JPH01179940A - Method for forming ultrahigh contrast negative image - Google Patents
Method for forming ultrahigh contrast negative imageInfo
- Publication number
- JPH01179940A JPH01179940A JP63003446A JP344688A JPH01179940A JP H01179940 A JPH01179940 A JP H01179940A JP 63003446 A JP63003446 A JP 63003446A JP 344688 A JP344688 A JP 344688A JP H01179940 A JPH01179940 A JP H01179940A
- Authority
- JP
- Japan
- Prior art keywords
- group
- developer
- silver halide
- atom
- groups
- 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
- 238000000034 method Methods 0.000 title claims description 22
- -1 silver halide Chemical class 0.000 claims abstract description 112
- 229910052709 silver Inorganic materials 0.000 claims abstract description 35
- 239000004332 silver Substances 0.000 claims abstract description 35
- 239000000839 emulsion Substances 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 27
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 15
- 150000002429 hydrazines Chemical class 0.000 claims abstract description 9
- 125000004429 atom Chemical group 0.000 claims abstract description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 4
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 4
- 125000005647 linker group Chemical group 0.000 claims abstract description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 3
- 150000001875 compounds Chemical group 0.000 claims description 38
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 10
- 239000000084 colloidal system Substances 0.000 claims description 9
- 238000012545 processing Methods 0.000 claims description 8
- 125000003277 amino group Chemical group 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 125000004434 sulfur atom Chemical group 0.000 claims description 4
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 150000004714 phosphonium salts Chemical group 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- 239000011669 selenium Substances 0.000 claims description 2
- 125000003739 carbamimidoyl group Chemical group C(N)(=N)* 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 9
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract 1
- 239000000975 dye Substances 0.000 description 24
- 239000010410 layer Substances 0.000 description 23
- 239000000243 solution Substances 0.000 description 17
- 125000003118 aryl group Chemical group 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 12
- 125000000217 alkyl group Chemical group 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 9
- 206010070834 Sensitisation Diseases 0.000 description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 8
- 230000008313 sensitization Effects 0.000 description 8
- 125000001424 substituent group Chemical group 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- 239000002202 Polyethylene glycol Substances 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 229920001223 polyethylene glycol Polymers 0.000 description 6
- 108010010803 Gelatin Proteins 0.000 description 5
- 125000003545 alkoxy group Chemical group 0.000 description 5
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 229920000159 gelatin Polymers 0.000 description 5
- 239000008273 gelatin Substances 0.000 description 5
- 235000019322 gelatine Nutrition 0.000 description 5
- 235000011852 gelatine desserts Nutrition 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 125000000565 sulfonamide group Chemical group 0.000 description 5
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 description 4
- 125000003710 aryl alkyl group Chemical group 0.000 description 4
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 4
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 4
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 4
- 125000002950 monocyclic group Chemical group 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 230000005070 ripening Effects 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- 230000001235 sensitizing effect Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea group Chemical group NC(=S)N UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- 150000003852 triazoles Chemical class 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Chemical class 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 3
- 235000010724 Wisteria floribunda Nutrition 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000005205 dihydroxybenzenes Chemical class 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 125000002883 imidazolyl group Chemical group 0.000 description 3
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- NDGRWYRVNANFNB-UHFFFAOYSA-N pyrazolidin-3-one Chemical class O=C1CCNN1 NDGRWYRVNANFNB-UHFFFAOYSA-N 0.000 description 3
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 2
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 2
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- OWIRCRREDNEXTA-UHFFFAOYSA-N 3-nitro-1h-indazole Chemical class C1=CC=C2C([N+](=O)[O-])=NNC2=C1 OWIRCRREDNEXTA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 229910021612 Silver iodide Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 2
- XCFIVNQHHFZRNR-UHFFFAOYSA-N [Ag].Cl[IH]Br Chemical compound [Ag].Cl[IH]Br XCFIVNQHHFZRNR-UHFFFAOYSA-N 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 125000004104 aryloxy 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
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 2
- 229940077388 benzenesulfonate Drugs 0.000 description 2
- 150000001565 benzotriazoles Chemical class 0.000 description 2
- 125000002619 bicyclic group Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 125000006165 cyclic alkyl group Chemical group 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 208000015181 infectious disease Diseases 0.000 description 2
- 230000002458 infectious effect Effects 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 150000002503 iridium Chemical class 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000006626 methoxycarbonylamino group Chemical group 0.000 description 2
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 2
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 2
- 125000006518 morpholino carbonyl group Chemical group [H]C1([H])OC([H])([H])C([H])([H])N(C(*)=O)C1([H])[H] 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000006179 pH buffering agent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000006678 phenoxycarbonyl group Chemical group 0.000 description 2
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 2
- 229920000120 polyethyl acrylate Polymers 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 230000002335 preservative effect Effects 0.000 description 2
- 230000003449 preventive effect Effects 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000003283 rhodium Chemical class 0.000 description 2
- 229910052703 rhodium Inorganic materials 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
- 235000017709 saponins Nutrition 0.000 description 2
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 2
- 229940045105 silver iodide Drugs 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 229940006186 sodium polystyrene sulfonate Drugs 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 125000005504 styryl group Chemical group 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 2
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 150000003536 tetrazoles Chemical class 0.000 description 2
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 125000001391 thioamide group Chemical group 0.000 description 2
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 2
- LMYRWZFENFIFIT-UHFFFAOYSA-N toluene-4-sulfonamide Chemical group CC1=CC=C(S(N)(=O)=O)C=C1 LMYRWZFENFIFIT-UHFFFAOYSA-N 0.000 description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical class OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- NJYFRQQXXXRJHK-UHFFFAOYSA-N (4-aminophenyl) thiocyanate Chemical compound NC1=CC=C(SC#N)C=C1 NJYFRQQXXXRJHK-UHFFFAOYSA-N 0.000 description 1
- AIGNCQCMONAWOL-UHFFFAOYSA-N 1,3-benzoselenazole Chemical compound C1=CC=C2[se]C=NC2=C1 AIGNCQCMONAWOL-UHFFFAOYSA-N 0.000 description 1
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical class C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 1
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 1
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical class C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- HXQHRUJXQJEGER-UHFFFAOYSA-N 1-methylbenzotriazole Chemical compound C1=CC=C2N(C)N=NC2=C1 HXQHRUJXQJEGER-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-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
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical class NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 1
- OCVLSHAVSIYKLI-UHFFFAOYSA-N 3h-1,3-thiazole-2-thione Chemical class SC1=NC=CS1 OCVLSHAVSIYKLI-UHFFFAOYSA-N 0.000 description 1
- NYYSPVRERVXMLJ-UHFFFAOYSA-N 4,4-difluorocyclohexan-1-one Chemical compound FC1(F)CCC(=O)CC1 NYYSPVRERVXMLJ-UHFFFAOYSA-N 0.000 description 1
- ZFIQGRISGKSVAG-UHFFFAOYSA-N 4-methylaminophenol Chemical compound CNC1=CC=C(O)C=C1 ZFIQGRISGKSVAG-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
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical group CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 1
- 244000105975 Antidesma platyphyllum Species 0.000 description 1
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical group NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 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 group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 229920002307 Dextran Polymers 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 101100130497 Drosophila melanogaster Mical gene Proteins 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
- KIWBPDUYBMNFTB-UHFFFAOYSA-N Ethyl hydrogen sulfate Chemical compound CCOS(O)(=O)=O KIWBPDUYBMNFTB-UHFFFAOYSA-N 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical class OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 101100345589 Mus musculus Mical1 gene Proteins 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- 241001061127 Thione Species 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000004442 acylamino group Chemical group 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- 125000005599 alkyl carboxylate group Chemical group 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 125000005110 aryl thio group Chemical group 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- KHBQMWCZKVMBLN-IDEBNGHGSA-N benzenesulfonamide Chemical group NS(=O)(=O)[13C]1=[13CH][13CH]=[13CH][13CH]=[13CH]1 KHBQMWCZKVMBLN-IDEBNGHGSA-N 0.000 description 1
- 150000001556 benzimidazoles Chemical class 0.000 description 1
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- 125000001231 benzoyloxy group Chemical group C(C1=CC=CC=C1)(=O)O* 0.000 description 1
- 125000000649 benzylidene group Chemical group [H]C(=[*])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 description 1
- 125000001584 benzyloxycarbonyl group Chemical group C(=O)(OCC1=CC=CC=C1)* 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 150000001661 cadmium Chemical class 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000005521 carbonamide group Chemical group 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 description 1
- 229940071161 dodecylbenzenesulfonate Drugs 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- ZCRZCMUDOWDGOB-UHFFFAOYSA-N ethanesulfonimidic acid Chemical compound CCS(N)(=O)=O ZCRZCMUDOWDGOB-UHFFFAOYSA-N 0.000 description 1
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 125000004705 ethylthio group Chemical group C(C)S* 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 235000009424 haa Nutrition 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- AKCUHGBLDXXTOM-UHFFFAOYSA-N hydroxy-oxo-phenyl-sulfanylidene-$l^{6}-sulfane Chemical class SS(=O)(=O)C1=CC=CC=C1 AKCUHGBLDXXTOM-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 125000001288 lysyl group Chemical group 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- HNQIVZYLYMDVSB-UHFFFAOYSA-N methanesulfonimidic acid Chemical group CS(N)(=O)=O HNQIVZYLYMDVSB-UHFFFAOYSA-N 0.000 description 1
- 125000005948 methanesulfonyloxy group Chemical group 0.000 description 1
- 125000006525 methoxy ethyl amino group Chemical group [H]N(*)C([H])([H])C([H])([H])OC([H])([H])[H] 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 125000004372 methylthioethyl group Chemical group [H]C([H])([H])SC([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 1
- 125000005740 oxycarbonyl group Chemical group [*:1]OC([*:2])=O 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
- ATGAWOHQWWULNK-UHFFFAOYSA-I pentapotassium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [K+].[K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O ATGAWOHQWWULNK-UHFFFAOYSA-I 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- HBCQSNAFLVXVAY-UHFFFAOYSA-N pyrimidine-2-thiol Chemical class SC1=NC=CC=N1 HBCQSNAFLVXVAY-UHFFFAOYSA-N 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 239000001397 quillaja saponaria molina bark Substances 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- BUOKUWQCVSZNCF-UHFFFAOYSA-N selenadiazole Chemical compound C1=C[se]N=N1 BUOKUWQCVSZNCF-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 229910001923 silver oxide Inorganic materials 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
- 230000003595 spectral effect Effects 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 150000003431 steroids Chemical class 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 1
- 125000004964 sulfoalkyl group Chemical group 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 description 1
- 125000005958 tetrahydrothienyl group Chemical group 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 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
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 150000003567 thiocyanates Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 125000005323 thioketone group Chemical group 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 150000004886 thiomorpholines Chemical class 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
- G03C1/061—Hydrazine compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
- G03C1/08—Sensitivity-increasing substances
- G03C1/10—Organic substances
- G03C2001/108—Nucleation accelerating compound
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明はハロゲン化銀写真材料及び、それ全周いた超硬
調な画像形成法に関するものであり、特に写真製版工程
に用いられる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 photographic material and a method for forming an ultra-high contrast image all around the material, and in particular to a silver halide photograph used in a photolithography process. It's about materials.
（従来技術）
グラフィック・アークの分野においては網点画像による
連続階調の画像の再生あるいは線画像の再生を良好なら
しめるために、超硬調（特にカンマｆ１０以上）の写真
特性を示す画像形成システムが必要である。(Prior Art) In the field of graphic arcs, image forming systems exhibit photographic characteristics of ultra-high contrast (especially comma f10 or higher) in order to improve the reproduction of continuous tone images using halftone images or the reproduction of line images. is necessary.
