JPH0460632A - Processing method for silver halide photographic sensitive material - Google Patents
Processing method for silver halide photographic sensitive materialInfo
- Publication number
- JPH0460632A JPH0460632A JP17218190A JP17218190A JPH0460632A JP H0460632 A JPH0460632 A JP H0460632A JP 17218190 A JP17218190 A JP 17218190A JP 17218190 A JP17218190 A JP 17218190A JP H0460632 A JPH0460632 A JP H0460632A
- Authority
- JP
- Japan
- Prior art keywords
- silver halide
- water
- developing
- sulfite
- sensitive material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- -1 silver halide Chemical class 0.000 title claims abstract description 44
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 28
- 239000004332 silver Substances 0.000 title claims abstract description 28
- 239000000463 material Substances 0.000 title claims abstract description 27
- 238000003672 processing method Methods 0.000 title description 2
- 238000012545 processing Methods 0.000 claims abstract description 29
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims description 40
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 7
- 230000003647 oxidation Effects 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000011109 contamination Methods 0.000 abstract 1
- 238000004090 dissolution Methods 0.000 abstract 1
- 239000000839 emulsion Substances 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- 239000000975 dye Substances 0.000 description 20
- 239000003795 chemical substances by application Substances 0.000 description 19
- 150000001875 compounds Chemical class 0.000 description 19
- 239000010410 layer Substances 0.000 description 17
- 239000000243 solution Substances 0.000 description 17
- 239000007788 liquid Substances 0.000 description 13
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 12
- 238000011161 development Methods 0.000 description 12
- 150000003839 salts Chemical class 0.000 description 12
- 230000001235 sensitizing effect Effects 0.000 description 12
- 239000002253 acid Substances 0.000 description 11
- 238000005406 washing Methods 0.000 description 11
- 108010010803 Gelatin Proteins 0.000 description 10
- 229920000159 gelatin Polymers 0.000 description 10
- 239000008273 gelatin Substances 0.000 description 10
- 235000019322 gelatine Nutrition 0.000 description 10
- 235000011852 gelatine desserts Nutrition 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 206010070834 Sensitisation Diseases 0.000 description 8
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 8
- 230000008313 sensitization Effects 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000004094 surface-active agent Substances 0.000 description 8
- 230000000087 stabilizing effect Effects 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 5
- 229940121375 antifungal agent Drugs 0.000 description 5
- 239000000084 colloidal system Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000003755 preservative agent Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000011241 protective layer Substances 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- 230000000843 anti-fungal effect Effects 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 230000001747 exhibiting effect Effects 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
- 230000001965 increasing effect Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 230000002335 preservative effect Effects 0.000 description 4
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 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 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000003242 anti bacterial agent Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 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
- 238000001035 drying Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 3
- 150000002429 hydrazines Chemical class 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 3
- 235000019252 potassium sulphite Nutrition 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 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
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- JEHKKBHWRAXMCH-UHFFFAOYSA-N benzenesulfinic acid Chemical compound O[S@@](=O)C1=CC=CC=C1 JEHKKBHWRAXMCH-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 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 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000006174 pH buffer Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920001281 polyalkylene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 150000003283 rhodium Chemical class 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 229910001923 silver oxide Inorganic materials 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 235000000346 sugar Nutrition 0.000 description 2
- 125000004964 sulfoalkyl group Chemical group 0.000 description 2
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical group [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 1
- QBSSUNKQVMSCSI-UHFFFAOYSA-N 2,3-dihydro-1H-benzo[f]selenochromen-1-ol Chemical group OC1CC[Se]c2ccc3ccccc3c12 QBSSUNKQVMSCSI-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
- 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
- LNMUJQNYBXGFMX-UHFFFAOYSA-N 2-ethenylsulfonyl-n-ethylacetamide Chemical compound CCNC(=O)CS(=O)(=O)C=C LNMUJQNYBXGFMX-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
- JSIAIROWMJGMQZ-UHFFFAOYSA-N 2h-triazol-4-amine Chemical class NC1=CNN=N1 JSIAIROWMJGMQZ-UHFFFAOYSA-N 0.000 description 1
- OWIRCRREDNEXTA-UHFFFAOYSA-N 3-nitro-1h-indazole Chemical compound 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
- 241000254032 Acrididae Species 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 102000009027 Albumins Human genes 0.000 description 1
- 108010088751 Albumins Proteins 0.000 description 1
- 241001135931 Anolis Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000218691 Cupressaceae Species 0.000 description 1
- HBQJTBXZMPSVBP-UHFFFAOYSA-N Cyanidine Natural products OC1=CC(=C2/Oc3cc(O)cc(O)c3C=C2O)C=CC1=O HBQJTBXZMPSVBP-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- HSRJKNPTNIJEKV-UHFFFAOYSA-N Guaifenesin Chemical compound COC1=CC=CC=C1OCC(O)CO HSRJKNPTNIJEKV-UHFFFAOYSA-N 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 241001051525 Tortus Species 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
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000004480 active ingredient Substances 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
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 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
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 239000013040 bath agent Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 150000001661 cadmium Chemical class 0.000 description 1
- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 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
- 239000002738 chelating agent Substances 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- VEVZSMAEJFVWIL-UHFFFAOYSA-O cyanidin cation Chemical compound [O+]=1C2=CC(O)=CC(O)=C2C=C(O)C=1C1=CC=C(O)C(O)=C1 VEVZSMAEJFVWIL-UHFFFAOYSA-O 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 150000002012 dioxanes Chemical class 0.000 description 1
- VNEBWJSWMVTSHK-UHFFFAOYSA-L disodium;3-hydroxynaphthalene-2,7-disulfonate Chemical compound [Na+].[Na+].C1=C(S([O-])(=O)=O)C=C2C=C(S([O-])(=O)=O)C(O)=CC2=C1 VNEBWJSWMVTSHK-UHFFFAOYSA-L 0.000 description 1
- XLNOKJLJDWVOQP-UHFFFAOYSA-L disodium;formaldehyde;sulfite Chemical compound [Na+].[Na+].O=C.[O-]S([O-])=O XLNOKJLJDWVOQP-UHFFFAOYSA-L 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 210000004709 eyebrow Anatomy 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000007789 gas Substances 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
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229910052811 halogen oxide Inorganic materials 0.000 description 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical class C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 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
- 239000003112 inhibitor Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 150000002500 ions Chemical class 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
- 230000001788 irregular Effects 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical class CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 230000003641 microbiacidal effect Effects 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 150000004957 nitroimidazoles Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 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
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 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
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 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
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- AEVLXTNMRFEOAG-UHFFFAOYSA-L potassium sodium hydrogen carbonate acetate Chemical compound [Na+].[K+].CC([O-])=O.OC([O-])=O AEVLXTNMRFEOAG-UHFFFAOYSA-L 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002028 premature Effects 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 compound SC1=NC=CC=N1 HBCQSNAFLVXVAY-UHFFFAOYSA-N 0.000 description 1
- 150000003248 quinolines Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 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
- BZHOWMPPNDKQSQ-UHFFFAOYSA-M sodium;sulfidosulfonylbenzene Chemical compound [Na+].[O-]S(=O)(=S)C1=CC=CC=C1 BZHOWMPPNDKQSQ-UHFFFAOYSA-M 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 150000003431 steroids Chemical class 0.000 description 1
- 210000002784 stomach Anatomy 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 125000003831 tetrazolyl group Chemical group 0.000 description 1
- 150000003475 thallium Chemical class 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 125000005323 thioketone group Chemical group 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-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
- 238000004804 winding Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Landscapes
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Abstract
Description
【発明の詳細な説明】
(産業上の利用分野)
不発明にハロゲン化銀N&光材料を硬調に現像する方法
に関するものでめジ、特にグラフイツタアークの印刷用
写Xi版工程に適し′fc高コントラストのネガティブ
画gRk形成する方法に関するtのでおる。Detailed Description of the Invention (Industrial Application Field) This invention relates to a method for developing silver halide N and optical materials in high contrast, and is particularly suitable for the printing process of graphite arc printing. The following describes a method for forming a high-contrast 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+1!!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1象形成/ステムが必要である。(Prior Art) In the field of graphic arcs, reproduction of continuous tone images using halftone images or +1! ! For good image reproduction, an image formation/stem exhibiting high contrast photographic properties is required.
従来この目的のためにはリス現像液と呼にnる特別な現
像液が用いらnてさた。リスIjL像液は塊澤王薬とし
てハイドロキノ/のみ全含み、その伝染現像性全阻害し
ない工うに保恒剤たる亜硫散塩?ホルムアルデヒドとの
付、vo’mの形にして用い遊離の亜硫酸イオ/の#度
を極めて低くしてるる。Hitherto, a special developer called a Lith developer has been used for this purpose. Risu IjL image solution contains all the hydroquinone as an active ingredient, and does not inhibit its infectious development property.It also contains sulfur dispersion, which is a preservative. When combined with formaldehyde, it is used in the form of VO'M to reduce the amount of free sulfite ions to an extremely low level.
そのためリス現塚液は極めて空気酸化を受けや丁く3日
を越える保存に耐えらnないという重大な欠点を持って
いる。Therefore, Risu Genzuka liquid has the serious drawback that it is extremely susceptible to air oxidation and cannot withstand storage for more than just three days.
近年高コ/トラス)k与える感光材料の処理を安定に、
η・つ迅速に行うことへの要求が高19、撫々の高コン
トラストネガティブ画像形成ンステムが提案、商品化さ
nている。In recent years, stable processing of photosensitive materials with high cost/truss) has been achieved.
As the demand for rapid imaging increases, a number of high-contrast negative image forming systems have been proposed and commercialized.
高コントラストの写真特性を安定な現像放音用いて得る
方法としては向えは米国特許第参、コλ44 、 ’1
0/号、同第$、/AJ’、り77号、同第e、/64
.7$2号、同第1I、31/、71/号、同第参、コ
アλ、tot号、同第q、コ//。A method for obtaining high contrast photographic properties using stable development sound emission is disclosed in U.S. Patent No. 44, '1.
0/No., same No. $, /AJ', ri No. 77, same No. e, /64
.. 7$2 No. 1I, 31/, 71/, No. 7, Core λ, tot No. q, Co//.
117号、同第弘、λ≠3,732号等に記載さnてい
るヒドラジ/誘導体を用いる方法がるる。There are methods using hydrazines/derivatives described in No. 117, No. 117, No. 3,732, etc.
