DE1290812B - Process for bleach-fixing silver photographic images - Google Patents
Process for bleach-fixing silver photographic imagesInfo
- Publication number
- DE1290812B DE1290812B DEA49448A DEA0049448A DE1290812B DE 1290812 B DE1290812 B DE 1290812B DE A49448 A DEA49448 A DE A49448A DE A0049448 A DEA0049448 A DE A0049448A DE 1290812 B DE1290812 B DE 1290812B
- Authority
- DE
- Germany
- Prior art keywords
- mercapto
- bleach
- bath
- amino
- compounds
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052709 silver Inorganic materials 0.000 title claims description 18
- 239000004332 silver Substances 0.000 title claims description 18
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims description 17
- 238000000034 method Methods 0.000 title claims description 9
- 239000000463 material Substances 0.000 claims description 15
- -1 mercapto compounds Chemical class 0.000 claims description 12
- 238000004061 bleaching Methods 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 6
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 6
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 6
- 229910052736 halogen Chemical group 0.000 claims description 5
- 150000002367 halogens Chemical group 0.000 claims description 5
- OXFSTTJBVAAALW-UHFFFAOYSA-N 1,3-dihydroimidazole-2-thione Chemical class SC1=NC=CN1 OXFSTTJBVAAALW-UHFFFAOYSA-N 0.000 claims description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 4
- 125000003282 alkyl amino group Chemical group 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- JAAIPIWKKXCNOC-UHFFFAOYSA-N 1h-tetrazol-1-ium-5-thiolate Chemical class SC1=NN=NN1 JAAIPIWKKXCNOC-UHFFFAOYSA-N 0.000 claims description 3
- PDQAZBWRQCGBEV-UHFFFAOYSA-N Ethylenethiourea Chemical class S=C1NCCN1 PDQAZBWRQCGBEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 150000007513 acids Chemical class 0.000 claims description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 125000004414 alkyl thio group Chemical group 0.000 claims description 2
- 239000003086 colorant Substances 0.000 claims description 2
- 238000011161 development Methods 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 230000000087 stabilizing effect Effects 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 2
- NBNQOWVYEXFQJC-UHFFFAOYSA-N 2-sulfanyl-3h-thiadiazole Chemical class SN1NC=CS1 NBNQOWVYEXFQJC-UHFFFAOYSA-N 0.000 claims 1
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 13
- 239000007844 bleaching agent Substances 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 7
- 229940101006 anhydrous sodium sulfite Drugs 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- AFBBKYQYNPNMAT-UHFFFAOYSA-N 1h-1,2,4-triazol-1-ium-3-thiolate Chemical compound SC=1N=CNN=1 AFBBKYQYNPNMAT-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000001488 sodium phosphate Substances 0.000 description 5
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 5
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 5
- 235000019801 trisodium phosphate Nutrition 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 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 4
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 4
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 4
- YMBVQFBLKKMFPL-UHFFFAOYSA-N C(C)(=O)O.C(C)(=O)O.C(C)(=O)O.C(C)(=O)O.[Na].[Na].[Na] Chemical compound C(C)(=O)O.C(C)(=O)O.C(C)(=O)O.C(C)(=O)O.[Na].[Na].[Na] YMBVQFBLKKMFPL-UHFFFAOYSA-N 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 150000002505 iron Chemical class 0.000 description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- JLAMDELLBBZOOX-UHFFFAOYSA-N 3h-1,3,4-thiadiazole-2-thione Chemical compound SC1=NN=CS1 JLAMDELLBBZOOX-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 description 1
- QNLOCRDTHDUXNV-UHFFFAOYSA-N 3-sulfanyl-2H-thiadiazol-5-amine Chemical compound SN1NSC(=C1)N QNLOCRDTHDUXNV-UHFFFAOYSA-N 0.000 description 1
- ZNBNBTIDJSKEAM-UHFFFAOYSA-N 4-[7-hydroxy-2-[5-[5-[6-hydroxy-6-(hydroxymethyl)-3,5-dimethyloxan-2-yl]-3-methyloxolan-2-yl]-5-methyloxolan-2-yl]-2,8-dimethyl-1,10-dioxaspiro[4.5]decan-9-yl]-2-methyl-3-propanoyloxypentanoic acid Chemical compound C1C(O)C(C)C(C(C)C(OC(=O)CC)C(C)C(O)=O)OC11OC(C)(C2OC(C)(CC2)C2C(CC(O2)C2C(CC(C)C(O)(CO)O2)C)C)CC1 ZNBNBTIDJSKEAM-UHFFFAOYSA-N 0.000 description 1
- DLLBXBCKFUPBJE-UHFFFAOYSA-N 4-amino-1h-1,2,4-triazole-5-thione Chemical compound NN1C=NNC1=S DLLBXBCKFUPBJE-UHFFFAOYSA-N 0.000 description 1
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 101001083370 Dictyostelium discoideum Hisactophilin-1 Proteins 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001739 density measurement Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 150000004989 p-phenylenediamines Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- ZUPBURDXKPOABZ-UHFFFAOYSA-M potassium thiourea iodide Chemical compound [I-].[K+].NC(=S)N ZUPBURDXKPOABZ-UHFFFAOYSA-M 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- UJMBCXLDXJUMFB-UHFFFAOYSA-K trisodium;5-oxo-1-(4-sulfonatophenyl)-4-[(4-sulfonatophenyl)diazenyl]-4h-pyrazole-3-carboxylate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)C1=NN(C=2C=CC(=CC=2)S([O-])(=O)=O)C(=O)C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 UJMBCXLDXJUMFB-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
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Description
Die Erfindung betrifft ein Verfahren zur Verarbeitung belichteter farbphotographischer Materialien, wobei Bleichfixierbäder verwendet werden, die Komplexsalze des dreiwertigen Eisens mit Aminopolycarbonsäuren enthalten.The invention relates to a method for processing exposed color photographic materials, using bleach-fix baths, the complex salts of trivalent iron with aminopolycarboxylic acids contain.
