EP0498950A1 - Processing colour photographic recording materials - Google Patents
Processing colour photographic recording materials Download PDFInfo
- Publication number
- EP0498950A1 EP0498950A1 EP91120702A EP91120702A EP0498950A1 EP 0498950 A1 EP0498950 A1 EP 0498950A1 EP 91120702 A EP91120702 A EP 91120702A EP 91120702 A EP91120702 A EP 91120702A EP 0498950 A1 EP0498950 A1 EP 0498950A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- bath
- bleaching
- alkyl
- carboxy
- complexing agent
- 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.)
- Withdrawn
Links
- 239000000463 material Substances 0.000 title claims abstract description 26
- 238000004061 bleaching Methods 0.000 claims abstract description 57
- -1 silver halide Chemical class 0.000 claims abstract description 20
- 239000008139 complexing agent Substances 0.000 claims abstract description 16
- 229910052709 silver Inorganic materials 0.000 claims abstract description 16
- 239000004332 silver Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000003463 adsorbent Substances 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 9
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000003647 oxidation Effects 0.000 claims abstract description 7
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 238000001179 sorption measurement Methods 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 4
- VFNOFXXKKALBEP-UHFFFAOYSA-N 4-(3,4-dimethyl-5-oxo-4h-pyrazol-1-yl)benzenesulfonic acid Chemical compound O=C1C(C)C(C)=NN1C1=CC=C(S(O)(=O)=O)C=C1 VFNOFXXKKALBEP-UHFFFAOYSA-N 0.000 claims description 3
- CSGQJHQYWJLPKY-UHFFFAOYSA-N CITRAZINIC ACID Chemical compound OC(=O)C=1C=C(O)NC(=O)C=1 CSGQJHQYWJLPKY-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 239000000975 dye Substances 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 230000002035 prolonged effect Effects 0.000 abstract description 3
- 239000007844 bleaching agent Substances 0.000 description 20
- 239000010410 layer Substances 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 10
- 108010010803 Gelatin Proteins 0.000 description 8
- 229920000159 gelatin Polymers 0.000 description 8
- 239000008273 gelatin Substances 0.000 description 8
- 235000019322 gelatine Nutrition 0.000 description 8
- 235000011852 gelatine desserts Nutrition 0.000 description 8
- 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 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 125000004181 carboxyalkyl group Chemical group 0.000 description 6
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 6
- 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 5
- 239000000839 emulsion Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 239000011241 protective layer Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- QVLXDGDLLZYJAM-UHFFFAOYSA-N 2,5-dioctylbenzene-1,4-diol Chemical compound CCCCCCCCC1=CC(O)=C(CCCCCCCC)C=C1O QVLXDGDLLZYJAM-UHFFFAOYSA-N 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 3
- 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 3
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical compound O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 3
- 239000002516 radical scavenger Substances 0.000 description 3
- 230000003716 rejuvenation Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910006069 SO3H Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-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
- 239000006096 absorbing agent Substances 0.000 description 2
- 125000004442 acylamino group Chemical group 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 229960004585 etidronic acid Drugs 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 150000004698 iron complex Chemical class 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- GTOOAPLRWMOITA-UHFFFAOYSA-N 2-(4-amino-n-ethyl-3-methylanilino)ethyl hydrogen sulfate Chemical compound OS(=O)(=O)OCCN(CC)C1=CC=C(N)C(C)=C1 GTOOAPLRWMOITA-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- 229920001174 Diethylhydroxylamine Polymers 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- DYRDKSSFIWVSNM-UHFFFAOYSA-N acetoacetanilide Chemical class CC(=O)CC(=O)NC1=CC=CC=C1 DYRDKSSFIWVSNM-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 1
- 229940051880 analgesics and antipyretics pyrazolones Drugs 0.000 description 1
- UMEAURNTRYCPNR-UHFFFAOYSA-N azane;iron(2+) Chemical compound N.[Fe+2] UMEAURNTRYCPNR-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- DGJMPUGMZIKDRO-UHFFFAOYSA-N cyanoacetamide Chemical class NC(=O)CC#N DGJMPUGMZIKDRO-UHFFFAOYSA-N 0.000 description 1
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical class CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229940083761 high-ceiling diuretics pyrazolone derivative Drugs 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229920000779 poly(divinylbenzene) Polymers 0.000 description 1
- 229920003053 polystyrene-divinylbenzene Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 229910001414 potassium ion Inorganic materials 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
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-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
- G03C7/3046—Processing baths not provided for elsewhere, e.g. final or intermediate washings
-
- 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
- the invention relates to a method for processing color photographic silver halide materials which prevents an increase in the fog of the photographic material due to developer solution carried into the bleaching bath.
- Iron complex salts of aminopolycarboxylic acids for example the iron ammonium complex salt of ethylenediaminetetraacetic acid (Ullmann's Encyclopedia of Industrial Chemistry; 4th ed., Vol. 18, p. 463) are usually used to bleach the silver formed during the development of color photographic materials. This and similar complexing agents that are also used are only very slowly biodegradable.
- the object of the invention was to provide a process suitable for processing color photographic silver halide materials which contains a bleaching bath with a readily biodegradable complexing agent and does not have the disadvantages mentioned above.
- Citrazinic acid is described by E. Klingsberg in The Chemistry of Heteryclic Compouds "Pyridine and Derivates Part one", p. 293, Interscience Publications Inc., New York.
- Examples include:
- the above-mentioned compounds for trapping the EOP can also be added to a bath that precedes the bleaching bath and that follows the developer.
- the connections are e.g. dragged into the bleaching bath with the material.
