JPS62177555A - Method for processing silver halide color photographic sensitive material - Google Patents
Method for processing silver halide color photographic sensitive materialInfo
- Publication number
- JPS62177555A JPS62177555A JP1924586A JP1924586A JPS62177555A JP S62177555 A JPS62177555 A JP S62177555A JP 1924586 A JP1924586 A JP 1924586A JP 1924586 A JP1924586 A JP 1924586A JP S62177555 A JPS62177555 A JP S62177555A
- Authority
- JP
- Japan
- Prior art keywords
- color
- processing
- present
- silver halide
- solvent
- 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
- 238000012545 processing Methods 0.000 title claims abstract description 55
- 239000000463 material Substances 0.000 title claims abstract description 46
- -1 silver halide Chemical class 0.000 title claims description 73
- 229910052709 silver Inorganic materials 0.000 title claims description 62
- 239000004332 silver Substances 0.000 title claims description 62
- 238000000034 method Methods 0.000 title claims description 57
- 238000011161 development Methods 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000002904 solvent Substances 0.000 claims abstract description 24
- 125000003118 aryl group Chemical group 0.000 claims abstract description 14
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 8
- 125000005843 halogen group Chemical group 0.000 claims abstract description 6
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 37
- 238000011282 treatment Methods 0.000 claims description 29
- 230000006641 stabilisation Effects 0.000 claims description 17
- 238000011105 stabilization Methods 0.000 claims description 17
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 claims description 12
- 238000003672 processing method Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 abstract description 42
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 5
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 abstract description 3
- 125000004422 alkyl sulphonamide group Chemical group 0.000 abstract description 3
- 125000003277 amino group Chemical group 0.000 abstract description 2
- 238000004040 coloring Methods 0.000 abstract description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 67
- 239000000975 dye Substances 0.000 description 55
- 239000000839 emulsion Substances 0.000 description 52
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 40
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 29
- 238000005406 washing Methods 0.000 description 25
- 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 20
- 230000000087 stabilizing effect Effects 0.000 description 16
- 108010010803 Gelatin Proteins 0.000 description 15
- 229920000159 gelatin Polymers 0.000 description 15
- 239000008273 gelatin Substances 0.000 description 15
- 235000019322 gelatine Nutrition 0.000 description 15
- 235000011852 gelatine desserts Nutrition 0.000 description 15
- 238000003860 storage Methods 0.000 description 14
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 13
- 235000019445 benzyl alcohol Nutrition 0.000 description 13
- 230000000694 effects Effects 0.000 description 13
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 10
- 238000000576 coating method Methods 0.000 description 9
- 235000019441 ethanol Nutrition 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- 230000001235 sensitizing effect Effects 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 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 8
- 230000008961 swelling Effects 0.000 description 8
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 8
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 7
- 238000005859 coupling reaction Methods 0.000 description 7
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000470 constituent Substances 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 6
- 239000003381 stabilizer Substances 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- XNCSCQSQSGDGES-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]propyl-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)C(C)CN(CC(O)=O)CC(O)=O XNCSCQSQSGDGES-UHFFFAOYSA-N 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000007844 bleaching agent Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 150000007524 organic acids Chemical class 0.000 description 5
- 235000005985 organic acids Nutrition 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000002738 chelating agent Substances 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 150000004820 halides Chemical class 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 230000005070 ripening Effects 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- RNMCCPMYXUKHAZ-UHFFFAOYSA-N 2-[3,3-diamino-1,2,2-tris(carboxymethyl)cyclohexyl]acetic acid Chemical compound NC1(N)CCCC(CC(O)=O)(CC(O)=O)C1(CC(O)=O)CC(O)=O RNMCCPMYXUKHAZ-UHFFFAOYSA-N 0.000 description 3
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 3
- KWYJDIUEHHCHCZ-UHFFFAOYSA-N 3-[2-[bis(2-carboxyethyl)amino]ethyl-(2-carboxyethyl)amino]propanoic acid Chemical compound OC(=O)CCN(CCC(O)=O)CCN(CCC(O)=O)CCC(O)=O KWYJDIUEHHCHCZ-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 3
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical group NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 206010070834 Sensitisation Diseases 0.000 description 3
- 229910021612 Silver iodide Inorganic materials 0.000 description 3
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 3
- MJOQJPYNENPSSS-XQHKEYJVSA-N [(3r,4s,5r,6s)-4,5,6-triacetyloxyoxan-3-yl] acetate Chemical compound CC(=O)O[C@@H]1CO[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O MJOQJPYNENPSSS-XQHKEYJVSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 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
- 239000002131 composite material Substances 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 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
- 230000008313 sensitization Effects 0.000 description 3
- 229940045105 silver iodide Drugs 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- JKRNNIGZNCVVHA-UHFFFAOYSA-N 2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate;trimethylazanium Chemical compound C[NH+](C)C.C[NH+](C)C.C[NH+](C)C.C[NH+](C)C.[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O JKRNNIGZNCVVHA-UHFFFAOYSA-N 0.000 description 2
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- VYTBPJNGNGMRFH-UHFFFAOYSA-N acetic acid;azane Chemical compound N.N.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O VYTBPJNGNGMRFH-UHFFFAOYSA-N 0.000 description 2
- LRSAWRZHGQQHBJ-UHFFFAOYSA-N acetic acid;benzene-1,2-diamine Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.NC1=CC=CC=C1N LRSAWRZHGQQHBJ-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- 239000000298 carbocyanine Substances 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- DEFVIWRASFVYLL-UHFFFAOYSA-N ethylene glycol bis(2-aminoethyl)tetraacetic acid Chemical compound OC(=O)CN(CC(O)=O)CCOCCOCCN(CC(O)=O)CC(O)=O DEFVIWRASFVYLL-UHFFFAOYSA-N 0.000 description 2
- 238000005562 fading Methods 0.000 description 2
- 239000006081 fluorescent whitening agent Substances 0.000 description 2
- 108010025899 gelatin film Proteins 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 2
- BVJSUAQZOZWCKN-UHFFFAOYSA-N p-hydroxybenzyl alcohol Chemical compound OCC1=CC=C(O)C=C1 BVJSUAQZOZWCKN-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- LQPLDXQVILYOOL-UHFFFAOYSA-I pentasodium;2-[bis[2-[bis(carboxylatomethyl)amino]ethyl]amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC(=O)[O-])CCN(CC([O-])=O)CC([O-])=O LQPLDXQVILYOOL-UHFFFAOYSA-I 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- GQSUOICHNSYYFD-UHFFFAOYSA-M sodium;cyanoformate Chemical compound [Na+].[O-]C(=O)C#N GQSUOICHNSYYFD-UHFFFAOYSA-M 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- KAMCBFNNGGVPPW-UHFFFAOYSA-N 1-(ethenylsulfonylmethoxymethylsulfonyl)ethene Chemical compound C=CS(=O)(=O)COCS(=O)(=O)C=C KAMCBFNNGGVPPW-UHFFFAOYSA-N 0.000 description 1
- GGZHVNZHFYCSEV-UHFFFAOYSA-N 1-Phenyl-5-mercaptotetrazole Chemical compound SC1=NN=NN1C1=CC=CC=C1 GGZHVNZHFYCSEV-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- FITNPEDFWSPOMU-UHFFFAOYSA-N 2,3-dihydrotriazolo[4,5-b]pyridin-5-one Chemical compound OC1=CC=C2NN=NC2=N1 FITNPEDFWSPOMU-UHFFFAOYSA-N 0.000 description 1
- IVRVINRWGRWDRQ-UHFFFAOYSA-N 2-(2,2-dihydroxyethylamino)acetic acid;2-hydroxypropane-1,2,3-tricarboxylic acid Chemical compound OC(O)CNCC(O)=O.OC(=O)CC(O)(C(O)=O)CC(O)=O IVRVINRWGRWDRQ-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 description 1
- JVXHQHGWBAHSSF-UHFFFAOYSA-L 2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate;hydron;iron(2+) Chemical compound [H+].[H+].[Fe+2].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O JVXHQHGWBAHSSF-UHFFFAOYSA-L 0.000 description 1
- JESFPXPFYDUKJP-UHFFFAOYSA-N 2-methyl-1,3-benzothiazol-3-ium;chloride Chemical compound Cl.C1=CC=C2SC(C)=NC2=C1 JESFPXPFYDUKJP-UHFFFAOYSA-N 0.000 description 1
- KRTDQDCPEZRVGC-UHFFFAOYSA-N 2-nitro-1h-benzimidazole Chemical compound C1=CC=C2NC([N+](=O)[O-])=NC2=C1 KRTDQDCPEZRVGC-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- RYYXDZDBXNUPOG-UHFFFAOYSA-N 4,5,6,7-tetrahydro-1,3-benzothiazole-2,6-diamine;dihydrochloride Chemical compound Cl.Cl.C1C(N)CCC2=C1SC(N)=N2 RYYXDZDBXNUPOG-UHFFFAOYSA-N 0.000 description 1
- LRUDIIUSNGCQKF-UHFFFAOYSA-N 5-methyl-1H-benzotriazole Chemical compound C1=C(C)C=CC2=NNN=C21 LRUDIIUSNGCQKF-UHFFFAOYSA-N 0.000 description 1
- 102000009027 Albumins Human genes 0.000 description 1
- 108010088751 Albumins Proteins 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LEVWYRKDKASIDU-QWWZWVQMSA-N D-cystine Chemical compound OC(=O)[C@H](N)CSSC[C@@H](N)C(O)=O LEVWYRKDKASIDU-QWWZWVQMSA-N 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical group CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 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
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical group NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
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- 229910019142 PO4 Inorganic materials 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
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- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
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- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 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
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- QMHAHUAQAJVBIW-UHFFFAOYSA-N [methyl(sulfamoyl)amino]methane Chemical compound CN(C)S(N)(=O)=O QMHAHUAQAJVBIW-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 1
- HTKFORQRBXIQHD-UHFFFAOYSA-N allylthiourea Chemical compound NC(=S)NCC=C HTKFORQRBXIQHD-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229940107816 ammonium iodide Drugs 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
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- 125000004391 aryl sulfonyl group Chemical group 0.000 description 1
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- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- 229910001864 baryta Inorganic materials 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
- 150000001556 benzimidazoles Chemical class 0.000 description 1
- 238000009835 boiling Methods 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
- 229940006460 bromide ion Drugs 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Chemical group 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- ZEUDGVUWMXAXEF-UHFFFAOYSA-L bromo(chloro)silver Chemical compound Cl[Ag]Br ZEUDGVUWMXAXEF-UHFFFAOYSA-L 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 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
- 239000000460 chlorine Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical compound NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 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
