstract description 5
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 claims abstract description 4
- 239000000084 colloidal system Substances 0.000 claims description 15
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000005647 linker group Chemical group 0.000 claims description 2
- 239000000839 emulsion Substances 0.000 abstract description 73
- 239000002253 acid Substances 0.000 abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 24
- 230000003595 spectral effect Effects 0.000 abstract description 17
- 239000011248 coating agent Substances 0.000 abstract description 5
- 238000000576 coating method Methods 0.000 abstract description 5
- 230000002411 adverse Effects 0.000 abstract description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 2
- 231100000989 no adverse effect Toxicity 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 77
- 239000000975 dye Substances 0.000 description 51
- 235000002639 sodium chloride Nutrition 0.000 description 31
- 239000000243 solution Substances 0.000 description 31
- 238000000034 method Methods 0.000 description 28
- 150000003839 salts Chemical class 0.000 description 27
- 150000001875 compounds Chemical class 0.000 description 26
- 239000003795 chemical substances by application Substances 0.000 description 24
- 238000012545 processing Methods 0.000 description 21
- 238000005406 washing Methods 0.000 description 20
- 238000011161 development Methods 0.000 description 19
- 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
- 239000002904 solvent Substances 0.000 description 15
- 125000004432 carbon atom Chemical group C* 0.000 description 13
- 239000002738 chelating agent Substances 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 13
- 230000008569 process Effects 0.000 description 13
- 239000004848 polyfunctional curative Substances 0.000 description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 10
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 10
- 150000007513 acids Chemical class 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 230000035945 sensitivity Effects 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 229910001447 ferric ion Inorganic materials 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000003381 stabilizer Substances 0.000 description 7
- 239000004094 surface-active agent Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000007844 bleaching agent Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 239000003112 inhibitor Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- 239000003755 preservative agent Substances 0.000 description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 6
- 230000006641 stabilisation Effects 0.000 description 6
- 238000011105 stabilization Methods 0.000 description 6
- 230000000087 stabilizing effect Effects 0.000 description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 6
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical class C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 125000004093 cyano group Chemical group *C#N 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 description 5
- 235000011181 potassium carbonates Nutrition 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 229960000583 acetic acid Drugs 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 4
- 229910021538 borax Inorganic materials 0.000 description 4
- 239000006172 buffering agent Substances 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 239000003623 enhancer Substances 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 150000002443 hydroxylamines Chemical class 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 150000004989 p-phenylenediamines Chemical class 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 230000002265 prevention Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 235000010339 sodium tetraborate Nutrition 0.000 description 4
- 239000004328 sodium tetraborate Substances 0.000 description 4
- 150000003568 thioethers Chemical class 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical class C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical group C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 3
- 239000003899 bactericide agent Substances 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 238000004061 bleaching Methods 0.000 description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000006081 fluorescent whitening agent Substances 0.000 description 3
- 150000002505 iron Chemical class 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 235000017550 sodium carbonate Nutrition 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 239000001488 sodium phosphate Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 3
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical class C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 2
- 125000000143 2-carboxyethyl group Chemical group [H]OC(=O)C([H])([H])C([H])([H])* 0.000 description 2
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- 101100501963 Caenorhabditis elegans exc-4 gene Proteins 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 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 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- 101100221809 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cpd-7 gene Proteins 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 241001061127 Thione Species 0.000 description 2
- 235000010724 Wisteria floribunda Nutrition 0.000 description 2
- 235000011054 acetic acid Nutrition 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 229940121375 antifungal agent Drugs 0.000 description 2
- 239000003429 antifungal agent Substances 0.000 description 2
- CJPQIRJHIZUAQP-MRXNPFEDSA-N benalaxyl-M Chemical compound CC=1C=CC=C(C)C=1N([C@H](C)C(=O)OC)C(=O)CC1=CC=CC=C1 CJPQIRJHIZUAQP-MRXNPFEDSA-N 0.000 description 2
- JEHKKBHWRAXMCH-UHFFFAOYSA-N benzenesulfinic acid Chemical compound O[S@@](=O)C1=CC=CC=C1 JEHKKBHWRAXMCH-UHFFFAOYSA-N 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
- 230000003139 buffering effect Effects 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 229920006317 cationic polymer Polymers 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- DEFVIWRASFVYLL-UHFFFAOYSA-N ethylene glycol bis(2-aminoethyl)tetraacetic acid Chemical compound OC(=O)CN(CC(O)=O)CCOCCOCCN(CC(O)=O)CC(O)=O DEFVIWRASFVYLL-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 150000004694 iodide salts Chemical class 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 229940057995 liquid paraffin Drugs 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- CLJDCQWROXMJAZ-UHFFFAOYSA-N n-[2-(4-amino-n-ethyl-3-methylanilino)ethyl]methanesulfonamide;sulfuric acid Chemical compound OS(O)(=O)=O.CS(=O)(=O)NCCN(CC)C1=CC=C(N)C(C)=C1 CLJDCQWROXMJAZ-UHFFFAOYSA-N 0.000 description 2
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- ZJAOAACCNHFJAH-UHFFFAOYSA-N phosphonoformic acid Chemical class OC(=O)P(O)(O)=O ZJAOAACCNHFJAH-UHFFFAOYSA-N 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 description 2
- 229940099427 potassium bisulfite Drugs 0.000 description 2
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 description 2
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- 235000019252 potassium sulphite Nutrition 0.000 description 2
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- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- 229910001864 baryta Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 150000001556 benzimidazoles Chemical class 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical class C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 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
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 150000001661 cadmium Chemical class 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Substances OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 235000019797 dipotassium phosphate Nutrition 0.000 description 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 1
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000002228 disulfide group Chemical group 0.000 description 1
- SRPOMGSPELCIGZ-UHFFFAOYSA-N disulfino carbonate Chemical class OS(=O)OC(=O)OS(O)=O SRPOMGSPELCIGZ-UHFFFAOYSA-N 0.000 description 1
- PCAXGMRPPOMODZ-UHFFFAOYSA-N disulfurous acid, diammonium salt Chemical compound [NH4+].[NH4+].[O-]S(=O)S([O-])(=O)=O PCAXGMRPPOMODZ-UHFFFAOYSA-N 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- LTHCIVZEQZAFPI-UHFFFAOYSA-N ethane-1,2-diamine;2-(2-hydroxyphenyl)acetic acid Chemical compound NCCN.OC(=O)CC1=CC=CC=C1O LTHCIVZEQZAFPI-UHFFFAOYSA-N 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- BTCSSZJGUNDROE-UHFFFAOYSA-N gamma-aminobutyric acid Chemical compound NCCCC(O)=O BTCSSZJGUNDROE-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002332 glycine derivatives Chemical class 0.000 description 1
- 159000000011 group IA salts Chemical class 0.000 description 1
- UYTPUPDQBNUYGX-UHFFFAOYSA-N guanine Chemical class O=C1NC(N)=NC2=C1N=CN2 UYTPUPDQBNUYGX-UHFFFAOYSA-N 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- 150000004820 halides Chemical class 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
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- AKCUHGBLDXXTOM-UHFFFAOYSA-N hydroxy-oxo-phenyl-sulfanylidene-$l^{6}-sulfane Chemical class SS(=O)(=O)C1=CC=CC=C1 AKCUHGBLDXXTOM-UHFFFAOYSA-N 0.000 description 1
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 description 1
- PTFYQSWHBLOXRZ-UHFFFAOYSA-N imidazo[4,5-e]indazole Chemical compound C1=CC2=NC=NC2=C2C=NN=C21 PTFYQSWHBLOXRZ-UHFFFAOYSA-N 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 150000002503 iridium Chemical class 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- ZLTPDFXIESTBQG-UHFFFAOYSA-N isothiazole Chemical compound C=1C=NSC=1 ZLTPDFXIESTBQG-UHFFFAOYSA-N 0.000 description 1
- 150000002613 leucine derivatives Chemical class 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- HNQIVZYLYMDVSB-UHFFFAOYSA-N methanesulfonimidic acid Chemical compound CS(N)(=O)=O HNQIVZYLYMDVSB-UHFFFAOYSA-N 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- LQPLDXQVILYOOL-UHFFFAOYSA-I pentasodium;2-[bis[2-[bis(carboxylatomethyl)amino]ethyl]amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC(=O)[O-])CCN(CC([O-])=O)CC([O-])=O LQPLDXQVILYOOL-UHFFFAOYSA-I 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- CMCWWLVWPDLCRM-UHFFFAOYSA-N phenidone Chemical class N1C(=O)CCN1C1=CC=CC=C1 CMCWWLVWPDLCRM-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 150000004986 phenylenediamines Chemical class 0.000 description 1
- 208000026435 phlegm Diseases 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- RWPGFSMJFRPDDP-UHFFFAOYSA-L potassium metabisulfite Chemical compound [K+].[K+].[O-]S(=O)S([O-])(=O)=O RWPGFSMJFRPDDP-UHFFFAOYSA-L 0.000 description 1
- 229940043349 potassium metabisulfite Drugs 0.000 description 1
- 235000010263 potassium metabisulphite Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001500 prolyl group Chemical class [H]N1C([H])(C(=O)[*])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical compound O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 1
- NDGRWYRVNANFNB-UHFFFAOYSA-N pyrazolidin-3-one Chemical class O=C1CCNN1 NDGRWYRVNANFNB-UHFFFAOYSA-N 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
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- HBCQSNAFLVXVAY-UHFFFAOYSA-N pyrimidine-2-thiol Chemical class SC1=NC=CC=N1 HBCQSNAFLVXVAY-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003283 rhodium Chemical class 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical class OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 1
- 150000003870 salicylic acids Chemical class 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 238000004062 sedimentation Methods 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
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 235000011083 sodium citrates Nutrition 0.000 description 1
- 229940001584 sodium metabisulfite Drugs 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 229960004025 sodium salicylate Drugs 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 238000012421 spiking Methods 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- LESFYQKBUCDEQP-UHFFFAOYSA-N tetraazanium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound N.N.N.N.OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O LESFYQKBUCDEQP-UHFFFAOYSA-N 0.000 description 1
- 150000003475 thallium Chemical class 0.000 description 1
- JJJPTTANZGDADF-UHFFFAOYSA-N thiadiazole-4-thiol Chemical class SC1=CSN=N1 JJJPTTANZGDADF-UHFFFAOYSA-N 0.000 description 1
- 150000003548 thiazolidines Chemical class 0.000 description 1
- 150000003567 thiocyanates Chemical class 0.000 description 1
- 125000005323 thioketone group Chemical group 0.000 description 1
- 150000004886 thiomorpholines 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
- NBOMNTLFRHMDEZ-UHFFFAOYSA-N thiosalicylic acid Chemical compound OC(=O)C1=CC=CC=C1S NBOMNTLFRHMDEZ-UHFFFAOYSA-N 0.000 description 1
- 229940103494 thiosalicylic acid Drugs 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 1
- 235000019798 tripotassium phosphate Nutrition 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- XWNXEWLCHSLQOI-UHFFFAOYSA-K trisodium;triacetate Chemical compound [Na+].[Na+].[Na+].CC([O-])=O.CC([O-])=O.CC([O-])=O XWNXEWLCHSLQOI-UHFFFAOYSA-K 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 150000003679 valine derivatives Chemical class 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- 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)
本発明は染色された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関し、写真化学的に不活性であると
ともに写真処理過程において容易に脱色および/または
溶出される染料を含有する親木性コロイド層を有してな
るハロゲン化銀写真感光材料に関するものである。Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a silver halide photographic light-sensitive material having a dyed hydrophilic colloid layer, which is photochemically inactive and easily decolorized during photographic processing. The present invention also relates to a silver halide photographic material having a wood-philic colloid layer containing a dye to be eluted.
(従来の技術)
ハロゲン化銀写真感光材料において、特定の波長域の光
を吸収させる目的で、写真乳剤層またはその他の層を着
色することがしばしば行なわれる。(Prior Art) In silver halide photographic materials, photographic emulsion layers or other layers are often colored for the purpose of absorbing light in a specific wavelength range.
写真乳剤層に入射すべき光の分光組成を制御することが
必要なとき、写真感光材料上の写真乳剤層よりも支持体
から遠い側に着色層が設けられる。When it is necessary to control the spectral composition of light incident on the photographic emulsion layer, a colored layer is provided on the photographic light-sensitive material on the side farther from the support than the photographic emulsion layer.
このような着色層はフィルター層と呼ばれる。多層カラ
ー感光材料の如く写真乳剤層が複数ある場合にはフィル
ター層がそれらの中間に位置することもある。Such a colored layer is called a filter layer. When there are a plurality of photographic emulsion layers, such as in a multilayer color light-sensitive material, a filter layer may be located between them.
写真孔・剤層を通過する際あるいは透過後に散乱された
光が、乳剤層と支持体の界面、あるいは乳剤層と反対側
の感光材料の表面で反射されて再び写真乳剤層中に入射
することにもとずく画像のボケ、すなわちハレーション
を防止することを目的として、写真乳剤層と支持体の間
、あるいは支持体の写真乳剤層とは反対の面に着色層を
設けることが行なわれる。このような着色層はハレーシ
ョン防止層と呼ばれる。多層カラー感光材料の場合には
、各層の中間にハレーション防止層がおがれることもあ
る。Light scattered during or after passing through the photographic hole/former layer is reflected at the interface between the emulsion layer and the support, or at the surface of the light-sensitive material on the opposite side of the emulsion layer, and enters the photographic emulsion layer again. For the purpose of preventing blurring of images, that is, halation, which is caused by image blurring, a colored layer is provided between the photographic emulsion layer and the support, or on the opposite side of the support from the photographic emulsion layer. Such a colored layer is called an antihalation layer. In the case of a multilayer color photosensitive material, an antihalation layer may be placed between each layer.
写真乳剤層中での光の散乱にもとすく画像鮮鋭度の低下
(この現象は一般にイラジェーシツンと呼ばれている)
を防止するために、写真乳剤層を着色することも行なわ
れる。Image sharpness decreases due to light scattering in the photographic emulsion layer (this phenomenon is generally called irradiation)
In order to prevent this, the photographic emulsion layer is also colored.
これらの着色すべき層は、親水性コロイドから成る場合
が多くしたがってその着色のためには通常、水溶性染料
を層中に含有させる。この染料は下記のような条件を満
足することが必要である。These layers to be colored are often composed of hydrophilic colloids, and therefore, for coloring them, a water-soluble dye is usually incorporated into the layer. This dye must satisfy the following conditions.
+11 使用目的に応じた適正な分光吸収を有するこ
と。+11 Must have appropriate spectral absorption according to the purpose of use.
(2)写真化学的に不活性であること、つまりハロゲン
化銀写真乳剤層の性能に化学的な意味での悪影響、たと
えば感度の低下、潜像退行、あるいはカブリを与えない
こと。(2) It is photochemically inert, that is, it does not adversely affect the performance of the silver halide photographic emulsion layer in a chemical sense, such as a decrease in sensitivity, latent image regression, or fog.
(3) 写真処理過程において脱色されるか、溶解除
去されて、処理後の写真感光材料上に有害な着色を残さ
ないこと。(3) No harmful coloring will remain on the photographic material after processing by being bleached or dissolved away during the photographic processing process.
これらの条件をみたす染料を見出すために当業者により
多くの努力がなされており以下に挙げる染料が知られて
いる。例えば英国特許第506゜385号、同1,17
7.429号、同1.311.884号、同1,338
.799号、同l。Many efforts have been made by those skilled in the art to find dyes that meet these conditions, and the dyes listed below are known. For example, British Patent No. 506°385, British Patent No. 1,17
No. 7.429, No. 1.311.884, No. 1,338
.. No. 799, Ibid.
385.371号、同1,467.214号、同1.4
33.102号、同1,553.516号、特開昭48
−85.130号、同49−114゜420号、同55
−161.233号、同59−111.640号、同6
2−273527号、米国特許第3.247,127号
、同3,469゜985号、同4,078.933号等
に記載されたピラゾロン核やバルビッール成核を有する
オキソノール染料、米国特許第2.533.472号、
同3,379.533号、英国特許第1,278゜62
1号等記載されたその他のオキソノール染料、などが挙
げられる。385.371, 1,467.214, 1.4
No. 33.102, No. 1,553.516, Japanese Unexamined Patent Publication No. 1973
-85.130, 49-114゜420, 55
-161.233, 59-111.640, 6
No. 2-273527, U.S. Pat. No. 3,247,127, U.S. Pat. No. 3,469.985, U.S. Pat. No. 4,078.933, etc.; No. .533.472,
3,379.533, British Patent No. 1,278゜62
Other oxonol dyes described such as No. 1 and the like can be mentioned.