さらに別法として現像生薬としてノ・イドロキノンのみ
t含み保恒剤たる亜硫酸塩濃度を高くして突気酸化に対
して安定にしてかつ高コントラスト画像を得る方法が特
公昭SS−≠りλりを号、特開昭II−/ 90 、り
参3号、特開昭6o−++。Another method is to use only hydroquinone as a developing drug and increase the concentration of sulfite as a preservative to stabilize against sudden oxidation and obtain high contrast images. No., Japanese Patent Application Publication No. 1986-2-/90, Risan No. 3, Japanese Patent Application Publication No. 1987-6o-++.
−弘r号等に記載さ扛ている。- It is written in the Hiro issue etc.
さらに別法として!−二トロイ/ダゾール、tニトロイ
ンダゾール、j−クロロインダゾール、j−シアノイン
ダゾール等を用いて高コントラストにする方法がGBコ
、Qコア、り、20Aに記載さnている。Yet another option! - A method of achieving high contrast using nitroindazole, t-nitroindazole, j-chloroindazole, j-cyanoindazole, etc. is described in GB Co., Q Core, 20A.
(発明が解決しようとする問題点)
こnらの′fjL像処理技術は高コントラスト画像形成
処理の安定化、迅速化のニーズ全満次しているが、いず
nl処理准の高pH化、高亜硫#l!@濃度化、高温処
理化を伴っている。(Problems to be Solved by the Invention) These 'fjL image processing techniques satisfy the needs for stabilizing and speeding up high contrast image formation processing, but they do not have the same high pH as nl processing. , high sulfite #l! @It is accompanied by increased concentration and high temperature treatment.
ところで、/り600年代エフ黒白ノ・ロゲン化銀感光
材料の処理には自動現僚機が使用さnるようになって8
皮。自動現像I!(以下自現機と略称する)については
ウッドリーフ・トーツス・ジュニア(〜oodlief
Thomas JR,1編の5PSEバントブツ
ク・オブ・フォトグラフィック・サイエンス・アンド・
工/ジニアリング(5FSE )landbook
of PhotographicScience
and Engineering ) 6
93〜666頁(/り73年)、Gohn Wille
y &5ons (N、 Y )、ジョン・M・ストア
ジ(GohnM、Storge)@、 ネブレツツ・
ノ・/ドブツク・オブ・フォトグラフィ・アンド・レブ
ログラフイ(Neblette s )1andboo
k of Photo −graphy and
Reprography )第7版≠26〜j12
頁(lり77年) Van NorstrandRei
nhold Co、、 等に記載さnているし、現
実に多数のFM檜が使用さnている。By the way, in the 1960s, automated modern aircraft began to be used to process black and white silver halide photosensitive materials.
leather. Automatic development I! (hereinafter abbreviated as automatic processing machine) is Woodleaf Tortus Jr. (~oodlief
Thomas JR, 1 edition of 5PSE book of photographic science and...
Engineering/Geneering (5FSE) landbook
of Photographic Science
and Engineering) 6
pp. 93-666 (/1973), Gohn Wille
y &5ons (N, Y), John M. Storge (GohnM, Storge) @, Nebrets
ノ・/Dobutsuku of Photography and Reblogography (Neblette's) 1andboo
k of Photo-graphy and
Reprography) 7th edition≠26~j12
Page (1977) Van NorstrandRei
It is described in Hold Co., etc., and a large number of FM cypresses are actually used.
自現機としては、従来、吊下は式自現機、ンネ自現機、
ロー2−搬送自現機、ディスクフィルム用回転式自現機
、回転ドラム自現機、リール巻付自′fjta*等が実
巾化さnている。自現機にFXX青々方式めるが、1ち
1ちな大きさのシート状の黒白フィルム感光材料が多用
される製版感光材料やX線感光材料の分野では、操作性
、迅速性、安定性等工90−ラー搬送型が主流となって
いる。Conventional automatic processors include hanging type processors, vertical processors,
Row 2-conveying automatic processors, rotary processors for disc films, rotary drum processors, reel-winding automatic processors, and the like have become commercially available. Although the FXX blue method is commonly used in automatic processors, in the fields of plate-making photosensitive materials and X-ray photosensitive materials, where individually sized sheet-shaped black and white film photosensitive materials are often used, it is difficult to use the FXX Aoi method in terms of operability, speed, stability, etc. The mainstream is the 90-Lar conveyor type.
黒白感光材料の処理に用いらnる自現機に蝶、通常現像
、定着、水洗の多槽が設けら【、こnらの各種にはいず
fLtPf&元材料を順次自動的に供給するための感光
材料通路が設けらnる。そのため各処理液の空気と接す
る六面積が大きく、突気酸化による処理液の劣化そして
蒸発が大きい問題がるる。轡にローラー搬送型の自現機
では開口率が大きくなり易い。ここで開口率とは現像槽
部の処理液と空気の抵触面積偲 を現像タンク液量12
で割り7C%のでるる。ローラーが液界面にるる場合に
はローラー径の2倍全抵触面積に加算する。Automatic processors used for processing black-and-white photosensitive materials are equipped with multiple tanks for normal development, fixing, and washing. A photosensitive material passage is provided. Therefore, the surface area of each treatment liquid in contact with the air is large, and there is a problem that deterioration and evaporation of the treatment liquid due to sudden oxidation are large. Automatic processors that use roller conveyance tend to have a large aperture ratio. Here, the aperture ratio is the area of contact between the processing solution and air in the developer tank.
Divide by and get 7C%. If the roller is on the liquid surface, add twice the roller diameter to the total contact area.
現用さnている自現機の開口iに一般には0.0jP−
/、jでめる。Generally, the aperture i of the automatic processor currently in use is 0.0jP-
/, j demeru.
前述した高亜硫酸塩濃度化した処理液を用いる迅速安定
な高コントラスト画儂形属@は現在市場で通常使用さn
ている開口率の大きい自現機と組合せて用匹らnると以
下述べる様な種々の問題点がろる。The above-mentioned rapid and stable high-contrast photoforms using processing solutions with high sulfite concentrations are currently not commonly used on the market.
When used in combination with an automatic processor with a large aperture ratio, various problems as described below will occur.
(a) 自現機の梶勤申に窒気酸化勿受は易く、机像
王薬や保@剤の劣化が激しい。(a) Nitrogen oxidation is easily caused by automatic processors, and the deterioration of the image processing agent and preservative is severe.
(bJ その劣化を少くするために亜伝酸塩濃を高く
することが必髪でめる。(bJ) In order to reduce this deterioration, it is essential to increase the densite concentration.
(C) 処理液中の亜硫#R塩siが高くなるとハロ
ゲノ化銀の溶解が多くなりいわゆる銀河fが多くなる。(C) When the sulfite #R salt si in the treatment solution increases, more silver halide is dissolved, and so-called galaxies f increase.
(d) 空気接触界面が大のため水分の蒸発が多く、
処理液が崇縮し易い。(d) Because the air contact interface is large, there is a lot of water evaporation;
Processing liquid tends to shrink.
(e)機器中で結露し又塩析物が出て機器故障が起り易
い。(e) Dew condensation occurs in the equipment, and salt precipitates appear, which can easily cause equipment failure.
こγLらの問題点は低コントラストの通常感光材料の処
理ではその性能への影響は少ないか、特に高コントラス
ト画像形成処理で顕著となる。The problems of γL and the like have little effect on the performance when processing low-contrast ordinary light-sensitive materials, or become particularly noticeable when processing high-contrast images.
(問題点を解決するための手段)
上記の問題点は以下の本発明に工って解決さnた。丁な
わち不発明は露光妊nたハロゲン化銀4真ll1c光材
料を亜硫酸塩濃度が(7,Jモル/l以下の水溶性アル
カリ現像液を用いて現像部の開口率か0.03以下の自
動現gR機を用いて現像することを特徴とする高コント
ラストハロゲン化銀写真感光材料の処理方法でるる。(Means for Solving the Problems) The above problems were solved by the following invention. In other words, the non-inventive method is to use a silver halide optical material that has been exposed to light and to develop an aperture ratio of 0.03 or less using a water-soluble alkaline developer with a sulfite concentration of 7.0 J mol/l or less. A method for processing a high-contrast silver halide photographic light-sensitive material, which is characterized by developing it using an automatic developing machine.
水溶性アルカリ現1R液の亜硫酸塩濃度が0.3モル/
l以下でめることに工9ハロゲン化銀の溶旌が少くいわ
ゆる銀河nが少い。自現機の現像槽部の開口率1に0.
03以下にすることによ!llll窒化酸化くかつ裡々
の処理環境条件−rなわち、冬期夏期などの温度・湿度
条件、大気中のC(J2ガスa度(通常条件、ストーブ
など)などの変動に対しても安定した性能が得ら【る。The sulfite concentration of the water-soluble alkaline 1R solution is 0.3 mol/
Below l, there is less melting of silver halide in the workpiece 9, and there are fewer so-called galaxies n. The aperture ratio of the developer tank of the automatic processor is 1 to 0.
Make it below 03! It is stable against fluctuations in nitriding and oxidizing process environmental conditions, such as temperature and humidity conditions such as winter and summer, and atmospheric C (J2 gas a degree (normal conditions, stove, etc.)). Performance can be obtained.
不発明においては現像槽部の開口率が0.0コ、o、o
oiでめる場合が特に好ましい。In the case of non-invention, the aperture ratio of the developer tank is 0.0, o, o.
It is particularly preferable to use oi.
開口率を低下さゼる方法としては特開平/−/660参
〇号に記載の万床を用いることができる。As a method for reducing the aperture ratio, the method described in Japanese Patent Application Laid-Open No. 1996-0660 can be used.
不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−アミノ
フェノール系現像生薬又は3−ビラゾリド/系現傷生薬
を用いるのが好しム。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-aminophenol-based developing agent or a 3-virazolid/based deteriorating herbal agent as an auxiliary developing agent.