- 229960003067 cystine Drugs 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- KZNICNPSHKQLFF-UHFFFAOYSA-N dihydromaleimide Natural products O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- FGRVOLIFQGXPCT-UHFFFAOYSA-L dipotassium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [K+].[K+].[O-]S([O-])(=O)=S FGRVOLIFQGXPCT-UHFFFAOYSA-L 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229940091173 hydantoin Drugs 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions 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
- 230000007257 malfunction Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000006174 pH buffer Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229940067107 phenylethyl alcohol Drugs 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- QWYZFXLSWMXLDM-UHFFFAOYSA-M pinacyanol iodide Chemical compound [I-].C1=CC2=CC=CC=C2N(CC)C1=CC=CC1=CC=C(C=CC=C2)C2=[N+]1CC QWYZFXLSWMXLDM-UHFFFAOYSA-M 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002006 poly(N-vinylimidazole) polymer Polymers 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 1
- 229940116357 potassium thiocyanate Drugs 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical compound O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 1
- NDGRWYRVNANFNB-UHFFFAOYSA-N pyrazolidin-3-one Chemical class O=C1CCNN1 NDGRWYRVNANFNB-UHFFFAOYSA-N 0.000 description 1
- MCSKRVKAXABJLX-UHFFFAOYSA-N pyrazolo[3,4-d]triazole Chemical compound N1=NN=C2N=NC=C21 MCSKRVKAXABJLX-UHFFFAOYSA-N 0.000 description 1
- 239000001044 red dye Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000015067 sauces Nutrition 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 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
- 230000003381 solubilizing effect Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 150000003567 thiocyanates Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 1
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 210000004885 white matter Anatomy 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
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/407—Development processes or agents therefor
- G03C7/413—Developers
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Abstract
Description
〔産業上の利用分野〕
本発明はハロゲン化銀カラー写真感光材料（以下感光材
料という。）の発色現像処理方法に関し、詳しくは、極
めて短時間の発色現像処理を行っても安定な色素濃度が
得られ、かつ暗所に於ける保存安定性に浸れた画像が得
られ、かつ水洗をせずに補充量の少ない安定液で処理す
ることの出来る迅速な無水洗安定化処理方法に関するも
のである。
〔従来技術〕
カラー感光材料の処理は、基本的には発色現像と脱銀、
水洗の３工程からなり、脱銀は漂白と定着工程又は漂白
と定着を同一浴で行う漂白定着工程のいずれかになる。
最近では水洗工程の代りに安定化処理と呼ばれる無水洗
処理が提案され、発色現像、漂白定着、安定処理の３工
程からなる処理が盛んに行なわれていることは周知であ
る。
これらのカラー写真システムにおいては、一般に写真乳
剤層中に非拡散性のカプラーを含有させ、発色現像液中
の発色現像主薬で現像するが、発色現像液中に拡散性の
水溶性カプラーを含有せしめカプリング反応を写真材料
中で起こさしめる方法も知られているっ又感光材料中に
含有せしめろカプラーは一般には非水溶性の高沸点有機
溶媒に分散せしめ添加することによって非拡散性を持た
せることが行われている。
この方法はカプラーに高分子のアルキル側鎖をパラスト
基とに導入せしめ非拡散性とするよりは色再現性、色純
度、画像の保存安定性等の点で有利とされ壬極めて一般
的に行われている。
〔発明が解決しようとしている問題点〕このような感光
材料を処理する発色現鐵液には芳香渡第１級アミンカラ
ー現像主薬と貧溶解性の有機溶媒（ｌｏｇ ｐ ０．４
以上の溶媒）が含有されることも周知である。この種の
有機溶媒として最も良く知られているものは、貧溶解性
アルコールであり、カラー現像主薬と画像形成カップラ
ーとの反応を促進するため、すなわち、カップリング反
応の効率を高めるために用いられる。この種のアルコー
ルはしばしば゛現像促進剤“又は゛現像ブースター“と
呼ばれろ。米国特許２，３０４，９２５号又は第３．８
１４，６０６号明細書にみられるようにベンジルアルコ
ールが特にこの目的に有効である。
カップラーを分散したオイル球中に発色現像主薬を短時
間に多量供給せしめること、更に現像液バルク中よりも
膨潤したゼラチン被膜中に相対的に多量の発色現像主薬
を分配させるために、発色現像が促進されろと考えられ
ている貧溶解性アルコール、即ちベンジルアルコールの
如き物質を用いることは処理中の感光材料中のオイルや
ゼラチン中での発色現像主薬の濃度が高いため現像後の
残留濃度も高くなるという欠点を持ち、色素画像の保存
安定性を悪化させる最大の原因となっていた。更にこの
問題を顕在化させ、強調したのは処理時間の合計が短縮
された昨今の迅速化処理であり、更にも５１つの大きな
原因は多量の水洗水が供給され、感光材料がきれいに洗
浄されていた水洗処理という処理工程が写真処理から取
り除かれわずかの補充量が供給される安定化処理が水洗
処理にとって代って行われ始めたことである。これらの
無水洗安定化処理は、特開昭５８−１４８３４号、同５
８−１０５１４５号、同５８−１３４６３４号、同５８
−１８６３１号、並びに特願昭５８−２７０９号、同５
９−８９２８８号等の明細書に詳細が延べられている。
これらの方法ではいずれも感光材料中のゼラチン膜に吸
着した発色現像主薬やカップラー分散オイル中に分配し
た発色現像主薬を充分洗浄し、残留濃度を低下せしめる
ことができないために色素画像の保存安定性が著しく劣
化することである。
更に全く別の問題としてｌｏｇ ｐが０．４以上のベン
ジルアルコールの如き貧溶解性の溶媒は、水中に於ける
これら化合物の溶解性が乏しいため長い間離しい問題を
生じてきた。たとえば現像液を調整する際にはベンジル
アルコールの溶解はきわめて緩慢な傾向を示し、徹底的
な強制的攪拌および／又は溶解水の加熱を必要とする。
ベンジルアルコールが一部分でも不溶解で残るとこの部
分に発色現像主薬が高濃度に分配し溶解するため数日後
に酸化されて“タール“の生成を見るという重大な故障
を紹くことになる。
ベンジルアルコールをカラー現像液中に含有せしめる一
解決方法はｌｏｇ ｐが０．４未満の水以外の溶媒たと
エバエチレングリコールやジエチレングリコール、又は
ポリエチレンイミン、トリエタノールアミン等を添加す
ることＫより、ベンジルアルコールを可溶化させる方法
が知られている。
この方法は米国特許第３，５７４，６１９号明細書に記
載されている。更にこのベンジルアルコールの如き溶媒
の欠点は発色現像主薬の液中の溶解性を悪化させるため
にカラー現像液中の発色現像主薬の濃度が充分高められ
ず、思ったより現像が促進されず迅速化は中途半端とな
っていることである。
特に重大な問題は作業が省力化できる点で有利とさせる
補充量が少なくてすむ濃厚低補充処理がベンジルアルコ
ールを含む現像液の場合には補充液に溶解できる発色現
像主薬の量に限界があり、一定量以上濃厚化できない点
にある。
それゆえに、ピラゾリドン誘導体を感光材料中に含有さ
せ、発色現像液中のベンジルアルコールを低濃度に抑え
る方法も知られている（特開昭５８−５０５３２ ）。
しかしながら、これによっても迅速化は十分でなく、一
定時間以上の処理時間が必要なことと、カップリング反
応にくらべ、銀現像反応のみが速められるために、結果
的には十分な色素濃度を得ることができない。
本発明者らは、これらの問題を解決するためにｔｏｇ
ｐが０．５以上の貧溶解性浴媒を実質的に含有せず、特
定の発色現像主薬を一定濃度以上含ｇｐＨ１０，３以上
の高アルカリ現像液にて、実質的に塩臭化銀乳剤からな
るカラー写真材料を処理することを提案した。このこと
により、色素画像の保存安定性を高め、かつ貧溶解性溶
媒を使用せずとも、カンプリング反応のスピードを高め
ることが可能となった。
しかしながら、さらに短時間迅速処理を達成しようとす
ると、カプラーと発色現像主薬の酸化物とのカップリン
グスピードが十分に達しているために、・。ゲン化銀の
現像スピードの方がかえって律速となるためか、十分な
色素濃度を得ることができない。
また一方、経済上および公害上の問題から発色現像液の
オーバーフロー液を減少させることが近年盛んに行われ
ている。特に少量処理ラボが台頭して（るにおよんで、
補充液を濃縮化し、少量補充する所謂濃厚低補充方式が
行われ、さらなる低補充のニーズも高まっている。
しかしながら補充量を低減すると感光材料中から溶出す
るハロゲンイオン等の現像抑制物質の濃度が高まり、ハ
ロゲン化銀の現像スピードが抑制されるため貧溶性有機
溶媒が存在しないような系では、短時間処理による色素
濃度の低下は拡大されることが判明した。
また、低補充を行うことにより、処理液の停滞時間が延
び、発色現像主薬の酸化体等の濃度が上昇するため、か
ぶりを生じ易いという問題も起っている。
〔発明の目的〕
本発明の目的は、第１に迅速で安定な色素画像を得られ
ろカラー写真感光材料の処理方法を提供することにあり
、第２には水洗処理をなくし、水質源を守り、かつ、処
理した写真材料に有害な処理薬品が残留せず、安全−〇
かつ保存の優れたカラー写真の得られる処理方法を提供
するにあり、第３には溶解が容易で簡単に処理液が調整
できるカラー写真処理方法を提供するにある。
本発明の他の目的は、本明細書の以下の記載から明らか
となろう。
〔問題を解決するための手段〕
本発明者らは、上述の本発明の目的を達成するために種
々検討した結果、実質的に塩臭化銀からなるハロゲン化
銀カラー写真感光材料を発色現像、漂白定着、安定化処
理の３工程にて処理する処理方法において、発色現像液
がｐＨ１０，３以上で、アルキルスルホンアミドアルキ
ル基を芳香核上又はアミン窒素に結合したｐ−フェニレ
ンジアミン系の発色現像生薬の少くとも１種を少くとも
１．５×１０ モル含有し、溶媒が水と水以外のｌｏ
ｇ ｐ ０．３未満の溶媒の容量に対するｌｏｇ ｐ
０．４以上の溶媒の容量の比が０．００３以下の溶媒か
ら構成されており、現像が３０℃以上であり１２０秒以
内にて下記一般式〔Ｉ〕で示される化合物の少くとも一
種の存在下に処理することにより達成されることを見い
出したものである。
Ｒ。
式中、Ｘは水素原子又はアセチル基を表わし、Ｒ１はア
リール基を表わし、Ｒ２ｒ Ｒ３、Ｒ４及びＲ３はそれ
ぞれ水素原子、ハロゲン原子、アルキル基又はアリール
基を表わす。
本発明は特定の発色現像主薬と特定の発色現像液のｐＨ
，及び特定のハロゲン化銀乳剤の組み合わせることによ
って、カラー画像の画像安定性を損わずにカプラーと発
色現像主薬とのカップリング速度を高めた状態で、さら
に特定の現像促進剤を用いることにより達成されるが詳
しくは後述する。
本発明者らは、本発明の一般式で示される現像促進剤が
貧溶性有機溶媒が実質的に存在せず、本発明の発色現像
主薬を一定濃度以上含む高ｐＨの発色現像液で処理した
場合に９０秒以下の短時間迅速処理において、特異的に
有効果であることを見い出した。貧溶性有機溶媒が実質
的に存在せず、本発明の発色現像主薬を一定濃度以上含
む高ｐＨの発色現像液で処理することにより、カプラー
と発色現像主薬とのカップリングスピードを迅速化させ
、さらに本発明の現像促進剤を使用することにより、お
そらくハロゲン化銀の現像スピードを迅速化させ、カッ
プリングスピードとハロケン化銀の現像スピードの両君
が等しくなった時に色素の形成スピードが最大の効率で
行われ、極めて高い迅速性が得られ、本発明の目的を達
成するに至ったものである。
また、補充量の減少による臭化物イオンの如き、ハロゲ
ンイオンや有機抑制剤の蓄積増加に効果を発揮し、その
蓄積量が多いほど有効果であるため、極端な低補充化が
可能であることも判明した。
更に本発明者らは検討を続けた結果、ハロゲン化銀乳剤
が塩臭化銀であり、特に臭化銀含有率が９０モル％以下
であり、乳剤のバインダーの膜膨潤速度Ｔ１／２がｍ秒
以下である場合であり、かつ、発色現像処理が３０秒以
下で処理した場合には、本発明の効果は著しく得られる
。
即ち、色素画像の安定性を損わず、極めて高い迅速性と
極端な低補充化が得られるという驚くべき事実を発見す
るに至り、本発明の目的を達成することに成功したもの
である。
本発明の一般式〔Ｉ〕で表わされる化合物において、Ｘ
は好ましくｔ工水素原子である。
一般式〔Ｉ〕のＲ１で表わされるアリール基としては、
例えばフェニル基、ナフチル基等を挙げることができる
が、フェニル基が好ましい。このアリールえばアルキル
基（例えばメチル基、エチル基、プロピル基等）、ハロ
ゲン原子（例えば塩素原子、臭素原子等）、アルコキシ
基（例えばメトキシ基、エトキシ基、ブトキシ基等）、
アルキルスルホニル基、アリールスルホニル基、アミド
基（例えばメチルアミド基、エチルアミド基、スルホ基
等）等を挙げることができる。これらの置換基のうち好
ましくはメチル基である。これらの置換基は、１個又は
それ以上有することかでき、かつ任意の位置に有するこ
とができるが、アリール基がフェニル基の場合、その置
換基は４位が好ましい。
一般式〔Ｉ〕のＲ２、Ｒ３＋ Ｒ４及びＲ６において表
わされるアルキル基としては、好ましくは水素原子、ハ
ロゲン原子及び炭素数１〜１０個のアルキル基（例えば
メチル基、エチル基、ブチル基等）が挙げられる。この
アルキル基は置換基を有することカテキる。置換基とし
てはヒドロキシル基、アミン基、アシルオキシ基が好ま
しい。
またＲ２． Ｒ，、Ｒ，及びＲ５において表わされるア
リール基としては、例えばフェニル基、ナフチル基等が
挙げられ、好ましくはフェニル基である。
このアリール基はその任意の位置に１個又はそれ以上の
置換基を有していてもよく、置換基としては、例えばア
ルキル基（例えばメチル基、エチル基、プロピル基等）
、ハロゲン原子（例えば塩素原子、臭素原子等）、アル
コキシ基（例えばメトキシ基、エトキシ基等）及びヒド
ロキシル基等が挙げられる。
本発明に用いられる一般式〔Ｉ〕で表わされる化合物の
代表的具体例を以下に示すが本発明の化合物はこれらに
限定されない。
〔例示化合物〕
Ｉ ３ ＣＨ３Ｉ ４ Ｃ
ＨｓＩ −１９Ｉ −２０
１−２１Ｉ −２２
Ｉ −２３Ｉ −２４
Ｉ −２５１−２Ｇ
ＣＩ ＯＣＲ５Ｉ −
２７Ｉ −２８
Ｉ −３３Ｉ−馴
Ｉ −３５Ｉ −３６
Ｉ −３７Ｉ −３８
Ｈｓ
Ｉ
Ｉ −４５Ｉ −４６
上記の代表的な化合物のうち、本発明にとってより好ま
しいものは、Ｉ−１、Ｉ−２、Ｉ −４。
ｌ−１３，ｌ−１４，ｌ−１５，ｌ−１６，ｌ−１７，
Ｉ −１８、Ｉ −２３、ｌ−２４，ｌ−２５，Ｉ −
２６、ｌ−３４゜ｌ−３５，ｌ−３６，Ｉ−羽、ｌ−４
９である。
一般式〔Ｉ〕で表わされる化合物は、市販されているも
のがあるが、米国特許２，６８８．０２４号、同２，７
０４，７６２号、特開昭５６−６４３３９号及び同５８
−５０５３５号等に準じて合成することができる。
本発明の化合物〔Ｉ〕は、感光材料中に含有させてもよ
いし、また、発色現像液中に含有させてもよい。感光材
料中に添加する場合の化合物〔■〕の添加量は、ハロゲ
ン化銀１モル当り０．００１モル〜１モルであり、好ま
しくは０００５モル〜０．５モルである。
化合物〔■〕は、各乳剤層（青感層、緑感層、赤感層）
の各々に添加されてもよ（、又非乳剤である中間層や保
護層に添力ｎされても良い。また、全ての乳剤層に添加
してもよい。さらには乳剤隣接層÷に添ヵｎしてもよい
。一般的には下塗層、下塗層上農する最下層、または乳
剤層中の最下層に添加するのが好ましい。
添加方法は、乳剤中に直接分散するか、あるいは水又は
アルコール類に溶解した後忙、ゼラチン中もしくは乳剤
中に分散するのが好ましい。
本発明の一般式Ｃ１）で表わされる化合物の現像液中の
含有量は、化合物により異なるが、５ Ｘ １０”モル
／ｌ〜５×１０ モル／ｌが好ましく、より好ましくば
５×１０ モル／ｌ〜５×１０ モル／ｌである。
本発明の一般式ＣＩＩで表わされる化合物は、現像液中
に直接添加されてもよいし、前浴中に添加されハロゲン
化銀カラー写真感光材料によって持ち込まれてもよい。
本明細書において、「実質的に塩臭化銀乳剤」とは、塩
臭化銀の他に微量の沃化銀を含んでもよいことであり、
例えば０．３モ内下、より好ましくは０．１モル以下の
沃化銀を含有してもよいことを意味する。しかしながら
本発明では沃化銀を含まない塩臭化銀乳剤が最も好まし
い。
以下、本発明について更に詳述する。
カラー写真感光材料の−・ロダン化銀を塗布するために
使用する親水性のバインダーは、ｋ’ＦＸはゼラチンを
使用するが、高分子ポリマーを用〜゛る場合もあり、膜
膨潤速度Ｔ１／２が２０秒より小さくなければならず、
バインダーの膜膨潤速度Ｔ１／２ばこの技術分野におい
て公知な任意の手法に従い測定することができ、例えば
Ａ、Ｇｒｅｃｎ及びＧ、 １． Ｐ。
Ｌｅｖｅｎｓｏｎ、 Ｊ、 ｐｈｏｔｏ、 ｓｃｉ ・
・・２０ 、Ｐ ２０５〜２１０に記載のタイプのスエ
ロメータ（膨潤膜）を使用することによって測定するこ
とかでき、Ｔ１／２は発色現像で（９）℃、３分Ｉ秒処
理したときに到達する最大膨潤膜厚の９０％を飽和膜厚
とし、この１／２の膜厚に到達する迄の時間と定義する
（第２図参照）。
本発明のハロゲン化銀カラー写真感光材料に用いられる
写真荷成層のバインダーは、その膨潤速度Ｔ１／２が囚
秒以下であり、小さい程好ましいが、下限はあまり小さ
いと硬膜されずにスクラッチ等の故障が生じ易くなるた
め２秒以上が好ましい。特に好ましくは、１５秒以下、
最も好ましくは１０秒以下である。２０秒より大の場合
は色素画像の保存安定性が低くなる傾向があり、かつ充
分迅速な現像時間も得られず短時間に充分な色素形成が
得られない。膜膨潤速度Ｔ１／２は硬膜剤の使用量によ
って調望することができる。
本発明によって処理されるハロゲン化銀カラー写真感光
材料の感光性乳剤層は、少なくともその１層が゛実質的
に塩臭化銀乳剤から成ればよいが、感光性乳剤層の全て
が塩臭化銀乳剤から成ることが好ましい。該塩臭化銀は
臭化銀のモル％が小さい程、発色現像が短時間でも充分
な色素形成が得られるため、臭化銀含有率９０モル％以
下が好ましり、７０モル％以下４０モル％以上が最も好
ましい結果となる。
更に塗布銀量は小さい程、短時間でも充分な色素形成が
行える点で好ましく、１ｆｌ／ｒｒｌ以下、特に好まし
くは０．８．！７／ゴ以下、更に０．７．９層ｍ：以下
のとき最大の効果が得られる。発色現像の処理は３０℃
以上、１２０秒以下、好ましくは３３℃以上、１２０秒
以下、特に好ましくは３３℃以上、９０秒以下、最も好
ましくは３３℃以上６０秒以下で処理することであり、
３０℃以上、１５０秒以上の処理を行うときには色素の
保存安定性が悪化する。特に温度より処理時間が重要で
あり、１５０秒を越えると赤色色素の暗褪色性が著しく
低下し好ましくない。処理温度に色素の保存安定性より
むしろ短時間に現像を終了させるために上昇させるもの
であり、３０ ’Ｃ以上、５０℃以下であれば高い程短
時間処理が可能となり好ましいが、画像保存安定性から
はあまり高（ない方が良く、３３℃以上、４５℃以下で
処理することが望ましい。
本発明で現像液中に添力ｎされる事が好ましくないｌｏ
ｇ ｐ ０．４以上の溶媒とは、脂肪族アルコール、脂
肪族グリコールエーテル、脂環式アルコール又は芳香族
アルコールでありこれらのうち炭素数５〜２０個のもの
である。具体例としては、ベンジルアルコール
ｌｏｇ ｐ １．１００−ヒドロキシベンジルアル
コール ｌｏｇ ｐ ０．７３シクロヘキサンール
ｌｏｇ ｐ １．２３２−ベンジルオキシエ
タノール ｌｏｇ ｐ ０．４１ァニシルアルコー
ル ｌｏｇ ｐ ０．７０１−ペンタノー
ル
フェニルエチルアルコール ｌｏｇ ｐ １．３
６ｐ−トリルカルビノール
ｎ−ブタノール ｌｏｇ ｐ Ｏ．
４以上フェノール ｌｏｇ ｐ
０．４以上ｐ−ヒドロキシベンジルアルコール ｌｏ
ｇ ｐ ０．４以上ベンジルアミン
ｌｏｇ ｐ Ｏ．４以上ジエチレンクリコールモノプ
チルエーｆルｌｏｇ ｐ Ｏ．４ １などがあげられる
。
ｆ；、 タｌｏｇ ｐ Ｏ．４未満の溶媒としては脂肪
族アルコール、有機酸など炭素数０〜４までのものが主
でれないが具体例としては、
酢酸
エタノール
アセトン
プロピオン酸
プロパツール
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
トリエタノールアミン
ジェタノールアミン
等があげられる。
本発明において、特に好ましく゛ｐーフェニレンジアミ
ン系カラー現像主薬は芳香核又はアミノ窒素に結合した
アルキルスルホンアミドアルキル置換基を少（とも１個
有するものであり、具体的には
Ｈ２
ｈ２
Ｈ２
（“ｌ ＣＨ８ＳＯ２ＮＨＣ，臥、・°″ＮＨ。
等があげられる。
これらの発色現像剤は塩酸塩、硫酸塩、隣酸塩、ｐ−）
ルエン硫酸塩等塩の型で使用される。
本発明の発色現像液のｐＨは１０．３以上で使用するが
、好ましくは１０．５０以上、特に好ましくは１０、７
５以上であり、上限は写真乳剤のカプリ性と関係するが
、一般には高い程好ましくｉｏ．ｓ〜１３の範囲で使用
される。
本発明では発色現像主薬の水に対する溶解度は著しく高
いため、その使用量は処理液１１当り１、５×１０モル
の範囲で使用することが好ましく、より好ましくは１．
５〜１５ Ｘ １０モルの範囲で使用される。
これら本発明のアルキルスルホンアミドアルキル置換−
Ｐ−フェニレンジアミン誘導体は、ジャーナル オプ
アメリカン ケミカル ソサイアティー７３巻， ３１
００項（１９５１年）に記載の方法で容易に合成できる
。
本発明の発色現像液は臭化物イオン濃度が５×１０ モ
ル以上であることが好ましいが、本発明では臭化物は高
い程補充量が下げられるため好ましい。
従来の現像方式では臭化物は現像反応を抑制し低い程好
ましいとされていたが、本発明のカラー写真感光材料と
現像液の組合せでは、本発明のカラー写真感光材料は青
感性乳剤層、緑感性乳剤層、赤感性乳剤層の各々を含む
３層以上の多層カラー写真感光材料において、その膜膨
潤時間が最大となる迄の時間の１／２即ち膜膨潤速度Ｔ
１／２が２０秒以下である時に最大の効果を発揮するが
、その金膜の厚みは乾燥時に１３μｍ以下、好ましくは
１２μｍ以下、特に好ましくは１０μｍ以下であるが、
いずれの場合にもＴ１／２は２０秒以下であることが好
ましい。
本発明の写真感光材料の処理方式は、前記本発明に係わ
る発色現像主薬を含有する発色現像液を用いることが可
能である。また、浴処理を始めとして他の各種の方法、
例えば処理液を噴霧状にするスプレ一式、又は処理液を
含浸させた担体との接触によるウェッブ方式、あるいは
粘性処理液による現像方法等各種の処理方式を用いるこ
ともできるが、処理工程は実質的に発色現像、漂白定着
、及び安定化処理の３工程からなる。
本発明において用いられる発色現像液には、更に通常添
加されている種々の成分、例えば水酸化ナトリウム、炭
酸ナトリウム等のアルカリ剤、アルカリ金属亜硫酸塩、
アルカリ金属亜硫酸水素塩、アルカリ金属チオシアン酸
塩、アルカリ金属ノ）ロダン化物、ポリスチレンスルフ
ォン酸、水軟化剤、エチレングリコール、ジエチレング
リコール、トリエタノールアミン、濃厚化剤および現像
促進剤等を任意に含有させることもできる。
前記発色現像液に添加される上記以外の添加剤としては
、例えば臭化カリウム、臭化アンモニウム等の臭化物、
沃化アルカリ、ニトロベンゾイミダゾール、メルカプト
ベンシイミグゾール、５−メチル−ベンゾトリアゾール
、１−フェニル−５−メルカプトテトラゾール等の迅速
処理液用化合物を始めとして、スティン防止剤、スラッ
ジ防止剤、保恒剤、重層効果促進剤、キレート剤等があ
る。
また、発色現像液中に添加される臭化カリウム、臭化ア
ンモニウム等の臭化物イオンの濃度は感光材料甲に含有
される量と、発色現像液の補充量によって決まるが、本
発明の効果をより効果的に発揮させるためには、発色現
像液１１当９０．２ ｇ以上が好ましく、さらに好まし
くは０．５．９以上である。
現像液中のキレート剤としては、アミノポリカルボン酸
塩や有機ホスホン酸塩が主に使用される。
本発明における水洗代替安定液のｐＨは本発明をより効
果的に達成するためには、好ましくは５．５〜１０．０
の範囲であり、更に好ましくはｐＨ６，３〜９．５の範
囲であり、特に好ましく ｈｘ ｐ ７．０〜９．０の