Bei der Herstellung von Farbbildern und Farbfilmen mit Hilfe der chromogenen Entwicklung ist es notwendig, das neben dem Farbbild entstandene Silberbild zu entfernen. Dazu muß das Silber des Silberbildes oxidiert und mit einem Halogensilberlösungsmittel entfernt werden. Das kann geschehen durch Behandlung mit einem Kaliumferricyanidbleichbad und anschließend mit einem Natriumthiosulfatbad. In the production of color pictures and color films with the help of chromogenic development it is necessary to remove the silver image that has arisen next to the color image. For this, the silver of the The silver image can be oxidized and removed with a halide silver solvent. That can happen by treatment with a potassium ferricyanide bleach bath and then with a sodium thiosulfate bath.
Um die Verarbeitung zu vereinfachen, kann man auch die in der deutschen Patentschrift 866 605 beschriebenen Bleichfixierbäder verwenden. Sie enthalten als Halogensilberlösungsmittel Thiosulfat und als Oxydationsmittel Komplexe des dreiwertigen Eisens, z. B. den Komplex der Äthylendiamintetraessigsäure. Das Bleichvermögen eines solchen Bleichfixierbades ist aber geringer als das eines Kaliumferricyanidbleichbades. In order to simplify the processing, one can also use the information in German patent specification 866 605 use the bleach-fix baths described. They contain thiosulfate and halogen silver solvents as oxidizing agent complexes of trivalent iron, e.g. B. the complex of ethylenediaminetetraacetic acid. However, the bleaching power of such a bleach-fix bath is lower than that of a potassium ferricyanide bleach bath.
In der deutschen Patentschrift 947 221 wird deshalb vorgeschlagen, zur Erhöhung der Bleichwirkung dem Bleichfixierbad Thioharnstoff zuzusetzen.In the German patent specification 947 221 is therefore suggested adding thiourea to the bleach-fixer to increase the bleaching effect.
Diese Substanz hat jedoch den großen Nachteil, daß sie in geringsten Spuren als Verunreinigung im Farbentwickler auch in den unbelichteten Bildteilen einen starken Farbschleier verursacht. Damit wird die Verarbeitung des photographischen Materials vor allem in kontinuierlich arbeitenden Entwicklungsmaschinen außerordentlich erschwert. Die Einschleppung sehr geringer Mengen thioharnstoffhaltigen Bleichfixierbades durch die endlose Transportkette in den Farbentwickler kann nicht oder nur mit großem Aufwand vermieden werden. Außerdem verringert sich die Wirksamkeit eines thioharnstoffhaltigen Bleichfixierbades auch ohne Durchsatz während des Stehens.However, this substance has the major disadvantage that it is in the slightest traces as an impurity in the Color developer also causes a strong color haze in the unexposed parts of the image. So that will the processing of the photographic material, especially in continuously operating developing machines, is extremely difficult. The introduction very small amounts of thiourea-containing bleach-fix bath through the endless transport chain in the color developer cannot be avoided or can only be avoided with great effort. aside from that the effectiveness of a thiourea-containing bleach-fix bath decreases even without throughput while standing.
Zur Erhöhung der Bleichwirkung eines Bleichfixierbades wird in der deutschen Patentschrift 1 127 715 die Verwendung von Jodid vorgeschlagen. Die beschleunigende Wirkung von Jodid ist jedoch nur bei einem photographischen Material zu beobachten, das Halogensilberemulsionen enthält, die mit bleichhemmenden Stabilisatoren stabilisiert sind, z. B. mit 2-Phenyl-5-mercapto-thiadiazoI-thion-(3).To increase the bleaching effect of a bleach-fixing bath, the German patent 1 127 715 suggested the use of iodide. The accelerating effect of iodide is however only observed in a photographic material containing halogen silver emulsions which are stabilized with anti-bleach stabilizers, e.g. B. with 2-phenyl-5-mercapto-thiadiazoI-thione- (3).
Wird ein photographisches Material verwendet, das keine oder nicht bleichhemmende Stabilisatoren enthält, so tritt sogar eine bleichhemmende Wirkung durch Jodid ein.If a photographic material is used that contains no or non-bleach-inhibiting stabilizers, iodide even has a bleach-inhibiting effect.