これらの中で2個のピラゾロン核を有するオキソノール
染料は亜硫酸塩を含む現像液中で脱色される性質をもち
、写真乳剤に悪い作用を及ぼすことが少く有用な染料と
して感光材料の染色に用いられてきた。Among these, oxonol dyes, which have two pyrazolone nuclei, have the property of being decolorized in developing solutions containing sulfites, and are used as useful dyes for dyeing photographic materials as they have little negative effect on photographic emulsions. It's here.
しかし、この系統に属する染料の中には写真乳剤そのも
のには影響が少くても分光増悪された乳剤に対しては、
不必要な領域に分光増感したり、または増悪色素を脱着
せしめることに起因すると思われる感度の低下をひきお
こす欠点を有している。However, some dyes belonging to this family have little effect on the photographic emulsion itself, but they have a negative effect on the emulsion that has been spectrally enhanced.
It has the disadvantage of causing a decrease in sensitivity, which may be caused by spectral sensitization in unnecessary areas or by detachment of aggravating dyes.
また近年行われるようになった現像処理の迅速化によっ
ては処理後に残るものがある。これを解決するために亜
硫酸イオンとの反応性の高い染料を用いることが提案さ
れているが、この場合には写真膜中での安定性が充分で
なく、経時によっては濃度の低下をおこし、所望の写真
的効果を得られないという欠点を有している。Furthermore, due to the speeding up of development processing that has been carried out in recent years, some residual particles may remain after processing. In order to solve this problem, it has been proposed to use dyes that are highly reactive with sulfite ions, but in this case, the stability in the photographic film is insufficient, and the concentration may decrease over time. It has the disadvantage that the desired photographic effect cannot be obtained.
(発明が解決しようとする問題点)
本発明の目的は第一にハロゲン化銀乳削層の写真特性に
有害な影響を与えない新規な水溶性染料によって親水性
コロイド層が染色されたハロゲン化銀写真感光材料を提
供することである。(Problems to be Solved by the Invention) The object of the present invention is firstly to provide a hydrophilic colloid layer dyed with a novel water-soluble dye that does not have a detrimental effect on the photographic properties of the silver halide emulsion layer. An object of the present invention is to provide a silver photographic material.
本発明の目的は第二に処理により脱色性のすぐれた新規
な水溶性染料によって親水性コロイド層が染色されたハ
ロゲン化銀写真感光材料を提供することである。A second object of the present invention is to provide a silver halide photographic material in which a hydrophilic colloid layer is dyed with a novel water-soluble dye that exhibits excellent decolorization properties through processing.
本発明の目的は第三に染色された親水性コロイド層が経
時しても安定な新規な水溶性染料を含有するハロゲン化
銀写真感光材料を提供することである。A third object of the present invention is to provide a silver halide photographic material in which the dyed hydrophilic colloid layer contains a novel water-soluble dye that is stable over time.
(問題点を解決するための手段)
本発明のこれらの目的は一般式(I)によって示される
染わ1の少くとも一種を含有することにより達成される
。(Means for solving the problems) These objects of the present invention are achieved by containing at least one type of stain 1 represented by general formula (I).
R+ Rs
式中、R,及びR2は各々少くとも1個のカルボン酸基
又はスルホン酸基を有するアリール基、アラルキル基、
アルキル基又は複素環基を表わし、カルボン酸基又はス
ルホン酸基は2価の連結基を介してアリール基、アラル
キル基、アルキル基又は複素環基に結合してもよい。R + Rs In the formula, R and R2 each represent an aryl group or an aralkyl group having at least one carboxylic acid group or sulfonic acid group,
It represents an alkyl group or a heterocyclic group, and the carboxylic acid group or sulfonic acid group may be bonded to the aryl group, aralkyl group, alkyl group, or heterocyclic group via a divalent linking group.
7′
/\′
R2及びR4は各々−3O!R5、SO!NR5,R6
又は−3ORs (ここにR3はアルキル基、アラルキ
ル基又は了り−ル基を表わし、R6は水素原子、アルキ
ル基、アラルキル基又はアリール基を表わし、R2とR
1は連結して5又は6員環を形成していても良い、)を
表わし、t、t 、 t、z及びR3は各々メチン基を
表わし、nは0.1又は2を表わし、Moは水素又はそ
の他のカチオンを表わす。7'/\' R2 and R4 are each -3O! R5, SO! NR5, R6
or -3ORs (where R3 represents an alkyl group, an aralkyl group, or an aryl group, R6 represents a hydrogen atom, an alkyl group, an aralkyl group, or an aryl group, and R2 and R
1 may be linked to form a 5- or 6-membered ring), t, t, t, z and R3 each represent a methine group, n represents 0.1 or 2, Mo is Represents hydrogen or other cations.
次に一般式(I)で表わされる染料について詳細に説明
する。Next, the dye represented by general formula (I) will be explained in detail.
R1及びR3におけるアリール基、アラルキル基、アル
キル基又は複素環基が有するカルボン酸基又はスルホン
酸基は、アリール基、アラルキル基、アルキル基又は複
素環基に直接結合するだけでなく2価の連結基(例えば
アルキレンアミノ基(例えば2−スルホエチルアミノ、
3−スルホプロピルアミノ、2−カルボキシエチルアミ
ノ)、アルキレンオキシ基(例えば2−カルボキシエト
キシ、4−スルホブトキシ)、アルキレンアシルアミノ
基(例えばβ−カルボキシプロピオニルアミノ)、フェ
ニレン基(例えば0=フルホフエニル)等)を介して結
合していても良い。The carboxylic acid group or sulfonic acid group possessed by the aryl group, aralkyl group, alkyl group, or heterocyclic group in R1 and R3 not only directly bonds to the aryl group, aralkyl group, alkyl group, or heterocyclic group, but also forms a divalent bond. groups (e.g. alkylene amino groups (e.g. 2-sulfoethylamino,
3-sulfopropylamino, 2-carboxyethylamino), alkyleneoxy groups (e.g. 2-carboxyethoxy, 4-sulfobutoxy), alkyleneacylamino groups (e.g. β-carboxypropionylamino), phenylene groups (e.g. 0=flufophenyl) etc.).
R1及びR5におけるアリール基、アラルキル基、アル
キル基又は複素環基は、カルボン酸、スルホン酸以外の
置換基(例えばフッ素、塩素、臭素等のハロゲン原子、
水酸基、シアノ基、ニトロ基、炭素数1〜4のアルキル
基(例えばメチル、エチル、イソプロピル、n−ブチル
)、アリール基(例えばフェニル、ナフチル)、炭素数
1〜6のアルコキシ基(例えばメトキシ、エトキシ、n
−ブトキシ、2−メトキシエトキシ、2−ヒドロキシエ
トキシ)、アリールオキシ基(例えばフェノキシ)アミ
ノ基(例えばジメチルアミノ、ジエチルアミノ)、アシ
ルアミノ基(例えばアセチルアミノ)等)を有していて
も良い。The aryl group, aralkyl group, alkyl group, or heterocyclic group in R1 and R5 is a substituent other than carboxylic acid or sulfonic acid (for example, a halogen atom such as fluorine, chlorine, or bromine,
Hydroxyl group, cyano group, nitro group, alkyl group having 1 to 4 carbon atoms (e.g. methyl, ethyl, isopropyl, n-butyl), aryl group (e.g. phenyl, naphthyl), alkoxy group having 1 to 6 carbon atoms (e.g. methoxy, ethoxy, n
-butoxy, 2-methoxyethoxy, 2-hydroxyethoxy), an aryloxy group (eg, phenoxy), an amino group (eg, dimethylamino, diethylamino), an acylamino group (eg, acetylamino), etc.).
R1及びR3におけるアリール基は少くとも1個のカル
ボン酸基又はスルホン酸基を有するフェニル基(例えば
4−スルホフェニル、4−カルボキシフェニル、2−メ
チル−4−スルホフェニル、3−スルホフェニル、2.
4−ジスルホフェニル、3、 5−ジスルホフェニル、
2−クロロ−4−スルホフェニル、2−メトキシ−4−
スルホフェニル、4−クロル−3−スルホフェニル、2
−メトキシ−5−スルホフェニル、2−ヒドロキシ、4
−スルホフェニル、2.5−ジクロル−4−スルホフェ
ニル、4−フェノキシ−3−スルホフェニル、4−(3
−スルホプロピルオキシ)フェニル、4−(N−メチル
−N−スルホエチルアミノ)フェニル、3−カルボキシ
−2−ヒドロキシ−5−スルホフェニル、2,6−ジエ
チル−4−スルホフェニル)又はナフチル基(例えば3
.6−ジスルホ−α−ナフチル、8−ヒドロキシ−3,
6−ジスルホ−α−ナフチル、5−ヒドロキシ−7−ス
ルホ−β−ナフチル、6.8−ジスルホ−β−ナフチル
)が好ましい。The aryl group in R1 and R3 is a phenyl group having at least one carboxylic acid group or sulfonic acid group (e.g. 4-sulfophenyl, 4-carboxyphenyl, 2-methyl-4-sulfophenyl, 3-sulfophenyl, 2 ..
4-disulfophenyl, 3, 5-disulfophenyl,
2-chloro-4-sulfophenyl, 2-methoxy-4-
Sulfophenyl, 4-chloro-3-sulfophenyl, 2
-methoxy-5-sulfophenyl, 2-hydroxy, 4
-sulfophenyl, 2,5-dichloro-4-sulfophenyl, 4-phenoxy-3-sulfophenyl, 4-(3
-sulfopropyloxy)phenyl, 4-(N-methyl-N-sulfoethylamino)phenyl, 3-carboxy-2-hydroxy-5-sulfophenyl, 2,6-diethyl-4-sulfophenyl) or naphthyl group ( For example 3
.. 6-disulfo-α-naphthyl, 8-hydroxy-3,
6-disulfo-α-naphthyl, 5-hydroxy-7-sulfo-β-naphthyl, 6,8-disulfo-β-naphthyl) are preferred.
R1及びR1におけるアラルキル基は少くとも1個のカ
ルボン酸基又はスルホン酸基を有する炭素数7〜15の
アラルキル基(例えば、4−スルホベンジル、2−スル
ホベンジル、2.4−ジスルホベンジル、2− (4−
スルホブチルオキシ)ベンジル、4−メチル−2−スル
ホベンジル、4−スルホフェネチル、4−カルボキシベ
ンジル、2.4−ジー(3−スルホプロとルオキシ)ベ
ンジル、2−ヒドロキシ−4−(2−スルホエトキシ)
ベンジル)が好ましい。The aralkyl group in R1 and R1 is an aralkyl group having 7 to 15 carbon atoms and having at least one carboxylic acid group or sulfonic acid group (for example, 4-sulfobenzyl, 2-sulfobenzyl, 2,4-disulfobenzyl, 2- (4-
Sulfobutyloxy)benzyl, 4-methyl-2-sulfobenzyl, 4-sulfophenethyl, 4-carboxybenzyl, 2,4-di(3-sulfoprooxy)benzyl, 2-hydroxy-4-(2-sulfoethoxy) )
benzyl) is preferred.
R,及びR2におけるアルキル基は、少くとも1個のカ
ルボン酸基又はスルホン酸基を有する炭素数1〜6のア
ルキル基(例えば、スルホメチル、カルボキシメチル、
2−スルホエチル、2−カルボキシエチル、3−スルホ
エチル、3−スルホ−2−メチルプロピル、3−スルホ
−2,2−ジメチルプロピル、4−スルホブチル、4−
カルボキシブチル、5−スルホペンチル、6−スルホヘ
キシル、5−カルボキシペンチル、6−カルボキシヘキ
シル)が好ましい。The alkyl group in R and R2 is an alkyl group having 1 to 6 carbon atoms and having at least one carboxylic acid group or sulfonic acid group (for example, sulfomethyl, carboxymethyl,
2-sulfoethyl, 2-carboxyethyl, 3-sulfoethyl, 3-sulfo-2-methylpropyl, 3-sulfo-2,2-dimethylpropyl, 4-sulfobutyl, 4-
carboxybutyl, 5-sulfopentyl, 6-sulfohexyl, 5-carboxypentyl, 6-carboxyhexyl) are preferred.
R3及びR1における複素環基は少くとも1個のカルボ
ン酸基又はスルホン酸基を有し、かつ少くとも1個の窒
素原子を有する5又は6員の含窒素複素環基(例えば5
−スルホピリジン−2−イル、5−カルボキシピリジン
−2−イル、6−スルホキノリン−2−イル、6−スル
ホキノリン−4−イル、5−スルホベンゾチアゾール−
2−イル、5−カルボキシベンゾチアゾール−2−イル
、6−スルホベンゾオキサゾール−2−イル、6−カル
ボキシベンゾオキサゾール−2−イル、6−スルホメチ
ルピリジン−2−イル、5−スルホピリミジン−2−イ
ル)が好ましい。The heterocyclic group in R3 and R1 is a 5- or 6-membered nitrogen-containing heterocyclic group having at least one carboxylic acid group or sulfonic acid group and at least one nitrogen atom (for example, 5
-Sulfopyridin-2-yl, 5-carboxypyridin-2-yl, 6-sulfoquinolin-2-yl, 6-sulfoquinolin-4-yl, 5-sulfobenzothiazole-
2-yl, 5-carboxybenzothiazol-2-yl, 6-sulfobenzoxazol-2-yl, 6-carboxybenzoxazol-2-yl, 6-sulfomethylpyridin-2-yl, 5-sulfopyrimidine-2 -il) is preferred.
R3又はR,におけるアルキル基は置換基(例えばフッ
素、塩素等のハロゲン原子、水酸基、カルボン酸基、ス
ルホン酸基、炭素数1〜6.のアルコキシ基(例えばメ
トキシ、エトキシ、n−ブトキシ)、シアノ基、アミノ
基(例えばジメチルアミノ、ジエチルアミノ))を有し
ていても良く、炭素数1〜8のアルキル基(例えばメチ
ル、エチル、n−プロピル、イソプロピル、n−ブチル
、5ec−ブチル、t−ブチル、イソブチル、n−ペン
チル、5ec−ペンチル、イソアミル、n−ヘキシル、
n−へブチル、n−オクチル、2−エチルヘキシル、2
−エチルブチル、トリフルオロメチル、2−クロロエチ
ル、2−ヒドロキシエチル、4−ヒドロキシブチル、5
−ヒドロキシペンチル、6−ヒドロキシヘキシル、7−
ヒドロキシペンチル、2−スルホエチル、2−カルボキ
シエチル、4−スルホブチル、2−シアノエチル、4−
ジメチルアミノブチル、ベンジルフェネチル)又は炭素
数5〜7の脂環式アルキル基(例えばシクロペンチル、
シクロヘキシル)が好ましい。The alkyl group in R3 or R is a substituent (for example, a halogen atom such as fluorine or chlorine, a hydroxyl group, a carboxylic acid group, a sulfonic acid group, an alkoxy group having 1 to 6 carbon atoms (for example, methoxy, ethoxy, n-butoxy), cyano group, amino group (e.g. dimethylamino, diethylamino)), and an alkyl group having 1 to 8 carbon atoms (e.g. methyl, ethyl, n-propyl, isopropyl, n-butyl, 5ec-butyl, t -butyl, isobutyl, n-pentyl, 5ec-pentyl, isoamyl, n-hexyl,
n-hebutyl, n-octyl, 2-ethylhexyl, 2
-ethylbutyl, trifluoromethyl, 2-chloroethyl, 2-hydroxyethyl, 4-hydroxybutyl, 5
-Hydroxypentyl, 6-hydroxyhexyl, 7-
Hydroxypentyl, 2-sulfoethyl, 2-carboxyethyl, 4-sulfobutyl, 2-cyanoethyl, 4-
dimethylaminobutyl, benzylphenethyl) or alicyclic alkyl groups having 5 to 7 carbon atoms (e.g. cyclopentyl,
cyclohexyl) is preferred.
R3又はR6におけるアラルキル基は置換基(例えばフ
ッ素、塩素等のハロゲン原子、水酸基、スルホン酸基、
カルボン酸基、炭素数1〜4のアルキル基(例えばメチ
ル、エチル、n−プロピル、n−ブチル)、炭素数1〜
6のアルコキシ基(例えばメトキシ、エトキシ、n−ブ
トキシ)、シアノ基、ニトロ基、アルコキシカルボニル
基(例えばカルベトキシ、メトキシカルボニル)、アミ
ノ基(例えばジメチルアミノ、ジエチルアミノ))を有
していても良く、炭素数7〜15のアラルキル基(例え
ばヘンシル、フェネチル、4−メチルベンジル、2−ク
ロロベンジル、4−メトキシベンジル)が好ましい。The aralkyl group in R3 or R6 is a substituent (for example, a halogen atom such as fluorine or chlorine, a hydroxyl group, a sulfonic acid group,
Carboxylic acid group, alkyl group having 1 to 4 carbon atoms (e.g. methyl, ethyl, n-propyl, n-butyl), 1 to 4 carbon atoms
6 alkoxy groups (e.g. methoxy, ethoxy, n-butoxy), cyano groups, nitro groups, alkoxycarbonyl groups (e.g. carbetoxy, methoxycarbonyl), amino groups (e.g. dimethylamino, diethylamino)), Aralkyl groups having 7 to 15 carbon atoms (eg hensyl, phenethyl, 4-methylbenzyl, 2-chlorobenzyl, 4-methoxybenzyl) are preferred.