範囲である。本発明の水洗代替安定液に含有することが
できるｐＨ調整剤は、一般に知られているアルカリ剤ま
たは酸剤のいかなるものも使用できる。
本発明は安定浴への水洗代替安定液の補充量が少ない場
合に効果が大きく、該補充量が処理される感光材料の単
位面積当たりの前浴からの持ち込−み量の１〜５０倍の
範囲が好ましく、２〜２０倍の範囲において本発明の効
果が特に顕著である。
安定化処理の処理温度は、１５℃〜６０℃、好ましくは
２０℃〜４５℃の範囲がよい。また処理時間も迅速処理
の観点から短時間であるほど好ましいが、通常加秒〜１
０分間、最も好ましくは１分〜３分であり、複数槽安定
化処理の場合は前段槽はど短時間で処理し、後段槽はど
処理時間が長いことが好ましい。特に前槽の加％〜５０
％増しの処理時間で順次処理する事が望ましい。本発明
による安定化処理の後には水洗処理を全（必要としない
が、極く短時間内での少量水洗によるリンス、表面洗浄
などは必要に応じて任意に行うことはできる。
本発明に係る安定化処理工程での水洗代替安定液の供給
方法は、多槽カウンターカレント方式にした場合、後浴
に供給して前浴からオーバーフローさせることが好まし
い。もちろん単槽で処理することもできる。上記化合物
を添加する方法としては、安定化槽に濃厚液として添加
するか、または安定化槽に供給する水洗代替安定液に上
記化合物及びその他の添加剤を加え、これを水洗代替安
定補充液に対する供給液とするか等各種の方法があるが
、どのような添加方法によって添加してもよい。
従来は、感光材料を発色現像後、漂白定着液で処理し、
次いで水洗代替安定液で処理する処理方法において、連
続処理の結果、水洗代替安定化処理の最終槽内の水洗代
替安定液の２４℃における比重が１．００２以上になる
と未露光部の汚染発生が甚しくなる傾向があるが、本発
明によればこのような条件における汚染発生も顕著に改
良される。
本発明において、漂白定着液で処理し、引き続いて実質
的に水洗することなく、水洗代替安定液で処理されろ、
即ち、漂白定着浴の次に直接水洗代替安定液で処理する
ことを示すものであり、この処理工程を工従来から知ら
れている漂白定着浴の後、水洗処理し、安定液で処理す
る工程とは全く異なっている。
このように本発明において、安定液による処理とは漂白
定着液による処理後直ちに安定化処理してしまい実質的
に水洗処理を行わない安定化処理のための処理を指し、
該安定化処理に用いる処理液を水洗代替安定液といい、
処理慴を安定浴又は安定槽という。
本発明において安定槽＆工１〜５槽であるとき本発明の
効果が太き（、特に好ましくは１〜３槽であり、多（て
も９槽以下であることが好ましい。
本発明に用いる漂白定着液に使用することができる漂白
剤は有機酸の金属錯塩である。該錯塩は、アミノポリカ
ルボン酸又は蓚酸、クエン酸等の有機酸で鉄、コバルト
、銅等の金属イオンを配位したものである。このような
有機酸の金属錯塩な形成するために用いられる最も好ま
しい有機酸としては、ポリカルボン酸が挙げられる。こ
れらのポリカルボン酸又はアミノポリカルボン酸はアル
カリ金属塩、アンモニウム塩もしくは水溶性アミン塩で
あっても良い。これらの具体例としては次の如きものを
挙げる事ができる。
〔１〕 エチレンジアミンテトラ酢酸〔２〕 ジエ
チレントリアミンペンタ酢酸〔３〕 エチレンジアミ
ン−Ｎ−（β−オキシエチル） −Ｎ、 Ｎ’、Ｎ’−
）り酢酸〔４〕 プロピレンジアミンテトラ酢酸〔５
〕 ニトリロトリ酢酸
〔６〕 シクロヘキサンジアミンテトラ酢酸〔７〕
イミノジ酢酸
〔８〕 ジヒドロキシエチルグリシンクエン酸（又は
酒石酸）[Industrial Field of Application] The present invention relates to a color development processing method for silver halide color photographic light-sensitive materials (hereinafter referred to as light-sensitive materials). The present invention relates to a rapid water-free stabilization processing method that allows images to be obtained that are highly stable in storage in the dark, and that can be processed without washing with water and with a small amount of stabilizing solution refilled. . [Prior art] Processing of color photosensitive materials basically involves color development, desilvering,
It consists of three steps: washing with water, and desilvering is either a bleaching and fixing step or a bleach-fixing step in which bleaching and fixing are performed in the same bath. Recently, instead of the water-washing process, a waterless washing process called stabilization process has been proposed, and it is well known that the process consisting of the three steps of color development, bleach-fixing, and stabilization process is widely used. In these color photographic systems, a non-diffusible coupler is generally contained in the photographic emulsion layer, and development is carried out using a color developing agent in a color developing solution. Methods of causing a coupling reaction in a photographic material are also known.Furthermore, the coupler contained in a photographic material is generally made non-diffusible by being dispersed and added to a water-insoluble high-boiling organic solvent. is being carried out. This method is considered to be more advantageous in terms of color reproducibility, color purity, image storage stability, etc. than the method of introducing a polymer alkyl side chain into the coupler and making it non-diffusible, and is extremely commonly carried out. It is being said. [Problems to be solved by the invention] The color developing solution for processing such light-sensitive materials contains aromatic primary amine color developing agents and poorly soluble organic solvents (log p 0.4).
It is also well known that the above solvents are contained. The best known organic solvents of this type are poorly soluble alcohols, which are used to facilitate the reaction between color developing agents and imaging couplers, i.e. to increase the efficiency of the coupling reaction. . This type of alcohol is often referred to as a ``development accelerator'' or ``development booster.'' U.S. Patent No. 2,304,925 or 3.8
Benzyl alcohol is particularly useful for this purpose, as seen in US Pat. No. 14,606. In order to supply a large amount of color developing agent in a short time into the oil spheres in which the coupler is dispersed, and to distribute a relatively large amount of color developing agent into the swollen gelatin film than in the bulk of the developer, color development is performed. The use of poorly soluble alcohols, such as benzyl alcohol, which is thought to promote the process, increases the residual concentration after development due to the high concentration of the color developing agent in the oil and gelatin in the photosensitive material during processing. This has the disadvantage of being expensive, which is the biggest cause of deterioration in the storage stability of dye images. Furthermore, what has brought this problem to light and emphasized it is the recent rapid processing that has shortened the total processing time.Furthermore, the major cause is that a large amount of washing water is supplied, and the photosensitive materials are not washed properly. The processing step known as water washing was removed from photographic processing, and stabilization processing, in which a small amount of replenishment was supplied, began to replace washing. These waterless washing stabilization treatments are described in JP-A-58-14834 and JP-A-58-14834.
No. 8-105145, No. 58-134634, No. 58
-18631, and Japanese Patent Application No. 58-2709, same No. 5
Details are given in specifications such as No. 9-89288. In all of these methods, it is not possible to sufficiently wash the color developing agent adsorbed to the gelatin film in the light-sensitive material or the color developing agent distributed in the coupler dispersion oil and reduce the residual concentration, resulting in poor storage stability of the dye image. is markedly deteriorated. As a completely different problem, poorly soluble solvents such as benzyl alcohol with a log p of 0.4 or more have long caused separate problems due to the poor solubility of these compounds in water. For example, when preparing a developer solution, benzyl alcohol tends to dissolve very slowly, requiring extensive forced stirring and/or heating of the solution water. If even a portion of the benzyl alcohol remains undissolved, the color developing agent will be distributed and dissolved in this portion at a high concentration, resulting in oxidation and the formation of tar after a few days, resulting in a serious malfunction. One solution to incorporating benzyl alcohol into a color developer is to add a solvent other than water with a log p of less than 0.4 and evaporated ethylene glycol, diethylene glycol, polyethyleneimine, triethanolamine, etc. A method of solubilizing is known. This method is described in US Pat. No. 3,574,619. Furthermore, the disadvantage of a solvent such as benzyl alcohol is that it deteriorates the solubility of the color developing agent in the solution, so the concentration of the color developing agent in the color developing solution cannot be sufficiently increased, and development is not promoted as much as expected, making it difficult to speed up the process. This means that it is only half-hearted. A particularly serious problem is that when using a developer containing benzyl alcohol, there is a limit to the amount of color developing agent that can be dissolved in the replenisher. The problem is that it cannot be enriched beyond a certain amount. Therefore, a method is known in which a pyrazolidone derivative is contained in a light-sensitive material to suppress the concentration of benzyl alcohol in a color developing solution to a low level (Japanese Patent Laid-Open No. 58-50532). However, even this method does not speed up the process sufficiently; it requires a certain amount of processing time or more, and compared to the coupling reaction, only the silver development reaction is accelerated, resulting in sufficient dye density. I can't. In order to solve these problems, the present inventors
Substantially no silver chlorobromide emulsion containing a poorly soluble bath medium with p of 0.5 or more and containing a specific color developing agent at a certain concentration or more in a highly alkaline developer with a pH of 10.3 or more. proposed to process color photographic materials consisting of. This has made it possible to increase the storage stability of the dye image and to increase the speed of the camping reaction without using a poorly soluble solvent. However, when trying to achieve even faster processing in a shorter period of time, the coupling speed between the coupler and the oxide of the color developing agent has already reached a sufficient level. It is not possible to obtain a sufficient dye density, probably because the development speed of silver generide becomes rate-limiting. On the other hand, due to economic and pollution problems, efforts have recently been made to reduce the overflow of color developing solutions. Especially with the rise of small-volume processing laboratories (Luniyon),
A so-called concentrated low replenishment method, in which the replenisher is concentrated and replenished in small amounts, is being used, and the need for even lower replenishment is increasing. However, when the amount of replenishment is reduced, the concentration of development inhibiting substances such as halogen ions eluted from the photosensitive material increases, and the development speed of silver halide is suppressed. It was found that the decrease in dye density caused by Furthermore, low replenishment lengthens the stagnation time of the processing solution and increases the concentration of oxidized products of the color developing agent, resulting in the problem of easy fogging. [Object of the Invention] The object of the present invention is, firstly, to provide a method for processing color photographic materials that allows rapid and stable dye images to be obtained, and secondly, to eliminate the water washing process and to reduce the water quality source. The purpose of the present invention is to provide a processing method that can produce color photographs that are safe and have excellent storage properties, without leaving any harmful processing chemicals on the photographic materials that have been processed. To provide a color photographic processing method in which the liquid can be adjusted. Other objects of the invention will become apparent from the description below. [Means for Solving the Problem] As a result of various studies to achieve the above-mentioned object of the present invention, the present inventors developed a silver halide color photographic light-sensitive material consisting essentially of silver chlorobromide, which was developed by color development. , bleach-fixing, and stabilization processing, in which the color developing solution has a pH of 10.3 or higher, and p-phenylenediamine-based coloring in which an alkylsulfonamide alkyl group is bonded to an aromatic nucleus or to an amine nitrogen is used. Contains at least 1.5 x 10 mol of at least one crude drug for development, and the solvent is water or lo
log p for the volume of solvent with g p less than 0.3
It is composed of a solvent with a volume ratio of 0.4 or more and 0.003 or less, and development is performed at 30°C or higher and within 120 seconds, at least one of the compounds represented by the following general formula [I] We have discovered that this can be achieved by processing in the presence of R. In the formula, X represents a hydrogen atom or an acetyl group, R1 represents an aryl group, and R2r R3, R4 and R3 each represent a hydrogen atom, a halogen atom, an alkyl group or an aryl group. The present invention focuses on the pH of a specific color developing agent and a specific color developing solution.
