JPH0673005B2 - Silver halide photographic light-sensitive material - Google Patents
Silver halide photographic light-sensitive materialInfo
- Publication number
- JPH0673005B2 JPH0673005B2 JP60011459A JP1145985A JPH0673005B2 JP H0673005 B2 JPH0673005 B2 JP H0673005B2 JP 60011459 A JP60011459 A JP 60011459A JP 1145985 A JP1145985 A JP 1145985A JP H0673005 B2 JPH0673005 B2 JP H0673005B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- silver halide
- emulsion
- sensitive material
- compound
- 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.)
- Expired - Fee Related
Links
- -1 Silver halide Chemical class 0.000 title claims description 81
- 229910052709 silver Inorganic materials 0.000 title claims description 75
- 239000004332 silver Substances 0.000 title claims description 75
- 239000000463 material Substances 0.000 title claims description 39
- 239000000839 emulsion Substances 0.000 claims description 71
- 150000001875 compounds Chemical class 0.000 claims description 58
- 239000000084 colloidal system Substances 0.000 claims description 7
- 239000010410 layer Substances 0.000 description 38
- 239000000975 dye Substances 0.000 description 25
- 238000000034 method Methods 0.000 description 20
- 239000002667 nucleating agent Substances 0.000 description 19
- 239000000243 solution Substances 0.000 description 19
- 108010010803 Gelatin Proteins 0.000 description 16
- 239000008273 gelatin Substances 0.000 description 16
- 229920000159 gelatin Polymers 0.000 description 16
- 235000019322 gelatine Nutrition 0.000 description 16
- 235000011852 gelatine desserts Nutrition 0.000 description 16
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 15
- 239000013078 crystal Substances 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 10
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 10
- 230000001235 sensitizing effect Effects 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 125000003118 aryl group Chemical group 0.000 description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 9
- 238000012545 processing Methods 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 229920001515 polyalkylene glycol Polymers 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 125000001424 substituent group Chemical group 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 238000011161 development Methods 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 125000000623 heterocyclic group Chemical group 0.000 description 7
- 150000002429 hydrazines Chemical class 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 125000002947 alkylene group Chemical group 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 150000003283 rhodium Chemical class 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- 125000003545 alkoxy group Chemical group 0.000 description 5
- 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 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
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000004040 coloring Methods 0.000 description 4
- RIFGWPKJUGCATF-UHFFFAOYSA-N ethyl chloroformate Chemical compound CCOC(Cl)=O RIFGWPKJUGCATF-UHFFFAOYSA-N 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- AGBQKNBQESQNJD-UHFFFAOYSA-N lipoic acid Chemical compound OC(=O)CCCCC1CCSS1 AGBQKNBQESQNJD-UHFFFAOYSA-N 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 125000002950 monocyclic group Chemical group 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- 230000005070 ripening Effects 0.000 description 4
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- LRUDIIUSNGCQKF-UHFFFAOYSA-N 5-methyl-1H-benzotriazole Chemical compound C1=C(C)C=CC2=NNN=C21 LRUDIIUSNGCQKF-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229940126062 Compound A Drugs 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 206010070834 Sensitisation Diseases 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000000274 adsorptive effect Effects 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 235000010323 ascorbic acid Nutrition 0.000 description 3
- 125000002619 bicyclic group Chemical group 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 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
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 3
- NDGRWYRVNANFNB-UHFFFAOYSA-N pyrazolidin-3-one Chemical class O=C1CCNN1 NDGRWYRVNANFNB-UHFFFAOYSA-N 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 230000008313 sensitization Effects 0.000 description 3
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical class NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 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
- DSVIHYOAKPVFEH-UHFFFAOYSA-N 4-(hydroxymethyl)-4-methyl-1-phenylpyrazolidin-3-one Chemical compound N1C(=O)C(C)(CO)CN1C1=CC=CC=C1 DSVIHYOAKPVFEH-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical class [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- XCFIVNQHHFZRNR-UHFFFAOYSA-N [Ag].Cl[IH]Br Chemical compound [Ag].Cl[IH]Br XCFIVNQHHFZRNR-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical class C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 2
- 150000001661 cadmium Chemical class 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- ZUIVNYGZFPOXFW-UHFFFAOYSA-N chembl1717603 Chemical compound N1=C(C)C=C(O)N2N=CN=C21 ZUIVNYGZFPOXFW-UHFFFAOYSA-N 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000012992 electron transfer agent Substances 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 150000002505 iron Chemical class 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 125000003170 phenylsulfonyl group Chemical group C1(=CC=CC=C1)S(=O)(=O)* 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical class [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000120 polyethyl acrylate Polymers 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 2
- 150000003464 sulfur compounds Chemical class 0.000 description 2
- 125000001391 thioamide group Chemical group 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea group Chemical group NC(=S)N UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- AOSZTAHDEDLTLQ-AZKQZHLXSA-N (1S,2S,4R,8S,9S,11S,12R,13S,19S)-6-[(3-chlorophenyl)methyl]-12,19-difluoro-11-hydroxy-8-(2-hydroxyacetyl)-9,13-dimethyl-6-azapentacyclo[10.8.0.02,9.04,8.013,18]icosa-14,17-dien-16-one Chemical compound C([C@@H]1C[C@H]2[C@H]3[C@]([C@]4(C=CC(=O)C=C4[C@@H](F)C3)C)(F)[C@@H](O)C[C@@]2([C@@]1(C1)C(=O)CO)C)N1CC1=CC=CC(Cl)=C1 AOSZTAHDEDLTLQ-AZKQZHLXSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- UVNPEUJXKZFWSJ-LMTQTHQJSA-N (R)-N-[(4S)-8-[6-amino-5-[(3,3-difluoro-2-oxo-1H-pyrrolo[2,3-b]pyridin-4-yl)sulfanyl]pyrazin-2-yl]-2-oxa-8-azaspiro[4.5]decan-4-yl]-2-methylpropane-2-sulfinamide Chemical compound CC(C)(C)[S@@](=O)N[C@@H]1COCC11CCN(CC1)c1cnc(Sc2ccnc3NC(=O)C(F)(F)c23)c(N)n1 UVNPEUJXKZFWSJ-LMTQTHQJSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-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
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical class C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- GGZHVNZHFYCSEV-UHFFFAOYSA-N 1-Phenyl-5-mercaptotetrazole Chemical compound SC1=NN=NN1C1=CC=CC=C1 GGZHVNZHFYCSEV-UHFFFAOYSA-N 0.000 description 1
- JAAIPIWKKXCNOC-UHFFFAOYSA-N 1h-tetrazol-1-ium-5-thiolate Chemical class SC1=NN=NN1 JAAIPIWKKXCNOC-UHFFFAOYSA-N 0.000 description 1
- HAZJTCQWIDBCCE-UHFFFAOYSA-N 1h-triazine-6-thione Chemical class SC1=CC=NN=N1 HAZJTCQWIDBCCE-UHFFFAOYSA-N 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- GPNPYLFVYDZBHS-UHFFFAOYSA-N 2,5-dihydroxy-4-pentadecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCCCCC1=CC(O)=C(S(O)(=O)=O)C=C1O GPNPYLFVYDZBHS-UHFFFAOYSA-N 0.000 description 1
- ZKEGGSPWBGCPNF-UHFFFAOYSA-N 2,5-dihydroxy-5-methyl-3-(piperidin-1-ylamino)cyclopent-2-en-1-one Chemical compound O=C1C(C)(O)CC(NN2CCCCC2)=C1O ZKEGGSPWBGCPNF-UHFFFAOYSA-N 0.000 description 1
- YKUDHBLDJYZZQS-UHFFFAOYSA-N 2,6-dichloro-1h-1,3,5-triazin-4-one Chemical compound OC1=NC(Cl)=NC(Cl)=N1 YKUDHBLDJYZZQS-UHFFFAOYSA-N 0.000 description 1
- AXCGIKGRPLMUDF-UHFFFAOYSA-N 2,6-dichloro-1h-1,3,5-triazin-4-one;sodium Chemical compound [Na].OC1=NC(Cl)=NC(Cl)=N1 AXCGIKGRPLMUDF-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- YSUIQYOGTINQIN-UZFYAQMZSA-N 2-amino-9-[(1S,6R,8R,9S,10R,15R,17R,18R)-8-(6-aminopurin-9-yl)-9,18-difluoro-3,12-dihydroxy-3,12-bis(sulfanylidene)-2,4,7,11,13,16-hexaoxa-3lambda5,12lambda5-diphosphatricyclo[13.2.1.06,10]octadecan-17-yl]-1H-purin-6-one Chemical compound NC1=NC2=C(N=CN2[C@@H]2O[C@@H]3COP(S)(=O)O[C@@H]4[C@@H](COP(S)(=O)O[C@@H]2[C@@H]3F)O[C@H]([C@H]4F)N2C=NC3=C2N=CN=C3N)C(=O)N1 YSUIQYOGTINQIN-UZFYAQMZSA-N 0.000 description 1
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 1
- PHPYXVIHDRDPDI-UHFFFAOYSA-N 2-bromo-1h-benzimidazole Chemical class C1=CC=C2NC(Br)=NC2=C1 PHPYXVIHDRDPDI-UHFFFAOYSA-N 0.000 description 1
- AYPSHJCKSDNETA-UHFFFAOYSA-N 2-chloro-1h-benzimidazole Chemical class C1=CC=C2NC(Cl)=NC2=C1 AYPSHJCKSDNETA-UHFFFAOYSA-N 0.000 description 1
- KRTDQDCPEZRVGC-UHFFFAOYSA-N 2-nitro-1h-benzimidazole Chemical class C1=CC=C2NC([N+](=O)[O-])=NC2=C1 KRTDQDCPEZRVGC-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- JSIAIROWMJGMQZ-UHFFFAOYSA-N 2h-triazol-4-amine Chemical class NC1=CNN=N1 JSIAIROWMJGMQZ-UHFFFAOYSA-N 0.000 description 1
- CBHTTYDJRXOHHL-UHFFFAOYSA-N 2h-triazolo[4,5-c]pyridazine Chemical class N1=NC=CC2=C1N=NN2 CBHTTYDJRXOHHL-UHFFFAOYSA-N 0.000 description 1
- OCVLSHAVSIYKLI-UHFFFAOYSA-N 3h-1,3-thiazole-2-thione Chemical class SC1=NC=CS1 OCVLSHAVSIYKLI-UHFFFAOYSA-N 0.000 description 1
- AJKLCDRWGVLVSH-UHFFFAOYSA-N 4,4-bis(hydroxymethyl)-1-phenylpyrazolidin-3-one Chemical compound N1C(=O)C(CO)(CO)CN1C1=CC=CC=C1 AJKLCDRWGVLVSH-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
- SJSJAWHHGDPBOC-UHFFFAOYSA-N 4,4-dimethyl-1-phenylpyrazolidin-3-one Chemical compound N1C(=O)C(C)(C)CN1C1=CC=CC=C1 SJSJAWHHGDPBOC-UHFFFAOYSA-N 0.000 description 1
- UWOZQBARAREECT-UHFFFAOYSA-N 4-(hydroxymethyl)-4-methyl-1-(4-methylphenyl)pyrazolidin-3-one Chemical compound C1=CC(C)=CC=C1N1NC(=O)C(C)(CO)C1 UWOZQBARAREECT-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
- ZVNPWFOVUDMGRP-UHFFFAOYSA-N 4-methylaminophenol sulfate Chemical compound OS(O)(=O)=O.CNC1=CC=C(O)C=C1.CNC1=CC=C(O)C=C1 ZVNPWFOVUDMGRP-UHFFFAOYSA-N 0.000 description 1
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- UTMDJGPRCLQPBT-UHFFFAOYSA-N 4-nitro-1h-1,2,3-benzotriazole Chemical class [O-][N+](=O)C1=CC=CC2=NNN=C12 UTMDJGPRCLQPBT-UHFFFAOYSA-N 0.000 description 1
- WSGURAYTCUVDQL-UHFFFAOYSA-N 5-nitro-1h-indazole Chemical compound [O-][N+](=O)C1=CC=C2NN=CC2=C1 WSGURAYTCUVDQL-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
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-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 compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229940126657 Compound 17 Drugs 0.000 description 1
- 150000000996 L-ascorbic acids Chemical class 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- NUGPIZCTELGDOS-QHCPKHFHSA-N N-[(1S)-3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-pyridin-3-ylpropyl]cyclopentanecarboxamide Chemical compound C(C)(C)C1=NN=C(N1C1CCN(CC1)CC[C@@H](C=1C=NC=CC=1)NC(=O)C1CCCC1)C NUGPIZCTELGDOS-QHCPKHFHSA-N 0.000 description 1
- 229920002164 Polyalkylene glycol copolymer Polymers 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 description 1
- 241000555745 Sciuridae Species 0.000 description 1