従来この目的のためにはリス現像液と呼ばれる特別な現
像液が用いられてき九。リス現像液は現像生薬としてハ
イドロキノンのみを含み、その伝染現像性を阻害しない
ように保恒剤たる亜硫酸塩をホルムアルデヒドとの付加
物の形にして用い遊離の亜硫酸イオンの濃度を極めて低
く（通常００１モル／を以下）しである。そのためリス
現像液は極めて空気酸化を受けやすく３日を越える保存
に耐えられないという重大な欠点を持っている。Conventionally, a special developer called a lith developer has been used for this purpose. Lith developer contains only hydroquinone as a developing drug, and uses sulfite as a preservative in the form of an adduct with formaldehyde so as not to inhibit its infectious development properties, and the concentration of free sulfite ions is extremely low (usually 001 mol/ is below). Therefore, the Lith developer has a serious drawback in that it is extremely susceptible to air oxidation and cannot be stored for more than 3 days.
高コントラストの写真特性を安定な現像液音用いて得る
方法としては米国特許第≠、コ２弘、弘０７号、同＄ｕ
、 ／ ｌ、 １．？ ７７号、同ｉ％！、／Ａｔ、
７１７２号、同第４４，３１１，７１／号、同第４１，
２７２，６０６号、同第１Ｉ、 ２１１． １ｊ７号、
同第μ、２弘３，７３り号等に記載されてｂるヒドラジ
ン誘導体を用いる方法がある。この方法によれば、超硬
調で感度の高い写真特性が得られ、更に現像液中に高濃
度の亜硫酸塩？加えることが許容されるので、現像液の
空気酸化に対する安定性はリス現像液に比べて飛躍的に
向上する。As a method for obtaining high contrast photographic properties using stable developer sound, US Pat.
, / l, 1. ? No. 77, i%! ,/At,
No. 7172, No. 44,311,71/, No. 41,
No. 272,606, No. 1I, 211. 1j No. 7,
There is a method using a hydrazine derivative described in the same No. μ, 2 Ko. 3,73, etc. According to this method, photographic characteristics with ultra-high contrast and high sensitivity can be obtained, and in addition, a high concentration of sulfite in the developer solution can be obtained. The stability of the developer against air oxidation is dramatically improved compared to the lithium developer.
しかしながら、ヒドラジン誘導体により、超硬調な画儂
ヲ形成させるためにはｐＨ１ｉ、ｏ以上でなければなら
ず、そのため現像主薬が酸化されやすく、又空気中のＣ
０２の吸収などによってもｐＨが変動しやすぐ、安定し
た写真性が得にくいという欠点があった。従って、現像
液の安定性を維持するために、ｐ）（／／、０以下で高
濃度の亜硫酸塩の存在下で超硬調な画像が得られる方法
が望まれていた。However, in order to form ultra-high contrast images using hydrazine derivatives, the pH must be at least 1i,0, which makes the developing agent easy to oxidize, and carbon dioxide in the air.
There was a drawback that the pH fluctuated quickly due to absorption of 0.02, making it difficult to obtain stable photographic properties. Therefore, in order to maintain the stability of the developer, there has been a desire for a method in which ultra-high contrast images can be obtained in the presence of a high concentration of sulfite at p)(//, 0 or less).
ヒドラジンによる硬調化を促進したりする手段が強く望
まれており、特開昭Ｊ／−／乙７り３りにはホスホニウ
ム塩化合物、特開昭４／−／り了ｌ弘７にはジスルフィ
ド化合物、特開昭ｊＯ−／≠０３μ０にはアミン系化合
物が硬調化剤として開示されている。しかしこれら化合
物を用いてもｐＨ／ ／以下での硬調化を促進するのは
困難であった。There is a strong desire for a means to promote high contrast using hydrazine, and phosphonium salt compounds are used in JP-A-1996/-/Otsu 7, and disulfide compounds are used in JP-A-4/-/Ryo1. An amine compound is disclosed as a contrast enhancing agent in Japanese Patent Application Laid-Open Publication No. 2003-030303. However, even when these compounds are used, it is difficult to promote high contrast at pH levels below .
一層ヒドラジン化合物を用いて低感度の明室用感光材料
を得ようとする場合、例えば特開昭乙０−ｒ３ｏ３ｒお
よび同６０−／ｌｒ２，２≠６には水溶性ロジウム塩を
含む）・ロゲン化銀感光材料が開示されている。しかし
ながら感度金工げるのに充分な量のロジウムを添加する
と、ヒドラジン化合物による硬調化が阻害され、所望の
充分硬調な画像が得られなかった。When trying to obtain a photosensitive material for bright room use with low sensitivity by using a hydrazine compound, for example, Japanese Patent Application Publication No. 2003-110000-r3o3r and 60-/lr2,2≠6 contain water-soluble rhodium salts). A silver oxide photosensitive material is disclosed. However, when rhodium is added in an amount sufficient to increase the sensitivity, the high contrast caused by the hydrazine compound is inhibited, and the desired sufficiently high contrast images cannot be obtained.
（発明の目的）
本発明の目的は、ヒドラジン化合物を用いた系において
、現像液のｐＨが／／、θ〜９．６で超硬調化する方法
を提供することであり、第λの目的は、安定な現像液で
性能を安定に維持できる超硬調な画偉形成法金提供する
ことである。(Objective of the Invention) The object of the present invention is to provide a method for achieving ultra-high contrast in a system using a hydrazine compound, when the pH of the developer is //, θ ~ 9.6, and the objective of the λth is The purpose of the present invention is to provide an ultra-high contrast image formation method that can maintain stable performance using a stable developer.
（発明の構成）
本発明の上記の目的は、
支持体上に少なくとも一層のハロゲン化銀乳剤層を有し
、該乳剤層又はその他の親水性コロイド層にヒドラジン
誘導体を少なくとも一種類と下記−紋穴ＣＩ）であられ
される化合物を少なくとも−ｍ類含むこと全特徴とする
超硬調ネガ型ハロゲン化銀写真材料を、ｐＨ／１．θ〜
り、ｒの現像液で処理すること全特徴とする超硬調なネ
ガ画像の形成方法によって達成された。(Structure of the Invention) The above-mentioned object of the present invention is to have at least one silver halide emulsion layer on a support, and the emulsion layer or other hydrophilic colloid layer contains at least one hydrazine derivative and the following pattern. An ultra-high contrast negative-working silver halide photographic material containing at least -m compounds formed by hole CI) was prepared at pH/1. θ～
This was achieved by a method of forming an ultra-high contrast negative image, which is characterized by processing with a R developer.
一般式（＋） ＭＳ＋Ｘ＋−Ａ−Ｂ 更に詳細に説明する。General formula (+) MS+X+-A-B This will be explained in more detail.
Ｘのへテロ環としては、窒素、酸素、セレン又は硫黄を
少なくとも一種含むｊ及び６員のへテロ環で炭素芳香環
またＦｉ複累芳香環と縮合していてもよい。ヘテロ環と
して好ましくは芳香族のもので例えば、テトラゾール、
トリアゾール、チアジアゾール、オキサジアゾール、セ
レナジアゾール、イミダゾール、チアゾール、オキサゾ
ール、ベンズイミダゾール、ベンズチアゾール、ベンズ
オキサゾール、ベンズセレナゾール、ピリミジンなとで
ある。このうち特にテトラゾールとチアジアゾールが好
ましい。The heterocycle of X may be a j- and 6-membered heterocycle containing at least one of nitrogen, oxygen, selenium, or sulfur, and may be fused with a carbon aromatic ring or an Fi complex aromatic ring. The heterocycle is preferably aromatic, such as tetrazole,
These include triazole, thiadiazole, oxadiazole, selenadiazole, imidazole, thiazole, oxazole, benzimidazole, benzthiazole, benzoxazole, benzselenazole, and pyrimidine. Among these, tetrazole and thiadiazole are particularly preferred.
またこれらのへテロ環はニトロ基、ハロゲン原子（例え
ば塩素原子、臭素原子等）、メルカプト基、シアノ基、
それぞれ置換もしくは無置換のアルキル基（例えば、メ
チル基、エチル基、プロピル基、ｔ−ブチル基、シアノ
エチル基、メトキシエチル基、メチルチオエチル基等）
、了リール基（例工ばフェニル基、ψ−メタンスルホン
了ミドフエ＝ｈＭｓ ｔｉ−メチルフェニルＭ、３＊ｔ
ｔ−ジクロルフェニル基、ナフチル基、等）、アルタニ
ル基（例えばアリル基、等）、アラルキル基（例えばベ
ンジル基、≠−メチルベンジル基、フェネチル基、等）
、アルコキシ基（例えばメトキシ基、エトキシ基等）、
アリールオキシ基（例えばフェノキシ基、弘−メトキシ
フェノキシ基等）、アルキルチオ基（例えばメチルチオ
基、エチルチオ基、メトキシエチルチオ基）、アリール
チオ基（例えばフェニルチオ基）、スルホニル基（例え
ばメタンスルホニル基、エタンスルホニルＭ、ｐ−トル
エンスルホニルｉ、等）、カルバモイル！（例、ｔば無
１置換カルバモイル基、メチルカルバモイル基、フェニ
ルカルバモイル基、等）、スルファモイル基（例工ば無
置換スルファモイル基、メチルスルファモイル基、フェ
ニルカルバモイル基、等）、カルボン了ミド基（例えば
アセトアミド基、ベンズアミド基、等）、スルホンアミ
ド基（例えばメタンスルホンアミド基、ベンゼンスルホ
ンアミド基、ｐ−トルエンスルホンアミド基、等）、了
シルオキシ基（例えば了セチルオキシ基、ベンゾイルオ
キシ基、等）、スルホニルオキシ基（例工ばメタンスル
ホニルオキシ基、等）、ウレイド基（例えば無置換のウ
レイド基、メチルウレイド基、エチルウレイド基、フェ
ニルウレイド基、等）、チオウレイド基（例えば無置換
のチオウレイド基、メチルチオウレイド基、等）、アシ
ル基（例えばアセチル基、ベンゾイル基、等）、ヘテロ
環基（例えばｌ−モルホリノ基、／−ピはリジ７基、２
−ピリジル基、弘−ピリジル基、２−チエニル基、／−
ピラゾリル基、／−イミダゾリル基、λ−テトラヒドロ
フリル基、テトラヒドロチエニル基、等）、オキシカル
ボニル基（例えばメトキシ力ルホニＡ基、フェノキシカ
ルボニル！、等）、オキシカルボニルアミノ基（例えば
メトキシカルボニルアミノ基、フェノキシカルボニルア
ミノ基、λ−エチルへキシルオキシカルボニル了ミノ基
、等）、アミノ基（汎えｄ無置換アミノ基、ジメチル了
ミノ基、メトキシエチルアミノ基Ｊｊｌす１１、等カル
ボン′Ｍまたはその塩、スルホン酸またはその塩、ヒド
ロキシル基などで置換されていてもよい。These heterocycles also include nitro groups, halogen atoms (e.g. chlorine atoms, bromine atoms, etc.), mercapto groups, cyano groups,
Substituted or unsubstituted alkyl groups (e.g., methyl group, ethyl group, propyl group, t-butyl group, cyanoethyl group, methoxyethyl group, methylthioethyl group, etc.)
, Ryl group (for example, phenyl group, ψ-methanesulfone Romidophe=hMs ti-methylphenyl M, 3*t
t-dichlorophenyl group, naphthyl group, etc.), artanyl group (e.g. allyl group, etc.), aralkyl group (e.g. benzyl group, ≠-methylbenzyl group, phenethyl group, etc.)