本発明に用いるジヒドロキ7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/、ブロモハイ
ドロキノン、イソプロピルノ1イドロキノン、メナルハ
イト′ロキノン、コ、3−ジクロロハイドロキノン、コ
、3−ジブロモハイドロキノン、λ、!−ジメチルハイ
ドロキノン等がるるか、なかでも特にノー・イドロキノ
ンが好ましい。The dihydro-7benzene developing agents used in the present invention include hydroquinone, chlorohydroquino/, bromohydroquinone, isopropylnohydroquinone, menalhyto'quinone, co,3-dichlorohydroquinone, co,3-dibromohydroquinone, λ,! -dimethylhydroquinone, among others, hydroquinone is particularly preferred.
補助現像主薬としての7−フェニル−3−ビラシソトン
又は七の誘導体の列としては/−7二二ルー3−ピラゾ
リドン、/−フェニル−弘、弘−ジメチル−3−ピラゾ
リドン、などがるる。A series of derivatives of 7-phenyl-3-biracisotone or 7 as auxiliary developing agents include /-722-3-pyrazolidone, /-phenyl-hiro, hiro-dimethyl-3-pyrazolidone.
p−アミン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−アミノフェノール、N
−(β−ヒドロキ/エテル)−p−アミンフェノール、
p−ベンジルアミノフ五ノール等があるが、fz70−
で%lNlN−メチル−p−アミノフェノールましい。Examples of the p-aminephenol auxiliary developing agent include N-methyl-p-aminephenol, p-aminophenol, and N-methyl-p-aminephenol.
-(β-hydroxy/ether)-p-aminephenol,
There are p-benzylaminophonol, etc., but fz70-
and %lNlN-methyl-p-aminophenol is preferred.
ジヒドロキシベンゼン系現像主薬は通常09Ojモル/
1l−0,/rモル/lの量で用いらnるの力E好!L
い。Iたジヒドロキシベ/ゼン類トi −フェニル−3
−ビラゾリド/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0.0!モル/ l S−
0、jモル/l、後者2o。The dihydroxybenzene developing agent is usually 0.9 Oj mol/
The force used in the amount of 1l-0,/rmol/l is good! L
stomach. I-dihydroxybe/zene-i-phenyl-3
- When using a combination with virazolid/s or p-amino-phenols, the former is 0.0! Mol/l S-
0, j mol/l, the latter 2o.
06モル/11以下I:l)tで用いるのか好ましい。It is preferable to use 06 mol/11 or less I:l)t.
現像主薬は:4jIL材料、夕IJえはノ・ロケン化銀
写真乳剤層!fJ−は七nと水透過性関係にある層中に
存在させてもよい。その場合、現像は現像主薬を含冴し
ないアルカリ注水性准と写真材料會妥触さぜることによ
って行なうことかでさる。写真材料中での現像生薬の被
嶺率に輿」えはO1/〜!r f /F71”の範囲で
める。現像剤液中で由いるときには現像主薬は70〜6
oy7gの範囲の濃度で便用するのが好ましい。Developing agent: 4J IL material, Yu IJ Ehaha no silver saponide photographic emulsion layer! fJ- may be present in a layer having a water permeability relationship with 7n. In that case, development is carried out by mixing the photographic material with an alkaline aqueous solution containing no developing agent. The coverage rate of developing crude drugs in photographic materials is O1/~! r f /F in the range of 71". When dissolved in the developer solution, the developing agent is 70 to 6
Preferably, the concentration is in the range of 7 g oy.
本発明に由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、亜硫酸リテワム、重亜硫酸ナトリ
ウム、メタ重亜硫酸カリウム、ホルムアルデヒド1亜硫
酸ナトリウム等かめる。亜硫酸塩は0.3モル/l以下
用いらfる。好1しくはθ、/!−0.2jモル/lで
ある。Examples of the sulfite preservative according to the present invention include sodium sulfite, potassium sulfite, litewum sulfite, sodium bisulfite, potassium metabisulfite, and sodium formaldehyde monosulfite. The amount of sulfite used is 0.3 mol/l or less. Preferably θ, /! -0.2j mol/l.
本発明の現像液にはその他、ホウ酸、ホウ砂、ケイ酸塩
、第三す/酸ナトソワム、第三リン酸カリウムの如さp
H緩衝剤そn以外に特開昭60−タ34L、3Jに記載
のpH緩衝剤を由いることができる緩@剤のalI度に
0.3モルフ8以上が好lしい。In addition, the developer of the present invention includes boric acid, borax, silicates, tertiary acid/natosoam, and tertiary potassium phosphate.
In addition to the H buffer, the pH buffer described in JP-A-60-134L, 3J can be used.The alI degree of the pH-relaxing agent is preferably 0.3 morph 8 or more.
:臭化カリウム、沃化カリウムの如さ埃像抑制剤:エテ
レングリコール、ジエチレングリコール、トリエチレン
クリコール、ジメチルホルムアミド、メテルセロソルフ
゛、ヘキシレングリコール、エタノール、メタノールの
如きM機浴剤:!−=トロインダンール等のインダゾー
ル系化合物、コーメルカプトベ/ツイばダン°−ルーj
−スルホン酸ナトリワム、j−メチルベンツトリアゾー
ルなどのペンツトリアゾール系化合物等のカブリ防止剤
ないし黒ポア(black pepper )防止剤
;を含んでもよく、米国特許t、コ6り、りλり号に記
載さnているアミン化合物金含有してもよい。: Dust image suppressants such as potassium bromide and potassium iodide: M bath agents such as ethylene glycol, diethylene glycol, triethylene glycol, dimethyl formamide, mether cellosol, hexylene glycol, ethanol, and methanol:! −=Indazole compounds such as troindanol, Komelcaptobe/Twibadan °−ruj
- antifoggants or black pore inhibitors such as sodium sulfonate and penttriazole compounds such as j-methylbenztriazole, as described in U.S. Pat. The amine compound may contain gold.
更に必要に応じ又色調剤、界面活性剤、硬水軟化剤、f
ijl膜剤lどt含んでもよい。Furthermore, if necessary, color toning agents, surfactants, water softeners, f
It may also contain an ijl film agent.
本発明に用いる定y#液はチオ硫鐵塩全含む水溶液でめ
ジ、p)ij 、11以上、好1しくはり、2〜1.1
”l−Mする。。The constant y # solution used in the present invention is an aqueous solution containing all thiosulfate salts, p) ij, 11 or more, preferably 1, 2 to 1.1.
``l-M.''
定着剤としてはチオfi7c酸ナトリウム、チオ硫酸ア
ンモニウムなどがあるが、定着速度の点からチオ硫酸ア
ンモニウムが特に好ましい。定fr埠1の!用tは適宜
変えることかでさ、一般には約0./〜約約3ルル/l
ある。Examples of the fixing agent include sodium thiofic acid and ammonium thiosulfate, and ammonium thiosulfate is particularly preferred from the viewpoint of fixing speed. Fixed fr 1! The value of t may be changed as appropriate, but it is generally about 0. / ~ approx. 3 lulu/l
be.
定着液には硬膜剤として作用する水溶性アルごニウム塩
を含んでもよく、そnらに汀、向えど塩化アルミニウム
、硫酸アルミニウム、カリ明げんなどがある。The fixer may also contain water-soluble argonium salts that act as hardeners, such as aluminum chloride, aluminum sulfate, potassium chloride, and the like.
定着液には、酒石酸、クエン酸、グルコ/酸あるいはそ
nらの誘導体を単独であるいはλ穐以上用いることかで
さる。こnらの化合Pf!!Jは定着Q/JKっ@o、
oojモル以上含むものが有効で、特に0.01モル/
l−0.03モル/lが特に有効である。In the fixing solution, tartaric acid, citric acid, gluco/acid or derivatives thereof may be used alone or in an amount of λ or more. These compounds Pf! ! J is fixed Q/JK@o,
Those containing more than ooj mol are effective, especially 0.01 mol/
1-0.03 mol/l is particularly effective.
定着液には所望にエリ保恒剤(例えは、亜硫酸塩、重亜
硫酸塩)、pH緩衝剤(例えば、酢酸、硼酸)、pH調
整剤(例えは、硫酸)、硬水軟化能のめるキレート剤や
特開昭62−71j6/号記載の化合物を含むことがで
きる。The fixing solution may optionally contain preservatives (e.g., sulfites, bisulfites), pH buffers (e.g., acetic acid, boric acid), pH adjusters (e.g., sulfuric acid), chelating agents to enhance water softening ability, etc. Compounds described in JP-A No. 62-71j6/ may be included.
上記本発明における処理方法でに、現儂、定着工程の故
、水洗水lたrr、安定化液で処理ざf、次いで乾燥ざ
rLる。In the above-mentioned processing method of the present invention, in the fixing step, the film is washed with water, treated with a stabilizing solution, and then dried.
水洗水の補光t’t−少なくする方法として、古くより
多段回流方式(例えば−段、3段なと〕が矧らnている
。この多段向流方式全本発明に適用すnは定着後の感光
材料は命々に清、争な方向、つ1り定着液で汚nていな
い処理液の万に順次接触して処理さfて行くので、さら
に効率の艮い水洗がなさnるっ
上記の節水処理1′f−は無配管処理には、水洗水また
は安定化液に防はい手段t−施すことが好lしい。Multi-stage circulation systems (for example, - stage, 3 stages) have been used as a method for reducing the supplementary light t't of washing water for a long time. Subsequently, the photosensitive material is processed in a very clean and direct manner by sequentially contacting the processing solution uncontaminated by the fixing solution, which further improves efficiency and eliminates the need for water washing. For the above water-saving treatment 1'f-, it is preferable to apply a barrier to the washing water or stabilizing liquid for piping-free treatment.
防ばい手段としては、%開昭60−コロ3り3り号に記
さnた紫外線照射法、1司60−λ63り4Ao号に記
さnた磁場を用いる方圧、同6/−/3/63λ号に記
σnfCイオ/交換樹脂を用いて純水にする方法、特開
昭6r−iijisv号、同6λ−153962号、%
開1@&j−λλOり51号、同62−209!32号
に記載の防菌剤を用いる方法を用いることができる。As a means of prevention, the ultraviolet irradiation method described in 1986-1960-Colo 3-3-3, the atmospheric pressure using a magnetic field described in 1-60-λ63-4Ao, 6/-/3/ Method of purifying water using σnfC ion/exchange resin, described in No. 63λ, JP-A No. 6R-iiijisv, No. 6λ-153962, %
The method using the antibacterial agent described in Publication No. 1@&j-λλO 51 and No. 62-209!32 can be used.