R3又はR4におけるアリール基は置換基(例えばフッ
素、塩素等のハロゲン原子、水酸基、カルボン酸基、ス
ルホン酸基、炭素数1〜4のアルキル基(例えばメチル
、エチル、イソプロピル、n−プロピル、n−ブチル)
、炭素数1〜6のアルコキシ基(例えばメトキシ、エト
キシ、n−ブトキシ)、シアノ基、ニトロ基、アルコキ
シカルボニル基(例えばカルベトキシ、メトキシカルボ
キル)、アミノ基(例えばジメチルアミノ、ジエチルア
ミノ))を有していても良く、フェニル基(例えば無置
換のフェニル基、3−スルホフェニル、4−スルホフェ
ニル、4−カルボキシフェニル、4−ヒドロキシフェニ
ル、2−ヒドロキシフェニル、2−スルホフェニル、4
−シアノフェニル、3.4−ジクロルフェニル、4−メ
トキシフェニル、4−(3−スルホプロポキシ)フェニ
ル、4−ニトロフェニル、4−カルベトキシフェニル、
4−メチルフェニル、2−メチルフェニル、4−フルオ
ロフェニル)又はナフチル基が好ましい。The aryl group in R3 or R4 is a substituent (for example, a halogen atom such as fluorine or chlorine, a hydroxyl group, a carboxylic acid group, a sulfonic acid group, an alkyl group having 1 to 4 carbon atoms (for example, methyl, ethyl, isopropyl, n-propyl, n -butyl)
, an alkoxy group having 1 to 6 carbon atoms (e.g. methoxy, ethoxy, n-butoxy), a cyano group, a nitro group, an alkoxycarbonyl group (e.g. carbetoxy, methoxycarboxyl), an amino group (e.g. dimethylamino, diethylamino)). phenyl group (for example, unsubstituted phenyl group, 3-sulfophenyl, 4-sulfophenyl, 4-carboxyphenyl, 4-hydroxyphenyl, 2-hydroxyphenyl, 2-sulfophenyl, 4
-cyanophenyl, 3.4-dichlorophenyl, 4-methoxyphenyl, 4-(3-sulfopropoxy)phenyl, 4-nitrophenyl, 4-carbethoxyphenyl,
4-methylphenyl, 2-methylphenyl, 4-fluorophenyl) or naphthyl groups are preferred.
Rs、Riが連結して形成される5又は6員環はピロリ
ジン環、ピペリジン環、モルホリン環を挙げることがで
きる。Examples of the 5- or 6-membered ring formed by linking Rs and Ri include a pyrrolidine ring, a piperidine ring, and a morpholine ring.
L+ 、Lx 、Lxにおけるメチン基は置換基(例え
ばメチル、エチル、スルホエチル、塩素原子、シアノ等
)を有していても良い。The methine group in L+, Lx, and Lx may have a substituent (eg, methyl, ethyl, sulfoethyl, chlorine atom, cyano, etc.).
Moにおける水素以外のカチオンは、金属イオン(例え
ばNa” 、K” )又は無機もしくは有機アンモニウ
ムイオン(例えばNH,°、(Czlls) Jl+’
、ピリジニウム)が好ましい。Cations other than hydrogen in Mo can be metal ions (e.g. Na'', K'') or inorganic or organic ammonium ions (e.g. NH, °, (Czlls) Jl+'
, pyridinium) are preferred.
上記一般式(I)においてカルボン酸基又はスルホン酸
基は遊離の酸でも塩(例えばNa塩、K塩、(Call
s) JH塩、ピリジニウム塩、アンモニウム塩等)を
形成していても良い。In the above general formula (I), the carboxylic acid group or sulfonic acid group may be a free acid or a salt (e.g. Na salt, K salt, (Call
s) JH salt, pyridinium salt, ammonium salt, etc.).
上記一般式(I)において好ましいものは、R8及びR
1が少(とも1個のスルホン酸基を有するフェニル基、
少くとも1個のスルホン酸基を有する炭素数1〜4のア
ルキル基、又は少くとも1個のスルホン酸基を有するベ
ンジル基もしくはフェネチル基を表わすものである。In the above general formula (I), preferred are R8 and R
1 is less (a phenyl group having at least one sulfonic acid group,
It represents an alkyl group having 1 to 4 carbon atoms having at least one sulfonic acid group, or a benzyl group or phenethyl group having at least one sulfonic acid group.
以下に一般式(I)で表わされる染料の具体例を示すが
、本発明はこれらに限定されるものではない。Specific examples of the dye represented by the general formula (I) are shown below, but the present invention is not limited thereto.
一般式(I)に示される染料をフィルター染料、イラジ
ェーション防止染料又はアンチハレーション層料として
使用するときは、効果のある任意の量を使用できるが、
光学濃度が0.05ないし、3.0の範囲になるように
使用するのが好ましい、添加時期は塗布される前のいか
なる工程でもよい。When the dye represented by general formula (I) is used as a filter dye, anti-irradiation dye or antihalation layer material, any effective amount can be used;
It is preferable to use it so that the optical density is in the range of 0.05 to 3.0, and it may be added at any step before coating.
本発明による染料は、乳剤層その他の親水性コロイド層
(中間層、保5IIJ、アンチハレーション層、フィル
ター層など)中に種々の知られた方法で分散することが
できる。The dyes according to the invention can be dispersed in emulsion layers and other hydrophilic colloid layers (interlayers, storage layers, antihalation layers, filter layers, etc.) by various known methods.
■ 本発明の染料を直接に乳剤層や親水性コロイド層に
溶解もしくは分散させる方法または水性溶液または溶媒
に溶解もしくは分散させた後、乳剤層や親水性コロイド
層に用いる方法、適当な溶媒、例エバ、メチルアルコー
ル、エチルアルコール、プロピルアルコール、メチルセ
ルソルブ、特開昭48−9715号、米国特許3,75
6.830号に記載のハロゲン化アルコール、アセトン
、水、ピリジンなどあるいは、これらの混合溶媒などの
中に溶解され溶液の形で、乳剤へ添加することもできる
。■ A method of directly dissolving or dispersing the dye of the present invention in an emulsion layer or a hydrophilic colloid layer, or a method of dissolving or dispersing it in an aqueous solution or solvent and then using it in an emulsion layer or a hydrophilic colloid layer, an appropriate solvent, etc. EVA, methyl alcohol, ethyl alcohol, propyl alcohol, methyl cellosolve, JP-A-48-9715, US Patent 3,75
It can also be added to the emulsion in the form of a solution dissolved in a halogenated alcohol, acetone, water, pyridine, etc., or a mixed solvent thereof, as described in No. 6.830.
■ 染料イオンと反対の荷電をもつ親水性ポリマーを媒
染剤として層に共存させ、これを染料分子との相互作用
によって、染料を特定層中に局在化させる方法。■ A method in which a hydrophilic polymer with a charge opposite to that of the dye ions is made to coexist in the layer as a mordant, and this interacts with the dye molecules to localize the dye in a specific layer.
ポリマー媒染剤とは、二級および三級アミノ基を含むポ
リマー含窒素複素環部分をもつポリマーこれらの4級カ
チオン基を含むポリマーなどで分子量が5000以上の
ものが特に好ましくは10000以上のものである。The polymer mordant is a polymer containing a secondary and tertiary amino group, a polymer having a nitrogen-containing heterocyclic moiety, a polymer containing a quaternary cation group, etc., and a molecular weight of 5,000 or more, particularly preferably 10,000 or more. .
例えば米国特許2,548.564号明細書等に記載さ
れているビニルピリジンポリマー及びビニルピリジニウ
ムカチオンポリマー;米国特許4゜124.386号明
細凹等に開示されているビニルイミダゾリウムカチオン
ポリマー;米国特許3゜625.694号等に開示され
ているゼラチン等と架橋可能なポリマー媒染剤;米国特
許3,958.995号、特開昭54−115228号
明細凹等に開示されている水性ゾル型媒染型;米国特許
3,898.088号明1IIIIに開示されている水
不溶性媒染剤;米国特許4,168.976号明細書等
に開示の染料と共有結合を行うことのできる反応性媒染
剤;英国特許685.475号に記載されている如きジ
アルキルアミノアルキルエステル残基を有するエチレン
不飽和化合物から導かれたポリマー;英国特許850.
281号に記載されているようなポリビニルアルキルケ
トンとアミノグアニジンの反応によって得られる生成物
;米国特許3,445.231号に記載されているよう
な2−メチル−1−ビニルイミダゾールから導かれたポ
リマーなどを挙げることができる。For example, vinyl pyridine polymers and vinyl pyridinium cationic polymers disclosed in US Pat. No. 2,548.564; vinyl imidazolium cationic polymers disclosed in US Pat. No. 4,124.386; US patents 3゜625.694, etc., a polymer mordant crosslinkable with gelatin, etc.; an aqueous sol type mordant disclosed in U.S. Pat. ; Water-insoluble mordant disclosed in U.S. Pat. No. 3,898.088, IIII; Reactive mordant capable of covalent bonding with dyes disclosed in U.S. Pat. No. 4,168.976, etc.; British Patent No. 685 Polymers derived from ethylenically unsaturated compounds having dialkylaminoalkyl ester residues as described in British Patent No. 850.475;
Products obtained by the reaction of polyvinyl alkyl ketones with aminoguanidine as described in US Pat. No. 281; derived from 2-methyl-1-vinylimidazole as described in U.S. Pat. Examples include polymers.
■ 化合物を界面活性剤を用いて溶解する方法。■ A method of dissolving a compound using a surfactant.
有用な界面活性剤としては、オリゴマーないしはポリマ
ーであってもよい。Useful surfactants may be oligomers or polymers.
この重合体の詳細については、特開昭60−15843
7号(富士写真フィルム側により昭和59年1月26日
付で出願)の明細書第19頁〜27頁に記載されている
。For details of this polymer, please refer to JP-A-60-15843.
No. 7 (filed by Fuji Photo Film on January 26, 1980), pages 19 to 27 of the specification.
また、上記で得た親水性コロイド分散中に、例えば特公
昭51−39835号記載の親油性ポリマーのヒドロシ
ルを添加してもよい。Further, in the hydrophilic colloid dispersion obtained above, for example, hydrosyl, a lipophilic polymer described in Japanese Patent Publication No. 51-39835, may be added.
親水性コロイドとしては、ゼラチンが代表的なものであ
るが、その他写真用に使用しうるちのとして従来知られ
ているものはいずれも使用できる。Gelatin is a typical hydrophilic colloid, but any other conventionally known colloid used for photography can be used.
本発明に使用されるハロゲン化銀乳剤は、臭化銀、沃臭
化銀、沃塩臭化銀、塩臭化銀および塩化銀が好ましい。The silver halide emulsions used in the present invention are preferably silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride.
本発明に使用されるハロゲン化銀粒子は、立方体、八面
体のような規則的(rBular)な結晶形を有するも
の、また球状、板状などのような変則的(irregu
lar)な結晶形をもつもの、あるいはこれらの結晶形
の複合形をもつd¥ある。また種々の結晶形の粒子の混
合から成るものも使用できるが、°規則的な結晶形を使
用するのが好ましい。The silver halide grains used in the present invention include those having regular (rBular) crystal shapes such as cubic and octahedral, and those having irregular (rBular) crystal shapes such as spherical and plate shapes.
lar) crystal forms, or composite forms of these crystal forms. It is also possible to use particles consisting of a mixture of particles of various crystal forms, but it is preferable to use regular crystal forms.
本発明に使用されるハロゲン化銀粒子は内部と表層とが
異なる相をもっていても、均一な相から成っていてもよ
い、また潜像が主として表面に形成されるような粒子(
例えばネガ型乳剤)でもよく、粒子内部に主として形成
されるような粒子(例えば、内部潜像型乳剤、予めかぶ
らせた直接反転型乳剤)であってもよい、好ましくは、
潜像が主として表面に形成されるような粒子である。The silver halide grains used in the present invention may have different phases inside and on the surface, or may consist of a uniform phase.
For example, it may be a negative-tone emulsion), or it may be a grain that is mainly formed inside the grain (for example, an internal latent image type emulsion, a pre-fogged direct reversal type emulsion), and preferably,
These are particles on which a latent image is formed primarily on the surface.
本発明に使用されるハロゲン化銀乳剤は、厚みが0.5
ミクロン以下、好ましくは0.3ミクロン以下で径が好
ましくは0.6ミクロン以上であり、平均アスペクト比
が5以上の粒子が全投影面積の5偏差Sを直径1で除し
た値S/d)が20%以下である単分散乳剤が好ましい
、また平板粒子乳剤および単分散乳剤を2種以上混合し
てもよい。The silver halide emulsion used in the present invention has a thickness of 0.5
For particles with a diameter of 0.6 microns or less, preferably 0.3 microns or less, and an average aspect ratio of 5 or more, the value S/d is calculated by dividing 5 deviations S of the total projected area by diameter 1) A monodisperse emulsion in which the emulsion is 20% or less is preferred, and two or more types of tabular grain emulsions and monodisperse emulsions may be mixed.
本発明に用いられる写真乳剤はピー・ゲラフキデス(P
、 Giafkides)著、シミー・工・フイジーク
・フォトグラフィック(Chimie er Phys
iquePbotographeque) (ボール
モンテル社刊、1967年)、ジー・エフ・ダフィン(
G、 F、 Duffin)著、フォトグラフインク・
エマルジョン・ケミストリー(Photographi
c Emulsion Chemistry) (フォ
ーカルプレス刊、1966年)、ブイ・エル・ゼリクマ
ン(V、 L、 Zelikman)ら著、メーキング
・アンド・コーティング・フォトグラフィック・エマル
ジョン(Making and Coating Ph
otographic1!5ulsion) (フォ
ーカルプレス刊、1964年)などに記載された方法を
用いて調製することができる。The photographic emulsion used in the present invention is P.
, Giafkides), Chimie er Phys Photographic (Chimie er Phys Photographic)
iquePbotographique) (Ballmontel, 1967), G.F. Duffin (
G., F. Duffin), Photography Inc.
Emulsion Chemistry (Photography)
c Emulsion Chemistry) (Focal Press, 1966), V. L. Zelikman et al., Making and Coating Photographic Emulsions (Making and Coating Ph.
It can be prepared using the method described in ``Otographic 1!5ulsion'' (Focal Press, 1964).
またこのハロゲン化銀粒子の形成時には粒子の成長をコ
ントロールするためにハロゲン化銀溶剤として例えばア
ンモニア、ロダンカリ、ロダンアンモン、チオエーテル
化合物(例えば米国特許第3.271,157号、同第
3,574.628号、同第3.704,130号、同
第4. 297゜439号、同第4,276.374号
など)、チオン化合物(例えば特開昭53−14431
9号、同53−82408号、同55−77737号な
ど)、アミン化合物(例えば特開昭54−100717
号など)などを用いることができる。During the formation of silver halide grains, silver halide solvents such as ammonia, rhodanpotash, rhodanammonium, and thioether compounds (eg, U.S. Pat. Nos. 3,271,157 and 3,574) are used as silver halide solvents to control grain growth. No. 628, No. 3.704,130, No. 4.297.439, No. 4,276.374, etc.), thione compounds (e.g., JP-A No. 14431/1983)
No. 9, No. 53-82408, No. 55-77737, etc.), amine compounds (e.g., JP-A-54-100717)
etc.) can be used.
ハロゲン化銀粒子形成または物理熟成の過程において、
カドミウム塩、亜鉛塩、タリウム塩、イリジウム塩また
はその錯塩、ロジウム塩またはその錯塩、鉄塩または鉄
錯塩などを共存させてもよい。In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present together.
ハロゲン化銀乳剤は、通常は化学増感される。Silver halide emulsions are usually chemically sensitized.
化学増感のためには、例えばH,フリーゼル(l(。For chemical sensitization, for example H, Friesel (l(.
Fr1eser)[、デイ−・グルンドラーゲン・デル
・フォトグラフィジエン・プロツエセ・ミント・ジルベ
ルハロゲンデン(Die Grundlagen de
rPhotographischen Prozess
e sit Silberhalogeniden)(
アカデミッシェ フェルラグスゲゼルシャクト196B
)675〜734真に記載の方法を用いることができる
。Fr1eser)
rPhotographischen Prozess
e sit Silberhalogeniden) (
Akademische Ferlagsgesellschacht 196B
) 675-734 can be used.