- the adsorbents are substances which, due to their large surface area, are capable of selectively enriching certain substances at their interface. Common adsorbents are described in Ullmann's Encyclopedia of Industrial Chemistry (4th edition, Vol. 2, pp. 602 to 606).
- Particularly suitable adsorbents are all forms of activated carbon and adsorption resins as well as mixtures of these classes of substances.
- Preferred adsorption resins are polystyrene / polydivinylbenzene resins, e.g. Lewatit MP 500 A and phenol formaldehyde resins, e.g. Duolite S 587.
- the bleaching bath can be brought into contact with the adsorbents in any way. In batch processes, this can be done in a particularly simple manner in a stirred tank with subsequent filtration. In the case of continuous processing, contact can be made through a device inside the processor, e.g. the installation of an activated carbon filter or a column filled with adsorption resin in the circuit of the thermostat of the bleaching bath, or through a device outside the processor, e.g. the installation of an activated carbon filter or one with adsorption resin filled column in the cycle of rejuvenation of the bleaching bath.
- a device inside the processor e.g. the installation of an activated carbon filter or a column filled with adsorption resin in the circuit of the thermostat of the bleaching bath
- a device outside the processor e.g. the installation of an activated carbon filter or one with adsorption resin filled column in the cycle of rejuvenation of the bleaching bath.
- the treatment with adsorbents can also be carried out in a bath that precedes the bleaching bath and that follows the developer.
- An iron complex usually uses 0.005 to 1 mol / l.
- the additive for trapping the EOP is used in a concentration of 0.02 to 20 g / l, the invention in a preferred form containing 0.1 to 5 g / l of EOP scavenger.
- 1 l of adsorbent is used when using the method according to the invention.
- 500 to 1000 l bleach bath can preferably be cleaned with 1 l adsorbent.
- the bleaching bath according to the invention can contain ammonium, lithium, sodium or potassium ions.
- the bleach bath has a pH between 0 and 7 in particular.
- the bleaching bath preferably contains an excess of 1 to 120 mol%, preferably 5 to 50 mol%, based on the iron complex, of free complexing agent.
- the bleach bath When ready for use, the bleach bath preferably contains 0.05 to 2 mol / l halide and 0.01 to 2 mol / l nitrate.
- all substituents of the complexing agent carry a carboxy-C1-C10-alkyl radical.
- the iron (III) salt of nitrilodisigmonopropionic acid is preferably used as the complex compound and the 3,4-dimethyl-1- (4-sulfophenyl) -5-pyrazolone as the EOP scavenger.
- Other preferred ingredients are sodium nitrate, sodium bromide and the trisodium salt of nitrolodysigmonopropionic acid.
- the bleach bath has a pH between 2 and 5.
- the unexpected and surprising effect of the invention lies in the fact that the combination of the claimed complexing agents with the EOP scavengers used results in a readily biodegradable bleaching bath without increasing the fog of the photographic material after prolonged use.
- the EOP catcher must be added when the bleaching bath is added. An addition of the EOP catcher to a bleaching bath, its composition after prolonged use, this leads to increased fog formation in the photographic material, on the other hand, has no short-term effect.
- the treatment with the adsorbents according to the invention is also successful with a used bleaching bath.
- the bleaching bath according to the invention is particularly suitable for color photographic silver halide recording materials whose silver halide emulsions consist predominantly of AgBr, AgBrI, AgBrCl or AgCl.
- the color photographic material preferably contains on a reflective or transparent support (for example paper coated on both sides with polyethylene or cellulose triacetate film) at least one blue-sensitive, at least one green-sensitive and at least one red-sensitive silver halide emulsion layer, to which at least one yellow coupler, at least one magenta coupler and at least one cyan coupler in the order given assigned.
- the bleaching bath according to the invention is used within the usual processing method for color photographic silver halide materials and is suitable for bleaching all known photographic silver halide materials such as color negative films, color negative paper, color reversal films and color reversal paper.
- the processing method can be carried out continuously with constant rejuvenation of the individual processing baths.
- a color photographic recording material was produced by applying the following layers in the order given to a support on paper coated on both sides with polyethylene.
- the quantities given relate to 1 m2.
- the corresponding amounts of AgNO3 are given.
- the photographic material described above was processed unexposed as follows; Develop 45s 35 ° C To stop 30s 20 ° C Water 30s ⁇ 20 ° C bleaching 90s 20 ° C Water 45s ⁇ 20 ° C Fix 45s 20 ° C Water 90s approx. 30 ° C dry
- the individual processing baths had the following composition:
- the unexposed photographic material was processed as described in Example 1.
- the developer, the stop bath and the fixing bath had the same composition as in Example 1.
- the unexposed photographic material was processed as described in Example 1.
- the developer, the stop bath and the fixing bath had the same composition as in Example 1.
- the unexposed photographic material was processed as described in Example 1.
- the developer, the stop bath and the fixing bath had the same composition as in Example 1.
- the unexposed photographic material was processed as described in Example 1.
- the developer, the stop bath and the fixing bath had the same composition as in Example 1.
- the unexposed photographic material was processed as described in Example 1.
- the developer, the stop bath and the fixing bath had the same composition as in Example 1.
- Bleaching bath F was obtained from bleaching bath E by treatment with 50 g of activated carbon (powdered, pure) per liter of bleaching bath. The mixture was stirred at room temperature for 1 hour and then filtered.
- the unexposed photographic material was processed as described in Example 1.
- the developer, the stop bath and the fixing bath had the same composition as in Example 1.
- Bleach bath G was obtained from bleach bath E by treatment with Lewatit MP 500 A.
- a column ( ⁇ 25 mm) was charged with 50 ml of the adsorption resin.
- the bleaching bath was placed on the column and passed through the adsorbent resin at a flow rate of 6 liters of bleaching bath per hour.