In der deutschen Patentschrift 966 410 werden Polyäthylenoxide als Bleichbeschleuniger beschrieben. Diese Substanzen haben jedoch nur eine verhältnismäßig geringe Wirkung.In the German patent specification 966 410 polyethylene oxides are described as bleach accelerators. However, these substances have only a relatively minor effect.
Der Erfindung liegt die Aufgabe zugrunde, die Verarbeitung farbphotographischer Materialien zu beschleunigen durch Anwendung von Verbindungen, die das Ausbleichen des Silberbildes beschleunigen, ohne die photographischen Eigenschaften negativ zu beeinflussen.The invention is based on the task of processing color photographic materials accelerate by using compounds that accelerate the fading of the silver image, without adversely affecting the photographic properties.
Es wurde nun gefunden, daß Mercaptoverbindungen von 5gliedrigen Heterocyclen mit mindestens 2 Stickstoffatomen als Ringglieder in hervorragender Weise als Bleichbeschleuniger für Bleichfixierbäder die Komplexsalze des dreiwertigen Eisens mit Aminopolycarbonsäuren enthalten, geeignet sind.It has now been found that mercapto compounds of 5-membered heterocycles with at least 2 nitrogen atoms as ring members in an excellent way as a bleach accelerator for bleach-fix baths the complex salts of trivalent iron with aminopolycarboxylic acids are suitable.
Als besonders brauchbar erwiesen haben sich die folgenden Verbindungen oder Derivate davon: 3-Mercapto- 1,2,4-triazol, 2-Mercapto-thiadiazol, 2-Mercapto-imidazol, 2-Mercapto-imidazolin und 5-Mercapto-tetrazol.The following compounds or derivatives thereof have proven to be particularly useful: 3-mercapto-1,2,4-triazole, 2-mercapto-thiadiazole, 2-mercapto-imidazole, 2-mercapto-imidazoline and 5-mercapto-tetrazole.
Die vorstehend genannten Heterocyclen können in mannigfaltiger Weise substituiert sein. Wenig geeignet sind Derivate, die am Ring mit einer zweiten Mercaptogruppe oder einem Phenylring substituiert sind.The abovementioned heterocycles can be substituted in a variety of ways. Little Derivatives which are substituted on the ring by a second mercapto group or a phenyl ring are suitable are.
Vorzugsweise sind Verbindungen der folgenden allgemeinen Formeln geeignet:Compounds of the following general formulas are preferably suitable:
I. 3-Mercapto-l,2,4-triazoleI. 3-Mercapto-1,2,4-triazoles
N NN N
HSHS
HSHS
R3-N NR 3 -NN
HS -^ J-R2 HS - ^ JR 2
II. 2-MercaptothiadiazolII. 2-mercaptothiadiazole
N NN N
HS-Ix J-RiHS-I x J-Ri
III. 2-MercaptoimidazoleIII. 2-mercaptoimidazoles
N-N-
IV. 2-MercaptoimidazolineIV. 2-mercaptoimidazolines
N-N-
HSHS
.T/. T /
R2 HR 2 H
R3-N-HS R 3 -N-HS
R2 R 2
TTTT
V. 5-MercaptotetrazolV. 5-mercaptotetrazole
N NN N
In diesen Formeln bedeutet: Ri = Wasserstoff, Alkyl, vorzugsweise mit bis zu 5 C-Atomen, Amino oder Alkylamino, wobei die Alkylgruppen ebenfalls vorzugsweise bis zu 5 C-Atomen enthalten, R-2 = Wasserstoff, Alkyl, vorzugsweise mit bis zu 5 C-Atomen, Amino oder Alkylamino, wobei die Alkylgruppen ebenfalls vorzugsweise bis zu 5 C-Atomen enthalten, Alkylmercapto mit vorzugsweise bis zu 5 C-Atomen oder Halogen, wie Chlor oder Brom, R:j = Wasserstoffoder Alkyl mit vorzugsweise bis zu 5 C-Atomen.In these formulas: Ri = hydrogen, alkyl, preferably with up to 5 carbon atoms, amino or alkylamino, the alkyl groups likewise preferably containing up to 5 carbon atoms, R-2 = hydrogen, alkyl, preferably with up to 5 C atoms, amino or alkylamino, the alkyl groups also preferably containing up to 5 C atoms, alkyl mercapto with preferably up to 5 C atoms or halogen, such as chlorine or bromine, R : j = hydrogen or alkyl with preferably up to 5 C Atoms.
