JPS6333744A - High contrast negative image forming method - Google Patents
High contrast negative image forming methodInfo
- Publication number
- JPS6333744A JPS6333744A JP17661986A JP17661986A JPS6333744A JP S6333744 A JPS6333744 A JP S6333744A JP 17661986 A JP17661986 A JP 17661986A JP 17661986 A JP17661986 A JP 17661986A JP S6333744 A JPS6333744 A JP S6333744A
- Authority
- JP
- Japan
- Prior art keywords
- group
- developer
- developing agent
- silver
- atom
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims description 44
- -1 silver halide Chemical class 0.000 claims abstract description 53
- 229910052709 silver Inorganic materials 0.000 claims abstract description 34
- 239000004332 silver Substances 0.000 claims abstract description 34
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 33
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 13
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 8
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 5
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 3
- 125000004434 sulfur atom Chemical group 0.000 claims abstract description 3
- CMCWWLVWPDLCRM-UHFFFAOYSA-N phenidone Chemical compound N1C(=O)CCN1C1=CC=CC=C1 CMCWWLVWPDLCRM-UHFFFAOYSA-N 0.000 claims abstract 2
- 150000001875 compounds Chemical class 0.000 claims description 23
- 125000003118 aryl group Chemical group 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 7
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 1
- 229910001413 alkali metal ion Inorganic materials 0.000 claims 1
- 125000004429 atom Chemical group 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 abstract description 7
- 230000001788 irregular Effects 0.000 abstract description 2
- 229910021645 metal ion Inorganic materials 0.000 abstract description 2
- 239000000839 emulsion Substances 0.000 description 38
- 125000004432 carbon atom Chemical group C* 0.000 description 31
- 108010010803 Gelatin Proteins 0.000 description 20
- 229920000159 gelatin Polymers 0.000 description 20
- 239000008273 gelatin Substances 0.000 description 20
- 235000019322 gelatine Nutrition 0.000 description 20
- 235000011852 gelatine desserts Nutrition 0.000 description 20
- 239000000975 dye Substances 0.000 description 18
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 17
- 235000013339 cereals Nutrition 0.000 description 15
- 239000010410 layer Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 206010070834 Sensitisation Diseases 0.000 description 6
- 150000002429 hydrazines Chemical class 0.000 description 6
- 230000035945 sensitivity Effects 0.000 description 6
- 230000008313 sensitization Effects 0.000 description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- 239000002202 Polyethylene glycol Substances 0.000 description 5
- 229910021607 Silver chloride Inorganic materials 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 125000003342 alkenyl group Chemical group 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000000084 colloidal system Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- WSGURAYTCUVDQL-UHFFFAOYSA-N 5-nitro-1h-indazole Chemical compound [O-][N+](=O)C1=CC=C2NN=CC2=C1 WSGURAYTCUVDQL-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 4
- 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
- 239000011241 protective layer Substances 0.000 description 4
- 230000001235 sensitizing effect Effects 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- QTNLQPHXMVHGBA-UHFFFAOYSA-H hexachlororhodium Chemical compound Cl[Rh](Cl)(Cl)(Cl)(Cl)Cl QTNLQPHXMVHGBA-UHFFFAOYSA-H 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 239000003755 preservative agent Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 150000003283 rhodium Chemical class 0.000 description 3
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 3
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 3
- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- GGZHVNZHFYCSEV-UHFFFAOYSA-N 1-Phenyl-5-mercaptotetrazole Chemical compound SC1=NN=NN1C1=CC=CC=C1 GGZHVNZHFYCSEV-UHFFFAOYSA-N 0.000 description 2
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- LRUDIIUSNGCQKF-UHFFFAOYSA-N 5-methyl-1H-benzotriazole Chemical compound C1=C(C)C=CC2=NNN=C21 LRUDIIUSNGCQKF-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229910021612 Silver iodide Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 2
- 125000004423 acyloxy group Chemical group 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 125000004104 aryloxy group Chemical group 0.000 description 2
- JEHKKBHWRAXMCH-UHFFFAOYSA-N benzenesulfinic acid Chemical compound O[S@@](=O)C1=CC=CC=C1 JEHKKBHWRAXMCH-UHFFFAOYSA-N 0.000 description 2
- 150000001565 benzotriazoles Chemical class 0.000 description 2
- 150000001661 cadmium Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000005587 carbonate group Chemical group 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 235000010980 cellulose Nutrition 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 150000002344 gold compounds Chemical class 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000002335 preservative effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000005070 ripening Effects 0.000 description 2
- 229940045105 silver iodide Drugs 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 235000000346 sugar Nutrition 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 2
- 125000004964 sulfoalkyl group Chemical group 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical class OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- LUMLZKVIXLWTCI-NSCUHMNNSA-N (e)-2,3-dichloro-4-oxobut-2-enoic acid Chemical compound OC(=O)C(\Cl)=C(/Cl)C=O LUMLZKVIXLWTCI-NSCUHMNNSA-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
- SIQZJFKTROUNPI-UHFFFAOYSA-N 1-(hydroxymethyl)-5,5-dimethylhydantoin Chemical compound CC1(C)N(CO)C(=O)NC1=O SIQZJFKTROUNPI-UHFFFAOYSA-N 0.000 description 1
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- BIEFDNUEROKZRA-UHFFFAOYSA-N 2-(2-phenylethenyl)aniline Chemical group NC1=CC=CC=C1C=CC1=CC=CC=C1 BIEFDNUEROKZRA-UHFFFAOYSA-N 0.000 description 1
- HIGSPBFIOSHWQG-UHFFFAOYSA-N 2-Isopropyl-1,4-benzenediol Chemical compound CC(C)C1=CC(O)=CC=C1O HIGSPBFIOSHWQG-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
- PHPYXVIHDRDPDI-UHFFFAOYSA-N 2-bromo-1h-benzimidazole Chemical class C1=CC=C2NC(Br)=NC2=C1 PHPYXVIHDRDPDI-UHFFFAOYSA-N 0.000 description 1
- REFDOIWRJDGBHY-UHFFFAOYSA-N 2-bromobenzene-1,4-diol Chemical compound OC1=CC=C(O)C(Br)=C1 REFDOIWRJDGBHY-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
- OWIRCRREDNEXTA-UHFFFAOYSA-N 3-nitro-1h-indazole Chemical class C1=CC=C2C([N+](=O)[O-])=NNC2=C1 OWIRCRREDNEXTA-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
- NYYSPVRERVXMLJ-UHFFFAOYSA-N 4,4-difluorocyclohexan-1-one Chemical compound FC1(F)CCC(=O)CC1 NYYSPVRERVXMLJ-UHFFFAOYSA-N 0.000 description 1
- FJWJYHHBUMICTP-UHFFFAOYSA-N 4,4-dimethylpyrazolidin-3-one Chemical compound CC1(C)CNNC1=O FJWJYHHBUMICTP-UHFFFAOYSA-N 0.000 description 1
- SRYYOKKLTBRLHT-UHFFFAOYSA-N 4-(benzylamino)phenol Chemical compound C1=CC(O)=CC=C1NCC1=CC=CC=C1 SRYYOKKLTBRLHT-UHFFFAOYSA-N 0.000 description 1
- UTMDJGPRCLQPBT-UHFFFAOYSA-N 4-nitro-1h-1,2,3-benzotriazole Chemical class [O-][N+](=O)C1=CC=CC2=NNN=C12 UTMDJGPRCLQPBT-UHFFFAOYSA-N 0.000 description 1
- FIARATPVIIDWJT-UHFFFAOYSA-N 5-methyl-1-phenylpyrazolidin-3-one Chemical compound CC1CC(=O)NN1C1=CC=CC=C1 FIARATPVIIDWJT-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 102000009027 Albumins Human genes 0.000 description 1
- 108010088751 Albumins Proteins 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-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
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical class OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- WRUZLCLJULHLEY-UHFFFAOYSA-N N-(p-hydroxyphenyl)glycine Chemical compound OC(=O)CNC1=CC=C(O)C=C1 WRUZLCLJULHLEY-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- 125000005115 alkyl carbamoyl group Chemical group 0.000 description 1
- 125000005910 alkyl carbonate group Chemical group 0.000 description 1
- 125000004448 alkyl carbonyl group Chemical group 0.000 description 1
- 125000005599 alkyl carboxylate group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000005153 alkyl sulfamoyl group Chemical group 0.000 description 1
- 125000004644 alkyl sulfinyl group Chemical group 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 125000005281 alkyl ureido group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 125000005116 aryl carbamoyl group Chemical group 0.000 description 1
- 125000005129 aryl carbonyl group Chemical group 0.000 description 1
- 125000005161 aryl oxy carbonyl group Chemical group 0.000 description 1
- 125000004391 aryl sulfonyl group Chemical group 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- CJPQIRJHIZUAQP-MRXNPFEDSA-N benalaxyl-M Chemical compound CC=1C=CC=C(C)C=1N([C@H](C)C(=O)OC)C(=O)CC1=CC=CC=C1 CJPQIRJHIZUAQP-MRXNPFEDSA-N 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical class C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 235000010338 boric acid Nutrition 0.000 description 1
- 235000008429 bread Nutrition 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
- 244000309464 bull Species 0.000 description 1
- DNSISZSEWVHGLH-UHFFFAOYSA-N butanamide Chemical compound CCCC(N)=O DNSISZSEWVHGLH-UHFFFAOYSA-N 0.000 description 1
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 1
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 description 1
- 125000005521 carbonamide group Chemical group 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