- 229910021612 Silver iodide Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- SMEGJBVQLJJKKX-HOTMZDKISA-N [(2R,3S,4S,5R,6R)-5-acetyloxy-3,4,6-trihydroxyoxan-2-yl]methyl acetate Chemical compound CC(=O)OC[C@@H]1[C@H]([C@@H]([C@H]([C@@H](O1)O)OC(=O)C)O)O SMEGJBVQLJJKKX-HOTMZDKISA-N 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- 229940081735 acetylcellulose Drugs 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000004442 acylamino group Chemical group 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000002877 alkyl aryl 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
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- XIWMTQIUUWJNRP-UHFFFAOYSA-N amidol Chemical compound NC1=CC=C(O)C(N)=C1 XIWMTQIUUWJNRP-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000008378 aryl ethers Chemical class 0.000 description 1
- 125000004391 aryl sulfonyl group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- AJPXTSMULZANCB-UHFFFAOYSA-N chlorohydroquinone Chemical compound OC1=CC=C(O)C(Cl)=C1 AJPXTSMULZANCB-UHFFFAOYSA-N 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 238000001246 colloidal dispersion Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000002946 cyanobenzyl group Chemical group 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000003975 dentin desensitizing agent Substances 0.000 description 1
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 1
- 150000002012 dioxanes Chemical class 0.000 description 1
- 239000004815 dispersion polymer Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- AEOCXXJPGCBFJA-UHFFFAOYSA-N ethionamide Chemical compound CCC1=CC(C(N)=S)=CC=N1 AEOCXXJPGCBFJA-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 150000002344 gold compounds Chemical class 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- FBPFZTCFMRRESA-UHFFFAOYSA-N hexane-1,2,3,4,5,6-hexol Chemical class OCC(O)C(O)C(O)C(O)CO FBPFZTCFMRRESA-UHFFFAOYSA-N 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 150000005204 hydroxybenzenes Chemical class 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 230000002458 infectious effect Effects 0.000 description 1
- 150000002503 iridium Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical class [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- ONXUKUKYPIDVEE-UHFFFAOYSA-N n-(4-aminophenyl)acetohydrazide Chemical compound CC(=O)N(N)C1=CC=C(N)C=C1 ONXUKUKYPIDVEE-UHFFFAOYSA-N 0.000 description 1
- OOCBKVNFQWKILG-UHFFFAOYSA-N n-amino-n-(4-aminophenyl)formamide Chemical compound O=CN(N)C1=CC=C(N)C=C1 OOCBKVNFQWKILG-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- CMCWWLVWPDLCRM-UHFFFAOYSA-N phenidone Chemical compound N1C(=O)CCN1C1=CC=CC=C1 CMCWWLVWPDLCRM-UHFFFAOYSA-N 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000004584 polyacrylic acid Substances 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
- JVUYWILPYBCNNG-UHFFFAOYSA-N potassium;oxido(oxo)borane Chemical compound [K+].[O-]B=O JVUYWILPYBCNNG-UHFFFAOYSA-N 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- HBCQSNAFLVXVAY-UHFFFAOYSA-N pyrimidine-2-thiol Chemical class SC1=NC=CC=N1 HBCQSNAFLVXVAY-UHFFFAOYSA-N 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 125000004964 sulfoalkyl group Chemical group 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 125000000565 sulfonamide group Chemical group 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000004250 tert-Butylhydroquinone Substances 0.000 description 1
- 235000019281 tert-butylhydroquinone Nutrition 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
- 150000003557 thiazoles 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
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 150000003852 triazoles Chemical group 0.000 description 1
- IELLVVGAXDLVSW-UHFFFAOYSA-N tricyclohexyl phosphate Chemical compound C1CCCCC1OP(OC1CCCCC1)(=O)OC1CCCCC1 IELLVVGAXDLVSW-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 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
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
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感光材料に関するものであり、特
に、ヒドラジン系系化合物を含有するハロゲン化銀感光
材料に関するものである。TECHNICAL FIELD The present invention relates to a silver halide light-sensitive material, and particularly to a silver halide light-sensitive material containing a hydrazine-based compound.
（従来技術） ハロゲン化銀感光材料中にヒドラジン類を種々の目的で
用いることが知られているが、特に直接ポジ乳剤におけ
る造核剤として、あるいはネガ型乳剤との組合せにおい
て感度及びコントラストを高めるための素材として有効
である。(Prior Art) It is known to use hydrazines for various purposes in a silver halide light-sensitive material, and particularly to enhance sensitivity and contrast as a nucleating agent in a direct positive emulsion or in combination with a negative emulsion. It is effective as a material for
高コントラスト（ガンマ10以上）の写真特性を示す画像
形成システムは、網点画像による連続階調の画像の再生
や線画の再生を良好にするため、グラフイツク・アーツ
の分野において必要である。An image forming system exhibiting high-contrast (gamma of 10 or more) photographic characteristics is necessary in the field of graphic arts in order to improve reproduction of continuous tone images and half-tone images by halftone dot images.
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た。リス現像液は現像主薬としてハ
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
低くしてある。そのためリス現像液は極めて空気酸化を
受け易く３日を越える保存に耐えられないという重大な
欠点をもつている。Conventionally, a special developer called a lith developer has been used for this purpose. The squirrel developer contains only hydroquinone as a developing agent, and a sulfite salt, which is a preservative, is used in the form of an adduct with formaldehyde so as not to impair the infectious developing property, and the concentration of free sulfite ion is extremely low. . Therefore, the lith developer has a serious drawback that it is extremely susceptible to air oxidation and cannot be stored for more than 3 days.
超硬調の写真特性を安定な現像液を用いて得る方法とし
ては米国特許第4,224,401号、同4,168,977号、同4,166,
742号、同4,311,781号、同4,272,606号、同4,221,857
号、同4,243,739号等に記載されているヒドラジン誘導
体を用いる方法がある。この方法によれば、高コントラ
ストで感度の高い写真特性が得られ、更に現像液中に高
濃度の亜硫酸塩を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 a photographic property of ultra-high contrast using a stable developer, U.S. Pat.Nos. 4,224,401, 4,168,977, and 4,166,
742, 4,311,781, 4,272,606, 4,221,857
No. 4,243,739 and the like, there is a method using a hydrazine derivative. According to this method, high-contrast and high-sensitivity photographic characteristics are obtained, and since it is permissible to add a high concentration of sulfite to the developing solution, the stability of the developing solution against aerial oxidation does not affect the lith developer. Greatly improved compared to.
これらの目的に用いられるヒドラジン誘導体の好ましい
例は、Reseach Disclosure誌第23510項（1983年11
月）、およびそこに引用された特許、文献の他、特開昭
59−212829号などにそれぞれ特有の利点を有するものと
して開示されている。しかしながら、これら従来のヒド
ラジン化合物は、組合せるハロゲン化銀写真乳剤の性質
によつては高コントラストな写真特性を与えるという機
能を十分発揮し得ないことがあり、一方ある程度の高活
性を示すものは保存性に問題があるということが明らか
になつてきた。Preferred examples of hydrazine derivatives used for these purposes are described in Research Disclosure, Item 23510 (1983, 11
And the patents and literature cited therein,
No. 59-212829 and the like are disclosed as having respective unique advantages. However, these conventional hydrazine compounds may not sufficiently exhibit the function of providing high-contrast photographic characteristics depending on the properties of the silver halide photographic emulsion to be combined, while those showing a certain high activity are It has become clear that there is a problem with shelf life.
一方、直接ポジ写真法には種々あるが、予めカブらせた
ハロゲン化銀粒子を減感剤の存在下に露光した後、現像
する方法と、主としてハロゲン化銀粒子の内部に感光核
を有するハロゲン化銀乳剤を露光後、造核剤の存在下に
現像する方法とが最も有用である。ハロゲン化銀粒子内
部に主に感光核を有し、粒子内部に主として潜像が形成
されるようなハロゲン化銀乳剤は内部潜像型ハロゲン化
銀乳剤といわれており、主として粒子表面上に潜像を形
成するハロゲン化銀粒子とは区別されるものである。On the other hand, although there are various direct positive photographic methods, there is a method of exposing silver halide grains fogged in advance in the presence of a desensitizing agent and then developing, and having a photosensitive nucleus mainly inside the silver halide grains. The most useful method is to develop the silver halide emulsion in the presence of a nucleating agent after exposure. A silver halide emulsion having a photosensitive nucleus mainly inside the silver halide grain and forming a latent image mainly inside the grain is said to be an internal latent image type silver halide emulsion and is mainly formed on the surface of the grain. It is distinct from the silver halide grains that form the image.
内部潜像型ハロゲン化銀写真乳剤を造核剤の存在下で表
面現像することによつて直接ポジ像を得る方法及びその
ような方法に用いられる写真乳剤又は感光材料は例えば
米国特許第2,456,953号、同2,497,875号、同2,497,876
号、同2,588,982号、同2,592,250号、同2,675,318号、
同3,227,552号、同3,317,322号、英国特許1,011,062
号、、同1,151,363号、同1,269,640号、同2,011,391
号、特公昭43−29,405号、同49−38,164号、特開昭53−
16,623号、同137,133号、同54−37,732号、同54−40,62
9号、同54−74,536号、同54−74,729号、同55−52,055
号、同55−90,940号などで知られている。A method for directly obtaining a positive image by surface developing an internal latent image type silver halide photographic emulsion in the presence of a nucleating agent and a photographic emulsion or a light-sensitive material used in such a method are described in, for example, U.S. Pat.No. 2,456,953. , No. 2,497,875, No. 2,497,876
No., No. 2,588,982, No. 2,592,250, No. 2,675,318,
No. 3,227,552, No. 3,317,322, British patent 1,011,062
No. 1,1,153,363, 1,269,640, 2,011,391
No. 4, JP-B-43-29,405, JP-B-49-38,164, JP-A-53-
16,623, 137,133, 54-37,732, 54-40,62
No. 9, 54-74,536, 54-74,729, 55-52,055
No. 55-90,940.
上記の直接ポジ像を得る方法において造核剤は現像中に
添加してもよいが、感光材料の写真乳剤層またはその他
の適当な層に添加することによりハロゲン化銀粒子表面
に吸着させたときに、より良い反転特性を得ることがで
きる。In the above method for obtaining a direct positive image, the nucleating agent may be added during development, but when the nucleating agent is added to the photographic emulsion layer of the light-sensitive material or other appropriate layer so as to be adsorbed on the silver halide grain surface. In addition, a better reversal characteristic can be obtained.
上記の直接ポジ像を得る方法において使用する造核剤と
しては、米国特許2,563,785号、同2,588,982号に記載さ
れたヒドラジン類、および米国特許3,227,552号に記載
されたヒドラジンおよびヒドラジン系化合物が知られて
おり、この他にも種々の改良を施したものとして、米国
特許3,615,615号、同3,719,494号、同3,734,738号、同
4,094,683号および同4,115,122号、英国特許1,283,835
号、特開昭52−3426号および同52−69613号に記載の複
素環第４級塩化合物から成る造核剤、米国特許3,718,47
0号記載の造核作用のある置換基を有する増感色素、米
国特許4,030,925号、同4,031,127号、同4,139,387号、
同4,245,037号、同4,255,511号および同4,276,364号、
英国特許2,012,443号などに記載されるチオ尿素結合型
アシルフエニルヒドラジン系化合物、米国特許4,080,20
7号に記載されたヘテロ環チオアミドを吸着基として用
いたもの、英国特許2,011,391Bに記載されている吸着基
としてメルカプト基を有する複素環基をもつたフエニル
アシルヒドラジン系化合物、特開昭59−200230、59−21
2828、特開昭59−21289などに記載のヒドラジン類が知
られており、Research Disclosure誌第23510項（1983年
11月）にも多くの例が引用されている。As the nucleating agent used in the method for obtaining the above direct positive image, hydrazines described in U.S. Pat.Nos. 2,563,785 and 2,588,982, and hydrazine and hydrazine compounds described in U.S. Pat.No. 3,227,552 are known. In addition to these, U.S. Pat.Nos. 3,615,615, 3,719,494, 3,734,738 and US Pat.
4,094,683 and 4,115,122, British Patent 1,283,835
And nucleating agents comprising a heterocyclic quaternary salt compound described in JP-A Nos. 52-3426 and 52-69613, U.S. Pat. No. 3,718,47.
Sensitizing dyes having a nucleating substituent of 0, U.S. Pat.Nos. 4,030,925, 4,031,127, 4,139,387,
No. 4,245,037, No. 4,255,511 and No. 4,276,364,
Thiourea-bonded acylphenylhydrazine compounds described in British Patent No. 2,012,443, US Pat.
No. 7, which uses a heterocyclic thioamide as an adsorptive group, and a phenylacylhydrazine compound having a heterocyclic group having a mercapto group as an adsorptive group described in British Patent 2,011,391B, JP-A-59. -200230, 59-21
2828, hydrazines described in JP-A-59-21289 and the like are known, and Research Disclosure No. 23510 (1983
Many examples are also cited in (November).