すなわち、活性ゼラチンや銀と反応し得る硫黄を含む化
合物(例えば、チオ硫酸塩、チオ尿素類、メルカプト化
合物類、ローダニン類)を用いて硫黄増悪法;還元性物
質(例えば、第一すず塩、アミン類、ヒドラジン誘導体
、ホルムアミジンスルフィン酸、シラン化合物)を用い
る還元増悪法;貴金属化合物(例えば、全錯塩のほか、
pt、Ir、Pdなどの周期律表■族の金属の錯塩)を
用いる貴金属増悪法などを単独または組合せて用いるこ
とができる。That is, sulfur-enhanced methods using sulfur-containing compounds that can react with activated gelatin and silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines); reducing substances (e.g., stannous salts, reduction aggravation method using noble metal compounds (e.g., total complex salts,
A noble metal aggravation method using complex salts of metals of group 1 of the periodic table such as pt, Ir, and Pd can be used alone or in combination.
本発明に使用されるハロゲン化銀写真乳剤には、感光材
料の製造工程、保存中あるいは写真処理中のカブリを防
止し、あるいは写真性能を安定化させる目的で、種々の
化合物を含有させることができる。すなわち、アゾール
類たとえばベンゾチアゾリウム塩、ニトロインダゾール
類、トリアゾール類、ベンゾトリアゾール類、ベンズイ
ミダゾール類(特にニトロ−またはハロゲン置換体);
ヘテロ環メルカプト化合物類たとえばメルカプトチアゾ
ール類、メルカプトベンゾチアゾール類、メルカプトベ
ンズイミダゾール類、メルカプトチアジアゾール類、メ
ルカプトテトラゾール類(特に1−フェニル−5−メル
カプトテトラゾール)、メルカプトピリミジン類−カル
ボキシル基やスルホン基などの水溶性基を存する上記の
へテロ環メルカプト化合物類;チオケト化合物たとえば
オキサゾリンチオン;アザインデン類たとえばテトラア
ザインデンI(特に4−ヒドロキシ置換(I゜3.3a
、7)テトラアザインデン類);ベンゼンチオスルホン
酸類;ベンゼンスルフィン酸;などのようなカプリ防止
剤または安定剤肩口られた多くの化合物を加えることが
できる。The silver halide photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. can. That is, azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (particularly nitro- or halogen-substituted);
Heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines - carboxyl groups, sulfone groups, etc. The above-mentioned heterocyclic mercapto compounds bearing a water-soluble group; thioketo compounds such as oxazolinthione; azaindenes such as tetraazaindene I (especially 4-hydroxy substituted (I゜3.3a)
, 7) tetraazaindenes); benzenethiosulfonic acids; benzenesulfinic acid;
本発明のハロゲン化銀写真乳剤はシアン・カプラー、マ
ゼンタ・カプラー、イエロー・カプラーなどのカラー・
カプラー及びカプラーを分11にする化合物を含むこと
ができる。The silver halide photographic emulsion of the present invention can contain color pigments such as cyan coupler, magenta coupler, yellow coupler, etc.
It can include couplers and compounds that make the couplers part 11.
すなわち、発色現像処理において芳香族1級アミン現像
薬(例えば、フェニレンジアミン誘導体や、アミノフェ
ノール誘導体など)との酸化カフブリングによって発色
しうる化合物を含んでもよい0例えば、マゼンタカプラ
ーとして、5−ピラゾロンカプラー、ピラゾロベンツイ
ミダゾールカプラー、シアノアセチルクマロンカプラー
、ピラゾロトリアゾールカプラー、開鎖アシルアセトニ
トリルカプラー等があり、イエローカプラーとして、ア
シルアセトアミドカプラー(例えばベンゾイルアセトア
ニリド類、ピバロイルアセトアニリド類)、等があり、
シアンカプラーとして、ナフトールカプラーおよびフェ
ノールカプラー等がある。これらのカプラーは分子中に
バラスト基とよばれる疎水基を有する非拡散のものが望
ましい。That is, it may contain a compound that can develop color by oxidative cuffing with an aromatic primary amine developer (e.g., phenylene diamine derivative, aminophenol derivative, etc.) in color development treatment. For example, as a magenta coupler, a 5-pyrazolone coupler may be used. , pyrazolobenzimidazole couplers, cyanoacetylcoumarone couplers, pyrazolotriazole couplers, open-chain acylacetonitrile couplers, etc. Yellow couplers include acylacetamide couplers (e.g. benzoylacetanilides, pivaloylacetanilides), etc.
Examples of cyan couplers include naphthol couplers and phenol couplers. These couplers are preferably non-diffusive and have a hydrophobic group called a ballast group in the molecule.
カプラーは銀イオンに対し4当量性あるいは2当量性の
どちらでもよい、また色補正の効果をもつカラードカプ
ラー、あるいは現像にともなって現像抑制剤を放出する
カプラー(いわゆるDIRカプラー)であってもよい。The coupler may be either 4-equivalent or 2-equivalent to silver ions, and may be a colored coupler that has a color correction effect or a coupler that releases a development inhibitor during development (so-called DIR coupler). .
またDIRカプラー以外にも、カップリング反応の生成
物が無色であって現像抑制剤を放出する無呈色DIRカ
ンプリング化合物を含んでもよい。In addition to the DIR coupler, the coupling reaction product may contain a colorless DIR camping compound which is colorless and releases a development inhibitor.
本発明の写真乳剤には感度上昇、コントラスト上昇また
は現像促進の目的で、例えばポリアルキレンオキシドま
たはそのエーテル、エステル、アミンなどの誘導体、チ
オエーテル化合物、チオモルフォリン類、四級アンモニ
ウム塩化合物、ウレタン誘導体、尿素誘導体、イミダゾ
ール誘導体、3−ピラゾリドン類等を含んでもよい。For the purpose of increasing sensitivity, increasing contrast, or accelerating development, the photographic emulsion of the present invention may contain, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, quaternary ammonium salt compounds, and urethane derivatives. , urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like.
本発明のハロゲン化銀写真乳剤にはフィルター染料とし
ズ、あるいはイラジェーション防止その他種々の目的で
、本発明に開示される染料以外の公知の水溶性染料(例
えばオキソノール染料;ヘミオキソノール染料及びメロ
シアニン染料)と併用して用いてもよい、また分光増悪
剤として本発明に示される染料以外の公知のシアニン色
素、メロシアニン色素、ヘミシアニン色素と併用して用
いてもよい。The silver halide photographic emulsion of the present invention contains filter dyes and dyes, or known water-soluble dyes other than the dyes disclosed in the present invention (for example, oxonol dyes; hemioxonol dyes and It may be used in combination with a merocyanine dye), or may be used in combination with a known cyanine dye, merocyanine dye, or hemicyanine dye other than the dyes shown in the present invention as a spectral enhancer.
本発明の写真乳剤には塗布助剤、帯電防止、スベリ性改
良、乳化分散、接着防止および写真特性改良(例えば現
像促進、硬調化、増感)など種々の目的で種々の界面活
性剤を含んでもよい。The photographic emulsion of the present invention may contain various surfactants for various purposes such as coating aids, antistatic properties, improving slipperiness, dispersing emulsions, preventing adhesion, and improving photographic properties (for example, accelerating development, increasing contrast, and sensitizing). But that's fine.
また、本発明の感光材料には退色防止剤、硬膜剤、色カ
プリ防止剤、紫外線吸収剤、ゼラチン等の保護コロイド
、種々の添加剤に関して、具体的には、リサーチ・ディ
スクロージャーVo1.176(I97B、XI[)R
D−17643などに記載されている。In addition, the photosensitive material of the present invention contains anti-fading agents, hardening agents, anti-color capri agents, ultraviolet absorbers, protective colloids such as gelatin, and various additives, as detailed in Research Disclosure Vol. 1.176 ( I97B, XI[)R
D-17643 etc.
完成(finished)乳剤は、適切な支持体、例え
ばバライタ紙、レジンコート紙、合成紙、トリアセテー
トフィルム、ポリエチレンテレフタレートフィルム、そ
の他のプラスチックベースまたはガラス板の上に塗布さ
れる。The finished emulsion is coated onto a suitable support such as baryta paper, resin coated paper, synthetic paper, triacetate film, polyethylene terephthalate film, other plastic bases or glass plates.
本発明のハロゲン化銀写真感光材料としては、カラーポ
ジフィルム、カラーペーパー、カラーネガフィルム、カ
ラー反転(カプラーを含む場合もあり、含まぬ場合もあ
る)、製版用写真感光材料(例えばリスフィルム、リス
デユープフィルムなど)、陰極線管デイスプレィ用感光
材料(例えば乳剤X線記録用感光材料、スクリーンを用
いる直接及び間接撮影用材料)、銀塩拡tik転写プロ
セス(Silver 5alt diffusion
transfer process)用感光材料、カラ
ー拡散転写プロセス用感光材料、グイ・トランスファー
・プロセス(i+abibit!ontransfer
process)用感光材料、銀色素漂白法に用いる
感光材料、プリントアウト像を記録する感光材料、光現
像型焼出しくDirect Pr1nt image)
感光材料、熱現像用感光材料、物理現像用感光材料など
を挙げることができる。The silver halide photographic light-sensitive materials of the present invention include color positive films, color papers, color negative films, color reversals (which may or may not contain couplers), and photographic materials for platemaking (for example, lithium film, lithography), and color reversal films (which may or may not contain couplers). eup film, etc.), photosensitive materials for cathode ray tube displays (e.g., photosensitive materials for emulsion X-ray recording, materials for direct and indirect photography using screens), silver salt diffusion tik transfer process (Silver 5 alt diffusion)
transfer process), photosensitive materials for color diffusion transfer process, Gui transfer process (i+abibit!ontransfer)
photosensitive materials for use in the silver dye bleaching method, photosensitive materials for recording printout images, photodevelopable printouts (Direct Pr1nt image)
Examples include photosensitive materials, photosensitive materials for thermal development, and photosensitive materials for physical development.
写真像を得るための露光は通常の方法を用いて行えばよ
い、すなわち、自然光(日光)、タングステン電灯、螢
光灯、水銀灯、キセノンアーク灯、炭素アーク灯、キセ
ノンフラッシュ灯、陰極線管フライングスポットなど公
知の多種の光源をいずれでも用いることができる。露光
時間は通常171000秒から30秒の露光時間である
が、171000秒より短い露光、たとえばキセノン閃
光灯や陰極線管を用いたl/10’〜1/10’秒の露
光を用いることもできるし、30秒より長い露光を用い
ることもできる。必要に応じて色フィルターで露光に用
いられる光の分光組成を調節することができる。露光に
レーザー光を用いることもできる。また電子線、x*、
r線、α線などによって励起させた螢光体から放出する
光によって露光されてもよい。Exposure to obtain photographic images may be carried out using conventional methods: natural light (sunlight), tungsten lamps, fluorescent lamps, mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots. Any of a variety of known light sources can be used. The exposure time is usually from 171,000 seconds to 30 seconds, but an exposure shorter than 171,000 seconds, for example, an exposure of 1/10' to 1/10' second using a xenon flash lamp or cathode ray tube, can also be used. Exposures longer than 30 seconds can also be used. If necessary, the spectral composition of the light used for exposure can be adjusted using a color filter. Laser light can also be used for exposure. Also, electron beam, x*,
Exposure may be performed by light emitted from a phosphor excited by r-rays, alpha-rays, etc.
本発明を用いて作られる感光材料の写真処理には、例え
ばリサーチ・ディスクロージャー(Research
Disclosure ) 176号、第28〜30頁
(RD−17643)に記載されているような、公知め
方法及び公知の処理液のいずれをも適用することができ
る。この写真処理は、目的に応じて、−1像を形成する
写真処理(黒白写真処理)、あるいは色素像を形成する
写真処理(カラー写真処理)のいずれであってもよい、
処理温度は普通18から50℃の間に選ばれるが、18
℃より低い温度または50℃を越える温度としてもよい
。Photographic processing of light-sensitive materials made using the present invention includes, for example, Research Disclosure (Research Disclosure).
Any of the known methods and known treatment liquids as described in Disclosure No. 176, pages 28-30 (RD-17643) can be applied. This photographic processing may be either photographic processing that forms a -1 image (black and white photographic processing) or photographic processing that forms a dye image (color photographic processing), depending on the purpose.
The processing temperature is usually chosen between 18 and 50°C, but 18
The temperature may be lower than 50°C or higher than 50°C.
カラー写真処理方法については特に制限はな(、あらゆ
る方法が適用できる0例えばその代表的なものとしては
、露光後、発色現像、漂白定着処理を行ない、必要に応
じさらに水洗、安定化処理を行なう方式、露光後、発色
現像、漂白と定着を分離した処理を行ない、必要に応じ
さらに水洗、安走化処理を行なう方式、露光後、黒白現
像主薬を含有する現像液で現像し、−様露光を与えた後
、発色現像、漂白定着処理を行ない、必要に応しさらに
水洗、安定化処理を行なう方式あるいは露光後、黒白現
像主薬を含有する現像液で現像し、さらにカプラシ剤(
例えば水素化ホウ素ナトリウム)を含有する発色現像液
で現像してから漂白定着処理を行ない、必要に応じさら
に水洗、安定化処理を行なう方式がある。There are no particular restrictions on the color photographic processing method (any method can be applied). For example, after exposure, color development, bleach-fixing are carried out, and if necessary, washing with water and stabilization are carried out. Method: After exposure, color development, bleaching and fixing are performed separately, and if necessary, washing with water and stabilizing treatment are performed. After exposure, development is performed with a developer containing a black and white developing agent, followed by --like exposure. After applying a color development agent, color development and bleach-fixing are carried out, and if necessary, washing with water and stabilization are carried out, or after exposure, development is carried out with a developer containing a black and white developing agent, and then a caplacing agent (
For example, there is a method in which the image is developed with a color developing solution containing (for example, sodium borohydride) and then subjected to bleach-fixing treatment, followed by further washing with water and stabilization treatment as required.
本発明において発色現像液で使用される芳香族第一級ア
ミン系発色現像主薬は種々のカラー写真プロセスにおい
て広範に使用されている公知のものが包含される。これ
らの現像主薬は了ミノフェノール系およびp−フェニレ
ンジアミン系誘導体が含まれる。好ましい例はp−フェ
ニレンジアミン誘導体であり代表例を以下に示すが、こ
れらに限定されるものではない。The aromatic primary amine color developing agents used in the color developing solution of the present invention include known ones that are widely used in various color photographic processes. These developing agents include monophenolic and p-phenylenediamine derivatives. Preferred examples are p-phenylenediamine derivatives, and representative examples are shown below, but the invention is not limited thereto.
D−IN、N−ジエチル−p−フェニレンジアミン
D−22−アミノ−5−ジエチル7ミノトルより−32
−アミノ−5−(N−エチル−N−ラウリルアミノ)ト
ルエン
D−44−(N−エチル−N−(β−ヒドロキシエチル
)アミノコアニリン
D−52−メチル−4−(N−cチJtz−N−(β−
ヒドロキシエチル)アミノコアニリン
D−6N−エチル−N−(β−メタンスルホンアミドエ
チル)−3−メチル−4−アミノアニリン
D−7N−(2−アミノ−5−ジエチルアミノフェニル
エチル)メタンスルホンアミドD−8N、N−ジメチル
−p−フェニレンジアミン
D−94−アミノ−3−メチル−N−エチル−N−メト
キシエチルアニリン
D−104−アミノ−3−メチル−N−エチル−N−β
−エトキシエチルアニリン
D−114−アミノ−3−メチル−N−エチル−N−β
−ブトキシエチルアニリン
また、これらのp−フェニレンジアミン誘導体は硫酸塩
、塩酸塩、亜硫酸塩、り−)ルエンスルホン酸塩などの
塩であってもよい、上記化合物は、米国特許2,193
,015号、同2,552゜241号、同2,566.
271号、同2,592.364号、同3,656.9
50号、同3゜698.525号等に記載されている。D-IN, N-diethyl-p-phenylenediamine D-22-amino-5-diethyl 7 minotr-32
-Amino-5-(N-ethyl-N-laurylamino)toluene D-44-(N-ethyl-N-(β-hydroxyethyl)aminocoaniline D-52-methyl-4-(N-c-Jtz -N-(β-
hydroxyethyl)aminocoaniline D-6N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline D-7N-(2-amino-5-diethylaminophenylethyl)methanesulfonamide D -8N,N-dimethyl-p-phenylenediamine D-94-amino-3-methyl-N-ethyl-N-methoxyethylaniline D-104-amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline D-114-amino-3-methyl-N-ethyl-N-β
-butoxyethylaniline These p-phenylenediamine derivatives may also be salts such as sulfate, hydrochloride, sulfite, ri-)luenesulfonate, etc. The above compounds are described in U.S. Pat.
, No. 015, No. 2,552゜241, No. 2,566.
No. 271, No. 2,592.364, No. 3,656.9
No. 50, No. 3゜698.525, etc.