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- UOCJDOLVGGIYIQ-PBFPGSCMSA-N cefatrizine Chemical group S([C@@H]1[C@@H](C(N1C=1C(O)=O)=O)NC(=O)[C@H](N)C=2C=CC(O)=CC=2)CC=1CSC=1C=NNN=1 UOCJDOLVGGIYIQ-PBFPGSCMSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 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
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- BBLSYMNDKUHQAG-UHFFFAOYSA-L dilithium;sulfite Chemical compound [Li+].[Li+].[O-]S([O-])=O BBLSYMNDKUHQAG-UHFFFAOYSA-L 0.000 description 1
- 150000002012 dioxanes Chemical class 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- IYBUGHSUXJVLBQ-UHFFFAOYSA-L dipotassium;bromide;iodide Chemical compound [K+].[K+].[Br-].[I-] IYBUGHSUXJVLBQ-UHFFFAOYSA-L 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 150000002473 indoazoles Chemical class 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 compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- ZAKLKBFCSHJIRI-UHFFFAOYSA-N mucochloric acid Natural products OC1OC(=O)C(Cl)=C1Cl ZAKLKBFCSHJIRI-UHFFFAOYSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000004957 nitroimidazoles Chemical class 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 125000005740 oxycarbonyl group Chemical group [*:1]OC([*:2])=O 0.000 description 1
- QUBQYFYWUJJAAK-UHFFFAOYSA-N oxymethurea Chemical compound OCNC(=O)NCO QUBQYFYWUJJAAK-UHFFFAOYSA-N 0.000 description 1
- 229950005308 oxymethurea Drugs 0.000 description 1
- 239000006174 pH buffer Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 125000005496 phosphonium group Chemical group 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 description 1
- 229920002006 poly(N-vinylimidazole) polymer Polymers 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920000120 polyethyl acrylate Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- RWPGFSMJFRPDDP-UHFFFAOYSA-L potassium metabisulfite Chemical compound [K+].[K+].[O-]S(=O)S([O-])(=O)=O RWPGFSMJFRPDDP-UHFFFAOYSA-L 0.000 description 1
- 229940043349 potassium metabisulfite Drugs 0.000 description 1
- 235000010263 potassium metabisulphite Nutrition 0.000 description 1
- 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
- 239000002244 precipitate Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- NDGRWYRVNANFNB-UHFFFAOYSA-N pyrazolidin-3-one Chemical compound O=C1CCNN1 NDGRWYRVNANFNB-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- HBCQSNAFLVXVAY-UHFFFAOYSA-N pyrimidine-2-thiol Chemical class SC1=NC=CC=N1 HBCQSNAFLVXVAY-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229930182490 saponin Natural products 0.000 description 1
- 150000007949 saponins Chemical class 0.000 description 1
- 235000017709 saponins Nutrition 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- AMZPPWFHMNMIEI-UHFFFAOYSA-M sodium;2-sulfanylidene-1,3-dihydrobenzimidazole-5-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C2NC(=S)NC2=C1 AMZPPWFHMNMIEI-UHFFFAOYSA-M 0.000 description 1
- UOULCEYHQNCFFH-UHFFFAOYSA-M sodium;hydroxymethanesulfonate Chemical compound [Na+].OCS([O-])(=O)=O UOULCEYHQNCFFH-UHFFFAOYSA-M 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 150000003431 steroids Chemical class 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium group Chemical group [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 125000003831 tetrazolyl group Chemical group 0.000 description 1
- 150000003475 thallium Chemical class 0.000 description 1
- JJJPTTANZGDADF-UHFFFAOYSA-N thiadiazole-4-thiol Chemical class SC1=CSN=N1 JJJPTTANZGDADF-UHFFFAOYSA-N 0.000 description 1
- 150000003567 thiocyanates Chemical class 0.000 description 1
- 125000005323 thioketone group Chemical group 0.000 description 1
- 125000003396 thiol group Chemical class [H]S* 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- 229940062627 tribasic potassium phosphate Drugs 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 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
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
- G03C5/29—Development processes or agents therefor
- G03C5/305—Additives other than developers
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
Abstract
Description
【発明の詳細な説明】
(産業上の利用分野)
本発明はハロゲン化銀写真感光材料を硬調に現像する方
法に関するものであり、特にグラフィック・アークの印
刷用写真製版工程に適した高コントラストのネガティブ
画像を形成する方法に関するものである。Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a method for developing silver halide photographic materials with high contrast, and in particular, a high contrast method suitable for the photolithography process for printing graphic arcs. The present invention relates to a method of forming a negative image.
(従来の技術)
グラフィック・アークの分野においては網点画像による
連続階調の画像の再生あるいは線画像の再生を良好なら
しめるために、高コントラストの写真特性を示す画像形
成システムが必要である。BACKGROUND OF THE INVENTION In the field of graphic arcs, there is a need for an imaging system that exhibits high contrast photographic characteristics in order to provide good reproduction of continuous tone images with halftone images or reproduction of line 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
くしである。Traditionally, a special developer called a Lith developer has been used for this purpose. Lith developer contains only hydroquinone as a developing agent, and uses sulfite as a preservative in the form of an adduct with formaldehyde to keep the concentration of free sulfite ions extremely low so as not to inhibit its infectious development properties. .
そのためリス現像液は極めて空気酸化を受けやすく3日
を越える保存に耐えられないという重大な欠点を持って
いる。Therefore, the Lith developer has a serious drawback in that it is extremely susceptible to air oxidation and cannot be stored for more than 3 days.
高コントラストの写真特性を安定な現像液を用いて得る
方法としては米国特許第4224401号、同第416
&977号、同第4,166.742号、同第431L
781号、同第4272,606号、同第4,21L8
57号、同第4243,739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、更忙
現偉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 high contrast photographic properties using a stable developer, US Pat. Nos. 4,224,401 and 416
&977, same No. 4,166.742, same No. 431L
No. 781, No. 4272,606, No. 4,21L8
There is a method using a hydrazine derivative described in No. 57, No. 4243,739, and the like. This method provides photographic properties with high contrast and high sensitivity, and because it allows the addition of high concentrations of sulfite in the developing solution, the stability of the developer against air oxidation is reduced by the lithographic process. Dramatically improved compared to liquid.
(発明が解決しようとする問題点)
しかし、このヒドラジン誘導体を用いる方法では現像液
のpHが通常のリス現像液のpHよシも高めに設定され
ているため、当業界で通常行われている自動現像機でハ
ロゲン化銀写真感光材料を処理する際、現像ムラが発生
しやすいという欠点をもっている。(Problem to be Solved by the Invention) However, in the method using this hydrazine derivative, the pH of the developer is set higher than that of a normal lithium developer, so it is not commonly practiced in the industry. When processing silver halide photographic materials with automatic processors, they have the disadvantage that uneven development tends to occur.
現像ムラの発生機構は明らかではないが、現像液のpH
が通常のリス現偉液並みに低ければ現像ムラは生じない
が、とPラジン誘導体を含有する感光材料の硬調化が起
らない。硬調化が起る高pH現像液でも補助現像主薬を
含まないハイドロキノン単独の現像液では現像ムラは生
じない。但しハイドロキノン単独の現像液の場合には自
動現像機で連続的にハロゲン化銀感光材料が処理されて
現像液中のハロゲンイオン(主にブロマイドイオン)が
増加すると写真感度の低下が生じるという欠点をもって
いる。The mechanism by which uneven development occurs is not clear, but the pH of the developer
If it is as low as a normal Lith developing solution, uneven development will not occur, but the contrast of the photosensitive material containing the P-radin derivative will not increase. Even with a high pH developer that causes high contrast, a developer containing only hydroquinone without an auxiliary developing agent will not cause uneven development. However, in the case of a developer containing only hydroquinone, the silver halide photosensitive material is continuously processed in an automatic processor, and when the halogen ions (mainly bromide ions) in the developer increase, the photographic sensitivity decreases. There is.
一方、ヒドラジン誘導体を用いずに硬調な画像を得る方
法においては、上記の如き高いpH値や補助現像主薬は
現像液に必須ではないため、現像ムラの問題はそれ程深
刻ではない。しかしながら、ヒドラジン誘導体を用いな
い系においても上記の高pHかつ補助現像主薬含有現像
液を用いて硬調な画像を形成することは可能であり、特
に同一の自動現像機を用いてヒト9ラジン系及び非ヒド
ラジン系の両方の系を交互に実施する場合には非ヒビラ
ジン系においても高pHかつ補助現像主薬含有現像液を
用いることが必要となってくる。その場合にヒドラジン
系の場合と同様に現像ムラが発生しやすいという欠点が
ある。On the other hand, in a method for obtaining a high-contrast image without using a hydrazine derivative, the problem of uneven development is not so serious because the above-mentioned high pH value and auxiliary developing agent are not essential to the developer. However, even in systems that do not use hydrazine derivatives, it is possible to form high-contrast images using the above-mentioned high pH developer containing an auxiliary developing agent. When both non-hydrazine systems are used alternately, it is necessary to use a developer having a high pH and containing an auxiliary developing agent even in the non-hydrazine system. In this case, there is a drawback that development unevenness tends to occur, similar to the case of hydrazine type.
高pHの補助現像主薬を含有する現像液を用いて硬調化
を起こさせ、かつ自動現像機で連続的にハロゲン化銀感
光材料を処理させても、写真感度の変化がなく安定な性
能を有しながら現像ムラの欠陥を解消する化合物を使用
しなければならないが、かかる観点に照らしてどのよう
な化合物が適当かという点については、従来全く知られ
ていなかった。Even if a developer containing a high pH auxiliary developing agent is used to increase the contrast and the silver halide photosensitive material is continuously processed in an automatic processor, there is no change in photographic sensitivity and the performance is stable. However, it is necessary to use a compound that eliminates the defect of uneven development, but it has not been known at all as to what kind of compound is suitable from this point of view.