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Abstract
Description
Die Erfindung betrifft ein Verfahren zur Verarbeitung farbfotografischer Silberhalogenidmaterialien, das eine Erhöhung des Schleiers des fotografischen Materials durch in das Bleichbad eingeschleppte Entwicklerlösung verhindert.The invention relates to a method for processing color photographic silver halide materials which prevents an increase in the fog of the photographic material due to developer solution carried into the bleaching bath.
Zum Bleichen des bei der Entwicklung farbfotografischer Materialien entstandenen Silbers verwendet man üblicherweise Eisenkomplexsalze von Aminopolycarbonsäuren, beispielsweise das Eisenammoniumkomplexsalz der Ethylendiamintetraessigsäure (Ullmanns Encyklopädie der technischen Chemie; 4. Aufl., Bd. 18, S. 463). Dieser und ähnliche, ebenfalls verwendete Komplexbildner sind biologisch nur sehr langsam abbaubar.Iron complex salts of aminopolycarboxylic acids, for example the iron ammonium complex salt of ethylenediaminetetraacetic acid (Ullmann's Encyclopedia of Industrial Chemistry; 4th ed., Vol. 18, p. 463) are usually used to bleach the silver formed during the development of color photographic materials. This and similar complexing agents that are also used are only very slowly biodegradable.
Bei der Verwendung von Bleichbädern mit biologisch leicht abbaubaren Komplexbildnern kommt es nach längerer Benutzung zu einer Erhöhung der Minimaldichte des fotografischen Materials. Eine der möglichen Ursachen für diese unerwünschte Schleiererhöhung ist die Einschleppung von Entwicklerlösung in das Bleichbad. Dieser Vorgang ist in automatischen Entwicklungsprozessen auch bei der Verwendung von Abstreif- oder Abquetschvorrichtungen und der Durchführung einer Wässerung zwischen dem Entwickler und dem Bleichbad nicht vollständig vermeidbar. Die auf diese Weise in das Bleichbad gelangende Entwicklersubstanz wird dort langsam oxidiert. Hierbei entstehen relativ hydrophobe und dunkel gefärbte Oxidationsprodukte, die sich in den Minimaldichten selbst in sehr geringer Konzentration bemerkbar machen.When using bleaching baths with easily biodegradable complexing agents, the minimum density of the photographic material increases after a long period of use. One of the possible causes for this undesirable increase in fog is the introduction of developer solution in the bleach bath. This process cannot be completely avoided in automatic development processes, even when using stripping or squeezing devices and when washing between the developer and the bleaching bath. The developer substance entering the bleaching bath in this way is slowly oxidized there. This creates relatively hydrophobic and dark-colored oxidation products, which are noticeable in the minimum densities even in very low concentrations.
Aufgabe der Erfindung war die Bereitstellung eines für die Verarbeitung farbfotografischer Silberhalogenidmaterialien geeigneten Verfahrens, das ein Bleichbad mit einem biologisch gut abbaubaren Komplexbildner enthält und die vorstehend genannten Nachteile nicht aufweist.The object of the invention was to provide a process suitable for processing color photographic silver halide materials which contains a bleaching bath with a readily biodegradable complexing agent and does not have the disadvantages mentioned above.
Gegenstand der Erfindung ist somit ein Verfahren zur Verarbeitung farbfotografischer Silberhalogenidmaterialien mit wenigstens den Schritten bildmäßige Belichtung, Entwicklung und Bleichen und gegebenfalls einem zwischen Entwicklung und Bleichen vorgesehenen Wässerungsbad oder einem Stoppbad mit einem Bleichbad, das ein Eisen(III)-komplexsalz eines biologisch abbaubaren Komplexbildners enthält, dadurch gekennzeichnet, daß man
- (1) dem Bleichbad, dem Wässerungsbad oder dem Stoppbad eine Verbindung zugibt, die das Oxidationsprodukt von eingeschleppter Entwicklerlösung abfängt und mit dieser zu einer farblosen Substanz reagiert oder
- (2) das Bleichbad, das Wässerungsbad oder das Stoppbad mit einem Adsorptionsmittel behandelt oder
- (3) beide Maßnahmen durchführt.
- (1) Adds a compound to the bleaching bath, the washing bath or the stopping bath which intercepts the oxidation product from the developer solution introduced and reacts with it to form a colorless substance or
- (2) treating the bleaching bath, the washing bath or the stopping bath with an adsorbent or
- (3) carries out both measures.
Ein weiterer Gegenstand der Erfindung ist ein Bleichbad, das (1) ein Eisen(III)-komplexsalz, dessen Komplexbildner der Formel I
- R₁
- = Carboxy-C₁-C₁₀-alkyl
- R₂
- = H, C₁-C₁₀-Alkyl, Carboxy-C₁-C₁₀-alkyl
- R₃
- = H, C₁-C₁₀-Alkyl, Carboxy-C₁-C₁₀-alkyl
- (2) eine Verbindung, die das Oxidationsprodukt von eingeschleppter Entwicklerlösung abfängt und mit dieser zu einer farblosen Substanz reagiert, enthält.
- R₁
- = Carboxy-C₁-C₁₀ alkyl
- R₂
- = H, C₁-C₁₀ alkyl, carboxy-C₁-C₁₀ alkyl
- R₃
- = H, C₁-C₁₀ alkyl, carboxy-C₁-C₁₀ alkyl
- (2) contains a compound which intercepts the oxidation product from the developer solution that has been introduced and reacts with it to form a colorless substance.