Für das erfindungsgemäße Verfahren ist es wesentlich, daß die in der erfindungsgemäßen Weise zu verwendenden Verbindungen während der Bleichung des Silberbildes in dem Bleichbad vorhanden sind. Die Verbindungen können daher dem Bleichfixierbad in Mengen von 0,05 bis 20 g, vorzugsweise 0,5 bis 20 g pro Liter, zugesetzt werden. Es ist jedoch auch möglich, die heterocyclischen Mercaptoverbindungen einem anderen Bad zuzusetzen, das zwischen dem Farbentwicklungsbad und dem Bleichfixierbad angewendet wird. Derartige Bäder sind z. B. Stoppoder Stoppfixierbäder. In diesen Bädern werden die erfindungsgemäßen Verbindungen in ähnlichen Konzentrationen angewendet.For the method according to the invention, it is essential that the in the manner according to the invention using compounds are present during the bleaching of the silver image in the bleach bath. The compounds can therefore be added to the bleach-fix bath in amounts of 0.05 to 20 g, preferably 0.5 to 20 g per liter can be added. However, it is also possible to use the heterocyclic mercapto compounds add another bath applied between the color developing bath and the bleach-fix bath will. Such baths are z. B. Stop or Stop Fixing Baths. In these baths the Compounds according to the invention applied in similar concentrations.
Die heterocyclischen Mercaptoverbindungen sind für alle farbphotographischen Verfahren geeignet, bei denen chromogen entwickelt wird, d. h. eine belichtete Silberhalogenemulsionsschicht in Gegenwart von Farbkupplern mit einem Farbentwickler, insbesondere einem Entwickler mit einer primären aromatischen Aminogruppe, vorzugsweise aus der Reihe der p-Phenylendiamine, entwickelt und anschließend das entstandene Silberbild in üblicher Weise gebleicht wird.The heterocyclic mercapto compounds are suitable for all color photographic processes which is chromogenically developed, d. H. an exposed silver halide emulsion layer in the presence of Color couplers with a color developer, especially a developer with a primary aromatic Amino group, preferably from the series of p-phenylenediamines, developed and then the resulting silver image is bleached in the usual way.
Die erfindungsgemäßen Verbindungen besitzen gegenüber dem bekannten Thioharnstoff den großen Vorteil, daß die in Entwicklungsmaschinen oft eintretende Verunreinigung des Farbentwicklers mit Spuren Bleichfixierbades in den Weißen des farbphotographischen Materials keinen Farbschleier mehr verursacht.Compared to the known thiourea, the compounds according to the invention are large The advantage that the color developer is often contaminated in developing machines Traces of the bleach-fixer in the whites of the color photographic material no longer show any color haze caused.
Mit einer Verunreinigung des Farbentwicklers, die einer Thioharnstoffkonzentration von 0,0001 g pro Liter Farbentwickler entspricht, erhält man bereits völlig unbrauchbare Ergebnisse. Ein Farbentwickler mit der gleichen oder sogar zehnfachen Menge 3-Mercapto-l,2,4-triazol verunreinigt, ergibt dagegen keinen Faibschleier. Die Farbdichtemessungen dieses Farbschleiers sind in der Tabelle 1 aufgeführt. Die Verarbeitung der Proben erfolgte dem Beispiel 1 entsprechend in Material, Bäderfolge und Behandlungszeiten. With an impurity in the color developer that has a thiourea concentration of 0.0001 g per Liter of color developer corresponds to completely unusable results. A color developer Contaminated with the same or even ten times the amount of 3-mercapto-1,2,4-triazole, on the other hand, does not result in any Faib veil. The color density measurements of this color haze are listed in Table 1. The processing the samples were carried out in accordance with Example 1 in terms of material, bath sequence and treatment times.
4040
1. 1 I Farbentwickler
ohne Zusatz 1. 1 l color developer
without addition
Dichten des FarbschleiersDensifying the veil of color
Gelbyellow
0,1100.110
Purpurpurple
0,115 Beispiel 1
Ein mehrschichtiges farbphotographisches Material, dessen Halogensilberemulsionen mit 2-Phenyl-5-mercapto-thiadiazoIthion-(3)
stabilisiert wurden und das als blaugrünen Farbkuppler in der obersten rotempfindlichen Schicht l-Hydroxy^-sulfo^-naphthoesäure-oktadecylamid
enthält, in der mittleren grünempfindlichen Schicht als purpurnen Farbkuppler l-(4'-Phenoxy-3'-sulfophenyl)-3-heptadecylpyrazolon-(5)
und als gelben Farbkuppler in der untersten blauempfindlichen Schicht 3-(p-Stearoylaminobenzoxylacetamino)-isophthalsäure,
wird bildmäßig belichtet und in folgenden Bädern verarbeitet:0.115 Example 1
A multilayer color photographic material, the halogen silver emulsions of which have been stabilized with 2-phenyl-5-mercapto-thiadiazoIthione- (3) and which contains l-hydroxy ^ -sulfo ^ -naphthoic acid-octadecylamide as a blue-green color coupler in the uppermost red-sensitive layer, in the middle green-sensitive one Layer as a purple color coupler 1- (4'-phenoxy-3'-sulfophenyl) -3-heptadecylpyrazolone- (5) and as a yellow color coupler in the lowest blue-sensitive layer 3- (p-stearoylaminobenzoxylacetamino) isophthalic acid, is imagewise exposed and in the following Baths processed:
Natriumhexametaphosphat 2 gSodium hexametaphosphate 2 g
Hydroxylaminsulfat 4 gHydroxylamine sulfate 4 g
Natriumsulfit, wasserfrei 4 gSodium sulfite, anhydrous 4 g
Kaliumbromid IgPotassium bromide Ig
Kaliumcarbonat, wasserfrei 100 gPotassium carbonate, anhydrous 100 g
N-Butyl-fi-suIfobutyl-paraphenylen-N-butyl-fi-suIfobutyl-paraphenylene-
diamin 6 gdiamine 6 g
Mit Wasser auf 1000 ml auffüllen. Wässerung, Stoppfixierbad, Behandlungszeit 3 Minuten. Make up to 1000 ml with water. Rinsing, stop-fix bath, treatment time 3 minutes.