咳芳香族第−級アミン発色現像主薬の使用量は現像溶液
12当り約0.1g〜約20g、更に好ましくは約0.
5g〜約10gの濃度である。The amount of aromatic primary amine color developing agent to be used is about 0.1 g to about 20 g per 120 g of developer solution, more preferably about 0.1 g to about 20 g per 12 g of developer solution.
The concentration is from 5g to about 10g.
本発明で使用される発色現像液中には、周知のようにヒ
ドロキシルアミン類を含むことができる。As is well known, the color developer used in the present invention may contain hydroxylamines.
ヒドロキシルアミン類は、発色現像液中において遊離ア
ミンの形で使用することができるというものの水溶性の
酸塩の形でそれを使用するのがより一般的である。この
ような塩類の一般的な例は、硫酸塩、シュウ酸塩、塩化
物、リン酸塩、炭酸塩、酢酸塩その他である。ヒドロキ
シルアミン類は置換又は無置換のいずれであってもよく
、ヒドロキシルアミン類の窒素原子がアルキル基によっ
て置換されていてもよい。Although hydroxylamines can be used in the free amine form in color developers, it is more common to use them in the form of water-soluble acid salts. Common examples of such salts are sulfates, oxalates, chlorides, phosphates, carbonates, acetates, and others. The hydroxylamines may be substituted or unsubstituted, and the nitrogen atom of the hydroxylamines may be substituted with an alkyl group.
ヒドロキシルアミンの添加量は発色現像液12当り0g
〜10gが好ましく、さらに好ましくは0〜5gである
0発色現像液の安定性が保たれるのならば、添加量は少
ない方が好ましい。The amount of hydroxylamine added is 0g per 12 color developer.
The amount added is preferably from 10 g to 10 g, more preferably from 0 to 5 g, as long as the stability of the color developing solution is maintained.
また保恒剤として、亜硫酸ナトリウム、亜硫酸カリウム
、重亜硫酸ナトリウム、重亜硫酸カリウム、メタ亜硫酸
ナトリウム、メタ亜硫酸カリウム等の亜硫酸塩や、カル
ボニル亜硫酸付加物を含有することが好ましい、これら
の添加量はOg〜20 g/Itが好ましく更に好まし
くはOg〜5g/lであり、発色現像液の安定性が保た
れるならば、少ない方が好ましい。In addition, as a preservative, it is preferable to contain sulfites such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, and carbonyl sulfite adducts. The amount is preferably 20 g/It, more preferably 0 g/1 to 5 g/l, and the smaller the amount, the more preferable it is, as long as the stability of the color developer is maintained.
その他保恒剤としては、特開昭52−49828号、同
56−47038号、同56−32140号、同59−
160142号および米国特許3746544号記載の
芳香族ポリヒドロキシ化合物;米国特許3,615,5
03号および英国特許1,306,176号記載のヒド
ロキシアセトン類;特開昭52−143020号および
同53−89425号記載のα−アミノカルボニル化合
物;特開昭57−44148号および同57−5374
9号等に記載の各種金属類;特開昭52−102727
号記載の各種糖類;同52−27638号記載のヒドロ
キサム酸類;同59−1601411記WIiのα、α
゛−ジカルボニル化合物;同59−180588号記載
のサリチル酸類;同54−3・532号記載のアルカノ
ールアミン類;同56−94349号記載のポリ(アル
キレンイミン)類;同56−75647号記載のグルコ
ン酸誘導体等をあげることができる。これらの保恒剤は
必要に応じて2種以上、併用しても良い、特に4.5−
ジヒドロキシ−m−ベンゼンジスルホン酸、ポリ (エ
チレンイミン)およびトリエタノールアミン等の添加が
好ましい。Other preservatives include JP-A Nos. 52-49828, 56-47038, 56-32140, and 59-
Aromatic polyhydroxy compounds described in US Pat. No. 1,601,42 and US Pat. No. 3,746,544; US Pat. No. 3,615,5
03 and British Patent No. 1,306,176; α-aminocarbonyl compounds described in JP-A-52-143020 and JP-A-53-89425; JP-A-57-44148 and JP-A-57-5374
Various metals described in No. 9 etc.; JP-A-52-102727
Various saccharides described in No. 52-27638; hydroxamic acids described in No. 52-27638; α, α of WIi in No. 59-1601411
-dicarbonyl compounds; salicylic acids described in No. 59-180588; alkanolamines described in No. 54-3/532; poly(alkylene imines) described in No. 56-94349; Examples include gluconic acid derivatives. Two or more of these preservatives may be used in combination as necessary, especially 4.5-
Additions such as dihydroxy-m-benzenedisulfonic acid, poly(ethyleneimine) and triethanolamine are preferred.
本発明に使用される発色現像液のpHは、好ましくは9
〜12、より好ましくは9〜11であり、そのカラー現
像液には、その他に既知の現像液成分の化合物を含ませ
ることができる。The pH of the color developer used in the present invention is preferably 9.
-12, more preferably 9-11, and the color developer may contain other known developer component compounds.
上記pHを保持するためには、各種緩衝剤を用いるのが
好ましい、緩衝剤としては、炭酸塩、リン酸塩、ホウ酸
塩、四ホウ酸塩、ヒドロキシ安息香酸塩、グリシン塩、
N、Nジメチルグリシン塩、ロイシン塩、ノルロイシン
塩、グアニン塩、3゜4−ジヒドロキシフェニルアラニ
ン塩、アラニン塩、アミノ酪酸塩、2−アミノ−2−メ
チル−1゜3−プロパンジオール塩、バリン塩、プロリ
ン塩、トリスヒドロキシアミツメクン塩、リシン塩等を
用いることができる。特に炭酸塩、リン酸塩、四ホウ酸
塩、ヒドロキシ安息香酸塩は、溶解性やpH9,0以上
の高pHa域での緩衝能に優れ、カラー現像液に添加し
ても写真性能面への悪影響(カプリなど)がなく、安価
であるといった利点を有し、これらのa街剤を用いるこ
とが特に好ましい。In order to maintain the above pH, it is preferable to use various buffering agents. Examples of the buffering agent include carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycine salt,
N,N dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3゜4-dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 2-amino-2-methyl-1゜3-propanediol salt, valine salt, Proline salts, trishydroxyamitumecun salts, lysine salts, etc. can be used. In particular, carbonates, phosphates, tetraborates, and hydroxybenzoates have excellent solubility and buffering ability in the high pH range of pH 9.0 or higher, and even when added to color developers, they have no effect on photographic performance. It is particularly preferable to use these agglutinants because they have the advantages of having no adverse effects (such as capri) and being inexpensive.
これらの緩衝剤の具体例としては、炭酸ナトリウム、炭
酸カリウム、重炭酸ナトリウム、重炭酸カリウム、リン
酸三ナトリウム、リン酸三カリウム、リン酸二ナトリウ
ム、リン酸二カリウム、ホウ酸す゛トリウム、ホウ酸カ
リウム、四ホウ酸ナトリウム(ホウ砂)、四ホウ酸カリ
ウム、0−ヒドロキシ安息香酸ナトリウム(サリチル酸
ナトリウム)、O−ヒドロキシ安息香酸カリウム、5−
スルホ−2−ヒドロキシ安息香酸ナトリウム(5−スル
ホサリチル酸ナトリウム)、5−スルホ−2−ヒドロキ
シ安息香酸カリウム(5−スルホサリチル酸カリウム)
などを挙げることができる。しかしながら本発明は、こ
れらの化合物に限定されるものではない。Specific examples of these buffers include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, ditrium borate, and boron. Potassium acid, sodium tetraborate (borax), potassium tetraborate, sodium 0-hydroxybenzoate (sodium salicylate), potassium O-hydroxybenzoate, 5-
Sodium sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate)
etc. can be mentioned. However, the present invention is not limited to these compounds.
該緩衝剤の発色現像液への添加量は、0.1モル/1以
上であることが好ましく、特に0.1モル/l−0,4
モル/lであることが特に好ましい。The amount of the buffer added to the color developing solution is preferably 0.1 mol/l or more, particularly 0.1 mol/l-0.4
Particular preference is given to mol/l.
その他、発色現像液中にはカルシウムやマグネシウムの
沈澱防止剤として、あるいは発色現像液の安定性向上の
ために、各種キレート剤を用いることができる。In addition, various chelating agents can be used in the color developer as agents for preventing precipitation of calcium and magnesium, or to improve the stability of the color developer.
キレート剤としては有機酸化合物が好ましく、例えば特
公昭4B−030496号および同44−30232号
記載の7ミノポリカルボン酸類、特開昭56−9734
7号、特公昭56−39359号および***特許2,2
27,639号記載の有機ホスホン酸類、特開昭52−
102726号、同53−42730号、同54−12
1127号、同55−126241号および同55−6
5956号等に記載のホスホノカルボン酸類、その他特
開昭58−195845号、同58−203440号お
よび特公昭53−40900号等に記載の化合物をあげ
ることができる。以下に具体例を示すがこれらに限定さ
れるものではない。The chelating agent is preferably an organic acid compound, such as the 7-minopolycarboxylic acids described in Japanese Patent Publications No. 4B-030496 and No. 44-30232, and JP-A-56-9734.
No. 7, Special Publication No. 56-39359 and West German Patent No. 2,2
Organic phosphonic acids described in No. 27,639, JP-A-52-
No. 102726, No. 53-42730, No. 54-12
No. 1127, No. 55-126241 and No. 55-6
Examples include phosphonocarboxylic acids described in JP-A-58-195845, JP-A-58-203440, and JP-B-Sho 53-40900. Specific examples are shown below, but the invention is not limited to these.
・ニトリロ三酢酸
・ジエチレンアミノ五酢酸
・エチレンジアミン四酢酸
・トリエチレンテトラミン六酢酸
・N、N、N−)リメチレンホスホン酸・エチレンジア
ミン−N、N、N’、N’−テトラメチレンホスホン酸
・1.3−ジアミノ−2−プロパノ−ルー4酢酸・トラ
ンスシクロヘキサンジアミン四酢酸・ニトリロ三プロピ
オン酸
・1.2−ジアミノプロパン四酢酸
・ヒドロキシエチルイミノニ酢酸
・グリコールエーテルジアミン四酢酸
・ヒドロキシエチレンジアミン三酢酸
・エチレンジアミンオルトヒドロキシフェニル酢酸
・2−ホスホノブタン−1,2,4−)リカルボン酸
・1−ヒドロキシエタン−1,1−ジホスホン酸・N、
N’−ビス(2−ヒドロキシベンジル)エチレンジアミ
ン−N、N’−ジ酢酸
これらのキレート剤は必要に応じて2種以上併用しても
良い、これらのキレート剤の添加量は発色現像液中の金
属イオンを封鎖するのに充分な量であれば良い0例えば
11当り0.1g〜10g程度である。・Nitrilotriacetic acid ・Diethyleneaminopentaacetic acid ・Ethylenediaminetetraacetic acid ・Triethylenetetraminehexaacetic acid ・N,N,N-)limethylenephosphonic acid ・Ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid ・1 .3-diamino-2-propanol-tetraacetic acid, transcyclohexanediaminetetraacetic acid, nitrilotripropionic acid, 1,2-diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethylenediaminetriacetic acid, Ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-)licarboxylic acid, 1-hydroxyethane-1,1-diphosphonic acid, N,
N'-bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid Two or more of these chelating agents may be used in combination as necessary. The amount may be sufficient as long as it is sufficient to sequester metal ions, for example, about 0.1 to 10 g per 11.
発色現像液には必要により任意の現像促進剤を添加でき
る。Any development accelerator can be added to the color developing solution if necessary.
現像促進剤としては、ベンジルアルコールの他、特公昭
37−16088号、同37−5987号、同38−7
826号、同44−12380号、同45−9019号
および米国特許3813247号等に記載のチオエーテ
ル系化合物;特開昭52−49829号および同50−
15554号に記載のp−フェニレンジアミン系化合物
、特開昭50−137726号、特公昭44−3007
4号、特開昭56−156826号および同52−43
429号等に記載の4級アンモニウム塩類;米国特許2
,610,122号および同4,119゜462号に記
載のp−アミノフェノール類:米国特許2,494.9
03号、同3. 128. 182号、同4,230,
796号、同3. 253゜919号、特公昭41−1
1431号、米国特許2.482,546号、同2,5
96.926号および同3,582,346号等に記載
のアミン系化合物;特公昭37−16.088号、同4
2−25201号、米国特許3,128,183号、特
公昭41−11431号、同42−23883号および
米国特許3,532,501号等に記載のポリアルキレ
ンオキサイド、その他、1−フェニル−3−ピラゾリド
ン類、ヒドラジンQ、メソイオン型化合物、チオン型化
合物、イミダゾール類、等を必要に応じて添加すること
ができる。特にチオエーテル系の化合物や1−フェニル
−3−ビラプリトン類が好ましい。As a development accelerator, in addition to benzyl alcohol, Japanese Patent Publications No. 37-16088, No. 37-5987, and No. 38-7
826, No. 44-12380, No. 45-9019, and U.S. Pat. No. 3,813,247, etc.;
p-phenylenediamine compounds described in No. 15554, JP-A-50-137726, JP-B-Sho 44-3007
No. 4, JP-A-56-156826 and JP-A No. 52-43
Quaternary ammonium salts described in No. 429, etc.; US Patent 2
, 610,122 and 4,119°462: US Pat. No. 2,494.9
No. 03, same 3. 128. No. 182, 4,230,
No. 796, 3. No. 253゜919, Special Publication No. 41-1
No. 1431, U.S. Pat. No. 2,482,546, U.S. Pat.
96.926 and 3,582,346, etc.; Japanese Patent Publication No. 37-16.088 and 4
2-25201, U.S. Patent No. 3,128,183, Japanese Patent Publication No. 11431/1983, Japanese Patent Publication No. 42-23883, and U.S. Patent No. 3,532,501, etc., 1-phenyl-3 -Pyrazolidones, hydrazine Q, meso ion type compounds, thione type compounds, imidazoles, etc. can be added as necessary. Particularly preferred are thioether compounds and 1-phenyl-3-virapritones.
本発明の発色現像液には、必要により任意のカブリ防止
剤を添加できる。カブリ防止剤としては臭化カリウム、
塩化ナトリウム、沃化カリウム等のアルカリ金属ハロゲ
ン化物および有機カブリ防止剤が使用できる。有機カプ
リ防止剤としては、例えばベンゾトリアゾール、6−ニ
トロベンズイミダゾール、5−ニトロイソインダゾール
、5−メチルベンゾトリアゾール、5−ニトロベンゾト
リアゾール、5−クロロベンゾトリアゾール、2−チア
ゾリルベンズイミダゾール、2−チアゾリルメチルベン
ズイミダゾール等の含窒素へテロ環化合物、2−メルカ
プトベンズイミダゾール、2−メルカプトベンゾチアゾ
ール等のメルカプト!換へテロ環化合物、アデニン、さ
らにはチオサリチル酸のようなメルカプ)!換の芳香族
化合物が使用できる。これらのカブリ防止剤は、処理中
にハロゲン化銀カラー写真感光材料中から溶出し、発色
現像液中に蓄積しても良いが、排出量低減の観点で、こ
れらの蓄積量は少ない方が好ましい。If necessary, any antifoggant can be added to the color developing solution of the present invention. As an antifoggant, potassium bromide,
Alkali metal halides such as sodium chloride, potassium iodide, and organic antifoggants can be used. Examples of organic anti-capri agents include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chlorobenzotriazole, 2-thiazolylbenzimidazole, 2 - Nitrogen-containing heterocyclic compounds such as thiazolylmethylbenzimidazole, mercapto such as 2-mercaptobenzimidazole and 2-mercaptobenzothiazole! Heterocyclic compounds, adenine, and even mercaps like thiosalicylic acid)! Other aromatic compounds can be used. These antifoggants may be eluted from the silver halide color photographic light-sensitive material during processing and may accumulate in the color developing solution, but from the viewpoint of reducing the amount of emissions, it is preferable that the amount of these accumulated is small. .
本発明の発色現像液には、螢光増白剤を含有するのが好
ましい、螢光増白剤としては、4.4−ジアミノ−2,
2′−ジスルホスチルベン系化合物が好ましい、添加量
は0〜5g/l好ましくは0.1g〜2g/j!である
。The color developing solution of the present invention preferably contains a fluorescent whitening agent. Examples of the fluorescent whitening agent include 4,4-diamino-2,
2'-disulfostilbene compounds are preferred, and the amount added is 0 to 5 g/l, preferably 0.1 g to 2 g/l! It is.
また必要に応じて、アルキルホスホン酸、了り−ルホス
ホン酸、脂肪族カルボン酸、芳香族カルボン酸等の各種
界面活性剤を添加しても良い。Moreover, various surfactants such as alkylphosphonic acid, alkylphosphonic acid, aliphatic carboxylic acid, and aromatic carboxylic acid may be added as necessary.