Die Zusätze zum Abfangen des Entwickleroxidationsproduktes (nachfolgend EOP genannt) gehören den Verbindungsklassen a), b), c) oder d) an:
- a) Sulfit,
- b) Citrazinsäure,
- c) Kuppler mit einer aktivierten Methylengruppe, bei der ein Wasserstoff durch Alkyl, Cycloalkyl, Aryl oder Aralkyl ersetzt ist,
- d) Kuppler, die im Bleichbad instabile oder sehr leicht wasserlösliche Farbstoffe bilden.
- a) sulfite,
- b) citrazinic acid,
- c) couplers with an activated methylene group in which a hydrogen is replaced by alkyl, cycloalkyl, aryl or aralkyl,
- d) couplers which form unstable or very easily water-soluble dyes in the bleaching bath.
Citrazinsäure ist beschrieben durch E. Klingsberg in The Chemistry of Heteryclic Compouds "Pyridine and Derivates Part one", S. 293, Interscience Publications Inc., New York.Citrazinic acid is described by E. Klingsberg in The Chemistry of Heteryclic Compouds "Pyridine and Derivates Part one", p. 293, Interscience Publications Inc., New York.
Als farblos kuppelnde Komponente gemäß Punkt c) können Verbindungen vom Typ der Pyrazolone, Benzoyl- und Acetessigester, Benzoyl- und Acetessigsäureanilide, Cyanacetylverbindungen und Cyanacetamide verwendet werden, bei denen ein Wasserstoffatom der aktivierten Methylengruppe durch Alkyl, Aryl oder Aralkyl ersetzt ist.Compounds of the pyrazolone type, benzoyl and acetoacetic esters, benzoyl and acetoacetic anilides, cyanoacetyl compounds and cyanoacetamides in which a hydrogen atom of the activated methylene group is replaced by alkyl, aryl or aralkyl can be used as the colorless coupling component according to point c).
Die in Frage kommenden Benzoyl- und Acetessigesterverbindungen werden analog der in Can. J. Chem. 31, S. 1025 (1953) gegebenen Vorschrift hergestellt.The benzoyl and acetoacetic ester compounds in question are analogous to those in Can. J. Chem. 31 , p. 1025 (1953).
Farblos kuppelnde Pyrazolonderivate sind in DE-AS 1 155 675 beschrieben.Colorless coupling pyrazolone derivatives are described in DE-AS 1 155 675.
Geeignet sind folgende farbloskuppelnde Pyrazolone der allgemeinen Formel II:
worin
- R₄, R₅
- Alkyl, Alkoxy, Aryl, Carboxy, Carboxyalkyl,
- R₆
- Halogen, -CN, -CF₃, Acylamino, Sulfamoyl, Alkylsulfamyl, -SO₃H, Carboxy, Carboxyalkyl und
- n
- 0-3 bedeuten.
wherein
- R₄, R₅
- Alkyl, alkoxy, aryl, carboxy, carboxyalkyl,
- R₆
- Halogen, -CN, -CF₃, acylamino, sulfamoyl, alkylsulfamyl, -SO₃H, carboxy, carboxyalkyl and
- n
- 0-3 mean.
Beispielhaft seien folgende bevorzugte Verbindungen genannt:
Kuppler, die im Bleichbad instabile oder sehr leicht wasserlösliche Farbstoffe bilden, besitzen folgende allgemeine Formel III:
worin
- R₇
- Alkyl, Carboxy, Carboxyalkyl und
- R₈
- H, p-Sulfoaryl bedeuten.
wherein
- R₇
- Alkyl, carboxy, carboxyalkyl and
- R₈
- H, p-sulfoaryl mean.
Beispielhaft seien genannt:
Die genannten Verbindungen zum Abfangen des EOP können auch einem Bad zugesetzt werden, das dem Bleichbad vorausgestellt und dem Entwickler nachgestellt ist. Die Verbindungen werden z.B. mit dem Material in das Bleichbad eingeschleppt.The above-mentioned compounds for trapping the EOP can also be added to a bath that precedes the bleaching bath and that follows the developer. The connections are e.g. dragged into the bleaching bath with the material.
Die Adsorptionsmittel sind Substanzen, die aufgrund ihrer großen Oberfläche befähigt sind, bestimmte Stoffe an ihrer Grenzfläche selektiv anzureichern. Gebräuchliche Adsorptionsmittel sind in Ullmanns Encyklopädie der technischen Chemie (4. Aufl., Bd. 2, S. 602 bis 606) beschrieben.The adsorbents are substances which, due to their large surface area, are capable of selectively enriching certain substances at their interface. Common adsorbents are described in Ullmann's Encyclopedia of Industrial Chemistry (4th edition, Vol. 2, pp. 602 to 606).
Besonders geeignete Adsorptionsmittel sind alle Formen von Aktivkohle und Adsorptionsharze sowie Mischungen aus diesen Substanzklassen. Bevorzugte Adsorptionsharze sind Polystyrol/Polydivinylbenzol-Harze, z.B. Lewatit MP 500 A und Phenolformaldehyd-Harze, z.B. Duolite S 587.Particularly suitable adsorbents are all forms of activated carbon and adsorption resins as well as mixtures of these classes of substances. Preferred adsorption resins are polystyrene / polydivinylbenzene resins, e.g. Lewatit MP 500 A and phenol formaldehyde resins, e.g. Duolite S 587.