Natriumhexametaphosphat 2 gSodium hexametaphosphate 2 g
Kaliumdihydrogenphosphat 30 gPotassium dihydrogen phosphate 30 g
Natriumsulfit, wasserfrei 4 gSodium sulfite, anhydrous 4 g
Natriumthiosulfat, wasserfrei 100 gSodium thiosulphate, anhydrous 100 g
Mit Kaliumcarbonat auf pH 7,2 einstellen und mit Wasser auf 1000 ml auffüllen. Bleichfixierbad, Behandlungszeit 5 Minuten.Adjust to pH 7.2 with potassium carbonate and make up to 1000 ml with water. Bleach-fix bath, treatment time 5 minutes.
Trinatriumtetraessigsäure 30 gTrisodium tetraacetic acid 30 g
Trinatriumphosphat, wasserfrei .... 25 g Eisensalz der Äthylendiamintetra-Trisodium phosphate, anhydrous .... 25 g of the iron salt of the ethylenediamine tetra-
essigsäure 30 gacetic acid 30 g
Natriumsulfit, wasserfrei 2 gSodium sulfite, anhydrous 2 g
Natriumthiosulfat, wasserfrei 120 gSodium thiosulphate, anhydrous 120 g
3-Mercapto-l,2,4-triazol 2 g3-mercapto-1,2,4-triazole 2 g
Mit Kaliumdihydrogenphosphat auf pH 7,5 einstellen und mit Wasser auf 1000 ml auffüllen.Adjust to pH 7.5 with potassium dihydrogen phosphate and make up to 1000 ml with water.
Verarbeitet man eine Probe des gleichen Materials in der gleichen Weise, jedoch ohne das 3-Mercapto-0,090 1,2.4-triazol im Bleichfixierbad, wird das SilberbildProcess a sample of the same material in the same way, but without the 3-mercapto-0.090 1,2,4-triazole in the bleach-fix bath, the silver image becomes
5555
6060
BlaugrünBlue green
bei gleichen Behandlungszeiten nicht vollständig entfernt. Man erhält verschwärzlichte Farben.not completely removed with the same treatment times. Blackened colors are obtained.
Der beschleunigende Effekt der erfindungsgemäßen Verbindungen ergibt sich aus den folgenden Vergleichsversuchen, wobei das oben beschriebene Material in der gleichen Weise, jedoch unter Anwendung anderer Bleichbeschleuniger, verarbeitet wurde. Gemessen wurde dabei die Bleichzeit, die erforderlich ist, um das Silberbild vollständig zu entfernen.The accelerating effect of the compounds according to the invention results from the following comparative experiments, using the material described above in the same way but using other bleach accelerator. The bleaching time required was measured is to completely remove the silver image.
gilot
gi
MinutenBleaching time
Minutes
2
2
2
2
2
25
2
2
2
2
2
2
13
7
3,75
3
3
3
3,517th
13th
7th
3.75
3
3
3
3.5
Polyäthylenoxid
Kaliumiodid
Thioharnstoff
Erfindungsgemäße Sub
stanzen
3-Mercapto-l,2,4-triazol..
4-Amino-3-mercapto-
1,2,4-triazol
2-Mercapto-5-amino-thia-
3,4-diazol
2-Mercapto-imidazol ....Known substances
Polyethylene oxide
Potassium iodide
Thiourea
According to the invention sub
punch
3-mercapto-1,2,4-triazole ..
4-amino-3-mercapto-
1,2,4-triazole
2-mercapto-5-amino-thia-
3,4-diazole
2-mercapto-imidazole ....
Die Entwicklung und Wässerung des Materials erfolgt, wie im Beispiel 1 angegeben. Dann wird 3 Minuten in einem Bad folgender Zusammensetzung stoppfixiert:The material is developed and washed as indicated in Example 1. Then it will be 3 minutes in a bath with the following composition:
Natriumhexametaphosphat 2 gSodium hexametaphosphate 2 g
Kaliumdihydrogenphosphat 30 gPotassium dihydrogen phosphate 30 g
Natriumsulfit, wasserfrei '4 gSodium sulphite, anhydrous 4 g
Natriumthiosulfat, wasserfrei 100 gSodium thiosulphate, anhydrous 100 g
3-Mercapto-4-amino-l,2,4-triazol .. 2 g3-mercapto-4-amino-1,2,4-triazole .. 2 g
3535
4040
4545
Mit Trinatriumphosphat auf pH 7,2 einstellen und mit Wasser auf 1000 ml auffüllen.Adjust to pH 7.2 with trisodium phosphate and make up to 1000 ml with water.