しかしながらこれらの化合物は造核剤としての活性が不
十分であつたり、また活性が高いものは保存性が不十分
であるという欠点のあることがわかつてきた。However, it has been found that these compounds have a drawback that they have insufficient activity as a nucleating agent, and that those having a high activity have insufficient storage stability.
（発明の目的） 本発明の目的は第１に、グラフイツク・アーツ用に適し
た高画質と高いコントラストのネガ画像を、種々のネガ
型ハロゲン化銀乳剤との組合せにおいて与える高活性な
造核剤を含有するハロゲン化銀写真感光材料を提供する
ことであり、第２に高活性な造核剤を含有する直接ポジ
ハロゲン化銀写真感光材料を提供することであり、第３
に、感光材料の保存性を悪化させない造核剤を含有する
上記のハロゲン化銀写真感光材料を提供することであ
る。(Object of the Invention) The first object of the present invention is to provide a highly active nucleating agent which gives a negative image of high image quality and high contrast suitable for graphic arts in combination with various negative type silver halide emulsions. A second object is to provide a silver halide photographic light-sensitive material containing the second, and a second object is to provide a direct positive silver halide photographic light-sensitive material containing a highly active nucleating agent.
Another object of the present invention is to provide the above silver halide photographic light-sensitive material containing a nucleating agent that does not deteriorate the storage stability of the light-sensitive material.
（発明の構成） 本発明者らは種々検討した結果、ハロゲン化銀写真乳剤
層を少なくとも１つ有するハロゲン化銀写真感光材料に
おいて、該写真乳剤層又は、他の少くとも一つの親水性
コロイド層に下記一般式（Ｉ）で表わされる化合物を含
有させることにより本発明の目的を達成した。(Structure of the Invention) As a result of various studies by the present inventors, in a silver halide photographic light-sensitive material having at least one silver halide photographic emulsion layer, the photographic emulsion layer or at least one other hydrophilic colloid layer. The object of the present invention was achieved by incorporating a compound represented by the following general formula (I) into
一般式（Ｉ） 一般式（Ｉ）において、R1で表わされる芳香族基は、単
環もしくは２環のアリール基または不飽和ヘテロ環基で
ある。ここで不飽和ヘテロ環基は単環もしくは２環のア
リール基と縮合してヘテロアリール基を形成してもよ
い。このR1の芳香族基は置換基を有していてもよく、ま
た好ましくは（置換基のある場合それも含めて）炭素数
30以下である。好ましい置換基の例としては、直鎖、分
岐もしくは環状のアルキル基、アルコキシ基、置換アミ
ノ基、アシルアミノ基、スルホンアミド基、チオ尿素
基、チオアミド基、炭素−窒素２重結合を有する（Ｃ
＝Ｎ−）、ヘテロ環基又はこれらの組合せ等が挙げられ
る。これら置換基の詳細については、特開昭57−129436
号等に記載されている。General formula (I) In the general formula (I), the aromatic group represented by R 1 is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be condensed with a monocyclic or bicyclic aryl group to form a heteroaryl group. The aromatic group of R 1 may have a substituent, and preferably has a carbon number (including the substituent, if any).
30 or less. Examples of preferred substituents include linear, branched or cyclic alkyl groups, alkoxy groups, substituted amino groups, acylamino groups, sulfonamide groups, thiourea groups, thioamide groups, and carbon-nitrogen double bonds (C
= N-), a heterocyclic group, or a combination thereof. For details of these substituents, see JP-A-57-129436.
No. etc.
一般式（Ｉ）おいてR2の表すアルキル基としては、好ま
しくは炭素数１〜４のアルキル基であつて、ハロゲン原
子、シアノ基、カルボキシ基、スルホ基、アルコキシ
基、フエニル基などの置換基を有していてもよい。The alkyl group represented by R 2 in the general formula (I) is preferably an alkyl group having 1 to 4 carbon atoms and substituted with a halogen atom, a cyano group, a carboxy group, a sulfo group, an alkoxy group, a phenyl group or the like. It may have a group.
一般式（Ｉ）において、R2で表される基のうち置換され
ていてもよいアリール基は単環または２環のアリール基
で、例えばベンゼン環を含むものである。このアリール
基は、例えばハロゲン原子、アルキル基、シアノ基、カ
ルボキシル基、スルホ基などで置換されていてもよい。In the general formula (I), the aryl group which may be substituted among the groups represented by R 2 is a monocyclic or bicyclic aryl group and includes, for example, a benzene ring. This aryl group may be substituted with, for example, a halogen atom, an alkyl group, a cyano group, a carboxyl group, a sulfo group or the like.
一般式（Ｉ）のR2で表される基のうち置換されてもよい
アルコキシ基としては炭素数１〜８のアルコキシ基であ
つて、ハロゲン原子、アリール基などで置換されていて
もよい。The alkoxy group which may be substituted among the groups represented by R 2 in the general formula (I) is an alkoxy group having 1 to 8 carbon atoms, which may be substituted with a halogen atom, an aryl group or the like.
一般式（Ｉ）においてR2で表される基のうち置換されて
もよいアリールオキシ基として単環のものが好ましく、
また置換基としてはハロゲン原子などがある。Of the groups represented by R 2 in the general formula (I), an optionally substituted aryloxy group is preferably a monocyclic group.
Further, the substituent includes a halogen atom and the like.
R2で表される基のうちで好ましいものは、Ｇがカルボニ
ル基の場合には水素原原子、メチル基、メトキシ基、エ
トキシ基、置換または無置換のフエニル基であり、特に
水素原子が好ましい。Of the groups represented by R 2 , preferred are a hydrogen atom, a methyl group, a methoxy group, an ethoxy group, and a substituted or unsubstituted phenyl group when G is a carbonyl group, and a hydrogen atom is particularly preferred. .
Ｇがスルホニル基の場合にはR2としてはメチル基、エチ
ル基、フエニル基、４−メチルフエニル基が好ましく、
特にメチル基が好適である。When G is a sulfonyl group, R 2 is preferably a methyl group, an ethyl group, a phenyl group or a 4-methylphenyl group,
A methyl group is particularly preferable.
Ｇがホスホリル基の場合には、R2としてはメトキシ基、
エトキシ基、ブトキシ基、フエノキシ基、フエニル基が
好ましく特にフエノキシ基が好適である。When G is a phosphoryl group, R 2 is a methoxy group,
An ethoxy group, a butoxy group, a phenoxy group and a phenyl group are preferable, and a phenoxy group is particularly preferable.
Ｇがスルホキシ基の場合、好ましいR2はシアノベンジル
基、メチルチオベンジル基などであり、ＧがＮ−置換ま
たは無置換イミノ基の場合、好ましいR2はメチル基、エ
チル基、置換または無置換のフエニル基である。When G is a sulfoxy group, preferred R 2 is a cyanobenzyl group, a methylthiobenzyl group, etc. When G is an N-substituted or unsubstituted imino group, preferred R 2 is a methyl group, an ethyl group, a substituted or unsubstituted group. It is a phenyl group.
一般式（Ｉ）のR1またはR2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８以上の炭
素数を有する写真性に対して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、フエニル基、アルキ
ルフエニル基、フエノキシ基、アルキルフエノキシ基な
どの中から選ぶことができる。R 1 or R 2 in the general formula (I) may have a ballast group incorporated therein which is commonly used in a non-moving photographic additive such as a coupler. The ballast group is a group having a carbon number of 8 or more, which is relatively inert to photographic properties,
For example, it can be selected from an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group, an alkylphenoxy group and the like.
一般式（Ｉ）のR1またはR2はその中ににハロゲン化銀粒
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4,385,108号に記載された基があげられ
る。R 1 or R 2 in the general formula (I) may be one in which a group for enhancing adsorption to the surface of the silver halide grain is incorporated. Examples of the adsorptive group include groups described in US Pat. No. 4,385,108 such as thiourea group, heterocyclic thioamide group, mercaptoheterocyclic group and triazole group.
一般式（Ｉ）においてQ1又はQ2で表わされるアルキルス
ルホニル基およびアリールスルホニル基は炭素数20以下
のものであり、好ましくはフエニルスルホニル基又はハ
メツトの置換基定数の和が−0.5以上となるように置換
されたフエニルスルホニル基であり;Q1又はQ2で表わさ
れるアシル基は炭素数20以下のものであり、好ましくは
ベンゾイル基又はハメツトの置換基定数の和が−0.5以
上となるように置換されたベンゾイル基、あるいは炭素
数８以下の直鎖又は分枝状、又は環状の脂肪族アシル基
及びそのハロゲン置換体、又はエーテル結合、スルホン
アミド結合、カルボンアミド結合、水酸基、カルボキシ
ル基、スルホン酸基を有する炭素数８以下の基による置
換である。The alkylsulfonyl group and arylsulfonyl group represented by Q 1 or Q 2 in the general formula (I) have a carbon number of 20 or less, and preferably the sum of the substituent constants of a phenylsulfonyl group or a hamet is −0.5 or more. A phenylsulfonyl group substituted so that the acyl group represented by Q 1 or Q 2 has a carbon number of 20 or less, preferably the sum of the substituent constants of benzoyl group or hamet is -0.5 or more. A substituted benzoyl group, or a linear, branched, or cyclic aliphatic acyl group having 8 or less carbon atoms and a halogen-substituted product thereof, or an ether bond, a sulfonamide bond, a carbonamide bond, a hydroxyl group, or a carboxyl group. And a group having a sulfonic acid group and having 8 or less carbon atoms.
一般式（Ｉ）においてR2又はR2上に置換するジスルフイ
ド結合を有する基は炭素数20以下のものであり、好まし
くはジスルフイド結合が４ないし12員の環の一部となつ
ているものであり、この環とR1又はR2とは直接又は炭素
数１ないし18の有機基を介して連結するが、この連結基
を形成する原子団は好ましくは、直鎖状、分枝状、又は
環状のアルキレン基、置換又は無置換のフエニレン基、
−Ｏ−、CONR−、−SO2NR−、−COO−、−Ｓ−、−NR
−、−CO−、−SO−、−SO2−、−OCOO−、−NRCONR′
−、−NRCOO−、−NRSO2NC′（ここでＲ、Ｒ′はそれぞ
れ水素原子、炭素数17以下の置換又は無置換のアルキル
基、炭素数17以下の置換フエニル基又はフエニル基をわ
す）より単独または組合せて選ばれる。In the general formula (I), R 2 or a group having a disulfide bond substituted on R 2 has a carbon number of 20 or less, and preferably the disulfide bond is part of a 4- to 12-membered ring. The ring and R 1 or R 2 are linked directly or via an organic group having 1 to 18 carbon atoms, and the atomic group forming the linking group is preferably linear, branched, or Cyclic alkylene group, substituted or unsubstituted phenylene group,
-O-, CONR -, - SO 2 NR -, - COO -, - S -, - NR
-, - CO -, - SO -, - SO 2 -, - OCOO -, - NRCONR '
-, -NRCOO-, -NRSO 2 NC '(wherein R and R'represent a hydrogen atom, a substituted or unsubstituted alkyl group having a carbon number of 17 or less, a substituted phenyl group or a phenyl group having a carbon number of 17 or less) They are selected alone or in combination.
一般式（Ｉ）で表わされる化合物のうち特に好ましいも
のは下記一般式（II）で表わされる化合物である。Among the compounds represented by the general formula (I), particularly preferred are the compounds represented by the following general formula (II).
一般式（II） 一般式（Ｉ）で示される化合物の具体例を以下に示すが
本発明の範囲はこれらの化合物に限定されるものではな
い。General formula (II) Specific examples of the compound represented by formula (I) are shown below, but the scope of the present invention is not limited to these compounds.
本発明において、一般式（Ｉ）で表わされる化合物を写
真感光材料中に含有させるときは、アルコール類（例え
ばメタノール、エタノール）、エステル類（例えば酢酸
エチル）、ケトン類（例えばアセトン）などの水に混和
しうる有機溶媒の溶液とするか、水溶性の場合には水溶
液として、親水性コロイド溶液に添加すればよい。 In the present invention, when the compound represented by the general formula (I) is contained in the photographic light-sensitive material, water such as alcohols (eg methanol, ethanol), esters (eg ethyl acetate), ketones (eg acetone), etc. It may be added to the hydrophilic colloid solution as a solution of an organic solvent that is miscible with, or as an aqueous solution when it is water-soluble.
写真乳剤中に添加する場合、その添加は化学熟成の開始
から塗布前までの任意の時期に行つてよいが、化学熟成
終了後に行うのが好ましい。When it is added to the photographic emulsion, it may be added at any time from the start of chemical ripening to before coating, but it is preferably added after the completion of chemical ripening.