Zur Erreichung des erfindungsgemäßen Effekts kann das Bleichbad auf beliebige Weise mit den Adsorptionsmitteln in Kontakt gebracht werden. Bei chargenweisen Prozessen kann dies in besonders einfacher Weise in einem Rührkessel mit nachfolgender Filtration geschehen. Bei kontinuierlichen Verarbeitungsprozessen kann der Kontakt durch eine Vorrichtung innerhalb der Entwicklungsmaschine, z.B. den Einbau eines Aktivkohlefilters oder einer mit Adsorptionsharz gefüllten Säule in den Kreislauf des Thermostaten des Bleichbads, oder durch eine Vorrichtung außerhalb der Entwicklungsmaschine, z.B. den Einbau eines Aktivkohlefilters oder einer mit Adsorptionsharz gefüllten Säule in den Kreislauf der Rejuvenierung des Bleichbads, erreicht werden.To achieve the effect according to the invention, the bleaching bath can be brought into contact with the adsorbents in any way. In batch processes, this can be done in a particularly simple manner in a stirred tank with subsequent filtration. In the case of continuous processing, contact can be made through a device inside the processor, e.g. the installation of an activated carbon filter or a column filled with adsorption resin in the circuit of the thermostat of the bleaching bath, or through a device outside the processor, e.g. the installation of an activated carbon filter or one with adsorption resin filled column in the cycle of rejuvenation of the bleaching bath.
Die Behandlung mit Adsorptionsmitteln kann auch an einem Bad vorgenommen werden, das dem Bleichbad vorausgestellt und dem Entwickler nachgestellt ist.The treatment with adsorbents can also be carried out in a bath that precedes the bleaching bath and that follows the developer.
An Eisenkomplex werden üblicherweise 0,005 bis 1 Mol/l eingesetzt.An iron complex usually uses 0.005 to 1 mol / l.
Der Zusatz zum Abfangen des EOP wird in einer Konzentration von 0,02 bis 20 g/l verwendet, wobei die Erfindung in einer bevorzugten Form 0,1 bis 5 g/l an EOP-Fänger enthält.The additive for trapping the EOP is used in a concentration of 0.02 to 20 g / l, the invention in a preferred form containing 0.1 to 5 g / l of EOP scavenger.
Für die Reinigung von 100 bis 5000 l Bleichbad wird bei Anwendung des erfindungsgemäßen Verfahrens 1 l Adsorptionsmittel eingesetzt. Vorzugsweise lassen sich mit 1 l Adsorptionsmittel 500 bis 1000 l Bleichbad reinigen.For the cleaning of 100 to 5000 l of bleaching bath, 1 l of adsorbent is used when using the method according to the invention. 500 to 1000 l bleach bath can preferably be cleaned with 1 l adsorbent.
Außer den erfindungsgemäßen Komponenten enthält das Bleichbad in einer bevorzugten Ausführungsform noch folgende Bestandteile:
- freien Komplexbildner,
- Bromid- oder Chlorid-Ionen als Rehalogenierungsmittel,
- Nitrat-Ionen als Korrosionsschutzmittel.
- free complexing agent,
- Bromide or chloride ions as rehalogenizing agents,
- Nitrate ions as anti-corrosion agents.
Weiterhin kann das erfindungsgemäße Bleichbad Ammonium-, Lithium-, Natrium- oder Kalium-Ionen enthalten.Furthermore, the bleaching bath according to the invention can contain ammonium, lithium, sodium or potassium ions.
Das Bleichbad hat insbesondere einen pH-Wert zwischen 0 und 7.The bleach bath has a pH between 0 and 7 in particular.
Vorzugsweise enthält das Bleichbad einen Überschuß von 1 bis 120 Mol-%, vorzugsweise 5 bis 50 Mol-%, bezogen auf den Eisenkomplex, an freiem Komplexbildner.The bleaching bath preferably contains an excess of 1 to 120 mol%, preferably 5 to 50 mol%, based on the iron complex, of free complexing agent.
Im gebrauchsfertigen Zustand enthält das Bleichbad bevorzugt 0,05 bis 2 Mol/l Halogenid und 0,01 bis 2 Mol/l Nitrat.When ready for use, the bleach bath preferably contains 0.05 to 2 mol / l halide and 0.01 to 2 mol / l nitrate.
In einer bevorzugten Form des Bleichbades tragen alle Substituenten des Komplexbildners einen Carboxy-C₁-C₁₀-alkylrest.In a preferred form of the bleach bath, all substituents of the complexing agent carry a carboxy-C₁-C₁₀-alkyl radical.
In einem Bleichbad für die Colorpapierverarbeitung wird vorzugsweise als Komplexverbindung das Eisen(III)-salz der Nitrilodiessigmonopropionsäure und als EOP-Fänger das 3,4-Dimethyl-1-(4-sulfophenyl)-5-pyrazolon verwendet. Weitere bevorzugte Bestandteile sind Natriumnitrat, Natriumbromid und das Trinatriumsalz der Nitrolodiessigmonopropionsäure. In der bevorzugten Ausführungsform hat das Bleichbad einen pH-Wert zwischen 2 und 5.In a bleaching bath for color paper processing, the iron (III) salt of nitrilodisigmonopropionic acid is preferably used as the complex compound and the 3,4-dimethyl-1- (4-sulfophenyl) -5-pyrazolone as the EOP scavenger. Other preferred ingredients are sodium nitrate, sodium bromide and the trisodium salt of nitrolodysigmonopropionic acid. In the preferred embodiment, the bleach bath has a pH between 2 and 5.
Der unerwartete und überraschende Effekt der Erfindung liegt darin, daß bei der Kombination der beanspruchten Komplexbildner mit den verwendeten EOP-Fängern ein biologisch leicht abbaubares Bleichbad entsteht, ohne daß es nach längerem Gebrauch zu einer Schleiererhöhung beim fotografischen Material kommt. Der Zusatz des EOP-Fängers muß beim Ansatz des Bleichbades erfolgen. Eine Zugabe des EOP-Fängers zu einem Bleichbad, dessen Zusammensetzung nach längerem Gebrauch schon zu einer erhöhten Schleierbildung beim fotografischen Material führt, zeigt dagegen keine kurzfristig beobachtbare Wirkung.The unexpected and surprising effect of the invention lies in the fact that the combination of the claimed complexing agents with the EOP scavengers used results in a readily biodegradable bleaching bath without increasing the fog of the photographic material after prolonged use. The EOP catcher must be added when the bleaching bath is added. An addition of the EOP catcher to a bleaching bath, its composition after prolonged use, this leads to increased fog formation in the photographic material, on the other hand, has no short-term effect.