さらには、L 、F’ 、 vVest 、 ” VV
aterQuality Cr1teria ″
Photo、 Sci。Furthermore, L, F', vVest, "VV
aterQuality Cr1teria ″
Photo, Sci.
& Eng、 Vol、 タ /FaA (
/9AI)、〜i、Vv。& Eng, Vol, Ta/FaA (
/9AI), ~i, Vv.
」;噛reach 、 ” Microb+o
logical (jrowthsin Mot
ion−picture )’rocessing
8MPTE Journal Vol、rj、
(15’76)、R,Q 、Deegan、“Phot
o )’rocessingWash Water
Biocides” J 、ImagingTech
t O%AA (/りZa)お工ひ特開昭j7−jr
j4L2号、Pl!7−311173号、同jr−10
!/仏j号、同67−/3λ/4t6号、同61−/1
63/号、同!7−97jJO号、同、t7−/!7コ
≠ケ号なとに記載ざtている防菌剤、防ばい剤、界面活
性剤などを併用することもできる。"; bite reach, "Microb+o
logical (jrowthsin Mot
ion-picture)'rocessing
8MPTE Journal Vol, rj,
(15'76), R,Q, Deegan, “Photo
o)'rocessingWash Water
Biocides” J, ImagingTech
t O%AA (/riZa) Okuhi Tokukai Showa J7-jr
j4L2, Pl! No. 7-311173, same jr-10
! /Buddha j, 67-/3λ/4t6, 61-/1
63/issue, same! 7-97jJO issue, same, t7-/! Antibacterial agents, antifungal agents, surfactants, etc., which are not listed in 7.
さらに・水洗浴または安定化浴には、R,T。Additionally, in the washing bath or stabilizing bath, R, T.
Kreiman著、J 、 Image、 Tech
i 01(6)24c2頁(/り(a)に記載ざnたイ
ンテアゾリン系化合物、Re5earch Disc
losure 第201巻、iKhコosii、(i
りt/年j月号)に記載ちnたインテアゾリン系化合物
、同第−2−2r巻、IO2−gψj(/りζ3年参列
号〕に記載ざnたインテアゾリン系化合物、%開昭42
−202j3−2号に記載さfた化合物などを防菌剤1
(Microbiocide )とLT併m−rること
%Tきる。Kreiman, J. Image, Tech.
i 01(6) Page 24c2 (Inteazoline compounds not mentioned in (a), Re5earch Disc
losure Volume 201, iKh osii, (i
Inteazoline compounds not described in Volume 2-2r of the same volume, IO2-gψj (Participated in 3rd issue of 1977), %
- The compounds described in No. 202j3-2 are used as antibacterial agents 1.
(Microbiocide) and LT can be combined.
七の他、「防菌防黴の化学」堀口博著、三共出版(昭和
57)、1防菌防黴技術ハンドブツク」日本防閑防黴学
会・博報堂(昭和67)に記載きjしている工うな化合
物を含んでもよい。In addition to 7, "Chemistry of Antibacterial and Antifungal" by Hiroshi Horiguchi, Sankyo Publishing (1987), 1. Handbook of Antibacterial and Antifungal Technology, Japanese Society of Antifungal and Antifungal Research, Hakuhodo (1988). It may also contain chemical compounds.
本発明■万tE:VCおいて少量の水洗水で水洗すると
きには%開昭63−/!rjsO号に記載のスクイズロ
ーラー洗浄槽を設けることがよりt8−’!Lい。This invention ■ 10,000 tE: When washing with a small amount of washing water in VC, the opening rate is 63-/! Providing the squeeze roller cleaning tank described in the rjsO issue is even better! L.
また、特開昭63−7弘35弘j号のような水洗工程の
構成をとることも好ましい。Further, it is also preferable to employ a water washing step configuration as disclosed in Japanese Patent Application Laid-open No. 35-35-1983.
ざらに、本発明の方法で永久lたは安定化浴に防ばい手
段金施した水金処理に応じて補光することV?−工って
生ずる水洗’E7’Cは安定化浴力・らのオーバーフロ
ーの一部Iたは全部は特開昭60−−23!733号に
記載きtている工うにその前の処理工程である定着能t
iする処理液に利用することもできる。In general, in the method of the present invention, it is possible to supplement the light according to the water metal treatment applied to the permanent or stabilizing bath as a protective measure. -Water washing 'E7'C generated during processing is a stabilizing bath power. Part or all of the overflow is the processing step before that described in JP-A-60-23!733. Fixing ability t
It can also be used as a processing solution.
不発明における現像処理では、現像時間が5秒〜3分、
好でしくにr秒〜2分、その現像湛震は/I ’C−4
0’C75E好Iしく、20°CA−u 。In the development process according to the invention, the development time is 5 seconds to 3 minutes,
Preferably, the development time is /I'C-4 for r seconds to 2 minutes.
0'C75E preferred, 20°CA-u.
QCが工9好フしい。QC is 9 times better.
定着塩度お工ひ時間は約ir 0c〜約6o 0Cで5
秒〜3分が好1しく、20°C−≠o ’Cで6秒〜λ
分がより好ましい。この範囲内で十分な定着かでさ、残
色ゲ生じない程度に眉lへ色素全溶出さぞることがでさ
るっ
水洗(または安定各月・ておける温度お↓ひ時間nO〜
jO°cでg秒〜3分子i;2−1”EL<、/j0C
〜μo 0CでA秒〜λ分つ・:す好ましい。Fixing salinity processing time is about IR 0C to about 6O 5 at 0C
Preferably seconds to 3 minutes, 6 seconds to λ at 20°C-≠o'C
minutes is more preferred. Within this range, there is sufficient fixation, and all of the pigment can be eluted to the eyebrows without causing any residual color.
g seconds ~ 3 molecules i at jO°c; 2-1”EL<, /j0C
~ μo A seconds ~ λ minutes at 0C: Preferable.
現像、定Nあ・よひ水洗(4fC,に安定化)芒f念感
光材料は水洗水をしぼり切る、すなわちスクイズローラ
ーを経て乾燥さnる。乾燥は約弘0 °C〜約10o
0cで行7) jL 、乾燥時間は周囲の状態によって
適宜変えらnるが、通常は約5秒〜3分でよく、待によ
り好lしくに≠θ〜(0”Cで約j秒〜λ分である。After development, washing with water (stabilized at 4fC), the photosensitive material is dried by squeezing out the washing water, that is, passing through a squeeze roller. Drying time: approx. 0°C to approx. 10o
At 0C, line 7) jL, the drying time can be changed as appropriate depending on the surrounding conditions, but usually it is about 5 seconds to 3 minutes, and the drying time is preferably ≠θ~ (about j seconds at 0"C). It is λ minutes.
Dry to Dry で100秒以下の境塚処理
?すると1には、迅速処理考方の現1ムラケ防+hする
九めに特開昭63−isiり≠3号公報に記載さnてい
る工うlゴムM寅のローラーケ埃像メ/り出口のローラ
ーに適用することや、特開昭63−/!/り弘を号公報
に記載式nているようンζ現像徹夕/り内の現像液攪拌
のための吐出流速を10m1分以上にすることや、はら
には、%開゛柚6j−264L7jt1号公報に記載さ
rているLうに少なくとも現像処理中は待囁中L9ぽい
攪拌全することが工9好ましい。さらに迅速処理のため
(先は、%に定N徹夕/り90−ラーの構成は、定着速
度を速めるために、対同ローラーでめ已ことかより好〕
しい。対向ローラーで傷g′Tることによって、ローン
−の本Fiケ少なくでさ、処理夕/りを小をくでさる。Sakaizuka processing in less than 100 seconds with Dry to Dry? Then, in 1, the method described in Japanese Unexamined Patent Application Publication No. 1983-ISI ≠ No. 3 which prevents unevenness due to the rapid processing concept is used. It can be applied to the rollers of JP-A-63-/! /Rhihiro has the formula described in the publication. It is preferable to stir completely at least during the development process as described in the above publication. Furthermore, for faster processing (formerly, it is preferable to use a fixed N overnight/90 roller configuration in order to speed up the fixing speed).
Yes. By scratching with the opposing rollers, there is less damage to the lawn and processing time is reduced.
丁lvち自境磯を工9コ/バクトにすることが可能とな
る。It becomes possible to turn your own area into 9 pieces/bakuto.
本発明において、高コントラストとは、=9具体的には
階調rとして参以上のものを言う。In the present invention, high contrast refers to gradation r=9 or higher.
この工うl高コントラストなネガ画111!を侍る方法
としては公知の手段音用いることかでさる。、トjえは
、ハロゲン1r銀乳剤の粒子サイズ分布ケ卓分散化丁@
方法(万伝■う、)・ログ/化藏乳斧jυつ・・ロゲ/
組底を塩r−銀%)シ<は塩臭化銀とする万0(方法■
)、ヒドラジン化合PPIJもしくはテトラゾリウム塩
化合物の存在下で現像する万伝(万伝■バロジクム項寺
の\■族族金属化初物ケバコゲ/化銀乳剤含有さぞる方
法(方法■)など用いることができる。This technique produces 111 high-contrast negative images! The best way to attend is by using known means. , the table shows the grain size distribution of halogen 1r silver emulsion.
Method (Manden ■u)・Log/Kazo Milk Ax... Loge/
The bottom of the set is salt r-silver%) and is silver chlorobromide (method).
), the method of developing in the presence of a hydrazine compound PPIJ or a tetrazolium salt compound (Manden ■ Balodicum Hangji's \■ group metallized first product Kebakoge / silver oxide emulsion containing method (method ■)) can be used. .
万伝■において単分散の程度とに、後述の如き程度が好
フしい。The degree of monodispersity in Manden (2) is preferably as described below.
万伝■において、堰1こ銀苫■童としてばjO〜100
モル饅が好ましい。In Manden■, if one of the weirs is Ginto, then jO ~ 100.
Mole buns are preferred.
万伝■におい又、ヒドラジ/化扮物を用いる万伝につい
ては詳しくは前述の米国特許に記載さrしている。Manden ■ Also, Manden using hydrazi/monsters is described in detail in the above-mentioned US patent.
この方rE’lこて用いら71.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。具体的化合物グ]と
しでは、米国特許第≠、−一≠、 4toi号、同第!