Das sofort anschließende Bleichfixierbad, Behandlungszeit 5 Minuten, hat folgende Zusammensetzung:The immediately following bleach-fix bath, treatment time 5 minutes, has the following composition:
Trinatriumtetraessigsäure 30 gTrisodium tetraacetic acid 30 g
Trinatriumphosphat, wasserfrei 25 gTrisodium phosphate, anhydrous 25 g
Eisensalz der Äthylendiamintetra-Iron salt of ethylene diamine tetra
essigsäure 30 gacetic acid 30 g
Natriumsulfit, wasserfrei 2 gSodium sulfite, anhydrous 2 g
Natriumthiosulfat, wasserfrei 120 gSodium thiosulphate, anhydrous 120 g
Das photographische Material wird, wie im Beispiel 1 angegeben, entwickelt und anschließend sofort in einem Stoppfixierbad folgender Zusammensetzung behandelt:The photographic material is developed as indicated in Example 1 and then immediately treated in a stop-fix bath with the following composition:
Natriumhexametaphosphat 2 gSodium hexametaphosphate 2 g
Kaliumdihydrogenphosphat 30 gPotassium dihydrogen phosphate 30 g
Natriumsulfit, wasserfrei 4 gSodium sulfite, anhydrous 4 g
Natriumthiosulfat, wasserfrei 100 gSodium thiosulphate, anhydrous 100 g
3-Mercapto-5-amino-thiadiazol 2 g3-mercapto-5-amino-thiadiazole 2 g
Mit Trinatriumphosphat auf pH 7,2 einstellen und mit Wasser auf 1000 ml auffüllen.Adjust to pH 7.2 with trisodium phosphate and make up to 1000 ml with water.
Im anschließenden Bleichfixierbad folgender Zusammensetzung wird das Material 5 Minuten behandelt :The material is treated for 5 minutes in the subsequent bleach-fix bath of the following composition :
Trinatriumtetraessigsäure 30 gTrisodium tetraacetic acid 30 g
Trinatriumphosphat, wasserfrei 25 gTrisodium phosphate, anhydrous 25 g
Eisensalz der Äthylendiamintetra-Iron salt of ethylene diamine tetra
essigsäure 30 gacetic acid 30 g
Natriumsulfit, wasserfrei 2 gSodium sulfite, anhydrous 2 g
Natriumthiosulfat, wasserfrei 120 gSodium thiosulphate, anhydrous 120 g
2-Mercapto-imidazol 2 g2-mercapto-imidazole 2 g
Mit Kaliumdihydrogenphosphat auf pH 7,5 einstellen und mit Wasser auf 1000 ml auffüllen.Adjust to pH 7.5 with potassium dihydrogen phosphate and make up to 1000 ml with water.
Das Material wird dann gewässert und nach Behandlung mit einem formalinhaltigen Stabilisierbad vom pH-Wert 7,0 getrocknet. Man erhält ein Farbbild in Schwärzen und Farbflächen frei von Restsilber.The material is then watered and treated with a stabilizing bath containing formalin dried from pH 7.0. A color image is obtained in blackness and color areas free of residual silver.
Läßt man in obigen Verarbeitungsbädern die heterocyclischen Verbindungen fort, so erhält man unvollständig gebleichte Produkte.If the heterocyclic compounds are left out in the above processing baths, one obtains incompletely bleached products.
Claims (4)
HS-. >—R,R 3 -N - N
HS-. > —R,
IiN-
Ii
]N-
]
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEA49448A DE1290812B (en) | 1965-06-11 | 1965-06-11 | Process for bleach-fixing silver photographic images |
| CH95866A CH490696A (en) | 1965-06-11 | 1966-01-25 | Process for producing color photographic images |
| FR47874A FR1466194A (en) | 1965-06-11 | 1966-01-31 | Bleaching-fixing process for silver photographic images |
| GB4217/66A GB1138842A (en) | 1965-06-11 | 1966-01-31 | Bleach-fixing for photographic silver images |
| NL6607222A NL6607222A (en) | 1965-06-11 | 1966-05-25 | |
| BE682426D BE682426A (en) | 1965-06-11 | 1966-06-13 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEA49448A DE1290812B (en) | 1965-06-11 | 1965-06-11 | Process for bleach-fixing silver photographic images |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1290812B true DE1290812B (en) | 1969-03-13 |
Family
ID=6936877
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEA49448A Pending DE1290812B (en) | 1965-06-11 | 1965-06-11 | Process for bleach-fixing silver photographic images |
Country Status (6)
| Country | Link |
|---|---|
| BE (1) | BE682426A (en) |
| CH (1) | CH490696A (en) |
| DE (1) | DE1290812B (en) |
| FR (1) | FR1466194A (en) |
| GB (1) | GB1138842A (en) |
| NL (1) | NL6607222A (en) |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0266797A2 (en) | 1986-11-07 | 1988-05-11 | Fuji Photo Film Co., Ltd. | Method of processing silver halide color photographic material and photographic color developing composition |
| EP0313083A2 (en) | 1987-10-22 | 1989-04-26 | Fuji Photo Film Co., Ltd. | Silver halide color photographic material |