本発明における発色現像液の処理温度は、30〜50℃
が好ましく、さらに好ましくは33〜42℃である。補
充量は感光材料IM当たり30〜2000−であり、好
ましくは30〜1500+、+7である。廃液量低減の
観点で、これらの補充量は少ない方が好ましい。The processing temperature of the color developing solution in the present invention is 30 to 50°C.
is preferable, and more preferably 33 to 42°C. The replenishment amount is 30 to 2000-, preferably 30 to 1500+, +7 per photosensitive material IM. From the viewpoint of reducing the amount of waste liquid, it is preferable that the amount of these replenishments be small.
本発明に用いられる漂白液または漂白定着液における漂
白剤としては、第2鉄イオン錯塩が一般に用いられる。Ferric ion complex salts are generally used as the bleaching agent in the bleach solution or bleach-fix solution used in the present invention.
第2鉄イオン錯塩は、第2鉄イオンとアミノポリカルボ
ン酸、アミノポリホスホン酸あるいはそれらの塩などの
キレート剤との錯体である。アミノポリカルボン酸塩あ
るいはアミノポリホスホン酸塩はアミノポリカルボン酸
あるいはアミノポリホスホン酸のアルカリ金属、アンモ
ニウム、水溶性アミンとの塩である。アルカリ金属とし
てはナトリウム、カリウム、リチウム等であり、水溶性
アミンとしてはメチルアミン、ジエチルアミン、トリエ
チルアミン、ブチルアミンの如きアルキルアミン、シク
ロヘキシルアミンの如き指環式アミン、アニリン、m
−)ルイジンの如きアルキルアミンおよびピリジン、モ
ルホリン、ピペリジンの如き複素環アミンである。A ferric ion complex salt is a complex of ferric ion and a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid, or a salt thereof. Aminopolycarboxylic acid salts or aminopolyphosphonic acid salts are salts of aminopolycarboxylic acids or aminopolyphosphonic acids with alkali metals, ammonium, or water-soluble amines. Examples of alkali metals include sodium, potassium, and lithium, and examples of water-soluble amines include alkyl amines such as methylamine, diethylamine, triethylamine, butylamine, ring amines such as cyclohexylamine, aniline, m
-) Alkylamines such as luidine and heterocyclic amines such as pyridine, morpholine, piperidine.
これらのアミノポリカルボン酸及びアミノポリホスホン
酸あるいはそれらの塩などのキレート剤の代表例として
は、
エチレンジアミンテトラ酢酸
エチレンジアミンテトラ酢酸ジナトリウム塩エチレンジ
アミンテトラ酢酸ジアンモニウム塩エチレンジアミンテ
トラ酢酸テトラ(トリメチルアンモニウム)塩
エチレンジアミンテトラ酢酸テトラカリウム塩エチレン
ジアミンテトラ酢酸テトラナトリウム塩
エチレンジアミンテトラ酢酸トリナトリウム塩ジエチレ
ントリアミンペンタ酢酸
ジエチレントリアミンペンタ酢酸ペンタナトリウム塩
エチレンジアミン−N−(β−オキシエチル)−N、N
”、N’−)り酢酸
エチレンジアミン−N−(β−オキシエチル)−N、N
”、N’−)り酢酸トリナトリウム塩
エチレンジアミン−N−(β−オキシエチル)−N、N
’、N”−)り酢酸トリアンモニウム塩
プロピレンジアミンテトラ酢酸
プロピレンジアミンテトラ酢酸ジナトリウム塩ニトリロ
トリ酢酸
ニトリロトリ酢酸トリナトリウム塩
シクロヘキサンジアミンテトラ酢酸
シクロヘキサンジアミンテトラ酢酸ジナトリウム塩
イミノジ酢酸
ジヒドロキシエチルグリシン
エチルエーテルジアミンテトラ酢酸
グリコールエーテルジアミンテトラ酢酸エチレンジアミ
ンテトラプロピオン酸
フェニレンジアミンテトラ酢酸
1.3−ジアミノプロパノ−ルーN、N、N’。Typical examples of chelating agents such as these aminopolycarboxylic acids and aminopolyphosphonic acids or their salts include: ethylenediaminetetraacetic acid ethylenediaminetetraacetic acid disodium salt ethylenediaminetetraacetic acid diammonium salt ethylenediaminetetraacetic acid tetra(trimethylammonium) salt ethylenediamine Tetraacetic acid tetrapotassium salt Ethylenediaminetetraacetic acid tetrasodium salt Ethylenediaminetetraacetic acid trisodium salt Diethylenetriaminepentaacetic acid Diethylenetriaminepentaacetic acid pentasodium salt Ethylenediamine-N-(β-oxyethyl)-N,N
”, N'-) ethylene diamine acetate-N-(β-oxyethyl)-N,N
”,N'-) trisodium acetate salt ethylenediamine-N-(β-oxyethyl)-N,N
',N''-) triammonium acetate propylene diamine tetraacetic acid propylene diamine tetraacetic acid disodium salt nitrilotriacetic acid nitrilotriacetic acid trisodium salt cyclohexanediamine tetraacetic acid cyclohexane diamine tetraacetic acid disodium salt iminodiacetic acid dihydroxyethylglycine ethyl ether diamine tetraacetic acid Glycol ether diamine tetraacetic acid ethylene diamine tetrapropionic acid phenylene diamine tetraacetic acid 1,3-diaminopropanol-N,N,N'.
N゛−テトラメチレンホスホン酸
エチレンジアミン−N、N、N’、N’−テトラメチレ
ンホスホン酸
1.3−プロピレンジアミン−N、N、N’。N'-tetramethylenephosphonic acid ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid 1,3-propylenediamine-N,N,N'.
N′−テトラメチレンホスホン酸
などを挙げることができるが、もちろんこれらの例示化
合物に限定されない。Examples include N'-tetramethylenephosphonic acid, but the compound is not limited to these exemplified compounds.
第2鉄イオン錯塩は錯塩の形で使用しても良いし、第2
鉄塩、例えば硫酸第2鉄、塩化第2鉄、硝酸第2鉄、硫
酸第2鉄アンモニウム、リン酸第2鉄等とアミノポリカ
ルボン酸、アミノポリホスホン酸、ホスホノカルボン酸
などのキレート剤とを用いて溶液中で第2鉄イオン錯塩
を形成させてもよい、錯塩の形で使用する場合は、1種
類の錯塩を用いてもよいし、また2種類以上の錯塩を用
いてもよい、一方、第2鉄塩とキレート剤を用いて溶液
中で錯塩を形成する場合は第2鉄塩を1種類または2種
類以上使用してもよい、さらにキレート剤を1種類又は
2種類以上使用してもよい。The ferric ion complex salt may be used in the form of a complex salt, or as a ferric ion complex salt.
Iron salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate, etc. and chelating agents such as aminopolycarboxylic acids, aminopolyphosphonic acids, phosphonocarboxylic acids, etc. A ferric ion complex salt may be formed in a solution using On the other hand, when forming a complex salt in a solution using a ferric salt and a chelating agent, one or more types of ferric salts may be used, and one or more types of chelating agent may be used. You may.
また、いずれの場合にも、キレート剤を第2鉄イオン錯
塩を形成する以上に過剰に用いてもよい。In any case, the chelating agent may be used in excess of the amount needed to form the ferric ion complex.
鉄錯体のなかでもアミノポリカルボン酸鉄錯体が好まし
く、その添加量は0.01〜1.0mol / It、
好ましくは0.05〜0.50mol / Rである。Among the iron complexes, aminopolycarboxylic acid iron complexes are preferred, and the amount added is 0.01 to 1.0 mol/It.
Preferably it is 0.05 to 0.50 mol/R.
また漂白液又は漂白定着液には、必要に応じて漂白促進
剤を使用することができる。有用な漂白促進剤の具体例
としては、米国特許第3.893゜858号、***特許
筒1,290,812号、同2.059,988号、特
開昭53−32736号、同53−57831号、同3
7418号、同53−65732号、同53−7262
3号、同53−95630号、同53−95631号、
同53−104232号、同53−124424号、同
53−141623号、同53−28426号、リサー
チ・ディスクロージャ1b17129号(I978年7
月)等に記載のメルカプト基またはジスルフィド基を有
する化合物;特開昭50−140129号に記載のチア
ゾリジン誘導体:特公昭45−8506号、特開昭52
−20832号、同53−32735号、米国特許第3
,706゜561号に記載のチオ尿素誘導体;***特許
第1゜127.715号、特開昭58−16235号に
記載の沃化物:***特許第966.410号、同2.7
48,430号に記載のポリエチレンオキサイド頻;特
公昭45−8836号に記載のポリアミン化合物;その
他特開昭49−42434号、同49−59644号、
同53−94927号、同54−35727号、同55
−26506号および同58−163940号記載の化
合物および沃素、臭素イオン等を挙げることができる。Further, a bleach accelerator can be used in the bleaching solution or the bleach-fixing solution, if necessary. Specific examples of useful bleach accelerators include U.S. Pat. No. 3,893.858, West German Pat. No. 57831, same 3
No. 7418, No. 53-65732, No. 53-7262
No. 3, No. 53-95630, No. 53-95631,
No. 53-104232, No. 53-124424, No. 53-141623, No. 53-28426, Research Disclosure No. 1b17129 (July 1978)
Compounds having a mercapto group or disulfide group as described in Japanese Patent Application Publication Nos. 1983-140129; thiazolidine derivatives described in JP-A No. 45-8506, JP-A No. 52
-20832, No. 53-32735, U.S. Patent No. 3
, 706゜561; Iodides described in West German Patent No. 1゜127.715, JP-A-58-16235: West German Patent No. 966.410, JP-A-1987-16235;
Polyethylene oxide compounds described in Japanese Patent Publication No. 48,430; polyamine compounds described in Japanese Patent Publication No. 45-8836; others, Japanese Patent Publication No. 49-42434, Japanese Patent Publication No. 49-59644,
No. 53-94927, No. 54-35727, No. 55
Examples include the compounds described in No. 26506 and No. 58-163940, as well as iodine and bromide ions.
なかでもメルカプト基またはジスルフィド空を有する化
合物が促進効果が大きい観点で好ましく、特に米国特許
第3,893,858号、***特許第1゜290.81
2号、特開昭53−95630号に記載の化合物が好ま
しい。Among these, compounds having a mercapto group or a disulfide vacancy are preferred from the viewpoint of a large promoting effect, and are particularly preferred, as described in US Pat. No. 3,893,858 and West German Patent No. 1.290.81.
No. 2, JP-A No. 53-95630 is preferred.
その他、本発明の漂白液または漂白定着液には、臭化物
(例えば臭化カリウム、臭化ナトリウム、臭化アンモニ
ウム)または塩化物(例えば塩化カリウム、塩化ナトリ
ウム、塩化アンモニウム)または沃化物(例えば沃化ア
ンモニウム)の再ハロゲン化剤を含むことができる。必
要に応じホウ酸、ホウ砂、メタホウ酸ナトリウム、酢酸
、酢酸ナトリウム、炭酸ナトリウム、炭酸カリウム、亜
リン酸、リン酸、リン酸ナトリウム、クエン酸、クエン
酸ナトリウム、酒石酸等のpH11衝能を有する1種類
以上の無機酸、有機酸およびこれらのアルカリ金属また
はアンモニウム塩、さらに硝酸アンモニウム、グアニジ
ン等の腐蝕防止剤を添加することができる。Additionally, the bleach or bleach-fix solutions of the invention may contain bromides (e.g. potassium bromide, sodium bromide, ammonium bromide) or chlorides (e.g. potassium chloride, sodium chloride, ammonium chloride) or iodides (e.g. iodide). ammonium) rehalogenating agents. If necessary, it has pH 11 buffering capacity for boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc. One or more inorganic acids, organic acids and alkali metal or ammonium salts thereof, as well as corrosion inhibitors such as ammonium nitrate, guanidine, etc. can be added.
本発明の漂白定着液又は定着液に使用される定着剤は、
公知の定着剤、即ちチオ硫酸ナトリウム、チオ硫酸アン
モニウム等のチオ硫酸塩;チオシアン酸ナトリウム、チ
オシアン酸アンモニウム等のチオシアン酸塩:エチレン
ビスチオグリコール酸、3.6−シチアー1.8−オク
タンジオール等のチオエーテル化合物およびチオ尿素類
等の水溶性のハロゲン化銀溶解剤であり、これらを1種
あるいは2種以上混合して使用することができる。また
特開昭55−155354号に記載された定着剤と多量
の沃化カリウムの如きハロゲン化物などの組み合わせか
らなる特殊な漂白定着液等も用いることができる0本発
明においては、チオ硫酸塩特にチオ硫酸アンモニウム塩
の使用が好ましい。The fixing agent used in the bleach-fixing solution or fixing solution of the present invention is:
Known fixing agents, namely thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; ethylene bisthioglycolic acid, 3,6-cythia-1,8-octanediol, etc. These are water-soluble silver halide dissolving agents such as thioether compounds and thioureas, and these can be used alone or in combination of two or more. In addition, a special bleach-fixing solution consisting of a combination of a fixing agent described in JP-A-55-155354 and a large amount of a halide such as potassium iodide can also be used.In the present invention, thiosulfate, especially Preference is given to using ammonium thiosulfate salts.
11あたりの定着剤の量は、0.3〜2モルが好ましく
、更に好ましくは0.5〜1.0モルの範囲である。The amount of fixing agent per 11 is preferably in the range of 0.3 to 2 moles, more preferably in the range of 0.5 to 1.0 moles.
本発明に於る漂白定着液又は定着液のpH領域は、3〜
10が好ましく、更には4〜9が特に好ましい、pHが
これより低いと脱銀性は向上するが、液の劣化及びシア
ン色素のロイコ化が促進される。逆にpHがこれより高
いと脱銀が遅れかつスティンが発生し易くなる。The pH range of the bleach-fix solution or fix solution in the present invention is 3 to 3.
10 is preferred, and 4 to 9 is particularly preferred. If the pH is lower than this, the desilvering properties will be improved, but the deterioration of the solution and the leucoization of the cyan dye will be promoted. On the other hand, if the pH is higher than this, desilvering is delayed and staining is likely to occur.
pHを調整するためには、必要に応じて塩酸、硫酸、硝
酸、酢酸(氷酢酸)、重炭酸塩、アンモニア、水酸化カ
リウム、水酸化ナトリウム、炭酸ナトリウム、炭酸カリ
ウム等を添加する事ができる。To adjust the pH, hydrochloric acid, sulfuric acid, nitric acid, acetic acid (glacial acetic acid), bicarbonate, ammonia, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, etc. can be added as necessary. .
また漂白定着液には、その他各種の螢光増白剤や消泡剤
あるいは界面活性剤、ポリビニルピロリドン、メタノー
ル等の有機溶媒を含有させることができる。The bleach-fix solution may also contain various other fluorescent brighteners, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol.
本発明の漂白定着液や定着液は、保恒剤として亜硫酸塩
(例えば亜硫酸ナトリウム、亜硫酸カリウム、亜硫酸ア
ンモニウム、など)、重亜硫酸塩(例えば重亜硫酸アン
モニウム、重亜硫酸ナトリウム、重亜硫酸カリウム、な
ど)、メタ重亜硫酸塩(例えばメタ重亜硫酸カリウム)
、メタ重亜硫酸ナトリウム、メタ重亜硫酸アンモニウム
、など)等の亜硫酸イオン放出化合物を含有する。これ
らの化合物は亜硫酸イオンに換算して約0.02〜O,
SOモル/i含有させることが好ましく、更に好ましく
は0.04〜0.40モル/lである。The bleach-fix solution and fixer of the present invention contain sulfites (e.g., sodium sulfite, potassium sulfite, ammonium sulfite, etc.) and bisulfites (e.g., ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.) as preservatives. , metabisulfites (e.g. potassium metabisulfite)
, sodium metabisulfite, ammonium metabisulfite, etc.). These compounds have a concentration of about 0.02 to O in terms of sulfite ions,
It is preferable to include SO mol/i, more preferably 0.04 to 0.40 mol/l.
保恒剤としては、亜硫酸塩の添加が一般的であるが、そ
の他、アスコルビン酸や、カルボニル重亜硫酸付加物、
あるいは、カルボニル化合物等を添加しても良い。Sulfites are commonly added as preservatives, but other preservatives include ascorbic acid, carbonyl bisulfite adducts,
Alternatively, a carbonyl compound or the like may be added.
さらには緩衝剤、螢光増白剤、キレート剤、防カビ剤等
を必要に応じて添加しても良い。Furthermore, buffering agents, fluorescent whitening agents, chelating agents, antifungal agents, etc. may be added as necessary.