、 /At 、り77号、同@4t、/GA、744
−号、同第+、3//、71/号、同第μ、27λ、6
06号、同第≠、iii、rs”y号、同第4′l−2
4′j、73り号等に記載式nているヒドラジ/誘導体
がろる。また、テトラゾリウムを用いる方法については
詳しくは、%開昭jコーir3/7号、同!3−/77
/?号、同jfJ−/7720号などに記載さnている
。This way rE'l trowel is used 71. As the hydrazine, known ones can be used. Specific compounds] and US Patent Nos. ≠, -1≠, 4toi, and US Patent No.
, /At, ri No. 77, @4t, /GA, 744
− issue, same issue +, 3//, 71/ issue, same issue μ, 27λ, 6
No. 06, No. ≠, iii, No. rs"y, No. 4'l-2
The hydrazines/derivatives having the formula n described in No. 4'j, No. 73, etc. are included. For details on the method using tetrazolium, see %Kaisho J Co. IR No. 3/7, same! 3-/77
/? No. JFJ-/7720, etc.
また、この方法■を用いた場合にはr値70以上のもの
會得ることもできる。Further, when this method (2) is used, it is also possible to obtain an r value of 70 or more.
方法■においては、列えげロジウム塩を10−7〜lO
モル1モル−Ag程度含有さぜることによって行なうこ
とができる
本発明は特に方法■のうちヒトランフ化合物金用いる高
コ/トラスト画儂形成方法に利用するのに適している。In method ①, the amount of rhodium salt is 10-7 to 1O.
The present invention, which can be carried out by stirring a mixture containing about 1 mole of Ag, is particularly suitable for use in method (2) of forming a high co/trust image using a human trampf compound with gold.
本発明において用いらnるハロゲン化銀乳剤のハログツ
組成としては、塩化銀、塩臭化銀、沃臭化銀翫臭化銀、
沃臭塩化銀等々どの組成の中から適当なもの?選択して
用いることができる。The halide composition of the silver halide emulsion used in the present invention includes silver chloride, silver chlorobromide, silver iodobromide, silver bromide,
Which composition is suitable, such as silver iodobromochloride? It can be used selectively.
本発明に用いらC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
粒子サイズ分布金持つことが好I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り0%を占める粒
子のサイズが平均粒子サイズの士≠θ%以内にるること
が好Iしい。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 grains accounting for 0% of the total weight or number of silver halide grains is within the average grain size. It is preferable that it be within ≠θ%.
(一般にこのような乳剤は単分散乳剤と呼unる)。(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)の万が好tL<、%にO9≠μ以下が好
lしい。The silver halide grains used in the present invention are preferably fine grains (for example, 0.7 μm or less), and preferably tL<,% and O9≠μ or less.
写真乳剤中のハロゲン化銀粒子は立方体、八面体の=う
な規則的(regular)l結晶体を翌するものでも
よく、また球状、板状などのLプな変則的(irreg
ular )な結晶を持つもの、めるいはこnらの結晶
形の複合形t”%’:)ものでろりても工い。The silver halide grains in the photographic emulsion may be regular crystals such as cubic or octahedral, or irregular crystals such as spherical or plate-like.
Items with ular) crystals can also be made from composite forms of these crystal forms.
ハロゲン化銀粒子は内部と六層が均一な相〃・ら成って
いても、異なる相からなりていてもよい。The interior and six layers of the silver halide grain may be composed of uniform phases or may be composed of different phases.
別々に形成したコ徨以上のハロゲン化銀乳剤を混会し1
使用してもよい。By mixing silver halide emulsions of more than 100%, which were formed separately, 1
May be used.
不発明に用いるハロゲン化銀乳剤ににノ・ログ/化銀粒
子の形Iy、lfcに物理熟成の過程においてカドミウ
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、ロジウム塩もしくに七の錯塩などを共存
さぞてもよい。In the silver halide emulsion used in the invention, cadmium salts, sulfites, lead salts, thallium salts, iridium salts or their complex salts, rhodium salts or It is also possible to coexist with a complex salt of 7.
・・ロゲン化銀乳剤は、化学増gを行わない、いわゆる
未後熟乳剤(プ+) ミテイブ乳剤)を用いることもで
きるが、化学増感ざnて%1よい。化学増感のためには
フリーザー著「デイ・グルンドラーゲ/・デア°フオト
グライツシエン・プロゼツセ・ミツト・ジルパーハログ
ニデン」、アカデミツシエ・フエルラーゲスゲゼルシャ
フト、lり6!r(H,Fr1eser、 Die (
)rund 1agen derPhotograph
ischen Prozesse matSilver
halogeniden 、Akademisc
heVerlagsgesselschaft、/りt
r)等に記載の方法を用いることができる。As the silver halide emulsion, a so-called immature emulsion (premature emulsion) which is not subjected to chemical sensitization may be used, but chemical sensitization may be less than 1%. For chemical sensitization, see Frieser's ``Dei Grundrage/der °Fotogleitsien Prosetsse Mitsut Zilperhalogniden'', Akademitsier Fuerlagesgesellschaft, lli 6! r(H, Fr1eser, Die (
)rund 1agen derPhotograph
ischen Prozesse matSilver
halogeniden, Akademisc
heVerlagsgesselschaft, /rit
r), etc. can be used.
丁なわち、活性ゼラテ/や銀と反応しうる硫黄を含む化
合*(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(
例えは第−丁ず塩、アばン類、ヒドラジ/誘導体、ホル
ムアミン/スルフィン酸、シラン化合物づ金柑いる還元
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六第■族金属の錯塩
)を用いる貴金属増感法など全単独或いは組み会わせて
実施することができる。In other words, sulfur sensitization using active gelate/compounds containing sulfur that can react with silver (e.g. thiosulfates, thioureas, mercapto compounds, rhodanines), reducing substances (
For example, the reduction sensitization method using metal salts, vanes, hydrazines/derivatives, formamine/sulfinic acids, silane compounds, precious metal compounds (e.g., gold compounds, periodic compounds such as platinum, iridium, palladium, etc.) A noble metal sensitization method using complex salts of Group 6 metals (complex salts of Group 6 metals) can be carried out singly or in combination.
本発明の感光材料の乳剤層や中間層に用いることのでさ
る結合剤Ifcは保護コロイドとしては、ゼラテ/をも
ちいるのがM利でろるが、そ′i″L以外の親水性コロ
イドも用いることができる。As the binder Ifc used in the emulsion layer and intermediate layer of the light-sensitive material of the present invention, it is preferable to use gelate as a protective colloid, but hydrophilic colloids other than that may also be used. be able to.
飼えばゼラテ/誘導体、ゼラテ/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i白i;ヒド
ロキシエチルセルロース、カルボキンメチルセルロース
、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纂ポリ
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−ビニルピロリドン、ポリアクリル酸、ポ
リメタクリル酸、ポリアクリルアミド、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
合体の如き多徨の什成親水性高分子物tを用いることが
できる。Gelate/derivatives, graft polymers of gelate/and other polymers such as albumin, casein, etc.; A variety of hydrophilic substances such as single or copolymers of sugar derivatives such as polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Polymeric material t can be used.
ゼラチンとしては石灰処理ゼラテ/のほか、酸処理ゼラ
テ/やブラティ/・オブ・ザ・ソサエティ・オブ・サイ
エンティフィック・フォトグラフインク・ジャ、Rン(
Bull、Soc、Cci、Phot。In addition to lime-processed gelatin, gelatin is available from acid-processed gelate and bratty gelatin from the Society of Scientific Photography, Inc., R.N.
Bull, Soc, Cci, Phot.
Japan)A/ A、30頁(/り66)に記載さn
た工うな酵素処理ゼラチンを用いても工く、また、ゼラ
チンの770水分M物や酵素分解物も用いることができ
る。Japan) A/A, page 30 (/ri66) n
Alternatively, enzyme-treated gelatin can be used, and 770 water content of gelatin or an enzymatic decomposition product can also be used.
本発明の感光性ハロゲ/化銀乳剤は、増感色素によって
比較的長波長の宵色九、緑色光、赤色光1fCは赤外光
に分光増感さnてもよい。増感色素として、ンアニン色
素、メロシアニン色素、コ/プレックスシアニン色素、
コ/プレックスメロシアニン色累、ホロホーラー/アニ
7色累、ステリル色素、ヘミシアニ/色素、オキンノー
ル色累、ヘミオキノノール色素等金中いることができる
。The photosensitive halogen/silver oxide emulsion of the present invention may be spectrally sensitized to relatively long-wavelength evening light, green light, red light, or infrared light using a sensitizing dye. As sensitizing dyes, n-anine dye, merocyanine dye, co/plex cyanine dye,
Co/plex merocyanine color, holohole/ani7 color, steryl dye, hemicyani/pigment, oquinol color, hemioquinonol dye, etc. can be found in gold.
本発明に使用さnる翌用な増感色素は列えばRESEA
RCHDISCLCJSL)kLE Item/74
4t3■−A項(/り7!r年/j月p、2j)、同I
tem/yj/X項(/り7り年r月p、+37)に記
載%L<は引用さγした文献に記載きnている。The next sensitizing dye used in the present invention is RESEA.
RCHDISCLCJSL)kLE Item/74
4t3■-A term (/ri7!r year/j month p, 2j), same I
Described in the tem/yj/X term (/ri7 r month p, +37) %L< is described in the cited literature.
物に各種スキャナー光源の分光特性に通した分光感度を
有する増感色素を有利に選択テることができる。Sensitizing dyes can be advantageously selected that have spectral sensitivities that match the spectral characteristics of various scanner light sources.
輿」えは、A)アルゴンレーザー光源に対しては、%開
昭60−/6ハ日7号、%開平2−i)!3、米国特許
−、/l、/、33/号、***特許Fjt、o7/号記
載のン/プルメロンアニ/撃;B)ヘリウム−ネオ/レ
ザーに光源に対しては、特開昭60−621123号、
同611−/1726号、同!ター10λ2.2り号に
示cnた三核シア二/色素類;c)LED元源光源して
は特公昭≠ざ一弘2/7λ号、同j/−760り号、同
5s−32111r号、特開昭62−コrμ3≠3に記
載ざt″Lだテアカルlンアニ/類、D)半導体レーザ
ー光源に対しては特開昭52−/り103−号、特開昭
6O−rot弘7号に記載さtたトリ力ルボノアニ/撃
、%開昭jター/り2コ≠λ号に記載きt″した≠−キ
ノリン核全含有するジカルボシアニン類などが有利に選
択ざfる。A) For the argon laser light source, %Kaisei 60-/6Ha day 7,%Kaisei 2-i)! 3. U.S. Patent No. 33/, West German Patent Fjt, O7/; issue,
611-/1726, same! c) Trinuclear cyanidine/pigments shown in Tar No. 10λ2.2; c) LED source light source: Tokuko Sho≠Zahiro No. 2/7λ, No. J/-760, No. 5s-32111r. , JP-A-62-103-103-, JP-A-62-103, JP-A-62-103-1, JP-A-62-103-103, JP-A-62-103 Dicarbocyanines containing the entire quinoline nucleus, etc., described in No. 7 and % Kaishojter/Li 2 ≠ λ described in No. 7 are advantageously selected. .