, and a specific silver halide emulsion, the coupling rate between the coupler and the color developing agent is increased without impairing the image stability of the color image, and further by using a specific development accelerator. This will be achieved, but will be discussed in detail later. The present inventors have developed a method in which the development accelerator represented by the general formula of the present invention is substantially free of poorly soluble organic solvents and is treated with a high pH color developing solution containing the color developing agent of the present invention at a certain concentration or more. It has been found that in some cases, short-term rapid treatment of 90 seconds or less is particularly effective. By processing with a high pH color developing solution that is substantially free of poorly soluble organic solvents and contains the color developing agent of the present invention at a certain concentration or more, the coupling speed between the coupler and the color developing agent is accelerated, Furthermore, by using the development accelerator of the present invention, the development speed of the silver halide is presumably accelerated, and the dye formation speed is maximized when the coupling speed and the development speed of the silver halide are equal. The process was carried out efficiently and with extremely high speed, thus achieving the object of the present invention. In addition, it is effective in increasing the accumulation of halogen ions and organic inhibitors such as bromide ions by reducing the amount of replenishment, and the greater the amount of accumulation, the more effective it is, so extremely low replenishment is possible. found. Furthermore, as a result of continued studies, the present inventors found that the silver halide emulsion is silver chlorobromide, in particular, the silver bromide content is 90 mol% or less, and the film swelling rate T1/2 of the binder of the emulsion is m When the time is less than 30 seconds and the color development process is performed for 30 seconds or less, the effects of the present invention can be significantly obtained. That is, we have discovered the surprising fact that extremely high speed and extremely low replenishment can be obtained without impairing the stability of dye images, and we have succeeded in achieving the object of the present invention. In the compound represented by the general formula [I] of the present invention,
is preferably a hydrogen atom. As the aryl group represented by R1 in general formula [I],
For example, phenyl group, naphthyl group, etc. can be mentioned, but phenyl group is preferable. This aryl includes an alkyl group (e.g. methyl group, ethyl group, propyl group, etc.), a halogen atom (e.g. chlorine atom, bromine atom, etc.), an alkoxy group (e.g. methoxy group, ethoxy group, butoxy group, etc.),
Examples include an alkylsulfonyl group, an arylsulfonyl group, an amide group (eg, a methylamide group, an ethylamide group, a sulfo group, etc.). Among these substituents, a methyl group is preferred. One or more of these substituents may be present and may be present at any position; however, when the aryl group is a phenyl group, the substituent is preferably at the 4-position. The alkyl group represented by R2, R3+ R4 and R6 in general formula [I] is preferably a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, a butyl group, etc.). Can be mentioned. This alkyl group is classified as having a substituent. As the substituent, a hydroxyl group, an amine group, and an acyloxy group are preferred. Also R2. Examples of the aryl group represented by R, , R, and R5 include phenyl group, naphthyl group, etc., and phenyl group is preferable. This aryl group may have one or more substituents at any position thereof, such as an alkyl group (for example, a methyl group, an ethyl group, a propyl group, etc.).
, halogen atoms (eg, chlorine atoms, bromine atoms, etc.), alkoxy groups (eg, methoxy groups, ethoxy groups, etc.), and hydroxyl groups. Typical specific examples of the compound represented by the general formula [I] used in the present invention are shown below, but the compound of the present invention is not limited thereto. [Exemplary compound] I 3 CH3I 4 C
HsI -19I -20 1-21I -22 I -23I -24 I -251-2G CI OCR5I -
27I -28 I -33I-I -35I -36 I -37I -38 Hs I I -45I -46 Among the above representative compounds, those more preferred for the present invention are I-1, I-2, I-4. l-13, l-14, l-15, l-16, l-17,
I-18, I-23, l-24, l-25, I-
26, l-34゜l-35, l-36, I-feather, l-4
It is 9. Compounds represented by general formula [I] are commercially available, but US Pat.
No. 04,762, JP-A-56-64339 and JP-A No. 58
It can be synthesized according to No.-50535. The compound [I] of the present invention may be contained in a light-sensitive material or in a color developing solution. When added to the light-sensitive material, the amount of compound [■] added is 0.001 mol to 1 mol, preferably 0.005 mol to 0.5 mol, per 1 mol of silver halide. Compound [■] is added to each emulsion layer (blue-sensitive layer, green-sensitive layer, red-sensitive layer)
(or may be added to each of the non-emulsion intermediate layers and protective layers. Also, it may be added to all emulsion layers. Furthermore, it may be added to each layer adjacent to the emulsion divided by the layer adjacent to the emulsion. Generally, it is preferable to add it to the undercoat layer, the bottom layer above the undercoat layer, or the bottom layer of the emulsion layer.Addition methods include direct dispersion in the emulsion, Alternatively, it is preferable to dissolve the compound in water or alcohol and then disperse it in gelatin or in an emulsion.The content of the compound represented by the general formula C1) of the present invention in the developer solution varies depending on the compound, but 5 The amount of the compound represented by the general formula CII of the present invention is preferably from 10" mol/l to 5 x 10 mol/l, more preferably from 5 x 10 mol/l to 5 x 10 mol/l. It may be added directly, or it may be added in a pre-bath and brought into the silver halide color photographic light-sensitive material. In this specification, "substantially silver chlorobromide emulsion" means silver chloride bromide emulsion. In addition, it may contain a small amount of silver iodide,
For example, this means that silver iodide may be contained in an amount of 0.3 mole or less, more preferably 0.1 mole or less. However, silver chlorobromide emulsions containing no silver iodide are most preferred in the present invention. The present invention will be explained in more detail below. The hydrophilic binder used for coating silver rhodide in color photographic light-sensitive materials is gelatin in k'FX, but high-molecular polymers are also used in some cases, and the film swelling rate T1/ 2 must be less than 20 seconds,
The film swelling rate T1/2 of the binder can be measured according to any method known in the art, such as A, Grecn and G, 1. P. Levenson, J. photo, sci.
It can be measured by using a swellometer (swelling membrane) of the type described in ...20, pp. 205-210, and T1/2 is reached when color development is performed at (9) °C for 3 minutes and 1 seconds. The saturated film thickness is defined as 90% of the maximum swollen film thickness, and is defined as the time required to reach 1/2 of this film thickness (see Figure 2). The binder for the photographic layer used in the silver halide color photographic light-sensitive material of the present invention has a swelling rate T1/2 of less than a second, and the smaller the better, but if the lower limit is too small, the film will not be hardened and scratches may occur. 2 seconds or more is preferable because failures are likely to occur. Particularly preferably, 15 seconds or less,
Most preferably it is 10 seconds or less. If it is longer than 20 seconds, the storage stability of the dye image tends to be low, and a sufficiently rapid development time cannot be obtained, making it impossible to obtain sufficient dye formation in a short period of time. The membrane swelling rate T1/2 can be adjusted by adjusting the amount of hardener used. It is sufficient that at least one of the light-sensitive emulsion layers of the silver halide color photographic light-sensitive material processed according to the present invention "substantially consists of a silver chlorobromide emulsion, but all of the light-sensitive emulsion layers have a salt odor". Preferably, it is made of a silver oxide emulsion. As for the silver chlorobromide, the silver bromide content is preferably 90 mol% or less, and 70 mol% or less, because the smaller the mol% of silver bromide, the more sufficient dye formation can be obtained even in a short color development time. The most preferable result is when the amount is mol% or more. Further, the coating silver amount is preferably as small as possible in that sufficient dye formation can be achieved even in a short time, and 1 fl/rrl or less, particularly preferably 0.8. ! The maximum effect can be obtained when the thickness is 7/g or less, and further 0.7.9 layers m or less. Color development process at 30℃
As mentioned above, the treatment time is 120 seconds or less, preferably 33°C or more and 120 seconds or less, particularly preferably 33°C or more and 90 seconds or less, most preferably 33°C or more and 60 seconds or less,
When the treatment is carried out at 30° C. or higher and for 150 seconds or longer, the storage stability of the dye deteriorates. In particular, processing time is more important than temperature; if the processing time exceeds 150 seconds, the fading resistance of the red dye will be markedly reduced, which is not preferred. The processing temperature is raised to finish the development in a short time rather than the storage stability of the dye, and it is preferable that the temperature is higher than 30'C and lower than 50°C because the processing can be done in a shorter time, but the storage stability of the image is In terms of the properties, it is better not to have too high a temperature, and it is desirable to process at a temperature of 33°C or higher and 45°C or lower.
The solvent having a gp of 0.4 or more is an aliphatic alcohol, an aliphatic glycol ether, an alicyclic alcohol, or an aromatic alcohol, and among these, those having 5 to 20 carbon atoms are used. A specific example is benzyl alcohol
log p 1.100-hydroxybenzyl alcohol log p 0.73 cyclohexanol
log p 1.232-benzyloxyethanol log p 0.41anisyl alcohol log p 0.701-pentanol phenylethyl alcohol log p 1.3
6p-Tolylcarbinol n-butanol log p O.
4 or more phenols log p
0.4 or more p-hydroxybenzyl alcohol lo
g p 0.4 or more benzylamine
log p O. 4 or more diethylene glycol monobutyl ether log p O. 4 1 etc. f;, Talog p O. Examples of solvents with less than 4 carbon atoms include aliphatic alcohols and organic acids with carbon atoms of 0 to 4, but specific examples include: acetic acid ethanol acetone propionate propatool ethylene glycol diethylene glycol triethylene glycol triethanolamine jetanol Examples include amines. In the present invention, particularly preferred p-phenylenediamine color developing agents have at least one alkylsulfonamide alkyl substituent bonded to an aromatic nucleus or an amino nitrogen, specifically H2 h2 H2 ( These color developers include hydrochloride, sulfate, phosphate, p-).
It is used in the form of luene sulfate. The color developing solution of the present invention is used at a pH of 10.3 or higher, preferably 10.50 or higher, particularly preferably 10.7 or higher.
5 or more, and the upper limit is related to the capricity of the photographic emulsion, but generally the higher the io. It is used in the range of s to 13. In the present invention, the solubility of the color developing agent in water is extremely high, so the amount used is preferably within the range of 1.5 x 10 mol, more preferably 1.5 x 10 mol per 11 of the processing solution.
It is used in a range of 5 to 15 x 10 moles. These alkyl sulfonamide alkyl-substituted -
P-phenylenediamine derivatives are published in Journal Op.
American Chemical Society Volume 73, 31
It can be easily synthesized by the method described in Section 00 (1951). The color developing solution of the present invention preferably has a bromide ion concentration of 5 x 10 mol or more, and in the present invention, the higher the bromide, the lower the amount of bromide to be replenished. In conventional development methods, bromide suppresses the development reaction, and it has been said that the lower the bromide content, the better; however, in the combination of the color photographic light-sensitive material and developer of the present invention, the color photographic material of the present invention has a blue-sensitive emulsion layer, a green-sensitive emulsion layer, and a green-sensitive emulsion layer. In a multilayer color photographic material having three or more layers including each of an emulsion layer and a red-sensitive emulsion layer, the film swelling time is 1/2 of the time until the film reaches its maximum, that is, the film swelling rate T.
The maximum effect is exhibited when 1/2 is 20 seconds or less, and the thickness of the gold film when dried is 13 μm or less, preferably 12 μm or less, particularly preferably 10 μm or less,
In either case, T1/2 is preferably 20 seconds or less. In the processing method of the photographic light-sensitive material of the present invention, it is possible to use a color developing solution containing the color developing agent according to the present invention. In addition, various other methods including bath treatment,
For example, various processing methods can be used, such as a spray set in which the processing liquid is atomized, a web method in which contact is made with a carrier impregnated with the processing liquid, or a developing method using a viscous processing liquid. It consists of three steps: color development, bleach-fixing, and stabilization treatment. The color developer used in the present invention further contains various commonly added components, such as alkaline agents such as sodium hydroxide and sodium carbonate, alkali metal sulfites,
Optionally contain alkali metal bisulfite, alkali metal thiocyanate, alkali metal rhodanide, polystyrene sulfonic acid, water softener, ethylene glycol, diethylene glycol, triethanolamine, thickening agent, development accelerator, etc. You can also do it. Examples of additives other than the above added to the color developing solution include bromides such as potassium bromide and ammonium bromide;
Compounds for quick processing liquids such as alkali iodide, nitrobenzimidazole, mercaptobenziimiguzole, 5-methyl-benzotriazole, 1-phenyl-5-mercaptotetrazole, as well as anti-stain agents, anti-sludge agents, and preservatives. agents, interlayer effect promoters, chelating agents, etc. Furthermore, the concentration of bromide ions such as potassium bromide and ammonium bromide added to the color developer is determined by the amount contained in the photosensitive material A and the amount of replenishment of the color developer. In order to exhibit the effect effectively, the amount is preferably 90.2 g or more per 11 parts of the color developing solution, and more preferably 0.5.9 or more. As the chelating agent in the developer, aminopolycarboxylic acid salts and organic phosphonates are mainly used. In order to achieve the present invention more effectively, the pH of the water washing alternative stabilizer in the present invention is preferably 5.5 to 10.0.
The pH is more preferably in the range of 6.3 to 9.5, and particularly preferably the pH is in the range of 7.0 to 9.0. As the pH adjusting agent that can be contained in the water washing alternative stabilizer of the present invention, any commonly known alkaline agents or acid agents can be used. The present invention is most effective when the amount of water-washing substitute stabilizing solution refilled into the stabilizing bath is small, and the replenishing amount is 1 to 50 times the amount brought in from the previous bath per unit area of the photographic material to be processed. The effect of the present invention is particularly significant in a range of 2 to 20 times. The treatment temperature for the stabilization treatment is preferably in the range of 15°C to 60°C, preferably 20°C to 45°C. In addition, from the viewpoint of rapid processing, it is preferable that the processing time be as short as possible;
The treatment time is 0 minutes, most preferably 1 to 3 minutes, and in the case of stabilizing treatment with multiple tanks, it is preferable that the first stage tank be treated for a short time and the second stage tank be treated for a long time. Especially in the anterior tank ~50%
It is desirable to process sequentially with increasing processing time. After the stabilization treatment according to the present invention, it is not necessary to completely wash with water, but rinsing with a small amount of water within a very short period of time, surface cleaning, etc. can be performed as necessary. In the stabilization treatment process, when using a multi-tank counter current method, it is preferable to supply the stabilizing solution as an alternative to washing with water to the after bath and overflow from the front bath.Of course, it is also possible to process in a single tank.The above-mentioned The compound can be added as a concentrated liquid to the stabilization tank, or the above compounds and other additives may be added to the washing alternative stabilizing solution supplied to the stabilizing tank, and then added to the washing alternative stabilizing replenishment solution. There are various ways to add it, such as making it into a liquid, but it can be added by any method. Conventionally, after color development of a photosensitive material, it is treated with a bleach-fix solution.