次に本発明の水洗工程について説明する0本発明では通
常の“水洗処理”のかわりに実質的な水洗工程を設けず
、いわゆる“安定化処理”だけを行なうなどの筒便な処
理方法を用いることもできる。このように本発明でいう
「水洗処理」とは上記のような広い意味で用いられてい
る。Next, the water washing process of the present invention will be explained.In the present invention, instead of the usual "water washing process", a convenient processing method is used, such as not providing a substantial water washing process and only performing a so-called "stabilization process". You can also do that. As described above, the term "water washing treatment" as used in the present invention is used in the broad meaning described above.
本発明の水洗水量は、多段向流水洗の浴数や感光材料の
前浴成分を持込み量によって異なるために、その規定は
困難であるが、本発明においては最終水洗浴における漂
白定着液成分がlXl0−’以下であれば良い0例えば
3タンク向流水洗の場合には感光材料1rrr当り約1
000−以上用いるのが好ましく、より好ましくは、5
ooo−以上である。また節水処理の場合には感光材料
1rrl当り100〜1000−用いるのがよい。The amount of washing water in the present invention is difficult to specify because it varies depending on the number of baths in multistage countercurrent washing and the amount of pre-bath components of the photosensitive material brought in. However, in the present invention, the amount of bleach-fix solution in the final washing bath is It is sufficient if it is less than l
It is preferable to use 000- or more, more preferably 5
ooo- that's it. In addition, in the case of water-saving treatment, it is preferable to use 100 to 1000 ml per rrl of the photosensitive material.
水洗温度は15℃〜45℃、より好ましくは20℃〜3
5℃である。The water washing temperature is 15°C to 45°C, more preferably 20°C to 3°C.
The temperature is 5°C.
水洗処理工程には、沈澱防止や水洗水の安定化目的で、
各種の公知化合物を添加しても良い0例えば、無機リン
酸、アミノポリカルボン酸、有機ホスホン酸等のキレー
ト剤、各種のバクテリアや藻やカビの発生を防止する殺
菌剤や防パイ剤(例えば、「ジャーナル・オプ・アンチ
バクチリアル・アンド・アンチフユンガル・エージエン
ツ」(J、 Antibact、 Antifung、
AgenLs)Vol、 11、阻合物、マグネシウ
ム塩やアルミニウム塩に代表される金属塩、アルカリ全
屈およびアンモニウム塩、あるいは乾燥負荷やムラを防
止するための界面活性剤等を必要に応じて添加すること
ができる。あるいはウェスト著[フォトグラフィック・
サイエンス・アンド・エンジニアリングu (Phot
、 Sci。In the washing process, for the purpose of preventing sedimentation and stabilizing the washing water,
Various known compounds may be added. For example, chelating agents such as inorganic phosphoric acid, aminopolycarboxylic acid, and organic phosphonic acid; bactericidal agents and anti-spiking agents that prevent the growth of various bacteria, algae, and molds (e.g. , “Journal of Antibacterial and Antifungal Agents” (J. Antibact, Antifung,
Add inhibitors, metal salts such as magnesium salts and aluminum salts, alkaline salts and ammonium salts, surfactants to prevent dry load and unevenness, etc. as necessary. be able to. Or by West [Photographic
Science and Engineering u (Photo
, Sci.
Eng、) 、第6巻、344〜359ページ(I96
5)等に記載の化合物を添加しても良い。Eng.), Volume 6, pp. 344-359 (I96
The compounds described in 5) etc. may be added.
さらにキレート剤や殺菌剤、防パイ剤を水洗水に添加し
、2槽以上の多段向流水洗により水洗水量を大幅に節減
する場合において、本発明は特に有効である。また通常
の水洗工程のかわりに、特開昭57−8543号記載の
ような多段向流安定化処理工程(いわゆる安定化処理)
を実施する場合にも、特に有効である。これらの場合、
最終浴の漂白定着成分は5X10−”以下好ましくは1
×10−”以下であれば良い。Further, the present invention is particularly effective in cases where a chelating agent, a bactericide, or an anti-piping agent is added to the washing water, and the amount of washing water is significantly reduced by multistage countercurrent washing using two or more tanks. Also, instead of the usual water washing process, a multi-stage countercurrent stabilization process (so-called stabilization process) as described in JP-A No. 57-8543
It is also particularly effective when implementing. In these cases,
The bleach-fix components of the final bath should be less than or equal to 5 x 10-'', preferably 1
It is sufficient if it is not more than ×10-”.
本安定化浴中には画像を安定化する目的で各種化合物が
添加される0例えば膜pHを調整する。Various compounds are added to this stabilizing bath for the purpose of stabilizing the image.For example, the pH of the membrane is adjusted.
(例えばpH3〜8にする)ための各種の緩衝剤(例え
ばホウ酸塩、メタホウ酸塩、ホウ砂、リン酸塩、炭酸塩
、水酸化カリウム、水酸化ナトリウム、アンモニア水、
モノカルボン酸、ジカルボン酸、ポリカルボン酸等を組
み合わせて使用)やホルマリン等のアルデヒドを代表例
として挙げることができる。その他、キレート剤(無機
リン酸、アミノポリカルボン酸、有機ホスホン酸、アミ
ノポリホスホン酸、系スホノカルボン酸等)、殺菌剤(
チアゾール系、イソチアゾール系、ハロゲン化フェノー
ル、スルファニルアミド、ベンゾトリアゾール等)、界
面活性剤、螢光増白剤、硬膜剤等の各種添加剤を使用し
てもよく、同一もしくは異種の目的の化合物を二種以上
併用しても良い。Various buffering agents (e.g., borates, metaborates, borax, phosphates, carbonates, potassium hydroxide, sodium hydroxide, ammonia water,
Typical examples include monocarboxylic acids, dicarboxylic acids, polycarboxylic acids, etc.) and aldehydes such as formalin. In addition, chelating agents (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphonic acid, aminopolyphosphonic acid, sulfonocarboxylic acids, etc.), bactericidal agents (
Various additives such as thiazole type, isothiazole type, halogenated phenol, sulfanilamide, benzotriazole, etc.), surfactants, fluorescent brighteners, and hardening agents may be used, and they can be used for the same or different purposes. Two or more kinds of compounds may be used in combination.
また、処理後の膜pH3lJ整剤として塩化アンモニウ
ム、硝酸アンモニウム、硫酸アンモニウム、リン酸アン
モニウム、亜硫酸アンモニウム、チオ硫酸アンモニウム
等の各種アンモニウム塩を添加するのが画像保存性を良
化するために好ましい。Further, it is preferable to add various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate as a membrane pH3lJ adjuster after treatment in order to improve image storage stability.
以上のような水洗水量を大幅に節減した場合には、水洗
水のオーバーフロー液の一部または全部を前浴である漂
白定着浴や安定浴に流入させる場合が排液量減少の目的
から好ましい。When the amount of washing water is significantly reduced as described above, it is preferable for the purpose of reducing the amount of waste water to flow some or all of the overflow liquid of the washing water into the bleach-fixing bath or stabilizing bath, which is a pre-bath.
本処理工程においては連続処理に際して、各処理液の補
充液を用いて、液組成の変動を防止することによって一
定の仕上がりが得られる。補充量は、コスト低減などの
ため標準補充量の半分あるいは半分以下に下げることも
できる。In this treatment step, during continuous treatment, a constant finish can be obtained by using a replenisher for each treatment solution to prevent fluctuations in the liquid composition. The replenishment amount can be reduced to half or less than the standard replenishment amount to reduce costs.
各処理浴内には、必要に応じて、ヒーター、温度センサ
ー、液面センサー、循環ポンプ、フィルター、各種浮き
ブタ、各種スクイジー、窒素攪拌、エアー攪拌等を設け
ても良い。Each treatment bath may be provided with a heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, various floating pigs, various squeegees, nitrogen stirring, air stirring, etc., as necessary.
カラー写真処理は、発色現像液を使用する処理ならば、
いかなる処理工程にも適用できる0例えばカラーペーパ
ー、カラー反転ペーパー、カラーポジフィルム、カラー
ネガフィルム、カラー反転フィルム等の処理に適用する
ことができる。Color photographic processing is a process that uses a color developing solution.
It can be applied to any processing process, such as color paper, color reversal paper, color positive film, color negative film, color reversal film, etc.
(実施例) 次に、本発明を実施例に基づきさらに詳細に説明する。(Example) Next, the present invention will be explained in more detail based on examples.
実施例−1
ポリエチレンで両面ラミネートした紙支持体の上に、以
下に示す層構成の多層カラープリント用試料(すを作製
した。Example 1 A multilayer color print sample having the layer structure shown below was prepared on a paper support laminated on both sides with polyethylene.
層構成
以下に各層の組成を示す。数字は塗布ffk (g/d
)を表わす、但しハロゲン化銀乳剤は銀換算塗布量であ
る。Layer structure The composition of each layer is shown below. Numbers are applied ffk (g/d
), provided that the silver halide emulsion is coated in terms of silver.
支持体
ポリエチレンラミネート祇〔第一層側のポリエチレンに
白色顔料(Tilt)と青味染料(群青)を含む、〕
第−層(青感性ハロゲン化銀乳剤層)
分光増悪剤(Son−1)を添加した単分散塩臭化銀乳
剤(EM−1) 0.16分光増感剤(Se
n−1)を添加した単分散塩臭化銀乳剤(EM−2)
0.10カブリ防止剤(Cpd−1)
0.004ゼラチン 1・
83イエローカプラー(ExY) 0.83色
像安定剤(Cpd−2) o、03ポリマー
(Cpd−3) 0.08溶媒(Solv−
1と5olv−2
体積比1:1) 0.35硬膜剤(H
d) 0.02第二層(混色防止
層)
ゼラチン 1.25混色防止剤
(Cpd−4) o、04溶媒(Solv−
3と5olv−4
体積比11) 0.20硬膜剤(H
d) 0.02第三層(緑感性ハ
ロゲン化銀乳剤層)
分光増感剤(Sen−2,3)を添加した単分散塩臭化
銀乳剤(EM−3) 0.05分光増感剤(Se
n−2,3)を添加した単分散塩臭化銀乳剤(EM−4
) 0.11カブリ防止剤(Cpd−5)
0.001ゼラチン 1.79
マゼンタカプラー(ExM) 0.32色像安
定剤(Cpd−6) 0.20色像安定剤(C
pd−7) 0.03色像安定剤(Cpd−8
) 0.03溶媒(Solv−3と5OIv
−5
体積比1:2) 0.65硬膜剤(H
d) 0.01第四層(紫外線吸
収層)
ゼラチン 1.58紫外線吸収
剤(UV−1/2/3
モル比1:4:4) 0.62混色防止
剤(Cpd−4) 0.05溶媒(Solv−
6) 0.34染料(Dy−1)
0.005染料(Dy−2>
0. O15硬膜剤()(d)
0.01第五層(赤感性ハロゲン化銀乳剤層)
分光増感剤(Sen−4,5)を添加した単分散塩臭化
銀乳剤(EM−5) 0.07分光増感剤(Sen
−4,5)を添加した単分散塩臭化銀乳剤(EM−6)
0.15カプリ防止剤(Cpd−9) 0.0
002ゼラチン 1.34シア
ンカプラー(ExC−1) 0.15シアンカプ
ラー(ExC−2) 0.18紫外線吸収剤(U
V−1/3/4
モル比1:3:3) 0.17ボリマー
(Cpd−3) 0.33溶媒(Solv−
1) 0.23硬膜剤(Hd)
0.01第六層(紫外線吸収N)
ゼラチン 0.53紫外線吸収
剤(UV−1/2/3
モル比1:4:4) 0.21溶媒(S
olv−6) 0.08硬膜剤(Hd)
0.01第七層(保護層)
ゼラチン 1.33ポリビニル
アルコールのアク
リル変性共重合体(変性度
17%) 0.17流動パラ
フイン 0.03上記試料に用いたハ
ロゲン化銀乳剤の詳細を第−表に示した−
第一表
変動係数=標準偏差/平均粒子径
(Sen−1) 6X10−’モル/Agモル(C
Ht)aSO3−(CHり、5O3H−N((、Hs)
3(Sen−2) 4X10−’モル/Agモル(S
en−3) 8X10−’モル/Agモル(Sen−
4)1.8X10−’モル/AgモルCsH+ +
I−CtHi
(sen−s) 3X10−’モル/Agモル(ExY
)
(ExM)
(ExC−1)
H
(ExC−2)
(Hd)
(Cpd−1)
H
(Cpd−2)
(Cpd−3)
+cug−cu−*
CONlC0N1IC4l1 分子量 約6000
0(Cpd−4)
0■
H
(Cpd−5)
(Cpd−6)
し113 LII+。Support polyethylene laminate (the polyethylene on the first layer side contains a white pigment (Tilt) and a bluish dye (ulmarine))] -th layer (blue-sensitive silver halide emulsion layer) Spectral enhancer (Son-1) Added monodispersed silver chlorobromide emulsion (EM-1) 0.16 Spectral sensitizer (Se
Monodisperse silver chlorobromide emulsion (EM-2) added with n-1)
0.10 antifoggant (Cpd-1)
0.004 gelatin 1.
83 Yellow coupler (ExY) 0.83 Color image stabilizer (Cpd-2) o, 03 Polymer (Cpd-3) 0.08 Solvent (Solv-
1 and 5olv-2 volume ratio 1:1) 0.35 Hardener (H
d) 0.02 second layer (color mixing prevention layer) Gelatin 1.25 color mixing prevention agent (Cpd-4) o, 04 solvent (Solv-
3 and 5olv-4 volume ratio 11) 0.20 hardener (H
d) 0.02 third layer (green-sensitive silver halide emulsion layer) Monodispersed silver chlorobromide emulsion (EM-3) with added spectral sensitizer (Sen-2, 3) 0.05 spectral sensitizer (Se
Monodisperse silver chlorobromide emulsion (EM-4
) 0.11 Antifoggant (Cpd-5)
0.001 gelatin 1.79
Magenta coupler (ExM) 0.32 color image stabilizer (Cpd-6) 0.20 color image stabilizer (C
pd-7) 0.03 color image stabilizer (Cpd-8
) 0.03 solvent (Solv-3 and 5OIv
-5 Volume ratio 1:2) 0.65 Hardener (H
d) 0.01 Fourth layer (ultraviolet absorption layer) Gelatin 1.58 Ultraviolet absorber (UV-1/2/3 molar ratio 1:4:4) 0.62 Color mixing inhibitor (Cpd-4) 0.05 Solvent (Solv-
6) 0.34 dye (Dy-1)
0.005 dye (Dy-2>
0. O15 hardener () (d)
0.01 Fifth layer (red-sensitive silver halide emulsion layer) Monodisperse silver chlorobromide emulsion (EM-5) added with a spectral sensitizer (Sen-4, 5) 0.07 Spectral sensitizer (Sen-4, 5)
-4,5) Monodisperse silver chlorobromide emulsion (EM-6)
0.15 Anti-capri agent (Cpd-9) 0.0
002 Gelatin 1.34 Cyan coupler (ExC-1) 0.15 Cyan coupler (ExC-2) 0.18 Ultraviolet absorber (U
V-1/3/4 molar ratio 1:3:3) 0.17 polymer (Cpd-3) 0.33 solvent (Solv-
1) 0.23 hardener (Hd)
0.01 Sixth layer (UV absorption N) Gelatin 0.53 Ultraviolet absorber (UV-1/2/3 molar ratio 1:4:4) 0.21 Solvent (S
olv-6) 0.08 Hardener (Hd)
0.01 Seventh layer (protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.17 Liquid paraffin 0.03 Details of the silver halide emulsion used in the above sample Shown in the table - Table 1 Coefficient of variation = standard deviation/average particle diameter (Sen-1) 6X10-' mol/Ag mol (C
Ht)aSO3-(CH,5O3H-N((,Hs)
3(Sen-2) 4X10-'mol/Agmol(S
en-3) 8X10-' mol/Ag mol (Sen-
4) 1.8X10-' mol/Ag mol CsH+ +
I-CtHi (sen-s) 3X10-' mol/Ag mol (ExY
) (ExM) (ExC-1) H (ExC-2) (Hd) (Cpd-1) H (Cpd-2) (Cpd-3) +cug-cu-* CONlC0N1IC4l1 Molecular weight approximately 6000
0 (Cpd-4) 0■ H (Cpd-5) (Cpd-6) 113 LII+.
(Cpd−7)
■
0COCtJ、l!(n)
■
■
0OCJs
(Cpd−8)
(Cpd−9)
■
(UV−1)
(tJV−2)
(UV−3)
(UV−4)
(Solv−1)
υ
(Solv−2)
0− P +oce+目+v(iso))i(Solv
−3)
(Solv−4)
Js
o=p÷0CLCI(CaL) !