次に本発明をコントラストの高い画像形成方法に用いる
ハロゲン化銀写真感光材料に適用する場合について説明
する。Next, the case where the present invention is applied to a silver halide photographic light-sensitive material used in an image forming method with high contrast will be described.
本発明において高コントラスト画像形成に用いられるハ
ロゲン化銀感光材料はネガ型のハロゲン化銀乳剤からな
る乳剤層を少なくとも１層有するものである。The silver halide light-sensitive material used for high contrast image formation in the present invention has at least one emulsion layer composed of a negative type silver halide emulsion.
使用するハロゲン化銀乳剤のハロゲン組成には特別な限
定はなく、塩化銀、塩臭化銀、沃臭化銀、沃臭塩化銀
等、どの組成であつてもかまわない。There is no particular limitation on the halogen composition of the silver halide emulsion to be used, and any composition such as silver chloride, silver chlorobromide, silver iodobromide, silver iodobromochloride can be used.
沃化銀の含量は５モル％以下で、さらに３モル％以下で
あることが好ましい。The content of silver iodide is 5 mol% or less, preferably 3 mol% or less.
本発明に用いられる写真乳剤中のハロゲン化銀粒子は、
比較的広い粒子サイズ分布をもつこともできるが、せま
い粒子サイス分布をもつことが好ましく、特にハロゲン
化銀粒子の重量又は数に関して全体の90％を占める粒子
のサイズが平均粒子サイズの±40％以内にあることが好
ましい。（一般にこのような乳剤は単分離乳剤とよばれ
る）。The silver halide grains in the photographic emulsion used in the present invention are
Although it is possible to have a relatively wide grain size distribution, it is preferable to have a narrow grain size distribution, and especially the grain size which accounts for 90% of the total weight or number of silver halide grains is ± 40% of the average grain size. It is preferably within the range. (In general, such emulsions are called single-separation emulsions).
本発明で用いるハロゲン化銀粒子は、微粒子（例えば0.
7μ以下）の方が好ましく、特に0.4μ以下が好ましい。The silver halide grains used in the present invention are fine grains (for example, 0.
7μ or less) is preferable, and 0.4μ or less is particularly preferable.
写真乳剤中のハロゲン化銀粒子は、立方体、八面体のよ
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つ
てもよい。The silver halide grains in the photographic emulsion may have regular crystal bodies such as cubes and octahedra, and irregular grains such as spheres and plates.
It may have various crystals, or may have a composite form of these crystal forms. It may consist of a mixture of particles of different crystal forms.
ハロゲン化銀粒子は内部と表層とが均一な相から成つて
いても、単なる相をもつていてもよい。The silver halide grains may have a uniform phase in the inside and the surface layer, or may have a simple phase.
別々に形成した２種以上のハロゲン化銀乳剤を混合して
用いてもよい。Two or more kinds of silver halide emulsions formed separately may be mixed and used.
本発明に用いるハロゲン化銀乳剤にはハロゲン化銀粒子
の形成または物理熟成の過程においてカドミウム塩、亜
硫塩、鉛塩、タリウム塩、イリジウム塩ももしくはその
錯塩、ロジウム塩もしくはその錯塩、または鉄塩もしく
はその鉄塩などを共存させてもよい。The silver halide emulsion used in the present invention includes a cadmium salt, a sulfite salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, or an iron salt during the formation or physical ripening of silver halide grains. Alternatively, its iron salt or the like may coexist.
特にロジウム塩又はその錯塩の使用は迅速処理適性を更
に高める効果を奏するので好ましい。ロジウム塩は代表
的には、ロジウムクロライド、ロジウムトリクロライ
ド、ロジウムアンモニウムクロライドなどが用いられる
が、さらに錯塩を用いることもできる。ロジウム塩の添
加時間は乳剤製造時の第１熟成終了前であればよいが、
特に粒子形成中に添加されるのが望ましく、その添加量
は銀１モルあたり１×10-8モルから８×10-6モルの範囲
にありさらに、１×10-7モルから５×10-6モルの範囲が
特に好ましい。In particular, use of a rhodium salt or a complex salt thereof is preferable because it has the effect of further enhancing suitability for rapid processing. As the rhodium salt, rhodium chloride, rhodium trichloride, rhodium ammonium chloride, etc. are typically used, but a complex salt can also be used. The rhodium salt may be added before the first ripening at the time of emulsion production,
Particularly desirable is added during grain formation, the amount added is more in the range of 8 × 10 -6 mol 1 × 10 -8 mol per 1 mol of silver, 1 × 10 -7 mol 5 × 10 - A range of 6 moles is particularly preferred.
ハロゲン化銀乳剤に、ロジウム塩が添加されると、硬調
化と同時に感度低下をもたらすが、本発明の乳剤は、前
記一般式（Ｉ）で表わされる化合物により感度が回復す
ると同時に著しく、硬調化するのが特徴である。When a rhodium salt is added to the silver halide emulsion, the contrast becomes high and at the same time the sensitivity is lowered. However, the emulsion of the present invention is remarkably increased in the contrast at the same time as the sensitivity is restored by the compound represented by the general formula (I). The feature is to do.
一般式（Ｉ）で表わされる化合物を高コントラスト用感
材に用いる場合の使用量は、ハロゲン化銀乳剤層中の銀
１モル当り１×10-6〜５×10-2モル、特に１×10-5〜２
×10-2モルであることが好ましい。When the compound represented by the general formula (I) is used in a light-sensitive material for high contrast, the amount used is 1 × 10 −6 to 5 × 10 −2 mol, and especially 1 × 1 mol per mol of silver in the silver halide emulsion layer. 10 -5 to 2
It is preferably × 10 -2 mol.
写真乳剤の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、それ以外の天然又は合成
された親水性コロイドを用いることもできる。As the binder or protective colloid of the photographic emulsion, it is advantageous to use gelatin, but other natural or synthetic hydrophilic colloid can also be used.
ゼラチンとしては石灰処理ゼラチンのほか、酸処理ゼラ
チンを用いてもよく、ゼラチン加水分解物、ゼラチン酵
素分解物も用いることができる。As the gelatin, acid-treated gelatin may be used in addition to lime-treated gelatin, and gelatin hydrolyzate and gelatin enzyme-decomposed product may also be used.
本発明の方法で用いるハロゲン化銀乳剤は化学増感され
ていなくてもよいが、化学増感されているのが好まし
い。ハロゲン化銀乳剤の化学増感の方法として、硫黄増
感、、還元増感及び貴金属増感法が知られており、これ
らのいずれをも単独で用いても、又併用して化学増感し
てもよい。これらについては前記GlafkidesまたはZelik
manらの著書あるいはH.Frieser編Die Grundlagen der P
hotographischen Prozesse mit Silberhalogeniden （A
kademische Verlagsgesellschaft,1968）に記載されて
いる。The silver halide emulsion used in the method of the present invention may not be chemically sensitized, but is preferably chemically sensitized. As a method of chemically sensitizing a silver halide emulsion, sulfur sensitization, reduction sensitization and noble metal sensitization are known, and any of these may be used alone or in combination. May be. For these, see Glafkides or Zelik above.
Books by man et al. or edited by H. Frieser Die Grundlagen der P
hotographischen Prozesse mit Silberhalogeniden (A
kademische Verlagsgesellschaft, 1968).
貴金属増感法のうち金増感法はその代表的なもので金化
合物、主として金錯塩を用いる。金以外の貴金属、たと
えば白金、パラジウム、イリジウム等の錯塩を含有して
も差支えない。Among the noble metal sensitizing methods, the gold sensitizing method is a typical one, which uses a gold compound, mainly a gold complex salt. Noble metals other than gold, for example, complex salts of platinum, palladium, iridium, etc. may be contained.
硫黄増感剤としては、ゼラチン中に含まれる硫黄化合物
のほか、種々の硫黄化合物、たとえばチオ硫酸塩、チオ
尿素類、チアゾール類、ローダニン類等を用いることが
できる。As the sulfur sensitizer, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanins and the like can be used in addition to the sulfur compounds contained in gelatin.
還元増感剤としては第一すず塩、アミン類、ホルムアミ
ジンスルフイン酸、シラン化合物などを用いることがで
きる。As the reduction sensitizer, a primary tin salt, amines, formamidine sulfinic acid, a silane compound or the like can be used.
本発明の感光材料には、感光材料の製造工程、保存中あ
るいは写真処理中のカブリを防止しあるいは写真性能を
安定化させる目的で、種々の化合物を含有させることが
できる。すなわちアゾール類たとえばベンゾチアゾリウ
ム塩、ニトロインダゾール類、ニトロベンズイミダゾー
ル類、クロロベンズイミダゾール類、ブロモベンズイミ
ダゾール類、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、アミノトリアゾール類、ベ
ンゾチアゾール類、ニトロベンゾトリアゾール類、メル
カプトテトラゾール類（特に１−フエニル−５−メルカ
プトテトラゾール）など：メルカプトピリミジン類；メ
ルカプトトリアジン類；たとえばオキサゾリンチオンの
ようなチオケト化合物；アザインデン類、たとえばトリ
アザインデン類、テトラアザインデン類（特に４−ヒド
ロキシ置換（1,3,3a,7）テトラザインデン類）、ペンタ
アザインデン類など；ベンゼンチオスルフオン酸、ベン
ゼンスルフイン酸、ベンゼンスルフオン酸アミド等のよ
うなカブリ防止剤または安定剤として知られた多くの化
合物を加えることができる。これらのものの中で、特に
好ましいのはベンゾトリアゾール類（例えば、５−メチ
ル−ベンゾトリアゾール）及びニトロインダゾール類
（例えば５−ニトロインダゾール）である。また、これ
らの化合物を処理液に含有させてもよい。The light-sensitive material of the present invention may contain various compounds for the purpose of preventing fog during the manufacturing process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. , Benzothiazoles, nitrobenzotriazoles, mercaptotetrazoles (particularly 1-phenyl-5-mercaptotetrazole) and the like: mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes, for example triazaindene , Tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetrazaindenes), pentaazaindenes, etc .; Benze Chiosurufuon acid, can be added benzenesulfonic fins acid, many compounds known as antifoggants or stabilizers such as benzene Huong acid amide. Of these, particularly preferred are benzotriazoles (eg 5-methyl-benzotriazole) and nitroindazoles (eg 5-nitroindazole). Further, these compounds may be contained in the treatment liquid.
本発明で用いられる感光材料には、特開昭55−52050号
第45頁〜53頁に記載された増感色素（例えば、シアニン
色素、メロシアニン色素など。単独でも、組合せて用い
てもよい。）、強色増感剤（例えば、アミノスチルベン
化合物、 芳香族有機酸ホルムアルデヒド縮合物、カドミウム塩、
アザインデン化合物など。）、 水溶性染料（フイルター又はイラジエーシヨン防止が目
的。例えば、オキソノール染料、ヘミオキソノール染
料、メロシアニン染料など）、硬膜剤（例えば、クロム
塩、アルデヒド塩、Ｎ−メチロール化合物、ジオキサン
誘導体、活性ビニル化合物、活性ハロゲン化合物な
ど）、 界面活性剤（例えば、公知の種々の非イオン性、アニオ
ン性、カチオン性、両性界面活性剤。特に、特開昭54−
37732号に記載のポリオキシアルキレン類は有用であ
る。）、 等を含有させることができる。The sensitizing dyes described in JP-A-55-52050, pages 45 to 53 (eg, cyanine dyes, merocyanine dyes, etc.) may be used alone or in combination in the light-sensitive material used in the present invention. ), A supersensitizer (for example, an aminostilbene compound, an aromatic organic acid formaldehyde condensate, a cadmium salt,
Azaindene compounds, etc. ), Water-soluble dyes (for the purpose of preventing filters or irradiation, for example, oxonol dyes, hemioxonol dyes, merocyanine dyes, etc.), hardeners (eg chromium salts, aldehyde salts, N-methylol compounds, dioxane derivatives, active vinyl) Compounds, active halogen compounds, etc., surfactants (eg, various known nonionic, anionic, cationic, amphoteric surfactants. In particular, JP-A-54-
The polyoxyalkylenes described in 37732 are useful. ), Etc. can be contained.
本発明に好ましく用いられるポリアルキレンオキサイド
またはその誘導体は、分子量が少くとも600であり、該
ポリアルキレンオキサイドまたまその誘導体は、ハロゲ
ン化銀感光材料中に含有せしめてもよいし、現像液中に
含有せしめてもよい。The polyalkylene oxide or its derivative preferably used in the present invention has a molecular weight of at least 600, and the polyalkylene oxide or its derivative may be contained in the silver halide light-sensitive material, or in a developing solution. You may make it contain.