以下に−f:n−らの増感色素の代六的化合物をボテ。Below are six typical compounds of sensitizing dyes such as -f:n-.
A)の具体的化合物 A−/) A−2) S03H−N(C2H5)3 A−3) B)の具体的化合物 B−/ A−≠9 A−s) −j B−≠ C)の具体的化合物 下式(A)で表わはjLる化合物 (A) 基、ハロゲン原子で置換さnてもよい。Specific compounds of A) A-/) A-2) S03H-N(C2H5)3 A-3) Specific compounds of B) B-/ A-≠9 A-s) −j B-≠ Specific compounds of C) A compound represented by the following formula (A) (A) n may be substituted with a halogen atom.
R1、凡2にそnぞn低級アルキル基、スルホ基lたは
カルホキ7基ゲ有するアルキル基金式す。R1 and 2 each have an alkyl group having a lower alkyl group, a sulfo group, or a carboxy group.
凡、に低級アルキル基全人丁。Xlはアニオ/衣わ丁。Generally, lower alkyl groups are used. XL is Anio/Kirowacho.
nl、n2はO又は/全人わ丁。nはO又は/を表V″
j(分子内塩を作るときにOである)。nl, n2 is O or /zenninwading. n is O or / is V''
j (O when making an inner salt).
具体的には
C−/
〔式中Y□及びY2は各々ベンンーテアゾール環、ヘン
ゾセレナン′−ル環、ナフトテアンール環、ナフトセレ
ナンール環、またはキノ1)/環の工うな複素環を形成
するのに心安な非金属原子群を我し、こnらの複素環は
低級アルキル基、アルコキシ基、ヒドロキシ基、アリー
ル基、アルコキシカルホニC−コ
−j
C−弘
−j
−r
D)の具体的化合物
D−≠
J)−/
L)−3
1θ
−A
←つH−
C9f(5
e
αO0
特にIN記C)の増感色素との組合せは高感化が可能′
にな9好ましい。Specifically, C-/ [in the formula, Y□ and Y2 each form a heterocycle such as a ben-theazole ring, a henzoselenan'-l ring, a naphthotheanyl ring, a naphthoselenanol ring, or a kino1)/ring. These heterocycles include lower alkyl groups, alkoxy groups, hydroxy groups, aryl groups, and alkoxycarbonyl groups. A specific compound of D-≠ J)-/L)-3 1θ -A ← H- C9f (5 e αO0 Especially in combination with a sensitizing dye of IN C), high sensitivity can be achieved.
9 preferred.
cILらの増感色素は単独に用いてもLl/′1が、そ
tらの組合せを用いても工く、増感色素の組合せに考に
、増色増感の目的でしばしば弔いらr−る。The sensitizing dyes of cIL et al. can be used alone or in combination. -ru.
増感色素とともに、そt自身分光増感作用ケもたない色
素あるいは可視光を実質的に吸収しない物質でめって、
強色増感を示す物質全乳剤中に含んでも工い。Along with sensitizing dyes, dyes that themselves have no spectral sensitizing effect or substances that do not substantially absorb visible light are rarely used.
A substance exhibiting supersensitization may be included in the entire emulsion.
有用な増感色素、強色増感を示す色素の組合せ及び強色
増感を示す物質はりサーチ・ディスクロージャ(%es
earch Disclosure )/ 7A巻/
76弘3(/り7 lr/iE/ 、!月発行)第λ3
頁■の5項に記載さnている。Useful sensitizing dyes, combinations of dyes exhibiting supersensitization, and substances exhibiting supersensitization
arch Disclosure)/Volume 7A/
76 Ko 3 (/ri7lr/iE/,! issue) No. λ3
It is described in page 5, item 5.
本発明に弔いら扛る写真乳剤には、感光材料の製造工程
、保存中めるいは写真処理中のカブリ?防止し、あるい
は写真性能全安定化させる目的で権々の化合物?含有さ
せることができる。すなわちアノール類、例えばべ/シ
ナアゾリウム塩、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卿、メル
カプトベ/ン′チアゾール類、メルカブトベ/ズイミダ
ゾール類、ノルカブトナアジアゾール類、アミノトリア
ゾール類、イノシト’)アゾール串、ニトロペン、ノ゛
ト1ノアノール類、メルカプトテトラン”a (WK/
−フェニル−!−メルカプトテトラゾール)なと;メル
カプトピリミジ/類;メルカプトトリアン/類:たとえ
はイキブドリンテオ/のようなチオケト化会物;アザイ
ンデン類、たとえはトリアザイ/デ/類、テトラアザイ
ンデン烟(特に≠−ヒドロキン信二換(’ + 3+
3a+ 7)テトラアザイ/デ/類)、ぺ/タアザイン
デ7類なト;へ/ゼ/テオスルフオ/類、べ/ゼンスル
フィン酸、ベンゼンスルフォン酸アξド等のようなカブ
リ防止剤またに安定剤として知らnた多く■化8’a
k 71Ωえることができる。The photographic emulsion that concerns the present invention does not suffer from fog during the manufacturing process of the light-sensitive material, during storage, or during photographic processing. Compounds of authority for the purpose of preventing or totally stabilizing photographic performance? It can be included. Namely, anoles such as be/sinaazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobe/n'thiazoles, merkabutobe/zimidazoles, norkabutnasia. Sols, aminotriazoles, inocyto') azole skewers, nitropenes, No. 1 noanols, mercaptotetran'a (WK/
-Phenyl-! mercaptopyrimidine/s; mercaptotrians/s: thioketo compounds such as quibudrintheo/; azaindenes, such as triazai/de/s, tetraazaindene smoke (especially ≠-hydroquine); Shinji exchange (' + 3 +
3a+ 7) As an antifoggant or stabilizer such as tetraazai/de/, tetraazai/de/, tetraazai/teosulfur, benzenesulfinic acid, benzenesulfonic acid, etc. I don't know much about it8'a
k can be increased to 71Ω.
こγしらの中で、特に好ましいのはべ/シトリアソーA
顔f、?りえはよ一メテルベ/シトリアゾール)でろる
71之、こnらの化合物ケ処理液に宮有三ぜても工い。Among these, particularly preferred is Habe/Citriaso A.
Face f,? Rie Hayoichi (Meterbe/Citriazole) and Roru 71, these compounds are also used in the treatment solution.
本発明の4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に石壁の硬膜剤全含有してよい。In the photosensitive material of the present invention, the photographic emulsion layer and other hydrophilic colloid layers may entirely contain an inorganic or stone hardening agent.
列えはクロム塩(クロムミョウ・マン、酢酸クロムlど
ハアルデヒド撃(、ホルムアルデヒド、クリオキサール
、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、メテロールジメテルヒダントイ
/′すど)、ジオキサン誘導体(2,3−ジヒドロキ7
ジオキサ77′:ど)、活性ビニル化分wJ(/、Jl
−’−トリアクリロイルーへキサヒドロ−5−i 17
アン/、/ 3−ビニルスルホニルーーーブロノζ/゛
−ルなど)、活性ハロゲン化合物(j、4’−フクロル
ー6−ヒドロキン−S−)リアシフfxど)、ムコノ゛
ロゲ/&a(ムコクロル酸、ムコフェノキ/クロル酸な
と)、などを単独または組み合わぞて用いることができ
る。The list includes chromium salts (chromium acetate, chromium acetate, formaldehyde, cryoxal, geltaraldehyde, etc.), N-, methylol compounds (dimethylol urea, methylol dimethyl hydrant), dioxane Derivative (2,3-dihydrox7
Dioxa 77': d), active vinylated component wJ(/, Jl
-'-Triacryloyl-hexahydro-5-i 17
active halogen compounds (J, 4'-fuchloro-6-hydroquine-S-) rear shift fx, etc.), mucologe/&a (mucochlor Acid, mucophenoxia/chloroacid), etc. can be used alone or in combination.
不発明全明いて作らnる感覚材料の写真乳剤層1念に他
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N防止及び写真特性改良(列えば、
現儂促進、硬調化、増感)等徨々の目的で、梅々の界面
活性剤を含んでも工い。The photographic emulsion layer of the sensory material made without invention should be noted for the other hydrophilic colloid layers, including coating aids, antistatic properties, improvement in slipperiness, emulsification dispersion, prevention of contact with N, and improvement in photographic properties (for example,
For various purposes such as enhancing contrast, increasing contrast, and increasing sensitization, it may also contain surfactants.