| EP0317983A2 (en) | 1987-11-27 | 1989-05-31 | Fuji Photo Film Co., Ltd. | Silver halide color photographic material |
| EP0320939A2 (en) | 1987-12-15 | 1989-06-21 | Fuji Photo Film Co., Ltd. | Silver halide color photographic material |
| US5004677A (en) * | 1988-02-19 | 1991-04-02 | Fuji Photo Film Co., Ltd. | Method for processing a silver halide color photographic material |
| US5019850A (en) * | 1988-08-19 | 1991-05-28 | Fuji Photo Film Co., Ltd. | Photographic developing apparatus |
| EP0435334A2 (en) | 1989-12-29 | 1991-07-03 | Fuji Photo Film Co., Ltd. | Silver halide color photographic material containing yellow colored cyan coupler |
| USH953H (en) | 1988-08-05 | 1991-08-06 | Fuji Photo Film Co., Ltd. | Method for processing silver halide color photographic material |
| EP0440195A2 (en) | 1990-01-31 | 1991-08-07 | Fuji Photo Film Co., Ltd. | Silver halide color photographic material |
| EP0452984A1 (en) | 1985-09-25 | 1991-10-23 | Fuji Photo Film Co., Ltd. | Process for processing silver halide color photographic material for photographing use |
| EP0456210A2 (en) | 1990-05-09 | 1991-11-13 | Fuji Photo Film Co., Ltd. | Method for processing a silver halide photographic material and light-sensitive material for photographing |
| EP0476327A1 (en) | 1990-08-20 | 1992-03-25 | Fuji Photo Film Co., Ltd. | Data-retainable photographic film product and process for producing color print |
| EP0562476A1 (en) | 1992-03-19 | 1993-09-29 | Fuji Photo Film Co., Ltd. | A silver halide photographic emulsion and a photographic light-sensitive material |
| EP0563708A1 (en) | 1992-03-19 | 1993-10-06 | Fuji Photo Film Co., Ltd. | Silver halide photographic emulsion and light-sensitive material using the same |
| EP0563985A1 (en) | 1992-04-03 | 1993-10-06 | Fuji Photo Film Co., Ltd. | Silver halide color photographic material |
| EP0631185A1 (en) | 1993-06-11 | 1994-12-28 | Fuji Photo Film Co., Ltd. | Method for continuously processing silver halide color photosensitive material |
| EP0654705A2 (en) | 1993-11-24 | 1995-05-24 | Fuji Photo Film Co., Ltd. | Photographic processing composition and method of photographic processing using the same |
| EP0686875A1 (en) | 1994-06-09 | 1995-12-13 | Fuji Photo Film Co., Ltd. | Method of processing silver halide color photographic materials |
| EP0720049A2 (en) | 1990-05-09 | 1996-07-03 | Fuji Photo Film Co., Ltd. | Photographic processing composition and processing method using the same |
| EP0724194A1 (en) | 1995-01-30 | 1996-07-31 | Fuji Photo Film Co., Ltd. | Silver halide color photographic material |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1380269A (en) * | 1970-12-22 | 1975-01-08 | Eastman Kodak Co | Photographic materials containing an auxiliary silver halide layer |
| JPS5258532A (en) * | 1975-11-10 | 1977-05-14 | Konishiroku Photo Ind Co Ltd | Processing of silver halide photographic light sensitive material |
| JPS53147529A (en) * | 1977-05-27 | 1978-12-22 | Mitsubishi Paper Mills Ltd | Silver halide photosensitive materials for color photograph |
| JPS5452534A (en) * | 1977-10-03 | 1979-04-25 | Konishiroku Photo Ind Co Ltd | Processing method of silver halide color photographic material |
| JPS6061749A (en) * | 1983-09-16 | 1985-04-09 | Fuji Photo Film Co Ltd | Method for processing silver halide color photosensitive material |
| JPS6175353A (en) * | 1984-09-21 | 1986-04-17 | Fuji Photo Film Co Ltd | Method for processing color photosensitive material |
| JPS6175352A (en) * | 1984-09-21 | 1986-04-17 | Fuji Photo Film Co Ltd | Method for processing color photosensitive material |
| JPS6280649A (en) * | 1985-10-04 | 1987-04-14 | Fuji Photo Film Co Ltd | Method for processing color photographic sensitive material |
| JPS6292951A (en) * | 1985-10-19 | 1987-04-28 | Fuji Photo Film Co Ltd | Method for developing silver halide color photographic sensitive material |
| US4780398A (en) * | 1986-08-28 | 1988-10-25 | Olin Hunt Specialty Products, Inc. | Bleaching composition and process for color photographic materials |
| EP0310125B1 (en) * | 1987-10-02 | 1995-04-19 | Fuji Photo Film Co., Ltd. | Silver halide color photographic material |
| US4839262A (en) * | 1988-03-01 | 1989-06-13 | Eastman Kodak Company | Bleach-accelerating compositions comprising sorbitan ester compounds and use thereof in photographic color processing |