Next, in the treatment method of processing with a washing substitute stabilizing solution, if the specific gravity of the washing substitute stabilizing solution at 24°C in the final tank of the washing substitute stabilization treatment becomes 1.002 or more as a result of continuous processing, contamination of the unexposed area will occur. According to the present invention, the occurrence of contamination under such conditions is also significantly improved, although this tends to be severe. In the present invention, processing with a bleach-fix solution and subsequent treatment with a water wash substitute stabilizing solution without substantial washing with water,
In other words, it indicates that a bleach-fix bath is followed by direct washing with a stabilizing solution instead of water, and this treatment process is a conventional process in which a bleach-fixing bath is followed by washing with water and then a stabilizing solution. It's completely different. In this way, in the present invention, treatment with a stabilizing solution refers to a treatment for stabilization treatment that is performed immediately after treatment with a bleach-fixing solution and does not substantially involve washing with water.
The processing liquid used for this stabilization treatment is called a water washing alternative stabilizing liquid,
The treatment chamber is called a stabilization bath or stabilization tank. In the present invention, the effect of the present invention is greater when the number of stabilizing tanks and tanks is 1 to 5 (especially preferably 1 to 3 tanks, and even more preferably 9 or less tanks. Bleaching agents that can be used in bleach-fix solutions are metal complex salts of organic acids.The complex salts coordinate metal ions such as iron, cobalt, copper, etc. with aminopolycarboxylic acids or organic acids such as oxalic acid and citric acid. The most preferred organic acids used to form metal complexes of such organic acids include polycarboxylic acids.These polycarboxylic acids or aminopolycarboxylic acids are It may be a salt or a water-soluble amine salt. Specific examples thereof include the following: [1] Ethylenediaminetetraacetic acid [2] Diethylenetriaminepentaacetic acid [3] Ethylenediamine-N-(β- (oxyethyl) -N, N', N'-
) triacetic acid [4] Propylenediaminetetraacetic acid [5]
] Nitrilotriacetic acid [6] Cyclohexanediaminetetraacetic acid [7]
Iminodiacetic acid [8] Dihydroxyethylglycine citric acid (or tartaric acid)
〔９〕 エチルエーテルジアミンテトラ酢酸〔１０〕
クリコールエーテルジアミンテトラ酢酸〔１１〕 エ
チレンジアミンテトラプロピオン酸〔１２〕 フェニ
レンジアミンテトラ酢酸〔１３〕 エチレンジアミン
テトラ酢酸ジナトリウム塩〔１４〕 エチレンジアミ
ンテトラ酢酸テトラ（トリメチルアンモニウム）塩
〔１５〕 エチレンジアミンテトラ酢酸テトラナトリ
ウム塩
〔１６〕 ジエチレントリアミンペンタ酢酸ペンタナ
トリウム塩
〔１７〕 エチレンジアミン−Ｎ−（β−オキシエチ
ル−Ｎ 、 Ｎ’ 、 Ｎ’−トリ酢酸ナトリウム塩〔
Ｉ８〕 プロピレンジアミンテトラ酢酸ナトリウム塩
〔］９〕 ニトリロ酢酸ナトリウム塩〔２０〕 シ
クロヘキサンジアミンテトラ酢酸ナトリウム塩
これらの漂白剤シま５〜４５０ ｇ／ｌ 、より好まし
くは２０〜２５０ ｊ９／ｌで使用する。漂白定着液に
は前記の如き漂白剤以外にハロゲン化銀定着剤を含有し
、必要に応じ又保恒剤として亜硫酸塩を含有する組成の
液が適用される。また、エチレンジアミン四酢酸鉄（［
）錯塩漂白剤と前記のハロゲン化銀定着剤の他の臭化ア
ンモニウムの如さハロゲン化物全少量添加した組成から
なる漂白定着液、あるいは逆に臭化アンモニウム如きハ
ロゲン化物を多量に添加した組成からなる漂白定着液、
さらにはエチレンジアミン四酢酸鉄（ｍ）錯塩漂白剤と
多量の臭化アンモニウムの如きハロゲン化物との組み合
わせからなる組成の特殊な漂白定着液等も用いることが
できる。前記ハロゲン化物としては、臭化アンモニウム
の他に塩化水素酸、臭化水素酸、臭化リチウム、臭化ナ
トリウム、臭化カリウム、沃化ナトリウム、沃化カリウ
ム、沃化アンモニウム等も使用することができる。
漂白定着液に含まれる前記ハロゲン化銀定着剤としては
通常の定着処理に用いられるようなハロゲン化銀と反応
して水溶性の錯塩な形成する化合物、例えば、チオ硫酸
カリウム、チオ硫酸ナトリクム、チオ硫酸アンモニウム
の如きチオ硫酸塩、チオシアン酸カリウム、チオシアン
酸ナトリウム、チオシアン酸アンモニウムの如きチオシ
アン酸塩、チオ尿素、チオエーテル等がその代表的なも
のである。これらの定着剤は５９／１以上、溶解できる
範囲の量で使用するが、一般には７０〜２５０ｆ！／ｌ
で使用する。
なお、漂白定着液には硼酸、硼砂、水酸化ナトリウム、
水酸化カリウム、炭酸ナトリウム、炭酸カリウム、重炭
酸ナトリウム、重炭酸カリウム、酢酸、酢酸ナトリウム
、水酸化アンモニウム等の各種ｐＨ緩衝剤を単独ある〜
・は２種以上組み合わせて含有せしめることができる。
さらにまた、各種の蛍尤増白剤や消泡剤あるいは界面活
性剤を含有せしめることもできる。またヒドロキシルア
ミン、ヒドラジン、アルデヒド化合物の重亜硫酸付加物
等の保恒剤、アミノポリカルボン酸等の有機キレート化
剤あるいはニトロアルコール、硝酸塩環ノ安定剤、メタ
ノール、ジメチルスルホアミド、ジメチルスルホキシド
等の有機溶媒等を適宜含有せしめろことができる。
本発明に用いる漂白定着液には、特開昭・１６−２８０
号、特公昭４５−８５０６号、同４６−５５６号、ベル
ギー特許第７７０，９１０号、特公昭４５−８８３６号
、同５３−９８５４号、特開昭５４．−７１６３４号及
び同４９−４２３４９号等に記載されている種々のξ白
促進剤を添加することができる。
漂白定着液のｐＨは４．０以上で用いられるが、一般に
はｐＨ５，０以上ｐＨ９，５以下で使用され、望ましく
はｐＨ６，０以上ｐＨ８，５以下で使用され、更に述べ
れば最も好まし℃・ｐＨは６．５以上８．５以下で処理
される。処理の温度は８０℃以ドで発色現像槽の処理液
温度よりも３℃以上、好ましくは５℃以上低い温度で使
用されるが、望ましくは５５℃以下で蒸発等を抑えて使
用する。
本発明のハロゲン化銀カラー写真感光材料の写真構成層
には、水溶性または発色現像液で脱色する染料（ＡＩ染
料）を添加することができ、該ＡＩ染料としては、オキ
ソノール染料、ヘミオキソノール染料、メロシアニン染
料及びアゾ染料が包含される。中でもオキソノール染料
、ヘミオキソノール染料及びメロシアニン染料等が有用
である。
用い得るＡＩ染料の例としては、英国特許５８４゜６０
９号、同１，２７７．４２９号、特開昭４８−８５１３
０号、同４９−９９６２０号、同４９−１１４４２０号
、同４９−１２９５３７号、同５２−１０８１１５号、
同５９−２５８４５号、同５９−１１１６４０号、同５
９−１１１６４１号、米国特許２，２７４，７８２号、
同２゜５３３．４７２号、同２，９５６，８７９号、同
３，１２５゜４４８号、同３，１４８．１８７号、同３
，１７７．０７８号、同３，２４７．１２７号、同３，
２６０，６０１号、同３．５４０．８８７号、同３ 、
５７５ 、７０４号、同３゜６５３．９０５号、同３，
７１８．４７２号、同４，０７１゜３１２号、同４．０
’７０，３５２号に記載されているものを挙げることが
できる。
これらのＡＩ染料は、一般に乳剤層中の銀１モル当り２
Ｘ１０〜５Ｘ１０ そル用いることが好ましく、より
好ましくは１×１０〜１×ｌＯモルを用いる。
ハロゲン化銀粒子の結晶は、正常晶でも双晶でもその他
でもよく、［１，０．Ｏ’１１面と（：１．１．１）面
の比率は任意のものが使用できる。更に、これらのハロ
ゲン化銀粒子の結晶構造は、内部から外部まで均一なも
のであっても、内部と外部が異質の層状構造（コア・シ
ェル型）をしたものであってもよい。また、これらのハ
ロゲン化銀に潜像を主として表面に形成する型のもので
も、粒子内部に形成する型のものでもよい。さらに平板
状・・ロダン化銀粒子（特開昭５８−１１３９３４号、
特願昭５９−１７００７０号参照）を用いることもでき
る。
本発明には迅速処理と画像色素の安定性が向上できる点
で特に好ましく用いられるハロゲン化銀粒子として、実
質的に単分散性のものであり、コア・シェル乳剤が良い
。これは酸性法、中性法またはアンモニア法等のいずれ
の調整法により得られたものでもよい。
また例えば種粒子を酸性法でつくり、更に、成長速度の
速いアンモニア、法により成長させ、所定の大きさまで
成長させる方法でもよい。ハロゲン化銀粒子を成長させ
る場合に反応釜内のｐＨ，ｐＡｇ等をコントロールし、
例えば特開昭５４−４８５２１号に記載されているよう
な・・ロダン化銀粒子の成長速度に見合った量の銀イオ
ンと７・ライドイオンを逐次同時に注入混合することが
好ましい。
本発明に係わるハロゲン化銀粒子の調製は以上のように
して行われるのが好ましい。該ハロゲン化銀粒子を含有
する組成物を、本明細書においてハロゲン化銀乳剤とい
う。
これらのハロゲン化銀乳剤は、活性ゼラチン；硫黄増感
剤例えばアリルチオカルバミド、チオ尿素、シスチン等
の硫黄増感剤；セレン増感剤；還元増感剤例えば第１ス
ズ塩、二酸化チオ尿素、ポリアミン等；貴金属増感剤例
えば金増感剤、具体的にはカリウムオーリチオシアネー
ト、カリウムクロロオーレート、２−オーロチオー３−
メチルベンゾチアゾリウムクロライド等あるいは例えば
ルテニクム、パラジウム、白金、ロジウム、イリジウム
等の水溶性塩の増感剤、具体的にはアンモニウムクロロ
バラデート、カリウムクロロオーレ−トおよびナトリウ
ムクロロバラデート（これらの成る種のものは量の大小
によって増感剤あるいはカプリ抑制剤として作用する。
〕等により単独であるいは適宜併用（例えば金増感剤と
硫黄増感剤の併用、金増感剤とセレン増感剤との併用等
）して化学的に増感されてもよい。
本発明に係わるハロゲン化銀乳剤は、含硫黄化合物を添
加して化学熟成し、この化学熟成する前、熟成中、又は
熟成後、少な（とも１種のヒドロキシテトラザインデン
およびメルカプト基を有する含窒素へテロ環化合物の少
なくとも１種を含有せしめてもよい。
本発明に用いられるハロゲン化銀は、各々所望の感光波
長域に感光性を付与するために、適当な増感色素をハロ
ゲン化銀１モルに対して５×１０−８〜３×１０ モル
添加して光学増感させてもよい。
増感色素としては種々のものを用いることができ、また
各々増感色素を１種又は２種以上組合せて用いることが
できる。本発明において有利に使用される増感色素とし
ては例えば次の如きものを挙げることができる。
即ち、背感性ハロゲン化銀乳剤に用いられる増感色素と
しては、例えば***特許９２９．０８０号、米国特許２
，２３１．６５８号、同２，４９３，７４８号、同２，
５０３，７７６号、同２，５１９，００１号、同２゜９
１２．３２９号、同３，６５６，９５９号、同３．６７
２゜８９７号、同３，６９４，２１７号、同４，０２５
，３４９号、同４，０４６，５７２号、英国特許１ 、
２４２．５８８号、特公昭４４−１４０３０号、同５２
−２４８４４号等に記載されたものを挙げることができ
る。また緑感性ハロゲン化銀乳剤に用いられる増感色素
としては、例えば米国特許１，９３９．２０１号、同２
゜０７２．９０８号、同２，７３９，１４９号、同２
、９４５゜７６３号、英国特許５０５，９７９号に記載
されている如きシアニン色素、メロシアニン色素または
複合シアニン色素をその代表的なものとして挙げること
ができる。さらに、赤感性ハロゲン化銀乳剤に用いられ
る増感色素としては、例えば米国特許２．２６９．２３
４号、同２，２７０．３７８号、同２゜４４２．７１０
号、同２，４５４，６２９号、同２ 、７７６ 。
２８０号等に記載されている如きシアニン色素、メロシ
アニン色素または複合シアニン色素をその代表的なもの
として挙げることができる。更にまた米国特許２，２１
３，９９５号、同２，４９３，７４８号、同２，５１９
，００１号、***特許９２９．０８０号等に記載されて
いる如きシアニン色素、メロシアニン色素または複合シ
アニン色素を緑感性ハロゲン化銀乳剤または赤感性ハロ
ゲン化銀乳剤に有利に用いることができる。
これらの増感色素は単独で用いてもよく、またこれらを
組合せて用いてもよい。
本発明の写真感光材料は必要に応じてシアニン或はメロ
シアニン色素の単用又は組合せによる分光増感法にて所
望の波長域に光学増感がなされていてもよい。
特に好ましい分光増感法としては代表的なものは例えば
、ベンズイミダゾロカルボシアニンとペンツオキサゾロ
カルボシアニンとの組合せに関する特公昭４３−４９３
６号、同４３−２２８８４号、同４５−１８４３３号、
同４７−３７４４３号、同４８−２８２９３号、同４９
−６２０９号、同５３−１２３７５号、特開昭５２−２
３９３１号、同５２−５１９３２号、 同５４−８０１
１８号、同５８−１５３９２６号、同５９−１１６６４
６号、同５９−１１６６４７号等に記載の方法が挙げら
れる。
又、ベンズイミダゾール核を有したカルボシアニンと他
のシアニン或はメロシアニンとの組合セに関するものと
しては例えば特公昭４５−２５８３１号、同４７−１１
１１４号、同４７−２５３７９号、同４８−３８４０６
号、同４８−３８４０７号、同５４−３４５３５号、同
５５−１５６９号、特開昭５０−３３２２０号、同５０
−３８５２６号、同５１−１０７１２７号、同５１−１
１５８２０号、同５１−１３５５２８号、同５２−１０
４、９１６号、同５２−１０４９１７号等が挙げられる
。
サラにベンゾオキサゾロカルボシアニン（オキサ・カル
ボシアニン）と他のカルボシアニンとの組合せに関する
ものとしては例えば特公昭４４−３２７５３号、同４６
−１１６２７号、特開昭５７−１４８３号、メロシアニ
ンに関するものとしては例えば特公昭４８−３８４０８
号、同４８−４１２０４号、同５Ｏ−４Ｏｆ’ｉ６２号
２．特開昭５６−２５７２８号、同５８−１０７５３号
、同５８−９１４４５号、同５９−１１６６４５号、同
５０−３３８２８号等が挙げられる。
又、チアカルボシアニンと他のカルボシアニンとの組合
せに関するものとしては例えば特公昭４３−４９３２号
、同４３−４９３３号、同４５−２６４７０号、同４６
−１８１０７号、同４７−８７４１号、特開昭５９−１
１４５３３号等があり、さらにゼロメチン又はジメチン
メロシアニン、モノメチン又はトリメチンシアニン及び
スチリール染料を用いる特公昭４９−６２０７号に記載
の方法を有利に用いることができる。
これらの増感色素を本発明に係るハロゲン化銀乳剤に添
加するには予め色素溶液として例えばメチルアルコール
、エチルアルコール、アセトン、ジメチルフォルムアミ
ド、或は特公昭５０−４０６５９号記載のフッ素化アル
コール等の親水性有機溶媒に溶解して用いられる。
添加の時期はハロゲン化銀乳剤の化学熟成開始時、熟成
中、熟成終了時の任意の時期でよ（、場合によっては乳
剤塗布直前の工程に添加してもよい０
本発明に係わるハロゲン化銀乳剤層にはそれぞれカプラ
ー、即ち、発色現像主薬の酸化体と反応して色素を形成
し得る化合物を含有させることができる。
本発明において使用できる上記カプラーとしては各種イ
エローカプラー、マゼンタカプラーおよびシアンカプラ
ーを特別の制限なく用いることができる。これらのカプ
ラーはいわゆる２当＃型であってもよいし４当量型カプ
ラーであってもよく、またこれらのカプラーに組合せて
、拡散性色素放出型カプラー等を用いることも可能であ
る。
前記イエローカプラーとしては、開鎖ケトメチレン化合
物さらにいわゆる２当量型カプラーと称される活性点−
６−アリール置換カプラー、活性点−〇−アシル置換カ
プラー、活性点ヒダントイン化合物置換カプラー、活性
点クラゾール化合物置換カプラーおよび活性点コハク酸
イミド化合物置換カプラー、活性点フッ素置換カプラー
、活性点塩素あるいは臭素置換カプラー、活性点−〇−
スルホニル置換カプラー等が有効なイエローカプラーと
して用いることができる。用い得るイエローカプラーの
具体例としては、米国特許２ 、８７５ 。
０５７号、同３，２６５．５０６号、同３，４０８，１
９４号、同３，５５１．１５５号、同３，５８２，３２
２号、同３．７２５，０７２号、同３，８９１，４４５
号、***特許１，５４７．８６８号、***出願公開２，
２１９゜９１７号、同２，２６１．３６１号、同２，４
１４．００６号、英国特許１，４２５．０２０号、特公
昭５１−１０７８３号、特開昭４７−２６１３３号、同