従って本発明の目的は、高pH現像液で高コントラスト
画像形成方法において現像ムラの少なく且つ感度や網点
品質などの性能の良好な写真フィルム画像を提供するこ
とにある。Accordingly, an object of the present invention is to provide a photographic film image with less unevenness in development and with good performance such as sensitivity and halftone dot quality in a high contrast image forming method using a high pH developer.
(問題点を解決するための手段)
本発明の目的は、ハロゲン化銀写真感光材料を下記(1
)〜(4)の成分を含み且つ11.0〜12.3のpH
値を有する現像液で処理することによって達成された。(Means for Solving the Problems) The object of the present invention is to provide silver halide photographic materials as follows (1)
) to (4) and has a pH of 11.0 to 12.3
This was achieved by processing with a developer having a value of .
(11ジヒドロキシベンゼン系現像主薬。(11 dihydroxybenzene developing agent.
12) r−フェニル−3−ピラゾリドン系補助現像
主薬及び/又はp−アミノ−フェノール系補助現像主薬
。12) r-phenyl-3-pyrazolidone-based auxiliary developing agent and/or p-amino-phenol-based auxiliary developing agent.
、(3)・・0.3モル/旦以上の亜硫酸塩。, (3)...0.3 mol/day or more of sulfite.
(4)少なくとも1種の下記一般式(1)で表わされる
化合物。(4) At least one compound represented by the following general formula (1).
一般式(1) N−N M8スエ(オ、。General formula (1) N-N M8 Sue (Oh,.
式中、Xは硫黄原子又は酸素原子を表わし、Lば一0C
OO−、−NR2CONR3−、−NR2Coo−、−
0CONR2−又は−NRSo NR−を表わしくR2
,R3は同一でも互いに異なってもよく各々水素原子、
アルキル基又はアリール基を表わす)、R工は水素原子
、脂肪族基又は芳香族基を表わし、Mは水素原子、7に
キル金属イオン、四級アンモニウムイオン又は四級ホス
ホニウムイオンを表わす。nはO又は1を表わす。In the formula, X represents a sulfur atom or an oxygen atom, and L
OO-, -NR2CONR3-, -NR2Coo-, -
0CONR2- or -NRSo NR- is R2
, R3 may be the same or different and each is a hydrogen atom,
(represents an alkyl group or aryl group), R represents a hydrogen atom, an aliphatic group, or an aromatic group, M represents a hydrogen atom, and 7 represents a kill metal ion, a quaternary ammonium ion, or a quaternary phosphonium ion. n represents O or 1.
本発明においては、一般式(1)で表わされる化合物を
現像液中に含有させることにより、補助現像主薬を併用
し且つ高いpH値を有する現像液を用いて高コントラス
トネガ画像を形成する場合に発生しやすい現像ムラを良
好に防止するものである。In the present invention, by incorporating the compound represented by the general formula (1) into a developer, it is possible to form a high contrast negative image using a developer having a high pH value in combination with an auxiliary developing agent. This effectively prevents uneven development that tends to occur.
従って、本発明は上記の如き現像液において補助現像主
薬の併用と高pHが必要であるヒドラジン系化合物を用
いる方法の場合に特に有効であるが、それ以外のヒーラ
ジン系化合物を用いずに高コントラスト(例えば階調4
以上)ネガ画像を形成する場合にも本発明の方法により
有効に現像ムラを良化することができる。従って、特に
ヒビラジン系及び非ヒドラジン系の両方の系を同一の現
保機を用いて交互に実施する場合に、現像液を入れ替え
ることなく連続的作業が可能である点でも本発明は有利
である。Therefore, the present invention is particularly effective in the case of a method using a hydrazine compound, which requires the combination of an auxiliary developing agent and a high pH in the developer as described above. (For example, gradation 4
Above) Even when forming a negative image, development unevenness can be effectively improved by the method of the present invention. Therefore, the present invention is also advantageous in that continuous operation is possible without replacing the developer, especially when both hydrazine-based and non-hydrazine-based systems are used alternately using the same developing machine. .
一般式(1)で表わされる化合物について詳述する。The compound represented by general formula (1) will be explained in detail.
一般式(1)においてR□ で表わされる脂肪族基及び
芳香族基としては、好ましくは炭素数1〜20のアルキ
ル基(直鎖1分岐鎖又は環状のいずれのアルキル基でも
よく、例えばメチル基、エチル基、n7’チル基、ナフ
チル基、t−アミル基、n−ヘキシル基、シクロヘキシ
ル基など)、炭素数2〜20のアルケニルT5(直鎖、
分岐鎖又は環状アルケニル基、例えば、ビニル基、プロ
にニル基、イソプロペニル基など)、炭素数6〜20の
アリール基(例えばフェニル基、ナフチル基なト)、ヲ
挙げることができ、R1はこれらのアルキル基、アルケ
ニル基、アリール基が−8−、−0−、−N、:。The aliphatic group and aromatic group represented by R□ in general formula (1) are preferably an alkyl group having 1 to 20 carbon atoms (any linear, monobranched or cyclic alkyl group, such as a methyl group). , ethyl group, n7' thyl group, naphthyl group, t-amyl group, n-hexyl group, cyclohexyl group, etc.), alkenyl T5 having 2 to 20 carbon atoms (straight chain,
branched or cyclic alkenyl groups (e.g., vinyl, pro-pronyl, isopropenyl, etc.), aryl groups having 6 to 20 carbon atoms (e.g., phenyl, naphthyl, etc.), and R1 is These alkyl groups, alkenyl groups, and aryl groups are -8-, -0-, -N, and so on.
−、CO,、−So−9−802−などから構成される
連結基を介して更に同−又は異なるアルキル基、アルケ
ニル基又はアリール基と連結したものでもよい。It may be further connected to the same or different alkyl group, alkenyl group, or aryl group via a connecting group composed of -, CO,, -So-9-802-, etc.
さらに、R□ で表わされるアルギル基、アルケニル基
、アリール基は置換基を有していてもよく、具体的置換
基としては例えばハロゲン原子(フッ素、塩素、臭素)
、アルキル基(好ましくは炭素数1〜20のもの)、ア
リール基(好ましくは炭素数6〜20のもの)、アルコ
キシ基(好ましくは炭素数1〜20のもの)、アリール
オキシ基(好ましくは炭素数6〜20のもの)、アルキ
ルチオ基(好ましくは炭素数1〜20のもの)、了り−
ルチオ基(好ましくは炭素数6〜20のもの)、アシル
オキシ基(好ましくは炭素数2〜20のもの)、アミン
基(無置換アミン、好ましくは炭素数1〜20のアルキ
ル基−または炭素数6〜20のアリール基で置換した2
級または3級のアミノ基)、カルボンアミド基(好まし
くは炭素数1〜20のアルキルカルボンアミド基、炭素
数6〜20のアリールカルボンアミド9基)、ウレイド
9基(好ましくは炭素数1〜20のアルキルウレイド基
、炭素数6〜20のアリールオキシ基)、カルボキシ基
、炭酸エステル基(好ましくは炭素数1〜20のアルキ
ル炭酸エステル基、炭素数6S20のアリール炭酸エス
テル基)、オキシカルボニル基(好ましくは炭素数1〜
20のアルキルオキシカルボニル基、炭素数6〜20の
アリールオキシカルボニル基)、カルバモイル基(好ま
しくは炭素数1〜20のアルキルカルバモイル基、炭素
数6〜20のアリールカルバモイル基)、アシル基(好
ましくは炭素数1〜20のアルキルカルボニル基、炭素
数6へ20のアリールカルボニル基)、スルホ基、スル
ホニル基(好ましくは1〜20のアルキルスルホニル基
、炭素数6〜2oのアリールスルホニル基)、スルフィ
ニルg<好−tしくけ炭素数1〜20のアルキルスルフ
ィニル基、炭素数6〜20の7リールスルフイニル基)
、ス/l/7アモイル基(好ましくは炭素数1〜20の
アルキルスルファそイル基、炭素数6〜20のアリール
スルファモイル基)、シアノ基、ニトロ基ヲ挙げること
ができる。特にカルボキシ基、スルホ基が好ましく、置
換基が2個以上あるときは同じでも異っていてもよい。Furthermore, the argyl group, alkenyl group, and aryl group represented by R□ may have a substituent, and specific substituents include, for example, a halogen atom (fluorine, chlorine, bromine).
, an alkyl group (preferably one having 1 to 20 carbon atoms), an aryl group (preferably one having 6 to 20 carbon atoms), an alkoxy group (preferably one having 1 to 20 carbon atoms), an aryloxy group (preferably one having 1 to 20 carbon atoms), (6 to 20 carbon atoms), alkylthio group (preferably one with 1 to 20 carbon atoms),
ruthio group (preferably one with 6 to 20 carbon atoms), acyloxy group (preferably one with 2 to 20 carbon atoms), amine group (unsubstituted amine, preferably an alkyl group with 1 to 20 carbon atoms), or acyloxy group (preferably one with 2 to 20 carbon atoms), 2 substituted with ~20 aryl groups
or tertiary amino group), carbonamide group (preferably 9 alkylcarbonamide groups having 1 to 20 carbon atoms, 9 arylcarbonamide groups having 6 to 20 carbon atoms), 9 ureido groups (preferably 9 arylcarbonamide groups having 1 to 20 carbon atoms) an alkylureido group, an aryloxy group having 6 to 20 carbon atoms), a carboxy group, a carbonate group (preferably an alkyl carbonate group having 1 to 20 carbon atoms, an aryl carbonate group having 6S20 carbon atoms), an oxycarbonyl group ( Preferably carbon number 1~
20 alkyloxycarbonyl group, aryloxycarbonyl group having 6 to 20 carbon atoms), carbamoyl group (preferably an alkylcarbamoyl group having 1 to 20 carbon atoms, arylcarbamoyl group having 6 to 20 carbon atoms), acyl group (preferably Alkylcarbonyl group having 1 to 20 carbon atoms, arylcarbonyl group having 6 to 20 carbon atoms), sulfo group, sulfonyl group (preferably alkylsulfonyl group having 1 to 20 carbon atoms, arylsulfonyl group having 6 to 2 o carbon atoms), sulfinyl g <Preferable alkylsulfinyl group having 1 to 20 carbon atoms, 7-arylsulfinyl group having 6 to 20 carbon atoms)
, S/l/7 amoyl group (preferably an alkylsulfamoyl group having 1 to 20 carbon atoms, an arylsulfamoyl group having 6 to 20 carbon atoms), a cyano group, and a nitro group. Particularly preferred are a carboxy group and a sulfo group, and when there are two or more substituents, they may be the same or different.
R2,R3としては好ましくは水素原子、炭素数1〜1
0の置換もしくは無置換のアルキル基、炭素数6〜10
の置換もしくは無置換のアリール基であり、置換基とし
ては例えばR1の置換基と同じものを挙げることができ
る。R2 and R3 are preferably hydrogen atoms, with 1 to 1 carbon atoms.
0 substituted or unsubstituted alkyl group, carbon number 6-10
is a substituted or unsubstituted aryl group, and the substituents include, for example, the same substituents as R1.
本発明に用いられる化合物の好ましい具体例を以下に挙
げる。Preferred specific examples of the compounds used in the present invention are listed below.
−N
N
−N
2H5
■
CH2C00H
これらの化合物は現像液ll当、!710g以下よシ好
ましくは39/皇以下20η/f1以上で用いることが
適当である。さらにこれらの化合物は単独で用いても2
種類以上のものを併用して用いることもできる。-N N -N 2H5 ■ CH2C00H These compounds are per liter of developer! It is appropriate to use it at 710 g or less, preferably 39/f1 or less, and 20η/f1 or more. Furthermore, even when these compounds are used alone, 2
More than one type can also be used in combination.
一般式(■)で示される化合物は以下の文献に記載され
ている公知の方法によシ合成することができる。The compound represented by the general formula (■) can be synthesized by a known method described in the following literature.
J、 Am、 Chem、 Soc、、第44巻、15
02〜1510゜
米国特許ス017.270号、英国特許94Q、169
号特公昭494334.%開昭55−59463Adv
anced in Heterocyclic
ChemIStr7+ L165〜209(1968
)
西独特許2,716,707号
本発明において、高コントラストとは、より具体的には
階調γとして4以上のものを言う。J, Am, Chem, Soc,, vol. 44, 15
02-1510゜U.S. Patent No. 017.270, British Patent No. 94Q, 169
Special Publication No. 494334. % Kaisho 55-59463Adv
anced in Heterocyclic
ChemIStr7+ L165-209 (1968
) West German Patent No. 2,716,707 In the present invention, high contrast refers more specifically to gradation γ of 4 or more.
このような基コントラストなネガ画像を得る方法として
は公知の手段音用いることができる。例えば、ハロゲン
化銀乳剤の粒子サイズ分布を単分散化する方法(方法■
)、ハロゲン化銀乳剤のハロゲン組成を塩化銀もしくは
塩臭化銀とする方法(方法■)、ヒト9ラジン化合物も
しくはテトラゾリウム塩化合物の存在下で現像する方法
(方法■)、ロジウム塩等の■族金属化合物をハロゲン
化銀乳剤に含有させる方法(方法■)など用いることが
できる。As a method for obtaining such a negative image with basic contrast, known means can be used. For example, a method for monodispersing the grain size distribution of a silver halide emulsion (method
), a method in which the halogen composition of the silver halide emulsion is silver chloride or silver chlorobromide (method ■), a method in which development is carried out in the presence of a human 9 radine compound or a tetrazolium salt compound (method ■), a method ■ in which rhodium salts, etc. A method of incorporating a group metal compound into a silver halide emulsion (method ①) can be used.
方法■において重分数の程度とは、後述の如き程度が好
ましい。In method (2), the degree of multiple fractions is preferably as described below.
方法■において、塩化銀含有量としては50〜100モ
ルチが好ましい。In method (2), the silver chloride content is preferably 50 to 100 mol.
方法■において、ヒト9ラジン化合物を用いる方法につ
いては詳しくは前述の米国特許に記載されている。The method of using human 9-radine compound in Method 2 is described in detail in the above-mentioned US patent.
この方法にて用いられるヒドラジンとしては公知のもの
を用いることができる。具体的化合物例としては、米国
特許第4224401号、同第416a977号、同第
41645742号、同第43LL781号、同第42
72.606号、同第421L857号、同第4243
739号等に記載されているヒドラジン訪導体がある。As the hydrazine used in this method, any known hydrazine can be used. Specific compound examples include U.S. Pat. No. 4,224,401, U.S. Pat. No. 416a977, U.S. Pat.
No. 72.606, No. 421L857, No. 4243
There is a hydrazine visiting conductor described in No. 739 and the like.
また、テトラゾリウムを用いる方法については詳しくは
、特開昭52−18317号、同53−17719号、
同53−17720号などに記載されている。For details on the method using tetrazolium, see JP-A-52-18317 and JP-A-53-17719.
It is described in No. 53-17720.
また、この方法■を用いた場合にはγ値10以上のもの
を得ることもできる。Further, when this method (2) is used, a γ value of 10 or more can be obtained.
方法■においては、例えばロジウム塩を10−7へ10
モル1モル−Ag程度含有させること釦よって行なう
ことができる。In method ①, for example, rhodium salt is added to 10-7 to 10
It is possible to contain about 1 mol of Ag by pressing the button.
本発明の画像形成方法は現像主薬としてジヒドロキシベ
ンゼン系現像主薬を用い補助現像主薬としてp−アミン
フェノール系現像主薬又は3−ピラゾリドン系現像主薬
を用するのが好ましい。In the image forming method of the present invention, it is preferable to use a dihydroxybenzene-based developing agent as a developing agent and a p-aminephenol-based developing agent or a 3-pyrazolidone-based developing agent as an auxiliary developing agent.
本発明に用いるジヒドロキシベンゼン系現像主薬として
はハイドロキノン、クロロハイドロキノン、ブロモハイ
ド90キノン、イソプロピルハイドロキノン、メチルハ
イド90キノン、z3−ジクロロハイドロキノン、a3
−ジブロモハイド90キノン、ZS−ジメチルハイドロ
キノン等があるが、なかでも侍にハイ)−″ロキノンが
好マl、い。The dihydroxybenzene-based developing agent used in the present invention includes hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, z3-dichlorohydroquinone, a3
-Dibromohyde 90quinone, ZS-dimethylhydroquinone, etc., among which samurai prefers -'' quinone.
補助現像主薬としての1−フェニル−3−ピラゾリト0
ン又はその誘導体の例としては1−フエニに−3−ピ7
ゾI)Vン、1−フェニル−44−ジメチル−3−ピラ
ゾリドン、1−フェニル−4−メチル−4−ヒドロキシ
メチル−3−ピラゾリト1ン、l−フェニル−44−シ
ヒビロキシメチルー3−ヒラソl))’ン、1−フェニ
ル−5−メチル−3−ピラゾリドン、1−p−アミノフ
ェニル−44−ジメチル−3−ピラゾリト1ン、1−p
−)リルー夷4−ジメチルー3−ピラゾリドンなどがあ
る。1-phenyl-3-pyrazolito as auxiliary developing agent
Examples of 1-phenylene or its derivatives include 1-phenyl-3-py7
zoI) V, 1-phenyl-44-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolito-1, l-phenyl-44-dimethyl-3- Hirasol 1))', 1-phenyl-5-methyl-3-pyrazolidone, 1-p-aminophenyl-44-dimethyl-3-pyrazolito1, 1-p
-) 4-dimethyl-3-pyrazolidone and the like.
p−アミノフェノール系補助現像主薬としてはN−メチ
ル−p−アミンフェノール、p−アミンフェノール、N
−(β−ヒト90キシエチル)−p−アミノフェノール
、N−(4−ヒドロキシフェニル)グリシン、2−メチ
ル−p−アミンフェノール、p−ベンジルアミノフェノ
ール等があるが、なかでもN−メチル−p−アミンフェ
ノールが好ましい。As the p-aminophenol auxiliary developing agent, N-methyl-p-aminephenol, p-aminephenol, N
-(β-human 90xethyl)-p-aminophenol, N-(4-hydroxyphenyl)glycine, 2-methyl-p-aminephenol, p-benzylaminophenol, etc., among which N-methyl-p -Aminphenols are preferred.
ジヒドロキシベンゼン系現像主薬は通常0.05モル/
j〜0.8モル/lの量で用いられるのが好ましい。ま
たジヒドロキシ(ンゼン類と1−フェニル−3−ピラゾ
リ上9ン類又はp−アミノ−フェノール類との組合せを
用いる場合には前者を0.05モル/fl〜0.5モル
/旦、後者を0.06モル/ft以下の量で用いるのが
好ましい。Dihydroxybenzene developing agent is usually 0.05 mol/
Preferably, it is used in an amount of j to 0.8 mol/l. In addition, when using a combination of dihydroxy (benzenes) and 1-phenyl-3-pyrazolyne compounds or p-amino-phenols, the former is used at 0.05 mol/fl to 0.5 mol/day, and the latter is Preferably, it is used in an amount of 0.06 mol/ft or less.
本発明に用いる亜硫酸塩保恒剤としては亜硫酸ナトリウ
ム、亜硫酸カリウム、亜硫酸リチウム、重量硫酸ナトリ
ウム、メタ重亜硫酸カリウム、ホルムアルデヒド重亜硫
酸ナトリウム等がある。亜硫酸塩は0.3モル/9.以
上用いられるが、余りに多量添加すると現像液中で沈澱
して液汚染を引き起こすので、上限は12モル/fiと
するのが好ましい。Sulfite preservatives used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, sodium gravisulfate, potassium metabisulfite, formaldehyde sodium bisulfite, and the like. Sulfite is 0.3 mol/9. However, if too large a quantity is added, it will precipitate in the developing solution and cause solution contamination, so the upper limit is preferably 12 mol/fi.
本発明の現侭液はその他、ホウ酸、ホウ砂、第三リン酸
ナトリウム、第三リン酸カリウムの如きpH緩衝剤それ
以外に特開昭60−93433に記載のpH緩衝剤を用
いることができる;臭化カリウム、沃化カリウムの如き
現像抑制剤;エチレングリコール、ジエチレングリコー
ル、トリエチレングリコール、ジメチルホルムアミビ、
メチルセロソルフ、ヘキシレングリコール、エタノール
、メタノールの如き有機溶剤;5−ニトロインダゾール
等のインダゾール系化合物、2−メルカプトベンツイミ
ダゾール−5−スルホン酸ナトリウム、5−メチルベン
ツトリアゾールなどのベンツトリアゾール系化合物等の
カプリ防止剤ないしは黒ボッ(black peppe
r)防止剤;を含んでもよく、特に5−ニトロインダゾ
ール等の化合物を用いるときはジヒドロキシベンゼン系
現像主薬や亜硫酸塩保恒剤を含む部分とは別の部分にあ
らかじめ溶解しておき使用時に画部分を混合して水を加
えること等が一般的である。さらに5−ニトロインダゾ
ールの溶解せしめる部分をアルカリ性にしておくと黄色
く着色し取扱い等に便利である。In addition to the present solution of the present invention, pH buffers such as boric acid, borax, trisodium phosphate, and tribasic potassium phosphate may be used. development inhibitors such as potassium bromide and potassium iodide; ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamibi,
Organic solvents such as methyl cellosol, hexylene glycol, ethanol, and methanol; Capri such as indazole compounds such as 5-nitroindazole, benztriazole compounds such as sodium 2-mercaptobenzimidazole-5-sulfonate, and 5-methylbenztriazole; inhibitor or black peppe
r) Inhibitor; In particular, when using a compound such as 5-nitroindazole, it should be dissolved in advance in a separate area from the area containing the dihydroxybenzene developing agent and sulfite preservative. It is common to mix the parts and add water. Furthermore, if the part where 5-nitroindazole is dissolved is made alkaline, it will be colored yellow and will be convenient for handling.
更に必要に応じて色調剤、界面活性剤、硬水軟定着液と
しては一般に用いられている組成のものを用いることが
できる。定着剤としてはチオ硫酸塩、チオシアン酸塩の
ほか、定着剤としての効果が知られている有機硫黄化合
物を用いることができる。定着液には硬膜剤として水溶
性アルミニウム塩、例えば硫酸アルミニウム、明パンな
どを含んでもよい。ここで水溶性アルミニウム塩の量と
しては通常0〜3.(lAfi/N である。また酸
化剤としてエチレンジアミン四酢酸F e (m )錯
塩を用いてもよい。Furthermore, as the color toning agent, surfactant, and hard water/soft fixer, those having compositions commonly used can be used as necessary. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as fixing agents can be used. The fixing solution may contain a water-soluble aluminum salt such as aluminum sulfate, light bread, etc. as a hardening agent. Here, the amount of water-soluble aluminum salt is usually 0 to 3. (lAfi/N). Ethylenediaminetetraacetic acid F e (m) complex salt may also be used as the oxidizing agent.
処理温度は通常18℃から50℃の間に選ばれるが、1
8℃より低い温度または50℃゛をこえる温度としても
よい。The treatment temperature is usually selected between 18°C and 50°C, but 1
The temperature may be lower than 8°C or higher than 50°C.
本発明の方法は特に自動現像機を用いる迅速処理に適し
ている。自動現像機としてはローラー搬送のもの、ベル
ト搬送のものその他のいずれでも使用できる。処理時間
は短くてよく、トータルで2分以内、特に100秒以下
、そのなかで現像に割り当てられる時間15〜60秒と
いう迅速現像に対しても充分効果を発揮する。The method of the invention is particularly suitable for rapid processing using automatic processors. As the automatic developing machine, any of roller conveyance type, belt conveyance type, and other types can be used. The processing time may be short, and is sufficiently effective for rapid development within 2 minutes in total, particularly 100 seconds or less, within which the time allotted for development is 15 to 60 seconds.
本発明において用いられるハロゲン化銀乳剤のハロゲン
組成には特別な制限はなく、塩化銀、塩臭化銀、沃臭化
銀、臭化銀、法具塩化銀等などの組成であってもよい。There is no particular restriction on the halogen composition of the silver halide emulsion used in the present invention, and compositions such as silver chloride, silver chlorobromide, silver iodobromide, silver bromide, silver chloride, etc. may be used. .
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持つこともできるが、狭い
粒子サイズ分布を持つことが好ましく、特にハロゲン化
銀粒子の重量または数に関して全体の90チを占める粒
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2(一般にこのような乳剤は単分散乳剤と呼
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, especially when the size of the grains that make up 90 cm of the total grain size in terms of weight or number of silver halide grains is ±40% of the average grain size. 2 (such emulsions are generally called monodisperse emulsions).
本発明でもち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04μ以下が好ま
しい。The silver halide grains used in the present invention are preferably fine grains (for example, 0.7 microns or less), particularly preferably 04 microns or less.
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(irr
egular) な結晶を持つもの、あるいはこれらの
結晶形の複合形をもつものであってもよい。Silver halide grains in photographic emulsions may have regular crystal structures such as cubes and octahedrons, or irregular crystal structures such as spherical and plate shapes.
It may have crystals such as egular or a composite of these crystal forms.
ハロゲン化銀粒子は内部と表層が均一な相から成ってい
ても、異なる相からなっていてもよい。The interior and surface layers of the silver halide grains may be composed of uniform phases or may be composed of different phases.
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
使用してもよい。Two or more silver halide emulsions formed separately may be used in combination.
本発明に用いるハロゲン化銀乳剤にはノ・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9ミウム塩
、亜硫酸塩、鉛塩、タリウム塩、イリジウム塩もしくは
その錯塩、ロジウム塩もしくはその錯塩などを共存させ
てもよい。Silver halide emulsions used in the present invention include cadmium salts, sulfites, lead salts, thallium salts, iridium salts or complex salts thereof, rhodium salts or complex salts thereof, etc. during the formation of silver halide grains or during physical ripening. may coexist.
ハロゲン化銀乳剤は、化学増感を行わない、いわゆる未
後熟乳剤(プリミティブ乳剤)を用いることもできるが
、化学増感されてもよい。化学増感のためにはフリーザ
ー著「デイ・グルントラーゲン・デア・フォトグラフイ
ツシエン・プロゼツセ・ミツト拳ジルバーハロゲニデン
」、アカデミツシエ・フエルラーゲスゲゼルシャフト、
1968(HeFrieser、 Die Grund
−1agen der Photo−graphisc
hen Prozesse mit 5ilver h
aloge−niden、 Akademische
Verlagsgesselschaft。As the silver halide emulsion, a so-called immature emulsion (primitive emulsion) which is not chemically sensitized can be used, but it may also be chemically sensitized. For chemical sensitization, see Frieser's ``Dei Grundlagen der Fotographischen Prosetsse Mitsutoshi Silver Halogenidene'', Akademitsier Fuerlages Gesellschaft,
1968 (HeFrieser, Die Grund
-1agen der Photo-graphisc
hen Prozesse mit 5ilver h
aloge-niden, Akademische
Verlaggesselschaft.
1968) 等に記載の方法を用いることができる。1968) etc. can be used.
すなわち、活性ゼラチンや銀と反応しうる硫黄を金化合
物(例えばチオ硫酸塩、チオ尿素類、メルカプト化合物
、ローダニン類)を用いる硫黄増感法、還元性物質(例
えば第一すず塩、アミン類、ヒドラジン誘導体、ホルム
アミジンスルフィン酸。Namely, sulfur sensitization method using gold compounds (e.g. thiosulfates, thioureas, mercapto compounds, rhodanines), reducing substances (e.g. stannous salts, amines, Hydrazine derivatives, formamidine sulfinic acid.
シラン化合物)を用いる還元増感法、貴金属化合物(例
えば金化合物の他、白金、イリジウム、パラジウムなど
の周期律表第■族金属の錯塩)を用いる貴金属増感法な
どを単独或いは組み合わせて実施することができる。A reduction sensitization method using a silane compound), a noble metal sensitization method using a noble metal compound (for example, a gold compound or a complex salt of a Group I metal of the periodic table such as platinum, iridium, palladium, etc.) are carried out singly or in combination. be able to.
本発明の感光材料の乳剤層や中間層に用いることのでき
る結合剤または保護コロイドとしては、ゼラチンをもち
いるのが有利であるが、それ以外の親水性コロイドも用
いることができる。As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used.
例えばゼラチン誘導体、ゼラチンと他の高分子とのグラ
フトポリマー、アルブミン、カゼイン等の蛋白it;ヒ
ドロキシエチルセルロース、カルボキシメチルセルロー
ス、セルロース硫酸エステル類等の如きセルロース誘導
体、アルギン酸ソーダ、澱粉誘導体などの糖誘導体;ポ
リビニルアルコール、ポリビニルアルコール部分アセタ
ール、ポリ−N−ビニルピロリド9ン、ポリアクリル酸
、ポリメタクリル酸、承りアクリルアミド、ポリビニル
イミダゾール、ポリビニルピラゾール等の単一あるいは
共重合体の如き多種の合成親水性高分子物質を用いるこ
とができる。For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl Various synthetic hydrophilic polymeric substances such as single or copolymers of alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, acrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Can 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
チンやプラテインeオブ・ザ・ソサエティ・オプ・サイ
エンティフィック−フォトグラフィック・シャラミン(
Bull、 Soc、 Cci、 Phot。In addition to lime-processed gelatin, acid-processed gelatin and Platin e of the Society of Scientific - Photographic Shalamin (
Bull, Soc, Cci, Phot.
Japan) A 16.30頁(1966)に記載さ
れたような酵素処理ゼラチンを用いてもよく、マた、ゼ
ラチンの加水分解物や5F素分解物も用いることができ
る。Enzyme-treated gelatin as described in Japan) A, p. 16.30 (1966) may be used, and gelatin hydrolysates and 5F elementary decomposition products may also be used.
本発明に用いられる写真乳剤は、メチン色素類その他に
よって分光増感されてもよい。用いられる色素には、シ
アニン色素、メロシアニン色2、複合シアニン色素、複
合メロシアニン色素、ホロポーラ−シアニン色素、ヘミ
シアニン色素、スチリル色素およびヘミオキソノール色
素が包含される。特に有用な色素は、シアニン色素、メ
ロシアニン色素、および複合メロシアニン色素に属する
色素である。これらの色素を強色増感効果が得られるよ
う組合せて使用してもよい。The photographic emulsions used in the present invention may be spectrally sensitized with methine dyes and others. The dyes used include cyanine dyes, merocyanine color 2, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. These dyes may be used in combination to obtain a supersensitizing effect.
増感色素とともに1それ自身分光増感作用をもた々い色
素あるいは可視光を実質的に吸収しない物質であって、
強色増感を示す物質を乳剤中に含んでもよい。例えば、
含窒素異部環境で置換されたアミノスチルベン化合物(
たとえば米国特許2.9]3390号、同363572
1号に記載のもの)、芳香族有機酸ホルムアルデヒド縮
合物(たとえば米国特許a74:&510号に記載のも
の)%カドミウム塩、アザインデン化合物などを含んで
もよい。米国特許3.61 a613号、同361り6
41号、同a617.295号、同3635721号に
記載の組合せは特に有用である。Along with the sensitizing dye, 1 is a dye that itself has a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion. for example,
Aminostilbene compounds substituted in a nitrogen-containing heterogeneous environment (
For example, U.S. Pat. No. 2.9] 3390, U.S. Pat.
% cadmium salts, azaindene compounds, etc. U.S. Patent No. 3.61 a613, U.S. Patent No. 361-6
The combinations described in No. 41, No. 617.295 and No. 3635721 are particularly useful.
本発明に用いられる写真乳剤には、感光材料の製造工程
、保存中あるいは写真処理中のカブリを防止し、あるい
は写真性能を安定化させる目的で種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、例えばインジ
チアゾリウム塩、ニトロイミダゾール類、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、ベンゾトリアゾール類、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−フェニル
−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;たとえばオキサド
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,:L 3ay 7)
テトラアザインデン類)、ペンタアザインデン類ナト;
ヘンゼンチオスル7オン酸、ベンゼンスルフィン酸、ベ
ンゼンスルフォン酸アミビ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。The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. Namely, azoles such as indithiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. such as benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadorinthion; azaindenes,
For example, triazaindenes, tetraazaindenes (
Especially 4-hydroxy substituted (1,:L 3ay 7)
tetraazaindenes), pentaazaindenes;
Many compounds known as antifoggants or stabilizers can be added, such as henzenethiosulfonic acid, benzenesulfinic acid, amibibenzenesulfonic acid, and the like.
これらの中で、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。Among these, particularly preferred are benzotriazoles (eg, 5-methylbenzotriazole) and nitroindazoles (eg, 5-nitroindazole). Further, these compounds may be included in the treatment liquid.
本発明の写真感光材料には、写真乳剤層その他の親水性
コロイド層に無機または有機の硬膜剤を含有してよい。The photographic material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer.
例えばクロム塩(クロムミョウバン、酢酸クロムなど)
、アルデヒド9類(ホルムアルデヒド、グリオキサール
、ゲルタールアルデヒドなど)、N−メチロール化合物
(ジメチロール尿素、メチロールジメチルヒダントイン
など)、ジオキサン誘導体(23−ジヒドロキシジオキ
サンなど)、活性ビニル化合物(L35− トリアクリ
ロイル−へキサヒドロ−8−トリアジン、L3−ビニル
スルホニル−2−プロハノールナト)、活性ハロゲン化
合物<24−ジクロル−6−ヒドロキシ−s−トリアジ
ンなト)、ムコハロゲン酸類(ムコクロル酸、ムコフェ
ノキシクロルMなど)、などを単独または組み合わせて
用いることができる。For example, chromium salts (chromium alum, chromium acetate, etc.)
, aldehyde 9 (formaldehyde, glyoxal, geltaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (23-dihydroxydioxane, etc.), activated vinyl compounds (L35-triacryloyl-hexahydro) -8-triazine, L3-vinylsulfonyl-2-prohanol), active halogen compounds <24-dichloro-6-hydroxy-s-triazine), mucohalogen acids (mucochloric acid, mucophenoxychlor M, etc.), etc. Can be used alone or in combination.
本発明を用いて作られる感光材料の写真乳剤層ま之は他
の親水性コロイド層には塗布助剤、帯電防止、スベリ性
改良、乳化分散、接着防止及び写真特性改良(例えば、
現僚促進、硬調化、増感)等種々の目的で、種々の界面
活性剤を含んでもよい。In addition to the photographic emulsion layer of the light-sensitive material produced using the present invention, other hydrophilic colloid layers include coating aids, antistatic properties, slip property improvement, emulsification dispersion, adhesion prevention, and photographic property improvement (e.g.
Various surfactants may be included for various purposes such as enhancement, contrast enhancement, and sensitization.
例えばサポニン(ステロイド系)、アルキレンオキサイ
ド誘導体(例えばポリエチレングリコール、 、i’?
IJエチレンクリコール/ポリプロピレングリコール
縮金物%ポリエチレングリコールアルキルエーテル類又
はポリエチレングリコールアルキルアリールエーテル類
、pvエチレンクリコールエステル類、ポリエチレング
リコールソルビタンエステル類、ポリアルキレングリコ
ールアルキルアミン又はアミド類、シリコーンのポリエ
チレンオキサイド付加物類)、グリシドール誘導体(例
えばアルケニルコハク酸ポリグリセリド、アルキルフェ
ノールポリグリセリド)、多価アルコールの脂肪酸エス
テル類、糖のアルキルエステル類などの非イオン性界面
活性剤;アルキルカルボン酸塩、アルキルスルフォン酸
塩、アルキルベンゼンスルフォ/酸tLアルキルナフタ
レンスルフォン酸塩、アルキル硫酸エステル類、アルキ
ルリン酸エステル類、N−アシル−N−アルキルタウリ
ン類、スルホコハク酸エステル類、スルホアルキルポリ
オキシエチレンアル中層フェニルエーテル類、ポリオキ
シエチレンアルキルリン酸エステル類などのような、カ
ルボキシ基、スルホ基、ホスホ基、硫酸エステル基、リ
ン酸エステル基等の酸性基を含むアニオン界面活性剤;
アミノ酸類、アミノアルキルスルホン酸類、アミノアル
キル硫酸又はリン酸エステル類、アルキルベタイン類、
アミンオキシド類などの両性界面活性剤;アルキルアミ
ン塩類、脂肪族あるいは芳香族第4級アンモニウム塩類
、ピリジニウム、イミダゾリウムなどの複素環第4級ア
ンモニウム塩類、及び脂肪族又は複素環を含むホスホニ
ウム又はスルホニウム塩類などのカチオン界面活性剤を
用いることができる。For example, saponins (steroids), alkylene oxide derivatives (such as polyethylene glycol, i'?
IJ ethylene glycol/polypropylene glycol condensate% polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, pv ethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkyl amines or amides, polyethylene oxide addition of silicone nonionic surfactants such as glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars; alkyl carboxylates, alkyl sulfonates , alkylbenzene sulfo/acid tL alkylnaphthalene sulfonate, alkyl sulfate esters, alkyl phosphate esters, N-acyl-N-alkyl taurines, sulfosuccinate esters, sulfoalkyl polyoxyethylene al middle layer phenyl ethers, Anionic surfactants containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, such as polyoxyethylene alkyl phosphate esters;
Amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphoric acid esters, alkyl betaines,
Amphoteric surfactants such as amine oxides; alkylamine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, and phosphoniums or sulfoniums containing aliphatic or heterocyclic rings. Cationic surfactants such as salts can be used.
特に本発明において好ましく用いられる界面活性剤は特
公昭58−9412号公報に記載された分子8600以
上のポリアルキレンオキサイド類である。In particular, surfactants preferably used in the present invention are polyalkylene oxides having a molecular weight of 8,600 or more and described in Japanese Patent Publication No. 58-9412.
本発明に用いる写真感光材料には、写真乳剤層その他の
親水性コロイド層に寸度安定性の改良などの目的で、水
不溶又は難溶性合成ポリマーの分散物を含むことができ
る。例えばアルキル(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。The photographic light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer in the photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability. For example, alkyl (meth)acrylate, alkoxyalkyl (meth)acrylate, glycidyl (meth)acrylate.
(メタ)アクリルアミド9、ビニルエステル(例工ば酢
酸ビニル)、アクリロニトリル、オレフィン、スチレン
などの単独もしくは組合せ、又はこれらとアクリル酸、
メタクリル酸、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、スルホアルキル(メ
タ)アクリレート、スチレンスルホン酸等の組合せを単
量体成分とするポリマーを用いることができる。(meth)acrylamide 9, vinyl ester (for example, vinyl acetate), acrylonitrile, olefin, styrene, etc. alone or in combination, or these and acrylic acid,
A polymer containing a combination of methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth)acrylate, sulfoalkyl (meth)acrylate, styrene sulfonic acid, etc. as a monomer component can be used.
(実施例) 以下に実施例を掲げ、本発明を更に詳細に説明する。(Example) The present invention will be explained in more detail with reference to Examples below.
実施例1
2.5モルチの沃化物を含有している0、 3μの立方
体沃臭化銀乳剤にアンヒドローへ5−ジクロロ−9−エ
チル−33−ビス(3−スルホプロピル)オキサカルボ
シアニンヒト90キシr・ナトリウム塩(増感色素)を
230η/銀1モルとヒドラジン誘導体、■−ホルミル
ー(2−4−(2−(Z4−ジ−t−ペンチルフェノキ
シ)ブチルアミド〕フェニル)ヒビラジ)#を1.09
/銀1モル、ポリエチレングリコール(分子、量的1
000)を30011v/銀1モル加え、更に5−メチ
ル(ンットリアゾール、4−ヒドロキシ−6−メチル−
Lλ3a。Example 1 5-dichloro-9-ethyl-33-bis(3-sulfopropyl)oxacarbocyanine 90 was added to anhydro to a 0.3μ cubic silver iodobromide emulsion containing 2.5 mol of iodide. xyr sodium salt (sensitizing dye) at 230η/1 mole of silver, hydrazine derivative, ■-formyl-(2-4-(2-(Z4-di-t-pentylphenoxy)butyramide]phenyl)hibiradi) #1 .09
/ silver 1 mole, polyethylene glycol (molecular, quantitative 1
000) was added in 30011v/1 mole of silver, and further 5-methyl (nttriazole, 4-hydroxy-6-methyl-
Lλ3a.
7−チトラザインデン、ポリエチルアクリレートの分散
物、2−ヒドロキシ−L&5− トリアジンナトリウム
塩を加えた働
このようにして調製した塗布液をポリエチレンテレフタ
レートフィルム支持体上に銀塗布量が4.09/m2、
ゼラチン童布量が2..511)/rrL2になるよう
に塗布してフィルムを得た。さらにその上層に保護層と
してゼラチン19/m となるように塗布してフィル
ムを得た。これをフィルム/l61とする。The thus prepared coating solution containing 7-titrazaindene, a dispersion of polyethyl acrylate, and 2-hydroxy-L&5-triazine sodium salt was coated on a polyethylene terephthalate film support at a silver coverage of 4.09/m2.
The amount of gelatin cloth is 2. .. 511)/rrL2 to obtain a film. Furthermore, gelatin was coated as a protective layer on top of the gelatin at a concentration of 19/m 2 to obtain a film. This is referred to as film/l61.
これらのフィルムに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ェッジを通して
露光した。The films were exposed through a sensitometric exposure wedge using a 150 line magenta contact screen.
さらに次の様にしてフィルム/l62を作成した。Further, a film/l62 was prepared in the following manner.
I液:水1000虞11ゼラチン20g、pH=4.0
■液: AgNO2200g、水60〇−■液: KB
r 4.29、NaC1759ph(4320〜、水
60〇−
45℃に保ったIQのゼラチン水溶液中に■液と■液を
同時に一定の速度で30分間で添加した。Solution I: Water 1000g, 11 gelatin 20g, pH=4.0 ■Liquid: AgNO2200g, water 600- ■Liquid: KB
r 4.29, NaC 1759ph (4320~, water 600°C - Solution 2 was added simultaneously to an aqueous gelatin solution of IQ kept at 45°C at a constant rate for 30 minutes.
この乳剤を当業界でよく知られた常法で可溶性塩類を除
去した後ゼラチンを加え化学熟成せずに安定剤として2
−メチル−4−ヒドロキシ−L313a、 7−チト
ラアザインデンを添加した。この乳剤の平均粒子サイズ
は0.28μmであり乳剤の収量はIIKg、含有する
ゼラチン量は709であった。After removing soluble salts from this emulsion using a conventional method well known in the art, gelatin was added as a stabilizer without chemical ripening.
-Methyl-4-hydroxy-L313a, 7-thitraazaindene was added. The average grain size of this emulsion was 0.28 μm, the yield of the emulsion was II kg, and the amount of gelatin contained was 709.
この乳剤に硬膜剤2−ヒドロキシ−46−ジクロロ−1
,3,5−)リアジン・ナトリウム塩を加えた後、ポリ
エチレンテレフタレートフィルム上にITrL2 当り
銀!4.5gになるように塗布した。さらにその上層に
保護層としてゼラチン1ll)/m となるようにし
て塗布してフィルムを得た。このフィルムを腐2とする
。A hardener 2-hydroxy-46-dichloro-1 was added to this emulsion.
,3,5-) silver per ITrL2 on polyethylene terephthalate film after addition of riazine sodium salt! It was applied in an amount of 4.5 g. Furthermore, gelatin was applied as a protective layer on top of the gelatin at a concentration of 1 liter/m 2 to obtain a film. This film is called Fu2.
このフィルム試料を用いて網点フィルムの原稿に密着さ
せ、大日本スクリーン製−P607型プリンターで露光
した。This film sample was brought into close contact with a dot film original and exposed using a P607 printer manufactured by Dainippon Screen.
さらに次の様にしてフィルム/I63を作成fる。Further, film/I63 is prepared as follows.
硝酸銀水溶液と、臭化カリウム沃化カリウム水溶液を、
アンモニアの存在下でpAgを7.9に保ちつつダブル
ジェット法によシ混合し、平均粒子サイズO,2ミクロ
ンの単分散立方体の沃臭化銀乳剤A(沃化銀2モルチ、
臭化銀98モルチ)を作った。これとは別に硝酸銀水溶
液と臭化カリウム水溶液をアンモニアの存在下で%pA
gを7.9に保ちつつダブルジェット法によシ混合し、
平均粒子サイズ0.3 s ミクロンの単分散立方体の
臭化銀乳剤Bを作った。乳剤Aはチオ硫酸ナトリウムで
硫黄増感を行った。Silver nitrate aqueous solution and potassium bromide potassium iodide aqueous solution,
A monodispersed cubic silver iodobromide emulsion A (2 mol of silver iodide, 2 mol of silver iodide,
silver bromide (98 molti) was prepared. Separately, a silver nitrate aqueous solution and a potassium bromide aqueous solution were prepared at %pA in the presence of ammonia.
Mixing by double jet method while keeping g at 7.9,
A monodisperse cubic silver bromide emulsion B with an average grain size of 0.3 s microns was prepared. Emulsion A was sulfur sensitized with sodium thiosulfate.
また、各乳剤A、Bともに、増感色素ras’−ジクロ
ロ−33’−ジ(3−スルホプロピル)−9−エチル−
オキサカルボシアニンナトリウム塩」を、乳剤Aおよび
Bに対して銀1モルあたシそれぞれ6×10 モル、4
.5X10 モル添加して分光増感した。Furthermore, in both emulsions A and B, the sensitizing dye ras'-dichloro-33'-di(3-sulfopropyl)-9-ethyl-
oxacarbocyanine sodium salt, 6 x 10 mol per mol of silver for emulsions A and B, respectively, 4
.. Spectral sensitization was performed by adding 5×10 mol.
さらに安定剤として4−ヒrロキシ−6−メチル−1,
33a、7−チトラザインデンを添加した。Furthermore, as a stabilizer, 4-hydroxy-6-methyl-1,
33a,7-chitrazaindene was added.
この乳剤A、Bをハロゲン化銀重量比で6対4のような
比率になるように混合したのち、次の化合物を0.40
’j/m2になるように添加した。These emulsions A and B were mixed at a silver halide weight ratio of 6:4, and then the following compound was added at a ratio of 0.40 to 4.
'j/m2.
さらに、次の式で示されるヒト9ラジン誘導体を銀1モ
ルにつき4×10 モル添加した。Furthermore, a human 9-radine derivative represented by the following formula was added at 4×10 6 mol per mol of silver.
さらに界面活性剤として、アルキルベンゼンスルホン酸
塩を添加し、乳剤のpHを5.8になるように調製した
のち、膜厚100ミクロンのポリエチレンテレフタレー
ト支持体上に、上記調製した各乳剤を塗布銀量3.Og
/rrL2 となるように塗布し、さらにその上層に保
護層としてゼラチン1g/rrL2となるように塗布し
て、フィルム/l63を作成した。3200’にのタン
グステン光で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光学クサビを通して5秒間無
光した。Furthermore, an alkylbenzene sulfonate was added as a surfactant to adjust the pH of the emulsion to 5.8, and each emulsion prepared above was coated on a polyethylene terephthalate support with a film thickness of 100 microns. 3. Og
/rrL2, and further coated as a protective layer on top of the gelatin at a ratio of 1 g/rrL2 to prepare a film /163. A tungsten light at 3200' was passed through a sensitometric optical wedge using a 150-line magenta contact screen and blinded for 5 seconds.
さらに次の様にしてフィルム/l64を作成する。Further, a film/l64 was prepared as follows.