, alkoxy groups (e.g. methoxy group, ethoxy group, etc.),
Aryloxy groups (e.g. phenoxy group, Hiro-methoxyphenoxy group, etc.), alkylthio groups (e.g. methylthio group, ethylthio group, methoxyethylthio group), arylthio groups (e.g. phenylthio group), sulfonyl groups (e.g. methanesulfonyl group, ethanesulfonyl group) M, p-toluenesulfonyl i, etc.), carbamoyl! (e.g., unsubstituted carbamoyl group, methylcarbamoyl group, phenylcarbamoyl group, etc.), sulfamoyl group (e.g., unsubstituted sulfamoyl group, methylsulfamoyl group, phenylcarbamoyl group, etc.), carbonyl carbamoyl group (e.g. acetamide group, benzamide group, etc.), sulfonamide group (e.g. methanesulfonamide group, benzenesulfonamide group, p-toluenesulfonamide group, etc.), ryosyloxy group (e.g. cetyloxy group, benzoyloxy group, etc.) ), sulfonyloxy groups (for example, methanesulfonyloxy groups, etc.), ureido groups (for example, unsubstituted ureido groups, methylureido groups, ethylureido groups, phenylureido groups, etc.), thioureido groups (for example, unsubstituted thioureido groups) group, methylthioureido group, etc.), acyl group (e.g., acetyl group, benzoyl group, etc.), heterocyclic group (e.g., l-morpholino group, /-pi is a di7 group, 2
-pyridyl group, Hiro-pyridyl group, 2-thienyl group, /-
pyrazolyl group, /-imidazolyl group, λ-tetrahydrofuryl group, tetrahydrothienyl group, etc.), oxycarbonyl group (e.g., methoxycarbonylamino group, phenoxycarbonyl!, etc.), oxycarbonylamino group (e.g., methoxycarbonylamino group, phenoxycarbonylamino group, λ-ethylhexyloxycarbonyl-termino group, etc.), amino group (uniformly unsubstituted amino group, dimethyl-termino group, methoxyethylamino group, etc.), carbon'M or its salt , a sulfonic acid or a salt thereof, a hydroxyl group, etc.
Ａの二価の連結基としては、炭素原子、窒素原子、酸素
原子、硫黄原子から選ばれた原子または原子群よりなる
二価の連結基であり、例えは−５−１−〇−１−へ−、
Ｒ２、Ｒ３、几４、Ｒ５、Ｒ６、几７、Ｒ８、Ｒ３およ
びＲ１゜は水素原子、それぞれ置換もしくは無置換のア
ルキル基（例えば、メチル基、エチル基、プロピル基、
ｎ−ブチル基、等）、置換もしくは無置換のアリール基
（例えば、フェニル基、！−メチルフェニル基、等）、
置換もしくは無置換ノアル々ニル基（例えば、プロ投ニ
ル基、／−メチルビニル基、等）、または置換もしくは
無置換のアラルキル基（例えば、ベンジル基、フェネチ
ル基、等）を表わす。）、直鎖または分岐のアルキレン
基（例えば、メチレン基、エチレン基、プロピレン基、
ブチレン基、ヘキシレンｉ、／−メチルエチレン基、等
）、直鎖または分岐の了ル々ニレン基（例えば、ビニレ
ン基、／−メチルビニレン基、等）、直鎖または分岐の
アラルキレン基（例えば、ベンジリデン基、等）、直鎖
または分岐リアルキニレン（例えば、−ＣＨ−Ｃ−Ｃ−
ＣＨ−基等）、了り−レン基（例えば、フェニレン、ナ
フチレン、等）等が挙げられる。Ａで表わされる上記の
基は更に任意の組合せで、連結基金形成してもよい。Ｂ
のアミノ基は置換基を有していてもよく、好ましくは一
般式（■）で表わされるものである。The divalent linking group of A is a divalent linking group consisting of an atom or atom group selected from carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms, for example -5-1-〇-1- -, R2, R3, R4, R5, R6, R7, R8, R3 and R1° are hydrogen atoms, substituted or unsubstituted alkyl groups (e.g., methyl group, ethyl group, propyl group,
n-butyl group, etc.), substituted or unsubstituted aryl group (e.g., phenyl group, !-methylphenyl group, etc.),
It represents a substituted or unsubstituted noartanyl group (eg, protonyl group, /-methylvinyl group, etc.), or a substituted or unsubstituted aralkyl group (eg, benzyl group, phenethyl group, etc.). ), linear or branched alkylene groups (e.g. methylene group, ethylene group, propylene group,
butylene group, hexylene group, /-methylethylene group, etc.), straight-chain or branched arylene group (e.g., vinylene group, /-methylvinylene group, etc.), straight-chain or branched aralkylene group (e.g., benzylidene group, etc.), linear or branched realkynylene (e.g. -CH-C-C-
(CH- group, etc.), and -lene groups (eg, phenylene, naphthylene, etc.). The above groups represented by A may further be combined in any combination to form a consolidated fund. B
The amino group may have a substituent, and is preferably represented by the general formula (■).
一般式（Ｘｌｌ）
（式中Ｂｌｌ、Ｂ１２は同一であっても異なってもよく
、各々、水素原子、１４換もしくは無置換の炭素数／〜
３０のアルキル基、アル々ニル基またはアラルキル基を
表わし、これらの基は直鎖（例えばメチル基、エチル基
、ｎ−プロピル基、ｎ−ブチル基、ｎ−オクチル基、ア
リル基、３−ブテニル基、ベンジル基、／−ナフチルメ
チル基等）、分岐（例えばｉｓｏプロピル基、ｔ−オク
チル基等）、または環状（例えばンクロヘキシル基等）
でもよい。General formula (Xll) (In the formula, Bll and B12 may be the same or different, and each has a hydrogen atom, a 14-substituted or unsubstituted carbon number/~
30 alkyl, artanyl or aralkyl groups, and these groups are straight-chain (e.g. methyl, ethyl, n-propyl, n-butyl, n-octyl, allyl, 3-butenyl). group, benzyl group, /-naphthylmethyl group, etc.), branched (e.g. isopropyl group, t-octyl group, etc.), or cyclic (e.g. ncrohexyl group, etc.)
But that's fine.
又、１（，１１と１（１２は連結して環？形成してもよ
く、その中に１つまたはそれ以上めヘテロ原子（例えば
酸素原子、硫黄原子、窒素原子など）を含んだ飽和のヘ
テロ環を形成するように環化されていてもよく、例えば
ピロリジル基、ピはリジル基、モルホリノ基など１挙げ
ることができる。又、Ｒ１Ｂ１２の置換基としては、例
えば、カルボキシル基、スルホ基、シアノ基、ハロゲン
原子（例えばフッ素原子、塩素原子、臭素原子である。In addition, 1(, 11 and 1(12) may be connected to form a ring, which is a saturated ring containing one or more heteroatoms (e.g., oxygen atom, sulfur atom, nitrogen atom, etc.). It may be cyclized to form a heterocycle, and examples include a pyrrolidyl group, a lysyl group, and a morpholino group.As substituents for R1B12, for example, a carboxyl group, a sulfo group, Cyano group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom).
）、ヒドロキシ基、炭素数２０以下のアルコキシカルボ
ニル基（例えばメトキシカルボニル基、エトキシカルボ
ニル基、フェノキシカルボニル基、ベンジルオキシカル
ボニル基なと）、炭素数、２０以下のアルコキシ基、（
例えばメトキシ基、エトキシ基、ベンジルオキシ基、フ
ェネチルオキシ基など）、炭素数２Ｑ以下の単環式のア
リールオキシ基（例えばフェノキシ基、ｐ−トリルオキ
シ基など）、炭素数２０以下のアシルオキシ基（例えば
アセチルオキシ基、プロピオニルオキシ基など）、炭素
数２０以下のアシル基（例えばアセチル基、プロピオニ
ル基、ベンゾイル基、メシル基など）、カルバモイル基
（例えばカルバモイル基、へ、ヘージメチル力ルバモイ
ル基、モルホリノカルボニル基、ピはリジ７カルボニル
基など）、スルファモイル基（例工ばスルファモイル基
、Ｎ、Ｎ−ジメチルスルファモイル基、モルホリノカル
ボニル基、ヒはリジノスルホニル基など）、炭素数２θ
以下のアシルアミノ基（例えばアセチルアミ７基、プロ
ピオニルアミノ基、ベンゾイル了ミノ基、メシルアミノ
基など）、スルホンアミド基（エチルスルホンアミドａ
、ｐ−トルエンスルホンアミド基なと）、炭素数２０以
下のカルボンアミド基（例えばメチルカンポンアミド基
、フェニルカルボンアミド基など）、炭素数２０以下の
ウレイド基（例えばメチルウレイド基、フェニルウレイ
ド基など）、アミノ基（−紋穴（■）と同義のもの）な
どが挙げられる。), hydroxy group, alkoxycarbonyl group having 20 or less carbon atoms (e.g. methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl group, benzyloxycarbonyl group), alkoxy group having 20 or less carbon atoms, (
For example, methoxy group, ethoxy group, benzyloxy group, phenethyloxy group), monocyclic aryloxy group having 2Q or less carbon atoms (e.g. phenoxy group, p-tolyloxy group, etc.), acyloxy group having 20 or less carbon atoms (e.g. acetyloxy group, propionyloxy group, etc.), acyl group having 20 or less carbon atoms (e.g. acetyl group, propionyl group, benzoyl group, mesyl group, etc.), carbamoyl group (e.g. carbamoyl group, hedimethyl group, hedimethyl group, morpholinocarbonyl group) , Pi is a 7-carbonyl group, etc.), a sulfamoyl group (for example, a sulfamoyl group, N,N-dimethylsulfamoyl group, a morpholinocarbonyl group, H is a lysinosulfonyl group, etc.), carbon number 2θ
The following acylamino groups (e.g. acetylamino group, propionylamino group, benzoyl ryamino group, mesylamino group, etc.), sulfonamide groups (ethylsulfonamide a
, p-toluenesulfonamide group), carbonamide group having 20 or less carbon atoms (e.g. methylcamponamide group, phenylcarbonamide group, etc.), ureido group having 20 or less carbon atoms (e.g. methylureido group, phenylureido group, etc.) ), an amino group (synonymous with -monna (■)), and the like.
Ｂのアンモニウム基はイ道換基を有していてもよく、好
ｆしくは一般式（Ｘｌｌ）で表わされるものである。The ammonium group of B may have an i-do substituent, and is preferably represented by the general formula (Xll).
一般式（Ｘｌ）
（式中、几１３、Ｂ １４、Ｂ１５は上述の一般式（Ｉ
Ｉ）におけるＲ およびＲと同様の基であり、ｚｅはア
ニオンを表わし、例えばハライドイオン（例エバｃｌ”
、 Ｂ ｒＯｌＩＯなど）、スＡ＊ｆ−Ｍオン（例工
ばトリフルオロメタンスルホナート、ハラトルエンスル
ホｆ−ト、ベンゼンスルホナート、）（ラクロＯベンゼ
ンスルホナートナト）、スルファトイオン（例工ばエチ
ルスル７アート、メチルスルフアートなど）、パークロ
ラート、テトラフルオロボラートなどが挙げられる。ｐ
はＯまたは／′？！：表わし、化合物が分子内塩を形成
する場合はθである。）
Ｂの含窒素へテロ環は、少なくとも１つ以上の窒素原子
を含んだｊまたは６員環であり、それらの環は置換基を
有していてもよく、また他の環と縮合していてもよい。General formula (Xl) (wherein 几13, B14, B15 are the general formula (I
It is a group similar to R and R in I), and ze represents an anion, such as a halide ion (e.g.
, B rOlIO, etc.), sulfate ions (eg trifluoromethanesulfonate, halatoluenesulfonate, benzenesulfonate), sulfate ions (eg trifluoromethanesulfonate, halatoluenesulfonate, benzenesulfonate), ethyl sulfate, methyl sulfate, etc.), perchlorate, tetrafluoroborate, etc. p
Is O or /'? ! : Represents θ when the compound forms an inner salt. ) The nitrogen-containing heterocycle of B is a j or 6-membered ring containing at least one nitrogen atom, and these rings may have a substituent and may not be fused with another ring. You can.
含窒素へテロ環としては例えばイミダゾリル基、ピリジ
ル基、チアゾリル基などが挙げられる。Examples of the nitrogen-containing heterocycle include an imidazolyl group, a pyridyl group, and a thiazolyl group.
Ｍのアルカリ金属としては、ｒＶＩａ＋、Ｋ＋１Ｌｉ＋
などがある。As the alkali metal of M, rVIa+, K+1Li+
and so on.
アルカリ土類金属としてはこＣａ＋＋、Ｍｇ＋＋、など
がある。Examples of alkaline earth metals include Ca++, Mg++, and the like.
Ｍの四級アンモニウム塩としては、炭素数μ〜３０から
なるもので、例えば（ＣＨ３）４ へ■、（Ｃ２Ｈ５）
４への、（Ｃ４Ｉ−１，）４Ｎ■、Ｃ６Ｈ３ＣＨ□へ■
（ＣＨ３）３、Ｃ１６Ｈ３３ＮＯ（ＣＨ３）３などであ
る。The quaternary ammonium salt of M is one consisting of carbon number μ~30, for example, (CH3)4 to ■, (C2H5)
to 4, (C4I-1,)4N■, to C6H3CH□■
(CH3)3, C16H33NO(CH3)3, etc.
四級ホスホニウム塩としては、（Ｃ４Ｈｇ ） ４ Ｐ
■、Ｃ１６Ｈ３Ｐ■（ＣＩ（３）３、Ｃ６Ｉ１５ＣＩ−
１２Ｐ■（ＣＩ−１３）などである。As the quaternary phosphonium salt, (C4Hg) 4P
■, C16H3P■ (CI(3)3, C6I15CI-
12P■ (CI-13), etc.
アルカリ条件下でＭ ＝ Ｈ！たけアルカリ金属原子と
なりうる基としては例えば、アセチル基、シアノエチル
基、メタンスルホニルエチル基などである。Under alkaline conditions M = H! Examples of groups that can serve as alkali metal atoms include acetyl group, cyanoethyl group, and methanesulfonylethyl group.
以下に一般式（］）で表わされる化合物の具体例を挙げ
る。Specific examples of the compound represented by the general formula (]) are listed below.
Ｒ
・［
１− ／、２
・１−１α
・Ｈｃｌ！
１−／ｊ
・ｌ−１α
・Ｈα
・ＨＣ７！
・Ｉ−Ｉ ＣＩ！
ニー、２コ
ニ−２３
Ｈ
８）ｌ
・ＩＩα
ニー、２♂
・ｌ−１α
ニー≠ｊ （ＨＯＣＩ−１２ＣＨ□ ）２へ
Ｃ１１２Ｃ１−１２８１−１本発明で用いられる一般式
（１）で表わされる化合物は、ベリヒテ・デア・ドイツ
チェン・ヘミツシエン・ゲゼルシャフト（ＢｅｒｉＣｈ
ｔｅ ｄｅｒＤｅｕｔｓｃｈｅｎ ＣｈｅｍｉｓＣｈｅ
ｎ Ｇｅ５ｅｌｌｓＣｈａｆＬ）互、７７（／ｆ？り、
特開昭３０−３７弘３６号、同３；／−３２３／号、米
国特許３，２りｊ。R ・[ 1- /, 2 ・1-1α ・Hcl! 1-/j ・l-1α ・Hα ・HC7!・I-I CI! Ni, 2coni-23 H 8)l ・IIα Ni, 2♂ ・l-1α Ni≠j (HOCI-12CH□ )2 to C112C1-1281-1 Compound represented by general formula (1) used in the present invention Berichte der Deutschen Hemitsien Gesellschaft (BeriCh
te der Deutschen Chemische
n Ge5ellsChafL) mutual, 77(/f?ri,
JP-A No. 30-37-36, No. 3;/-323/, U.S. Patent No. 3,2.
り７６号、米国特許３，３７６．３１０号、ベリヒテ・
デア・ドイツチェン・ヘミツシエン・ゲゼルシャフト（
ＢｅｒｉＣｈｔｅ ｄｅｒ Ｄｅｕｔｓｒ、ｈｅｎＣｈ
ｅｍｉｓＣｈｅｎ Ｇｅ５ｅｌｌｓｒ、ｈａｆｔ） 、
２，２．３６１（／ｆ♂り）、同よ！、！弘ｇ３（／ざ
７６）、ジャーナル・オプ・々ミカル・ソサイアテイ（
Ｊ、Ｃｈｅｍ、５ｏＣ０） ７２３！、／ざ０６、ジャ
ーナル・オプ・ジ・アメリカン・々ミカル・ソサイ了テ
ィ（Ｊ 、Ａｍ、（：’ｈｅｍ、Ｓａｔ：、）７／、ｔ
ｔｏ。No. 76, U.S. Pat. No. 3,376.310, Berichte et al.
Der Deutschchen Hemitsien Gesellschaft (
BeriChte der Deutsr,henCh
emisChen Ge5ellsr, haft),
2,2.361 (/f♂ri), same! ,! Hirog3 (/za76), Journal Op.Mical Society (
J, Chem, 5oC0) 723! ,/za06, Journal of the American Society (J, Am, (:'hem, Sat:,)7/, t
to.
Ｏ（／り弘７）、米国特許！、ｊざ！、３１ｒ号、同ｙ
、 ５ｔｔｉ 、り！≠号、アドバンシイズ・イン・
ヘテロサイクリック・々ミスドリー
（ＡｄｖａｎＣｅｓ ｉｎ Ｈｅｔｅｒｏｃ、ｙｃ、目
Ｃ（：ｈｅｍｉｓｔｒｙ）！；’、／Ａｊ（１５’４．
ｒ）、オーガニック・シンセシス（Ｑｒｇａｎｉｒ、
５ｙｎｔｈｅｓｉｓ）■、ｊ６Ｆ（／り６３）、ジャー
ナル・オブ・ジ・アメリカン・ケミカル・ソサイアテイ
（Ｊ、Ａｍ。O (/Rihiro7), US patent! , jza! , No. 31r, same y
, 5tti, ri! ≠ issue, Advances in
AdvanCes in Heteroc, yc, 目C(:hemistry)!;', /Aj(15'4.
r), Organic Synthesis (Qrganir,
5ynthesis) ■, j6F (/ri63), Journal of the American Chemical Society (J, Am.
Ｃｈｅｍ、ＳｏＣ，）＜４３．．２Ｊり（７（／りλ３
）、ヘミシｘ−ベリヒテ（Ｃｈｅｍｉｓｅｈｅ Ｂｅｒ
ｉＣｈｔｅ）り、ｔＡ６ｊ（／ざ７６）、特公昭弘０−
２１１Ａり６号、特開昭３０−ざ７０３’Ａ号、米国特
許３゜１０６．１Ａｌｐ７号、同３．弘、２０，１ｓ７
０号、同２、λ７／、、？、２り号、同３．／３７．．
３７を号、同３．／≠ｇ、０６６号、同３．Ｊ／／、６
１ｓ３号、同３．０＆０．０λｇ号、同３，２７／、Ｉ
ｊｔＡ号、同３．．２Ｊ／、ｌ、り７号、同３．ｊ７♂
。Chem, SoC, )<43. ．． 2Jri(7(/riλ3
), Chemisehe Ber
iChte)ri, tA6j(/za76), Tokuko Akihiro 0-
No. 211A-6, JP-A No. 30-703'A, U.S. Pat. Hiroshi, 20, 1s7
No. 0, same 2, λ7/,,? , No. 2, No. 3. /37. ．．
No. 37, 3. /≠g, No. 066, 3. J//, 6
1s3, 3.0 & 0.0λg, 3,27/, I
jtA No. 3. ．． 2J/, l, ri No. 7, same 3. j7♂
.
３７２号、同３．／４Ｌざ、０６６号、特公昭≠３−弘
／３３号、米国特許３．６１ｊ、ｌ５ＩＡ号、同Ｊ、Ｉ
ＩＬλθ、６６弘号、同３．０７／、ｌｌ−１，；号、
同コ、≠弘弘、６０ｊ号、同、２，４ＣｔＡ≠、６０６
号、同λ、ｑ≠弘、６０７号、同ユ、９３！；。No. 372, 3. /4Lza, No. 066, Tokuko Sho≠3-Hiroshi/33, U.S. Patent No. 3.61j, I5IA, same J, I
ILλθ, No. 66, 3.07/, ll-1, ; No.
Same, ≠ Hirohiro, No. 60j, same, 2,4CtA≠, 606
No., same λ, q≠Hiroshi, No. 607, same Yu, 93! ;.
≠０す号等に記載されている方法や以下に示した代表的
な合成例に準じて合成できる。It can be synthesized according to the method described in ≠0, etc. or the typical synthesis examples shown below.
一般式（１）の化合物は、化合物の種類によって最適添
加量が異なるが／、Ｏ×１０−３〜Ｏ０ｊ Ｆ ／ ｒ
ｒｌ、好ましくはＪ、０ｘＩＱ−３〜Ｑ、ＩＰ ／ ｒ
ｒｌの範囲で用いるのが望ましい。これらの促進剤は適
当な溶媒（水、メタノールやエタノールナトのアルコー
ル類、アセトン、ジメチルホルム了ミド、メチルセルソ
ルブなど）心溶解して塗布液に添加される。これらの添
加剤を複数の種類を併用してもよい。The optimum amount of the compound of general formula (1) to be added varies depending on the type of compound;
rl, preferably J, 0xIQ-3~Q, IP/r
It is desirable to use it within the range of rl. These accelerators are dissolved in a suitable solvent (water, alcohols such as methanol or ethanol, acetone, dimethylformamide, methylcellosolve, etc.) and then added to the coating solution. A plurality of types of these additives may be used in combination.
本発明に用いられるヒドラジン誘導体としては、米国特
許筒≠≠７ｆ９２ｇ号に記載せるスルフィニル基を有す
るヒドラジン誘導体及び下記一般式（ＩＩ）で表わされ
る化合物をあげることができる。Examples of the hydrazine derivatives used in the present invention include hydrazine derivatives having a sulfinyl group described in US Patent No. 7f92g and compounds represented by the following general formula (II).
一般式（…） Ｒ１−ＮＨＮＩ（−ＣＨＯ 式中Ｒ１は脂肪族基または芳香族基を表わす。General formula (…) R1-NHNI(-CHO In the formula, R1 represents an aliphatic group or an aromatic group.
一般式（ｎ）において、Ｒ１で表される脂肪族基は好ま
しくは炭素数／〜３０のものであって、特に炭素数／〜
λＯの直鎖、分岐または環状のアルキル基である。ここ
で分岐アルキル基はその中に７つまたはそれ以上のへテ
ロ原子に含んだ飽和のへテロ環を形成するように環化さ
れていてもよい。またこのアルキル基は、了り−ル基、
アルコキシ基、スルホキシ基、スルホンアミド基、カル
ポン了ミド基等の置換基を有していてもよい。In general formula (n), the aliphatic group represented by R1 preferably has carbon atoms/~30, particularly carbon atoms/~30.
λO is a linear, branched or cyclic alkyl group. The branched alkyl group herein may be cyclized to form a saturated heterocycle containing seven or more heteroatoms therein. In addition, this alkyl group is a ryoryl group,
It may have a substituent such as an alkoxy group, a sulfoxy group, a sulfonamide group, or a carponylamide group.
例えばｔ−ブチル基、ｎ−オクチル基、ｔ−オクチル基
、シクロヘキシル基、ピロリジル基、イミダゾリル基、
テトラヒドロフリル基、モルフォリノ基などをその例と
して挙げることができる。For example, t-butyl group, n-octyl group, t-octyl group, cyclohexyl group, pyrrolidyl group, imidazolyl group,
Examples include a tetrahydrofuryl group and a morpholino group.
−紋穴（ｎ）においてＲ１で表される芳香族基は単環ま
たはｄ環の了り−ル基または不飽和へテロ環基である。- The aromatic group represented by R1 in the hole (n) is a monocyclic or d-ring ring group or an unsaturated heterocyclic group.
ここで不飽和へテロ環基は単環または２環の了り−ル基
と縮合してヘテロアリール基を形成してもよい。Here, the unsaturated heterocyclic group may be condensed with a monocyclic or bicyclic ring group to form a heteroaryl group.
例えばベンゼン環、ナフタレン環、ピリジン環、ピリミ
ジン環、イミダゾール環、ピロリジル基、キノリン環、
イソキノリン環、ベンズイミダゾール環、チアゾール環
、ベンゾチアゾール環等があるがなかでもベンゼン環を
含むものが好ヱしい。For example, benzene ring, naphthalene ring, pyridine ring, pyrimidine ring, imidazole ring, pyrrolidyl group, quinoline ring,
Examples include isoquinoline ring, benzimidazole ring, thiazole ring, and benzothiazole ring, among which those containing a benzene ring are preferred.
Ｒ１として特に好ましいものはアリール基である。Particularly preferred as R1 is an aryl group.
Ｒ１のアリール基または芳香族基は置換基１持っていて
もよい。The aryl group or aromatic group of R1 may have one substituent.
代表的な置換基としては、直鎖、分岐または環状のアル
キル基（好ましくは炭素数／〜２０のもの）、アラルキ
ル基（好ましくはアルキル部分の炭素数が／〜３の単環
または２環のもの）、アルコキシ基（好ましくは炭素数
／〜λ０のもの）、置換アミノ基（好ましくは炭素数／
−２０のアルキル基で置換されたアミ７基）、了シルア
ミノ基（好ましくは炭素数２〜３０を持つもの）、スル
ホンアミド基（好ましくは炭素数ｌ〜３０を持つもの）
、ウレイド基（好ましくは炭素数／〜３０を持つもの）
などがある。Typical substituents include straight-chain, branched or cyclic alkyl groups (preferably those with a carbon number of up to 20), aralkyl groups (preferably monocyclic or bicyclic alkyl groups with an alkyl moiety of up to 3 carbon atoms). ), alkoxy groups (preferably those with carbon number/~λ0), substituted amino groups (preferably those with carbon number/~λ0),
-20 alkyl groups), cylamino groups (preferably those with 2 to 30 carbon atoms), sulfonamide groups (preferably those with 1 to 30 carbon atoms)
, ureido group (preferably having carbon number/~30)
and so on.
一般式（Ｕ）のＲ１はその中にカプラー等の不動性写真
用添加剤において常用されているバラスト基が組み込ま
れているものでもよい。バラスト基はざ以上の炭素数を
有する写真性に対し℃比較的不活性な基であり、例えば
アルキル基、アルコキシ基、フェニル基、アルキルフェ
ニル基、フェノキシ基、アルキルフェノキシ基などの中
から選ぶことができる。R1 in the general formula (U) may have a ballast group commonly used in immobile photographic additives such as couplers incorporated therein. A ballast group is a group that is relatively inert to photographic properties and has a carbon number of more than 100%, and can be selected from, for example, an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group, an alkylphenoxy group, etc. Can be done.
一般式（ｎ）のＲ１はその中にハロゲン化銀粒子表面に
対する吸着を強める基が組み込まれているものでもよい
。かかる吸着基としては、チオ尿素基、複素環チオアミ
ド基、メルカプト複素環基、トリアゾール基などの米国
特許第≠、３１３．１０♂号に記載された基があげられ
る。R1 in general formula (n) may have a group incorporated therein that enhances adsorption to the silver halide grain surface. Such adsorption groups include groups described in US Pat. No. 313.10♂, such as thiourea group, heterocyclic thioamide group, mercapto heterocyclic group, and triazole group.
これらの化合物の合成法は特開昭３３−２０７２／号、
同３３−２０９２２号、同３３−６６７３２号、同ｊ３
−２０３ＩＩ号などに記載されている。Synthesis methods for these compounds are described in JP-A No. 33-2072/,
No. 33-20922, No. 33-66732, j3
-203II, etc.
本発明において、−紋穴（ＩＩ）で表される化合物を写
真感光材料中に含有させるときには、ハロゲン化銀乳剤
層に含有させるのが好ましいがそれ以外の非感光性の親
水性コロイド層（例えば保護層、中間層、フィルター層
、ハレーション防止層など）に含有させてもよい。具体
的には使用する化合物が水溶性の場合には水溶液として
、また難水溶性の場合にはアルコール類、エステル類、
々トン類などの水と混和しうる有機溶媒の溶液として、
親水性コロイド溶液に添加すればよい。ハロゲン化銀乳
剤層に添加する場合は化学熟成の開始から塗布前までの
任意の時期に行ってよいが、化学熟成終了後から塗布前
の間に添加するのが好ましい。特に塗布のために用意さ
れた塗布液中に添加するのがよい。In the present invention, when the compound represented by pattern (II) is contained in a photographic light-sensitive material, it is preferably contained in a silver halide emulsion layer, but it is preferably contained in a non-photosensitive hydrophilic colloid layer (e.g. It may be included in a protective layer, an intermediate layer, a filter layer, an antihalation layer, etc.). Specifically, if the compound to be used is water-soluble, it can be used as an aqueous solution, or if it is poorly water-soluble, it can be used as an alcohol, ester, or
As a solution of water-miscible organic solvents such as
It can be added to a hydrophilic colloid solution. When added to the silver halide emulsion layer, it may be added at any time from the start of chemical ripening to before coating, but it is preferably added between after the end of chemical ripening and before coating. In particular, it is preferable to add it to a coating solution prepared for coating.
本発明の一般式（、■）で表される化合物の含有量はハ
ロゲン化銀乳剤の粒子径、ハロゲン組成、化学増感の方
法と程度、該化合物を含有させる層とハロゲン化銀乳剤
層の関係、カプリ防止化合物の種類などに応じて最適の
量を選択することが望ましく、その選択のための試験の
方法は当業者のよく知るところである。通常は好ましく
はハロゲン化銀１モル当り１０−６モルないし／Ｘ１０
’モル、特に１０−５ないし≠×ｌ０−２モルの範
囲で用いられる。The content of the compound represented by the general formula (, ■) of the present invention is determined by the grain size of the silver halide emulsion, the halogen composition, the method and degree of chemical sensitization, and the layer containing the compound and the silver halide emulsion layer. It is desirable to select the optimal amount depending on the relationship, the type of anti-capri compound, etc., and testing methods for this selection are well known to those skilled in the art. Usually preferably from 10-6 mol to /X10 per mol of silver halide
'moles, particularly in the range of 10-5 to ≠×10-2 mols.
一般式（ＩＩ）で示される化合物の具体例を以下に示す
。但し本発明は以下の化合物に限定されるものではない
。Specific examples of the compound represented by general formula (II) are shown below. However, the present invention is not limited to the following compounds.
１−／
１−♂
１−／ 弘
１−／ｊ
■
Ｈ３
１−／ ７
Ｃ）１２Ｃ）１２Ｃ１−１２ＳＩ−１
１−／ｒ
１−／り
１−一１
１−２弘
Ｉ −Ｊ 弘
ニー３５
その他、米国特許第μ、’４７１． ５Ｐ２１号に記載
の
などがある。1-/ 1-♂ 1-/ Hiro 1-/j ■ H3 1-/ 7 C) 12C) 12C1-12SI-1 1-/r 1-/ri 1-1 1-2 Hiro I -J Hironi 35 et al., U.S. Patent No. μ, '471. There are some such as those described in 5P21.
本発明では一般式（ＩＩ’）の中で特に好ましい化合物
は、Ｒ１にノ・ロダン化銀粒子表面に対する吸Ｎ”を強
める基が組み込まれているものがよい。かかる吸着基と
しては、チオ尿素、複素環チオアミド基、メルカプト複
素環基、トリアゾール基などの米国特許第４４，３１５
．／−０１号に記載された基があげられる。又、Ｒ１の
アリール基または芳香族基の置換基は、アミド基、ウレ
イド基、チオ尿素基が好ましく、特にスルホンアミド基
が好ましい。In the present invention, a particularly preferable compound of the general formula (II') is one in which a group that enhances the adsorption of N'' to the surface of silver rhodanide grains is incorporated into R1. Such an adsorption group includes thiourea, , heterocyclic thioamide group, mercapto heterocyclic group, triazole group, etc. U.S. Pat. No. 44,315
．． Examples include the groups described in No./-01. Further, the substituent of the aryl group or aromatic group of R1 is preferably an amide group, a ureido group, or a thiourea group, and particularly preferably a sulfonamide group.
本発明に使用される一般式（Ｉ）の化合物はｌＷ ／
ｍ２〜２ ！ Ｏｍｙ ／ ｍ２が好ましく、特に３ｍ
１１〜／ｊＯη／ｆｉ２がよい。又−紋穴（Ｉ［）の化
合物は／〜３００■／ｆｉ２が好ましく、特にλ〜２０
０ ｍｇ ／ ｍ２がよい。さらに、Ｒ１にノ・ロダン
化銀粒子表面に対する吸着を強める基が組込まれている
ものでは、２〜ｌＯＯ〜／７７１２がよい。The compound of general formula (I) used in the present invention has lW/
m2~2! Omy/m2 is preferred, especially 3m
11~/jOη/fi2 is good. In addition, the compound of Monna (I[) preferably has a /~300/fi2, particularly λ~20
0 mg/m2 is good. Further, in the case where R1 has a group incorporated therein that enhances adsorption to the surface of silver rhodanide grains, a value of 2 to 100 to /7712 is preferable.
本発明の写真乳剤には、ハロゲン化銀として臭化銀、沃
臭化銀、沃塩臭化銀、塩臭化銀、沃化銀および塩化銀の
いずれを用いてもよりが、特に塩化銀が６０モル係以上
あることが好ましい。In the photographic emulsion of the present invention, any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, silver iodide, and silver chloride may be used as the silver halide, especially silver chloride. is preferably 60 molar or more.
粒子サイズ分布はせまくても広くてもいずれでもよい。The particle size distribution may be narrow or wide.
写真乳剤中のハロゲン化銀粒子は、立方体、八面体、１
４Ｌ面体、菱７２面体のような規則的（ｒｅｇｕｌａｒ
）な結晶体を有するものでもよく、また球状、板状など
のような変則的（ｉｒｒｅｇｕｌａｒ）な結晶形をもつ
もの、あるいはこれらの結晶形の複合形をもつものでも
よい。種々の結晶形の粒子の混合から成ってもよい。Silver halide grains in photographic emulsions are cubic, octahedral, 1
Regular (regular) such as 4L-hedron and rhomboid heptahedron
), or may have irregular crystal shapes such as spherical or plate-like, or a composite of these crystal shapes. It may also consist of a mixture of particles of various crystalline forms.
ハロゲン化銀粒子は内部と表層とが異なる和音もってい
ても、均−１相から成っていてもよい。The silver halide grains may have different chords between the inside and the surface layer, or may be composed of a homogeneous -1 phase.
また、写真乳剤中のハロゲン化銀粒子の粒子サイズ分布
は任意であるが単分散であってもよい。Further, the grain size distribution of silver halide grains in the photographic emulsion is arbitrary, but may be monodisperse.
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、それらの添
加量は、目的とする感光材料に応じて少量でも多量でも
よい。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, the amount of these additives may be small or large depending on the intended photosensitive material.
また、目的に応じて、すでに公知であるノ・ロダン化銀
溶剤（例えば、アンモニア、ロダンカリや米国特許第３
．２７／、１３７号、特開昭！／−／２ＥｔＯ号、特開
昭ｊ３−１２４１０１号、特開昭ｊ、３−／４ｔ１．ｔ
３／り号、特開昭３μｍ１００７／７号、特開昭ｓグー
ｉｔｓざ−ｒ号等に記載のチオエーテルやチオン化合物
）を用いることができる。In addition, depending on the purpose, known silver-rodanide solvents (for example, ammonia, rhodankali, US Patent No. 3
．． 27/, No. 137, Tokukai Sho! /-/2EtO No., JP-A No. 3-124101, JP-A No. 3-/4t1. t
Thioethers and thione compounds described in JP-A No. 3/R, JP-A No. 3 μm 1007/7, JP-A No. 1007-R, etc.) can be used.
ハロゲン化銀乳剤は、化学増感しても、しなくてもよい
。化学増感のためには、活性ゼラチンや銀と反応し得る
硫酸を含む化合物（例えば、チオ硫酸塩、チオ尿素類、
メルカプト化合物類、ローダニン類）を用いる硫黄増感
法：還元性物質（例えば、第一すず塩、アミン類、ヒド
ラジン誘導体、ホルムアミジンスルフィン酸、シラン化
合物）を用いる還元増感法：貴金属化合物（例えば、全
錯塩のほか、Ｐｔ、Ｉｒ、Ｐｄなどの周期律表■族の金
属の錯塩）を用いる貴金属増感法などを単独または組合
せて用いることができる。The silver halide emulsion may or may not be chemically sensitized. For chemical sensitization, active gelatin and compounds containing sulfuric acid that can react with silver (e.g., thiosulfates, thioureas,
Sulfur sensitization method using reducing substances (e.g., stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds): Noble metal compounds (e.g. In addition to total complex salts, noble metal sensitization methods using complex salts of metals of group 1 of the periodic table such as Pt, Ir, and Pd can be used alone or in combination.
本発明の写真乳剤には、感光材料の保存中あるいは写真
処理中のカブリを防止し、あるいは写真性能を安定化さ
せる目的で、種々の化合物を含有させることができる。The photographic emulsion of the present invention may contain various compounds for the purpose of preventing fogging during storage or photographic processing of the light-sensitive material, or for stabilizing photographic performance.
すなわちアゾール類たとえばベンゾチアゾリウム塩、ニ
トロインダゾール類、トリアゾール類、ベンゾトリアゾ
ール類、ベンズイミダゾール類（％にニトロ−またはハ
ロゲン置換体）：ヘテロ環メルカプト化合物類たとえば
メルカプトチアゾール類、メルカプトベンゾチアゾール
類、メルカプトベンズイミダゾール類、メルカプトチア
ジアゾール類、メルカプトテトラゾール類（特に／−フ
ェニル−よ−メルカプトテトラゾール）、メルカプトピ
リミジン類二カルボキシル基やスルホン基などの水溶性
基を有する上記のへテロ環メルカヅト化合物類：チオケ
ト化合物たとｔばオキサゾリンチオン：アザインデン類
たとえばテトラアザインデン類（特に弘−ヒドロキシ置
換（／、３．Ｊａ、７）テトラアザインデン類）：ベン
ゼンチオスルホン酸類：ベンゼンスルフイン酸二などの
ようなカプリ防止剤または安定剤として知られた多くの
化合物に加えることができる。Namely, azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (% nitro- or halogen substituted); heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, Mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially /-phenyl-mercaptotetrazole), mercaptopyrimidines The above-mentioned heterocyclic merkazu compounds having a water-soluble group such as a dicarboxyl group or a sulfone group: thioketo Examples of compounds include oxazolinthione: azaindenes such as tetraazaindene (especially Hiro-hydroxy-substituted (/, 3. Ja, 7) tetraazaindene): benzenethiosulfonic acids: capric acid such as benzenesulfinic acid di, etc. Many compounds known as inhibitors or stabilizers can be added.
本発明の感光材料において写真乳剤は、増感色素を用い
て比較的長波長の青色光、緑色光、赤色光または赤外光
に分光増感させてもよい。増感色素としては、シアニン
色素、メロシアニン色素、コンプレックスシアニン色素
、コンプレックスメロシアニン色素、ホロポーラ−シア
ニン色素、スチリル色素、ヘミシアニン色素、オキソノ
ール色素、ヘミオキソノール染料等を用いることができ
る。分光増感色素の具体的な例は、例えばベー・グラフ
キデ（Ｇｌａｆ’ｋｉｄｅｓ）著［ヘミ−・ホトグラフ
イーク（Ｃｈｉｍｉｅ Ｐｈｏｔｏｇｒａｐｈｉｑｕ
ｅ）Ｊ（２３４版、／り５７年：ポウムル・モントル、
／りり（Ｐａｕｌ Ｍｏｎｔｅｌ、Ｐａｒｉｓ））の
第３！章〜４（７章及びＦ、Ｍ、ヘイ？ −（Ｈａｍｅ
ｒ ）著［ザ・シアニン・アンド・リレーテッド・コ
ンパウンダ（Ｔｈｅ Ｃｙａｎｉｎｅ ａｎｄ Ｒ
ｅｌａｔｅｄＣｏｍｐｏｕｎｄｓ）Ｊ （インターサイ
エフ、ｘ、 （Ｉｎｔｅｒ −５ｃｉｅｎｃｅ）’）、
および米国特許２． ３０３． ７７６号、同Ｊ、 ４
１に？、 ５３３号、同３． ／７７゜２１０号、リ
サーチ・ディスクロージャー（Ｒｅｓｅａｒｃｈ Ｄｉ
ｓｃｌｏｓｕｒｅ） ／７６巻／７４４１３（／り７？
年１２月発行）第２３項■の５項等に記載されている。In the photographic material of the present invention, the photographic emulsion may be spectrally sensitized to relatively long wavelength blue light, green light, red light or infrared light using a sensitizing dye. As the sensitizing dye, cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, styryl dyes, hemicyanine dyes, oxonol dyes, hemioxonol dyes, etc. can be used. Specific examples of spectral sensitizing dyes include, for example, the book by Glaf'kides [Chimie Photographiq].
e) J (234th edition, / 1957: Poemle Montre,
/ Riri (Paul Montel, Paris)) No. 3! Chapter ~ 4 (Chapter 7 and F, M, Hey? - (Hame
The Cyanine and Related Compounder
elatedCompounds)J (Inter-ScienceF, x, (Inter-5science)'),
and US Patent 2. 303. No. 776, J, 4
To 1? , No. 533, 3. /77゜210, Research Disclosure
sclosure) /76 volumes/74413 (/ri7?
(Issued in December 2016) Section 23 (■), Section 5, etc.
本発明音用いて作られた感光材料には親水性コロイド層
にフィルター染料として、あるいはイラジェーション防
止その他種々の目的で、水溶性染料を含有してよい。こ
のような染料にはオキソノール染料、ヘミオキソノール
染料、スチリル染料、メロシアニン染料、シアニン染料
及びアゾ染料が包含される。中でもオキソノール染料；
ヘミオキソノール染料及びメロシアニン染料が有用であ
る。A photosensitive material made using the photosensitive material of the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes;
Hemioxonol dyes and merocyanine dyes are useful.
本発明の写真感光材料には、写真乳剤層その他の親水性
コロイド層に無機または有機の硬膜剤全含有してよい。In the photographic material of the present invention, the photographic emulsion layer and other hydrophilic colloid layers may entirely contain an inorganic or organic hardener.
例えば活性ビニル化合物（／、Ｊ。For example, activated vinyl compounds (/, J.
ｊ−）リアクリロイル−へキサセドロ−Ｓ −）リアジ
ン、１．３−ビニルスルホニル−２−プロパツールなど
）、活性ハロゲン化合物（，２９μｍジクロル−ｔ−ヒ
ドロキシ−５−トリアジンナト）などを単独または組合
わせて用いることができる本発明の感光材料の写真乳剤
層または他の親水性コロイド層には塗布助剤、帯電防止
、スベリ性改良、乳化分散、接着防止および写真特性改
良（たとえば現像促進、鈍調化、増感）など種々の目的
で種々の界面活性剤を含んでもよい。(j-) lyacryloyl-hexacedro-S-) liazine, 1,3-vinylsulfonyl-2-propatol, etc.), active halogen compounds (29 μm dichloro-t-hydroxy-5-triazinato), etc. alone or in combination. The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material of the present invention, which can be used in conjunction with the photosensitive material of the present invention, may contain coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and improvement of photographic properties (e.g., development acceleration, slowing down, etc.). Various surfactants may be included for various purposes such as conditioning and sensitization.
タトエば、サポニン（ステロイド系）、アルキレンオキ
サイド誘導体（例えばポリエチレングリコール、ポリエ
チレングリコール／ポリプロピレングリコール縮合物、
ポリエチレングリコールアルキルエーテル類またはポリ
エチレングリコールアルキルアリールエーテル類、ポリ
エチレングリコールエステル類、ポリエチレングリコー
ルソルビタンエステル類、ポリアルキレングリコールア
ルキルアミンまたはアミド類、シリコーンのポリエチレ
ンオキサイド付加物類）、グリシドール誘導体（たとえ
ばアルケニルコハク酸ポリグリセリド、アルキルフェノ
ールポリグリセリド）、多価アルコールの脂肪酸エステ
ル類、株のフルキルエステル類などの非イオン性界面活
性剤；アルキルカルボン酸塩、アルギルスルフォン酸塩
、アルキルベンゼンスルフォン酸塩、アルキルナフタレ
ンスルフォン酸塩、アルキル硫酸エステル類、アルキル
リン酸エステル類、Ｎ−アシル−Ｎ−アルキルタウリン
類、スルホコハク酸エステル類、スルホアルキルポリオ
キシエチレンアルキルフェニルエーテル類、ポリオキシ
エチレンアルキルリン酸エステル類などのような、カル
ボキシ基、スルホ基、ホスホ基、硫酸エステル基、燐酸
エステル基等の酸性基金含むアニオン界面活性剤；アミ
ノ酸類、アミノアルキルスルホン酸類、アミノアルキル
硫酸または燐酸エステル類、アルキルベタイン類、アミ
ンオキシド類などの両性界面活性剤；アルキルアミン塩
類、脂肪族あるいけ芳香族第ψ級アンモニウム塩類、ピ
リジニウム、イミダゾリウムなどの複素環第ｑ級アンモ
ニウム塩類、および脂肪族または芳香環を含むホスホニ
ウムまたはスルホニウム塩類などのカチオン界面活性剤
を用いることができる。Saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates,
polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkyl amines or amides, polyethylene oxide adducts of silicones), glycidol derivatives (e.g. Nonionic surfactants such as glycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, and fulkyl esters; alkyl carboxylates, argylsulfonates, alkylbenzenesulfonates, alkylnaphthalenesulfonates , alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphates, etc. Anionic surfactants containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups; amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphate esters, alkyl betaines, amine oxides, etc. amphoteric surfactants; such as alkylamine salts, aliphatic or aromatic ψ-class ammonium salts, heterocyclic q-class ammonium salts such as pyridinium and imidazolium, and phosphonium or sulfonium salts containing aliphatic or aromatic rings; Cationic surfactants can be used.
本発明の写真感光材料の写真乳剤層には感度上昇、コン
トラスト上昇、または現像促進の目的て例、ｔ ハポリ
アルキレンオキシドまたはそのエーブル、エステル、ア
ミンなどの誘導体、チオエーブル化合物、チオモルフォ
リン類、四級アンモニウム塩化合物、ウレタン誘導体、
尿素誘導体、イミダゾール誘導体、３−ピラゾリドン類
等を含んでもよい。For the purpose of increasing sensitivity, increasing contrast, or accelerating development, the photographic emulsion layer of the photographic light-sensitive material of the present invention may include, for example, hapolyalkylene oxide or its derivatives such as ethers, esters, and amines, thioable compounds, thiomorpholines, etc. Quaternary ammonium salt compounds, urethane derivatives,
It may also contain urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like.
本発明の感光材料の乳剤層や中間層に用いることのでき
る結合剤または保護コロイドとしては、ゼラチンを用い
るのが有利であるが、それ以外の親水性コロイドも用い
ることができる。As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used.
タトエばポリビニルアルコール、ポリビニルアルコール
音ｒ分アセタール、ポリ−Ｎ−ビニルピロリドン、ポリ
アクリル酸、ポリアクリルアミド、デキストラン等の親
水性高分子物質を用いることができる。Hydrophilic polymeric substances such as polyvinyl alcohol, polyvinyl alcohol acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polyacrylamide, and dextran can be used.
本発明のハロゲン化銀感光材料を用いて超硬調の写真特
性を得るには、従来の伝染現像液や米国特許第λ、≠／
Ｐ、 タフ３号に記載されたｐＨ／３に近い高アルカ
リ現像液を用いる必要はなく、安定な現像液を用りるこ
とかできる。In order to obtain ultra-high contrast photographic properties using the silver halide photosensitive material of the present invention, it is necessary to use a conventional infectious developer or U.S. Patent No. λ, ≠/
It is not necessary to use a highly alkaline developer with a pH close to 3 as described in P. Tough No. 3, and a stable developer can be used.
