JPH01254944A - Silver halide photographic sensitive material - Google Patents
Silver halide photographic sensitive materialInfo
- Publication number
- JPH01254944A JPH01254944A JP8254488A JP8254488A JPH01254944A JP H01254944 A JPH01254944 A JP H01254944A JP 8254488 A JP8254488 A JP 8254488A JP 8254488 A JP8254488 A JP 8254488A JP H01254944 A JPH01254944 A JP H01254944A
- Authority
- JP
- Japan
- Prior art keywords
- group
- silver halide
- layer
- silver
- tables
- 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
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 99
- 239000004332 silver Substances 0.000 title claims abstract description 99
- -1 Silver halide Chemical class 0.000 title claims abstract description 80
- 239000000463 material Substances 0.000 title claims abstract description 44
- 239000000839 emulsion Substances 0.000 claims abstract description 46
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 32
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 57
- 150000001875 compounds Chemical group 0.000 claims description 25
- 239000000126 substance Substances 0.000 claims description 16
- 125000000623 heterocyclic group Chemical group 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 125000005647 linker group Chemical group 0.000 claims description 5
- 239000000470 constituent Substances 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- 239000010410 layer Substances 0.000 abstract description 61
- 238000012545 processing Methods 0.000 abstract description 13
- 239000002245 particle Substances 0.000 abstract description 12
- 230000035945 sensitivity Effects 0.000 abstract description 12
- 239000011241 protective layer Substances 0.000 abstract description 10
- 239000000203 mixture Substances 0.000 abstract description 6
- 229910052736 halogen Inorganic materials 0.000 abstract description 5
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 abstract description 4
- 229910021612 Silver iodide Inorganic materials 0.000 abstract description 4
- 150000002367 halogens Chemical class 0.000 abstract description 4
- 229940045105 silver iodide Drugs 0.000 abstract description 4
- 230000003287 optical effect Effects 0.000 abstract description 3
- 239000000543 intermediate Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 37
- 108010010803 Gelatin Proteins 0.000 description 16
- 239000000975 dye Substances 0.000 description 16
- 239000008273 gelatin Substances 0.000 description 16
- 229920000159 gelatin Polymers 0.000 description 16
- 235000019322 gelatine Nutrition 0.000 description 16
- 235000011852 gelatine desserts Nutrition 0.000 description 16
- 239000003795 chemical substances by application Substances 0.000 description 15
- 125000001424 substituent group Chemical group 0.000 description 15
- 206010070834 Sensitisation Diseases 0.000 description 11
- 238000000576 coating method Methods 0.000 description 10
- 230000008313 sensitization Effects 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 9
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 9
- 230000001235 sensitizing effect Effects 0.000 description 9
- 238000011161 development Methods 0.000 description 8
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000002562 thickening agent Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 229910001961 silver nitrate Inorganic materials 0.000 description 4
- 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 4
- 239000011593 sulfur Substances 0.000 description 4
- 125000004434 sulfur atom Chemical group 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical group OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 3
- 125000005115 alkyl carbamoyl group Chemical group 0.000 description 3
- 125000004448 alkyl carbonyl group Chemical group 0.000 description 3
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 125000004104 aryloxy group Chemical group 0.000 description 3
- 150000001565 benzotriazoles Chemical class 0.000 description 3
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 3
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 3
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 description 3
- 125000002837 carbocyclic group Chemical group 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 125000005740 oxycarbonyl group Chemical group [*:1]OC([*:2])=O 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- HBCQSNAFLVXVAY-UHFFFAOYSA-N pyrimidine-2-thiol Chemical class SC1=NC=CC=N1 HBCQSNAFLVXVAY-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 3
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 3
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 3
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 3
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 3
- 125000001302 tertiary amino group Chemical group 0.000 description 3
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- GGZHVNZHFYCSEV-UHFFFAOYSA-N 1-Phenyl-5-mercaptotetrazole Chemical compound SC1=NN=NN1C1=CC=CC=C1 GGZHVNZHFYCSEV-UHFFFAOYSA-N 0.000 description 2
- BAXOFTOLAUCFNW-UHFFFAOYSA-N 1H-indazole Chemical compound C1=CC=C2C=NNC2=C1 BAXOFTOLAUCFNW-UHFFFAOYSA-N 0.000 description 2
- ZPSJGADGUYYRKE-UHFFFAOYSA-N 2H-pyran-2-one Chemical compound O=C1C=CC=CO1 ZPSJGADGUYYRKE-UHFFFAOYSA-N 0.000 description 2
- OWIRCRREDNEXTA-UHFFFAOYSA-N 3-nitro-1h-indazole Chemical compound C1=CC=C2C([N+](=O)[O-])=NNC2=C1 OWIRCRREDNEXTA-UHFFFAOYSA-N 0.000 description 2
- MAGFQRLKWCCTQJ-UHFFFAOYSA-N 4-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(C=C)C=C1 MAGFQRLKWCCTQJ-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical group NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- ISAKRJDGNUQOIC-UHFFFAOYSA-N Uracil Chemical compound O=C1C=CNC(=O)N1 ISAKRJDGNUQOIC-UHFFFAOYSA-N 0.000 description 2
- 235000010724 Wisteria floribunda Nutrition 0.000 description 2
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 125000004423 acyloxy group Chemical group 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000005153 alkyl sulfamoyl group Chemical group 0.000 description 2
- 125000004644 alkyl sulfinyl group Chemical group 0.000 description 2
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 2
- 125000004414 alkyl thio group Chemical group 0.000 description 2
- 125000005281 alkyl ureido group Chemical group 0.000 description 2
- 125000005129 aryl carbonyl group Chemical group 0.000 description 2
- 125000004391 aryl sulfonyl group Chemical group 0.000 description 2
- 125000005110 aryl thio group Chemical group 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
- 239000011230 binding agent Substances 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 150000001661 cadmium Chemical class 0.000 description 2
- 125000005521 carbonamide group Chemical group 0.000 description 2
- 125000005587 carbonate group Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 150000005205 dihydroxybenzenes Chemical class 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 description 2
- 229940071161 dodecylbenzenesulfonate Drugs 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- CMCWWLVWPDLCRM-UHFFFAOYSA-N phenidone Chemical compound N1C(=O)CCN1C1=CC=CC=C1 CMCWWLVWPDLCRM-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000001397 quillaja saponaria molina bark Substances 0.000 description 2
- PMZDQRJGMBOQBF-UHFFFAOYSA-N quinolin-4-ol Chemical compound C1=CC=C2C(O)=CC=NC2=C1 PMZDQRJGMBOQBF-UHFFFAOYSA-N 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 229930182490 saponin Natural products 0.000 description 2
- 150000007949 saponins Chemical class 0.000 description 2
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 229940006186 sodium polystyrene sulfonate Drugs 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
- XHLHPRDBBAGVEG-UHFFFAOYSA-N 1-tetralone Chemical compound C1=CC=C2C(=O)CCCC2=C1 XHLHPRDBBAGVEG-UHFFFAOYSA-N 0.000 description 1
- 101150072531 10 gene Proteins 0.000 description 1
- CARFETJZUQORNQ-UHFFFAOYSA-N 1h-pyrrole-2-thiol Chemical class SC1=CC=CN1 CARFETJZUQORNQ-UHFFFAOYSA-N 0.000 description 1
- JAAIPIWKKXCNOC-UHFFFAOYSA-N 1h-tetrazol-1-ium-5-thiolate Chemical class SC1=NN=NN1 JAAIPIWKKXCNOC-UHFFFAOYSA-N 0.000 description 1
- HAZJTCQWIDBCCE-UHFFFAOYSA-N 1h-triazine-6-thione Chemical class SC1=CC=NN=N1 HAZJTCQWIDBCCE-UHFFFAOYSA-N 0.000 description 1
- BUWPZNOVIHAWHW-UHFFFAOYSA-N 2,3-dihydro-1h-quinolin-4-one Chemical compound C1=CC=C2C(=O)CCNC2=C1 BUWPZNOVIHAWHW-UHFFFAOYSA-N 0.000 description 1
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical class NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- AYPSHJCKSDNETA-UHFFFAOYSA-N 2-chloro-1h-benzimidazole Chemical class C1=CC=C2NC(Cl)=NC2=C1 AYPSHJCKSDNETA-UHFFFAOYSA-N 0.000 description 1
- FVRYCPZDHKLBNR-UHFFFAOYSA-N 2-mercaptoindole Chemical class C1=CC=C2NC(S)=CC2=C1 FVRYCPZDHKLBNR-UHFFFAOYSA-N 0.000 description 1
- KRTDQDCPEZRVGC-UHFFFAOYSA-N 2-nitro-1h-benzimidazole Chemical class C1=CC=C2NC([N+](=O)[O-])=NC2=C1 KRTDQDCPEZRVGC-UHFFFAOYSA-N 0.000 description 1
- RZPFVRFSYMUDJO-UHFFFAOYSA-N 2h-naphthalen-1-one Chemical compound C1=CC=C2C(=O)CC=CC2=C1 RZPFVRFSYMUDJO-UHFFFAOYSA-N 0.000 description 1
- JSIAIROWMJGMQZ-UHFFFAOYSA-N 2h-triazol-4-amine Chemical class NC1=CNN=N1 JSIAIROWMJGMQZ-UHFFFAOYSA-N 0.000 description 1
- CBHTTYDJRXOHHL-UHFFFAOYSA-N 2h-triazolo[4,5-c]pyridazine Chemical class N1=NC=CC2=C1N=NN2 CBHTTYDJRXOHHL-UHFFFAOYSA-N 0.000 description 1
- GOLORTLGFDVFDW-UHFFFAOYSA-N 3-(1h-benzimidazol-2-yl)-7-(diethylamino)chromen-2-one Chemical compound C1=CC=C2NC(C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=NC2=C1 GOLORTLGFDVFDW-UHFFFAOYSA-N 0.000 description 1
- NZTVIVQQYCNWHY-UHFFFAOYSA-N 4-(5-sulfanylidene-2h-tetrazol-1-yl)benzenesulfonamide Chemical compound C1=CC(S(=O)(=O)N)=CC=C1N1C(=S)N=NN1 NZTVIVQQYCNWHY-UHFFFAOYSA-N 0.000 description 1
- ZJSVZVAZMJXQNA-UHFFFAOYSA-N 4-(5-sulfanylidene-2h-tetrazol-1-yl)benzenesulfonic acid Chemical compound C1=CC(S(=O)(=O)O)=CC=C1N1C(=S)N=NN1 ZJSVZVAZMJXQNA-UHFFFAOYSA-N 0.000 description 1
- GDVFHEXRJFFDDB-UHFFFAOYSA-N 4-(5-sulfanylidene-2h-tetrazol-1-yl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1N1C(=S)N=NN1 GDVFHEXRJFFDDB-UHFFFAOYSA-N 0.000 description 1
- GCNTZFIIOFTKIY-UHFFFAOYSA-N 4-hydroxypyridine Chemical compound OC1=CC=NC=C1 GCNTZFIIOFTKIY-UHFFFAOYSA-N 0.000 description 1
- UTMDJGPRCLQPBT-UHFFFAOYSA-N 4-nitro-1h-1,2,3-benzotriazole Chemical class [O-][N+](=O)C1=CC=CC2=NNN=C12 UTMDJGPRCLQPBT-UHFFFAOYSA-N 0.000 description 1
- NEJMFSBXFBFELK-UHFFFAOYSA-N 4-nitro-1h-benzimidazole Chemical compound [O-][N+](=O)C1=CC=CC2=C1N=CN2 NEJMFSBXFBFELK-UHFFFAOYSA-N 0.000 description 1
- VRJHQPZVIGNGMX-UHFFFAOYSA-N 4-piperidinone Chemical compound O=C1CCNCC1 VRJHQPZVIGNGMX-UHFFFAOYSA-N 0.000 description 1
- FBPSQQAGVARBNR-UHFFFAOYSA-N 5-[2-(dimethylazaniumyl)ethylsulfanyl]-1,3,4-thiadiazole-2-thiolate Chemical compound CN(C)CCSC1=NNC(=S)S1 FBPSQQAGVARBNR-UHFFFAOYSA-N 0.000 description 1