(Solv−6)
COOCHzCH(CzHs)CmHv(CH*)s
■
C00GHzCIl(C!1ls)CJq(Dy−1)
(Dy−2)
上記試料から、第四層の染料を変化させた試料(2)〜
(7)を作製した。構成を第二表に示した。(Cpd-7) ■ 0COCtJ, l! (n) ■ ■ 0OCJs (Cpd-8) (Cpd-9) ■ (UV-1) (tJV-2) (UV-3) (UV-4) (Solv-1) υ (Solv-2) 0- P +oce+eye+v(iso))i(Solv
-3) (Solv-4) Js o=p÷0CLCI(CaL)! (Solv-6) COOCHzCH (CzHs) CmHv (CH*)s ■ C00GHzCIl (C!1ls) CJq (Dy-1) (Dy-2) Sample in which the fourth layer dye was changed from the above sample (2) ~
(7) was produced. The composition is shown in Table 2.
第二表
試料(I1〜(8)について膜中の染料の安定性と露光
湿度依存性を調べた。染料の安定性については、生試料
を35℃−80%で2週間放置した後の染料の残存率で
評価した。また露光湿度依存性は、25℃−55%およ
び25℃−85%の条件で露光した後、下記の処理を行
い、光学濃度=1.0における相対感度を、変化の大き
い青感性ハロゲン化銀乳剤層について評価した。評価結
果は第三表に示した。The stability of the dye in the film and the exposure humidity dependence were investigated for the samples in Table 2 (I1 to (8)). The exposure humidity dependence was evaluated by the following treatment after exposure at 25°C-55% and 25°C-85%, and the relative sensitivity at optical density = 1.0 was changed. A blue-sensitive silver halide emulsion layer with a large opacity was evaluated.The evaluation results are shown in Table 3.
処理工程 1皮 龍
発色現像 33℃ 3分30秒漂白定着
33℃ 1分30秒水 洗 24〜34℃
3分乾 燥 70〜80℃ 1公
害処理液の組成は以下の通りである。Processing process 1 skin Dragon color development 33℃ 3 minutes 30 seconds bleach fixing
Wash at 33℃ for 1 minute and 30 seconds 24-34℃
Dry for 3 minutes at 70-80°C 1. The composition of the pollution treatment liquid is as follows.
衾負里儂遜
水 800+
dジエチレントリアミン五酢酸 1.0gニトリロ
三酢酸 1.5gベンジルアルコール
15−ジエチレングリコール
1〇−亜硫酸ナトリウム 2.0
g臭化カリウム 0.5g炭酸カリ
ウム 30gN−エチル−N−
(β−メタ
ンスルホンアミドエチル)
−3−メチル−4−アミノ
アニリン硫酸塩 5.0gヒドロキシル
アミン硫酸塩 4,0g蛍光増白剤(WRITE
X4B、住人
化学製) 1.0g水を加えて
1000*fpH(25℃)
10.20還亘定界痰
水 400
dチオ硫酸アンモニウム
(70%) 150−亜硫酸ナ
トリウム 18gエチレンジアミン四
酢酸鉄
(I[[)アンモニウム 55gエチレン
ジアミン四酢酸二ナ
トリウム 5g水を加えて
1000dpH(25℃)
6.70第三表
第三表で明らかなように、本発明の染料を用いた試料(
2)〜(8)は膜中での安定性に優れ、また25℃−5
5%の相対感度が高く、25℃−85%での感度低下も
少ない。School charge 800+
dDiethylenetriaminepentaacetic acid 1.0g Nitrilotriacetic acid 1.5g Benzyl alcohol 15-diethylene glycol
10-Sodium sulfite 2.0
g Potassium bromide 0.5 g Potassium carbonate 30 g N-ethyl-N-
(β-Methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0g Hydroxylamine sulfate 4.0g Optical brightener (WRITE)
X4B, made by Juju Chemical) Add 1.0g water to 1000*fpH (25℃)
10.20 return wading phlegm water 400
dAmmonium thiosulfate (70%) 150-Sodium sulfite 18g Iron ethylenediaminetetraacetate (I [[) Ammonium 55g Disodium ethylenediaminetetraacetate 5g Add water 1000dpH (25℃)
6.70 Table 3 As is clear from Table 3, samples using the dye of the present invention (
2) to (8) have excellent stability in the membrane, and
The relative sensitivity at 5% is high, and there is little decrease in sensitivity at 25°C-85%.
実施例−2
実施例−1と同様にして、以下の層構成の試料(9)を
作製した。Example-2 A sample (9) having the following layer structure was prepared in the same manner as in Example-1.
第−層(青感性ハロゲン化銀乳剤層)
分光増悪剤(Sen−6)を添加した単分散塩臭化銀乳
剤(EM−7) 0.27ゼラチン
1.86イエローカブラー(ExY)
0.82溶媒(Solv−4)
0.35硬膜剤()Id) 0
.02第二層(混色防止層)
ゼラチン 0.99混色防止剤
(Cpd−4) 0.06溶媒(Solv−3
と5olv−4
体積比1:1) 0.12硬膜剤(H
d) 0.02第三層(緑感性ハ
ロゲン化銀乳剤層)
分光増悪剤(Sen−7,3)を添加した単分散塩臭化
銀乳剤(EM−8) 0.45ゼラチン
1.24マゼンタカプラー(ExM)
0.35色像安定剤(Cpd−6)
0.20色像安定剤(Cpd−7) 0.
03色像安定剤(Cpd−8) 0.03溶
媒(Solv−3と5olv−5
体積比l:2) 0.65硬膜剤()
(d) 0.01第四7!(紫外
線吸収層)
ゼラチン 1.58紫外線吸収
剤(UV−1/2/3
モル比1:4:4) 0.62混色防止
剤(Cpd−4) 0.05溶媒(Solv
−6) 0.34染料(Dy−1)
0.005染料(Dy−2)
0.015硬膜剤(Hd)
0.01第五層(赤感性ハロゲン化銀乳剤層)
分光増感剤(Sen−4,5)を添加した単分散塩臭化
銀乳剤(EM−9) 0.20ゼラチン
0.92シアンカプラー(ExC−3
) 0.15シアンカプラー(ExC−4)
0.18紫外線吸収剤(UV−1/3/4
モル比1:3:3) 0.17溶媒(S
olv−4) 0.20硬液剤(Hd)
0.01第六層(紫外線吸収層
)
ゼラチン 0.53紫外線吸収
剤(UV−1/2/3
モル比1:4:4) 0.21溶媒(S
olv−6) 0.08硬膜剤(Hd)
0.01第七層(保護層)
ゼラチン 1.33ポリビニル
アルコールのアク
リル変性共重合体(変性度
17%) 0.17流動パラフ
イン 0.03上記試料に用いたハロ
ゲン化銀乳剤の詳細を第四表に示した。-th layer (blue-sensitive silver halide emulsion layer) Monodisperse silver chlorobromide emulsion (EM-7) with added spectral enhancer (Sen-6) 0.27 gelatin
1.86 Yellow Cabler (ExY)
0.82 Solvent (Solv-4)
0.35 Hardener ()Id) 0
.. 02 Second layer (color mixing prevention layer) Gelatin 0.99 Color mixing prevention agent (Cpd-4) 0.06 Solvent (Solv-3
and 5olv-4 volume ratio 1:1) 0.12 Hardener (H
d) 0.02 third layer (green-sensitive silver halide emulsion layer) Monodispersed silver chlorobromide emulsion (EM-8) with added spectral enhancer (Sen-7,3) 0.45 Gelatin
1.24 magenta coupler (ExM)
0.35 color image stabilizer (Cpd-6)
0.20 Color image stabilizer (Cpd-7) 0.
03 Color image stabilizer (Cpd-8) 0.03 Solvent (Solv-3 and 5olv-5 volume ratio l:2) 0.65 Hardener ()
(d) 0.01 4th 7! (Ultraviolet absorbing layer) Gelatin 1.58 Ultraviolet absorber (UV-1/2/3 molar ratio 1:4:4) 0.62 Color mixing inhibitor (Cpd-4) 0.05 Solvent (Solv
-6) 0.34 dye (Dy-1)
0.005 dye (Dy-2)
0.015 Hardener (Hd)
0.01 Fifth layer (red-sensitive silver halide emulsion layer) Monodisperse silver chlorobromide emulsion (EM-9) with added spectral sensitizer (Sen-4,5) 0.20 Gelatin
0.92 cyan coupler (ExC-3
) 0.15 cyan coupler (ExC-4)
0.18 Ultraviolet absorber (UV-1/3/4 molar ratio 1:3:3) 0.17 Solvent (S
olv-4) 0.20 hardener (Hd)
0.01 Sixth layer (ultraviolet absorption layer) Gelatin 0.53 Ultraviolet absorber (UV-1/2/3 molar ratio 1:4:4) 0.21 Solvent (S
olv-6) 0.08 Hardener (Hd)
0.01 Seventh layer (protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.17 Liquid paraffin 0.03 Details of the silver halide emulsion used in the above sample Shown in the table.
第四表
変動係数=標準偏差/平均粒子径
(Sen−6)
■
5OffH・N(CJs)s
(Sen−7)
(ExC−3)
C7!
(EXC−4)
H
上記試料から、第四層の染料を変化させた試料01−0
6)を作製した。構成を第五表に示した。Table 4 Coefficient of variation = standard deviation/average particle diameter (Sen-6) ■ 5OffH・N(CJs)s (Sen-7) (ExC-3) C7! (EXC-4) H Sample 01-0 in which the dye of the fourth layer was changed from the above sample.
6) was produced. The composition is shown in Table 5.
第五表
試料(9)〜0[9について膜中の染料の安定性と露光
湿度依存性を調べた。染料の安定性については、生試料
を35℃−80%で2週間放置した後の染料の残存率で
評価した。また露光湿度依存性は、25℃−55%およ
び25℃−85%の条件で露光した後、下記の処理を行
い、光学濃度=1.0における相対感度を、変化の大き
い青感性ハロゲン化銀乳剤層について評価した。評価結
果は第六表に示した。The stability of the dye in the film and the exposure humidity dependence were investigated for samples (9) to 0[9 in Table 5. The stability of the dye was evaluated by the residual rate of the dye after leaving the raw sample at 35° C.-80% for 2 weeks. In addition, the exposure humidity dependence was determined by performing the following treatment after exposure at 25°C - 55% and 25°C - 85%, and adjusting the relative sensitivity at optical density = 1.0 using blue-sensitive silver halide, which has a large change. The emulsion layer was evaluated. The evaluation results are shown in Table 6.
処理工程 徹皮 回置
発色現像 35℃ 45秒
漂白定着 30〜35℃ 45秒
リンス0 30〜35℃ 20秒
リンス■ 30〜35℃ 20秒
リンス■ 30〜35℃ 20秒
リンス■ 30〜35℃ 30秒
乾 燥 70〜80℃ 60秒(リンス■→■
への3タンク向流方式とした。)各処理液の組成は以下
の通りである。Processing process Peel-through Rotary color development 35℃ 45 seconds bleach-fix 30-35℃ 45 seconds rinse 0 30-35℃ 20-second rinse ■ 30-35℃ 20-second rinse ■ 30-35℃ 20-second rinse ■ 30-35℃ Dry for 30 seconds 70-80℃ 60 seconds (rinse ■→■
A three-tank countercurrent flow system was adopted. ) The composition of each treatment liquid is as follows.
又魚屋1浪
水 800−
エチレンジアミン−N、N。Mata Fish Shop 1 Namizu 800-
Ethylenediamine-N,N.
N’、N’−テトラメチジ
ンホスホン酸 1.5gトリエチレ
ンジアミン(I゜
4ジアザビシクロ(2,2゜
2〕オクタン) 5.0g塩化ナトリ
ウム 1.4g炭酸カリウム
25gN−エチル−N−(β−メタ
ンスルホンアミドエチル)
−3−メチル−4−アミノ
アニリン硫酸塩 5.0gN、N−ジエ
チルヒドロキシ
ルアミン 4.2g蛍光増白剤
(UVITEX Cにチバ
ガイギ社) 2.0g水を加え
て 100(i−pH(25℃)
10.10星亘定豊戒
水 400
dチオ硫酸アンモニウム
(70%> 100yd亜硫酸
ナトリウム 18gエチレンジアミ
ン四酢酸鉄
(I[I)アンモニウム 55gエチレン
ジアミン四酢酸二ナ
トリウム 3g臭化アンモ
ニウム 40g氷酢酸
8g水を加えて
1000+*ff1pH(25℃)5.5
リンス液
イオン交換水(カルシウム、マグネシウムは各々3pp
m以下)
第六表
第六表で明らかなように、本発明の染料を用いた試料Q
l −Olは膜中での安定性に優れ、また25℃−55
%の相対感度が高く、25℃−85%での感度低下も少
ない。N',N'-tetramethidinephosphonic acid 1.5g triethylenediamine (I゜4diazabicyclo(2,2゜2)octane) 5.0g sodium chloride 1.4g potassium carbonate
25g N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 5.0g N,N-diethylhydroxylamine 4.2g optical brightener (UVITEX C, Ciba Geigi) 2. Add 0g water to 100 (i-pH (25℃)
10.10 Star Wataru Sadaho Kaisui 400
dAmmonium thiosulfate (70% > 100ydSodium sulfite 18gIron(I) ammonium ethylenediaminetetraacetate 55gDisodium ethylenediaminetetraacetate 3gAmmonium bromide 40g Glacial acetic acid
Add 8g water
1000+*ff1pH (25℃) 5.5 Rinse liquid ion exchange water (calcium, magnesium 3pp each
m or less) As is clear from Table 6, Sample Q using the dye of the present invention
l-Ol has excellent stability in the membrane and is stable at 25℃-55℃.
% relative sensitivity is high, and there is little decrease in sensitivity at 25° C.-85%.
(発明の効果)
本発明によれば、写真処理において脱色および溶出され
、かつ写真乳剤の写真特性、特に分光増悪性に悪影響を
及ぼさない新規な染料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を得ることができる。(Effects of the Invention) According to the present invention, the silver halide has a hydrophilic colloid layer containing a novel dye that is decolorized and eluted during photographic processing and does not adversely affect the photographic properties of the photographic emulsion, particularly the spectral enhancement properties. A photographic material can be obtained.
また本発明によれば、経時安定性に優れた、かつ露光依
存性の小さいハロゲン化銀写真感光材料を得ることがで
きる。Further, according to the present invention, a silver halide photographic material having excellent stability over time and low exposure dependence can be obtained.
特許出願人 富士写真フィルム株式会社手続補正書Patent applicant: Fuji Photo Film Co., Ltd. Procedural amendment
Claims (1)
)で表わされる染料を含むことを特徴とするハロゲン化
銀写真感光材料。 ( I ) ▲数式、化学式、表等があります▼ 式中、R_1及びR_3は各々少くとも1個のカルボン
酸基又はスルホン酸基を有するアリール基、アラルキル
基、アルキル基又は複素環基を表わし、カルボン酸基又
はスルホン酸基は2価の連結基を介してアリール基、ア
ラルキル基、アルキル基又は複素環基に結合してもよい
。 R_2及びR_4は各々−SO_2R_5、−SO_2
NR_5R_6又は−SOR_5(ここにR_5はアル
キル基、アラルキル基又はアリール基を表わし、R_6
は水素原子、アルキル基、アラルキル基又はアリール基
を表わし、R_5とR_6は連結して5又は6員環を形
成していても良い。)を表わし、L_1、L_2及びL
_3は各々メチン基を表わし、nは0、1又は2を表わ
し、M^■は水素又はその他のカチオンを表わす。[Claims] At least one hydrophilic colloid layer contains the following general formula (I
) A silver halide photographic material comprising a dye represented by: (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_1 and R_3 each represent an aryl group, an aralkyl group, an alkyl group, or a heterocyclic group having at least one carboxylic acid group or sulfonic acid group, The carboxylic acid group or sulfonic acid group may be bonded to an aryl group, aralkyl group, alkyl group, or heterocyclic group via a divalent linking group. R_2 and R_4 are respectively -SO_2R_5 and -SO_2
NR_5R_6 or -SOR_5 (where R_5 represents an alkyl group, an aralkyl group, or an aryl group, and R_6
represents a hydrogen atom, an alkyl group, an aralkyl group, or an aryl group, and R_5 and R_6 may be connected to form a 5- or 6-membered ring. ), L_1, L_2 and L
Each of _3 represents a methine group, n represents 0, 1 or 2, and M^■ represents hydrogen or other cation.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP235388A JPH01179150A (en) | 1988-01-08 | 1988-01-08 | Silver halide photographic sensitive material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP235388A JPH01179150A (en) | 1988-01-08 | 1988-01-08 | Silver halide photographic sensitive material |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH01179150A true JPH01179150A (en) | 1989-07-17 |
Family
ID=11526907
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP235388A Pending JPH01179150A (en) | 1988-01-08 | 1988-01-08 | Silver halide photographic sensitive material |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH01179150A (en) |
-
1988
- 1988-01-08 JP JP235388A patent/JPH01179150A/en active Pending
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