Im Unterschied dazu ist die Behandlung mit den erfindungsgemäßen Adsorptionsmitteln auch bei einem gebrauchten Bleichbad erfolgreich.In contrast to this, the treatment with the adsorbents according to the invention is also successful with a used bleaching bath.
Das erfindungsgemäße Bleichbad eignet sich insbesonders für farbfotografische Silberhalogenidaufzeichnungsmaterialien, deren Silberhalogenidemulsionen überwiegend aus AgBr, AgBrI, AgBrCl oder AgCl bestehen. Vorzugsweise enthält das farbfotografische Material auf einem reflektierenden oder transparenten Träger (z.B. beidseitig mit Polyethylen beschichtetes Papier oder Cellulosetriacetatfilm) wenigstens eine blauempfindliche, wenigstens eine grünempfindliche und wenigstens eine rotempfindliche Silberhalogenidemulsionsschicht, denen in der angegebenen Reihenfolge wenigstens ein Gelbkuppler, wenigstens ein Purpurkuppler und wenigstens ein Blaugrünkuppler zugeordnet sind.The bleaching bath according to the invention is particularly suitable for color photographic silver halide recording materials whose silver halide emulsions consist predominantly of AgBr, AgBrI, AgBrCl or AgCl. The color photographic material preferably contains on a reflective or transparent support (for example paper coated on both sides with polyethylene or cellulose triacetate film) at least one blue-sensitive, at least one green-sensitive and at least one red-sensitive silver halide emulsion layer, to which at least one yellow coupler, at least one magenta coupler and at least one cyan coupler in the order given assigned.
Das erfindungsgemäße Bleichbad wird innerhalb des üblichen Verarbeitungsverfahrens für farbfotografische Silberhalogenidmaterialien eingesetzt und eignet sich zum Bleichen aller bekannten fotografischen Silberhalogenidmaterialien wie Colornegativfilmen, Colornegativpapier, Colorumkehrfilmen und Colorumkehrpapier.The bleaching bath according to the invention is used within the usual processing method for color photographic silver halide materials and is suitable for bleaching all known photographic silver halide materials such as color negative films, color negative paper, color reversal films and color reversal paper.
Das Verarbeitungsverfahren läßt sich unter ständigem Rejuvenieren der einzelnen Verarbeitungsbäder kontinuierlich ausführen.The processing method can be carried out continuously with constant rejuvenation of the individual processing baths.
Ein farbfotografisches Aufzeichnungsmaterial wurde hergestellt, indem auf einen Schichtträger auf beidseitig mit Polyethylen beschichtetem Papier die folgenden Schichten in der angegebenen Reihenfolge aufgetragen wurden. Die Mengenangaben beziehen sich jeweils auf 1 m². Für den Silberhalogenidauftrag werden die entsprechenden Mengen AgNO₃ angegeben.A color photographic recording material was produced by applying the following layers in the order given to a support on paper coated on both sides with polyethylene. The quantities given relate to 1 m². For the silver halide application, the corresponding amounts of AgNO₃ are given.
-
1. Schicht (Substratschicht):
0,2 g Gelatine1st layer (substrate layer):
0.2 g gelatin -
2. Schicht (blauempfindliche Schicht):
blauempfindliche Silberhalogenidemulsion (99,5 Mol-% Chlorid, 0,5 Mol-% Bromid, mittlerer Korndurchmesser 0,8 µm) aus 0,63 g AgNO₃ mit
1,38 g Gelatine
0,95 g Gelbkuppler Y
0,29 g Trikresylphosphat (TKP)2nd layer (blue-sensitive layer):
blue-sensitive silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.8 µm) from 0.63 g AgNO₃ with
1.38 g gelatin
0.95 g yellow coupler Y
0.29 g tricresyl phosphate (CPM) -
3. Schicht (Schutzschicht)
1,1 g Gelatine
0,06 g 2,5-Dioctylhydrochinon
0,06 g Dibutylphthalat (DBP)3rd layer (protective layer)
1.1 g gelatin
0.06 g 2,5-dioctylhydroquinone
0.06 g dibutyl phthalate (DBP) -
4. Schicht (grünempfindliche Schicht) grünsensibilisierte Silberhalogenidemulsion (99,5 Mol-% Chlorid, 0,5 Mol-% Bromid, mittlerer Korndurchmesser 0,6 µm) aus 0,45 g AgNO₃ mit
1,08 g Gelatine
0,41 g Purpurkuppler M
0,08 g 2,5-Dioctylhydrochinon
0,34 g DBP
0,04 g TKP4th layer (green-sensitive layer) green-sensitized silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.6 µm) from 0.45 g AgNO₃ with
1.08 g gelatin
0.41 g purple coupler M
0.08 g 2,5-dioctyl hydroquinone
0.34 g DBP
0.04 g CPM -
5. Schicht (UV-Schutzschicht)
1,15 g Gelatine
0,6 g UV-Absorber der Formel
0,04 g TKP5th layer (UV protective layer)
1.15 g gelatin
0.6 g UV absorber of the formula
0.04 g CPM -
6. Schicht (rotempfindliche Schicht) rotsensibilisierte Silberhalogenidemulsion (99,5 Mol-% Chlorid, 0,5 Mol-% Bromid, mittlerer Korndurchmesser 0,5 µm) aus 0,3 g AgNO₃ mit
0,75 g Gelatine
0,36 g Blaugrünkuppler C
0,36 g TKP6. Layer (red-sensitive layer) red-sensitized silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.5 µm) from 0.3 g of AgNO₃ with
0.75 g gelatin
0.36 g cyan coupler C
0.36 g CPM -
7. Schicht (UV-Schutzschicht)
0,35 g Gelatine
0,15 g UV-Absorber gemäß 5. Schicht
0,2 g TKP7th layer (UV protective layer)
0.35 g gelatin
0.15 g UV absorber according to the 5th layer
0.2 g CPM -
8. Schicht (Schutzschicht)
0,9 g Gelatine
0,3 g Härtungsmittel H der folgenden Formel8th layer (protective layer)
0.9 g gelatin
0.3 g of curing agent H of the following formula
Die verwendeten Komponenten haben folgende Formel:
Das oben beschriebene fotografische Aufzeichnungsmaterial wurde unbelichtet wie folgt verarbeitet;
Die einzelnen Verarbeitungsbäder hatten die folgende Zusammensetzung:The individual processing baths had the following composition:
pH-Wert Einstellung auf 10 mit KOH bzw. H₂SO₄. Mit Wasser auf 1 Liter auffüllen.
Adjust the pH to 10 with KOH or H₂SO₄. Make up to 1 liter with water.
3 gew.-%ige Essigsäure3% by weight acetic acid
Einstellung auf pH 7 mit Ammoniak oder Essigsäure. Mit Wasser auf 1 Liter auffüllen.Adjust to pH 7 with ammonia or acetic acid. Make up to 1 liter with water.
Ergebnis siehe Tabelle 1.For the result, see Table 1.
Die Verarbeitung des unbelichteten fotografischen Aufzeichnungsmaterials erfolgte wie in Beispiel 1 beschrieben. Der Entwickler, das Stoppbad und das Fixierbad hatten die gleiche Zusammensetzung wie in Beispiel 1.The unexposed photographic material was processed as described in Example 1. The developer, the stop bath and the fixing bath had the same composition as in Example 1.
Ergebnis siehe Tabelle 1.For the result, see Table 1.
Die Verarbeitung des unbelichteten fotografischen Aufzeichnungsmaterials erfolgte wie in Beispiel 1 beschrieben. Der Entwickler, das Stoppbad und das Fixierbad hatten die gleiche Zusammensetzung wie in Beispiel 1.The unexposed photographic material was processed as described in Example 1. The developer, the stop bath and the fixing bath had the same composition as in Example 1.
Ergebnis siehe Tabelle 1.For the result, see Table 1.
Die Verarbeitung des unbelichteteten fotografischen Aufzeichnungsmaterials erfolgte wie in Beispiel 1 beschrieben. Der Entwickler, das Stoppbad und das Fixierbad hatten die gleiche Zusammensetzung wie in Beispiel 1.The unexposed photographic material was processed as described in Example 1. The developer, the stop bath and the fixing bath had the same composition as in Example 1.
Ergebnis siehe Tabelle 1.For the result, see Table 1.
Die Verarbeitung des unbelichteteten fotografischen Aufzeichnungsmaterials erfolgte wie in Beispiel 1 beschrieben. Der Entwickler, das Stoppbad und das Fixierbad hatten die gleiche Zusammensetzung wie in Beispiel 1.The unexposed photographic material was processed as described in Example 1. The developer, the stop bath and the fixing bath had the same composition as in Example 1.
Bleichbad E wurde aus Bleichbad A durch ständige Rejuvenierung (= Aufbereitung) des Bleichbad-Überlaufs an einer Schleppband-Maschine erhalten. In diesem Bleichbad wurden ca. 15 m² des farbfotografischen Aufzeichnungsmaterials pro Liter Bleichbad verarbeitet.Bleach bath E was obtained from bleach bath A by constant rejuvenation (= preparation) of the bleach bath overflow on a drag belt machine. In this bleaching bath, approximately 15 m² of the color photographic recording material were processed per liter of bleaching bath.
Ergebnis siehe Tabelle 1.See table 1 for the result.
Die Verarbeitung des unbelichteteten fotografischen Aufzeichnungsmaterials erfolgte wie in Beispiel 1 beschrieben. Der Entwickler, das Stoppbad und das Fixierbad hatten die gleiche Zusammensetzung wie in Beispiel 1.The unexposed photographic material was processed as described in Example 1. The developer, the stop bath and the fixing bath had the same composition as in Example 1.
Bleichbad F wurde aus Bleichbad E durch Behandlung mit 50 g Aktivkohle (gepulvert, rein) pro Liter Bleichbad erhalten. Dabei wurde die Mischung 1 Stunde bei Raumtemperatur gerührt und anschließend filtriert.Bleaching bath F was obtained from bleaching bath E by treatment with 50 g of activated carbon (powdered, pure) per liter of bleaching bath. The mixture was stirred at room temperature for 1 hour and then filtered.
Ergebnis siehe Tabelle 1.For the result, see Table 1.
Die Verarbeitung des unbelichteten fotografischen Aufzeichnungsmaterials erfolgte wie in Beispiel 1 beschrieben. Der Entwickler, das Stoppbad und das Fixierbad hatten die gleiche Zusammensetzung wie in Beispiel 1.The unexposed photographic material was processed as described in Example 1. The developer, the stop bath and the fixing bath had the same composition as in Example 1.
Bleichbad G wurde aus Bleichbad E durch Behandlung mit Lewatit MP 500 A erhalten. Dabei wurde eine Säule (⌀ 25 mm) mit 50 ml des Adsorptionsharzes beschickt. Das Bleichbad wurde auf die Säule gegeben und lief mit einer Durchflußgeschwindigkeit von 6 l Bleichbad pro Stunde durch das Adsorptionsharz.Bleach bath G was obtained from bleach bath E by treatment with Lewatit MP 500 A. A column (⌀ 25 mm) was charged with 50 ml of the adsorption resin. The bleaching bath was placed on the column and passed through the adsorbent resin at a flow rate of 6 liters of bleaching bath per hour.
Ergebnis siehe Tabelle 1.
Aus Tabelle 1 ist zu ersehen, daß der im Gebrauchszustand im Bleichbad enthaltene Entwickler (Bad B im Vergleich zu Bad A) zu erhöhten Minimaldichten führt. Ebenfalls erhöhte Minimaldichten zeigt das "gebrauchte" Bleichbad E.It can be seen from Table 1 that the developer contained in the bleaching bath in use (bath B compared to bath A) leads to increased minimum densities. The "used" bleaching bath E also shows increased minimum densities.
Durch die Zugabe der erfindungsgemäßen EOP-Fänger beim Ansetzen des Bleichbades oder die Behandlung des gebrauchten Bleichbades mit den erfindungsgemäßen Adsorptionsmitteln wird die Erhöhung des Schleiers verhindert bzw. rückgängig gemacht.By adding the EOP scavenger according to the invention when preparing the bleach bath or treating the used bleach bath with the adsorbents according to the invention, the increase in the haze is prevented or reversed.
Bei den Beispielen 1 bis 4 (Bleichbäder A, B, C und D) wurden die Minimaldichten nach einer Standzeit der Bleichbäder von 5 Tagen gemessen.In Examples 1 to 4 (bleaching baths A, B, C and D), the minimum densities were measured after the bleaching bath had been left to stand for 5 days.
Claims (9)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5734992A JPH04320262A (en) | 1991-02-13 | 1992-02-10 | Working method for color-photograph recording material |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4104292 | 1991-02-13 | ||
DE19914104292 DE4104292A1 (en) | 1991-02-13 | 1991-02-13 | BLEACH BATH FOR PHOTOGRAPHIC MATERIAL |
Publications (1)
Publication Number | Publication Date |
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EP0498950A1 true EP0498950A1 (en) | 1992-08-19 |
Family
ID=6424923
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP91120702A Withdrawn EP0498950A1 (en) | 1991-02-13 | 1991-12-02 | Processing colour photographic recording materials |
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EP (1) | EP0498950A1 (en) |
DE (1) | DE4104292A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5670305A (en) * | 1993-09-28 | 1997-09-23 | Eastman Kodak Company | Photographic processing solution containing ternary ferric-complex salts |
WO2006056397A1 (en) * | 2004-11-23 | 2006-06-01 | A & O Imaging Solutions Gmbh | Bleach bath fixing concentrate for photographic material |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3579287A (en) * | 1969-06-11 | 1971-05-18 | Monsanto Co | Bleaching process |
WO1980000624A1 (en) * | 1978-09-14 | 1980-04-03 | Eastman Kodak Co | Photographic bleach compositions and methods of photographic processing |
US4204867A (en) * | 1977-02-12 | 1980-05-27 | Agfa-Gevaert, A.G. | Process for the production of color photographic images using new white coupler substances |
EP0128720A2 (en) * | 1983-06-03 | 1984-12-19 | Linkopia Ek För | Method and apparatus for separating and recovering color developing agent |
EP0358037A2 (en) * | 1988-09-03 | 1990-03-14 | Agfa-Gevaert AG | Method for processing a colour-photographic material |
EP0364845A2 (en) * | 1988-10-20 | 1990-04-25 | Agfa-Gevaert AG | Photographic-reversal process |
WO1991017478A1 (en) * | 1990-04-30 | 1991-11-14 | Kodak Limited | Method of processing photographic material |
-
1991
- 1991-02-13 DE DE19914104292 patent/DE4104292A1/en not_active Withdrawn
- 1991-12-02 EP EP91120702A patent/EP0498950A1/en not_active Withdrawn
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3579287A (en) * | 1969-06-11 | 1971-05-18 | Monsanto Co | Bleaching process |
US4204867A (en) * | 1977-02-12 | 1980-05-27 | Agfa-Gevaert, A.G. | Process for the production of color photographic images using new white coupler substances |
WO1980000624A1 (en) * | 1978-09-14 | 1980-04-03 | Eastman Kodak Co | Photographic bleach compositions and methods of photographic processing |
EP0128720A2 (en) * | 1983-06-03 | 1984-12-19 | Linkopia Ek För | Method and apparatus for separating and recovering color developing agent |
EP0358037A2 (en) * | 1988-09-03 | 1990-03-14 | Agfa-Gevaert AG | Method for processing a colour-photographic material |
EP0364845A2 (en) * | 1988-10-20 | 1990-04-25 | Agfa-Gevaert AG | Photographic-reversal process |
WO1991017478A1 (en) * | 1990-04-30 | 1991-11-14 | Kodak Limited | Method of processing photographic material |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5670305A (en) * | 1993-09-28 | 1997-09-23 | Eastman Kodak Company | Photographic processing solution containing ternary ferric-complex salts |
WO2006056397A1 (en) * | 2004-11-23 | 2006-06-01 | A & O Imaging Solutions Gmbh | Bleach bath fixing concentrate for photographic material |
DE102004056397B4 (en) * | 2004-11-23 | 2008-01-17 | A&O Imaging Solutions Gmbh | Bleach-fix bath concentrate for photographic material |
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DE4104292A1 (en) | 1992-08-20 |
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