すなわち、本発明のハロゲン化銀感光材料は、保恒剤と
しての亜硫酸イオンを０．／ｊモル／を以上含み、ｐＨ
／／、０〜り、ｔｌ特に／１．Ｏ〜１０．０の現像液に
よって充分に超硬調のネガ画像を得ることができる。That is, the silver halide photosensitive material of the present invention contains sulfite ions as a preservative at a concentration of 0. /j mol/ or more, pH
//, 0~ri, tl especially /1. A sufficiently high-contrast negative image can be obtained with a developer having a density of 0 to 10.0.
本発明の方法において用いうる現像主薬には特別な制限
はなく、例えばジヒドロキシベンゼン類（例エバハイド
ロキノン）、３−ピラゾリドン類（例えば／−フェニル
−３−ピラゾリドン、≠。There are no particular limitations on the developing agent that can be used in the method of the present invention, such as dihydroxybenzenes (e.g. evahydroquinone), 3-pyrazolidones (e.g. /-phenyl-3-pyrazolidone, ≠).
ｌ−ジメチル−７−フェニル−３−ビラソリトン）、ア
ミンフェノール類（例えばＮ−メチル−ｐ−アミノフェ
ノール）などを単独あるいは組み合わせてもちいること
ができる。l-dimethyl-7-phenyl-3-birasoliton), amine phenols (for example, N-methyl-p-aminophenol), etc. can be used alone or in combination.
本発明のハロゲン化銀感光材料は特に、主現像主薬とし
てジヒドロキシベンゼン類會、補助現像主薬として３−
ピラゾリドン類またはアミノフェノール類を含む現像液
で処理されるのに適している。好ましくは仁の現像液に
おいてジヒドロキシベンゼン類はｏ、ｏｒ〜０．ｊモル
／１１３−ピラゾリドン類またはアミンフェノール類は
０．０６モル／を以下の範囲で併用される。In particular, the silver halide light-sensitive material of the present invention contains dihydroxybenzenes as the main developing agent and 3-3 as the auxiliary developing agent.
Suitable for processing with developers containing pyrazolidones or aminophenols. Preferably, the dihydroxybenzenes in the developer are o, or ~0. j mol/113-Pyrazolidones or amine phenols are used in combination at 0.06 mol/in the following range.
また米国特許≠、２６り、りλり号に記載されているよ
うに、アミン類を現像液に添加することによって現像速
度を高め、現像時間の短縮化を実現することもできる。Furthermore, as described in US Pat.
現像液にはその他、アルカリ金属の亜硫酸塩、炭酸塩、
ホウ酸塩、及びリン酸塩の如きｐＨ緩衝剤、臭化物、沃
化物、及び有機カブリ防止剤（特に好ましくはニトロイ
ンダゾール類またはベンゾトリアゾール類）の如き現像
抑制剤ないし、カブリ防止剤などを含むことができる。The developer also contains alkali metal sulfites, carbonates,
Contains pH buffering agents such as borates and phosphates, development inhibitors or antifoggants such as bromides, iodides, and organic antifoggants (particularly preferably nitroindazoles or benzotriazoles). Can be done.
又必要に応じて、硬水軟化剤、溶解助剤、色調剤、現像
促進剤、界面活性剤（とくに好ましくは前述のポリアル
キレンオキサイド類）、消泡剤、硬膜剤、フィルムの銀
汚れ防止剤（例えばコーメルカブトベンズイミダゾール
スルホン酸類など）を含んでもよい。If necessary, water softeners, solubilizing agents, color toning agents, development accelerators, surfactants (especially preferably the aforementioned polyalkylene oxides), antifoaming agents, hardeners, and film silver stain preventive agents may be added. (eg, Komelkabutobenzimidazole sulfonic acids, etc.).
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などを含
んでもよい。The fixing solution may contain a water-soluble aluminum salt or the like as a hardening agent.
本発明の方法における処理温度は普通／ｒ’ｃからｊＯ
ｏＣの間に選ばれる。The processing temperature in the method of the present invention is usually from /r'c to jO
Selected during oC.
写真処理には自動現像機を用いるのが好ましいが、本発
明の方法により、感光材料を自動現像機に入れてから出
てくるまでのトータルの処理時間をりＯ秒〜／２０秒に
設定しても、充分に超硬調のネガ階調の写真特性が得ら
れる。It is preferable to use an automatic processor for photographic processing, but according to the method of the present invention, the total processing time from when the photosensitive material is put into the automatic processor until it comes out is set to 0 seconds to /20 seconds. However, it is possible to obtain photographic characteristics with sufficient ultra-high contrast and negative gradation.
本発明のｄ保液には銀汚れ防止剤として特開昭ｊ＆−２
１１．ｊ≠７号に記載の化合物を用いることができる。The d retaining liquid of the present invention contains JP-A-Shoj&-2 as a silver stain preventive agent.
11. The compound described in j≠7 can be used.
現像液中に添加する溶解助剤として特願昭６０−１０り
、７μ３号に記載の化合物を用いることができる。さら
に現像液に用いるｐＨ緩衝剤として特開昭ｔｏ−タＪ、
４ｔｊＪ号に記載の化合物あるいは研特弘ｔＪ／に記載
の化合物を用いることができる。As a solubilizing agent to be added to the developer, the compounds described in Japanese Patent Application No. 7μ3, No. 1988-1986 can be used. Furthermore, as a pH buffering agent used in the developer,
The compounds described in No. 4tjJ or the compounds described in Kentokuhiro tJ/ can be used.
実施例１
ダブルジェット法を用いて、塩沃臭化銀乳剤（沃化銀０
，１モル係、臭化銀３０モル幅）を調製した。この塩沃
臭化銀乳剤には、ロジウム塩として（ＮＨ４）３Ｒｈα
６をｊＸｌｏ ’モル／Ａｇモルになるようにハロゲ
ン水溶液を添加した。また同時にイリジウム塩として、
Ｋ３Ｉｒα６１に：４Ｌ×７０−７モル／Ａｇモル含有
するよう２、ロダン水溶液を添加した。Example 1 A silver chloroiodobromide emulsion (silver iodide 0
, 1 mol width, silver bromide 30 mol width) was prepared. This silver chloroiodobromide emulsion contains (NH4)3Rhα as a rhodium salt.
An aqueous halogen solution was added to the solution so that the ratio of 6 to 100% was jXlo' mol/Ag mol. At the same time, as an iridium salt,
An aqueous Rodan solution was added to K3Irα61 so as to contain 4 L×70 −7 mol/Ag mol.
このハロゲン水溶液と硝酸銀水溶液とｆ４Ａ１０ｃｔｏ
分間で混合し、平均粒子サイズＯ，コｊμの単分散立方
体乳剤を調製した。This halogen aqueous solution, silver nitrate aqueous solution and f4A10cto
The mixture was mixed for 1 minute to prepare a monodisperse cubic emulsion with an average grain size of 0,0 μm.
この乳剤は、水洗脱塩後、チオ硫酸ナトリウム？／ Ｘ
／ ０ モル／Ａｇモル加え、またカリウムクロロオ
ーレートで金増感を１ｘｌＯ−５モル／Ａｇモル加えた
。This emulsion is made of sodium thiosulfate after washing with water and desalting. /X
/ 0 mol/Ag mol was added, and gold sensitization with potassium chloroaurate was added at 1xlO-5 mol/Ag mol.
これら乳剤は増感色素として／ −（コーヒドロキシエ
トキシエチル）−ｊ−（ピリジンーコーイル）−ｊ−Ｃ
（Ｊ−スルホブチル−！−クロローコーベンゾオキサゾ
リニデン）エチリデン〕−コーチオヒダントンカリウム
塩ｆ！×１０ モル／Ａｇ１モル、安定剤として弘−
ヒドロキシ−６−メチル−／、 Ｊ、 Ｊａ、
７−チトラザインデンをｉ３ｙ、ハイドロキノンｆ２
ｆ、レゾルシンアルドキシム２ｆ、／−フ二二ルー！−
メルカフトテトラゾール１ｋＯ０／ｆ各々銀１モル当り
加えた。These emulsions were used as a sensitizing dye / -(cohydroxyethoxyethyl)-j-(pyridine-coyl)-j-C
(J-sulfobutyl-!-chlorocobenzoxazolinidene)ethylidene]-cochinohydantone potassium salt f! ×10 mol/Ag1 mol, Hiroshi as a stabilizer
Hydroxy-6-methyl-/, J, Ja,
7-chitrazaindene i3y, hydroquinone f2
f, resorcinaldoxime 2f, /-funi2ru! −
1 kO0/f of mercaftotetrazole was added per mole of silver in each case.
さらに塗布助剤として、下記化合物およびサポニンを
Ｃ１７Ｈ３３ＣＯＮ−ＣＨ２ＣＨ２８０ａＮａＣＨ３
硬膜剤として
ＣＨ２＝ ＣＨ８Ｏ２ＣＨ２Ｃ０ＮＨ（ＣＨ２）ｎ Ｎ
ＨＣＯＣＨ２Ｓ ０２ ＣＨ＝ ＣＨ３（ｎ−２，３）
を増粘剤としてポリスチレンスルホン酸ソーダを、ラテ
ックスポリマーとしてポリエチルアクリレートの分散物
を加えた。Furthermore, as a coating aid, the following compounds and saponin were used as C17H33CON-CH2CH280aNaCH3 as a hardening agent, CH2= CH8O2CH2C0NH(CH2)n N
Sodium polystyrene sulfonate was added using HCOCH2S 02 CH=CH3(n-2,3) as a thickener and a dispersion of polyethyl acrylate as a latex polymer.
さらに、ヒドラジン化合物として一般式（Ｘ）の中から
各々■−タ、Ｉ［−３１ｓ Ｉｆ−一０、■−３２、：
［−Ｊ ４ｃ、 ■−Ｊ ｊｔ−１又−紋穴（Ｉ）の中
からＩ−７を表−７に示す様に添加した。Further, as a hydrazine compound, from the general formula (X), ■-ta, I[-31s If-10, ■-32, respectively:
[-J 4c, ■-J jt-1 or - I-7 was added from Monnai (I) as shown in Table-7.
保護層としては、ゼラチン、ドデシルベンゼンスルホン
酸ンーダ、コロイダルシリカ、ポリエチルアクリレート
の分散物、ポリメチルメタアクリレートのマット剤およ
びポリスチレンスルホン酸ソーダの増粘剤からなるゼラ
チン水溶液を、ゼラチン塗布量として／、６９／ｍ２に
なるよう、また、乳剤は塗布銀量としてＪ、ｌ、７７ｍ
２になるよう乳剤層と保護層を同時塗布し九。As the protective layer, an aqueous gelatin solution consisting of gelatin, dodecylbenzenesulfonate, colloidal silica, a dispersion of polyethyl acrylate, a matting agent of polymethyl methacrylate, and a thickener of sodium polystyrene sulfonate was used as the coating amount of gelatin. , 69/m2, and the emulsion was coated with J, l, 77 m2 as the amount of coated silver.
Coat the emulsion layer and protective layer at the same time so that the layer becomes 2.9.
これらの各試料は３−〇θ°にのタングステン光でセン
シトメトリー用光学クサビを通して３秒間露光した後、
下記組成の現像液（Ａ）、（Ｂ）で、Ｊｒ０ＣＪＯ秒間
現慣し、定着、水洗、乾燥した。Each of these samples was exposed to 3-〇θ° tungsten light for 3 seconds through a sensitometric optical wedge.
It was developed with developing solutions (A) and (B) having the following compositions for Jr0CJO seconds, fixed, washed with water, and dried.