| US5026629A (en) * | 1990-02-07 | 1991-06-25 | Eastman Kodak Company | Fixing bath for black and white photographic elements |
| GB9005130D0 (en) * | 1990-03-07 | 1990-05-02 | Kodak Ltd | Silver removal from photographic products |
| JPH04445A (en) | 1990-04-17 | 1992-01-06 | Fuji Photo Film Co Ltd | Processing method for silver halide color photosensitive material |
| US5814437A (en) * | 1995-05-22 | 1998-09-29 | Konica Corporation | Method for processing silver halide photographic light-sensitive material |
| EP0779554A1 (en) * | 1995-12-14 | 1997-06-18 | Agfa-Gevaert N.V. | A correcting liquid for a silver imaged lithographic printing plate |
| EP0965883A1 (en) * | 1998-06-18 | 1999-12-22 | Agfa-Gevaert N.V. | Ecological cleaning liquid for photographic processor |
-
1965
- 1965-06-11 DE DEA49448A patent/DE1290812B/en active Pending
-
1966
- 1966-01-25 CH CH95866A patent/CH490696A/en not_active IP Right Cessation
- 1966-01-31 FR FR47874A patent/FR1466194A/en not_active Expired
- 1966-01-31 GB GB4217/66A patent/GB1138842A/en not_active Expired
- 1966-05-25 NL NL6607222A patent/NL6607222A/xx unknown
- 1966-06-13 BE BE682426D patent/BE682426A/xx unknown
Non-Patent Citations (1)
| Title |
|---|
| None * |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0452984A1 (en) | 1985-09-25 | 1991-10-23 | Fuji Photo Film Co., Ltd. | Process for processing silver halide color photographic material for photographing use |
| EP0266797A2 (en) | 1986-11-07 | 1988-05-11 | Fuji Photo Film Co., Ltd. | Method of processing silver halide color photographic material and photographic color developing composition |
| EP0313083A2 (en) | 1987-10-22 | 1989-04-26 | Fuji Photo Film Co., Ltd. | Silver halide color photographic material |
| EP0317983A2 (en) | 1987-11-27 | 1989-05-31 | Fuji Photo Film Co., Ltd. | Silver halide color photographic material |
| EP0320939A2 (en) | 1987-12-15 | 1989-06-21 | Fuji Photo Film Co., Ltd. | Silver halide color photographic material |
| US5004677A (en) * | 1988-02-19 | 1991-04-02 | Fuji Photo Film Co., Ltd. | Method for processing a silver halide color photographic material |
| USH953H (en) | 1988-08-05 | 1991-08-06 | Fuji Photo Film Co., Ltd. | Method for processing silver halide color photographic material |
| US5019850A (en) * | 1988-08-19 | 1991-05-28 | Fuji Photo Film Co., Ltd. | Photographic developing apparatus |
| EP0435334A2 (en) | 1989-12-29 | 1991-07-03 | Fuji Photo Film Co., Ltd. | Silver halide color photographic material containing yellow colored cyan coupler |
| EP0440195A2 (en) | 1990-01-31 | 1991-08-07 | Fuji Photo Film Co., Ltd. | Silver halide color photographic material |
| EP0456210A2 (en) | 1990-05-09 | 1991-11-13 | Fuji Photo Film Co., Ltd. | Method for processing a silver halide photographic material and light-sensitive material for photographing |
| EP0720049A2 (en) | 1990-05-09 | 1996-07-03 | Fuji Photo Film Co., Ltd. | Photographic processing composition and processing method using the same |
| EP0476327A1 (en) | 1990-08-20 | 1992-03-25 | Fuji Photo Film Co., Ltd. | Data-retainable photographic film product and process for producing color print |
| EP0562476A1 (en) | 1992-03-19 | 1993-09-29 | Fuji Photo Film Co., Ltd. | A silver halide photographic emulsion and a photographic light-sensitive material |
| EP0563708A1 (en) | 1992-03-19 | 1993-10-06 | Fuji Photo Film Co., Ltd. | Silver halide photographic emulsion and light-sensitive material using the same |
| EP0563985A1 (en) | 1992-04-03 | 1993-10-06 | Fuji Photo Film Co., Ltd. | Silver halide color photographic material |
| EP0631185A1 (en) | 1993-06-11 | 1994-12-28 | Fuji Photo Film Co., Ltd. | Method for continuously processing silver halide color photosensitive material |
| EP0654705A2 (en) | 1993-11-24 | 1995-05-24 | Fuji Photo Film Co., Ltd. | Photographic processing composition and method of photographic processing using the same |
| EP0686875A1 (en) | 1994-06-09 | 1995-12-13 | Fuji Photo Film Co., Ltd. | Method of processing silver halide color photographic materials |
| EP0724194A1 (en) | 1995-01-30 | 1996-07-31 | Fuji Photo Film Co., Ltd. | Silver halide color photographic material |
Also Published As
| Publication number | Publication date |
|---|---|
| BE682426A (en) | 1966-12-13 |
| FR1466194A (en) | 1967-01-13 |
| NL6607222A (en) | 1966-11-25 |
| GB1138842A (en) | 1969-01-01 |
| CH490696A (en) | 1970-05-15 |
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