、Ｈ−７３１４７号、同５１−１０２６３６号、同５０
−６３４１号、同５０−１２３３４２号、同５０−１３
０４４２号、同５１−２１８２７号、同５０−８７６５
０号、同５２−８２４２４号、同５２−１１５２１９号
、同５８−９５３４６号等に記載されたものを挙げるこ
とができる。
また本発明において用いられるマゼンタカプラーとして
は、ピラゾロン系、ピラゾロトリアゾール系、ピラゾリ
ノベンツイミダゾール系、インダシロン系の化合物を挙
げることができる。これらのマゼンタカプラーはイエロ
ーカプラーと同様４当量型カプラーだけでなく、２当量
型カプラーであってもよい。マゼンタカプラーの具体例
としては米国特許２，６００．７８８号、同２，９８３
，６０８号、同３，０６２，６５３号、同３，１２７，
２６９号、同３．３１１．４７６号、同３．４１９．３
９１号、同３゜５１９．４２９号、同３，５５８．３１
９号、同３ 、５８２ 。
３２２号、同３，６１５，５０６号、同３，８３４．９
０８号、同３，８９１，４４５号、***特許１，８１０
．４６４号、***特許出願（ＯＬＳ）２，４０８，６６
５号、同２．４１７，９４５号、同２，４１８，９５９
号、同２゜４２４．４６７号、特公昭４０−６０３１号
、特開昭５１−２０８２６号、同５２−５８９２２号、
同４９−１２９５３８号、同４９−７４０２７号、同５
０−１５９３３６号、同５２−４２１２１号、同４９−
７４０２８号、同５０−６０２３３号、同５ｌ−２６ｓ
４１号、同５３−５５１２２号、特願昭５５−１１０９
４３号等に記載されたものを挙げることができる。
さらに本発明において用いられる有用なシアンカプラー
としては、例えばフェノール系、ナフトール系カプラー
等を挙げろことができる。そ１−てこれらのシアンカプ
ラーはイエローカプラーと同様４当量型カプラーだけで
な（，２当量型カプラーであってもよい。シアンカプラ
ーの具体例としては米国特許２，３６９，９２９号、同
２．４３メ１，２７２号、同２，４７４，２９３号、同
２，５２１，９０８号、同２．８９５．８２６号、同３
．０３４．８９２号、同３゜３１１．４７６号、同３，
４５８．３１５号、同３，４７６゜５６３号、同３，５
８３．９７１号、同３，５９１．３８３号、同３，７６
７．４１１号、同３，７７２，００２号、同３．９３３
．４９４号、同４．００４．９２９号、***特許出願（
ＯＬＳ）２，４１４，８３０号、同２．・１５・ｌ 、
３２９号、特開昭４８−５９８３８号、同５１−２６０
３．１号、同４８−５０５５号、同５１−１４６８２７
号、同５２−６９６２４号、同５２−９０９３２号、同
５８−９５３＝１６号、特公昭４９−１１５７２号等に
記載のものを挙げることができる。
本発明のハロゲン化銀乳剤層、その他の写真構成層中に
は非拡散性ＤＩＲ化合物、カラードマゼンタ又はシアン
カプラー、ポリマーカプラー、拡散１ＤＩＲ化合物等の
カプラーを併用してもよい。
非拡散性ＤＩＲ化合物、カラードマゼンタ又はシアンカ
プラーについては本出願人による特願昭５９−１９３６
１１号の記載を、またポリマーカプラーについてに本出
願人による特願昭５９−１７２１５１号の記載を各々参
照できる。
本発明に使用できる上記カプラーを本発明の写真構成層
中に添加する方法は従前通りであり、また上記カプラー
の添加量は限定的ではないが、銀１モル当りｌＸｌ０〜
５モルが好ましく、より好ましくは１×１０〜５×１０
である。
本発明のハロゲン化銀カラー写真感光材料には他に各種
の写真用添加剤を含有せしめることができる、例えばリ
サーチ・ディスクロージャー誌１７６４３号に記載され
ているかぶり防止剤、安定剤、紫外線吸収剤、色汚染防
止剤、蛍光増白剤、色画像褪色防止剤、帯電防止剤、硬
膜剤、界面活性剤、可塑剤、湿潤剤等を用いることがで
きる。
本発明のハロゲン化銀カラー写真感光材料において、乳
剤を調整するために用いられる親水性コロイドには、ゼ
ラチン、誘導体ゼラチン、ゼラチンと他の高分子とのグ
ラシトポリマー、アルブミン、カゼイン等のｉ白質、ヒ
ドロキシエチルセルロース誘導体、カルボキンメチルセ
ルロース等のセルロース誘導体、澱粉誘導体、ポリビニ
ルアルコール、ポリビニルイミダゾール、ポリアクリル
アミド等の単一あるいは共重合体の合成親水性高分子等
の任意のものが包含される。
本発明のハロゲン化銀カラー写真感光材料の支持体とし
ては、例えばバライタ紙、ポリエチレン被覆紙、ポリプ
ロピレン合成紙、反射層を併設した、又は反射体を併用
する透明支持体、例えばガラス板、セルロースアヒテー
ト、セルロースナイトレート又はポリエチレンテレフタ
レート等のポリエステルフィルム、ポリアミドフィルム
、ポリカーボネートフィルム、ポリスチレンフィルム等
が挙げられ、その他通常の透明支持体であってもよい。
これらの支持体シエ感光材料の使用目的に応じて適宜選
択される。
本発明において用いられるノ・ロゲン化銀乳剤Ｊ１醤及
びその他の写真構成層の塗設には、ディッピング塗布、
エアードクター塗布、カーテン塗布、ホッパー塗布等様
々の塗布方法を用いることができる。また米国特許２，
７６１．７９１号、同２，９４１゜８９８号に記載の方
法による２層以上の同時塗布法を用いることもできる。
本発明においては各乳剤層の塗設位置を任意に定めるこ
とができる。例えばフルカラーの印画紙用感光材料の場
合には、支持体側から順次青感光性ハロゲン化銀乳剤層
、緑感光性ノ゛ロダン化銀乳剤層、赤感光性ハロゲン化
銀乳剤層の配列とすることが好ましい。これらの感光性
ハロゲン化銀乳剤層は各々２以上の層から成っていても
よい。そして、これら全ての感光性乳剤層が実質的に塩
臭化銀乳剤から成るときに本発明の効果が犬である。
本発明の感光材料において、目的に応じて適当な厚さの
中間層を設けることは任意であり、更にフィルタ一層、
カール防止層、保護層、アンチノ）レーション層等の種
々の層を構成層として適宜組合せて用いることができる
。これらの構成層には結合剤として前記のような乳剤層
に用いることのできる親水性コロイドを同様に用いるこ
とができ、またその層中には前記の如き乳剤層中に含有
せしめることかできる種々の写真用添加剤を含有せしめ
ることができる。
以下、実施例により本発明を具体的に説明するが２本発
明の実施の態様はこれにより限定されな℃１゜
実施例１
ポリエチレンでラミネートした紙支持体上に、下記の８
つの層を順番に塗設して、／Ｓロロダ化銀カラー写真感
光材料を調整した（以下、本発明試料Ａという）。なお
、以下に示す添加量は特に記載のない限り、１ｄ当たり
の量を示す。
層１・・・３Ｑ ｍｙの例示化合物（１−１）および１
・ＯＩのゼラチンを含有する層。
層２・・・１．２ｇのゼラチン、０．４９ （銀換算、
以下同様）の青感性塩臭化銀乳剤（臭化銀含有率８０モ
ル％、平均粒径Ｏ１５／ｊｍ）ｋよび０．５ｇのジオク
チルフタレートに溶解した。、ｓｏｇの下記に示すイエ
ローカプラー（Ｙ−１）を含有する層。
層３・・・０．７ｇのゼラチンを含有する層。（中間層
）層４・・・１．２９のゼラチン、０．４ｇの緑感性塩
臭化銀（臭化銀含有率７０そル％、平均粒径０．５μｍ
）および０．３ ｇのジオクチルフタレートに溶解した
０、６２．９の下記に示すマゼンタカプラー（Ｍ−１）
を含有する層。
層５・・・１，２ｇのゼラチンを含有する層。（中間層
）層６・・・１．４Ｉのゼラチン、０．３１，９の赤感
性塩臭化銀乳剤（臭化銀含有率７０モル％、平均粒径０
．４μｍ）および０．２ｇのジオクチルフタレートに溶
解した０、４５ ｇの下記に示すシアンカプラー（Ｃ−
１）を含有する層。
層７・・・１．０Ｉのゼラチンおよび０．２！ｌのジオ
クチルフタレートに溶解した０、３０ｐのチヌビン３２
８（チバガイギー社製）を含有する層っイエローカプラ
ー（Ｙ−１）
マゼンタカプラー（Ｍ−１）
（’Ｖ
ｌ
シアンカプラー（Ｃ−１）
なお、硬膜剤としてビス（ビニルスルホニルメチル）エ
ーテルを前記層１．３．５および８中にそれぞれゼラチ
ン１ｇ当たりｏ、ｏ ｉ ５ ｇになるように添加した
。以上の様にして作成Ｉ７たカラーペーパーを試料Ｂと
し、ついで層１から例示化合物（１−１）を除去し、他
は同様にして比較用試料Ａを作成して用いた。
前記方法で作製したカラーペーパーを分解露光又は中性
露光し、次の処理工程と処理液により現像処理を行った
。
基準処理工程
〔１〕発色現像 ３８℃ ４０秒〔２
〕漂白定着 ３８℃ ５０秒〔３〕水
洗代替安定液による処理 ５℃〜３５℃ ５０秒〔４〕
乾 燥 ６０〜８０℃ 約２分処理液組
成
〈発色現像液〉
〈漂白定着液ン
Ｌと共に水を加えて全量を１１とする。
〈水洗代替安定液〉
処理後の分解露光でイエローのみ発色された各試料の、
最高濃度部の青色反射濃度をサクラ光電濃度計ＰＤＡ−
６５（小西六写真工業■製）を用いて測定を行なった。
さらにこの試料を発色現像処理後停止定着処理して、し
かる後蛍光Ｘ線法にて現像銀量を測定した。
さらに、中性露光され処理された試料を８５℃、７０％
ｐＨ下で６週間保存し、保存後の試料の最高濃度部の濃
度低下率を求めた。
Ｎこ１５／
表１より明らかなように、発色現像液中のベンジルアル
コールの濃度が高い場合にはｐＨが低くても比較的現像
スピードは速いが、高温高湿で保存後のシアン色素の退
色率が大きい。一方発色現像液中のベンジルアルコール
の濃度を低くするか又は添加しない場合には、発色現像
主薬の濃度が本発明の如く比較的高濃度領域では、ｐＨ
を高くすることにより現像スピードを増すことができ、
本発明の化合物を添加した場合には飛躍的に現像スピー
ドが上昇し、またシアン色素の保存による退色率も小さ
い。さらに、本発明の化合物に、本発明のｐＨ領域であ
る高ｐＨ領域で現像促進効果が高いことも判明し、良好
な結果を示した。
また、ベンジルアルコール未添加でｐＨ１１，０の試料
について、青色反射発色濃度１．５の部分の現像銀量を
測定したところ、本発明の化合物を添加した場合には、
カラーペーパー１ｄ轟り０．２５．９の現像銀が存在し
たが本発明の化合物を添加しない場合には、カラーペー
パー１ｄ当り現像銀が０．２２ｇと少なく、本発明の化
合物を添加した場合には、ハロゲン化銀の現像が促進さ
れ、カプラーと発色現像主薬とのカン・プリング反応に
先行して起っているため、トータルの現像スピードが増
したものと思われる。
実施例２
実施例１で用いた試料Ａを実施例１と同様の処理工程に
従って処理を行った。ただし、発色現像液中のベンジル
アルコールの濃度は０とし、ｐＨは１１とし、下記表２
に示した本発明の化合物を各々発色現像液１１当り、１
００ ｍ９添加した。
結果を表２に示す。
表 ２
上記表２に示した如く、本発明の化合物を発色現像液中
に添加しても同様に十分な促進効果が得られた。また、
本発明の化合物ｌ−１３，ｌ−１４゜ｌ−１６，１−１
７，Ｉｉ８．ｌ−２３，ｌ−２４，１−２５、ｌ−２６
，ｌ−３５，ｌ−３６，Ｉ−羽、 Ｉ −５１について
も同様の効果が得られた。
実施例３
実験例１で用いた発色現像液中のベンジルアルコールを
次のものにそれぞれ変更し、現像液中のカラー主薬添加
量を適宜変化させて、他は実施例１と同様の実験を行な
った。
０−ヒドロキシベンジルアルコール ｌｏｇ ｐ
０．７３シクロヘキ丈ノール ｌｏ
ｇ ｐ １．２３フエニルエーテルアルコール
ｌｏｇ ｐ １．３６ジエチレンクリコールプチルエ
ーテル ｌｏｇ ｐ ０．４１その結果、カラー主薬
の濃度が低くても充分な発色濃度は得られるが、色素の
保存安定性は極めて悪（なる結果が得られた。
また別の効果として、これらｌｏｇ ｐが０．４以上の
溶媒の使用は処理液の溶解性が著しく悪くなるという欠
点を有しているが、本発明の処理液は容易に溶解し調整
が極めて簡便である効果が確認された。
これより、ｌｏｇｐが０．４以上の溶媒の使用を行なわ
ない方が本発明においては、より良好な結果を得ること
が判かる。
実施例４
実施例１で使用した試料Ａ、Ｂの他に実施列１で使用し
た本発明の化合物Ｉ−１のかわりにＩ〜２、Ｉ−４，ｌ
−１５，ｌ−４９，ｌ−２０を添加した試料を作成し、
それぞれ試料Ｃ，Ｄ、Ｅ、Ｆ、Ｇとした。
上記の試料を露光後、実施例１と同様の処理工程に従っ
て現像処理を行なった。各々の処理液の組成は、実施例
−１で使用したと同一のものを使用したが発色現像液中
の臭化カリウムの濃度を下記表３の如く変化した。ただ
し、発色現像液中のベンジルアルコールの濃度は０とし
、ｐＨは１１とし処理後の青色反射最高濃度を測定した
結果を表２に示す。
表 ３
上記表３に示した如（、発色現像液中の臭化カリウムの
濃度が増加すると本発明の化合物を含まない試料では、
発色濃度の低下が起こるが、本発明の化合物を含有した
試料では、低下はほとんどなく、十分な発色濃度が得ら
れた。従って、本発明の発色現像液に本発明の化合物〔
Ｉ〕を使用することにより、高ハロゲン濃度耐性が得ら
れ、低補充化が可能になることを示唆している。
実施例５
実施例４で使用したと同様の処理液を用い、試料Ｂを実
施例４と同様の処理工程に従って処理した。ただし、発
色現像液中の発色現像生薬ＣＤ−３の濃度を下記表４に
示す如く変化し、処理後のペーパーの最高濃度を測定し
た。
表 ４
上記表４に示した如（、本発明の発色現像主薬を１１当
り１．５Ｘ１０ モル以上使用し、本発明の化合物の
存在下に高ｐＨで処理することにより、迅速な現像スピ
ードが得られた。
実施例６
下記の５種の発色現像主薬を用いて実施例１の発色現像
液への溶解度を測定した。
発色現像主薬
Ｈ２
ＮＨ２
Ｈ２
Ｈ２
Ｈ２
この結果、ｐＨ１１，０での溶解性は■ＣＤ−３＞ＣＤ
−６＞ＣＤ−４＞ＣＤ−１）ＣＤ−２■の順となった。
特にＣＤ−３はｐＨが１０３以上では溶解度が著しく上
昇するという特異な効果がみられることが判った。
これらより、ＣＤ−３及びＣＤ−５は高ｐＨにすること
で高濃度化が可能であり、特にＣＤ−３は好ましいこと
が判った。一方、ＣＤ−３以外の発色現像主薬はｐＨを
高くしても溶解性は向上しないことがわかった。
特許出願人 小西六写真工業株式会社手粘臂相ＴｉＪ
兄書（方式）
％式％
２、発明の名称
ハ〔Ｉゲン化銀カラー写真感光材料の処理方法３、ｈｌ
ｆ正をする台
’ＩＴ件との関係 特許出願人
住所 東京都新宿区西新宿１丁目２６番２号連絡先
刊９Ｉ
東京都口野市さくら町１番地
小西六写真工業株式会社（０４２５−８３−１５２１）
特許部
５、補正の対象
明細書
６、補正の内容[9] Ethyl ether diamine tetraacetic acid [10]
glycol ether diamine tetraacetic acid [11] ethylenediaminetetrapropionic acid [12] phenylenediaminetetraacetic acid [13] ethylenediaminetetraacetic acid disodium salt [14] ethylenediaminetetraacetic acid tetra(trimethylammonium) salt [15] ethylenediaminetetraacetic acid tetrasodium salt [16] Diethylenetriaminepentaacetic acid pentasodium salt [17] Ethylenediamine-N-(β-oxyethyl-N,N',N'-triacetic acid sodium salt)
I8] Sodium salt of propylene diamine tetraacetate [9] Sodium nitriloacetate salt [20] Sodium salt of cyclohexane diamine tetraacetate These bleaching agents are used in amounts of 5 to 450 g/l, more preferably 20 to 250 g/l. . The bleach-fixing solution contains a silver halide fixing agent in addition to the above bleaching agent, and if necessary, a solution containing sulfite as a preservative is applied. In addition, iron ethylenediaminetetraacetate ([
) A bleach-fix solution consisting of a complex salt bleach and a composition in which a small amount of a halide such as ammonium bromide other than the above-mentioned silver halide fixer is added, or conversely, a composition in which a large amount of a halide such as ammonium bromide is added. bleach-fix solution,
Furthermore, a special bleach-fixing solution having a composition consisting of a combination of an ethylenediaminetetraacetic acid iron(m) complex salt bleaching agent and a large amount of a halide such as ammonium bromide may also be used. As the halides, in addition to ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. can also be used. can. The silver halide fixing agent contained in the bleach-fix solution includes compounds that react with silver halide to form water-soluble complex salts, such as potassium thiosulfate, sodium thiosulfate, and thiosulfate, which are used in ordinary fixing processes. Typical examples include thiosulfates such as ammonium sulfate, thiocyanates such as potassium thiocyanate, sodium thiocyanate, and ammonium thiocyanate, thioureas, and thioethers. These fixing agents are used in an amount of 59/1 or more, within the range that can be dissolved, but generally 70 to 250 f! /l
Use with. The bleach-fix solution contains boric acid, borax, sodium hydroxide,
Various pH buffers such as potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, etc.
- Can be contained in combination of two or more types. Furthermore, various fluorescent whitening agents, antifoaming agents, or surfactants can be contained. In addition, preservatives such as hydroxylamine, hydrazine, bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids, organic chelating agents such as nitroalcohol, nitrate ring stabilizers, methanol, dimethylsulfamide, dimethylsulfoxide, etc. A solvent or the like may be included as appropriate. The bleach-fix solution used in the present invention includes JP-A-16-280
No. 45-8506, Belgian Patent No. 46-556, Belgian Patent No. 770,910, Japanese Patent Publication No. 45-8836, Japanese Patent Publication No. 53-9854, Japanese Patent Publication No. 54-198. Various ξ white accelerators described in Japanese Patent Nos. 71634 and 49-42349 can be added. The pH of the bleach-fix solution is used at 4.0 or higher, but generally it is used at pH 5.0 or higher and pH 9.5 or lower, preferably at pH 6.0 or higher and pH 8.5 or lower, and most preferably at ℃・Processing is carried out at a pH of 6.5 or more and 8.5 or less. The processing temperature is 80°C or lower, which is 3°C or more, preferably 5°C or more lower than the temperature of the processing solution in the color developing tank, but preferably 55°C or lower to prevent evaporation. The photographic constituent layer of the silver halide color photographic light-sensitive material of the present invention may contain a water-soluble dye or a dye (AI dye) that can be decolorized with a color developing solution. Examples of the AI dye include oxonol dye, hemioxonol dye, Dyes, merocyanine dyes and azo dyes are included. Among them, oxonol dyes, hemioxonol dyes, merocyanine dyes, and the like are useful. Examples of AI dyes that can be used include British Patent No. 584.60.
No. 9, No. 1,277.429, Japanese Unexamined Patent Publication No. 48-8513
No. 0, No. 49-99620, No. 49-114420, No. 49-129537, No. 52-108115,
No. 59-25845, No. 59-111640, No. 5
No. 9-111641, U.S. Patent No. 2,274,782,
2゜533.472, 2,956,879, 3,125゜448, 3,148.187, 3
, No. 177.078, No. 3,247.127, No. 3,
No. 260,601, No. 3.540.887, No. 3,
575, No. 704, No. 3゜653.905, No. 3,
No. 718.472, No. 4,071゜312, No. 4.0
Examples include those described in '70,352. These AI dyes are generally used at a concentration of 2 per mole silver in the emulsion layer.
It is preferable to use 1×10 to 5×10 mol, more preferably 1×10 to 1×10 mol. The crystals of the silver halide grains may be normal crystals, twin crystals, or other crystals, and may be [1,0. Any ratio between the O'11 plane and the (:1.1.1) plane can be used. Further, the crystal structure of these silver halide grains may be uniform from the inside to the outside, or may have a layered structure (core-shell type) in which the inside and outside are different. Further, these silver halides may be of a type in which a latent image is mainly formed on the surface or a type in which a latent image is formed inside the grains. In addition, tabular silver rhodanide grains (JP-A-58-113934,
(See Japanese Patent Application No. 59-170070) can also be used. Silver halide grains which are particularly preferably used in the present invention from the viewpoint of rapid processing and improved stability of image dyes are substantially monodisperse grains, and are preferably core-shell emulsions. This may be obtained by any preparation method such as an acid method, a neutral method, or an ammonia method. Alternatively, for example, a method may be used in which seed particles are produced by an acidic method and further grown by an ammonia method, which has a high growth rate, to grow to a predetermined size. When growing silver halide grains, control the pH, pAg, etc. in the reaction vessel,
For example, as described in JP-A-54-48521, it is preferable to sequentially and simultaneously implant and mix silver ions and 7-ride ions in amounts commensurate with the growth rate of silver rhodanide grains. Preferably, the silver halide grains according to the present invention are prepared as described above. A composition containing the silver halide grains is referred to herein as a silver halide emulsion. These silver halide emulsions contain activated gelatin; sulfur sensitizers such as allylthiocarbamide, thiourea, cystine; selenium sensitizers; reduction sensitizers such as stannous salts, thiourea dioxide, Polyamines, etc.; noble metal sensitizers, such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-aurothiol-3-
Sensitizers such as methylbenzothiazolium chloride or water-soluble salts such as ruthenium, palladium, platinum, rhodium, iridium, etc., specifically ammonium chlorovaladate, potassium chloroaurate and sodium chlorovaladate (these Depending on the amount, these substances act as sensitizers or capri inhibitors. The silver halide emulsion according to the present invention may be chemically sensitized by adding a sulfur-containing compound, and then being chemically ripened before, during, or during the chemical ripening. After that, at least one nitrogen-containing heterocyclic compound having at least one hydroxytetrazaindene and mercapto group may be contained. In order to impart photosensitivity to the silver halide, an appropriate sensitizing dye may be added in an amount of 5 x 10-8 to 3 x 10 mol per mol of silver halide for optical sensitization.There are various sensitizing dyes. In addition, each sensitizing dye may be used alone or in combination of two or more. Examples of the sensitizing dyes that can be advantageously used in the present invention include the following: That is, as sensitizing dyes used in back-sensitive silver halide emulsions, for example, West German Patent No. 929.080 and U.S. Pat.
, 231.658, 2,493,748, 2,
No. 503,776, No. 2,519,001, No. 2゜9
No. 12.329, No. 3,656,959, No. 3.67
2゜897, 3,694,217, 4,025
, No. 349, No. 4,046,572, British Patent 1,
No. 242.588, Special Publication No. 44-14030, No. 52
-24844 etc. can be mentioned. In addition, examples of sensitizing dyes used in green-sensitive silver halide emulsions include, for example, U.S. Pat.
゜No. 072.908, No. 2,739,149, No. 2
Typical examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in , British Patent No. 505,979 and British Patent No. 505,979. Further, as a sensitizing dye used in a red-sensitive silver halide emulsion, for example, U.S. Patent No. 2.269.23
No. 4, No. 2,270.378, No. 2゜442.710
No. 2,454,629, No. 2, 776. Representative examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. 280 and the like. Furthermore, U.S. Patent 2,21
No. 3,995, No. 2,493,748, No. 2,519
Cyanine dyes, merocyanine dyes or composite cyanine dyes such as those described in German Pat. These sensitizing dyes may be used alone or in combination. The photographic material of the present invention may be optically sensitized in a desired wavelength range by a spectral sensitization method using cyanine or merocyanine dyes alone or in combination, if necessary. A typical particularly preferred spectral sensitization method is, for example, Japanese Patent Publication No. 43-493 concerning the combination of benzimidazolocarbocyanine and penzoxazolocarbocyanine.
No. 6, No. 43-22884, No. 45-18433,
No. 47-37443, No. 48-28293, No. 49
No.-6209, No. 53-12375, JP-A-52-2
No. 3931, No. 52-51932, No. 54-801
No. 18, No. 58-153926, No. 59-11664
6, No. 59-116647, and the like. Further, regarding combinations of carbocyanine having a benzimidazole nucleus with other cyanines or merocyanines, for example, Japanese Patent Publication Nos. 45-25831 and 47-11
No. 114, No. 47-25379, No. 48-38406
No. 48-38407, No. 54-34535, No. 55-1569, JP-A-50-33220, No. 50
-38526, 51-107127, 51-1
No. 15820, No. 51-135528, No. 52-10
4, No. 916, No. 52-104917, and the like. Regarding combinations of benzoxazolocarbocyanine (oxa-carbocyanine) and other carbocyanins, for example, Japanese Patent Publication No. 32753/1986 and No. 46
-11627, Japanese Unexamined Patent Publication No. 1483/1983, and Japanese Patent Publication No. 38408/1983 regarding merocyanine.
No. 48-41204, No. 5O-4Of'i62 2. Examples include JP-A-56-25728, JP-A-58-10753, JP-A-58-91445, JP-A-59-116645, and JP-A-50-33828. Regarding combinations of thiacarbocyanin and other carbocyanins, for example, Japanese Patent Publications Nos. 43-4932, 43-4933, 45-26470, and 46
-18107, No. 47-8741, JP-A-59-1
No. 14533, etc., and the method described in Japanese Patent Publication No. 49-6207, which uses zeromethine or dimethine merocyanine, monomethine or trimethine cyanine, and styryl dye, can be advantageously used. In order to add these sensitizing dyes to the silver halide emulsion according to the present invention, a dye solution such as methyl alcohol, ethyl alcohol, acetone, dimethylformamide, or fluorinated alcohol described in Japanese Patent Publication No. 40659/1984 is used in advance. It is used by dissolving it in a hydrophilic organic solvent. The silver halide emulsion may be added at any time such as at the start of chemical ripening, during ripening, or at the end of ripening (in some cases, it may be added in the step immediately before coating the emulsion). Each emulsion layer can contain a coupler, that is, a compound capable of forming a dye by reacting with an oxidized form of a color developing agent. Examples of the couplers that can be used in the present invention include various yellow couplers, magenta couplers, and cyan couplers. These couplers may be so-called 2-equivalent type couplers or 4-equivalent type couplers, and in combination with these couplers, diffusible dye-releasing couplers, etc. It is also possible to use an open-chain ketomethylene compound as the yellow coupler, and also a so-called two-equivalent type coupler.
6-aryl substituted couplers, active point -0-acyl substituted couplers, active point hydantoin compound substituted couplers, active point crazole compound substituted couplers and active point succinimide compound substituted couplers, active point fluorine substituted couplers, active point chlorine or bromine substituted couplers Coupler, active point -〇-
Sulfonyl-substituted couplers and the like can be used as effective yellow couplers. Specific examples of yellow couplers that can be used include US Pat. No. 2,875. No. 057, No. 3,265.506, No. 3,408,1
No. 94, No. 3,551.155, No. 3,582,32
No. 2, No. 3,725,072, No. 3,891,445
No., West German Patent No. 1,547.868, West German Application Publication No. 2,
219゜917, 2,261.361, 2,4
14.006, British Patent No. 1,425.020, Japanese Patent Publication No. 51-10783, Japanese Patent Publication No. 47-26133, Japanese Patent Publication No. 47-26133, Japanese Patent Publication No. H-73147, British Patent No. 51-102636, Japanese Patent Publication No. 50
-6341, 50-123342, 50-13
No. 0442, No. 51-21827, No. 50-8765
Examples include those described in No. 0, No. 52-82424, No. 52-115219, and No. 58-95346. Examples of magenta couplers used in the present invention include pyrazolone, pyrazolotriazole, pyrazolinobenzimidazole, and indacylon compounds. These magenta couplers may be not only 4-equivalent type couplers but also 2-equivalent type couplers like the yellow couplers. Specific examples of magenta couplers include U.S. Patent Nos. 2,600.788 and 2,983.