飼えはサボニ/(ステロイド系〕、アルキレンオキサイ
ド誘導体(列えはポリエチレングリコール、ポリエチレ
ングリコール/ポリプロビレ/グリコール縮合物、ポリ
エチレングリコールアルキルエーテル撃又はポリエチレ
ングリコールアルキルアリールエーテル類、ボリエテレ
/グリコールエステル類、ポリエテレ/グリコールソル
ビタ/エステル類、ポリアルキレ/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7109!l1l)、グリンドール誘導体(向え
ばアルケニルコハク散ポリグリセリド、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
ル撃、糖のアルキルエステル類などの非イオ/性界面活
性剤;アルキルカルホン酸塩、アルキルスルフォン酸塩
、アルキルベンゼンスルフォン散塩、アルキルナフタレ
/スルフォン酸塩、アルキル硫酸エステル類、アルキル
リ/#!エステル類、N−アノルーN−アルキルタウリ
ン酸、スルホコハク酸エステル撃、スルホアルキルポリ
オキ/エテレ/アルキルフェニルエーテル畑、ポリオキ
/エテレンアルキルリ:yeIRエステル類すどの工う
な、カルボキ7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全含ムアニオ/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
ン撃、アミ/オキ7ド類などの両性界面活性剤;アルキ
ルアミン塩撃、脂肪族あるいは芳香族第≠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a累環第
μ級アンモニワム塩類、及び脂肪族又は複累環紮含むホ
スホニウム又はスルホニウム塩類などのカテオ/界面活
性剤全用いることができる。The main ingredients are Saboni/(steroids), alkylene oxide derivatives (polyethylene glycol, polyethylene glycol/polypropylene/glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyether/glycol esters, polyether/glycol Sorvita/esters, polyalkylene/glycol alkylamines or amides, silicone with polyethylene oxide (7109!l1l), Grindol derivatives (such as alkenylsuccinic polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, Non-ionic/sexual surfactants such as alkyl esters of sugars; alkylcarphonates, alkylsulfonates, alkylbenzenesulfone powder salts, alkylnaphthalene/sulfonates, alkyl sulfates, alkyl ly/#! esters , N-anol-N-alkyl tauric acid, sulfosuccinic acid ester, sulfoalkyl polyoxy/ether/alkylphenyl ether field, polyoxy/ethylene alkyl: yeIR esters, carboxy 7 group, sulfo group, phosphor Amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfuric acids or phosphoric acid esters, alkyl betaine compounds, amide/oxidants, etc. amphoteric surfactants; alkylamine salts, aliphatic or aromatic secondary ammonium salts, a-cyclic μ-class ammonium salts such as pyridinium and imidazolium, and phosphonium or sulfonium salts containing aliphatic or multicyclic ligation All cateo/surfactants such as can be used.
待に本発明におい1好1しく用いらする界面活性剤は特
公昭sr−タ4/−/コ号公報に記載ざtた分子量60
0以上のポリアルキレ/オキサイド類でるる。The surfactant preferably used in the present invention has a molecular weight of 60 as described in Japanese Patent Publication No. 4/-/K.
0 or more polyalkylene/oxides.
本発明に用いる写X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
不溶又は難溶性台底ポリマーの分散物を含むことができ
る。列えはアルキル(メタ)アクリレート、アルコキン
アルキル(メタジアクリレート、グリ/ジル(メタ)ア
ジリレート、(メタ少アクリルアミド、ビニルエステル
(例工ば酢酸ビニル)、アクリロニトリル、オレフイ/
、ステン/などの単独もしくは組合ぜ、又はこnらとア
クリル酸、メタクリル酸、α、β−不飽和ジカルホ/酸
、ヒドロキシアルキル(メタ)アジリレート、スルホア
ルキル(メタ)アクリレート、スチレンスルホ/酸等の
@会せを単量体成分とするポリマー音用いることができ
る。The photographic X-sensitive material used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble base polymer in the photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability. The list includes alkyl(meth)acrylates, alkoxyalkyl(methadiacrylates, glyc/zyl(meth)azilylates, methacrylamides, vinyl esters (e.g. vinyl acetate), acrylonitrile, olefins/
, sten/etc., alone or in combination, or together with acrylic acid, methacrylic acid, α,β-unsaturated dicarpho/acid, hydroxyalkyl (meth)azilylate, sulfoalkyl (meth)acrylate, styrene sulfo/acid, etc. It is possible to use a polymer whose monomer component is @me.
(実施列)
以下、本発明を天施輿」に工って具淳的に説明するが、
本発明ばこnらKLって限定さnるものではない。(Implementation sequence) Hereinafter, the present invention will be explained in a detailed manner,
The present invention is not limited to this invention.
実施PJ 1
乳剤Aの調整
l液
水
ゼラチン
塩化ナトリウム
/、3−ジメテルイミダゾリジ
ンーーーテオン
ベンゼンチオスルホン酸ナトリ
ラム
/ 、04
λ 09
+20〜
g■
2液
水 ≠
00m1硝酸銀 1ooyJ
液
7X
≠00xl塩化ナトリウム 3
0・sy臭化カリウム /≠、37
ヘキサクロロイリジクム酸カリ
ラム(0,00/%水溶液) /jd!へキサ
クロロロジウム酸ア/モ
ニクム(0,00/%水溶液) 弘d3r 0c
、gf141.!に保fcnた/腋にufiと3液を攪
拌しながら同時に70分間にわたって加え、0./l、
μmの核粒子全形放した。続いて下記μ液、j液′に1
0分間にゎ次っで110えた。舌らにヨウ化カリウムo
、/j?knoえ粒子形&に終了し之。Implementation Project 1 Preparation of Emulsion A 1 Liquid Water Gelatin Sodium Chloride/, 3-Dimethelimidazolidine--Theone Sodium Benzenethiosulfonate/ , 04 λ 09 +20 ~ g ■ 2 Liquid Water ≠
00ml silver nitrate 1ooyJ
liquid 7x
≠00xl Sodium Chloride 3
0・sy potassium bromide /≠, 37
Potassium hexachloroiridicumate (0.00/% aqueous solution) /jd! A/monicum hexachlororhodate (0.00/% aqueous solution) Hiro d3r 0c
, gf141. ! Add the ufi and the 3 liquids to the armpit at the same time for 70 minutes while stirring. /l,
Whole microparticles of μm were released. Next, add 1 to the μ solution and J solution' below.
I gained 110 points in 0 minutes. Potassium iodide on the tongue
,/j? It ends in a particle shape &.
ダ液
水 ≠
00d硝酸銀 1002j
液
水 4
tooゴ塩化ナトリクム 30.jf
臭化カリウム /≠、31フェロ
/アン化カリウム 20mgその後1g法
にしたがってフロキュレーション法によって水洗し、ゼ
ラチン307f刀口えた。pHj、/X pAg7.j
ic調整し、チオ硫酸ナトリウムr wq、、!:塩化
金酸/−2I2v’!l”711]えbs’cにて最適
N&度を得るように化字増感金施し、安定剤として/、
!、3a、7−チトラアザインデン200〜を加え次。da liquid water ≠
00d Silver nitrate 1002j
liquid water 4
too sodium chloride 30. jf
Potassium bromide /≠, 31 ferro/potassium anide 20 mg was then washed with water by the flocculation method according to the 1 g method, and gelatin 307f was added. pHj, /X pAg7. j
Adjust ic, sodium thiosulfate r wq,,! :Chlorauric acid/-2I2v'! l"711] Apply sensitizing gold to obtain the optimum N & degree in Ebs'c, and use it as a stabilizer.
! , 3a, 7-chitraazaindene 200 ~ was added and then.
最終的に塩化銀fiOモル襲含0平均粒子径0120μ
mのヨウ塩臭化銀立方体粒子乳剤ケ得た。(変動係数2
%)
塗布試料の作成
上記の乳剤(て赤外増感色素(@記のD−t )全30
〜1モルAg加えて赤外増感全施し友。さらに強色増感
および安定化のために弘、≠′−ビスー(≠、6−ジナ
フトキシーピリミジ/−コーイルアi)〕−スステルベ
ラジスルホンジナトリウム項と2.j−ジメチル−3−
アリルーベ/ゾテアゾールヨード塩111モルに対しそ
扛ぞlf″l−30Q〜と1160〜770え友。Finally, silver chloride fiO molar concentration 0 average particle size 0120μ
A silver iodochlorobromide cubic grain emulsion of m was obtained. (Variation coefficient 2
%) Preparation of coating sample The above emulsion (with infrared sensitizing dye (@D-t) total 30
~1 mol Ag plus infrared sensitization. Furthermore, for supersensitization and stabilization, 2. j-dimethyl-3-
For 111 moles of allilube/zoteazole iodide salt, it is 1160-770 mol.
ざらにハイドロキノン100my/m 、 ポリエテ
ルアクリレートラテックスをゼラテ/(バインダー)に
対して一25重量饅、硬膜剤としてコービス(ビニルス
ルホニルアセトアミド)エタン2r6■/m2添加し、
ポリエステル支持体上に銀3゜Omy / m 2、ゼ
ラテ7/、Of/m2になるように塗布し九。Added hydroquinone at 100 my/m2, polyether acrylate latex at 1/25 weight per gelate/(binder), and Corbis (vinylsulfonylacetamido)ethane 2r6/m2 as a hardening agent.
Coat on a polyester support at a ratio of 3° Omy/m2 for silver and 7/m2 for gelate.
この上にゼラチン0,497m、 マット剤として粒径
コ、jμmのポリメチルメタクリレートtOR?/m
%粒径10mμのコロイダルシリカ70■/m k
含有し、塗布助剤としてドデ/ルベンゼンスルホ/酸す
l−IJウム塩、下」じ構造式■のフラノ系界面活性剤
碩I口した保護層上層及び、ゼラチン0.397m、
ポリエテルアクリレートラテックス12j〜/m 、
下記vR構造式■の染料全そnぞn10q/m と2
0RIj/m 、さらに塗布助剤としてドデ/ルベン
ゼンスルホン酸ナトリウム塩?添加した保護層下層を塗
布した。On top of this is gelatin 0,497m, and as a matting agent, polymethyl methacrylate tOR? with a particle size of Jμm. /m
% colloidal silica with a particle size of 10 mμ 70■/mk
The upper layer of the protective layer contains dode/rubenzene sulfo/acid salt as a coating aid, a furano surfactant with the same structural formula as shown below, and 0.397 m of gelatin.
Polyether acrylate latex 12j~/m,
All dyes with the following vR structural formula ■ are n10q/m and 2
0RIj/m, and dode/rubenzenesulfonic acid sodium salt as a coating aid? An added protective layer underlayer was applied.
なお、乳剤層、保護層下層、保護層上層の3層はP]時
多層塗i床に工9同時に塗布した。The three layers of the emulsion layer, the lower protective layer, and the upper protective layer were coated simultaneously on the multilayer coated floor in Step 9.
■ C8F 17S(J2N−C)−12cc+o
K(3H7
なお不実施グ」で便用した支持坏は下記組成のパック層
及びパンク保護#?Mする。■ C8F 17S (J2N-C)-12cc+o
The support layer used in ``3H7 Not Implemented'' has a pack layer and puncture protection of the following composition.