本発明に用いるポリアルキレンオキサイド化合物は、炭
素数２〜４のアルキレンオキサイド、たとえばエチレン
オキサイド、プロピレン−1,2−オキサイド、ブチレン
−1,2−オキサイドなど、好ましくはエチレンオキサイ
ドの、少くとも10単位から成るポリアルキレンオキサイ
ドと、水、脂肪族アルコール、芳香族アルコール、脂肪
酸、有機アミン、ヘキシトール誘導体などの活性水素原
子を少くとも１個有する化合物との縮合物あるいは二種
以上のポリアルキレンオキサイドのブロツクコポリマー
などを包含する。The polyalkylene oxide compound used in the present invention is an alkylene oxide having 2 to 4 carbon atoms, for example, ethylene oxide, propylene-1,2-oxide, butylene-1,2-oxide, etc., preferably at least 10 units of ethylene oxide. Or a block of two or more polyalkylene oxides, which is a condensate of a polyalkylene oxide consisting of 1) with water, an aliphatic alcohol, an aromatic alcohol, a fatty acid, an organic amine, a compound having at least one active hydrogen atom such as a hexitol derivative. Includes copolymers and the like.
すなわち、ポリアルキレンオキサイド化合物として、具
体的には ポリアルキレングリコール類 ポリアルキレングリコールアルキルエーテル類 ポリアルキレングリコールアリールエーテル類 ポリアルキレングリコール（アルキルアリール）エーテ
ル類 ポリアルキレングリコールエステル類 ポリアルキレングリコール脂肪酸アミド類 ポリアルキレングリコールアミン類 ポリアルキレングリコール・ブロック共重合体 ポリアルキレングリコールグラフト重合物 などを用いることができる。That is, as the polyalkylene oxide compound, specifically, polyalkylene glycols, polyalkylene glycol alkyl ethers, polyalkylene glycol aryl ethers, polyalkylene glycol (alkylaryl) ethers, polyalkylene glycol esters, polyalkylene glycol fatty acid amides, polyalkylene Glycol amines Polyalkylene glycol / block copolymers Polyalkylene glycol graft polymers and the like can be used.
ポリアルキレンオキサイド鎖は分子中に一つとは限ら
ず、二つ以上含まれてもよい。その場合個個のポリアル
キレンオキサイド鎖が10より少いアルキレンオキサイド
単位から成つてもよいが、分子中のアルキレンオキサイ
ド単位の合計は少くとも10でなければならない。分子中
に二つ以上のポリアルキレンオキサイド鎖を有する場
合、それらの各々は異るアルキレンオキサイド単位、た
とえばエチレンオキサイドとプロピレンオキサイドから
成つていてもよい。本発明で用いることができるポリア
ルキレンオキサイド化合物は、好ましは14以上100まで
のアルキレンオキサイド単位を含むものである。The number of polyalkylene oxide chains is not limited to one in the molecule, and may be two or more. In that case, the individual polyalkylene oxide chains may consist of less than 10 alkylene oxide units, but the total number of alkylene oxide units in the molecule must be at least 10. When having more than one polyalkylene oxide chain in the molecule, each of them may consist of different alkylene oxide units, such as ethylene oxide and propylene oxide. The polyalkylene oxide compound that can be used in the present invention preferably contains 14 to 100 alkylene oxide units.
本発明で用いられる感光材料には寸度安定性の改良など
の目的で、水不溶または難溶性合成ポリマーの分散物を
含むことができる。たとえばアルキル（メタ）アクリレ
ート、アルコキシアルキル（メタ）アクリレート、グリ
シジル（メタ）アクリレート、（メタ）アクリルアミ
ド、ビニルエステル（たとえば酢酸ビニル）、アクリロ
ニトリル、オレフイン、スチレンなどの単独もしくは組
合せや、またはこれらとアクリル酸、メタアクリル酸、
α，β−不飽和ジカルボン酸、ヒドロキシアルキル（メ
タ）アクリレート、スルフオアルキル（メタ）アクリレ
ート、スチレンスルフオン酸などの組合せを単量成分と
するポリマーを用いることができる。The light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability. For example, alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, vinyl ester (for example, vinyl acetate), acrylonitrile, olefin, styrene, etc., alone or in combination, or with acrylic acid. , Methacrylic acid,
A polymer having a combination of α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrene sulfonic acid, etc. as a monocomponent can be used.
本発明の如き硬調乳剤は線画の再生にも適しており、そ
のような用途では寸度安定性が重要であるから、このよ
うなポリマー分散物を含むことは好ましい。It is preferable to include such a polymer dispersion because the high-contrast emulsion as in the present invention is also suitable for the reproduction of line images, and the dimensional stability is important in such applications.
一般式（Ｉ）で表わされる化合物はネガ型乳剤と組合せ
て高コントラスト用感材に用いる他に、内部潜像型ハロ
ゲン化銀乳剤と組合せることもできるが、以下にその使
用態様について述べる。この場合、一般式（Ｉ）で表わ
される化合物は内部潜像型ハロゲン化銀乳剤層に含有さ
せるのが好ましいが、内部潜像型ハロゲン化銀乳剤層に
隣接する親水性コロイド層に含有させてもよい。そのよ
うな層は色材層、中間層、フイルター層、保護層、アン
チハレーシヨン層など、造核剤がハロゲン化銀粒子へ拡
散していくのを妨げない限り、どんな機能をもつ層であ
つてもよい。The compound represented by the general formula (I) can be used in combination with a negative type emulsion for a high contrast light-sensitive material, and can also be used in combination with an internal latent image type silver halide emulsion. The use mode thereof will be described below. In this case, the compound represented by the general formula (I) is preferably contained in the internal latent image type silver halide emulsion layer, but is contained in the hydrophilic colloid layer adjacent to the internal latent image type silver halide emulsion layer. Good. Such a layer is a layer having any function, such as a coloring material layer, an intermediate layer, a filter layer, a protective layer, an anti-halation layer, etc., as long as it does not prevent the nucleating agent from diffusing into the silver halide grains. May be.
層中での一般式（Ｉ）で表わされる化合物の含有量は内
部潜像型乳剤を表面現像液で現像したときに充分な最大
濃度（例えば銀濃度で1.0以上）を与えるような量であ
ることが望ましい。実際上は、用いられるハロゲン化銀
乳剤の特性、造核剤の化学構造及び現像条件によつて異
るので、適当な含有量は広い範囲にわたつて変化し得る
が、内部潜像型ハロゲン化銀乳剤中の銀１モル当り約0.
005mgから500mgの範囲が実際上有用で、好ましいのは銀
１モル当り約0.01mgから約100mgである。乳剤層に隣接
する親水性コロイド層に含有させる場合には、内部潜像
型乳剤層の同一面積に含まれる銀の量に対して上記同様
の量を含有させればよい。内部潜像型ハロゲン化銀乳剤
は露光によつて「内部型」現像液で現像した場合に達成
される最大濃度が「表面型」現像液で現像した場合に達
成される最大濃度より大であるという事により明確に定
義することができる。本発明に適する内部潜像型乳剤
は、そのハロゲン化銀乳剤を透明な支持体に塗布し、0.
01ないし１秒の固定された時間で露光を与え下記現像液
Ａ（内部型現像液）中で、20℃で３分間現像したとき通
常の写真濃度測定方法によつて測られる最大濃度が、上
記と同様にして露光したハロゲン化銀乳剤を下記現像液
Ｂ（表面現像液）中で20℃で４分間現像した場合に得ら
れる最大濃度の、少くとも５倍大きい濃度を有するもの
である。The content of the compound represented by the general formula (I) in the layer is such that an internal latent image type emulsion gives a sufficient maximum density (for example, 1.0 or more in silver density) when developed with a surface developer. Is desirable. In practice, the appropriate content may vary over a wide range as it depends on the properties of the silver halide emulsion used, the chemical structure of the nucleating agent and the development conditions, but internal latent image type halogenation About 0 per mole of silver in the silver emulsion.
A range of 005 mg to 500 mg is practically useful, with about 0.01 mg to about 100 mg per silver mole being preferred. When it is contained in the hydrophilic colloid layer adjacent to the emulsion layer, the same amount as the above may be contained with respect to the amount of silver contained in the same area of the internal latent image type emulsion layer. Internal latent image type silver halide emulsions have a maximum density achieved by exposure that is developed in an "internal" developer is greater than the maximum density achieved when developed in an "surface-type" developer. Therefore, it can be clearly defined. The internal latent image type emulsion suitable for the present invention is prepared by coating the silver halide emulsion on a transparent support,
The maximum density measured by the usual photographic density measuring method when exposed to light for a fixed time of 01 to 1 second and developed in the following developer A (internal type developer) at 20 ° C. for 3 minutes is It has a density at least 5 times higher than the maximum density obtained when the silver halide emulsion exposed in the same manner as in (1) was developed in the following developer B (surface developer) at 20 ° C. for 4 minutes.
本発明に使用される内部潜像型ハロゲン化銀乳剤は塩化
銀、臭化銀、塩臭化銀、沃臭化銀、塩沃臭化銀もしくは
これらの混合物の親水性コロイド状分散物であつて、ハ
ロゲン組成は感光材料の使用目的と処理条件に応じて選
択されるが、沃化物含量が10mole％以下、塩化物含量が
30mole％以下の臭化銀、沃臭化銀又は塩沃臭化銀が特に
好ましい。具体的には先に挙げた米国特許2,592,250号
に記載された乳剤の他に、英国特許1027,146号、米国特
許3,206,313号、同3,511,662、同第3,447,927号、同3,7
37,313号、同3,761,276号、同3,935,014号等に記載され
たコンバージヨン型乳剤、コア／シエル型乳剤、異種金
属をドープされた乳剤等を挙げることができる。しか
し、これらに限定されるものではない。 The internal latent image type silver halide emulsion used in the present invention is a hydrophilic colloidal dispersion of silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide or a mixture thereof. The halogen composition is selected according to the purpose of use of the light-sensitive material and the processing conditions, but the iodide content is 10 mole% or less and the chloride content is
Silver bromide, silver iodobromide or silver chloroiodobromide of 30 mole% or less is particularly preferable. Specifically, in addition to the emulsions described in the above-mentioned U.S. Patent 2,592,250, British Patent 1027,146, U.S. Patents 3,206,313, 3,511,662, 3,447,927, 3,7.
Examples thereof include the convergence type emulsions, core / shell type emulsions and emulsions doped with different metals described in 37,313, 3,761,276 and 3,935,014. However, it is not limited to these.
本発明の感光材料において内部潜像型乳剤は、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、コンプレツクスシアニ
ン色素、コンプレツクスメロシアニン色素、ホロポーラ
ーシアニン色素、スチリル色素、ヘミシアニン色素、オ
キソノール色素、ヘミオキソノール色素等を用いること
ができる。これらの増感色素には、例えば特開昭59−4
0,638号、同59−40,636号や同59−38,739号に記載され
たシアニン色素やメロシアニン色素が含まれる。In the light-sensitive material of the present invention, the internal latent image type emulsion may be spectrally sensitized to blue light, green light, red light or infrared light having a relatively long wavelength by using a sensitizing dye. As the sensitizing dye, a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a holopolar cyanine dye, a styryl dye, a hemicyanine dye, an oxonol dye, a hemioxonol dye and the like can be used. Examples of these sensitizing dyes include JP-A-59-4
Cyanine dyes and merocyanine dyes described in Nos. 0,638, 59-40,636 and 59-38,739 are included.
本発明の感光材料には色材として色像形成カプラーを含
有させることができる。あるいは色像形成カプラーを含
む現像液で現像することもできる。The light-sensitive material of the present invention may contain a color image-forming coupler as a coloring material. Alternatively, it can be developed with a developing solution containing a color image forming coupler.
本発明においては、ヒドロキシベンゼン類（例えばハイ
ドロキノン類）、アミノフエノール類、３−ピラゾリド
ン類等の如き現像主薬を乳剤中あるいは感光材料中に含
有させてもよい。In the present invention, a developing agent such as hydroxybenzenes (for example, hydroquinones), aminophenols, 3-pyrazolidones and the like may be contained in the emulsion or the light-sensitive material.
本発明に於て使用される写真乳剤は、ハロゲン化銀の現
像に対応して拡散性色素を放出するようなカラー拡散転
写法用色素像供与化合物（色材）と組合せて、適当な現
像処理ののち受像層に所望の転写像を得るのに用いるこ
ともできる。The photographic emulsion used in the present invention is combined with a dye image-providing compound (coloring material) for a color diffusion transfer method capable of releasing a diffusible dye in response to the development of silver halide, and subjected to an appropriate development treatment. After that, it can be used to obtain a desired transferred image on the image receiving layer.
