US3870520A - Photographic processing composition - Google Patents
Photographic processing composition Download PDFInfo
- Publication number
- US3870520A US3870520A US403293A US40329373A US3870520A US 3870520 A US3870520 A US 3870520A US 403293 A US403293 A US 403293A US 40329373 A US40329373 A US 40329373A US 3870520 A US3870520 A US 3870520A
- Authority
- US
- United States
- Prior art keywords
- acid
- bleaching
- solution
- salts
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 66
- 238000012545 processing Methods 0.000 title claims abstract description 46
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229910001447 ferric ion Inorganic materials 0.000 claims abstract description 47
- 150000001875 compounds Chemical class 0.000 claims abstract description 32
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 25
- 238000004061 bleaching Methods 0.000 claims description 148
- 150000003839 salts Chemical class 0.000 claims description 66
- -1 p-toluene sulfonate ion Chemical group 0.000 claims description 43
- 239000002253 acid Substances 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 29
- 229910052709 silver Inorganic materials 0.000 claims description 24
- 239000004332 silver Substances 0.000 claims description 24
- 238000011161 development Methods 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- 229910052783 alkali metal Inorganic materials 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 11
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 11
- 150000001340 alkali metals Chemical class 0.000 claims description 10
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical group [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 9
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 8
- 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 claims description 6
- 239000006179 pH buffering agent Substances 0.000 claims description 6
- SOBHUZYZLFQYFK-UHFFFAOYSA-K trisodium;hydroxy-[[phosphonatomethyl(phosphonomethyl)amino]methyl]phosphinate Chemical compound [Na+].[Na+].[Na+].OP(O)(=O)CN(CP(O)([O-])=O)CP([O-])([O-])=O SOBHUZYZLFQYFK-UHFFFAOYSA-K 0.000 claims description 6
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 claims description 5
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 5
- FSVCELGFZIQNCK-UHFFFAOYSA-N N,N-bis(2-hydroxyethyl)glycine Chemical compound OCCN(CCO)CC(O)=O FSVCELGFZIQNCK-UHFFFAOYSA-N 0.000 claims description 5
- 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 claims description 5
- 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 claims description 5
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 5
- 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 claims description 5
- 229960003330 pentetic acid Drugs 0.000 claims description 5
- 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 claims 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 claims description 4
- 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 claims description 4
- ROSLAEZYGNDMGI-UHFFFAOYSA-L disodium;2-[1-[bis(carboxymethyl)amino]propan-2-yl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)C(C)CN(CC(O)=O)CC(O)=O ROSLAEZYGNDMGI-UHFFFAOYSA-L 0.000 claims description 4
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 4
- DZCAZXAJPZCSCU-UHFFFAOYSA-K sodium nitrilotriacetate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CC([O-])=O DZCAZXAJPZCSCU-UHFFFAOYSA-K 0.000 claims description 4
- 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 claims description 3
- QZKRHPLGUJDVAR-UHFFFAOYSA-K EDTA trisodium salt Chemical compound [Na+].[Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O QZKRHPLGUJDVAR-UHFFFAOYSA-K 0.000 claims description 3
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims description 3
- JZBRFIUYUGTUGG-UHFFFAOYSA-J tetrapotassium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [K+].[K+].[K+].[K+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O JZBRFIUYUGTUGG-UHFFFAOYSA-J 0.000 claims description 3
- 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 claims description 3
- 229940006460 bromide ion Drugs 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 claims 3
- KYQODXQIAJFKPH-UHFFFAOYSA-N diazanium;2-[2-[bis(carboxymethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [NH4+].[NH4+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O KYQODXQIAJFKPH-UHFFFAOYSA-N 0.000 claims 2
- 125000000217 alkyl group Chemical group 0.000 abstract description 5
- 150000001450 anions Chemical group 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 90
- 239000007844 bleaching agent Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 9
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 6
- 239000002738 chelating agent Substances 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 6
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- 235000010265 sodium sulphite Nutrition 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 239000007864 aqueous solution Substances 0.000 description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 4
- 239000004327 boric acid Substances 0.000 description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 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
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229910021612 Silver iodide Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-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
- 229940125904 compound 1 Drugs 0.000 description 3
- 229940126214 compound 3 Drugs 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000001804 emulsifying effect Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 229940045105 silver iodide Drugs 0.000 description 3
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- JJYPMNFTHPTTDI-UHFFFAOYSA-N 3-methylaniline Chemical compound CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 description 2
- XZIIFPSPUDAGJM-UHFFFAOYSA-N 6-chloro-2-n,2-n-diethylpyrimidine-2,4-diamine Chemical compound CCN(CC)C1=NC(N)=CC(Cl)=N1 XZIIFPSPUDAGJM-UHFFFAOYSA-N 0.000 description 2
- 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 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 235000011126 aluminium potassium sulphate Nutrition 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 150000003931 anilides Chemical class 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- 229910021538 borax Inorganic materials 0.000 description 2
- 150000001649 bromium compounds Chemical class 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 229940050271 potassium alum Drugs 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 239000001509 sodium citrate Substances 0.000 description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 2
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 2
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 2
- 239000004328 sodium tetraborate Substances 0.000 description 2
- 235000010339 sodium tetraborate Nutrition 0.000 description 2
- 229940035044 sorbitan monolaurate Drugs 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 2
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 2
- 150000003585 thioureas Chemical class 0.000 description 2
- FIDRAVVQGKNYQK-UHFFFAOYSA-N 1,2,3,4-tetrahydrotriazine Chemical compound C1NNNC=C1 FIDRAVVQGKNYQK-UHFFFAOYSA-N 0.000 description 1
- SUVZGLSQFGNBQI-UHFFFAOYSA-N 2,5-bis(sulfanyl)hexanedioic acid Chemical compound OC(=O)C(S)CCC(S)C(O)=O SUVZGLSQFGNBQI-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- JTKNFGOPHHCXKK-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid hydroxylamine sulfuric acid Chemical compound C(CN(CC(=O)O)CC(=O)O)N(CC(=O)O)CC(=O)O.S(=O)(=O)(O)O.NO JTKNFGOPHHCXKK-UHFFFAOYSA-N 0.000 description 1
- CSDSSGBPEUDDEE-UHFFFAOYSA-N 2-formylpyridine Chemical compound O=CC1=CC=CC=N1 CSDSSGBPEUDDEE-UHFFFAOYSA-N 0.000 description 1
- HXJSYEGENNLCJV-UHFFFAOYSA-N 2-phenoxyheptanamide Chemical compound CCCCCC(C(N)=O)OC1=CC=CC=C1 HXJSYEGENNLCJV-UHFFFAOYSA-N 0.000 description 1
- LOHOHCTXIJCDQT-UHFFFAOYSA-N 3-[2-[bis(2-carboxyethyl)amino]ethyl-(2-carboxyethyl)amino]propanoic acid 2-[2-[bis(carboxymethyl)amino]-N-(carboxymethyl)anilino]acetic acid Chemical compound C1(=C(C=CC=C1)N(CC(=O)O)CC(=O)O)N(CC(=O)O)CC(=O)O.C(CN(CCC(=O)O)CCC(=O)O)N(CCC(=O)O)CCC(=O)O LOHOHCTXIJCDQT-UHFFFAOYSA-N 0.000 description 1
- FPFSGDXIBUDDKZ-UHFFFAOYSA-N 3-decyl-2-hydroxycyclopent-2-en-1-one Chemical compound CCCCCCCCCCC1=C(O)C(=O)CC1 FPFSGDXIBUDDKZ-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 1
- 239000005955 Ferric phosphate Substances 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- BSRUBDGNLNWCKG-UHFFFAOYSA-M O.C([O-])(O)=O.[Na+].O.O.C(C)(=O)O.C(C)(=O)O.C(C)(=O)O.C(C)(=O)O Chemical compound O.C([O-])(O)=O.[Na+].O.O.C(C)(=O)O.C(C)(=O)O.C(C)(=O)O.C(C)(=O)O BSRUBDGNLNWCKG-UHFFFAOYSA-M 0.000 description 1
- BROZVYJAZHSUDV-UHFFFAOYSA-L O.O.[Na+].[Na+].CC(O)=O.CC(O)=O.CC([O-])=O.CC([O-])=O Chemical compound O.O.[Na+].[Na+].CC(O)=O.CC(O)=O.CC([O-])=O.CC([O-])=O BROZVYJAZHSUDV-UHFFFAOYSA-L 0.000 description 1
- JUDJTDUKMPQMPC-UHFFFAOYSA-N O.S(=O)(=O)(O)O.OCCNC1=CC=CC=C1.S(=O)(=O)(O)O.S(=O)(=O)(O)O.OCCNC1=CC=CC=C1.O Chemical compound O.S(=O)(=O)(O)O.OCCNC1=CC=CC=C1.S(=O)(=O)(O)O.S(=O)(=O)(O)O.OCCNC1=CC=CC=C1.O JUDJTDUKMPQMPC-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- IUOODASIIHGRFI-UHFFFAOYSA-L [K+].C(C)(=O)O.C(C)(=O)[O-].[Na+].C(C)(=O)[O-] Chemical compound [K+].C(C)(=O)O.C(C)(=O)[O-].[Na+].C(C)(=O)[O-] IUOODASIIHGRFI-UHFFFAOYSA-L 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- RGCKGOZRHPZPFP-UHFFFAOYSA-N alizarin Chemical compound C1=CC=C2C(=O)C3=C(O)C(O)=CC=C3C(=O)C2=C1 RGCKGOZRHPZPFP-UHFFFAOYSA-N 0.000 description 1
- 229910001513 alkali metal bromide Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- KDKJYYNXYAZPIK-UHFFFAOYSA-J aluminum potassium disulfate hydrate Chemical compound O.[Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O KDKJYYNXYAZPIK-UHFFFAOYSA-J 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- OVIJIISQYVDAPV-UHFFFAOYSA-M azanium sodium dioxido-oxo-sulfanylidene-lambda6-sulfane sulfurothioic O-acid Chemical compound S(=S)(=O)([O-])[O-].[NH4+].S(=S)(=O)(O)O.[Na+] OVIJIISQYVDAPV-UHFFFAOYSA-M 0.000 description 1
- VTYVIFFJJXAHTG-UHFFFAOYSA-M azanium;sodium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [NH4+].[Na+].[O-]S([O-])(=O)=S VTYVIFFJJXAHTG-UHFFFAOYSA-M 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- KXDAEFPNCMNJSK-UHFFFAOYSA-N benzene carboxamide Natural products NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 1
- CODNYICXDISAEA-UHFFFAOYSA-N bromine monochloride Chemical compound BrCl CODNYICXDISAEA-UHFFFAOYSA-N 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- FGRVOLIFQGXPCT-UHFFFAOYSA-L dipotassium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [K+].[K+].[O-]S([O-])(=O)=S FGRVOLIFQGXPCT-UHFFFAOYSA-L 0.000 description 1
- RSCACTKJFSTWPV-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane;pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 RSCACTKJFSTWPV-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- OAEGRYMCJYIXQT-UHFFFAOYSA-N dithiooxamide Chemical compound NC(=S)C(N)=S OAEGRYMCJYIXQT-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- YAGKRVSRTSUGEY-UHFFFAOYSA-N ferricyanide Chemical compound [Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] YAGKRVSRTSUGEY-UHFFFAOYSA-N 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- UETZVSHORCDDTH-UHFFFAOYSA-N iron(2+);hexacyanide Chemical compound [Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] UETZVSHORCDDTH-UHFFFAOYSA-N 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-N methyl undecanoic acid Natural products CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- VGTPKLINSHNZRD-UHFFFAOYSA-N oxoborinic acid Chemical compound OB=O VGTPKLINSHNZRD-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- GNHOJBNSNUXZQA-UHFFFAOYSA-J potassium aluminium sulfate dodecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.[Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GNHOJBNSNUXZQA-UHFFFAOYSA-J 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- 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
- QQVLLZPVTXZNAS-UHFFFAOYSA-M potassium;bromide;dihydrate Chemical compound O.O.[K+].[Br-] QQVLLZPVTXZNAS-UHFFFAOYSA-M 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229940001593 sodium carbonate Drugs 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229940076133 sodium carbonate monohydrate Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 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
- 239000002904 solvent Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- 150000003567 thiocyanates Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
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
- G03C7/42—Bleach-fixing or agents therefor ; Desilvering processes
- G03C7/421—Additives other than bleaching or fixing agents
Definitions
- ABSTRACT A photographic processing composition, which comprises (l) a ferric ion complex or a persulfate and (2) a compound represented by the following general formula(l) S N I (I) in which R is R is an alkyl group or a QCH 9,, SO group, n is S or 4, and X is an anion, and being absent when R 15 a (-CH 50;, group.
- the basic processings of a silver halide color photographic light-sensitive material are color development and desilvering. That is to say, in an exposed silver halide color photographic material, the silver halide is reduced with a. color developing agent to form silver in the color development step and the oxidation product of the color developing agent reacts with a color coupler to give a dye image. Thereafter, the color photographic material is subjected to the desilvering step, where the silver formed in the preceding step is oxidized with an oxidizing agent which is called a bleaching agent and then dissolved using a complexing agent which is called a fixing agent". Thus, the silver is removed from the photographic material and only the dye image remains thereon.
- auxiliary processing steps in order to retain the photographic and physical properties of the image as well as to improve the storage properties of an image.
- these auxiliary processings are carried out using a hardening bath to prevent the light-sensitive layer(s) during processing from softening excessively, a stopping bath to stop the developing reaction effectively, an image stabilizing bath to stabilize the image and a film removing bath to remove the support backing layer.
- the above described desilvering step can be conducted either in one step using a bleaching and fixing bath wherein a bleaching agent and fixing agent are present in combination or in two steps using a bleaching bath and fixing bath separated.
- the bleaching solution potassium ferricyanide is generally used.
- the bleaching solution using potassium lcrricyanidc has the disadvantages that a latigued bleaching solution must be exchanged and the ferricyanide ion and the ferrocyanide ion in reduced form, which are discharged as an overflow during processing and as an entrainment in the washing water after bleaching, are subject to photochemical oxidation to thus form extremely toxic cyanide compounds. Therefore, it has been desired to develop a new bleaching agent which can be used in place of the potassium ferricyanide.
- potassium bichromate, ferric ion complex salts, persulfates, quinones and copper salts have hitherto been used as a bleaching agent in addition to the potassium ferricyanide, but they are inferior in the oxidizing capacity and in ease of handling.
- Ferric ion complex salts are used as a bleaching agent for a bleaching and fixing solution for color printing papers (German Pat. Nos. 866,605 and 966,410, and British Pat. Nos. 746,567, 933,088 and 1,014,396), but are not often used for color light-sensitive materials for photography, using silver iodobromide in a high concentration, since a bleaching and fixing agent containing a ferric ion complex salt has a low oxidizing capacity. Accordingly it is desirable to increase the oxidizing capacity of a bleaching and fixing solution or bleaching solution using a ferric ion complex salt.
- ferric ion complex salts can be used as a bleaching agent with bromides.
- the disadvantage of a ferric ion complex salt bleaching bath is that a long time is required for bleaching because of a low bleaching capacity.
- Persulfates are known as bleaching agents in addition to the ferric ion complex salts. Ordinarily persulfates are used with bromides in a bleaching bath, but the disadvantage of a persulfate bleaching bath is that a much longer time is necessary for bleaching because of a lower bleaching capacity than that of the ferric ion complex salts.
- a bleaching solution or bleaching and fixing solution using a ferric ion complex salt or a persulfate is not often used in color films using a high silver halide level and having a sensitivity sufficient for use in a camera, because of its weak bleaching capacity.
- R is an alkyl group (e.g., an alkyl group having from 1 to 5 carbon atoms) or -(-Cl-l -)-,,SO n is 3 or 4 and X is an anion (e.g., a sulfonate ion or halide ion such as Cl, Br, or I), with X being absent when R is 4 2+H 3 DETAILED DESCRIPTION OF THE INVENTION
- the ferric ion complex salt or persulfate used in the invention acts as a bleaching agent of silver image as is well known in the art.
- One embodiment of the photographic processing composition according to the invention comprises at least one of the ferric ion complex salt and the persulfate and the above described compound, while another embodiment of the invention comprises compound and at least one of the ferric ion complex salt and the persulfate the above described compound and in addition a fixing agent.
- R is as de- 1 s N N+ MP 260C Q- NIS Q I CH Compound 2 0 SIN N MP 265-265 c CH i Compound 2 Compound 3 MP 2820C CH) rs N ⁇ o 0354 2L; N S -(c1+1 --s0 MP 300 0 Compound 5
- the ferric ion complex used in the present invention is a complex of ferric ion with a chelating agent such as the aminopolycarboxylic acids, and the aminopolyphosphonic acids and their salts.
- a chelating agent such as the aminopolycarboxylic acids, and the aminopolyphosphonic acids and their salts.
- the salts of the aminopolycarboxylic acids and the aminopolyphosphonic acids are the alkali metal, ammonium and water-soluble amine salts.
- Suitable alkali metal salts are the sodium, potassium and lithium salts and suitable water-soluble amine salts are salts of aliphatic amines such as methylamine, diethylamine, triethylamine and butylamine, alicyclic amines such as cyclohexylamine, aromatic amines such as aniline and m-toluidine, and heterocyclic'amines such as pyridine, morpholine and piperidine.
- aminopolycarboxylic acids, aminopolyphosphonic acids and their salts which can be used as the chelating agents in this invention are Ethylenediaminetetraacetic Acid Disodium Ethylenediaminetetraacetate Diammonium Ethylenediaminetetraacetate Tetra(trimethylammonium) Ethylenediaminetetraacetate Tetrapotassium Ethylenediaminetetraacetate Tetrasodium Ethylenediaminetetraacetate Trisodium Ethylenediaminetetraacetate Diethylenetriaminepentaacetic Acid Pentasodium Diethylenetriaminepentacetate Ethylenediamine-N-(B-oxyethyl)-N,N,N'-triacetic Acid Trisodium Ethylenediamine-N-(B-oxyethyl)-N,N,N'-triacetic Acid Trisodium Ethylenediamine-N-(B
- the ferric ion complex salt can be used in the form of a complex salt or can be formed in solution using a ferric salt, for example, ferric sulfate. ferric chloride, ferric nitrate, ferric ammonium sulfate or ferric phosphate and a chelating agent, such as aminopolycarboxylic acid and an aminopolyphosphonic acid.
- a complex salt is employed, the complex salt can be used alone or a combination of two or more complex salts can be used.
- the complex salt is formed in solution from a ferric salt and a chelating agent, one or more ferric salts can be used and one or more chelating agents can be used. In either of these cases, the chelating agent can be used in excess for forming the ferric ion complex salt.
- the ferric ion complex salts are well known in the art, and described for example, in US. Pat. No. 3,582,322.
- the persulfate used as a bleaching agent in the invcw tion can be an alkali metal persulfate, such as potassium persulfate or sodium persulfate. or ammonium persulfate.
- a bromide for example, an alkali metal bromide such as potassium bromide, sodium bromide, or an ammonium bromide can be contained therein in addition to the ferric ion complex salt and the compound of the invention described above.
- one or more inorganic acids, organic acids or their salts having a pH buffering function for example, boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate and tartaric acid can be present.
- Per 1000 ml of a bleaching solution generally the quantity of the ferric ion complex salt or the persulfate is about 0.1 to 2 mols and that of the compound represented by the foregoing general formula is about 2 X 10 to 2 X 10 preferably 1 X 10 to l X 10 mols.
- the pH of a bleaching solution during use generally is 3.0 to 8.0, preferably 4.0 to 7.0 in the case of a ferric ion complex salt and 1.0 to 7.0, preferably 2.0 to 6.0, in the case of a persulfate.
- fixing agents can be used.
- Suitable examplesof these fixing agents are thiosulfates such as sodium thiosulfate, ammonium thiosulfate, ammonium sodium thiosulfate and potassium thiosulfate, thiocyanates such as sodium thiocyanate, ammonium thiocyanate and potassium thiocyanate, and thioether compounds such as ethylenebisthioglycolic acid and -3,6-dithia-l ,8- octanediol.
- the general quantity of the ferric ion complex salt or the persulfate is about 0.1 to 2 mols, that of the fixing agent is about 0.2 to 4 mols and that of the compound represented by the foregoing general formula is about 2 X 10 to 2 X 10 mol, preferably 1 X 10' to l X 10' mol.
- bleaching and fixing solution can be added the above described additives which are disclosed as being suitable for addition to the bleaching solution, and sulfites such as the alkali metal sulfites, e.g., sodium sulfite, potassium sulfite, and ammonium sulfite.
- sulfites such as the alkali metal sulfites, e.g., sodium sulfite, potassium sulfite, and ammonium sulfite.
- sulfites such as the alkali metal sulfites, e.g., sodium sulfite, potassium sulfite, and ammonium sulfite.
- the bleaching and fixing solution further can be added one or more compounds capable of accelerating the bleaching and fixing actions, for example, the polyamine compounds disclosed in Japanese Patent Publication Sho-45-8836, the thiourea derivatives disclosed in Japanese Patent Publication Sho-45-8506, the iodides described in German Pat.
- the pH of the bleaching and fixing solutiong during use is usually 4.0 to 80, preferably 5.0 to 7.0.
- the above described bleaching agent composition of this invention can be used for preparing a bleaching solution for use or as a solution to be used for replentishment and the above described bleaching and fixing agent composition can be used for preparing a bleaching and fixing solution for use or as a solution for replentishment.
- the bleaching capacity can be increased and the ferric ion complex salt can be dissolved in a high concentration, thus giving an excellent bleaching agent or bleaching and fixing agent composition.
- the pH of the ferric ion complex salt-containing agent can be further increased outside of the above mentioned pH range.
- the components above described for preparing the bleaching or bleaching and fixing solutions can be combined ahead of time into a composition for subsequent use or can be added individually at the time of use.
- the present invention can be suitably used and adapted to any of the processings for all types of color photographic materials using silver halide, for example, color papers, color negative films, color reversal films and color positive films as disclosed in U.S. Pat. No. 3,5 82,322.
- the photographic processing composition containing the compound represented by the foregoing general formula has a strong bleaching capacity and can bleach silver in a short time.
- This bleaching period of time gen-' erally is shorter than 2 minutes although this time is varied depending on the temperature, processing conditions etc., employed.
- a ferric ion complex can be contained therein and is not precipitated even at a low temperature, e.g., less than C.
- the bleaching and fixing agent composition according to the invention is superior to bleaching and fixing agent compositions of the prior art in that with the bleaching and fixing agent composition of the invention, it is possible to bleach and fix well color photographic materials having a sensitivity sufficient for camera speed, for example, color negative films and color reversal films, where as it is difficult to bleach and fix such materials with prior art compositions.
- EXAMPLE 1 This example was carried out using a color negative photographic material obtained by mixing and emulsifying a red-sensitive silver iodobromide emulsion (silver iodide 7 mol and l-hydroxy-4-chloro-2-ndodecylnaphthoamide as a cyan coupler, mixing and emulsifying a green-sensitive silver iodobromide (silver iodide 6 mol and l-(2',4',6-trichlorophenyl)-3- (3-(2", 4"' di-t amylphenoxyacetamide)ben- Compound* zamide)-5-pyrazolone as a magenta coupler and mixing and emulsifying a blue-sensitive silver iodobromide emulsion (silver iodide 6 mol /r) and a-(2- methylbenzoyl)-aceto-(2-chloro-5
- dibutyl phthalate and tricresyl phosphate were used as a coupler solvent
- sorbitan monolaurate and sodium dodecylbenzenesulfonate were used as an emulsifier
- sodium l-(pnonylphenoxytrioxyethylene)butane-4-sulfonate and the lauric acid ester of sucrose were added as a coating aid.
- Bleaching and Fixing Solution C 2 X 10 mol/liter of Compound 2- of the invention
- Bleaching and Fixing Solution F 2 X mol/liter of a known compound** was added to Bleaching and Fixing Solution A.
- the time for bleaching and fixing was determined by measuring the time required for complete desilvering as determined using X-ray fluorescent analysis. The results obtained are tabulated below:
- EXAMPLE 2 chlorobromide emulsion containing an emulsified cyan coupler dispersion (silver chloride 70 mol and a gelatin layer containing an ultraviolet light absorbent.
- Each coupler emulsion was prepared by dissolving the coupler in a mixture of dibutyl phthalate and tricresyl phosphate and dispersing in a gelatin solution an o/w type using sorbitan monolaurate, Turkey red oil and sodium dodecylbenzenesulfonate as an emulsifier.
- couplers l-(2, 4, 6-trichlorophenyl)-3-(3-(2", 4- "'-di-t-amylphenoxyacetamide)benzamide)- pyrazolone, 1-(hydroxy)-4-chloro-2-ndodecylnaphthamide and a-(2-methylbenzoyl)-aceto- (2-chloro-5'-dodecoxycarbonyl)anilide were used as the yellow, magenta and cyan couplers, respectively.
- ultra-violet absorbent the one mentioned in Japanese Patent Publication Sho-45-9586 was used.
- the sodium salt of 2,4-dichloro- 6-hydroxy-l,3,5-triazine was used as the emulsion hardener.
- the thus prepared color paper was exposed using a color printer and then subjected to the following color development process-
- the processing solutions used had the following compositions:
- Bleaching and Fixing Solution J 3 X mol/liter of Compound 1 of the invention was added to Bleaching and Fixing Solution l.
- Example 1 The same color film as that described in Example 1 was used and subjected to the same processing as described in Example 1.
- Example 4 Processing I of Example 1 was carried out using a bleaching solution and fixing solution each having the following composition in place of the bleaching and fixing solution:
- Bleaching Solution A Ferric Sodium Ethylenediumine- 100 g tetruucctate Dihydrate Potassium Bromide 50 g pH 6.0 Water to lOOO ml Bleaching Solution B 3 X l mol/liter of Compound 3 of the invention was added to Bleaching Solution A.
- Bleaching Solution Time for Bleaching A i 3 min 10 sec B l min
- the time required for bleaching was shortened when using Bleaching Solution B of the invention in comparison with the time required when using Bleaching Solution A.
- Bleaching Solution C Potassium Persulfate 50 g Potassium Bromide 5 g pH 3.2 g Water to 1000 ml Bleaching Solution D 5 X 10 mol/liter of Compound 1 of the invention was added to Bleaching Solution C.
- Bleaching Solution Time for Bleaching C 13 min D 2 min 30 sec and a bleaching and fixing solution which comprises (l) a ferric ion complex or a persulfate and (2) a compound represented by the following general formula (I) in which R is R is an alkyl group or a-Q-CH, -)-,,SO group; n is 3 or 4; and X is an anion, and being absent when R is a +CH +SO group.
- the photographic processing Composition composition of claim 4 wherein said ferric ion complex salt or or said persulfate is present at about 0.1 to 2 mols per liter of said bleaching solution, wherein said com pound of the general formula (I) is present at about 2 X 10' to 2 X 10' mols per liter of said bleaching solution and wherein the pH of said bleaching solution ranges from about 3 to 8 when said ferric ion complex is present and about 1 to 7 when said persulfate is pres- 6.
- said compound of the general formula (I) is 7.
- said composition is a bleaching and fixing solution. 7 l
- a method for development of an exposed light sensitive silver halide photographic element which comprises developing said silver halide photographic element and contacting said element with a bath containing the photographic processing composition of claim 1.
- ferric ion complex salt is a complex with a member selected from the group consisting of an aminopolycarboxylic acid, an aminopolyphosphonic acid and their salts, which salts are selected from the group consisting of alkali metal, ammonium and water-soluble amine salts.
- ferric ion complex salt is a complex with a member selected from the group consisting of an aminopolycarboxylic acid, an aminopolyphosphonic acid and their salts, which salts are selected from the group consisting of alkali metal, ammonium and watersoluble amine salts.
- ferric ion complex salt is a complex with a member selected from the group consisting of an aminopolycarboxylic acid, an aminopolyphosphonic acid and their salts, which salts are selected from the group consisting of alkali metal, ammonium and water-soluble amine salts.
- ferric ion complex is a complex with a member selected from the group consisting of an aminopolycarboxylic acid, and aminopolyphosphonic acid and their salts, which salts are selected from the group consisting of alkalimetal, ammonium and watersoluble amine salts, wherein said acid is selected from the group consisting of ethylenediaminetetraacetic acid, disodium ethylenediaminetetraacetate, diammo- S N N 1
- ethylenediaminetetraacetate trisodium ethylenediaminetetraacetate, diethylenetriaminepentaacetic acid, pentasodium diethylenetriaminepentaacetate, ethylenediamine-N-(B-oxyethyl)-N,N',N'-triacetic acid, trisodium ethylenediamine-N-(B-oxyethyl)-N,N',N- triacetate, triammonium ethylenediamine-N-(B-oxyethyl)-N,N',N-triacetate, propylenediaminetetraacetic acid, disodium propylenediaminetetraacetate, nitrilotriacetic acid, trisodium nitrilotriacetate, cyclohexanediaminetetraacetic acid, disodium cyclohexanediaminetetraacetate, iminodiacetic acid, dihydroxyethylglycine, eth
- diaminopropanol-N,N,N',N'-tetramethylenephosphonic acid ethylenediamine-N,N,N,N'-tetramethylenephosphonic acid, and 1,3-propylenediamine- N,N,N,N -tetramethylenephosphonic acid.
- ferric ion complex is a complex with a member selected from the group consisting of an aminopolycarboxylic acid, an aminopolyphosphonic acid and their salts, which salts are selected from the group consisting of allgali metal, ammonium and water-soluble amine salts, wherein said acid is selected from the group consisting of ethylenediaminetetraacetic acid, disodium ethylenediaminetetraacetate, diammonium ethylenedi yethylglycine, ethyletherdiaminetetraacetic acid, glycoletherdiaminetetraacetic acid, ethylenediaminetetrapropionic acid, phenylenediaminetetraacetic acid, 1 ,3-
- diaminop ropanol-N ,N,N ,N -tetramethylenephosphonic acid ethylenediamine-N,N,N',N-tetramethylenephosphonic acid
- l,3-propylenediamine- N,N,N',N'-tetramethylenephosphonic acid l,3-propylenediamine- N,N,N',N'-tetramethylenephosphonic acid.
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Abstract
R2 is an alkyl group or a -(CH2)-n SO3 group, n is 3 or 4, and X is an anion, and being absent when R2 is a -(CH2)- SO3 group.
in which R1 is
A photographic processing composition, which comprises (1) a ferric ion complex or a persulfate and (2) a compound represented by the following general formula (I)
in which R1 is
A photographic processing composition, which comprises (1) a ferric ion complex or a persulfate and (2) a compound represented by the following general formula (I)
Description
United States Patent [1 1 Shimamura et al.
[ PHOTOGRAPHIC PROCESSING COMPOSITION [73] Assignee:
[30] Foreign Application Priority Data Oct. 5, l972 Japan 47-100081 [52] US. Cl. 96/60 R, 96/60 BF, 96/22 [5]] Int. Cl G030 5/32, G03c 7/16 {58] Field of Search 96/60, 60 BF. 22, 53
[56] References Cited UNITED STATES PATENTS 3,748,136 7/1973 Willems 96/60 R Primary ExaminerMary F. Kelley Attorney. Agent. or Firm-Sughrue, Rothwell, Mion,
[ Mar. 11, 1975 [57] ABSTRACT A photographic processing composition, which comprises (l) a ferric ion complex or a persulfate and (2) a compound represented by the following general formula(l) S N I (I) in which R is R is an alkyl group or a QCH 9,, SO group, n is S or 4, and X is an anion, and being absent when R 15 a (-CH 50;, group.
27 Claims, No Drawings PHOTOGRAPHIC PROCESSING COMPOSITION BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a composition for photograhic processings and more particularly, it is concerned with an improved composition for bleaching and fixing.
2. Description of the Prior Art In general, the basic processings of a silver halide color photographic light-sensitive material are color development and desilvering. That is to say, in an exposed silver halide color photographic material, the silver halide is reduced with a. color developing agent to form silver in the color development step and the oxidation product of the color developing agent reacts with a color coupler to give a dye image. Thereafter, the color photographic material is subjected to the desilvering step, where the silver formed in the preceding step is oxidized with an oxidizing agent which is called a bleaching agent and then dissolved using a complexing agent which is called a fixing agent". Thus, the silver is removed from the photographic material and only the dye image remains thereon. Development which is generally practiced, in addition to the above mentioned basic two steps of the color development and desilvering, involves auxiliary processing steps in order to retain the photographic and physical properties of the image as well as to improve the storage properties of an image. For example, these auxiliary processings are carried out using a hardening bath to prevent the light-sensitive layer(s) during processing from softening excessively, a stopping bath to stop the developing reaction effectively, an image stabilizing bath to stabilize the image and a film removing bath to remove the support backing layer.
Moreover, the above described desilvering step can be conducted either in one step using a bleaching and fixing bath wherein a bleaching agent and fixing agent are present in combination or in two steps using a bleaching bath and fixing bath separated.
As the bleaching solution, potassium ferricyanide is generally used. However, the bleaching solution using potassium lcrricyanidc has the disadvantages that a latigued bleaching solution must be exchanged and the ferricyanide ion and the ferrocyanide ion in reduced form, which are discharged as an overflow during processing and as an entrainment in the washing water after bleaching, are subject to photochemical oxidation to thus form extremely toxic cyanide compounds. Therefore, it has been desired to develop a new bleaching agent which can be used in place of the potassium ferricyanide.
On the contrary, potassium bichromate, ferric ion complex salts, persulfates, quinones and copper salts have hitherto been used as a bleaching agent in addition to the potassium ferricyanide, but they are inferior in the oxidizing capacity and in ease of handling.
Ferric ion complex salts are used as a bleaching agent for a bleaching and fixing solution for color printing papers (German Pat. Nos. 866,605 and 966,410, and British Pat. Nos. 746,567, 933,088 and 1,014,396), but are not often used for color light-sensitive materials for photography, using silver iodobromide in a high concentration, since a bleaching and fixing agent containing a ferric ion complex salt has a low oxidizing capacity. Accordingly it is desirable to increase the oxidizing capacity of a bleaching and fixing solution or bleaching solution using a ferric ion complex salt.
Furthermore, ferric ion complex salts can be used as a bleaching agent with bromides. However, the disadvantage of a ferric ion complex salt bleaching bath is that a long time is required for bleaching because of a low bleaching capacity. Persulfates are known as bleaching agents in addition to the ferric ion complex salts. Ordinarily persulfates are used with bromides in a bleaching bath, but the disadvantage of a persulfate bleaching bath is that a much longer time is necessary for bleaching because of a lower bleaching capacity than that of the ferric ion complex salts.
As described above, a bleaching solution or bleaching and fixing solution using a ferric ion complex salt or a persulfate is not often used in color films using a high silver halide level and having a sensitivity sufficient for use in a camera, because of its weak bleaching capacity.
Therefore, it is an object of the invention to provide a photographic processing composition which has an accelerated bleaching action but which does not adversely affect the photographic characteristics.
It is another object of the invention to increase the bleaching capacity of a bleaching solution or bleaching and fixing solution containing a ferric ion complex salt or a persulfate.
It is a further object of the invention to provide a method of rapidly bleaching or bleaching and fixing a color photographic material having a photographic sensitivity.
SUMMARY OF THE INVENTION We, the inventors, have found as a result of our various studies that the above described objects canbe accomplished with a photographic processing composition comprising a ferric ion complex salt or a persulfate and a compound represented by the following general formula,
S /N 1 42 N S in which R, is
R is an alkyl group (e.g., an alkyl group having from 1 to 5 carbon atoms) or -(-Cl-l -)-,,SO n is 3 or 4 and X is an anion (e.g., a sulfonate ion or halide ion such as Cl, Br, or I), with X being absent when R is 4 2+H 3 DETAILED DESCRIPTION OF THE INVENTION The ferric ion complex salt or persulfate used in the invention acts as a bleaching agent of silver image as is well known in the art. One embodiment of the photographic processing composition according to the invention comprises at least one of the ferric ion complex salt and the persulfate and the above described compound, while another embodiment of the invention comprises compound and at least one of the ferric ion complex salt and the persulfate the above described compound and in addition a fixing agent. Compounds of the above general formula in which R, is as de- 1 s N N+ MP 260C Q- NIS Q I CH Compound 2 0 SIN N MP 265-265 c CH i Compound 2 Compound 3 MP 2820C CH) rs N\ o 0354 2L; N S -(c1+1 --s0 MP 300 0 Compound 5 The general method of synthesizing the compound represented by the general formula as follows:
Equimolar amounts of rubeanic acid and pyridine aldehyde are heated with refluxing for 3 hours in dimethylformamide and the resulting crystal is quaternized with a corresponding reagent to obtain the desired compound.
The ferric ion complex used in the present invention is a complex of ferric ion with a chelating agent such as the aminopolycarboxylic acids, and the aminopolyphosphonic acids and their salts. The salts of the aminopolycarboxylic acids and the aminopolyphosphonic acids are the alkali metal, ammonium and water-soluble amine salts. Suitable alkali metal salts are the sodium, potassium and lithium salts and suitable water-soluble amine salts are salts of aliphatic amines such as methylamine, diethylamine, triethylamine and butylamine, alicyclic amines such as cyclohexylamine, aromatic amines such as aniline and m-toluidine, and heterocyclic'amines such as pyridine, morpholine and piperidine.
Examples of suitable aminopolycarboxylic acids, aminopolyphosphonic acids and their salts which can be used as the chelating agents in this invention are Ethylenediaminetetraacetic Acid Disodium Ethylenediaminetetraacetate Diammonium Ethylenediaminetetraacetate Tetra(trimethylammonium) Ethylenediaminetetraacetate Tetrapotassium Ethylenediaminetetraacetate Tetrasodium Ethylenediaminetetraacetate Trisodium Ethylenediaminetetraacetate Diethylenetriaminepentaacetic Acid Pentasodium Diethylenetriaminepentaacetate Ethylenediamine-N-(B-oxyethyl)-N,N,N'-triacetic Acid Trisodium Ethylenediamine-N-(B-oxyethyl N,N,N'-triacetate Triammonium Ethylenediamine-N-( B-oxyethyl N,N',N'-triacetate Propylenediaminetetraacetic Acid Disodium Propylenediaminetetraacetate Nitrilotriacetic Acid Trisodium Nitrilotriacetate Cyclohexanediaminetetraacetic Acid Disodium Cyclohexanediaminetetraacetate lminodiacetic Acid Dihydroxyethylglycine Ethyletherdiaminetetraacetic Acid Glycoletherdiaminetetraacetic Acid Ethylenediaminetetrapropionic Acid Phenylenediaminetetraacetic Acid 1,3-Diaminopropanol-N ,N,N ,N -tetramethylenephosphonic Acid Ethylenediamine-N,N,N -tetramethylenephosphonic Acid 1,3Propylenediamine-N ,N,N,N '-tetramethylenephosphonic Acid These compounds are given as typical examples and the present invention is not intended to be limited thereby.
The ferric ion complex salt can be used in the form of a complex salt or can be formed in solution using a ferric salt, for example, ferric sulfate. ferric chloride, ferric nitrate, ferric ammonium sulfate or ferric phosphate and a chelating agent, such as aminopolycarboxylic acid and an aminopolyphosphonic acid. Where a complex salt is employed, the complex salt can be used alone or a combination of two or more complex salts can be used. Where the complex salt is formed in solution from a ferric salt and a chelating agent, one or more ferric salts can be used and one or more chelating agents can be used. In either of these cases, the chelating agent can be used in excess for forming the ferric ion complex salt. The ferric ion complex salts are well known in the art, and described for example, in US. Pat. No. 3,582,322.
The persulfate used as a bleaching agent in the invcw tion can be an alkali metal persulfate, such as potassium persulfate or sodium persulfate. or ammonium persulfate.
When the composition of the invention is used as a bleaching solution, a bromide, for example, an alkali metal bromide such as potassium bromide, sodium bromide, or an ammonium bromide can be contained therein in addition to the ferric ion complex salt and the compound of the invention described above. Furthermore, one or more inorganic acids, organic acids or their salts having a pH buffering function, for example, boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate and tartaric acid can be present.
Per 1000 ml of a bleaching solution, generally the quantity of the ferric ion complex salt or the persulfate is about 0.1 to 2 mols and that of the compound represented by the foregoing general formula is about 2 X 10 to 2 X 10 preferably 1 X 10 to l X 10 mols. The pH of a bleaching solution during use generally is 3.0 to 8.0, preferably 4.0 to 7.0 in the case of a ferric ion complex salt and 1.0 to 7.0, preferably 2.0 to 6.0, in the case of a persulfate.
When the composition of the invention is used as a bleaching and fixing agent, on the other hand,-one or more fixing agents can be used. Suitable examplesof these fixing agents are thiosulfates such as sodium thiosulfate, ammonium thiosulfate, ammonium sodium thiosulfate and potassium thiosulfate, thiocyanates such as sodium thiocyanate, ammonium thiocyanate and potassium thiocyanate, and thioether compounds such as ethylenebisthioglycolic acid and -3,6-dithia-l ,8- octanediol.
Per 1000 ml of a bleaching and fixing solution, the general quantity of the ferric ion complex salt or the persulfate is about 0.1 to 2 mols, that of the fixing agent is about 0.2 to 4 mols and that of the compound represented by the foregoing general formula is about 2 X 10 to 2 X 10 mol, preferably 1 X 10' to l X 10' mol.
To such bleaching and fixing solution can be added the above described additives which are disclosed as being suitable for addition to the bleaching solution, and sulfites such as the alkali metal sulfites, e.g., sodium sulfite, potassium sulfite, and ammonium sulfite. To the bleaching and fixing solution further can be added one or more compounds capable of accelerating the bleaching and fixing actions, for example, the polyamine compounds disclosed in Japanese Patent Publication Sho-45-8836, the thiourea derivatives disclosed in Japanese Patent Publication Sho-45-8506, the iodides described in German Pat. No, 1,127,715, the polyethylene oxides described in German Pat. No.
7 966,410, the nitrogen-containing heterocyclic compounds described in German Pat. No. 1,290,812 and other thioureas. The pH of the bleaching and fixing solutiong during use is usually 4.0 to 80, preferably 5.0 to 7.0.
The above described bleaching agent composition of this invention can be used for preparing a bleaching solution for use or as a solution to be used for replentishment and the above described bleaching and fixing agent composition can be used for preparing a bleaching and fixing solution for use or as a solution for replentishment. By the addition of the compound of the invention, the bleaching capacity can be increased and the ferric ion complex salt can be dissolved in a high concentration, thus giving an excellent bleaching agent or bleaching and fixing agent composition. In the case of the preparation of two or more solutions, therefore, the pH of the ferric ion complex salt-containing agent can be further increased outside of the above mentioned pH range. The components above described for preparing the bleaching or bleaching and fixing solutions can be combined ahead of time into a composition for subsequent use or can be added individually at the time of use.
The present invention can be suitably used and adapted to any of the processings for all types of color photographic materials using silver halide, for example, color papers, color negative films, color reversal films and color positive films as disclosed in U.S. Pat. No. 3,5 82,322.
The photographic processing composition containing the compound represented by the foregoing general formula has a strong bleaching capacity and can bleach silver in a short time. This bleaching period of time gen-' erally is shorter than 2 minutes although this time is varied depending on the temperature, processing conditions etc., employed. Moreover, a ferric ion complex can be contained therein and is not precipitated even at a low temperature, e.g., less than C. In particular, the bleaching and fixing agent composition according to the invention is superior to bleaching and fixing agent compositions of the prior art in that with the bleaching and fixing agent composition of the invention, it is possible to bleach and fix well color photographic materials having a sensitivity sufficient for camera speed, for example, color negative films and color reversal films, where as it is difficult to bleach and fix such materials with prior art compositions.
The following examples are given in order to illustrate the invention in greater detail without intending to limit the same. Unless otherwise indicated all percents and parts are by weight.
EXAMPLE 1 This example was carried out using a color negative photographic material obtained by mixing and emulsifying a red-sensitive silver iodobromide emulsion (silver iodide 7 mol and l-hydroxy-4-chloro-2-ndodecylnaphthoamide as a cyan coupler, mixing and emulsifying a green-sensitive silver iodobromide (silver iodide 6 mol and l-(2',4',6-trichlorophenyl)-3- (3-(2", 4"' di-t amylphenoxyacetamide)ben- Compound* zamide)-5-pyrazolone as a magenta coupler and mixing and emulsifying a blue-sensitive silver iodobromide emulsion (silver iodide 6 mol /r) and a-(2- methylbenzoyl)-aceto-(2-chloro-5-dodecoxycarbonyl ).anilide as a yellow coupler, and then applying the resulting emulsions to a triacetate film base. For the emulsification of the each coupler, dibutyl phthalate and tricresyl phosphate were used as a coupler solvent, sorbitan monolaurate and sodium dodecylbenzenesulfonate were used as an emulsifier, and sodium l-(pnonylphenoxytrioxyethylene)butane-4-sulfonate and the lauric acid ester of sucrose were added as a coating aid.
This film was exposed and then subjected to the fol lowing processing 1:
Processing l Color Development 12 min Stopping Bath 4 do. Hardening Bath 4 do. Water Washing 4 do. Bleaching and Fixing Bath shown in the following table Water Washing 8 do. Drying Composition of Color Developer Benzyl Alcohol 5 ml Sodium Hydroxide 0.5 g Diethylene Glycol 3 ml Sodium Hexametaphosphate 2 g Sodium Sulfite 2 g Potassium Bromide 2 g 4-Amino 3-methyl-N ethyl-fl- 5 g hydroxyethylaniline Sesquisulfate Monohydrate Metaboric Acid 0.5 g Sodium Metaborate 77 g Water to 1000 ml Stopping Solution Sodium Acetate 30 g Glacial Acetic Acid 8 ml Water to 1000 ml Hardening Bath Sodium Hexametaphosphate l g Borax Pentahydrate 20 g Formalin (37%) 10 ml Bleaching and Fixing Solution A Ferric Sodium Ethylenediamine- 80 g tetraacetate (dihydrate) Disodium Ethylenediamine- 15 g tetraacetate (dihydrate) Sodium Carbonate Monohydrate 17 g Boric Acid 5 g Sodium Sulfite 5 g Ammonium Thiosulfate ml (70% aqueous solution) 5 5 Water to 1000 ml Bleaching and Fixing Solution B 2 X 10' mol/liter of Compound 1 of the invention was added to Bleaching and Fixing Solution A.
Bleaching and Fixing Solution C 2 X 10 mol/liter of Compound 2- of the invention Bleaching and Fixing Solution F 2 X mol/liter of a known compound** was added to Bleaching and Fixing Solution A.
The time for bleaching and fixing was determined by measuring the time required for complete desilvering as determined using X-ray fluorescent analysis. The results obtained are tabulated below:
Compound M Bleaching and Fixing Solution Time for Bleaching and Fixing 4 min 20 sec 1 min 10 sec 1 min 40 sec 1 min 20 sec 3 min 20 sec 2 min 50 sec The time required for bleaching and fixing was shortened when using Bleaching and Fixing Solutions B, C and D of the invention in comparison with the time required for Bleaching and Fixing Solutions A, E and F.
EXAMPLE 2 chlorobromide emulsion containing an emulsified cyan coupler dispersion (silver chloride 70 mol and a gelatin layer containing an ultraviolet light absorbent. Each coupler emulsion was prepared by dissolving the coupler in a mixture of dibutyl phthalate and tricresyl phosphate and dispersing in a gelatin solution an o/w type using sorbitan monolaurate, Turkey red oil and sodium dodecylbenzenesulfonate as an emulsifier. As the couplers, l-(2, 4, 6-trichlorophenyl)-3-(3-(2", 4- "'-di-t-amylphenoxyacetamide)benzamide)- pyrazolone, 1-(hydroxy)-4-chloro-2-ndodecylnaphthamide and a-(2-methylbenzoyl)-aceto- (2-chloro-5'-dodecoxycarbonyl)anilide were used as the yellow, magenta and cyan couplers, respectively. As the ultra-violet absorbent, the one mentioned in Japanese Patent Publication Sho-45-9586 was used. As the emulsion hardener, the sodium salt of 2,4-dichloro- 6-hydroxy-l,3,5-triazine was used. The thus prepared color paper was exposed using a color printer and then subjected to the following color development process- The processing solutions used had the following compositions:
Color Developer Composition Benzyl Alcohol Diethylene Glycol Sodium Hydroxide Sodium Sulfite Potassium Bromide Sodium Chloride Borax Hydroxylamine Sulfate Ethylenediaminetetraacetic Acid 4-Amino-3-methyl-N-ethyl-N-(B- sulfonamideethyl)aniline Sesquisulfate Monohydrate Water to Stopping Solution Sodium Thiosulfate Ammonium Thiosulfate aqueous solution) Sodium Acetate Acetic Acid Potassium Alum Water to Stabilizing Solution Boric Acid 5 Sodium Citrate 5 Sodium Metaborate (tetrahydrate) 3 5 Potassium Alum Water to Bleaching and Fixing Solution G Ferric Sulfate Disodium Ethylenediaminetetraacetate Dihydrate Sodium Carbonate Monohydrate Sodium Sulfite Ammonium Thiosulfate (70% aqueous solution) Boric Acid 5 g pH 6.8 Water to O m Bleaching and Fixing Solution H l X 10 mol/liter of Compound 3 of the invention was added to Bleaching and Fixing Solution G.
The time required for bleaching and fixing was measured using Bleaching and Fixing Solutions G and H. The results obtained are tabulated below:
Time for Bleaching and Fixing Solution Bleaching and Fixing G 60 sec H 45 sec The time required for bleaching and fixing was shortened when using Bleaching and Fixing Solution H of the invention in comparison with the time required using Bleaching and Fixing Solution Gr EXAMPLE 3 Two bleaching and fixing solutions having the following compositions were prepared:
Bleaching and Fixing Solution J 3 X mol/liter of Compound 1 of the invention was added to Bleaching and Fixing Solution l.
The same color film as that described in Example 1 was used and subjected to the same processing as described in Example 1.
The time required for bleaching and fixing was measured using Bleaching and Fixing Solutions 1 and J. The results obtained are tabulated below:
Time for Bleaching and Fixing Solution Bleaching and Fixing l l min 30 sec J 45 sec The time required for bleaching and fixing was shortened when using Bleaching and Fixing Solution J of the invention in comparison with the time required using Bleaching and Fixing Solution I. The bleaching and fixing solution of the invention could also be used sufficiently as a bleaching and fixing solution for a commercially marketed internal-type reversal color film for example, as described in US. Pat. No. 3,582,322.
EXAMPLE 4 Processing I of Example 1 was carried out using a bleaching solution and fixing solution each having the following composition in place of the bleaching and fixing solution:
Bleaching Solution A Ferric Sodium Ethylenediumine- 100 g tetruucctate Dihydrate Potassium Bromide 50 g pH 6.0 Water to lOOO ml Bleaching Solution B 3 X l mol/liter of Compound 3 of the invention was added to Bleaching Solution A.
Fixing Solution Sodium Sulfite 4 g Sodium Bisulfite 4 g Ammonium Thiosulfate 140 ml (70% aqueous solution) Water to 1000 ml The time required for bleaching 'was measured using Bleaching Solutions A and B. Fixing was carried out for 6 minutes in any case. The results obtained are tabulated below:
Bleaching Solution Time for Bleaching A i 3 min 10 sec B l min The time required for bleaching was shortened when using Bleaching Solution B of the invention in comparison with the time required when using Bleaching Solution A.
EXAMPLE 5 A similar procedure to that described in Example 4v was repeated but using bleaching solutions each having the following composition:
Bleaching Solution C Potassium Persulfate 50 g Potassium Bromide 5 g pH 3.2 g Water to 1000 ml Bleaching Solution D 5 X 10 mol/liter of Compound 1 of the invention was added to Bleaching Solution C.
The time required for bleaching was measured using Bleaching Solution C and D. The results obtained are tabulated below:
Bleaching Solution Time for Bleaching C 13 min D 2 min 30 sec and a bleaching and fixing solution which comprises (l) a ferric ion complex or a persulfate and (2) a compound represented by the following general formula (I) in which R is R is an alkyl group or a-Q-CH, -)-,,SO group; n is 3 or 4; and X is an anion, and being absent when R is a +CH +SO group.
2. The photographic processing composition as set forth in claim l, wherein R is methyl, ethyl, -(-CH S0,, or -(-CH,+.,SO and wherein X" is a bromide ion or a p-toluene sulfonate ion.
3. The photographic processing composition of claim 1, wherein said composition is a bleaching solution.
4. The photographic processing composition of claim 3, wherein said bleaching solution contains a bromide and a pH buffering agent.
5. The photographic processing Composition composition of claim 4, wherein said ferric ion complex salt or or said persulfate is present at about 0.1 to 2 mols per liter of said bleaching solution, wherein said com pound of the general formula (I) is present at about 2 X 10' to 2 X 10' mols per liter of said bleaching solution and wherein the pH of said bleaching solution ranges from about 3 to 8 when said ferric ion complex is present and about 1 to 7 when said persulfate is pres- 6. The photographic processing composition of claim 1, wherein said compound of the general formula (I) is 7. The photographic processing composition of claim 1, wherein said composition is a bleaching and fixing solution. 7 l
8. The photographic processing composition of claim 7, wherein said solution contains a thiosulfate.
9. The photographic processing composition ofclaim 8, wherein said ferric ion complex salt or said persulfate is present at about 0.1 to 2 mols per liter of said bleaching and fixing solution, wherein said fixing agent is present at about 0.2 to 4 mols per liter of said bleaching and fixing solution, wherein said compound of the general formula (I) is present at about 2 X 10' to 2 X 10 mols per liter of said bleaching and fixing solution, and wherein the pH of said bleaching and fixing solution is about 4 to 8.
10. A method for development of an exposed light sensitive silver halide photographic element which comprises developing said silver halide photographic element and contacting said element with a bath containing the photographic processing composition of claim 1.
11. The method for development of claim 10, wherein said composition is a bleaching solution.
e S N- I /N 2 CH -Q-SO H O I2. The method for development of claim 11, wherein said bleaching solution contains additionally a bromide and a pH buffering agent.
13. The method for development of claim 10, wherein said compound of the general formula (I) is e s t N N ECH- ide photographic element which comprises subjecting said silver halide photographic element to a silner bleaching or a silner bleaching and fixing with a bath containing the photographic processing composition of 5 claim 1. r
17. The method of accelerating of claim 16, wherein said composition is a bleaching solution.
18. The method of accelerating of claim 17, wherein 55 said bleaching solution contains a bromide and a pH buffering agent.
19. The method of accelerating of claim 16, wherein said compound of the general formula (I) is a: s ,N N
20. The method of accelerating of claim 16, wherein said composition is a bleaching and fixing solution.
21. The method of accelerating of claim 20, wherein said solution contains a thiosulfate.
22. The photographic processing composition of claim 1, wherein said ferric ion complex salt is a complex with a member selected from the group consisting of an aminopolycarboxylic acid, an aminopolyphosphonic acid and their salts, which salts are selected from the group consisting of alkali metal, ammonium and water-soluble amine salts.
23. The method for development of claim 10, wherein said ferric ion complex salt is a complex with a member selected from the group consisting of an aminopolycarboxylic acid, an aminopolyphosphonic acid and their salts, which salts are selected from the group consisting of alkali metal, ammonium and watersoluble amine salts.
24. The method of accelerating of claim 16, wherein said ferric ion complex salt is a complex with a member selected from the group consisting of an aminopolycarboxylic acid, an aminopolyphosphonic acid and their salts, which salts are selected from the group consisting of alkali metal, ammonium and water-soluble amine salts.
25. The photographic processing composition of claim 1, wherein said ferric ion complex is a complex with a member selected from the group consisting of an aminopolycarboxylic acid, and aminopolyphosphonic acid and their salts, which salts are selected from the group consisting of alkalimetal, ammonium and watersoluble amine salts, wherein said acid is selected from the group consisting of ethylenediaminetetraacetic acid, disodium ethylenediaminetetraacetate, diammo- S N N 1| l- N S CH nium ethylenediaminetetraacetate, tetra(trimethylammonium) ethylenediaminetetraacetate, tetrapotassium ethylenediaminetetraacetate, tetrasodium ethylenediaminetetraacetate, trisodium minetetraacetate, diethylenetriaminepentaacetic acid, pentasodium diethylenetriaminepentaacetate, ethylenediamine-N-(B-oxyethyl)'N,N',N'-triacetic acid, trisodium ethylenediamine-N-(. -0xyethyl)-N,N,N'- triacetate, triammonium ethylenediamine-N-(B-oxyethyl)-N,N,N-triacetate, propylenediaminetetraacetic acid, disodium propylenediaminetetraacetate, nitrilotriacetic acid, trisodium nitrilotriacetate, cyclohexan deiaminetetraacetic acid, disodium cyclohexanediaminetetraacetate, iminidiacetic acid, dihydroxyethylglycine, ethyletherdiaminetetraacetic acid, glycoletherdiaminetetraacetic acid, ethylenediaminetetrapropionic acid, phenylenediaminetetraacetic acid, 1,3-
ethylenediaminetetraacetate, trisodium ethylenediaminetetraacetate, diethylenetriaminepentaacetic acid, pentasodium diethylenetriaminepentaacetate, ethylenediamine-N-(B-oxyethyl)-N,N',N'-triacetic acid, trisodium ethylenediamine-N-(B-oxyethyl)-N,N',N- triacetate, triammonium ethylenediamine-N-(B-oxyethyl)-N,N',N-triacetate, propylenediaminetetraacetic acid, disodium propylenediaminetetraacetate, nitrilotriacetic acid, trisodium nitrilotriacetate, cyclohexanediaminetetraacetic acid, disodium cyclohexanediaminetetraacetate, iminodiacetic acid, dihydroxyethylglycine, ethyletherdiaminetetraacetic acid, glycoletherdiaminetetraacetic acid, ethylencdiaminetetrapropionic acid, phenylenediaminetetraacetic acid, 1,3-
diaminopropanol-N,N,N',N'-tetramethylenephosphonic acid, ethylenediamine-N,N,N,N'-tetramethylenephosphonic acid, and 1,3-propylenediamine- N,N,N,N -tetramethylenephosphonic acid.
27. The method of accelerating of claim 16, wherein said ferric ion complex is a complex with a member selected from the group consisting of an aminopolycarboxylic acid, an aminopolyphosphonic acid and their salts, which salts are selected from the group consisting of allgali metal, ammonium and water-soluble amine salts, wherein said acid is selected from the group consisting of ethylenediaminetetraacetic acid, disodium ethylenediaminetetraacetate, diammonium ethylenedi yethylglycine, ethyletherdiaminetetraacetic acid, glycoletherdiaminetetraacetic acid, ethylenediaminetetrapropionic acid, phenylenediaminetetraacetic acid, 1 ,3-
diaminop ropanol-N ,N,N ,N -tetramethylenephosphonic acid, ethylenediamine-N,N,N',N-tetramethylenephosphonic acid, and l,3-propylenediamine- N,N,N',N'-tetramethylenephosphonic acid.
ethylenedia-'
Claims (27)
1. A PHOTOGRAPHIC SILVER BLEACHING COMPOSITION SELECTED FROM THE GROUP CONSISTING OF A BLEACHING SOLUTION AND A BLEACHING AND FIXING SOLUTION WHICH COMPRISES (1) A FERRIC ION COMPLEX OR A PERSULFATE AND (2) A COMPOUND REPRESENTED BY THE FOLLOWING GENERAL FORMULA (1)
1. A photographic silver bleaching composition selected from the group consisting of a bleaching solution and a bleaching and fixing solution, which comprises (1) a ferric ion complex or a persulfate and (2) a compound represented by the following general formula (I)
2. The photographic processing composition as set forth in claim 1, wherein R2 is methyl, ethyl, -CH2-3 SO3 or -CH2-4SO3 , and wherein X is a bromide ion or a p-toluene sulfonate ion.
3. The photographic processing composition of claim 1, wherein said composition is a bleaching solution.
4. The photographic processing composition of claim 3, wherein said bleaching solution contains a bromide and a pH buffering agent.
5. The photographic processing composition of claim 4, wherein said ferric ion complex salt or said persulfate is present at about 0.1 to 2 mols per liter of said bleaching solution, wherein said compound of the general formula (I) is present at about 2 X 10 6 to 2 X 10 2 mols per liter of said bleaching solution and wherein the pH of said bleaching solution ranges from about 3 to 8 when said ferric ion complex is present and about 1 to 7 when said persulfate is present.
6. The photographic processing composition of claim 1, wherein said compound of the general formula (I) is
7. The photographic processing composition of claim 1, wherein said composition is a bleaching and fixing solution.
8. The photographic processing composition of claim 7, wherein said solution contains a thiosulfate.
9. The photographic processing composition of claim 8, wherein said ferric ion complex salt or said persulfate is present at about 0.1 to 2 mols per liter of said bleaching and fixing solution, wherein said fixing agent is present at about 0.2 to 4 mols per liter of said bleaching and fixing solution, wherein said compound of the general formula (I) is present at about 2 X 10 6 to 2 X 10 2 mols per liter of said bleaching and fixing solution, and wherein the pH of said bleaching and fixing solution is about 4 to 8.
10. A method for development of an exposed light sensitive silver halide photographic element which comprises developing said silver halide photograpHic element and contacting said element with a bath containing the photographic processing composition of claim 1.
11. The method for development of claim 10, wherein said composition is a bleaching solution.
12. The method for development of claim 11, wherein said bleaching solution contains additionally a bromide and a pH buffering agent.
13. The method for development of claim 10, wherein said compound of the general formula (I) is
14. The method of development of claim 10, wherein said composition is a bleaching and fixing solution.
15. The method of development of claim 14, wherein said solution contains a thiosulfate.
16. A method of accelerating the silver bleaching or the silver bleaching and fixing of a silver halide photographic element in the development of said silver halide photographic element which comprises subjecting said silver halide photographic element to a silver bleaching or a silver bleaching and fixing with a bath containing the photographic processing composition of claim 1.
17. The method of accelerating of claim 16, wherein said composition is a bleaching solution.
18. The method of accelerating of claim 17, wherein said bleaching solution contains a bromide and a pH buffering agent.
19. The method of accelerating of claim 16, wherein said compound of the general formula (I) is
20. The method of accelerating of claim 16, wherein said composition is a bleaching and fixing solution.
21. The method of accelerating of claim 20, wherein said solution contains a thiosulfate.
22. The photographic processing composition of claim 1, wherein said ferric ion complex salt is a complex with a member selected from the group consisting of an aminopolycarboxylic acid, an aminopolyphosphonic acid and their salts, which salts are selected from the group consisting of alkali metal, ammonium and water-soluble amine salts.
23. The method for development of claim 10, wherein said ferric ion complex salt is a complex with a member selected from the group consisting of an aminopolycarboxylic acid, an aminopolyphosphonic acid and their salts, which salts are selected from the group consisting of alkali metal, ammonium and water-soluble amine salts.
24. The method of accelerating of claim 16, wherein said ferric ion complex salt is a complex with a member selected from the group consisting of an aminopolycarboxylic acid, an aminopolyphosphonic acid and their salts, which salts are selected from the group consisting of alkali metal, ammonium and water-soluble amine salts.
25. The photographic processing composition of claim 1, wherein said ferric ion complex is a complex with a member selected from the group consisting of an aminopolycarboxylic acid, an aminopolyphosphonic acid and their salts, which salts are selected from the group consisting of alkali metal, ammonium and water-soluble amine salts, wherein said acid is selected from the group consisting of ethylenediaminetetraacetic acid, disodium ethylenediaminetetraacetate, diammonium ethylenediaminetetraacetate, tetra(trimethylammonium) ethylenediaminetetraacetate, tetrapotassium ethylenediaminetetraacetate, tetrasodium ethylenediaminetetraacetate, trisodium ethylenediaminetetraacetate, diethylenetriaminepentaacetic acid, pentasodium diethylenetriaminepentaacetate, ethylenediamine-N-( Beta -oxyethyl)-N,N'',N''-triacetic acid, trisodium ethylenediamine-N-( Beta -oxyethyl)-N,N'',N''-triacetate, triammonium ethylenediamine-N-( Beta -oxyethyl)-N,N'',N''-triacetate, propylenediaminetetraacetic acid, disodium propylenediaminetetraacetate, nitrilotriacetic acid, trisodium nitrilotriacetate, cyclohexanediaminetetraacetic acid, disodium cyclohexanediaminetetraacetate, iminodiacetic acid, dihydroxyethylglycine, ethyletherdiaminetetraacetic acid, glycoletherdiaminetetraacetic acid, ethylenediaminetetrapropionic acid, phenylenediaminetetraacetic acid, 1,3-diaminopropanol-N,N, N'',N''-tetramethylenephosphonic acid, etHylenediamine-N,N,N'',N''-tetramethylenephosphonic acid, and 1,3-propylenediamine-N,N,N'', N''-tetramethylenephosphonic acid.
26. The method for development of claim 10, wherein said ferric ion complex is a complex with a member selected from the group consisting of an aminopolycarboxylic acid, an aminopolyphosphonic acid and their salts, which salts are selected from the group consisting of alkali metal, ammonium and water-soluble amine salts, wherein said acid is selected from the group consisting of ethylenediaminetetraacetic acid, disodium ethylenediaminetetraacetate, diammonium ethylenediaminetetraacetate, tetra(trimethylammonium) ethylenediaminetetraacetate, tetrapotassium ethylenediaminetetraacetate, tetrasodium ethylenediaminetetraacetate, trisodium ethylenediaminetetraacetate, diethylenetriaminepentaacetic acid, pentasodium diethylenetriaminepentaacetate, ethylenediamine-N-( Beta -oxyethyl)-N,N'',N''-triacetic acid, trisodium ethylenediamine-N-( Beta -oxyethyl)-N,N'',N''-triacetate, triammonium ethylenediamine-N-( Beta -oxyethyl)-N,N'',N''-triacetate, propylenediaminetetraacetic acid, disodium propylenediaminetetraacetate, nitrilotriacetic acid, trisodium nitrilotriacetate, cyclohexanediaminetetraacetic acid, disodium cyclohexanediaminetetraacetate, iminodiacetic acid, dihydroxyethylglycine, ethyletherdiaminetetraacetic acid, glycoletherdiaminetetraacetic acid, ethylenediaminetetrapropionic acid, phenylenediaminetetraacetic acid, 1,3-diaminopropanol-N,N, N'',N''-tetramethylenephosphonic acid, ethylenediamine-N,N,N'',N''-tetramethylenephosphonic acid, and 1,3-propylenediamine-N,N,N'', N''-tetramethylenephosphonic acid.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP47100081A JPS5128227B2 (en) | 1972-10-05 | 1972-10-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3870520A true US3870520A (en) | 1975-03-11 |
Family
ID=14264478
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US403293A Expired - Lifetime US3870520A (en) | 1972-10-05 | 1973-10-03 | Photographic processing composition |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US3870520A (en) |
| JP (1) | JPS5128227B2 (en) |
| DE (1) | DE2350209C2 (en) |
| GB (1) | GB1405047A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4113486A (en) * | 1973-10-22 | 1978-09-12 | Fuji Photo Film Co., Ltd. | Method for producing a photomask |
| US4277556A (en) * | 1976-08-18 | 1981-07-07 | Konishiroku Photo Industry Co., Ltd. | Process for treating light-sensitive silver halide color photographic materials |
| US4292401A (en) * | 1979-04-12 | 1981-09-29 | Fuji Photo Film Co., Ltd. | Bleaching composition for photographic processing |
| US4301236A (en) * | 1979-01-23 | 1981-11-17 | Fuji Photo Film Co., Ltd. | Photographic bleach solutions |
| US4328306A (en) * | 1979-08-29 | 1982-05-04 | Fuji Photo Film Co., Ltd. | Processing method for color photographic materials |
| US4508817A (en) * | 1983-05-20 | 1985-04-02 | Fuji Photo Film Co., Ltd. | Method of color photographic processing |
| US4552834A (en) * | 1984-08-06 | 1985-11-12 | Eastman Kodak Company | Enhanced bleaching of photographic elements containing silver halide and adsorbed dye |
| US5188927A (en) * | 1990-06-15 | 1993-02-23 | Fuji Photo Film Co., Ltd. | Composition and process for the processing of silver halide color photographic material |
| EP0605039A1 (en) * | 1992-12-29 | 1994-07-06 | Eastman Kodak Company | A method of bleaching and fixing a color photographic element containing high iodide emulsions |
| US5510232A (en) * | 1994-12-22 | 1996-04-23 | Eastman Kodak Company | Photographic processing composition and method using cationic hydroquinone as organic catalyst for persulfate bleaching agent |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH627006A5 (en) * | 1977-03-23 | 1981-12-15 | Ciba Geigy Ag | |
| JPS5469013U (en) * | 1977-10-24 | 1979-05-16 | ||
| JPS558696U (en) * | 1978-07-05 | 1980-01-21 | ||
| US4851327A (en) | 1986-07-17 | 1989-07-25 | Fuji Photo Film Co., Ltd. | Photographic color photosensitive material with two layer reflective support |
| JPH01108546A (en) | 1987-10-22 | 1989-04-25 | Fuji Photo Film Co Ltd | Silver halide color photographic sensitive material |
| JPH01140153A (en) | 1987-11-27 | 1989-06-01 | Fuji Photo Film Co Ltd | Silver halide color photographic sensitive material |
| JPH0833628B2 (en) | 1987-12-15 | 1996-03-29 | 富士写真フイルム株式会社 | Silver halide color photographic light-sensitive material |
| DE68919159T2 (en) * | 1988-08-19 | 1995-03-09 | Fuji Photo Film Co Ltd | Photographic processor. |
| EP0435334B1 (en) | 1989-12-29 | 1997-11-05 | Fuji Photo Film Co., Ltd. | Silver halide color photographic material containing yellow colored cyan coupler |
| EP0440195B1 (en) | 1990-01-31 | 1997-07-30 | Fuji Photo Film Co., Ltd. | Silver halide color photographic material |
| EP0476327B1 (en) | 1990-08-20 | 1999-11-17 | Fuji Photo Film Co., Ltd. | Data-retainable photographic film product and process for producing color print |
| US5418124A (en) | 1992-03-19 | 1995-05-23 | Fuji Photo Film Co. Ltd. | Silver halide photographic emulsion and a photographic light-sensitive material |
| EP0563708B1 (en) | 1992-03-19 | 2000-06-21 | Fuji Photo Film Co., Ltd. | Process for preparing a silver halide photographic emulsion |
| JP2777949B2 (en) | 1992-04-03 | 1998-07-23 | 富士写真フイルム株式会社 | Silver halide color photographic materials |
| JPH08202001A (en) | 1995-01-30 | 1996-08-09 | Fuji Photo Film Co Ltd | Silver halide color photographic sensitive material |
| KR100890145B1 (en) * | 2006-06-15 | 2009-03-20 | 주식회사 엘지화학 | Thiazolothiazole derivatives and organic electronic devices using the same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3748136A (en) * | 1970-08-10 | 1973-07-24 | Agfa Gevaert Nv | Photographic silver bleaching solution |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1297653A (en) * | 1969-12-23 | 1972-11-29 |
-
1972
- 1972-10-05 JP JP47100081A patent/JPS5128227B2/ja not_active Expired
-
1973
- 1973-10-03 GB GB4627173A patent/GB1405047A/en not_active Expired
- 1973-10-03 US US403293A patent/US3870520A/en not_active Expired - Lifetime
- 1973-10-05 DE DE2350209A patent/DE2350209C2/en not_active Expired
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3748136A (en) * | 1970-08-10 | 1973-07-24 | Agfa Gevaert Nv | Photographic silver bleaching solution |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4113486A (en) * | 1973-10-22 | 1978-09-12 | Fuji Photo Film Co., Ltd. | Method for producing a photomask |
| US4277556A (en) * | 1976-08-18 | 1981-07-07 | Konishiroku Photo Industry Co., Ltd. | Process for treating light-sensitive silver halide color photographic materials |
| US4301236A (en) * | 1979-01-23 | 1981-11-17 | Fuji Photo Film Co., Ltd. | Photographic bleach solutions |
| US4292401A (en) * | 1979-04-12 | 1981-09-29 | Fuji Photo Film Co., Ltd. | Bleaching composition for photographic processing |
| US4328306A (en) * | 1979-08-29 | 1982-05-04 | Fuji Photo Film Co., Ltd. | Processing method for color photographic materials |
| US4508817A (en) * | 1983-05-20 | 1985-04-02 | Fuji Photo Film Co., Ltd. | Method of color photographic processing |
| US4552834A (en) * | 1984-08-06 | 1985-11-12 | Eastman Kodak Company | Enhanced bleaching of photographic elements containing silver halide and adsorbed dye |
| US5188927A (en) * | 1990-06-15 | 1993-02-23 | Fuji Photo Film Co., Ltd. | Composition and process for the processing of silver halide color photographic material |
| EP0605039A1 (en) * | 1992-12-29 | 1994-07-06 | Eastman Kodak Company | A method of bleaching and fixing a color photographic element containing high iodide emulsions |
| US5464728A (en) * | 1992-12-29 | 1995-11-07 | Eastman Kodak Company | Method of bleaching and fixing a color photographic element containing high iodine emulsions |
| US5510232A (en) * | 1994-12-22 | 1996-04-23 | Eastman Kodak Company | Photographic processing composition and method using cationic hydroquinone as organic catalyst for persulfate bleaching agent |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5128227B2 (en) | 1976-08-18 |
| JPS4959644A (en) | 1974-06-10 |
| GB1405047A (en) | 1975-09-03 |
| DE2350209A1 (en) | 1974-04-11 |
| DE2350209C2 (en) | 1984-07-26 |
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