〔バッタ7#〕
ゼラテ//、≠y/m2
ドデ/ルベ/ゼ/スルホ/酸
ナトリウム fO■/m2染料■
70■/m2染料■
3j〜/m2染料■
タO■/m2/、3−ジビニルスルホニル
2−プロパツール 60〜/m2〔パック保護
層」
ゼラチン o、sy7m2ポリメチ
ルメタタリレート
(粒子サイズt、7μm)
トテンルヘンゼンスルホ/酸
ナトリウム
フッソ系界面活性剤(@記■)
7リコー/オイル
30rq/。2
.2ovq7m2
一2Tn9/m2
ioo〜/ m2
■
得らnた試料を7f Onmにピークをもつ干渉フィル
ターと連続ウエッジケ介し発光時間10−6秒のキセノ
/フラソ/ユ充で露光した。[Grasshopper 7#] Gelate //, ≠y/m2 Dode/Rubet/Ze/Sulfo/Sodium acid fO■/m2 Dye■
70■/m2 dye■
3j~/m2 dye■
taO■/m2/, 3-divinylsulfonyl 2-propatol 60~/m2 [Pack protective layer] Gelatin o, sy7m2 Polymethyl metatarylate (particle size t, 7 μm) Totenruhenzenesulfo/acid sodium fluoride system Surfactant (@Note■) 7 Ricoh/Oil 30rq/. 2. 2ovq7m2 -2Tn9/m2 ioo~/m2 (2) The obtained sample was exposed to xenon/furaso/yuri light with an emission time of 10-6 seconds through an interference filter having a peak at 7f Onm and a continuous wedge.
次いで、こnらの試料全現像槽の開口率がQ。Next, the aperture ratio of all developing tanks for these samples is Q.
oso又(Ho・oirv自現磯自現開平/−/260
≠Q号の第2図記載のものの浮きふたの大きざ′に震え
てこの値に設定した)を中いて処理した。osomata (Ho・oilvjigenisojigenkaihei/-/260
≠I set this value because of the size of the floating lid of the one shown in Figure 2 of No. Q).
使用した現像液は下記の現像液Y又はZで、定着gに富
士写真フィルム株式会社製CR−F/である。The developer used was the following developer Y or Z, and the fixer G was CR-F/ manufactured by Fuji Photo Film Co., Ltd.
現像液Y
亜硫酸カリウム po、oy(0,認
!M/l)
ハイドロキノ/
グーノナルーy−ヒドロキ/メ
チル−ノーフェニル−3−ピ
ラノリド/
ジエナレ/トリアS/・j酢酸
水酸化カリウム
炭酸ナトリウム(/水塩〕
、Z 3 、 Of
j 、 02
コ 、 01
//、Of/
// 、 0?
臭化カリウム 3.0?j−メチ
ルベンツトリアノール O11?−−メルカブトベ
/ノイミダゾ
ールーよ一スルフォン版 0,3fンエナレン
グ1ノコール 、2j、09水を加えて
/lとするpH=io、6sとす
る
現像gZ
税イ家液Yに亜硫酸カリウムを/e轟りλ7.0r71
Dえて曾肘で亜硫酸カリウムの濃度O0≠2M/lとし
たもの。Developer Y Potassium sulfite po, oy (0, recognized! M/l) Hydroquino/ Goononal-y-hydroxy/Methyl-nophenyl-3-pyranolide/ Dienare/Tria S/・j Potassium acetic hydroxide Sodium carbonate (/hydrate) ] , Z 3 , Of j , 02 Ko , 01 //, Of/ // , 0? Potassium bromide 3.0?j-Methylbenztrianol O11?--Merkabutobe/Neimidazole-Yoichi sulfone version 0,3f-enareng 1 Nokol, 2j, 09 Add water
pH = io to /l, development to 6s
The concentration of potassium sulfite was set to O0≠2M/l using the elbow.
現像に310Cis秒で行ったっ
得らf′l−た結果を第1衣に示した。なお第1衣にお
いてはall支3.0を与える蕗充菫のα数=r相対感
斐ヨとした。また特性曲線で濃度0./と3゜0の点を
紹ふ首級の傾さt「階調」とした。また、;Cn−’r
fnの現像8’cフイルム/m ”19200m1の
副台で補光しなから/θom のフィルムを処理しf
C後の[銀河flJ’に目視でj段階に評価した。The results obtained when the development was carried out at 310 Cis seconds are shown in the first column. In addition, in the first clothes, the α number of Sumire Fukimitsu which gives all support 3.0 was set as r relative sensitivity. Also, in the characteristic curve, the concentration is 0. The inclination of the neck level t, which introduces the points of / and 3°0, was defined as ``gradation''. Also, ;Cn-'r
Developed 8'c film/m of fn.
[Galaxy flJ' after C was visually evaluated as j grade.
フィルムの上に全く銀河nが発生しτいない状態t r
j」としフィルム−面に録再nが発生している状態會r
’/、、Jとした。1≠」はフィルム上の極く一部に録
再nが発生しているが犬山上に許各芒nるレベルである
。「3」以下は実由不可熊でるる、「最高濃度」とは光
分II、元でnた部分の黒化−度をめられ丁。さらにフ
ィルム処理を全く行わずに7週間自35!磯に放置し又
1日り時間スタンバイ状態を繰返した場合も行った(T
lvち7日り#間机像液p3t 0C1で昇混さぞる情
作t/週間行な:)た後、フィルム奮処理した時の結果
を調べたり。A state t r where no galaxy n is generated on the film and τ is not present.
j'' and recording/playback n occurs on the film surface.
'/,,J. 1≠", recording/reproduction occurs in a very small part of the film, but it is at a level that is comparable to Inuyama's. ``3'' and below are actually impossible, and ``maximum density'' refers to light minutes II, and the blackening of the part that was originally n is a serious matter. And 7 weeks without any film processing! This was also done when the fish was left on a rocky shore and the standby state was repeated for a day (T
After 7 days of #intermediate image liquid p3t 0C1 and the excitement of mixing with 0C1 for a week:), I investigated the results when I processed the film vigorously.
第1六の結果刀・ら次のことが明らかである。亜硫酸塩
を本発明の規定須紫越えて含有する現像層Z金用9へた
場合には自現Nの開口率に刀・〃・わらず100m2の
フィルム全処理した後の錯角nが多い。自現囁の開口率
が本発明の規定値を越えていると亜詭放塩のJ度が本発
明の規定値内の現l家履Y4用いた場合でもフィルム処
理なしで1週間経時した液は感度及び階調を劣化させて
し1つ。現像液の亜硫酸塩′a度と自現機の開口率全本
発明の規定値内にすることによって(実験番号3)、7
00m のフィルム全処理した後でも、フィルム全処
理せずに一週間経過し之後でも、感度・階調・最高#度
・錯角nが新液の状態を維持することができる。As a result of the 16th sword, the following is clear. When the developing layer Z contains sulfite in excess of the specified value of the present invention, the aperture ratio of the self-developed N has a large parallax n after processing the entire 100 m2 film. If the aperture ratio of the aperture exceeds the specified value of the present invention, the J degree of the subsalt may be within the specified value of the present invention. This results in deterioration of sensitivity and gradation. By keeping the sulfite content of the developer and the aperture ratio of the automatic processor within the specified values of the present invention (Experiment No. 3), 7
Even after a 00m film has been completely processed, even after a week has passed without the film being completely processed, the sensitivity, gradation, maximum # degree, and illusion angle (n) can maintain the state of the new solution.
手続補正書 平成3年Procedural amendment 1991
Claims (1)
0.3モル/l以下の水溶性アルカリ現像液を用いて現
像部の開口率が0.03以下の自動現像機を用いて現像
することを特徴とする高コントラストハロゲン化銀写真
感光材料の処理方法。Developing the exposed silver halide photographic light-sensitive material using a water-soluble alkaline developer with a sulfite concentration of 0.3 mol/l or less and an automatic developing machine with an aperture ratio of 0.03 or less in the developing area. A method for processing high-contrast silver halide photographic materials.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP17218190A JPH0460632A (en) | 1990-06-29 | 1990-06-29 | Processing method for silver halide photographic sensitive material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP17218190A JPH0460632A (en) | 1990-06-29 | 1990-06-29 | Processing method for silver halide photographic sensitive material |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH0460632A true JPH0460632A (en) | 1992-02-26 |
Family
ID=15937082
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP17218190A Pending JPH0460632A (en) | 1990-06-29 | 1990-06-29 | Processing method for silver halide photographic sensitive material |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0460632A (en) |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02125249A (en) * | 1988-11-02 | 1990-05-14 | Fuji Photo Film Co Ltd | Method for processing silver halide sensitive material |
-
1990
- 1990-06-29 JP JP17218190A patent/JPH0460632A/en active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02125249A (en) * | 1988-11-02 | 1990-05-14 | Fuji Photo Film Co Ltd | Method for processing silver halide sensitive material |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JPS589412B2 (en) | Method for developing silver halide photographic materials | |
JPH0429233A (en) | Processing method for silver halide photographic sensitive material | |
JP2828229B2 (en) | Direct positive silver halide emulsion | |
US20020001782A1 (en) | Concentrated fixing solution and method for processing silver halide photographic material using the same | |
JPS6255643A (en) | Silver halide photographic sensitive material and super-contrasty negative image forming method using it | |
GB2135467A (en) | Silver halide photographic light-sensitive materials | |
JPH0460632A (en) | Processing method for silver halide photographic sensitive material | |
JP2964019B2 (en) | Method for developing silver halide photographic material and developer | |
JPS6360372B2 (en) | ||
JPH0254534B2 (en) | ||
JP2709652B2 (en) | Silver halide photographic material | |
JPH037928B2 (en) | ||
JP2709653B2 (en) | Silver halide photographic material | |
JPS6147955A (en) | Photosensitive element for silver salt diffusion transfer process | |
JP3030142B2 (en) | Negative silver salt diffusion transfer material | |
JPS60220335A (en) | Image forming method | |
JPH0360108B2 (en) | ||
WO1990016015A1 (en) | Method of treating silver halide photographic material | |
JPH0349089B2 (en) | ||
JPS62247351A (en) | Silver halide photographic sensitive material | |
JPS61145546A (en) | Silver halide photographic sensitive material for plate making and its reduction processing method | |
JPH04296844A (en) | Silver halide photosensitive material and developing process thereof | |
JPH06130579A (en) | Method for developing silver halide photographic sensitive material | |
JPH075629A (en) | Silver halide photographic sensitive material | |
JPH01130155A (en) | Image forming method |