, No. 608, No. 3,062,653, No. 3,127,
No. 269, No. 3.311.476, No. 3.419.3
No. 91, No. 3゜519.429, No. 3,558.31
No. 9, 3, 582. No. 322, No. 3,615,506, No. 3,834.9
No. 08, No. 3,891,445, West German Patent No. 1,810
．． No. 464, West German Patent Application (OLS) 2,408,66
No. 5, No. 2,417,945, No. 2,418,959
No. 2゜424.467, Japanese Patent Publication No. 40-6031, Japanese Patent Publication No. 51-20826, Japanese Patent Publication No. 52-58922,
No. 49-129538, No. 49-74027, No. 5
No. 0-159336, No. 52-42121, No. 49-
No. 74028, No. 50-60233, No. 5l-26s
No. 41, No. 53-55122, patent application No. 55-1109
Examples include those described in No. 43 and the like. Furthermore, useful cyan couplers used in the present invention include, for example, phenolic couplers, naphthol couplers, and the like. First, these cyan couplers are not only 4-equivalent type couplers like the yellow couplers (but may also be 2-equivalent type couplers. Specific examples of cyan couplers include U.S. Pat. Nos. 2,369,929 and 2). .43 Me No. 1,272, Me 2,474,293, Me 2,521,908, Me 2.895.826, Me 3
．． No. 034.892, No. 311.476, No. 3,
No. 458.315, No. 3,476゜563, No. 3,5
No. 83.971, No. 3,591.383, No. 3,76
No. 7.411, No. 3,772,002, No. 3.933
．． No. 494, No. 4.004.929, West German patent application (
OLS) No. 2,414,830, 2.・15・l,
No. 329, JP-A-48-59838, JP-A No. 51-260
No. 3.1, No. 48-5055, No. 51-146827
No. 52-69624, No. 52-90932, No. 58-953=16, and Japanese Patent Publication No. 11572/1984. Couplers such as non-diffusible DIR compounds, colored magenta or cyan couplers, polymer couplers, and diffusing 1 DIR compounds may be used in combination in the silver halide emulsion layer of the present invention and other photographic constituent layers. Regarding non-diffusible DIR compounds, colored magenta or cyan couplers, patent application filed in 1983-1936 by the present applicant
11, and Japanese Patent Application No. 172151/1983 filed by the present applicant regarding polymer couplers. The above-mentioned coupler that can be used in the present invention can be added to the photographic constituent layer of the present invention by the conventional method, and the amount of the above-mentioned coupler added is not limited;
5 mol is preferable, more preferably 1 x 10 to 5 x 10
It is. The silver halide color photographic light-sensitive material of the present invention may contain various other photographic additives, such as antifoggants, stabilizers, ultraviolet absorbers, etc. described in Research Disclosure No. 17643, A color stain inhibitor, a fluorescent whitening agent, a color image fading inhibitor, an antistatic agent, a hardening agent, a surfactant, a plasticizer, a wetting agent, etc. can be used. In the silver halide color photographic light-sensitive material of the present invention, the hydrophilic colloids used to prepare the emulsion include gelatin, derivative gelatin, glacitopolymers of gelatin and other polymers, albumin, casein, and other white matter colloids. , hydroxyethyl cellulose derivatives, cellulose derivatives such as carboxyl methyl cellulose, starch derivatives, single or copolymer synthetic hydrophilic polymers such as polyvinyl alcohol, polyvinylimidazole, and polyacrylamide. Examples of the support for the silver halide color photographic light-sensitive material of the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, transparent supports with a reflective layer or a reflective material, such as glass plates, cellulose Examples include polyester films such as tate, cellulose nitrate, or polyethylene terephthalate, polyamide films, polycarbonate films, polystyrene films, and other common transparent supports. These supports are appropriately selected depending on the purpose of use of the light-sensitive material. Coating of silver halide emulsion J1 sauce and other photographic constituent layers used in the present invention includes dipping coating,
Various coating methods can be used, such as air doctor coating, curtain coating, and hopper coating. Also, US Patent 2,
761.791 and 2,941.898 can also be used, in which two or more layers are simultaneously coated. In the present invention, the coating position of each emulsion layer can be determined arbitrarily. For example, in the case of a full-color photosensitive material for photographic paper, a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer are arranged sequentially from the support side. is preferred. Each of these photosensitive silver halide emulsion layers may consist of two or more layers. The effects of the present invention are most effective when all of these photosensitive emulsion layers are substantially composed of silver chlorobromide emulsions. In the photosensitive material of the present invention, it is optional to provide an intermediate layer with an appropriate thickness depending on the purpose, and a filter layer,
Various layers such as an anti-curl layer, a protective layer, and an anti-nolation layer can be used in appropriate combinations as constituent layers. Hydrophilic colloids that can be used in the emulsion layers as described above can be used as binders in these constituent layers, and various types of colloids that can be contained in the emulsion layers as described above can be used in these layers. Photographic additives may be included. Hereinafter, the present invention will be specifically explained with reference to Examples, but the embodiments of the present invention are not limited thereto.
A /S silver color photographic material was prepared by sequentially applying the two layers (hereinafter referred to as sample A of the present invention). Note that the amounts added below are per 1 d unless otherwise specified. Layer 1...3Q my exemplary compound (1-1) and 1
- Gelatin-containing layer of OI. Layer 2...1.2g gelatin, 0.49 (in terms of silver,
The same applies hereinafter) was dissolved in a blue-sensitive silver chlorobromide emulsion (silver bromide content: 80 mol %, average grain size O15/jm) and 0.5 g of dioctyl phthalate. , sog, a layer containing the yellow coupler (Y-1) shown below. Layer 3: Layer containing 0.7 g of gelatin. (Intermediate layer) Layer 4...1.29 gelatin, 0.4 g of green-sensitive silver chlorobromide (silver bromide content 70%, average particle size 0.5 μm)
) and the magenta coupler shown below (M-1) of 0.62.9 dissolved in 0.3 g of dioctyl phthalate.
A layer containing. Layer 5: A layer containing 1.2 g of gelatin. (Intermediate layer) Layer 6...1.4I gelatin, 0.31.9 red-sensitive silver chlorobromide emulsion (silver bromide content 70 mol%, average grain size 0)
．． 4 μm) and 0.45 g of the cyan coupler shown below (C-
A layer containing 1). Layer 7...1.0I of gelatin and 0.2! 0.30 p Tinuvin 32 dissolved in l dioctyl phthalate
8 (manufactured by Ciba Geigy), a layered yellow coupler (Y-1), a magenta coupler (M-1), and a cyan coupler (C-1) containing bis(vinylsulfonylmethyl) ether as a hardening agent. o and o i 5 g per 1 g of gelatin were added to the layers 1.3.5 and 8, respectively. 1-1) was removed, and a comparative sample A was prepared and used in the same manner as above.The color paper prepared by the above method was subjected to decomposition exposure or neutral exposure, and then developed using the following processing step and processing solution. Standard processing step [1] Color development 38°C 40 seconds [2]
] Bleach-fixing 38°C 50 seconds [3] Treatment with water washing alternative stabilizer 5°C to 35°C 50 seconds [4]
Drying: 60-80°C for about 2 minutes Processing solution composition <Color developing solution><Water is added together with bleach-fix solution N to bring the total volume to 11. <Water washing alternative stabilizer> For each sample that developed only yellow color after decomposition exposure after processing,
Check the blue reflection density at the highest density using Sakura photoelectric densitometer PDA-
65 (manufactured by Konishiroku Photo Industry ■). Further, this sample was subjected to a color development process and then a stop and fixing process, and then the amount of developed silver was measured using a fluorescent X-ray method. Furthermore, the neutrally exposed and treated samples were heated at 85°C and 70%
The samples were stored under pH conditions for 6 weeks, and the rate of decrease in concentration of the highest concentration portion of the sample after storage was determined. Nko15/ As is clear from Table 1, when the concentration of benzyl alcohol in the color developer is high, the development speed is relatively fast even if the pH is low, but the cyan dye fades after storage at high temperature and high humidity. The rate is large. On the other hand, if the concentration of benzyl alcohol in the color developing solution is lowered or not added, in a relatively high concentration range of the color developing agent as in the present invention, the pH
The development speed can be increased by increasing the
When the compound of the present invention is added, the development speed increases dramatically, and the rate of discoloration of the cyan dye due to storage is also small. Furthermore, it was found that the compound of the present invention has a high development promoting effect in the high pH range, which is the pH range of the present invention, and showed good results. In addition, when we measured the amount of developed silver in a portion with a blue reflection color density of 1.5 for a sample with a pH of 11.0 without the addition of benzyl alcohol, we found that when the compound of the present invention was added,
There was developed silver of 0.25.9 per d of color paper, but when the compound of the present invention was not added, the amount of developed silver per 1 d of color paper was as low as 0.22 g, and when the compound of the present invention was added. It is thought that the development of silver halide is accelerated and occurs prior to the camp-pulling reaction between the coupler and the color developing agent, so that the total development speed is increased. Example 2 Sample A used in Example 1 was treated according to the same treatment steps as in Example 1. However, the concentration of benzyl alcohol in the color developer is 0, the pH is 11, and Table 2 below
1 of each of the compounds of the present invention shown in
00 m9 added. The results are shown in Table 2. Table 2 As shown in Table 2 above, even when the compound of the present invention was added to the color developer, a sufficient accelerating effect was similarly obtained. Also,
Compounds of the present invention l-13,l-14゜l-16,1-1
7, Ii8. l-23, l-24, 1-25, l-26
, l-35, l-36, I-feather, and I-51 had similar effects. Example 3 An experiment was carried out in the same manner as in Example 1 except that the benzyl alcohol in the color developing solution used in Experimental Example 1 was changed to the following, and the amount of coloring agent added in the developing solution was changed as appropriate. Ta. 0-Hydroxybenzyl alcohol log p
0.73 cyclohexyl length nol lo
g p 1.23 phenyl ether alcohol
log p 1.36 diethylene glycol butyl ether log p 0.41 As a result, even if the concentration of the coloring agent is low, sufficient color density can be obtained, but the storage stability of the dye is extremely poor (results were obtained). Another effect is that the use of these solvents with a log p of 0.4 or more has the disadvantage that the solubility of the processing solution is significantly deteriorated, but the processing solution of the present invention can be easily dissolved and adjusted. The effect of extremely simplicity was confirmed. From this, it can be seen that better results can be obtained in the present invention by not using a solvent with a logp of 0.4 or more. Example 4 Example 1 In addition to Samples A and B used in Example 1, in place of Compound I-1 of the present invention used in Example 1, I-2, I-4, and
-15, l-49, l-20 added samples were prepared,
Samples were named C, D, E, F, and G, respectively. After exposing the above sample, development processing was performed according to the same processing steps as in Example 1. The composition of each processing solution was the same as that used in Example-1, but the concentration of potassium bromide in the color developing solution was changed as shown in Table 3 below. However, the concentration of benzyl alcohol in the color developing solution was set to 0, the pH was set to 11, and the maximum density of blue reflection after processing was measured. Table 2 shows the results. Table 3 As shown in Table 3 above (as shown in Table 3 above), as the concentration of potassium bromide in the color developer increases,
Although a decrease in color density occurred, in the sample containing the compound of the present invention, there was almost no decrease and a sufficient color density was obtained. Therefore, the compound of the present invention [
It is suggested that by using [I], high halogen concentration tolerance can be obtained and low replenishment can be achieved. Example 5 Sample B was treated using the same treatment solution as used in Example 4 and according to the same treatment steps as in Example 4. However, the concentration of color developer crude drug CD-3 in the color developer was varied as shown in Table 4 below, and the maximum density of the paper after treatment was measured. Table 4 As shown in Table 4 above (by using the color developing agent of the present invention at 1.5 x 10 mol or more per 11 and processing at high pH in the presence of the compound of the present invention, rapid development speed can be obtained. Example 6 Using the following five color developing agents, the solubility in the color developing solution of Example 1 was measured.Color developing agent H2 NH2 H2 H2 H2 As a result, the solubility at pH 11.0 was ■CD-3>CD
The order was -6>CD-4>CD-1)CD-2■. In particular, it has been found that CD-3 has a unique effect in that its solubility significantly increases at a pH of 103 or higher. These results show that it is possible to increase the concentration of CD-3 and CD-5 by increasing the pH, and that CD-3 is particularly preferable. On the other hand, it was found that the solubility of color developing agents other than CD-3 did not improve even if the pH was increased. Patent applicant: Konishiroku Photo Industry Co., Ltd.
Brother's book (method) % formula % 2. Title of the invention C [I Processing method for silver-genide color photographic light-sensitive materials 3, hl
Relationship with the IT matter Patent applicant address: 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Contact information Publication 9I Konishiroku Photo Industry Co., Ltd., 1-Sakura-cho, Kuchino-shi, Tokyo (0425-83-) 1521)
Patent Department 5, Specification subject to amendment 6, Contents of amendment
Claims (4)
真感光材料を発色現像、漂白定着、安定化処理の３工程
にて処理する処理方法において、発色現像液がｐＨ１０
．３以上で、アルキルスルホンアミドアルキル基を芳香
核上又はアミノ窒素に結合したｐ−フェニレンジアミン
系の発色現像主薬の少くとも１種を少くとも１．５×１
０モル含有し、溶媒が水と水以外のｌｏｇｐ０．３未満
の溶媒の容量に対するｌｏｇｐ０．４以上の溶媒の容量
の比が０．００３以下の溶媒から構成されており現像が
３０℃以上であり、１２０秒以内にて下記一般式〔 I
〕で示される化合物の少くとも一種の存在下に処理され
ることを特徴とするハロゲン化銀カラー写真感光材料の
処理方法。 一般式〔 I 〕 ▲数式、化学式、表等があります▼ 式中、Ｘは水素原子又はアセチル基を表わし、Ｒ＿１は
アリール基を表わし、Ｒ＿２、Ｒ＿３、Ｒ＿４及びＲ＿
５はそれぞれ水素原子、ハロゲン原子、アルキル基又は
アリール基を表わす。(1) In a processing method in which a silver halide color photographic light-sensitive material consisting essentially of silver chlorobromide is processed in three steps of color development, bleach-fixing, and stabilization treatment, the color developer has a pH of 10
．． 3 or more, and at least 1.5
0 mol, the solvent is composed of water and a solvent in which the ratio of the volume of the solvent with a log p of 0.4 or more to the volume of a solvent other than water with a log p of less than 0.3 is 0.003 or less, and the development is performed at 30 ° C. or higher. , within 120 seconds, the following general formula [ I
] A method for processing a silver halide color photographic material, characterized in that it is processed in the presence of at least one of the compounds represented by the following. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, X represents a hydrogen atom or an acetyl group, R_1 represents an aryl group, R_2, R_3, R_4 and R_
5 each represents a hydrogen atom, a halogen atom, an alkyl group or an aryl group.
．４未満の溶媒からなり、実質的にｌｏｇｐ０．４以上
の溶媒を含有しないことを特徴とする特許請求範囲第１
項記載の処理方法。(2) The color developer has a log p0 of water and a solvent other than water.
．． Claim 1, characterized in that it consists of a solvent with a log p of less than 4 and does not substantially contain a solvent with a log p of 0.4 or more.
Treatment method described in section.
徴とする特許請求範囲第１項〜第６項いずれかに記載の
ハロゲン化銀カラー写真感光材料の処理方法。(3) The method for processing a silver halide color photographic material according to any one of claims 1 to 6, wherein the color developer has a pH of 10.5 or more.
特徴とする特許請求範囲第１項〜第７項のいずれかに記
載のハロゲン化銀カラー写真感光材料の処理方法。(4) The method for processing a silver halide color photographic material according to any one of claims 1 to 7, wherein the color developer has a pH of 10.75 or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1924586A JPS62177555A (en) | 1986-01-30 | 1986-01-30 | Method for processing silver halide color photographic sensitive material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1924586A JPS62177555A (en) | 1986-01-30 | 1986-01-30 | Method for processing silver halide color photographic sensitive material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62177555A true JPS62177555A (en) | 1987-08-04 |
Family
ID=11994023
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1924586A Pending JPS62177555A (en) | 1986-01-30 | 1986-01-30 | Method for processing silver halide color photographic sensitive material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62177555A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5210118A (en) * | 1990-06-12 | 1993-05-11 | Ciba-Geigy Corporation | Method for stabilizing synthetic thermoplastic materials against thermal degradation |
-
1986
- 1986-01-30 JP JP1924586A patent/JPS62177555A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5210118A (en) * | 1990-06-12 | 1993-05-11 | Ciba-Geigy Corporation | Method for stabilizing synthetic thermoplastic materials against thermal degradation |
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