硝酸銀水溶液と、銀1モルあた!D5XlOモルの六塩
化ロジウム(m)酸アンそニウムを含tri化ナトリウ
ム水溶液をダブルジェット法によシ40℃のゼラチン溶
液中でpHを2.3になるようにコントロールしつつ混
合し、平均粒子サイズ0.2ミクロンの単分散塩化銀乳
剤を作った。Silver nitrate aqueous solution and 1 mole of silver! An aqueous sodium chloride solution containing D5XlO mol of anthonium rhodium hexachloride (m) was mixed in a gelatin solution at 40°C by a double jet method while controlling the pH to 2.3 to obtain an average particle size. A monodisperse silver chloride emulsion with a size of 0.2 microns was prepared.
粒子形成後、当業界でよく知られているフロキュレーシ
ョン法により可溶性塩類を除去し、安定剤として4−ヒ
ト90キシ−6−メチル−L 3.3 a。After particle formation, soluble salts were removed by flocculation methods well known in the art, and 4-human90x-6-methyl-L 3.3a was added as a stabilizer.
7−チトラアザインデンおよび1−フェニル−5−メル
カプトテトラゾールを添加した。乳剤1に9中に含有さ
れるゼラチンは559、銀は105gであった。7-thitraazaindene and 1-phenyl-5-mercaptotetrazole were added. Emulsions 1 and 9 contained 559 g of gelatin and 105 g of silver.
この乳剤を用いて次の化合物を70”W/m になる
ように添加し、さらに硬膜剤として2.4−ジクロル−
6−ヒド90キシ−La5−トリアジンナトリウム塩を
添加して、1m あたシ3.59の銀量となるように
ポリエチレンテレフタレート透明支持体上にハロゲン化
銀乳剤層を塗布し、さらにその上層に保護層としてゼラ
チン層を塗布してフィルム/l64を作成した。このフ
ィルム/464を光学クサビを通して大日本スクリーン
社WP6t7DQプリンター(光源100V KWク
ォーツハロゲンランプ)で露光した。Using this emulsion, the following compound was added at a concentration of 70"W/m2, and 2.4-dichloro-
A silver halide emulsion layer was coated on a polyethylene terephthalate transparent support by adding 6-hydro90x-La5-triazine sodium salt to give a silver amount of 3.59 per meter, and the upper layer was further coated with a silver halide emulsion layer. Film/164 was prepared by applying a gelatin layer as a protective layer. This film/464 was exposed through an optical wedge using a Dainippon Screen Co., Ltd. WP6t7DQ printer (light source 100V KW quartz halogen lamp).
上記の様にそれぞれ露光したフィルム屑1、准2、/I
63、厘4を下記組成の現像液で34℃30秒間現像し
、定着、水洗、乾燥した(この処理には富士写真フィル
ム株式会社製自動現像機FG660Fを用いた)。Film scraps 1, 2, /I exposed as above, respectively
63, Rin 4 was developed at 34°C for 30 seconds with a developer having the following composition, fixed, washed with water, and dried (an automatic processor FG660F manufactured by Fuji Photo Film Co., Ltd. was used for this process).
得られた結果を表2に示す。現像液Aで処理した時に濃
度1.5を得るに要した露光量の逆数を100として相
対的に示した。Gは%性曲線上の濃度0.3と3.0を
直線で結んだtanθを表わす。The results obtained are shown in Table 2. The reciprocal of the exposure amount required to obtain a density of 1.5 when processed with developer A is expressed relative to 100. G represents tanθ, which is a straight line connecting concentrations 0.3 and 3.0 on the % sex curve.
網点品質は視覚的に5段階に評価したもので「5」が最
も良く「l」が最も悪い品質を示す。製版用網点原板と
しては網点品′fIi「5」「4」が実用可能で、「3
」 は粗悪だかぎりぎシ実用でき、「2」「l」 は実
用不可能な品質である。The halftone dot quality is visually evaluated on a five-level scale, with "5" being the best and "l" being the worst. Halftone products 'fIi "5" and "4" are practical as halftone original plates for plate making, and "3"
” is of such poor quality that it can barely be put to practical use, while “2” and “l” are of an impractical quality.
現像ムラはフィルム上に全く現像ムラが発生していない
状態を「5」 とし、フィルム−面に現像ムラが発生し
ている状態を「1」 として5段階に評価した。「4」
はフィルム上の極く一部に現像ムラが発生しているが
実用上は許容されるレベルであるが「3」 以下は実用
不可能である。The development unevenness was evaluated on a five-point scale, with a score of "5" indicating that no development unevenness occurred on the film, and a score of "1" indicating that development unevenness occurred on the film surface. "4"
Although development unevenness occurs in a very small portion of the film, it is at a practically acceptable level, but a rating of "3" or lower is not practical.
表2の結果から明らかな如く本発明の現像液B。As is clear from the results in Table 2, developer B of the present invention.
Cの場合には現像ムラが良い、比較のために一般式(1
)の化合物を含まない現像液Aの場合には現像ムラが多
く実用不可能である。さらに比較のためにメルカプト系
の化合物として現像液に添加することがよく知られてい
るl−フェニル−5−メルカプトテトラゾールを含む現
像液りの場合は現像ムラは良いが感度が低く網点品質が
悪い。In the case of C, the development unevenness is good.For comparison, the general formula (1
In the case of developer A which does not contain the compound (), there is a lot of uneven development and it is not practical. Furthermore, for comparison, in the case of a developer containing l-phenyl-5-mercaptotetrazole, which is well known to be added to developers as a mercapto-based compound, development unevenness is good, but sensitivity is low and halftone quality is poor. bad.
(発明の効果)
本発明に従えば高pH現像液で高コントラスト画像を形
成する場合に生じやすい現像ムラを感度や網点品質など
の性能を損なうむとなく有効に抑制することができる。(Effects of the Invention) According to the present invention, uneven development that tends to occur when forming a high contrast image using a high pH developer can be effectively suppressed without compromising performance such as sensitivity and halftone dot quality.
Claims (1)
ラストネガ画像形成方法において、該現像液が11.0
〜12.3のpH値を有し、且つ下記(1)〜(4) (1)ジヒドロキシベンゼン系現像主薬、 (2)1−フェニル−3−ピラゾリドン系補助現像主薬
及び/又はp−アミノ−フェノール系補助現薬主薬、 (3)0.3モル/l以上の亜硫酸塩および(4)少な
くとも1種の下記一般式( I )で表わされる化合物 を含有することを特徴とする高コントラストネガ画像形
成方法。 一般式( I ) ▲数式、化学式、表等があります▼ 式中、Xは硫黄原子又は酸素原子を表わし、Lは−CO
NR_2−、−NR_2CO−、−SO_2NR_2−
、−NR_2SO_2−、−OCO−−COO−、−S
−−NR_2−、−CO−、−SO−、−SO_2−、
−OCOO−、−NR_2CONR_3−、−NR_2
COO−、−OCONR_2−又は−NR_2SO_2
NR_3−を表わし(ここでR_2、R_3は同一でも
互いに異なつてもよく各々水素原子、アルキル基又はア
リール基を表わす)、R_1は、水素原子、脂肪族基又
は芳香族基を表わし、Mは水素原子、アルカリ金属イオ
ン、四級アンモニウムイオン又は四級ホスホニウムイオ
ンを表わし、nは0又は1を表わす。[Scope of Claims] A method for forming a high contrast negative image in which a silver halide photographic light-sensitive material is processed with a developer, wherein the developer is
-12.3, and the following (1) to (4) (1) dihydroxybenzene-based developing agent, (2) 1-phenyl-3-pyrazolidone-based auxiliary developing agent and/or p-amino- A high-contrast negative image characterized by containing a phenol-based auxiliary developer, (3) 0.3 mol/l or more of sulfite, and (4) at least one compound represented by the following general formula (I). Formation method. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, X represents a sulfur atom or an oxygen atom, and L is -CO
NR_2-, -NR_2CO-, -SO_2NR_2-
, -NR_2SO_2-, -OCO--COO-, -S
--NR_2-, -CO-, -SO-, -SO_2-,
-OCOO-, -NR_2CONR_3-, -NR_2
COO-, -OCONR_2- or -NR_2SO_2
NR_3- (where R_2 and R_3 may be the same or different and each represents a hydrogen atom, an alkyl group, or an aryl group), R_1 represents a hydrogen atom, an aliphatic group, or an aromatic group, and M represents hydrogen. It represents an atom, an alkali metal ion, a quaternary ammonium ion, or a quaternary phosphonium ion, and n represents 0 or 1.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP17661986A JPS6333744A (en) | 1986-07-29 | 1986-07-29 | High contrast negative image forming method |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP17661986A JPS6333744A (en) | 1986-07-29 | 1986-07-29 | High contrast negative image forming method |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS6333744A true JPS6333744A (en) | 1988-02-13 |
Family
ID=16016740
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP17661986A Pending JPS6333744A (en) | 1986-07-29 | 1986-07-29 | High contrast negative image forming method |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6333744A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5821040A (en) * | 1995-06-21 | 1998-10-13 | Fuji Photo Film Co., Ltd. | Method for developing silver haide photographic material |
US5821041A (en) * | 1996-03-05 | 1998-10-13 | Fuji Photo Film Co., Ltd. | Liquid developer for photographic silver halide photosensitive material and development method |
-
1986
- 1986-07-29 JP JP17661986A patent/JPS6333744A/en active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5821040A (en) * | 1995-06-21 | 1998-10-13 | Fuji Photo Film Co., Ltd. | Method for developing silver haide photographic material |
US5821041A (en) * | 1996-03-05 | 1998-10-13 | Fuji Photo Film Co., Ltd. | Liquid developer for photographic silver halide photosensitive material and development method |
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