なかでもはじめは非拡散性であるが現像主薬（又は電子
移動剤）の酸化生成物との酸化還元反応によつて開裂し
て拡散性色素を放出するタイプの色材（以下DRR化合物
と略す）の使用が好ましい。なかでもＮ−置換スルフア
モイル基を有するDRR化合物が好ましい。特に、本発明
の造核剤との併用で好ましいのは、米国特許44,055,428
号、同4,053,312号や同4,336,322号等に記載されている
ようなｏ−ヒドロキシアリールスルフアモイル基を有す
るDRR化合物や特開昭53−149328号に記載されているよ
うなレドツクス母核を有するDRR化合物である。このよ
うなDRR化合物と併用すると、特に処理時の温度依存性
が顕著に小さい。Among them, a coloring material that is initially non-diffusive but cleaves by the redox reaction with the oxidation product of the developing agent (or electron transfer agent) to release a diffusible dye (hereinafter abbreviated as DRR compound). Is preferably used. Of these, a DRR compound having an N-substituted sulfamoyl group is preferable. Particularly preferred in combination with the nucleating agent of the present invention, U.S. Pat.
Nos. 4,053,312 and 4,336,322, etc., and DRR compounds having an o-hydroxyarylsulfamoyl group, and DRR having a redox nucleus as described in JP-A-53-149328. It is a compound. When used in combination with such a DRR compound, the temperature dependence during treatment is remarkably small.
本発明の内部潜像型乳剤を用いる感光材料を現像するに
は、知られている種々の現像主薬を用いることができ
る。すなわちポリヒドロキシベンゼン類、たとえばハイ
ドロキノン、２−クロロハイドロキノン、２−メチルハ
イドロキノン、カテコール、ピロガロールなど；アミノ
フエノール類、たとえばｐ−アミノフエノール、Ｎ−メ
チル−ｐ−アミノフエノール、2,4−ジアミノフエノー
ルなど;3−ピラゾリドン類、例えば１−フエニル−３−
ピラゾリドン、4,4−ジメチル−１−フエニル−３−ピ
ラゾリドン、4,4−ジヒドロキシメチル−１−フエニル
−３−ピラゾリドン、４−メチル−４−ヒドロキシメチ
ル−１−フエニル−３−ピラゾリドン、４−メチル−４
−ヒドロキシメチル−１−ｐ−トリル−３−ピラゾリド
ン等；アスコルビン酸類などの、単独又は組合せを用い
ることができる。また、色素形成カプラーにより色素像
を得るには、芳香族一級アミン現像主薬、好ましくはｐ
−フエニレンジアミン系の現像主薬を用いることができ
る。To develop a light-sensitive material using the internal latent image type emulsion of the present invention, various known developing agents can be used. That is, polyhydroxybenzenes such as hydroquinone, 2-chlorohydroquinone, 2-methylhydroquinone, catechol, pyrogallol, etc .; aminophenols such as p-aminophenol, N-methyl-p-aminophenol, 2,4-diaminophenol, etc. 3-pyrazolidones, such as 1-phenyl-3-
Pyrazolidone, 4,4-dimethyl-1-phenyl-3-pyrazolidone, 4,4-dihydroxymethyl-1-phenyl-3-pyrazolidone, 4-methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone, 4- Methyl-4
-Hydroxymethyl-1-p-tolyl-3-pyrazolidone and the like; ascorbic acids and the like can be used alone or in combination. To obtain a dye image with a dye-forming coupler, an aromatic primary amine developing agent, preferably p
-A phenylenediamine-based developing agent can be used.
本発明においてDRR化合物を用いる場合、これをクロス
酸化できるものであれば、どのようなハロゲン化銀現像
薬（又は電子移動剤）でも使用することができるが、な
かでも３−ピラゾリドン類が好ましい。When a DRR compound is used in the present invention, any silver halide developing agent (or electron transfer agent) can be used as long as it can be cross-oxidized, and among them, 3-pyrazolidones are preferable.
現像液は保恒剤としては、亜硫酸ナトリウム、亜硫酸カ
リウム、アスコルビン酸、レダクトン類（たとえばピペ
リジノヘキソースレダクトン）などを含んでよい。The developer may contain, as preservatives, sodium sulfite, potassium sulfite, ascorbic acid, reductones (eg piperidinohexose reductone) and the like.
本発明の内潜型乳剤を用いる感光材料は、表面現像液を
用いて現像することにより直接ポジ画像を得ることがで
きる。表面現像液はそれによる現像過程が実質的に、ハ
ロゲン化銀粒子の表面にある潜像又はカブリ核によつて
誘起されるものである。ハロゲン化銀溶解剤を現像液に
含まないことが好ましいけれども、ハロゲン化銀粒子の
表面現像中心による現像が完結するまでに内部潜像が実
質的に寄与しない限り、ハロゲン化銀溶解剤（たとえば
亜硫酸塩）を多少は含んでもよい。The light-sensitive material using the inner latent type emulsion of the present invention can directly obtain a positive image by developing with a surface developing solution. A surface developer is one in which the development process thereby is substantially induced by latent images or fog nuclei on the surface of the silver halide grains. Although it is preferable not to include a silver halide dissolving agent in the developing solution, a silver halide dissolving agent (for example, sulfurous acid) may be used as long as the internal latent image does not substantially contribute until development by the surface development center of the silver halide grain is completed. Some may be included).
本発明の感光材料は粘性現像液で処理することもでき
る。The light-sensitive material of the present invention can be processed with a viscous developer.
本発明の感材を拡散転写写真法に用いる場合、その感材
はフイルムユニツトの形態である事が好ましい。写真フ
イルムユニツト、すなわち、一対の並置された押圧部材
の間にそのフイルムユニツトを通過せしめることにより
処理を行ない得るようにされているフイルムユニツト
は、基本的には下記の三要素： からなる。When the light-sensitive material of the present invention is used in diffusion transfer photography, the light-sensitive material is preferably in the form of a film unit. The photographic film unit, that is, the film unit which is designed to be processed by passing the film unit between a pair of juxtaposed pressing members, basically has the following three elements: Consists of.
この写真フイルムユニツトの好ましい形態は、重ね合わ
せて一体化したタイプであつて、ベルギー特許第757,95
9号に開示されているようなタイプのものである。この
態様によれば、透明な一つの支持体の上に、受像層、実
質的に不透明な光反射層（たとえばTiO2層とカーボンブ
ラツク層）、そしてDRR化合物と組み合わされた単数又
は複数のハロゲン化銀感光層からなる感光要素をこの順
に塗布し、さらにこの上に透明なカバーシートを面対面
に重ねる。不透明化剤（たとえばカーボンブラツク）を
含むアルカリ性処理組成物を含有する破裂可能な容器
は、上記感光層の最上層と透明なカバーシートに隣接し
て配置される。The preferred form of this photographic film unit is of the type integrated by superimposing, as described in Belgian Patent No. 757,95.
It is of the type disclosed in No. 9. According to this embodiment, on one transparent support, an image-receiving layer, a substantially opaque light-reflecting layer (eg, TiO 2 layer and carbon black layer), and one or more halogens combined with a DRR compound. Photosensitive elements consisting of a silver halide photosensitive layer are coated in this order, and a transparent cover sheet is then layered face to face. A rupturable container containing an alkaline processing composition containing an opacifying agent (eg, carbon black) is positioned adjacent to the top layer of the photosensitive layer and the transparent cover sheet.
以下に本発明に用いられる化合物の合成例及び本発明の
実施例を示すが、本発明はこれらに限定されるものでは
ない。The synthesis examples of the compounds used in the present invention and the examples of the present invention are shown below, but the present invention is not limited thereto.
合成例１ 化合物７の合成 N,N−ジメチルアセトアミド20ml、トリエチルアミン2
g、およびDL−リポ酸4.1gよりなる溶液を−15℃に冷却
し、クロロギ酸エチル1.67gを滴下した。15分間撹拌し
た後１−（４−アミノフエニル）−１−ホルミルヒドラ
ジン3gを10mlのN,N−ジメチルアセトアミドに溶解して3
0分間にわたつて滴下した。この際液温が−７℃を越え
ぬよう冷却した。30分間−15℃で撹拌した後、室温で２
時間45分撹拌し、２％炭酸水素ナトリウム水溶液200ml
に注入した。生じた結晶を取し、アセトニトリル−エ
ーテル−ジオキサン（それぞれ50ml、30ml、10ml）の混
合溶媒より再結晶した。結晶を取しエーテルで洗浄し
て乾燥した。Synthesis Example 1 Synthesis of compound 7 N, N-dimethylacetamide 20 ml, triethylamine 2
g, and a solution of 4.1 g of DL-lipoic acid were cooled to −15 ° C., and 1.67 g of ethyl chloroformate was added dropwise. After stirring for 15 minutes, 3 g of 1- (4-aminophenyl) -1-formylhydrazine was dissolved in 10 ml of N, N-dimethylacetamide.
It was dripped over 0 minutes. At this time, the liquid temperature was cooled so as not to exceed -7 ° C. After stirring at -15 ° C for 30 minutes, 2 at room temperature
Stir for 45 minutes, 200 ml of 2% sodium hydrogen carbonate solution
Injected. The resulting crystals were collected and recrystallized from a mixed solvent of acetonitrile-ether-dioxane (50 ml, 30 ml, 10 ml, respectively). The crystals were taken, washed with ether and dried.
収量1.4g（収率20.8％） 合成例２ 化合物９の合成 ３−（５−ベンゾイルアミノノペンチル）−1,2−ジチ
オラン6g、トリエチルアミン2g、N,N−ジメチルホルム
アミド40ml及び１−（４−アミノフエニル）−２−ホル
ミルヒドラジン3gよりなる溶液を50℃で２時間加熱し
た。反応混合物を混合物を300mlの水に注入し生じた結
晶を取し、アセトニトリルで洗浄した。粗結晶を少量
のN,N−ジメチルホルムアミドに溶解した後、メタノー
ルを加えて結晶を析出させた。結晶を取しメタノール
で洗浄後乾燥した。Yield 1.4 g (Yield 20.8%) Synthesis Example 2 Synthesis of Compound 9 3- (5-benzoylaminonopentyl) -1,2-dithiolane 6 g, triethylamine 2 g, N, N-dimethylformamide 40 ml and 1- (4- A solution consisting of 3 g of aminophenyl) -2-formylhydrazine was heated at 50 ° C. for 2 hours. The reaction mixture was poured into 300 ml of water, and the resulting crystals were collected and washed with acetonitrile. The crude crystal was dissolved in a small amount of N, N-dimethylformamide, and then methanol was added to precipitate the crystal. The crystals were collected, washed with methanol and dried.
収量1.2g（収率17.8％） 合成例３ 化合物10の合成 N,N−ジメチルアセトアミド20ml、トリエチルアミン2
g、およびDL−リポ酸4.1gよりなる溶液を−15℃に冷却
し、クロロギ酸エチル1.67gを滴下した。次いで15分間
撹拌した後１−アセチル−（４−アミノフエニル）ヒド
ラジン3.3gを10mlのN,N−ジメチルアセトアミドに溶解
して30分間にわたつて滴下した。この際液温が−７℃を
越えぬよう冷却した。30分間−15℃で撹拌した後、室温
で２時間撹拌し、２％炭酸水素ナトリウム水溶液200ml
に注入した。生じた結晶を取し、アセトニトリルとジ
オキサンの混合溶媒より再結晶した。結晶を取しエー
テルで洗浄して乾燥した。Yield 1.2 g (yield 17.8%) Synthesis Example 3 Synthesis of compound 10 20 ml of N, N-dimethylacetamide, triethylamine 2
g, and a solution of 4.1 g of DL-lipoic acid were cooled to −15 ° C., and 1.67 g of ethyl chloroformate was added dropwise. After stirring for 15 minutes, 3.3 g of 1-acetyl- (4-aminophenyl) hydrazine was dissolved in 10 ml of N, N-dimethylacetamide and added dropwise over 30 minutes. At this time, the liquid temperature was cooled so as not to exceed -7 ° C. After stirring at -15 ° C for 30 minutes, at room temperature for 2 hours, 2% aqueous sodium hydrogencarbonate solution (200 ml)
Injected. The generated crystals were collected and recrystallized from a mixed solvent of acetonitrile and dioxane. The crystals were taken, washed with ether and dried.