- LRUDIIUSNGCQKF-UHFFFAOYSA-N 5-methyl-1H-benzotriazole Chemical compound C1=C(C)C=CC2=NNN=C21 LRUDIIUSNGCQKF-UHFFFAOYSA-N 0.000 description 1
- WSGURAYTCUVDQL-UHFFFAOYSA-N 5-nitro-1h-indazole Chemical compound [O-][N+](=O)C1=CC=C2NN=CC2=C1 WSGURAYTCUVDQL-UHFFFAOYSA-N 0.000 description 1
- AOCDQWRMYHJTMY-UHFFFAOYSA-N 5-nitro-2h-benzotriazole Chemical compound C1=C([N+](=O)[O-])C=CC2=NNN=C21 AOCDQWRMYHJTMY-UHFFFAOYSA-N 0.000 description 1
- GIQKIFWTIQDQMM-UHFFFAOYSA-N 5h-1,3-oxazole-2-thione Chemical compound S=C1OCC=N1 GIQKIFWTIQDQMM-UHFFFAOYSA-N 0.000 description 1
- KWHUHTFXMNQHAA-UHFFFAOYSA-N 6,7,8,9-tetrahydrobenzo[7]annulen-5-one Chemical compound O=C1CCCCC2=CC=CC=C12 KWHUHTFXMNQHAA-UHFFFAOYSA-N 0.000 description 1
- XPAZGLFMMUODDK-UHFFFAOYSA-N 6-nitro-1h-benzimidazole Chemical compound [O-][N+](=O)C1=CC=C2N=CNC2=C1 XPAZGLFMMUODDK-UHFFFAOYSA-N 0.000 description 1
- 125000003341 7 membered heterocyclic group Chemical group 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 101150021665 CTH gene Proteins 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 1
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- HWGBHCRJGXAGEU-UHFFFAOYSA-N Methylthiouracil Chemical compound CC1=CC(=O)NC(=S)N1 HWGBHCRJGXAGEU-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- SJUCACGNNJFHLB-UHFFFAOYSA-N O=C1N[ClH](=O)NC2=C1NC(=O)N2 Chemical class O=C1N[ClH](=O)NC2=C1NC(=O)N2 SJUCACGNNJFHLB-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- CVQUWLDCFXOXEN-UHFFFAOYSA-N Pyran-4-one Chemical compound O=C1C=COC=C1 CVQUWLDCFXOXEN-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000005910 alkyl carbonate group Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 1
- 229940101006 anhydrous sodium sulfite Drugs 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000005116 aryl carbamoyl group Chemical group 0.000 description 1
- 125000005161 aryl oxy carbonyl group Chemical group 0.000 description 1
- 125000005135 aryl sulfinyl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 150000001556 benzimidazoles Chemical class 0.000 description 1
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical class C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 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
- 150000001721 carbon Chemical group 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- OTAFHZMPRISVEM-UHFFFAOYSA-N chromone Chemical compound C1=CC=C2C(=O)C=COC2=C1 OTAFHZMPRISVEM-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000012792 core layer Substances 0.000 description 1
- WZCRDVTWUYLPTR-UHFFFAOYSA-N cyclohept-2-en-1-one Chemical compound O=C1CCCCC=C1 WZCRDVTWUYLPTR-UHFFFAOYSA-N 0.000 description 1
- CGZZMOTZOONQIA-UHFFFAOYSA-N cycloheptanone Chemical compound O=C1CCCCCC1 CGZZMOTZOONQIA-UHFFFAOYSA-N 0.000 description 1
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohex-2-enone Chemical compound O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 150000002344 gold compounds Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- ICPGNGZLHITQJI-UHFFFAOYSA-N iminosilver Chemical compound [Ag]=N ICPGNGZLHITQJI-UHFFFAOYSA-N 0.000 description 1
- QNXSIUBBGPHDDE-UHFFFAOYSA-N indan-1-one Chemical compound C1=CC=C2C(=O)CCC2=C1 QNXSIUBBGPHDDE-UHFFFAOYSA-N 0.000 description 1
- 150000002503 iridium Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- JMJRYTGVHCAYCT-UHFFFAOYSA-N oxan-4-one Chemical compound O=C1CCOCC1 JMJRYTGVHCAYCT-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- XVZFXCWDIKQLAS-UHFFFAOYSA-N phenyl 2-[(2-sulfanylidene-3h-1,3,4-thiadiazol-5-yl)sulfanyl]acetate Chemical compound S1C(S)=NN=C1SCC(=O)OC1=CC=CC=C1 XVZFXCWDIKQLAS-UHFFFAOYSA-N 0.000 description 1
- AZBGAMJVNYEBLF-UHFFFAOYSA-N phenyl 2h-benzotriazole-5-carboxylate Chemical compound C1=CC2=NNN=C2C=C1C(=O)OC1=CC=CC=C1 AZBGAMJVNYEBLF-UHFFFAOYSA-N 0.000 description 1
- KTULKOYQXCVEQE-UHFFFAOYSA-N phenyl 3-(5-sulfanylidene-2h-tetrazol-1-yl)benzoate Chemical compound C=1C=CC(N2C(N=NN2)=S)=CC=1C(=O)OC1=CC=CC=C1 KTULKOYQXCVEQE-UHFFFAOYSA-N 0.000 description 1
- YZNRQBAXZXHQOA-UHFFFAOYSA-N phenyl 4-(5-sulfanylidene-2h-tetrazol-1-yl)benzoate Chemical compound C=1C=C(N2C(N=NN2)=S)C=CC=1C(=O)OC1=CC=CC=C1 YZNRQBAXZXHQOA-UHFFFAOYSA-N 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- NDGRWYRVNANFNB-UHFFFAOYSA-N pyrazolidin-3-one Chemical class O=C1CCNN1 NDGRWYRVNANFNB-UHFFFAOYSA-N 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 150000003283 rhodium Chemical class 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229940001482 sodium sulfite Drugs 0.000 description 1
- 235000010265 sodium sulphite Nutrition 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
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 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
- 150000003567 thiocyanates Chemical class 0.000 description 1
- 125000005323 thioketone group Chemical group 0.000 description 1
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- 229940035893 uracil Drugs 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/0051—Tabular grain emulsions
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、銀画像を観察するハロゲン化銀黒白写真感光
材料に関し、特に単位現像銀量当りの光学濃度（カバリ
ングパワー）が高く、しかも銀画像の色調に優れ、高温
迅速処理に適したハロゲン化銀写真材料に関するもので
ある。Detailed Description of the Invention (Industrial Application Field) The present invention relates to a silver halide black-and-white photographic light-sensitive material for observing silver images, and in particular has a high optical density (covering power) per unit amount of developed silver and This invention relates to a silver halide photographic material that has excellent image tone and is suitable for high-temperature, rapid processing.
本発明は特に銀画像をシャーカステン上で観察する医療
用写真感光材料において有効である。The present invention is particularly effective in medical photographic materials in which silver images are observed on a Scherkasten.
（従来の技術）
銀画像を観察するハロゲン化銀黒白写真感光材料におい
て銀画像の色調は重要なポイントである。(Prior Art) The color tone of the silver image is an important point in silver halide black-and-white photographic materials for observing silver images.
近年、写真感光材料の現像工程は高温迅速処理が急速に
普及し、各種感材の自動現像機処理においても、その処
理時間は大巾に短縮されてきたが、その結果、銀画像の
色調が温ａｌｌ（黄褐色傾向）になりすぎる欠点があっ
た。銀画像の色調を制御す−る方法としては、硫黄原子
を含み銀に吸着しやすい化合物（例えばメルカプト化合
物、チアゾリン−チオン化合物）が有名である。しかし
ながら、これらの化合物は、写真感度を低下させる欠点
があった。In recent years, high-temperature, rapid processing has rapidly become popular in the development process of photographic light-sensitive materials, and the processing time for automatic processing of various light-sensitive materials has been greatly shortened, but as a result, the color tone of silver images has become It had the disadvantage of becoming too warm (tendency to yellowish brown). As a method for controlling the color tone of silver images, compounds containing sulfur atoms and easily adsorbed to silver (for example, mercapto compounds and thiazoline-thione compounds) are well known. However, these compounds have the drawback of decreasing photographic sensitivity.
また別の方法として、特に透過型写真感光材料において
は、支持体または該写真感光材料の構成層中のいずれか
に、上記銀画像の色調（温調）を補償する色味（補色の
関係にある青い色味）の、水に不溶または難溶の化合物
を含有せしめることがある。しかし、この方法では、素
現部分の濃度（Ｄｍ ｉ ｎ）が高くなってヌケが悪く
なったり、あるいは素現部分が青っぽくなりすぎたりす
る。As another method, particularly in transmission-type photographic materials, a color tone (complementary color relationship) that compensates for the color tone (temperature tone) of the silver image is added to either the support or the constituent layers of the photographic material. It may contain compounds that are insoluble or sparingly soluble in water, with a certain blue tint. However, with this method, the density (Dmin) of the exposed area becomes high, resulting in poor removal or the exposed area becomes too bluish.
さらに補償濃度が一定のため、画像銀の濃度により色調
が異なる結果となる。従って、この方法では十分好まし
い色調の画像は得られない。Furthermore, since the compensation density is constant, the resulting color tone varies depending on the density of the image silver. Therefore, with this method, it is not possible to obtain an image with a sufficiently desirable tone.
また近年、ハロゲン化銀写真感光材料の省銀化のために
、カバリングパワーの高い平板状粒子からなる乳剤が用
いられる様になってきているが、上記の高温迅速処理に
おける銀画像の温調化は、平板状粒子乳剤の場合に特に
著しく、種々の方法をもってしても、感度が高く、しか
も画像の色調が好ましい写真感光材料は得られていない
。In addition, in recent years, emulsions consisting of tabular grains with high covering power have been used to save silver in silver halide photographic materials. This is particularly noticeable in the case of tabular grain emulsions, and even if various methods are used, no photographic material with high sensitivity and favorable image tone can be obtained.
（発明の目的）
本発明の目的は、銀画像を観察するハロゲン化銀黒白写
真感光材料において、特に単位現像銀量当りの光学濃度
（カバリングパワー）が高く、しかも画像銀の色調に優
れ、高温迅速処理に適したハロゲン化銀黒白写真感光材
料を提供することである。(Objective of the Invention) An object of the present invention is to provide a silver halide black-and-white photographic light-sensitive material for observing silver images, which has a particularly high optical density (covering power) per unit amount of developed silver, excellent color tone of image silver, and high temperature. An object of the present invention is to provide a silver halide black-and-white photographic material suitable for rapid processing.
（発明の構成）
本発明の上記目的は、
支持体上に少なくとも１層の感光性ハロゲン化銀乳剤層
を有する黒白写真感光材料において、該乳剤層中の乳剤
粒子が、全粒子の投影面積の総和の７０％以上がアスペ
クト比３以上の平板状粒子からなり
さらに、該写真感光材料の構成層中の少なくとも１層に
下記一般式（Ｉ）で表わされる化合物を少なくとも１つ
含有することを特徴とするハロゲン化銀写真感光材料に
よって達成された。(Structure of the Invention) The above object of the present invention is to provide a black-and-white photographic material having at least one light-sensitive silver halide emulsion layer on a support, in which the emulsion grains in the emulsion layer have a projected area of all grains. At least 70% of the total consists of tabular grains with an aspect ratio of 3 or more, and at least one of the constituent layers of the photographic light-sensitive material contains at least one compound represented by the following general formula (I). This was achieved using a silver halide photographic light-sensitive material.
一般式（Ｉ）
％式％）
式中、Ｘｌはへテロ原子を介して炭素原子に結合してい
る２価の連結基を表わし、ＡはＡのヘテロ原子を介して
Ｘｌに結合している銀画像の色調を調節する基を表わし
、Ｒ１，、Ｒ冨及びＲ３は水素原子又は置換可能な基を
表わし、Ｒ１とＲ２及びＲ１とＲ３は結合して炭素環、
または複素環を形成してもよい。General formula (I) %Formula%) In the formula, Xl represents a divalent linking group bonded to a carbon atom via a heteroatom, and A is bonded to Xl via a heteroatom of A. Represents a group that adjusts the color tone of a silver image, R1, R value and R3 represent a hydrogen atom or a substitutable group, R1 and R2 and R1 and R3 are bonded to form a carbocyclic ring,
Alternatively, a heterocyclic ring may be formed.
でＲ４、ＲＳ 、 Ｒｈ ＳＲ？およびＲ１は水素原子
または置換可能な基を表わす、）を表わし、ｎ及びｍは
０又は１を表わす、ただし、ｍ＝ｏのとき、Ａで表わさ
れる基はＡのへテロ原子を介して炭素原子と結合する。So R4, RS, Rh SR? and R1 represents a hydrogen atom or a substitutable group), n and m represent 0 or 1, provided that when m=o, the group represented by A connects carbon atoms through the heteroatom of A. Combine with atoms.
Ｒ１は水素原子又は置換可能な基を表わし、置換可能な
基としてはアルキル基（好ましくは゛炭素数１〜２０の
もの）、アルケニル基（好ましくは炭素数２〜２０のも
の）、アリール基（好ましくは炭素数６〜２０のもの）
、アルコキシ基（好ましくは炭素数１〜２０のもの）、
了り−ルオキシ基（好ましくは炭素数６〜２０のもの）
、アルキルチオ基（好ましくは炭素数１〜２０のもの）
、アリールチオ基（好ましくは炭素数６〜２０のもの）
、アミノ基（無置換アミノ、好ましくは炭素数１〜２０
のアルキル基または炭素数６〜２０のアリール基で置換
した２級または３級アミノ基）、ヒドロキシ基などを表
わす。R1 represents a hydrogen atom or a substitutable group, and examples of the substitutable group include an alkyl group (preferably one having 1 to 20 carbon atoms), an alkenyl group (preferably one having 2 to 20 carbon atoms), and an aryl group (preferably one having 2 to 20 carbon atoms). has 6 to 20 carbon atoms)
, an alkoxy group (preferably one having 1 to 20 carbon atoms),
Ori-ruoxy group (preferably one with 6 to 20 carbon atoms)
, alkylthio group (preferably one having 1 to 20 carbon atoms)
, arylthio group (preferably one having 6 to 20 carbon atoms)
, amino group (unsubstituted amino, preferably carbon number 1-20
represents a secondary or tertiary amino group substituted with an alkyl group or an aryl group having 6 to 20 carbon atoms), a hydroxy group, etc.
さらに、Ｒ１はＲ２又はＲ３と結合して炭素環または複
素環（例えば５〜７員環）を形成してもよい、Ｒｘ、Ｒ
３は同一でも異なってもよく、各々水素原子または置換
可能な基を表わし、置換可能な基としてはハロゲン原子
（フッ素、塩素、臭素）、アルキル基（好ましくは炭素
数１〜２０のもの）、アリール基（好ましくは炭素数６
〜２０のもの）、アルコキシ基（好ましくは炭素数１〜
２０のもの）、アリールオキシ基（好ましくは炭素数６
〜２０のもの）、アルキルチオ基（好ましくは炭素数１
〜２０のもの）、アリールチオ基（好ましくは炭素数６
〜２０のもの）、アシルオキシ基（好ましくは炭素数２
〜２０のもの）、アミノ基（無置換アミノ、好ましくは
炭素数１〜２０のアルキル基、または炭素数６〜２ｏの
アリール基で１換した２級または３級のアミノ基）、カ
ルボンアミド基（好ましくは炭素数１〜２ｏのアルキル
カルボンアミド基、炭素数６〜２ｏのアリールカルボン
アミド基）、ウレイド基（好ましくは炭素数１〜２０の
アルキルウレイド基、炭素数６〜２０の了り−ルウレイ
ド基）、カルボキシ基、炭酸エステル基（好ましくは炭
素数１〜２ｏのアルキル炭酸エステル基、炭素数６〜２
ｏの了り−ル炭酸エステル基）、オキシカルボニル基（
好ましくは炭素数１〜２０のアルキルオキシカルボニル
１５、炭素数６〜２０の了り−ルオキシ力ルボニル基）
、カルバモイル基（好ましくは炭素数１〜２０のアルキ
ルカルバモイル基、炭素数６〜２゜の了り−ルカルバモ
イル基）、了シル基（好ましくは炭素数１〜２０のアル
キルカルボニル基、炭素数６〜２０のアリールカルボニ
ル基）、スルホ基、スルホニル基（好ましくは炭素数１
〜２ｏのアルキルスルホニル基、炭素数６〜２０のアリ
ールスルホニル基）、スルフィニル基（好ましくは炭素
数１〜２０のアルキルスルフィニル基、炭素数６〜２０
の了り−ルスルフィニル基）、スルファモイル基（好ま
しくは炭素数１〜２０のアルキルスルファモイル基、炭
素数６〜２０のアリールスルファモイル基）、シアノ基
、ニトロ基を表わす。Furthermore, R1 may be combined with R2 or R3 to form a carbocyclic or heterocyclic ring (e.g., a 5- to 7-membered ring), Rx, R
3 may be the same or different and each represents a hydrogen atom or a substitutable group, and substitutable groups include a halogen atom (fluorine, chlorine, bromine), an alkyl group (preferably one having 1 to 20 carbon atoms), Aryl group (preferably 6 carbon atoms)
~20), alkoxy groups (preferably 1~20 carbon atoms),
20), aryloxy group (preferably carbon number 6)
~20), alkylthio groups (preferably 1 carbon number)
~20), arylthio group (preferably 6 carbon atoms)
~20), acyloxy group (preferably 2 carbon atoms)
~20), amino group (unsubstituted amino, preferably a secondary or tertiary amino group substituted with an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 2 o carbon atoms), carbonamide group (preferably an alkylcarbonamide group having 1 to 2 carbon atoms, an arylcarbonamide group having 6 to 2 carbon atoms), a ureido group (preferably an alkylureido group having 1 to 20 carbon atoms, an alkylcarbonamide group having 6 to 20 carbon atoms), roureido group), carboxy group, carbonate group (preferably an alkyl carbonate group having 1 to 2 carbon atoms, 6 to 2 carbon atoms)
o's carbonate group), oxycarbonyl group (
Preferably an alkyloxycarbonyl group having 1 to 20 carbon atoms, an alkyloxycarbonyl group having 6 to 20 carbon atoms)
, a carbamoyl group (preferably an alkylcarbamoyl group having 1 to 20 carbon atoms, an alkylcarbamoyl group having 6 to 2 carbon atoms), a ryosyl group (preferably an alkylcarbonyl group having 1 to 20 carbon atoms, an alkylcarbonyl group having 6 to 20 carbon atoms) 20 arylcarbonyl groups), sulfo groups, sulfonyl groups (preferably 1 carbon number)
-2o alkylsulfonyl group, arylsulfonyl group having 6 to 20 carbon atoms), sulfinyl group (preferably an alkylsulfinyl group having 1 to 20 carbon atoms, 6 to 20 carbon atoms)
sulfamoyl group (preferably an alkylsulfamoyl group having 1 to 20 carbon atoms or an arylsulfamoyl group having 6 to 20 carbon atoms), a cyano group, or a nitro group.
シアノ基またはニトロ基を表わし、Ｒ４、Ｒ５、Ｒ“
Ｒ？及びＲ１はたがいに同一でも異なってもよく、各々
水素原子または置換可能な基を表わし、具体的置換基と
してはアルキル基（好ましくは炭素数１〜２０のもの）
、アルケニル基（好ましくは炭素数２〜２０のもの）、
了り−ル基（好ましくは炭素数６〜２０のもの）、アル
コキシ基（好ましくは炭素数１〜２０のもの）、アリー
ルオキシ基（好ましくは炭素数６〜２ｏのもの）、アシ
ルオキシ基（好ましくは炭素数２〜２ｏのもの）、アミ
ノ基（無置換アミノ基、好ましくは炭素数１〜２０のア
ルキル基、または炭素数６〜２０の了り−ル基で置換し
た２級または３級アミノ基）、カルボンアミド基（好ま
しくは炭素数１〜２０のアルキルカルボンアミド基、炭
素数６〜２０のアリールカルボンアミド基）、ウレイド
基（好ましくは炭素数１〜２０のアルキルウレイド基、
炭素数６〜２０のアリールウレイド基）、オキシカルボ
ニル基（好ましくは炭素数Ｉ〜２ｏのアルキルオキシカ
ルボニル基、炭素数６〜２ｏのアリールオキシカルボニ
ル基）、カルバモイル基（＆［Ｌ＜は炭素数１〜２０の
アルキルカルバモイル基、炭素数６〜２０のアリールカ
ルバモイル基）、アシル基（好ましくは炭素数１〜２ｏ
のアルキルカルボニル基、炭素数６〜２０のアリールカ
ルボニル基）、スルホニル基（好ましくは炭素数１〜２
０のアルキルスルホニル基、炭素数６〜２０のアリール
スルホニル基）、スルフィニル基（好ましくは炭素数１
〜２０のアルキルスルフィニル基、炭素数６〜２０のア
リールスルフィニル基）、スルファモイル基（好ましく
は炭素数１〜２０のアルキルスルファモイル基、炭素数
６〜２０のアリールスルファモイル基）を表わす、この
うちＲ？、Ｒ１の好ましい置換基としては、オキシカル
ボニル基、カルバモイル基、アシル基、スルホニル基、
スルファモイル基、スルフィニル基、シアノ基、ニトロ
基を挙げることができる。これらの置換基は１個以上の
置換基を有してもよく、置換基が２個以上あるときは同
じでも異ってもよく、具体的置換基としては前記Ｒ１の
置換基と同じものを挙げることができる Ｒ１とＲ３又
はＲ１とＲ１が結合して炭素環又は複素環を形成する場
合、好ましいものとして
具体的には下記の一般式（ＩＩ）、（ＩＩＩ）で表わさ
れるものを挙げることができる。Represents a cyano group or a nitro group, R4, R5, R"
R? and R1 may be the same or different and each represents a hydrogen atom or a substitutable group, and specific examples of the substituent include an alkyl group (preferably one having 1 to 20 carbon atoms);
, alkenyl group (preferably one having 2 to 20 carbon atoms),
Aryloxy group (preferably one with 6 to 20 carbon atoms), alkoxy group (preferably one with 1 to 20 carbon atoms), aryloxy group (preferably one with 6 to 2 carbon atoms), acyloxy group (preferably one with 6 to 2 carbon atoms) is one having 2 to 2 carbon atoms), an amino group (an unsubstituted amino group, preferably an alkyl group having 1 to 20 carbon atoms, or a secondary or tertiary amino group substituted with an alkyl group having 6 to 20 carbon atoms) group), a carbonamide group (preferably an alkylcarbonamide group having 1 to 20 carbon atoms, an arylcarbonamide group having 6 to 20 carbon atoms), a ureido group (preferably an alkylureido group having 1 to 20 carbon atoms,
an aryl ureido group having 6 to 20 carbon atoms), an oxycarbonyl group (preferably an alkyloxycarbonyl group having 1 to 2 carbon atoms, an aryloxycarbonyl group having 6 to 2 carbon atoms), a carbamoyl group (&[L< is a carbon number alkylcarbamoyl group having 1 to 20 carbon atoms, arylcarbamoyl group having 6 to 20 carbon atoms), acyl group (preferably 1 to 2 carbon atoms)
alkylcarbonyl group, arylcarbonyl group having 6 to 20 carbon atoms), sulfonyl group (preferably 1 to 2 carbon atoms)
0 alkylsulfonyl group, arylsulfonyl group having 6 to 20 carbon atoms), sulfinyl group (preferably 1 carbon number)
~20 alkylsulfinyl group, a C6-20 arylsulfinyl group), a sulfamoyl group (preferably a C1-20 alkylsulfamoyl group, a C6-20 arylsulfamoyl group), Of these, R? , Preferred substituents for R1 include an oxycarbonyl group, a carbamoyl group, an acyl group, a sulfonyl group,
Examples include sulfamoyl group, sulfinyl group, cyano group, and nitro group. These substituents may have one or more substituents, and when there are two or more substituents, they may be the same or different, and specific substituents include the same as the substituent for R1 above. When R1 and R3 or R1 and R1 combine to form a carbocycle or a heterocycle, preferred examples include those represented by the following general formulas (II) and (III). I can do it.
一般式（ＩＩ）
一般式（ＩＩＩ）
°゛゛・艮゛パパ
一般式（ｎ）において、Ｚｌ は炭素環または複素環を
形成するのに必要な原子群を表わす。General formula (II) General formula (III) °゛゛・艮゛appa In the general formula (n), Zl represents an atomic group necessary to form a carbocycle or a heterocycle.
具体的には、たとえば５員環、６員環、あるいは７Ｒ環
の炭素環、あるいは１個以上の窒素、酸素あるいは硫黄
原子等を含む５員環、６員環あるいは７員環の複素環で
あり、これらの炭素環あるいは複素環は適当な位置で縮
合環を形成しているものも包含する。Specifically, for example, a carbocyclic ring such as a 5-membered ring, a 6-membered ring, or a 7R ring, or a 5-membered ring, a 6-membered ring, or a 7-membered heterocyclic ring containing one or more nitrogen, oxygen, or sulfur atoms, etc. These carbocycles or heterocycles also include those forming fused rings at appropriate positions.
具体的には、シクロベンテノン、シクロヘキセノン、シ
クロヘプテノン、ベンゾシクロへブテノン、ベンゾシク
ロベンテノン、ベンゾシクロヘキセノン、４−ピリドン
、４−キノロン、２−ピロン、４−ピロン、ｌ−チオ−
２−ピロン、１−チオ−４−ピロン、クマリン、クロモ
ン、ウラシルなどの他
０ ０ｇ
０ などを挙げることが出来る。こ
こで、これらの炭素環あるいは複素環は１個以上の置換
基を有してもよく、置換基が２個以上あるときは同じで
も異ってもよい。具体的置換基としては前記Ｒ１の置換
基と同じものを挙げることができる。Specifically, cyclobentenone, cyclohexenone, cycloheptenone, benzocyclohebutenone, benzocyclobentenone, benzocyclohexenone, 4-pyridone, 4-quinolone, 2-pyrone, 4-pyrone, l-thio-
Examples include 2-pyrone, 1-thio-4-pyrone, coumarin, chromone, uracil, and the like. Here, these carbocycles or heterocycles may have one or more substituents, and when there are two or more substituents, they may be the same or different. Specific substituents include the same substituents as those for R1 above.
また、一般式（ＩＩ［）におけるＺＸは一般式（ＩＩ）
の２＋ と同じものを意味し、具体的にはシクロペンタ
ノン、シクロヘキサノン、シクロヘプタノン、ベンゾシ
クロヘプタノン、ベンゾシクロペンタノン、ベンゾシク
ロヘキサノン、４−テトラヒドロピリドン、４−ジヒド
ロキノロン、４−テトラヒドロピロン等が挙げられる。Furthermore, ZX in general formula (II[) is general formula (II)
2+ means the same as cyclopentanone, cyclohexanone, cycloheptanone, benzocycloheptanone, benzocyclopentanone, benzocyclohexanone, 4-tetrahydropyridone, 4-dihydroquinolone, 4-tetrahydropyrone etc.
これら炭素環あるいは複素環は置換基を１個以上存して
もよく、置換基が２個以上あるときは同じでも異っても
よい。These carbocycles or heterocycles may have one or more substituents, and when there are two or more substituents, they may be the same or different.
具体的置換基は前記Ｒ１の置換基と同じものを挙げるこ
とができる。Specific substituents include the same substituents as those for R1 above.
Ｒａ 、Ｒ１、ＸＩ及びＡ、ｍは一般式（りで挙げたも
のと同じものである。Ra, R1, XI, A, and m are the same as those listed in the general formula.
次にＡはＡの中のへテロ原子（例えば硫黄原子、窒素原
子、酸素原子等）を介して直接結合していても（ｍ＝０
）、あるいはＸｌを介して結合していてもよい、（ｍ−
１）
Ｘｌは２価の連結基を表わし、連結基中のへテロ原子（
例えば、硫黄原子、窒素原子、酸素原子等）を介して結
合しており、処理時（より具体的にはｐＨ９〜１２の条
件下で）にＸ’ −Ａとして解裂した後、速やかにＡを
放出する基を表わす。Next, even if A is directly bonded to A through a heteroatom (e.g. sulfur atom, nitrogen atom, oxygen atom, etc.) (m=0
), or may be bonded via Xl, (m-
1) Xl represents a divalent linking group, and the heteroatom (
For example, sulfur atoms, nitrogen atoms, oxygen atoms, etc.) are bonded to each other, and after being cleaved as X'-A during treatment (more specifically under conditions of pH 9 to 12), A represents a group that releases
この様な連結基としては、特開昭５４−１４５１３５号
明細書（英国特許公開２，０１０．８１８Ａ号）、米国
特許第４，２４８．９６２号、同４．４０９．３２３号
、英国特許筒２，０９６゜７８３号に記載の分子内開環
反応によりＡを放出するもの、英国特許筒２，０７２，
３６３号、特開昭５７−１５４，２３４号明細書等に記
載の分子内電子移動によってＡを放出するもの、特開昭
５７−１７９．８４２号等に記載の炭酸ガスの脱離を伴
ってＡを放出するもの、あるいは特開昭５９−９３４２
２号に記載のホルマリンの脱離を伴うでＡを放出するも
の等の連結基を挙げることができる。Examples of such a linking group include those described in JP-A-54-145135 (British Patent Publication No. 2,010.818A), U.S. Pat. No. 2,096°783, which releases A by an intramolecular ring-opening reaction; British Patent No. 2,072;
363, those that release A by intramolecular electron transfer as described in JP-A No. 57-154,234, etc., and those that are accompanied by desorption of carbon dioxide gas as described in JP-A-57-179.842, etc. Those that emit A or JP-A-59-9342
Examples include linking groups such as those described in No. 2 that release A with the elimination of formalin.
ＸＩ としてどのようなものを用いるかは１．Ａの放出
のタイミング、放出のコントＤ−ル、用いられるＡの種
類などに応し゛Ｃ選択して用いられる。What to use as XI?1. C is selected and used depending on the timing of release of A, the control of release, the type of A used, etc.
Ａで表わされる銀画像の色調を制ｊｉＩする化合物の例
として、ヘテロ環に結合するメルカプト基を有する化合
物、例えば置換あるいは無置換のメルカプトアゾール類
（具体的には１−フェニル−５−メルカプトテトラゾー
ル、１−（４−カルボキシフニニル）−５−メルカプト
テトラゾール、１−（４−スルホフェニル）−５−メル
カプトテトラゾール、１−（４−スルファモイルフェニ
ル）−５−メルカプトテトラゾール、２−メチルチオ−
５−メルカプト−１，，３，４−チアジアゾール、２−
フェニル−５−メルカプＩ−−−１．２．４−トリアゾ
ール、２−（２−ジメチルアミノエチルチオ）−５−メ
ルカプト−１，３，４−チアジアゾール、２−メルカプ
トベンゾチアゾール、２−メルカプトベンツイミダゾー
ル、２−メルカプトベンゾチアゾール、２−フェニル−
５−メルカプ）−１，３，４−オキサジアゾール６、ｌ
−（３−（３−メチルウレイド）フェニル） −５−メ
ルカプトテトラゾール、など）、置換あるいは無置換の
メルカプトアザインデン類（具体的には、６−メチル−
４−メルカプト−１，３，３ａ、？−テトラザインデン
、６−フェニル−，１−ノルカプトテトラザインデン、
４．６−シメチルー２−メルカプト−１，３，３ａ、７
−チトラザ・インデンなど）、置換あるいは無置換のメ
ルカプトピリミジン類（具体的には２−メルカプトピリ
ミジン、２−メルカプト−４−メチル−６−ヒドロキシ
ピリミジン、など）などがある。イミノ銀生成可能なヘ
テロ環化合物としては、例えば置換あるいは無置換のベ
ンゾトリアゾール類（具体的には、ベンゾトリアゾール
、５−ニトロベンゾトリアゾール、５−メチルベンゾト
リアゾール、など）ｒｓ、換あるいは無置換のイミダゾ
ール類（具体的にはインダゾール、５−ニトロインダゾ
ール、３−ニトロインダゾールなど）、置換あるいは無
置換のベンツイミダゾール類（具体的には、５−ニトロ
ベンツイミダゾール、４−ニトロベンツイミダゾール、
など）などがあげられる。Examples of compounds that control the color tone of silver images represented by A include compounds having a mercapto group bonded to a heterocycle, such as substituted or unsubstituted mercaptoazoles (specifically, 1-phenyl-5-mercaptotetrazole). , 1-(4-carboxyphenyl)-5-mercaptotetrazole, 1-(4-sulfophenyl)-5-mercaptotetrazole, 1-(4-sulfamoylphenyl)-5-mercaptotetrazole, 2-methylthio-
5-Mercapto-1,,3,4-thiadiazole, 2-
Phenyl-5-mercap I---1.2.4-triazole, 2-(2-dimethylaminoethylthio)-5-mercapto-1,3,4-thiadiazole, 2-mercaptobenzothiazole, 2-mercaptobenz imidazole, 2-mercaptobenzothiazole, 2-phenyl-
5-Mercap)-1,3,4-oxadiazole 6,l
-(3-(3-methylureido)phenyl)-5-mercaptotetrazole, etc.), substituted or unsubstituted mercaptoazaindenes (specifically, 6-methyl-
4-Mercapto-1,3,3a,? -tetrazaindene, 6-phenyl-,1-norcaptotetrazaindene,
4.6-dimethyl-2-mercapto-1,3,3a,7
-titraza-indene, etc.), substituted or unsubstituted mercaptopyrimidines (specifically, 2-mercaptopyrimidine, 2-mercapto-4-methyl-6-hydroxypyrimidine, etc.). Examples of heterocyclic compounds capable of producing iminosilver include substituted or unsubstituted benzotriazoles (specifically, benzotriazole, 5-nitrobenzotriazole, 5-methylbenzotriazole, etc.), rs, substituted or unsubstituted benzotriazoles, etc. imidazoles (specifically indazole, 5-nitroindazole, 3-nitroindazole, etc.), substituted or unsubstituted benzimidazoles (specifically, 5-nitrobenzimidazole, 4-nitrobenzimidazole,
etc.) etc.
またＡは現像処理工程において、−Ｃ式（Ｉ）の母核か
ら放出された後、銀画像の色調を調節する作用を有する
化合物となるものである。この化合物は更にその後、実
質的に色調を調節する作用を存しないか、あるいは著し
く減少した化合物に変化するものであってもよい。Further, after A is released from the mother nucleus of the -C formula (I) in the development process, it becomes a compound having the effect of adjusting the color tone of a silver image. The compound may then be transformed into a compound having substantially no or significantly reduced tone-adjusting effect.
具体的には１−（３−フェノキシカルボニルフェニル）
−５−メルカプトテトラゾール、１−（４−フェノキシ
カルボニルフェニル）−５−メルカプトテトラゾール、
１〜 （３−゛ンレインイミドフェニル）−５−メルカ
プトテトラゾール、５−（フェノキシカルボニル）ベン
ゾトリアゾール、２−フェノキシカルボニルメチルチオ
−５−メルカプト−１，３，４−チアジアゾールなどが
あげられる。Specifically, 1-(3-phenoxycarbonylphenyl)
-5-mercaptotetrazole, 1-(4-phenoxycarbonylphenyl)-5-mercaptotetrazole,
Examples include 1-(3-enleinimidophenyl)-5-mercaptotetrazole, 5-(phenoxycarbonyl)benzotriazole, and 2-phenoxycarbonylmethylthio-5-mercapto-1,3,4-thiadiazole.
Ａで表わされる化合物として好ましくは、ヘテロ環に結
合するメルカプト基を有する化合物があげられる。Preferably, the compound represented by A is a compound having a mercapto group bonded to a heterocycle.
以下に、本発明の一般式（Ｉ）で表わされる化合物の具
体例を示すが、これによって本発明の化合物が限定され
るわけではない。Specific examples of the compound represented by the general formula (I) of the present invention are shown below, but the compounds of the present invention are not limited thereto.
１ｈ （Ｉ−６） ＣＩコ ｏｚＮｎｚ ＮＨＵＮｔｌＵｌｌｓ Ｈ１ （Ｉ＝１ｊ） Ｈｉ （Ｉ−１２） Ｈ３ ＣＨ。1h (I-6) CI co ozNnz NHUNtlUlls H1 (I=1j) Hi (I-12) H3 CH.
（＋−１９）
〇
一般式（Ｉ）で表わされるブロックされた写真試薬は、
特開昭５９−２０１０５７号、特開昭６１−４３７３９
号、特開昭６１−９５３４７号等に記載の公知の合成法
により合成することができる。(+-19) 〇The blocked photographic reagent represented by general formula (I) is
JP-A-59-201057, JP-A-61-43739
It can be synthesized by a known synthesis method as described in JP-A No. 61-95347 and the like.
本発明のブロックされた写真試薬は２種以上組合せて使
用してもよい。Two or more blocked photographic reagents of the present invention may be used in combination.
本発明の一般式（Ｉ）で表わされる化合物は、ハロゲン
化銀写真感光材料のハロゲン化銀乳剤層、下塗り層、保
護層、中間層、フィルター層、アンチハレーシラン層、
その他のどの層に添加してもよい。The compound represented by the general formula (I) of the present invention includes a silver halide emulsion layer, an undercoat layer, a protective layer, an intermediate layer, a filter layer, an antihalation silane layer of a silver halide photographic light-sensitive material,
It may be added to any other layer.
本発明の一般式（Ｉ）の化合物の添加時期は、製造工程
中のいかなる時期を選んでもよいが、−般には塗布する
直前が好ましい。The compound of general formula (I) of the present invention may be added at any time during the manufacturing process, but is generally preferably immediately before coating.
本発明の一般式（Ｉ）の化合物は広い範囲で使用するこ
とができる。具体的にはＡの種類にもよるが、１０４モ
ル／ｒｄ 〜１０−’モル／ｒｒｒ、特に２×１０４モ
ル／Ｍ〜２Ｘ１０−’モル／イの範囲が好ましい。The compounds of general formula (I) according to the invention can be used in a wide range of ways. Specifically, although it depends on the type of A, a range of 104 mol/rd to 10-' mol/rrr, particularly 2 x 104 mol/M to 2 x 10-' mol/rrr, is preferable.
次に本発明に用いる平板状ハロゲン化銀粒子について述
べる。Next, the tabular silver halide grains used in the present invention will be described.
本発明の平板状ハロゲン化銀粒子は、好ましくは、その
直径／厚みの比（アスペクト比）が３以上であり、より
好ましくは５以上２０以下、より好ましくは５以上１０
以下（特に好ましくは５以上８以下）である。The tabular silver halide grains of the present invention preferably have a diameter/thickness ratio (aspect ratio) of 3 or more, more preferably 5 or more and 20 or less, and more preferably 5 or more and 10 or more.
or less (particularly preferably 5 or more and 8 or less).
ここにハロゲン化銀粒子の直径とは、粒子の投影面積に
等しい面積の円の直径をいう０本発明に於て平板状ハロ
ゲン化銀粒子の直径は好ましくは０．３〜１０μ、より
好ましくは０．３〜５．０μ、特に好ましくは０．５〜
２．５μである。The diameter of the silver halide grains herein refers to the diameter of a circle with an area equal to the projected area of the grains. In the present invention, the diameter of the tabular silver halide grains is preferably 0.3 to 10μ, more preferably 0.3-5.0μ, particularly preferably 0.5-5.0μ
It is 2.5μ.
一般に、平板状ハロゲン化銀粒子は、２つの平行な面を
有する平板状であり、従って本発明に於ける「厚み」と
は平板状ハロゲン化銀粒子を構成する２つの平行な面の
距離で表わされる。In general, tabular silver halide grains are tabular with two parallel surfaces, and therefore "thickness" in the present invention refers to the distance between the two parallel surfaces constituting the tabular silver halide grains. expressed.
本発明が有効な厚みとしては０．３μｍ以下、好ましく
は０．２μｍ以下、０．０５μｍ以上がよい。The thickness for which the present invention is effective is 0.3 μm or less, preferably 0.2 μm or less, and 0.05 μm or more.
平板状ハロゲン化銀粒子のハロゲン組成としては塩化銀
、塩臭化銀、臭化銀、沃臭化銀、沃塩臭化銀のいずれを
用いてもよいが、特に沃化銀含量が１０モル％以下であ
ることが好ましい。The halogen composition of the tabular silver halide grains may be any of silver chloride, silver chlorobromide, silver bromide, silver iodobromide, and silver iodochlorobromide, but in particular silver iodide containing 10 mol % or less.
次に平板状ハロゲン化銀粒子の製法について述べる。Next, a method for producing tabular silver halide grains will be described.
平板状ハロゲン化銀粒子の製法としては、当業界で知ら
れた方法を適宜、組合せることにより成し得る。The tabular silver halide grains can be produced by appropriately combining methods known in the art.
たとえばｐＢｒｌ、３以下の比較的高ｐＡｇ値の雰囲気
中で平板状粒子が重量で４０％以上存在する種晶を形成
し、同程度のｐＢｒ値に保ちつつ銀及びハロゲン溶液を
同時に添加しつつ種晶を成長させることにより得られる
。For example, in an atmosphere with a relatively high pAg value of pBrl, 3 or less, a seed crystal in which tabular grains are present in an amount of 40% or more by weight is formed, and while maintaining the pBr value at the same level, silver and halogen solutions are simultaneously added. Obtained by growing crystals.
この粒子成長過程に於て、新たな結晶核が発生しないよ
うに銀及びハロゲン溶液を添加することが望ましい。During this grain growth process, it is desirable to add a silver and halogen solution to prevent the generation of new crystal nuclei.
平板状ハロゲン化銀粒子の大きさは、温度調節、溶剤の
種類や量の選択、粒子成長時に用いる銀塩、及びハロゲ
ン化物の添加速度等をコントロールすることにより調製
できる。The size of tabular silver halide grains can be adjusted by controlling temperature adjustment, selection of the type and amount of solvent, silver salt used during grain growth, rate of addition of halide, etc.
本発明の平板ハロゲン化銀粒子の製造時に、必要に応じ
てハロゲン化銀溶剤を用いることにより、粒子サイズ粒
子の形状（直径／厚み比など）、粒子のサイズ分布、粒
子の成長速度をコントロールできる。溶剤の使用量は反
応溶液の１０−”〜１゜０重量％、特に１０−！〜１０
−１重量％が好ましい。When producing the tabular silver halide grains of the present invention, grain size and shape (diameter/thickness ratio, etc.), grain size distribution, and grain growth rate can be controlled by using a silver halide solvent as necessary. . The amount of the solvent used is 10-'' to 1.0% by weight of the reaction solution, especially 10-! to 10% by weight.
-1% by weight is preferred.
例えば溶剤の使用量の増加とともに粒子サイズ分布を単
分散化し、成長速度を速めることが出来る。一方、溶剤
の使用量とともに粒子の厚みが増加する傾向もある。For example, as the amount of solvent used increases, the particle size distribution can be made monodisperse and the growth rate can be accelerated. On the other hand, there is also a tendency for the thickness of the particles to increase with the amount of solvent used.
しばしば用いられるハロゲン化銀溶剤としては、アンモ
ニア、チオエーテル、チオ尿素類を挙げることが出来る
。チオエーテルに関しては、米国特許第３，２７１，１
５７号、同第３． ７９０． ３８７号、同第３，５７
４．６２８号等を参考にすることが出来る。Often used silver halide solvents include ammonia, thioethers and thioureas. Regarding thioethers, U.S. Pat. No. 3,271,1
No. 57, same No. 3. 790. No. 387, same No. 3,57
4.628 etc. can be referred to.
本発明の平板状ハロゲン化銀粒子の製造時に、粒子成長
を速める為に添加する、銀塩溶液（例えばＡｇＮ０．水
溶液）とハロゲン化物溶液（例えばＫＢｒ水溶液）の添
加速度、添加量、添加濃度を上昇させる方法が好ましく
用いられる。When manufacturing the tabular silver halide grains of the present invention, the addition rate, amount, and concentration of silver salt solution (for example, AgN0. aqueous solution) and halide solution (for example, KBr aqueous solution) that are added to accelerate grain growth are determined. A method of raising the temperature is preferably used.
これらの方法に関しては例えば英国特許第１゜３３５．
９２５号、米国特許第３，６７２．９００号、同第３，
６５０，７５７号、同第４，２４２．４４５号、特開昭
５５−１４２３２９号、同５５−１５８１２４号等の記
載を参考にすることが出来る。These methods are described, for example, in British Patent No. 1°335.
No. 925, U.S. Patent No. 3,672.900, U.S. Patent No. 3,
650,757, 4,242.445, JP-A-55-142329, JP-A-55-158124, etc. can be referred to.
本発明の平板状ハロゲン化銀粒子は、必要により化学増
感をすることが出来る。The tabular silver halide grains of the present invention can be chemically sensitized if necessary.
化学増感方法としてはいわゆる金化合物による金増感法
（例えば米国特許第２．４４８，０６０号、同３，３２
０．０６９号）又はイリジウム、白金、ロジウム、パラ
ジウム等の金属による増悪法（例えば米国特許第２，４
４８，０６０号、同２．５６６．２４５号、同２，５６
６．２６３号）或いは含硫黄化合物を用いる硫黄増感法
（例えば米国特許第２．２２２．２６４号）、或いは錫
塩類、ポリアミン等による還元増感法（例えば米国特許
第２，４８７．８５０号、同２． ５１８． ６９８号
、同２，５２１，９２５号）、或いはこれらの２つ以上
の組あわせを用いることができる。Chemical sensitization methods include so-called gold sensitization methods using gold compounds (for example, U.S. Pat. Nos. 2,448,060 and 3,32).
No. 0.069) or aggravation methods using metals such as iridium, platinum, rhodium, palladium (e.g., U.S. Pat.
No. 48,060, No. 2.566.245, No. 2,56
6.263) or a sulfur sensitization method using a sulfur-containing compound (for example, U.S. Pat. No. 2,222.264), or a reduction sensitization method using tin salts, polyamines, etc. (for example, U.S. Pat. No. 2,487.850). , No. 2.518.698, No. 2,521,925), or a combination of two or more of these can be used.
特に省銀の観点から、本発明の平板状ハロゲン化銀粒子
は金増感又は硫黄増感、或いはこれらの併用が好ましい
。Particularly from the viewpoint of saving silver, the tabular silver halide grains of the present invention are preferably gold-sensitized, sulfur-sensitized, or a combination thereof.
本発明の平板状ハロゲン化銀粒子を含有する層中には、
該平板状粒子が核層の全ハロゲン化銀粒子に対して重量
比で４０％以上、特に６０％以上存在することが好まし
い。In the layer containing the tabular silver halide grains of the present invention,
It is preferable that the tabular grains are present in an amount of 40% or more, particularly 60% or more by weight of all the silver halide grains in the core layer.
平板状ハロゲン化銀粒子を含イｆする層の厚さは０．３
〜５．０Ｉノ、、特に０．５〜３．０μであることが好
ましい。The thickness of the layer containing tabular silver halide grains is 0.3
~5.0μ, particularly preferably 0.5~3.0μ.
又、平板状ハロゲン化銀％子の塗布量（ハ側について）
は０．５〜６ｇ／ｒｒｒ、特に０゜５〜４Ｇ／３ｆｆｌ
であることが好ましい。Also, the coating amount of tabular silver halide (for side C)
is 0.5~6g/rrr, especially 0゜5~4G/3ffl
It is preferable that
本発明の平板状ハロゲン化銀粒子を含有する層のその他
の構成、例えばバ１゛ンダー、硬化剤、カブリ防止剤、
ハロゲン化銀の安定化剤、界面活性剤、分光増感色素、
染料、紫外線吸収剤、化学増感剤、等については特に制
限はなく、例えばＢｅ５ｅａｒｅｈ Ｄｔｓｃｌｏｓ
ｕｒｅｌ ７６巻、２２〜２８１（Ｉ９７８年１２月）
の記載を参考にすることが出来る。Other constituents of the layer containing the tabular silver halide grains of the present invention, such as a binder, a hardening agent, an antifoggant,
Silver halide stabilizers, surfactants, spectral sensitizing dyes,
There are no particular restrictions on dyes, ultraviolet absorbers, chemical sensitizers, etc., such as Be5eareh Dtsclos.
Urel Volume 76, 22-281 (December 1978)
You can refer to the description.
本発明のハロゲン化銀写真感光材料の乳剤層には、平板
状ハロゲン化根粒子以り）に、通常のハロゲン化銀粒子
を含有させるこ志ができる。これらは、Ｐ、 Ｇｌａｆ
ｋｉｄｅｓ著 Ｃｈｉｍｉｅ ｅｔ Ｐｈｙｓｉｑ
ｕｅＰｈｏｔｏｇｒａｐｈｉｑｕｅ （Ｐａｕｌ Ｍ
ｏｎｔｅ１社刊 １９６７年）、Ｇ、 Ｆ、 Ｄｕ
ｆｆＩｎ著 ＰｈｏｔｏＲｒａｐｈｉｃ Ｉ！ｍｕｌ
ｓｉｏｒ＋Ｃｈｅｍｉ！１ｔｒｙ （ＴＩ化 Ｆｏｃ
ａｌ Ｐｒｅｓｓ刊１９６刊年９６６年 Ｌ、 Ｚｓ
ｌｉｋｍａｎ ｓｔ ａｌ著 Ｍａｋｉｎｇ ａ
ｎｄ Ｃｏａｔ、ｉｎｇＰｈｏｔｏｇｒａｐｈｉｃ
［ｉｍｕｌｓｉｏｎ （Ｔｈｅ Ｆｏｃａｌ Ｐ
ｒｅｓｓ １１１．１９６４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、°すなわち、酸性法、
中性法、アンモニア法等のいずれでもよく、また可溶性
銀塩と可溶性ハロゲン塩を反応させる形式としては片側
混合法、同時混合法、それらの組合せなどのいずれを用
いてもよい。The emulsion layer of the silver halide photographic light-sensitive material of the present invention may contain ordinary silver halide grains in addition to the tabular halide root grains. These are P, Glaf
Chimie et Physiq by kids
uePhotographique (Paul M
onte1, 1967), G, F, Du
Written by ffIn PhotoRraphic I! mul
sior+chemi! 1try (TI Foc
al Press Published 196 Year 966 L, Zs
Making a by likman st al
nd Coat, ingPhotographic
[imulsion (The Focal P
ress 111.1964), i.e., the acid method;
Any of the neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method, a combination thereof, or the like.
粒子を銀イオン過剰の下において形成させる方法（いわ
ゆる逆混合法）を用いることもできる。It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).
同時混合法の一つの形式とし７てハロゲン化銀の生成さ
れる液相中のｐＡｇを一定に保つ方法、すなわちいわゆ
るコンドロールド・ダブルジェット法を用いることもで
きる。As one type of simultaneous mixing method 7, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, the so-called Chondrald double jet method can also be used.
ハロゲン化銀としては、臭化銀、沃臭化銀、沃塩臭化銀
、塩臭化銀、塩化銀などいずれのものでもよい。The silver halide may be any one such as silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride.
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、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。また、必要により
、Ｖ板状ハロゲン化銀粒子と同じように化学増感をする
ことができる。In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present. Further, if necessary, chemical sensitization can be carried out in the same manner as the V plate-like silver halide grains.
本発明に用いられる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、種種の化合物を含有さ
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、ニトロベンズ
イミダゾール類、クロロベンズイミダゾール類、プロモ
ベンズイミグゾール類、メルカプト千アゾール類１、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、アミノトリア
ゾール類、ベンゾトリアゾール類、ニトロベンゾトリア
ゾール頓、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）など；メルカプｉピ
リミジン類；メルカプトトリアジン類；たとえばオキサ
ゾリンチオンのようなチオケト化合物；アザインデン類
、たとえば１−リアザインデン類、テトラアザインデン
類（特に４−ヒトミキシ置換（Ｉ，３，３ａ、７）テト
ラアザインデン類）、ペンタアザインデン類など；ベン
ゼン′ｆ−、ｔスルフォン酸、ベンゼンスルフィン酸、
ベントンスルフオン酸アミド等のようなカブリ防止剤ま
たは安定剤として知らイ１か多くの化合物苓加えること
ができる、例えば米国特許３゜９５４．４７４号、同３
，９８２．９４７号、特公昭５２−２８．６６０号に記
載されｌ−ものを用いることができる。The photographic emulsion used in the present invention includes steps in the manufacturing process of light-sensitive materials,
Various compounds can be included for the purpose of preventing fog during storage or photographic processing or for stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, promobenzimigzoles, mercaptothianazoles 1, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles. , aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), etc.; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinthione; azaindenes , such as 1-riazaindenes, tetraazaindenes (especially 4-human-mixi-substituted (I, 3, 3a, 7) tetraazaindenes), pentaazaindenes, etc.; benzene'f-, t-sulfonic acid, benzenesulfinic acid ,
One or more compounds known as antifoggants or stabilizers, such as bentone sulfonamide, etc., can be added, e.g., U.S. Pat. No. 3,954,474;
, No. 982.947 and Japanese Patent Publication No. 52-28.660 can be used.
本発明に用いられている写真乳剤し」１、メチン色素類
その他によって分光増感されてよい。The photographic emulsions used in the present invention may be spectrally sensitized with methine dyes and others.
有用な増感色素は例えばドイツ特許９２９．０８０号、
米国特許間２，４９３．７４８号、同２゜５０３．７７
６号、同２，５１９．００ｉ号、同２．９１２．３２９
号、同３，６５６，９５９号、同３，６７２．８９７号
、同３．６９４．２１７号、同４．０２５，３４９号、
同４． ０４６． ５７２号、英国特許１，２４２．５
８８号、特公昭４４−１４０３０号、同５２−２４８４
４号に記載されたものである。Useful sensitizing dyes include, for example, German Patent No. 929.080;
U.S. Patent No. 2,493.748, U.S. Pat. No. 2,503.77
No. 6, No. 2,519.00i, No. 2.912.329
No. 3,656,959, No. 3,672.897, No. 3.694.217, No. 4.025,349,
Same 4. 046. No. 572, British Patent No. 1,242.5
No. 88, Special Publication No. 14030/1973, No. 52-2484
This is what is described in No. 4.
これらの増感色素は単独に用いてもよいが、それらの組
合せを用いてもよく、増感色素の組合せは特に強色増感
の目的でしばしば用いられる。その代表例は米国特許２
，６８８．５４５号、同２゜９７７．２２９号、同３，
３９７，０６０号、同３．５２２．０５２号、同３，５
２７，６４１号、同３．６１７，２９３号、同３，６２
８．９６４号、同３，６６６．４８０号、同３． ６７
２． ８９８号、同３，６７９，４２８号、同３，７０
３゜３７７号、同３，８１４．６０９号、同３，８３７
．８６２号、同４，０２６，７０７号、英国特許１，３
４４，２８１号、同１，５０７．８０３号、特公昭４３
−４９３６号、同５３−１２３７５号、特開昭５２−１
１０６１８号、同５２−１０９９２５号に記載されてい
る。These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. A typical example is US Patent 2
, No. 688.545, No. 2゜977.229, No. 3,
No. 397,060, No. 3.522.052, No. 3.5
No. 27,641, No. 3.617,293, No. 3,62
No. 8.964, No. 3,666.480, No. 3. 67
2. No. 898, No. 3,679,428, No. 3,70
3゜377, 3,814.609, 3,837
．． No. 862, No. 4,026,707, British Patent No. 1, 3
No. 44,281, No. 1,507.803, Special Publication No. 1973
No.-4936, No. 53-12375, JP-A-52-1
No. 10618 and No. 52-109925.
増感色素とともに、それ自身分光増感作用をもたない色
素あるいは可視光を実質的に吸収しない物質であって、
強色増感を示す物質を乳剤中に含んでもよい、たとえば
含チッ素異節環基で置換されたアミノスチルベン化合物
（たとえば米国特許２．９３３，３９０号、同３，６３
５，７２１号に記載のもの）、芳香族有機酸ホルムアル
デヒド縮金物（たとえば米国特許３，７４３，５１０号
に記載のもの）、カドミウム塩、アザインデン化合物な
どを含んでもよい、米国特許３，６１５゜６１３号、同
３，６１５，６４１号、同３．６１７．２９５号、同３
，６３５，７２１号に記載の組合せは特に有用である。Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
The emulsion may contain a substance exhibiting supersensitization, such as an aminostilbene compound substituted with a nitrogen-containing heterocyclic group (for example, U.S. Pat. Nos. 2,933,390 and 3,63).
5,721), aromatic organic acid formaldehyde condensates (such as those described in U.S. Pat. No. 3,743,510), cadmium salts, azaindene compounds, etc., U.S. Pat. No. 613, No. 3,615,641, No. 3.617.295, No. 3
, 635,721 are particularly useful.
本発明のハロゲン化銀写真感光材料の乳剤層のその他の
構成については特に制限はなく、必要に応じて種々の添
加剤を用いることができる０例えば、Ｒｅ５ｅａｒｃｈ
Ｄｉｓｃｌｏｓｕｒｅｌ ７６巻２２〜２８頁（Ｉ９
７８年１２月）に記載されたバインダー、界面活性剤、
染料、紫外線吸収剤、硬膜剤、塗布助剤、増粘剤などを
用いることができる。There are no particular restrictions on other structures of the emulsion layer of the silver halide photographic light-sensitive material of the present invention, and various additives may be used as required.
Disclosure Vol. 76, pp. 22-28 (I9
binder, surfactant, described in December 1978)
Dyes, ultraviolet absorbers, hardeners, coating aids, thickeners, and the like can be used.
本発明の写真材料は、その表面に、ゼラチン或いは水溶
性ポリビニル化合物又はアクリルアミド重合体などの合
成高分子物質又は天然高分子物質（例えば米国特許第３
，１４２，５６８号、同３゜１９３．３８６号、同３，
０６２，６７４号）を主成分とする表面保護層を有する
ことが好ましい。The photographic material of the present invention has a synthetic or natural polymeric material such as gelatin, a water-soluble polyvinyl compound, or an acrylamide polymer on its surface (for example, US Pat.
, No. 142,568, No. 3゜193.386, No. 3,
062,674) as a main component.
表面保護層には、ゼラチン又は他の高分子物質の他に、
界面活性剤、帯電防止剤、マント剤、すべり剤、硬化剤
、増粘剤等を含有することが出来る。In addition to gelatin or other polymeric substances, the surface protective layer may include:
It can contain a surfactant, an antistatic agent, a capping agent, a slipping agent, a hardening agent, a thickening agent, and the like.
本発明の写真材料は、その他、必要に応じて、中間層、
フィルター層、ハレーシラン防止層などを有することが
できる。In addition, the photographic material of the present invention may optionally include an intermediate layer,
It can have a filter layer, a haleysilane prevention layer, etc.
本発明の写真感光材料において写真乳剤層その他の層は
写真感光材料に通常用いられているプラスチックフィル
ム、紙などの可撓性支持体に塗布される。可撓性支持体
として有用なものは、硝酸セルロース、酢酸セルロース
、酢酸酪酸セルロース、ポリスチレン、ポリ塩化ビニル
、ポリエチレンテレフタレート、ポリカーボネート等の
半合成または合成高分子から成るフィルム、バライタ層
またはα−オレフィンポリマー（例えばポリエチレン、
ポリプロピレン、エチレン／ブテン共重合体）等を塗布
またはラミネートした紙等である。In the photographic material of the present invention, the photographic emulsion layer and other layers are coated on a flexible support such as a plastic film or paper that is commonly used in photographic materials. Useful as flexible supports are films of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, baryta layers or alpha-olefin polymers. (e.g. polyethylene,
Paper coated or laminated with polypropylene, ethylene/butene copolymer, etc.
支持体は染料や顔料を用いて着色されてもよい。The support may be colored using dyes or pigments.
遮光の目的で黒色にしてもよい、これらの支持体の表面
は一般に、写真乳剤層等との接着をよくするために下塗
処理される。下塗層は、染料や顔料を用いて着色されて
もよい、支持体表面は下塗処理の前または後に、コロナ
放電、紫外線照射、火焔処理等を施してもよい。The surface of these supports, which may be black for the purpose of blocking light, is generally subjected to a subbing treatment to improve adhesion with photographic emulsion layers and the like. The undercoat layer may be colored using a dye or pigment, and the surface of the support may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. before or after the undercoat treatment.
本発明に於て、支持体上に平板粒子を含む層、乳剤層、
表面保護層を塗布する方法としては、特に制限はないが
、例えば米国特許第２，７６１゜４１８号、同第３，５
０８，９４７号、同第２゜７６１．７９１号等に記載の
多層同時塗布方法を好ましく用いることが出来る。In the present invention, a layer containing tabular grains, an emulsion layer,
There are no particular limitations on the method for applying the surface protective layer, but for example, U.S. Pat.
The multilayer simultaneous coating method described in Japanese Patent No. 08,947 and Japanese Patent No. 2761.791 can be preferably used.
本発明の写真材料の層構成については種々の態様をとり
うる０例えば、（Ｉ）支持体上に本発明に係わる平板ハ
ロゲン化銀粒子を含む層を設け、その上に比較的粒子サ
イズの大きい（０，５〜３゜０μ）高感度球状、又は直
径／厚み比が５以下の多面体のハロゲン化銀粒子を含有
するハロゲン化銀乳剤層を設け、さらにその上にゼラチ
ンその他の表面保護層を設ける、（２）支持体上に平板
ハロゲン化銀粒子を含む層を設け、さらにその上に複数
層のハロゲン化銀乳剤層を設け、さらにその上にゼラチ
ン表面保護層を設ける、（３）支持体上に１層のハロゲ
ン化銀乳剤層を設け、さらにその上に平板ハロゲン化銀
粒子を含む層を設け、さらにその上に高感度ハロゲン化
銀乳剤層を設け、さらにその上にゼラチン表面保護層を
設ける、く４）支持体上に紫外線吸収剤又は染料を含む
層、平板ハロゲン化銀粒子を含む層、ハロゲン化銀乳剤
層、ゼラチン表面保護層をこの順に設ける。The layer structure of the photographic material of the present invention can take various forms. For example, (I) a layer containing tabular silver halide grains according to the present invention is provided on a support, and a layer containing relatively large grains is provided on the support. (0.5-3°0μ) A silver halide emulsion layer containing highly sensitive spherical or polyhedral silver halide grains with a diameter/thickness ratio of 5 or less is provided, and a surface protective layer such as gelatin is further applied thereon. (2) providing a layer containing tabular silver halide grains on a support, further providing a plurality of silver halide emulsion layers thereon, and further providing a gelatin surface protective layer thereon; (3) supporting; One silver halide emulsion layer is provided on the body, a layer containing tabular silver halide grains is provided on top of that, a highly sensitive silver halide emulsion layer is provided on top of that, and a gelatin surface protection layer is further provided on top of that. 4) A layer containing an ultraviolet absorber or dye, a layer containing tabular silver halide grains, a silver halide emulsion layer, and a gelatin surface protective layer are provided on the support in this order.
（５）支持体上に平板ハロゲン化銀及び紫外線吸収剤又
は染料を含む層、ハロゲン化銀乳剤層、ゼラチン表面保
護層をこの順に設ける。これらの態様において、ハロゲ
ン化銀乳剤層は、必ずも一層である必要はなく、異なっ
た波長に分光増感された複数のハロゲン化銀乳剤層から
なっていてもよい。(5) A layer containing tabular silver halide and an ultraviolet absorber or dye, a silver halide emulsion layer, and a gelatin surface protective layer are provided in this order on the support. In these embodiments, the silver halide emulsion layer does not necessarily have to be a single layer, but may consist of a plurality of silver halide emulsion layers spectrally sensitized to different wavelengths.