（現像処理には、富士写真フィルム■製自動現像機ＦＧ
−６６ＯＦｔ−用いた。）
〔現像液（Ａ）処方〕
ハイドロキノン ！！、０ｆＮ−メ
チルーｐ−アミノフェノ
ール／／２硫酸塩 ｏ、ｒｙ水酸化ナト
リウム タ、ｏｙ第三リン酸カリウ
ム ７μ、Ｏｆ亜硫酸カリウム
タｏ、ｏｙエチレンジアミン四酢酸二ナト
リウム塩 ｌ・０？臭化カリ
ウム Ｊ、Ｏｆよ一メチルベンゾ
トリアゾール ｏ、ｔｔ３−ジエチルアミノ−７−
プロ
パツール ／ｊ、Ｏｆ水を加えて
／ｌ（ｐＨ＝／ ／、６
）
現像液として、酢酸を現像液（Ａ）に添加することによ
りｐＨ７，コ下げてｐｌ−１＝１０．ＩＩとしたものを
調液これｔ−（Ｄ）とし同様の方法で現像処理した。(For the developing process, use the automatic developing machine FG manufactured by Fuji Photo Film ■.
-66OFt- was used. ) [Developer (A) formulation] Hydroquinone! ! , OfN-methyl-p-aminophenol // 2 sulfate o, ry Sodium hydroxide Ta, oy Potassium triphosphate 7 μ, Of Potassium sulfite
Ta o, oy ethylenediaminetetraacetic acid disodium salt l・0? Potassium bromide J, Of 1-methylbenzotriazole o, tt3-diethylamino-7-
Propatool /j, Add water /l (pH=/ /, 6
) As a developer, by adding acetic acid to the developer (A), the pH was lowered by 7, and pl-1 = 10. The solution designated as II was prepared as t-(D) and developed in the same manner.
結果を表−／に示す。そしてＧ値を測定した。The results are shown in Table-/. Then, the G value was measured.
又、現像液（Ａ）、（Ｄ）ｋ／ｌのビーカーに／を入れ
て１週間放置した後、上記と同様、これらの液でも処理
しＧを測定した。Further, developer solutions (A) and (D) were placed in k/l beakers and allowed to stand for one week, and then treated with these solutions in the same manner as above, and G was measured.
本発明の一般式（Ｉ）の化合物の使用により、ｐＨ値が
低ぐてもＧが７０以上を保つことができ、かつ液経時し
ても安定であることがわかる。It can be seen that by using the compound of general formula (I) of the present invention, G can be maintained at 70 or more even at a low pH value, and the solution is stable over time.
実施例コ
実施例／で作製したフィルムＡ／／を、実施例１とｐＨ
値以外同様な現像液（Ｂ）、（Ｃ）、（Ｄ）、（Ｅ）、
（Ｆ）、（Ｇ）全調製し、実施例１と同様な方法で現像
処理し、Ｇｔ−測定した。又（Ａ）〜（Ｇ）の現像液＝
ｉ／ｌのビーカーに／を入れて７週間放置した後処理し
た結果も示す。The film A// produced in Example co/Example// was mixed with Example 1 and pH
Similar developers except for the values (B), (C), (D), (E),
(F) and (G) were all prepared, developed in the same manner as in Example 1, and measured for Gt. Also, the developing solutions (A) to (G) =
Also shown are the results of processing after placing / in an i/l beaker and leaving it for 7 weeks.
本発明の化合物の使用により、１１０以上の超硬調性を
維持でき、本発明のＤＨ域で、安定したＧｉ維持してい
ることがわかる。It can be seen that by using the compound of the present invention, ultrahigh contrast of 110 or more can be maintained, and stable Gi is maintained in the DH range of the present invention.
実施例３
実施例１のフィルム屋／／ヲ作製する際、造核促進剤Ｉ
−７のかわりにニー１０１１−Ｊ／を同様に添加し、フ
ィルム■、０を作製した。実施例／と同様に処理し、Ｇ
ｉ測測定た。Example 3 Nucleation accelerator I was used when producing the film of Example 1.
Ni 1011-J/ was added in the same manner instead of -7 to prepare films ① and 0. Treated in the same manner as in Example/G
I measured it.
本発明の化合物によυ、低ｐＨの現像液で０７０以上の
超硬調性と安定性を保っていることがわかる。It can be seen that the compound of the present invention maintains ultra-high contrast of 070 or higher and stability in a low pH developer.
特許出願人 富士写真フィルム株式会社１、事件の表示
昭和６３年特願第３≠４Ａ６号２、発明の名称
超硬調なネガ画像形成方法３、補正をする者
事件との関係 特許出願人性 所 神奈
川県南足柄市中沼２１０番地名 称（５２０）富士写真
フィルム株式会社連絡先 〒ＩＯＧ東京都港区西麻布２
丁口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」の項の記載を下記の通９
補正する。Patent applicant: Fuji Photo Film Co., Ltd. 1, Indication of case: 1986 Patent Application No. 3≠4A6 2, Title of invention: Ultra-high contrast negative image forming method 3, Relationship with the amendment person case Patent applicant: Location: Kanagawa 210 Nakanuma, Minamiashigara City, Prefecture Name (520) Fuji Photo Film Co., Ltd. Contact Address: IOG 2 Nishi-Azabu, Minato-ku, Tokyo
Chouguchi 26-30 No. 4, Subject of amendment: ``Detailed explanation of the invention'' column 5 of the specification, Contents of amendment The description of the ``Detailed explanation of the invention'' section of the specification is changed to the following 9.
to correct.
１）第３≠貞から第弘コ頁の全文を別紙の通９補正する
。1) The entire text of pages 3≠Sada to Hiroko No. 9 is revised in Appendix 9.
２）第ｊ６頁ｌ！行目の 「で金増感」 全削除する。2) No. j6 page l! row "Gold sensitization" Delete all.
ヌｔ１臥 「 学熟成終了後から塗布前の間に添加するのが好ましい。Nut1 wo " It is preferable to add it between after the completion of chemical ripening and before coating.
特に塗布のために用意された塗布液中に添加するのがよ
い。In particular, it is preferable to add it to a coating solution prepared for coating.
本発明の一般式（ＩＩ）で表される化合物の含有ＪＩＶ
ｉハロゲン化銀乳剤の粒子径、ハロゲン組成、化学増感
の方法と程度、該化合物を含有させる層とハロゲン化銀
乳剤層の関係、カプリ防止化合物の種類などに応じて最
適の量を選択することが望ましく、その選択のための試
験の方法は当業者のよく知るところである。通常は好ま
しくはハロゲン化銀１モル当り／Ｑ モルないし／Ｘ
１０−’モル、特に１０−５ないし弘ｘ１０−２モルの
範囲で用（・もれる。JIV containing the compound represented by the general formula (II) of the present invention
i Select the optimum amount depending on the grain size of the silver halide emulsion, the halogen composition, the method and degree of chemical sensitization, the relationship between the layer containing the compound and the silver halide emulsion layer, the type of anti-capri compound, etc. is desirable, and testing methods for its selection are well known to those skilled in the art. Usually preferably from /Q mole to /X per mole of silver halide
It is used in a range of 10-' mol, especially 10-5 to 10-2 mol.
一般式（ＩＮ）で示される化合物の具体例全以下に示す
。但し本発明は以下の化合物に限定されるものではない
。All specific examples of the compound represented by the general formula (IN) are shown below. However, the present invention is not limited to the following compounds.
］［−／
［−ｆ
■−ＩＯ
肛−７λ
１−／３
■−／弘
■−／ｊ
ｆｌ−／６
Ｈ３
ｕ−／７
嘗
Ｃ）１２Ｃ１−１２ＣＩ−１２８Ｈ
ＩＬ−／ ｆ
、ＩＩ−／り
■−２０
ＩＮ ｉＮ
亘−２２
■−２３
１−２弘
］［−ｕｊ
］−２９
［−ｊＯ
■−３２
１１−３弘
’ｆｆ−Ｊｊ
その他、米国特許第≠、’Ａ７１． タ２を号に記載
の] [-/ [-f ■-IO anus-7λ 1-/3 ■-/Hiroshi ■-/j fl-/6 H3 u-/7 嘗C) 12C1-12CI-128H IL-/ f, II-/ ri ■-20 IN iN Wataru-22 ■-23 1-2 Hiro] [-uj ]-29 [-jO ■-32 11-3 Hiro'ff-Jj Others, US Patent No. ≠, 'A71. Ta 2 is listed in the issue.
Claims (1)
を有し、該乳剤層又はその他の親水性コロイド層に、ヒ
ドラジン誘導体を少なくとも一種類と、下記一般式（
I ）であらわされる化合物を少なくとも一種類含むこと
を特徴とする超硬調ネガ型ハロゲン化銀写真材料をｐＨ
１１．０〜９．６の現像液で処理することを特徴とする
超硬調なネガ画像の形成方法 一般式（ I ） ▲数式、化学式、表等があります▼ 式中Ｘは、窒素、酸素、セレン若しくは硫黄原子を含む
二価のヘテロ環を表わす。 Ａは炭素原子、窒素原子、酸素原子、硫黄原子から選ば
れた原子または原子群よりなる二価の連結基を表わす。 Ｂはアミノ基、アンモニウム基、および含窒素ヘテロ環
を表わす。 ｎは０または１を表わす。 Ｍは水素原子、アルカリ金属、アルカリ土類金属、四級
アンモニウム塩、四級ホスホニウム塩、アミジノ基また
はアルカリ条件下で開裂する基を表わす。(1) It has at least one silver halide emulsion layer on a support, and the emulsion layer or other hydrophilic colloid layer contains at least one hydrazine derivative and the following general formula (
I) An ultra-high contrast negative-working silver halide photographic material containing at least one compound represented by
A method for forming ultra-high contrast negative images characterized by processing with a developing solution of 11.0 to 9.6 General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, Represents a divalent heterocycle containing a selenium or sulfur atom. A represents a divalent linking group consisting of an atom or a group of atoms selected from carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms. B represents an amino group, an ammonium group, or a nitrogen-containing heterocycle. n represents 0 or 1. M represents a hydrogen atom, an alkali metal, an alkaline earth metal, a quaternary ammonium salt, a quaternary phosphonium salt, an amidino group, or a group that is cleaved under alkaline conditions.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63003446A JPH01179940A (en) | 1988-01-11 | 1988-01-11 | Method for forming ultrahigh contrast negative image |
| EP89100317A EP0324426B1 (en) | 1988-01-11 | 1989-01-10 | Process for forming super high contrast negative images |
| DE68926687T DE68926687T2 (en) | 1988-01-11 | 1989-01-10 | Process for the generation of extremely high-contrast negative images |
| US07/653,480 US5139921A (en) | 1988-01-11 | 1991-02-12 | Process for forming super high contrast negative images |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63003446A JPH01179940A (en) | 1988-01-11 | 1988-01-11 | Method for forming ultrahigh contrast negative image |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01179940A true JPH01179940A (en) | 1989-07-18 |
Family
ID=11557566
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63003446A Pending JPH01179940A (en) | 1988-01-11 | 1988-01-11 | Method for forming ultrahigh contrast negative image |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01179940A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03274048A (en) * | 1990-03-23 | 1991-12-05 | Konica Corp | Method for processing silver halide photographic sensitive material |
| EP0782041A2 (en) | 1995-12-27 | 1997-07-02 | Fuji Photo Film Co., Ltd. | Silver halide photographic light-sensitive material |
| EP1333319A2 (en) | 2002-01-30 | 2003-08-06 | Fuji Photo Film Co., Ltd. | Silver halide photographic light-sensitive material |
-
1988
- 1988-01-11 JP JP63003446A patent/JPH01179940A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03274048A (en) * | 1990-03-23 | 1991-12-05 | Konica Corp | Method for processing silver halide photographic sensitive material |
| EP0782041A2 (en) | 1995-12-27 | 1997-07-02 | Fuji Photo Film Co., Ltd. | Silver halide photographic light-sensitive material |
| EP1333319A2 (en) | 2002-01-30 | 2003-08-06 | Fuji Photo Film Co., Ltd. | Silver halide photographic light-sensitive material |
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