収量1.7g（収率24.8％） 合成例４ 化合物17の合成 N,N−ジメチルアセトアミド20ml、トリエチルアミン1g
およびDL−リポ酸2gよりなる溶液を−15℃に冷却し、ク
ロロギ酸エチル835mgを滴下した。15分間撹拌した後４
−〔２−（2,4−ジ−tert−ペンチルフエノキシ）ブタ
ンアミド〕フエニルヒドラジン4.2gを10mlのN,N−ジメ
チルアセトアミドに溶かして、30分間にわたつて滴下し
た。この際液温が−５℃を越えぬよう冷却した。30分間
−15℃で撹拌した後室温で２時間撹拌し、２％炭酸水素
ナトリウム水溶液200mlに注入した。生じた油状物質を
酢酸エチルで抽出し、無水硫酸ナトリウムで乾燥した
後、溶媒を留去した。残渣をシリカゲルカラムクロマト
グラフイー（酢酸エチルとクロロホルムの混合溶媒で溶
離）にて精製した。Yield 1.7 g (yield 24.8%) Synthesis Example 4 Synthesis of compound 17 20 ml of N, N-dimethylacetamide, 1 g of triethylamine
And a solution of DL-lipoic acid (2 g) were cooled to -15 ° C, and 835 mg of ethyl chloroformate was added dropwise. After stirring for 15 minutes 4
4.2 g of [2- (2,4-di-tert-pentylphenoxy) butanamide] phenylhydrazine were dissolved in 10 ml of N, N-dimethylacetamide and added dropwise over 30 minutes. At this time, the liquid temperature was cooled so as not to exceed -5 ° C. The mixture was stirred for 30 minutes at −15 ° C., then at room temperature for 2 hours, and poured into 200 ml of a 2% sodium hydrogen carbonate aqueous solution. The resulting oily substance was extracted with ethyl acetate, dried over anhydrous sodium sulfate, and the solvent was evaporated. The residue was purified by silica gel column chromatography (eluted with a mixed solvent of ethyl acetate and chloroform).
収量1.3g 合成例５ 化合物26の合成 N,N−ジ−メチルアセトアミド20ml、トリエチルアミン2
g、およびDL−リポ酸4.1gよりなる溶液を−15℃に冷却
し、クロロギ酸エチル1.67gを滴下した。15分間撹拌し
た後１−（４−アミノ−２−メチルフエニル）−２−ホ
ルミルヒドラジン3.3gを10mlのN,N−ジメチルアセトア
ミドに溶解して30分間にわたつて滴下した。この際液温
が−５℃を越えぬよう冷却した。30分間−15℃で撹拌し
た後、室温で２時間撹拌し、２％炭酸水素ナトリウム水
溶液200mlに注入した。生じた結晶を取し、アセトニ
トリルとジオキサンの混合溶媒より再結晶した。結晶を
取しエーテルで洗浄して乾燥した。Yield 1.3 g Synthesis example 5 Synthesis of compound 26 N, N-di-methylacetamide 20 ml, triethylamine 2
g, and a solution of 4.1 g of DL-lipoic acid were cooled to −15 ° C., and 1.67 g of ethyl chloroformate was added dropwise. After stirring for 15 minutes, 3.3 g of 1- (4-amino-2-methylphenyl) -2-formylhydrazine was dissolved in 10 ml of N, N-dimethylacetamide and added dropwise over 30 minutes. At this time, the liquid temperature was cooled so as not to exceed -5 ° C. After stirring at -15 ° C for 30 minutes, the mixture was stirred at room temperature for 2 hours and poured into 200 ml of a 2% sodium hydrogen carbonate aqueous solution. The generated crystals were collected and recrystallized from a mixed solvent of acetonitrile and dioxane. The crystals were taken, washed with ether and dried.
収量1.9g（収率27％） 実施例１ コントロールダブルジエツト仕込にて粒子形成を行な
い、第１表に示す３種類の単分散ネガ型ハロゲン化銀乳
剤Ａ〜Ｃを作つた。なお、Ａ〜Ｃの乳剤は仕込温度を変
えることにより、平均粒子サイズを0.25μとなるよう調
製した。これらの乳剤を常法に従い水洗して可溶性塩類
を除去した後、安定剤として４−ヒドロキシ−６−メチ
ル−1,3,3a,7−テトラザインデンを添加した。Yield 1.9 g (Yield 27%) Example 1 Grains were formed by charging a control double jet to prepare three kinds of monodisperse negative silver halide emulsions A to C shown in Table 1. The emulsions A to C were prepared so that the average grain size was 0.25 μm by changing the charging temperature. These emulsions were washed with water in a conventional manner to remove soluble salts, and then 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added as a stabilizer.
これら３種類のハロゲン化銀乳剤を分割し、第１表に示
すように本発明の化合物７、９および比較化合物ａ、
ｂ、ｃを加えたのち、各々に増感色素として３−エチル
−５−〔２−（３−エチル−２（3H）−チアゾリニデン
−エチリデン〕ローダニンを加え、更に各々に５−メチ
ルベンゾトリアゾール、ポリエチルアクリートの分散
物、２−ヒドロキシ−4,6−ジクロロ−1,3,5−トリアジ
ンナトリウム塩を加えたのち、ポリエチレンテレフタレ
ートフイルム上に塗布銀量が4g/m2となるように塗布し
た。These three kinds of silver halide emulsions were divided into compounds, as shown in Table 1, compounds 7 and 9 of the present invention and comparative compound a,
After adding b and c, 3-ethyl-5- [2- (3-ethyl-2 (3H) -thiazolinidene-ethylidene] rhodamine was added to each as a sensitizing dye, and 5-methylbenzotriazole was further added to each. A dispersion of polyethyl acrylate and 2-hydroxy-4,6-dichloro-1,3,5-triazine sodium salt were added, and then coated on a polyethylene terephthalate film so that the coated silver amount was 4 g / m 2 . .
これらのフイルムに150線マゼンタコンタクトスクリー
ンを用いて、センシトメトリー用露光ウエツジを通して
露光した後、下記組成の現像液で38℃で20秒間現像し、
停止、定着、水洗、乾燥した。結果を第１表に示す。Using a 150-line magenta contact screen to these films, after exposing through an exposure wedge for sensitometry, developed with a developer having the following composition for 20 seconds at 38 ℃,
Stopped, fixed, washed with water and dried. The results are shown in Table 1.
現像液 比較化合物 以上の結果より本発明化合物は比較化合物ａ、ｂより少
ない添加量で、高ガンマな階調をあたえ、網点品質も優
れている。また比較化合物Ｃと較べても同一添加量で高
ガンマで、より良い網点品質をあたえることがわかつ
た。Developer Comparative compound From the above results, the compound of the present invention gives a high gamma gradation and is excellent in halftone dot quality with a smaller addition amount than the comparative compounds a and b. It was also found that even if the amount of addition was the same as that of the comparative compound C, a high gamma gave a better halftone dot quality.
本発明化合物を用いると、以上のように少ない添加量で
硬調な階調と、優れた網点を形成することができる。By using the compound of the present invention, it is possible to form a hard gradation and an excellent halftone dot with a small addition amount as described above.
実施例２ ロジウムアンモニウムクロライドの存在下で粒子形成を
行ない、各々ロジウム塩の添加量が第２表に示す値を持
つ２種の単分散ネガ型塩臭化銀乳剤（臭素含量30モル
％）Ｄ、Ｅを作つた。（平均粒子サイズ0.20μ） これらの乳剤を常法に従い水洗して可溶性塩類を除去し
た後、安定剤として４−ヒドロキシ−６−メチル−1,3,
3a,7−テトラザインデンを添加した。Example 2 Grain formation was carried out in the presence of rhodium ammonium chloride, and two kinds of monodisperse negative silver chlorobromide emulsions (bromine content 30 mol%) D each having a rhodium salt addition value shown in Table 2 were added. , Made E. (Average grain size 0.20μ) These emulsions were washed with water according to a conventional method to remove soluble salts, and 4-hydroxy-6-methyl-1,3,
3a, 7-Tetrazaindene was added.
これら２種類のハロゲン化銀乳剤を分割し、第２表に示
すように、本発明の化合物７、９および比較化合物ａ、
ｂ、ｃを加えたのち、ポリエチルアクリレートの分散
物、２−ヒドロキシ−4,6−ジクロロ−1,3,5−トリアジ
ンナトリウム塩を加えたのち、ポリエチレンテレフタレ
ートフイルム上に塗布銀量が3.5g/m2となるように塗布
した。These two kinds of silver halide emulsions were divided and, as shown in Table 2, compounds 7 and 9 of the present invention and comparative compound a,
After adding b and c, a dispersion of polyethyl acrylate and sodium salt of 2-hydroxy-4,6-dichloro-1,3,5-triazine were added, and the amount of silver coated on the polyethylene terephthalate film was 3.5 g. It was applied so as to be / m 2 .
これらのフイルムにセンシトメトリー用露光ウエツジを
通して大日本スクリーン社製Ｐ−607型プリンターで露
光したのち、実施例１記載の現像液で38℃で20秒間現像
し、停止、定着、水洗、乾燥した。結果を第２表に示
す。These films were exposed through a sensitometric exposure wedge with a P-607 model printer manufactured by Dainippon Screen Co., Ltd., and then developed with the developer described in Example 1 at 38 ° C. for 20 seconds, stopped, fixed, washed with water and dried. . The results are shown in Table 2.
第２表より、本発明の化合物は比較化合物ａ、ｂ、ｃに
較べRhを多量に含有した乳剤に対して、硬調化作用が著
しく、抜文字画質も優れていることがわかる。 It can be seen from Table 2 that the compound of the present invention has a remarkable contrast-enhancing effect and an excellent character image quality for an emulsion containing a large amount of Rh as compared with the comparative compounds a, b and c.
また比較化合物の中では硬調化作用の大きい化合物Ｃを
含有する試料23と本発明化合物７、９を含む試料24、25
を温度50℃、湿度75％RHに調整した部屋に３日間放置し
たものと、温度25℃、湿度60％RHの部屋に放置したもの
の現像処理したときのカブリ値を第３表に示す。Among the comparative compounds, sample 23 containing compound C, which has a large contrast-increasing effect, and samples 24 and 25 containing compounds 7 and 9 of the present invention.
Table 3 shows the fog values when the samples were left for 3 days in a room adjusted to a temperature of 50 ° C. and a humidity of 75% RH and to those developed in a room at a temperature of 25 ° C. and a humidity of 60% RH.
この結果から本発明化合物を添加した試料は、比較化合
物Ｃを添加した試料と比較して、経時でのカブリが小さ
く、保存性に優れていることがわかる。 From these results, it is understood that the sample to which the compound of the present invention is added has less fog over time and is excellent in storage stability as compared with the sample to which the comparative compound C is added.
実施例３ 硝酸銀と臭化カリウムを同時添加するハロゲン化銀結晶
生成法において粒子内部と粒子表面をそれぞれ金とイオ
ウで化学増感して得られた単分散の内部潜像型直接ポジ
臭化銀乳剤（銀の量６〜7wt％、ゼラチン5wt％）80g
に、本発明の造核剤として例示化合物７と９、および公
知の造核剤として比較化合物Ａをメタノール溶液あるい
は水−メタノール混合物溶液の形で、それぞれ乳剤1g当
たり10-10molから10-8mol添加した。これに、ゼラチン
やその他通常の乳剤用添加剤（硬膜剤、塗布助剤等）を
加えて完成した乳剤をセルローストリアセテート透明フ
イルム上に塗布し、（銀の量4.3g/m2、ゼラチン7.1g/
m2）乾燥した。このフイルムを400ルツクスのタングス
テン光源において1/100秒、ウエツジ露光した後、下記
組成の表面現像液を用いて８分間現像処理を行つた。ま
た、同現像液で現像時間を０〜８分の範囲で変えて得ら
れた現像銀濃度を測定した。Example 3 Monodisperse internal latent image type direct positive silver bromide obtained by chemically sensitizing the inside and the surface of a grain with gold and sulfur in a silver halide crystal forming method in which silver nitrate and potassium bromide are simultaneously added. Emulsion (silver amount 6-7wt%, gelatin 5wt%) 80g
In addition, the exemplified compounds 7 and 9 as the nucleating agent of the present invention, and the comparative compound A as a known nucleating agent in the form of a methanol solution or a water-methanol mixture solution, respectively, were added in an amount of 10 -10 mol to 10 -8 per 1 g of the emulsion. mol was added. To this, gelatin and other usual emulsion additives (hardeners, coating aids, etc.) were added and the finished emulsion was coated on a transparent film of cellulose triacetate (silver content 4.3 g / m 2 , gelatin 7.1 g /
m 2 ) dried. This film was subjected to a wet exposure with a tungsten light source of 400 lux for 1/100 second, and then a developing treatment was carried out for 8 minutes using a surface developing solution having the following composition. Further, the developed silver concentration obtained by changing the developing time in the range of 0 to 8 minutes with the same developing solution was measured.
比較化合物Ａ ＜表面現像液＞ Ｎ−メチル−ｐ−アミノフエノール硫酸塩 2.5g アスコルビン酸 10.0g メタホウ酸カリウム 35.0g 臭化カリウム 1.0g 水を加えて １ 第４表には造核剤の添加量と現像銀の最大濃度（Dmax）
との関係を示した。表の結果から明らかなように、本発
明の例示化合物はいずれも比較化合物に比べ著しく低い
添加レベルで充分なDmaxを与え、かつDmaxの飽和値も比
較化合物より本質的に高いことが示された。Comparative compound A <Surface developer> N-methyl-p-aminophenol sulfate 2.5 g Ascorbic acid 10.0 g Potassium metaborate 35.0 g Potassium bromide 1.0 g Water was added 1 Table 4 shows the amount of nucleating agent added and developed silver. Maximum concentration (Dmax)
The relationship with As is clear from the results in the table, it was shown that each of the exemplified compounds of the present invention gave a sufficient Dmax at a significantly lower addition level than the comparative compound, and the saturation value of Dmax was essentially higher than that of the comparative compound. .