本発明のハ目ゲン化銀写真感光材料は、具体的には、Ｘ
−レイ感光材料（間接Ｘ−レイ用、直接Ｘ−レイ用）、
リス型感光材料、黒白印画紙、黒白ネガフィルムなどの
黒白写真怒光材料を含むものである。Specifically, the silver halide photographic light-sensitive material of the present invention includes
- Ray-sensitive materials (for indirect X-ray, direct X-ray),
This includes black-and-white photographic materials such as squirrel-type photosensitive materials, black-and-white photographic paper, and black-and-white negative film.
本発明の感光材料の写真処理には、例えばリサーチ０デ
イスクロージ＋ −（Ｒｅｓｅａｒｃｈ Ｄｉｓｃｌ
ｏｓｕｒｅ）１７６号第２８〜３０頁（ＲＤ−１７６４
３）に記載されているような、公知の方法及び公知の処
理液のいずれをも適用することができる。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。For photographic processing of the light-sensitive material of the present invention, for example, Research Discl + - (Research Discl + -
osure) No. 176, pages 28-30 (RD-1764
Any of the known methods and known treatment liquids as described in 3) can be applied. The processing temperature is usually selected between 18°C and 50°C, but temperatures below 18°C or above 50°C may also be used.
黒白写真処理する場合に用いる現像液は、知られている
現像主薬を含むことができる。現像主薬としては、ジヒ
ドロキシベンゼン類（たとえばハイドロキノン）、３−
ピラゾリドン類（たとえば１−フェニル−３−ピラゾリ
ドン）、アミノフェノール類（たとえばＮ−メチル−ｐ
−アミンフェノールなどを単独もしくは組合せて用いる
ことができる。現像液には一般にこの他公知の保恒剤、
アルカリ剤、ｐＨ１ｌ衝剤、カブリ防止剤などを含み、
さらに必要に応じ溶解助剤、色調剤、現像促進剤（例え
ば４級塩、ヒドラジン、ベンジルアルコール）、界面活
性剤、消泡剤、硬水軟化剤、硬膜剤（例えばグルタルア
ルデヒド）、粘性付与剤などを含んでもよい。The developer used in black-and-white photographic processing can contain known developing agents. As developing agents, dihydroxybenzenes (e.g. hydroquinone), 3-
Pyrazolidones (e.g. 1-phenyl-3-pyrazolidone), aminophenols (e.g. N-methyl-p
-Amine phenols and the like can be used alone or in combination. The developer generally contains other known preservatives,
Contains alkaline agent, pH1L buffer agent, antifoggant, etc.
Furthermore, as required, solubilizing agents, color toners, development accelerators (e.g. quaternary salts, hydrazine, benzyl alcohol), surfactants, antifoaming agents, water softeners, hardeners (e.g. glutaraldehyde), viscosity imparting agents It may also include.
本発明の写真乳剤には、いわゆる「リス型」の現像処理
を適用することができる。「リス型」現像処理とは線画
像の、写真的再現、あるいはハーフトーン画像の網点に
よる写真的再現のために、通常ジヒドロキシベンゼン類
を現像主薬とし、低い亜硫酸イオン濃度の下で、現像過
程を伝染的に行なわせる現像処理のことをいう（詳細は
メースン著［フォトグラフインク・プロセッシング・ケ
ミストリーＪ （Ｉ９６６年） １６３〜１６５ペー
ジに記述されている）。The photographic emulsion of the present invention can be subjected to a so-called "lith type" development process. "Lith-type" development processing is a development process in which dihydroxybenzenes are usually used as a developing agent and a low sulfite ion concentration is used for photographic reproduction of line images or halftone dot photographic reproduction of halftone images. (Details are described in Mason, Photographic Ink Processing Chemistry J (1966), pages 163-165).
現像処理の特殊な形式として、現像主薬を感光材料中、
たとえば乳剤層中に含み、感光材料をアルカリ水溶液中
で処理して現像を行なわせる方法を用いてもよい、現像
主薬のうち疎水性のものはリサーチディスクロージャ１
６９号（ＲＤ−１６９２８）米国特許第２，７３９，８
９０号、英国特許第８１３，２５３号又は西独国特許第
１，５４７．７６３号などに記載の種々の方法で乳剤層
中に含ませることができる。このような現像処理は、チ
オシアン酸塩による銀塩安定化処理と組合せてもよい。As a special form of development processing, a developing agent is added to the light-sensitive material.
For example, hydrophobic developing agents may be included in the emulsion layer and developed by processing the photosensitive material in an alkaline aqueous solution, according to Research Disclosure 1.
No. 69 (RD-16928) U.S. Patent No. 2,739,8
They can be incorporated into the emulsion layer in a variety of ways, such as those described in US Pat. No. 90, UK Pat. Such development treatment may be combined with silver salt stabilization treatment with thiocyanate.
定着液としては一般に用いられる組成のものを用いるこ
とができる。定着剤としてはチオ硫酸塩、チオシアン酸
塩のほか、定着剤としての効果が知られている有機硫黄
化合物を用いることができる。As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as fixing agents can be used.
定着液には硬膜剤として水溶性アルミニウム塩を含んで
もよい。The fixing solution may contain a water-soluble aluminum salt as a hardening agent.
（実施例） 次に、本発明について具体的に説明する。(Example) Next, the present invention will be specifically explained.
実施例１
（Ｉ）比較用球状粒子乳剤Ａの調製
ダブルジェット法によりアンモニアの存在下で沃臭化銀
（沃化銀３モル％）のじゃが芋型粒子を形成しく平均投
影面積直径０．５２μｍ）、塩化金酸塩及びチオ硫酸ナ
トリウムで化学増感した。Example 1 (I) Preparation of comparative spherical grain emulsion A Potato-shaped grains of silver iodobromide (3 mol % silver iodide) were formed in the presence of ammonia by a double jet method (average projected area diameter 0.52 μm). , chemically sensitized with chlorauric acid salts and sodium thiosulfate.
化学増感終了後、カブリ防止剤４−ヒドロキシ−６−メ
チル−１，３，３ａ、？−テトラザインデンを添加し、
下記の構造式の増感色素（Ｘ−１）をハロゲン化銀粒子
１モル当り２００ｍｇ添加してオルソ増感をほどこした
。After chemical sensitization, antifoggant 4-hydroxy-6-methyl-1,3,3a, ? - adding tetrazaindene;
Ortho sensitization was carried out by adding 200 mg of a sensitizing dye (X-1) having the following structural formula per mole of silver halide grains.
（Ｘ−１）
ｉＨ５
ＣｔＨｓ （Ｃｕｔ） ＊５Ｏｓ−さらに
塗布助剤としてドデシルベンゼンスルホン酸塩および増
粘剤ボリポタシウムｐ−ビニルベンゼンスルホネートを
添加し、乳剤層の基本処方とした。この時の銀／ゼラチ
ンの重量比は１．３５であった。一方、表面像ＮＮとし
て、ゼラチンの他にポリメチルメタクリレート微粒子、
サポニン、ポリスチレンスルホン酸ソーダなどを含有し
た７ｗｔ％、ゼラチン水溶液を用意した。(X-1) iH5 CtHs (Cut) *5Os- Furthermore, dodecylbenzenesulfonate as a coating aid and polypotassium p-vinylbenzenesulfonate as a thickener were added to form the basic formulation of the emulsion layer. The weight ratio of silver/gelatin at this time was 1.35. On the other hand, as the surface image NN, in addition to gelatin, polymethyl methacrylate fine particles,
A 7 wt % gelatin aqueous solution containing saponin, sodium polystyrene sulfonate, etc. was prepared.
この乳剤層に、第１表に示すような割合で、本発明の化
合物を添加して、ポリエチレンテレフタレート支持体上
に同時に塗布、乾燥することにより写真材料■〜■を作
成した。塗布銀量は片面−２゜５ ｇ／ｌｄとし両面に
塗布した。The compounds of the present invention were added to this emulsion layer in the proportions shown in Table 1, and photographic materials 1 to 2 were prepared by simultaneously coating and drying on a polyethylene terephthalate support. The amount of silver coated was -2.5 g/ld on one side, and both sides were coated.
（２）平板状粒子乳剤Ｂの調製
水１１にゼラチン３０ｇ、臭化カリ６ｇを加え５０℃に
保った容器中に攪拌しながら硝酸銀水溶液（硝酸銀とし
て４ｇ）と沃化カリ０．１５ｇを含む臭化カリ水溶液を
１分間かけてダブルジェット法で添加した。さらに硝酸
銀水溶液（硝酸銀として１４５ｇ）と沃化カリ４．２ｇ
を含む臭化カリ水溶液をダブルジェット法で添加した。(2) Preparation of tabular grain emulsion B 30 g of gelatin and 6 g of potassium bromide were added to water 11, and while stirring in a container kept at 50°C, an odor containing an aqueous silver nitrate solution (4 g as silver nitrate) and 0.15 g of potassium iodide was added. The potassium chloride aqueous solution was added over 1 minute using a double jet method. Furthermore, silver nitrate aqueous solution (145g as silver nitrate) and potassium iodide 4.2g
An aqueous solution of potassium bromide containing was added using a double jet method.
こめ時の添加流速は、添加終了時の流速が、添加開始時
の５倍となるように流量加速をおこなった。The addition flow rate at the time of addition was accelerated so that the flow rate at the end of addition was five times that at the start of addition.
添加終了後、沈降法により３５℃にて可溶性塩類を除去
したのち４０℃に昇温しでゼラチン７５ｇを連添し、ｐ
Ｈを６．７に調製した。得られた乳剤は投影面積直径が
０．６２μｍ、平均厚み０゜０９５μｍの平板状粒子で
、沃化銀含量は３モル％であった。この乳剤に、金、イ
オウ増感を併用して化学増感をほどこした。化学増感終
了後、カブリ防止剤４−ヒドロキシ−６−メチル−１，
３゜３ａ、７−チトラザインデンを添加し、下記の構造
式の増感色素（Ｘ−２）をハロゲン化銀粒子１モル当り
６００ｍｇ添加してオルソ増感をほどこした。′さらに
塗布助剤としてドデシルベンゼンスルホン酸塩および増
粘剤ボリポタシウムｐ−ビニルベンゼンスルホネートを
添加し、乳剤層の基本処方とした。この時の銀／ゼラチ
ンの重量比は１゜０５であった。一方、表面保護層とし
て、ゼラチ（Ｘ−２）
（Ｃｕ鵞）ｓ （ＣＨｚ：ｈ
５０ｓＯＳＯＪａ
ンの他にポリメチルメタクリレート微粒子、サポニン、
ポリスチレンスルホン酸ソーダなどを含有した７ｗｔ％
ゼラチン水溶液を用意した。第１表に示すような割合で
、本発明の化合物を添加して、ポリエチレンテレフタレ
ート支持体上に表面保護層と同時に塗布、乾燥すること
により写真材料■〜［相］を作成した。After the addition, soluble salts were removed at 35°C by the sedimentation method, the temperature was raised to 40°C, and 75 g of gelatin was continuously added.
H was adjusted to 6.7. The resulting emulsion consisted of tabular grains with a projected area diameter of 0.62 .mu.m and an average thickness of 0.095 .mu.m, and the silver iodide content was 3 mol %. This emulsion was chemically sensitized using gold and sulfur sensitization. After chemical sensitization, antifoggant 4-hydroxy-6-methyl-1,
3°3a,7-chitrazaindene was added, and 600 mg of a sensitizing dye (X-2) having the following structural formula per mole of silver halide grains was added to effect ortho-sensitization. ' Furthermore, dodecylbenzenesulfonate as a coating aid and polypotassium p-vinylbenzenesulfonate as a thickener were added to form the basic formulation of the emulsion layer. The weight ratio of silver/gelatin at this time was 1.05. On the other hand, as a surface protective layer, gelatin (X-2) (Cu)s (CHz: h
In addition to 50sOSOJa, polymethyl methacrylate fine particles, saponin,
7wt% containing sodium polystyrene sulfonate etc.
An aqueous gelatin solution was prepared. The compounds of the present invention were added in the proportions shown in Table 1, coated on a polyethylene terephthalate support at the same time as the surface protective layer, and dried to prepare photographic materials (1) to [phase].
塗布銀量は片面１．８ｇ／イとし両面に塗布した。The amount of silver coated was 1.8 g/a per side, and the coating was applied to both sides.
（３）平板状粒子乳剤Ｃの調製
（２）の平板状粒子乳剤Ｂの調製条件に対してダブルジ
ェット法で添加したノ１０ゲン溶液中の沃化カリをすべ
て除いた０反応容器内の温度は５５℃とした。得られた
平板状乳剤は投影面積直径が０．７５μｍ１平均厚み０
．１２０μｍであった。(3) Preparation of Tabular Grain Emulsion C Temperature in the reaction vessel at which all potassium iodide in the No. 10 gene solution added by the double jet method was removed under the preparation conditions of Tabular Grain Emulsion B in (2). The temperature was 55°C. The resulting tabular emulsion has a projected area diameter of 0.75 μm and an average thickness of 0.
．． It was 120 μm.
この乳剤に金・イオウ増感を併用して化学増感をほどこ
した。This emulsion was chemically sensitized using gold/sulfur sensitization.
このあと増感色素（Ｘ−２）をハロゲン化銀粒子１モル
当り５５０ｍｇ添加してオルソ増悪をほどこした。Thereafter, 550 mg of sensitizing dye (X-2) was added per mole of silver halide grains to effect ortho-enhancement.
この乳剤の銀／ゼラチンの重量比は１．０５であった。The silver/gelatin weight ratio of this emulsion was 1.05.
（２）の平板状粒子乳剤Ｂの場合と同様に塗布助荊、増
粘剤等を添加し、表面保ｉｉ層と共に第１表のような構
成の試料を■〜■を塗布して作成した。Coating additives, thickeners, etc. were added in the same manner as in the case of tabular grain emulsion B in (2), and samples having the configurations shown in Table 1 together with the surface retaining layer were prepared by coating ■ to ■. .
塗布銀量は片面１．９ｇ／ｎ（と１２両面に塗布した。The amount of silver coated was 1.9 g/n on one side (and 12 coated on both sides).
（４）感度の評価
各々の試料に、連続ウェッジをとおして、白色光にて１
／１０３−ｉｔ光を与えたのち、富士写真フィルム■製
の自動現像機「富士Ｘレイブロセソザ−ＦＰＭ４０００
Ｊにて現像した。(4) Sensitivity evaluation Each sample was exposed to white light through a continuous wedge.
After applying /103-it light, the automatic processor "Fuji X Ray Processor FPM4000" manufactured by Fuji Photo Film
Developed at J.
現像液、定着液は下記の組成とした。The developer and fixer had the following compositions.
（現像液）
１−フェニル−３〜ピラゾリドン １．５ｇヒドロキ
ノン ３０ｇ５−二１０イン
ダゾール ０．２５ｇ臭化カリウム
３．０ｇ無水亜硫酸ナトリウム
５０ｇ水酸化カリウム
３０ｇ硼酸 １０ｇグ
ルタルアルデヒド ５ｇ水を加えて
全量を１７！とする。(Developer) 1-phenyl-3-pyrazolidone 1.5g Hydroquinone 30g 5-210 indazole 0.25g Potassium bromide
3.0g anhydrous sodium sulfite
50g potassium hydroxide
30g boric acid 10g glutaraldehyde 5g Add water to make the total amount 17! shall be.
（ｐＨは１０．２０に調製した。）
（定着液）
チオ硫酸アンモニウム ２００．０ｇ亜硫酸ナ
トリウム（無水） ２０．０ｇ硼酸
８．０ｇエチレンジアミン四
酢酸二ナトリウム
０．１ｇ
硫酸アルミニウム １５．０ｇ硫酸
２．０ｇ氷酢酸
２２．０ｇ水を加えて
１． （Ｉ（ｐＨは４．２０に調製する
。）
感度はカブリ濃度＋０．５の濃度を与える露光量の逆数
の対数で表わし１、相対感度は試料■の感度を１００と
して評価した。(The pH was adjusted to 10.20.) (Fixer) Ammonium thiosulfate 200.0g Sodium sulfite (anhydrous) 20.0g Boric acid
8.0g Disodium ethylenediaminetetraacetate 0.1g Aluminum sulfate 15.0g Sulfuric acid
2.0g glacial acetic acid
Add 22.0g water
1. (I (pH was adjusted to 4.20). Sensitivity was expressed as the logarithm of the reciprocal of the exposure amount that gives a density of fog density + 0.5, and relative sensitivity was evaluated based on the sensitivity of sample (2) as 100.
く５）色調の評価
各々の試料を富士写真フィルム＠製（、−４オルソ増感
紙にはさんでＸ線逼影し、感度の評価（４）と同様の方
法で現像処理を行い、得られた画像の色調を評価した。5) Evaluation of color tone Each sample was exposed to X-rays by sandwiching it between Fuji Photo Film@ (-4 ortho intensifying screens) and developed in the same manner as in sensitivity evaluation (4). The color tone of the image was evaluated.
Ｏ好ましい色調である。O is a desirable color tone.
へ やや劣る色調であるが実用上許容範囲である。Although the color tone is slightly inferior, it is within an acceptable range for practical purposes.
以との様にして得られた結果を第１表に示した８第１表
から明らかな様に、本発明の試料１０、試１１．１３の
みが、高感でカバリングパワーが高く、しかも色調が好
ましいことがよくわかる。The results obtained as described above are shown in Table 1.8 As is clear from Table 1, only Sample 10 and Trial 11.13 of the present invention had high sensitivity and high covering power, and also had a good color tone. It is clear that .
実施例２
実施例１の（２）と同様の方法で、第２表に示す本発明
の化合物を含む試料［相］〜［相］を塗布して作成した
。Example 2 Samples [phase] to [phase] containing the compounds of the present invention shown in Table 2 were coated and prepared in the same manner as in Example 1 (2).
実施例１の（４）〜（５）と同様にして感度、カバリン
グパワー、色調の評価を行い、得られた結果を第２表に
示した。相対感度は試料■の値１００とした。Sensitivity, covering power, and color tone were evaluated in the same manner as in (4) and (5) of Example 1, and the obtained results are shown in Table 2. The relative sensitivity was set to the value 100 for sample ■.
第２表から明らかな様に、本発明の試料［相］と［相］
〜［相］は感度、カバリングパワーが高く、しかも色調
が好ましいことがわかる。As is clear from Table 2, the sample [phase] and [phase] of the present invention
It can be seen that ~[phase] has high sensitivity and covering power, and has a preferable color tone.
手続補正書
１ｏ事件の表示 昭和６３年を願第ｔコお１号２
、発明の名称 ノ・ロゲン化銀写真感光材料３、補正
をする者
ル件との関係 胃許出願人住 所 神奈
川県南足柄市中沼２１０番地連絡先 〒１０６東京都港
区西麻布２丁目２６番３０号４、補正の対象 明細書
の「発明の詳細な説明」の欄
５、補正の内容
明細書の「発明の詳細な説明」の項の記ａｔ下記の通り
補正する。Indication of Procedural Amendment 1o Case Wishing for 1986 No. t Co. 1 No. 2
, Title of the invention: Silver halogenide photographic light-sensitive material 3, Person making the amendment Relationship with the matter: Address of applicant: 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Contact address: 2-26-30 Nishiazabu, Minato-ku, Tokyo 106 No. 4, Subject of amendment Column 5 of the "Detailed Description of the Invention" of the specification, contents of the amendment The entry in the "Detailed Description of the Invention" section of the specification is amended as follows.
ｌ）第１１行目の 「画像−の濃度」を 「画像の濃度」 と補正する。l) Line 11 "Image density" "Image density" and correct it.
２）第一２０頁（／−Ａ）の構造式？ 「 」 と補正する。2) Structural formula on page 120 (/-A)? " ” and correct it.
３）第２１頁（ｌ−？）の構造式合 「 」 と補正する。3) Structural formula combination on page 21 (l-?) " ” and correct it.
４）第コを頁１６行目の 「粒子サイズ粒子の形状」ｔ 「粒子サイズ、粒子の形状」 と補正する。4) Put No. 1 on page 16. "Particle size particle shape" "Particle size, particle shape" and correct it.
５）第３１頁７行目の ｒ／Ｊｍ”Ｊ’ｋ ｒ／ｍ”Ｊ と補正する。5) Page 31, line 7 r/Jm”J’k r/m”J and correct it.
６）第３１頁１３行目の ［Ｂｅ５ｅａｒｃｈ Ｊｋ ［Ｒｅ５ｅａｒｃｈ Ｊ と補正する。6) Page 31, line 13 [Be5arch Jk [Re5earch J and correct it.
７）第３−２頁コ行目の ｒ ＴＨＥ Ｊ ’ｋ 「Ｔｈｅ Ｊ と補正する。7) Page 3-2, line 7 r THE J’k “The J and correct it.
８）第Ｊ７ｊｉ（コＯ行目の 「エチレン／ブテン」を 「エチレン／ブテン」 と補正する。8) No. J7ji (row 0) "ethylene/butene" "Ethylene/Butene" and correct it.
９）第弘７頁ｌ／行目の ［試料ｔ■〜◎ｌ’ｋ 「試料■〜０を」 と補正する。9) Hiroshi 7th page l/line [Sample t■〜◎l’k "Sample ~0" and correct it.
１ｏ）第４ｃｔ員／／行目の 「ｌ１ｌＩ製し次。」ｔ 「調整し友。」 と補正する。1o) 4th ct member // line "I made it next time."t “Adjustment friend.” and correct it.
１１）第４ＣＰ頁２行目の 「調製する。」を 「調整する。」 と補正する。11) 2nd line of 4th CP page "Prepare." "adjust." and correct it.
１２）第≠２頁１７〜／Ｉ行目の 「本発明の試料１０．試料／ｊＪ茫 「本発明の試料ｑ）、試料◎」 と補正する。12) No. ≠ 2nd page 17th to /Ith line "Sample 10 of the present invention. Sample/jJ "Sample q) of the present invention, sample ◎" and correct it.
１３〕第ｊ／頁７行目の 「試料■の値」を 「実施ガ／の試料■の値を」 と補正する。13] No. j/page 7th line "Value of sample ■" "The value of the sample for the implementation." and correct it.
Claims (1)
を有する黒白写真感光材料において、該乳剤層中の乳剤
粒子が、全粒子の投影面積の総和の７０％以上がアスペ
クト比３以上の平板状粒子からなり、さらに、該写真感
光材料の構成層中の少なくとも１層に下記一般式（ I
）で表わされる化合物を少なくとも１つ含有することを
特徴とするハロゲン化銀写真感光材料。 一般式（ I ） ▲数式、化学式、表等があります▼ 式中、Ｘ＾１はヘテロ原子を介して炭素原子に結合して
いる２価の連結基を表わし、ＡはＡのヘテロ原子を介し
てＸ＾１に結合している銀画像の色調を調節する基を表
わし、Ｒ＾１、Ｒ＾２及びＲ＾３は水素原子又は置換可
能な基を表わし、Ｒ＾１とＲ＾２及びＲ＾１とＲ＾３は
結合して炭素環、または複素環を形成してもよい。 Ｙは▲数式、化学式、表等があります▼、▲数式、化学
式、表等があります▼、▲数式、化学式、表等がありま
す▼、 ▲数式、化学式、表等があります▼、▲数式、化学式、
表等があります▼、▲数式、化学式、表等があります▼ ▲数式、化学式、表等があります▼、シアノ基、または
ニトロ基（ここ でＲ＾４、Ｒ＾５、Ｒ＾６、Ｒ＾７およびＲ＾８は水素
原子または置換可能な基を表わす。）を表わし、ｎ及び
ｍは０又は１を表わす。ただし、ｍ＝０のときＡで表わ
される基はＡのヘテロ原子を介して炭素原子と結合する
。[Scope of Claims] A black-and-white photographic material having at least one light-sensitive silver halide emulsion layer on a support, in which the emulsion grains in the emulsion layer account for 70% or more of the total projected area of all grains. It is composed of tabular grains having an aspect ratio of 3 or more, and furthermore, at least one of the constituent layers of the photographic light-sensitive material has the following general formula (I
1. A silver halide photographic material containing at least one compound represented by: General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, X^1 represents a divalent linking group bonded to a carbon atom via a hetero atom, represents a group that adjusts the color tone of a silver image bonded to X^1, R^1, R^2 and R^3 represent a hydrogen atom or a substitutable group, and R^1, R^2 and R^1 and R^3 may be combined to form a carbocycle or a heterocycle. Y is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas ,
There are tables, etc. ▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ▲There are mathematical formulas, chemical formulas, tables, etc.▼, cyano group, or nitro group (here R^4, R^5, R^6, R^ 7 and R^8 represent a hydrogen atom or a substitutable group), and n and m represent 0 or 1. However, when m=0, the group represented by A is bonded to a carbon atom via the heteroatom of A.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8254488A JPH01254944A (en) | 1988-04-04 | 1988-04-04 | Silver halide photographic sensitive material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8254488A JPH01254944A (en) | 1988-04-04 | 1988-04-04 | Silver halide photographic sensitive material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01254944A true JPH01254944A (en) | 1989-10-11 |
Family
ID=13777445
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8254488A Pending JPH01254944A (en) | 1988-04-04 | 1988-04-04 | Silver halide photographic sensitive material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01254944A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5972194A (en) * | 1994-02-12 | 1999-10-26 | Schepers; Hans-Georg | Process for producing a base mold for electrolytically producing seamless rotary screen printing stencils |
-
1988
- 1988-04-04 JP JP8254488A patent/JPH01254944A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5972194A (en) * | 1994-02-12 | 1999-10-26 | Schepers; Hans-Georg | Process for producing a base mold for electrolytically producing seamless rotary screen printing stencils |
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