実施例４ ポリエチレンテレフタレート透明支持体上に下記の順に
各層を塗布して３種のカラー直接ポジ感材シート（Ａ）
〜（Ｄ）を作成した。 Example 4 Three types of color direct positive photosensitive material sheets (A) were prepared by coating each layer in the following order on a polyethylene terephthalate transparent support.
~ (D) were created.
（１） 下記の共重合体（3.0g/m2）とゼラチン（3.0g/
m2）を含む媒染層。(1) The following copolymer (3.0g / m 2 ) and gelatin (3.0g / m 2 )
mordant layer containing the m 2).
（２） 酸化チタン（18g/m2）およびゼラチン（2.0g/m
2）を含む白色反射層。 (2) Titanium oxide (18g / m 2 ) and gelatin (2.0g / m 2
2 ) including a white reflective layer.
（３） カーボンブラツク（2.0g/m2）およびゼラチン
（1.0g/m2）を含む遮光層。(3) A light-shielding layer containing carbon black (2.0 g / m 2 ) and gelatin (1.0 g / m 2 ).
（４） 下記構造式ＩのマゼンタDRR化合物（0.21g/
m2）、構造式IIマゼンタDRR化合物（0.11g/m2）、トリ
シクロヘキシルホスフエート（0.08g/m2）、2,5−ジ−t
ert−ペンタデシルハイドロキノン（0.009g/m2）および
ゼラチン（0.9g/m2）を含有する層。(4) Magenta DRR compound of structural formula I (0.21 g /
m 2 ), structural formula II magenta DRR compound (0.11 g / m 2 ), tricyclohexyl phosphate (0.08 g / m 2 ), 2,5-di-t
ert- pentadecylhydroquinone (0.009g / m 2) and a layer containing gelatin (0.9g / m 2).
（５） 色素増感された内部潜像型直接ポジ臭化銀乳剤
（銀の量で0.82g/m2）、ゼラチン（0.9g/m2）、２−ス
ルホ−５−ｎ−ペンダデシルハイドロキノン・ナトリウ
ム塩（0.08g/m2）および各感材シートについて下記の造
核剤（乳剤1g当り10-10molから10-9mol）を含む緑感性
乳剤層。 (5) Dye-sensitized internal latent image type direct positive silver bromide emulsion (0.82 g / m 2 in silver amount), gelatin (0.9 g / m 2 ), 2-sulfo-5-n-pentadecylhydroquinone A green-sensitive emulsion layer containing sodium salt (0.08 g / m 2 ) and the following nucleating agent (10 -10 mol to 10 -9 mol per 1 g of emulsion) for each light-sensitive material sheet.
感材シート（Ａ） 例示化合物７ 〃 （Ｂ） 例示化合物９ 〃 （Ｃ） 実施例（３）で用いた比較化合物Ａ 〃 （Ｄ） 米国特許3,227,552および同4,080,2
07に記載された（の請求範囲に含まれる）下記の比較化
合物Ｂ 比較化合物Ｂ （６） ゼラチン（1.0g/m2）を含む保護層。Photosensitive Material Sheet (A) Exemplified Compound 7 (B) Exemplified Compound 9 (C) Comparative Compound A Used in Example (3) (D) US Patents 3,227,552 and 4,080,2
Comparative Compound B below (included in the scope of claims) described in 07 Comparative Compound B (6) A protective layer containing gelatin (1.0 g / m 2 ).
上記感光シート（Ａ）〜（Ｄ）を次に示す処理要素及び
カバーシートと組み合わせて露光と現像を行つた。The photosensitive sheets (A) to (D) were combined with the following processing elements and a cover sheet, and exposed and developed.
＜処理液＞ １−フエニル−４−メチル−４−ヒドロキシメチル−３
−ピラゾリドン 8.0g tert−ブチルハイドロキノン 0.1g ５−メチルベンゾトリアゾール 2.5g ベンジルアルコール 1.5ml 亜硫酸ナトリウム（無水） 1.5g カルボキシメチルセルロースNa塩 61 ｇ 硝酸亜鉛・６水和物 0.4g カーボンブラツク 410 ｇ 水酸化カリウム 56 ｇ H2O 260 ml 上記組成の処理液0.8gずつを「加圧により破壊可能な容
器」に充填した。<Treatment liquid> 1-phenyl-4-methyl-4-hydroxymethyl-3
-Pyrazolidone 8.0g tert-Butylhydroquinone 0.1g 5-Methylbenzotriazole 2.5g Benzyl alcohol 1.5ml Sodium sulfite (anhydrous) 1.5g Carboxymethyl cellulose Na salt 61g Zinc nitrate hexahydrate 0.4g Carbon black 410g Potassium hydroxide 56 g H 2 O 260 ml 0.8 g each of the treatment liquid having the above composition was filled in a “container that can be broken by pressure”.
〔カバーシート〕 ポリエチレンテレフタレート支持体上に酸性ポリマー層
（中和層）としてポリアクリル酸（10重量％水溶液で粘
度約1,000cp）（15g/m2）およびその上に中和タイミン
グ層としてアセチルセルロース（3.8g/m2）およびスチ
レンと無水マレイン酸のコポリマー（組成（モル）比、
スチレン：無水マレイン酸＝約60:40、分子量約５万）
（0.2g/m2）を塗布したカバーシートを作成した。[Cover Sheet] Polyacrylic acid (viscosity about 1,000 cp in 10% by weight aqueous solution) (15 g / m 2 ) as an acidic polymer layer (neutralization layer) on a polyethylene terephthalate support, and acetyl cellulose as a neutralization timing layer thereon. (3.8 g / m 2 ) and a copolymer of styrene and maleic anhydride (composition (molar) ratio,
Styrene: maleic anhydride = about 60:40, molecular weight about 50,000)
A cover sheet coated with (0.2 g / m 2 ) was prepared.
上記カバーシートと前記感光シートを重ね合わせ、カバ
ーシートの側からタングステン光源にて1/100秒でウエ
ツジ露光したのち、両シートの間に、上記処理液を100
μの厚みになるように加圧ローラーを用いて展開した。
展開処理は、25℃で行つた。処理後、感光シートの透明
支持体を通して、受像層に生成した画像の緑色濃度をマ
クベス反射濃度計によつて処理１時間後に測定した。そ
の結果を第５表に示す。The cover sheet and the photosensitive sheet are superposed on each other, and after the wafer is exposed by a tungsten light source from the cover sheet side for 1/100 second, the treatment liquid is applied between the two sheets by 100.
It was developed using a pressure roller so as to have a thickness of μ.
Development processing was performed at 25 ° C. After the processing, the green density of the image formed on the image-receiving layer was measured by a Macbeth reflection densitometer one hour after the processing through the transparent support of the photosensitive sheet. The results are shown in Table 5.
実施例３の結果と同様に、表５から本発明の造核剤がカ
ラー直接ポジ感剤においても低添加量で高濃度を与える
点で優れていることがわかる。Similar to the results of Example 3, it can be seen from Table 5 that the nucleating agent of the present invention is excellent even in a color direct positive sensitizer in that it gives a high concentration with a low addition amount.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭55−151635（ＪＰ，Ａ) 特開 昭57−129433（ＪＰ，Ａ) 特開 昭57−129435（ＪＰ，Ａ) ─────────────────────────────────────────────────── --Continued from the front page (56) Reference JP-A-55-151635 (JP, A) JP-A-57-129433 (JP, A) JP-A-57-129435 (JP, A)
Claims (1)
し、該写真乳剤層又は、他の少くとも一つの親水性コロ
イド層に下記一般式（Ｉ）で表わされる化合物を含有す
ることを特徴とするハロゲン化銀写真感光材料 一般式（Ｉ） 1. A photographic emulsion layer having at least one silver halide photographic emulsion layer, and the photographic emulsion layer or at least one other hydrophilic colloid layer containing a compound represented by the following general formula (I). A silver halide photographic light-sensitive material characterized by the general formula (I)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60011459A JPH0673005B2 (en) | 1985-01-24 | 1985-01-24 | Silver halide photographic light-sensitive material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60011459A JPH0673005B2 (en) | 1985-01-24 | 1985-01-24 | Silver halide photographic light-sensitive material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61170733A JPS61170733A (en) | 1986-08-01 |
| JPH0673005B2 true JPH0673005B2 (en) | 1994-09-14 |
Family
ID=11778677
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60011459A Expired - Fee Related JPH0673005B2 (en) | 1985-01-24 | 1985-01-24 | Silver halide photographic light-sensitive material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0673005B2 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0812404B2 (en) * | 1986-07-18 | 1996-02-07 | 富士写真フイルム株式会社 | Direct positive color image forming method |
| JPH0727183B2 (en) * | 1986-09-01 | 1995-03-29 | 富士写真フイルム株式会社 | Direct positive image forming method |
| JPH0679137B2 (en) * | 1986-11-11 | 1994-10-05 | 富士写真フイルム株式会社 | Silver halide photographic light-sensitive material |
| JPS63231441A (en) * | 1987-03-20 | 1988-09-27 | Fuji Photo Film Co Ltd | Direct positive silver halide photographic sensitive material and color image forming method |
| JPH0833607B2 (en) * | 1988-08-16 | 1996-03-29 | 富士写真フイルム株式会社 | Direct positive image forming method |
| JP2824717B2 (en) | 1992-07-10 | 1998-11-18 | 富士写真フイルム株式会社 | Processing method of silver halide photographic material |
| EP0589460B1 (en) | 1992-09-24 | 2000-08-09 | Fuji Photo Film Co., Ltd. | Method for processing a black & white silver halide light-sensitive material |
| FR2707983A1 (en) * | 1993-07-21 | 1995-01-27 | Pf Medicament | New derivatives of lipoic and dihydrolipoic acid, their preparation and their application in human therapeutics |
| CZ96798A3 (en) * | 1997-04-02 | 1998-10-14 | Sankyo Company Limited | Dithiolane derivatives, their preparation and their therapeutic effects |
| JP2000169371A (en) * | 1998-10-02 | 2000-06-20 | Sankyo Co Ltd | Medicament containing dithiolane derivative |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5931692B2 (en) * | 1979-05-17 | 1984-08-03 | 富士写真フイルム株式会社 | Direct positive silver halide photosensitive material |
| JPS57129433A (en) * | 1981-02-03 | 1982-08-11 | Fuji Photo Film Co Ltd | Formation of photographic image |
| JPS57129435A (en) * | 1981-02-03 | 1982-08-11 | Fuji Photo Film Co Ltd | Formation of photographic image |
-
1985
- 1985-01-24 JP JP60011459A patent/JPH0673005B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61170733A (en) | 1986-08-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4168977A (en) | Silver halide photographic emulsion | |
| US4224401A (en) | Silver halide photographic emulsions and image forming process | |
| EP0130856B1 (en) | Radiation sensitive silver halide emulsion containing substituted arylhydrazides | |
| EP0283040B1 (en) | Silver halide photographic material | |
| EP0286840A1 (en) | Silver halide photographic materials | |
| US4555482A (en) | Silver halide photographic emulsion | |
| JPH0668614B2 (en) | Silver halide photographic light-sensitive material | |
| JPH0673005B2 (en) | Silver halide photographic light-sensitive material | |
| JPS63314541A (en) | Image forming method | |
| JPH07119940B2 (en) | Silver halide photographic light-sensitive material | |
| JP2793810B2 (en) | Photographic elements and high contrast photographic silver halide emulsion processing methods | |
| US5085970A (en) | Image forming method | |
| JPH0115855B2 (en) | ||
| US4728596A (en) | Light-sensitive element for silver salt diffusion transfer with iodine trapping layer | |
| JPH0738070B2 (en) | Silver halide photographic light-sensitive material | |
| JPH0734106B2 (en) | Silver halide photographic light-sensitive material | |
| JPH0558531B2 (en) | ||
| JPH0786666B2 (en) | Silver halide photographic light-sensitive material | |
| JPH0693082B2 (en) | Silver halide photographic light-sensitive material | |
| JPH073561B2 (en) | Silver halide photographic light-sensitive material | |
| US5221601A (en) | Roomlight handleable uv sensitive direct positive silver halide photographic material | |
| JPH04221950A (en) | Photograph material containing electron accepting agent | |
| JPH0786664B2 (en) | Silver halide photographic light-sensitive material | |
| JPS6289958A (en) | Image forming method | |
| JPH0738071B2 (en) | Silver halide photographic light-sensitive material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |