EP0364845B1 - Fotografisches Umkehrverfahren - Google Patents
Fotografisches Umkehrverfahren Download PDFInfo
- Publication number
- EP0364845B1 EP0364845B1 EP89118691A EP89118691A EP0364845B1 EP 0364845 B1 EP0364845 B1 EP 0364845B1 EP 89118691 A EP89118691 A EP 89118691A EP 89118691 A EP89118691 A EP 89118691A EP 0364845 B1 EP0364845 B1 EP 0364845B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- developer
- development
- primary
- bath
- alkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title claims description 27
- 238000011161 development Methods 0.000 claims description 65
- 239000000463 material Substances 0.000 claims description 30
- -1 silver halide Chemical group 0.000 claims description 23
- 229910052709 silver Inorganic materials 0.000 claims description 22
- 239000004332 silver Substances 0.000 claims description 21
- 239000000126 substance Substances 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 13
- 239000000839 emulsion Substances 0.000 claims description 13
- 230000008878 coupling Effects 0.000 claims description 12
- 238000010168 coupling process Methods 0.000 claims description 12
- 238000005859 coupling reaction Methods 0.000 claims description 12
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 9
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 9
- 125000000041 C6-C10 aryl group Chemical group 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 125000006274 (C1-C3)alkoxy group Chemical group 0.000 claims description 6
- CSGQJHQYWJLPKY-UHFFFAOYSA-N CITRAZINIC ACID Chemical compound OC(=O)C=1C=C(O)NC(=O)C=1 CSGQJHQYWJLPKY-UHFFFAOYSA-N 0.000 claims description 6
- 125000004181 carboxyalkyl group Chemical group 0.000 claims description 6
- 239000000975 dye Substances 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 150000002443 hydroxylamines Chemical class 0.000 claims description 5
- 229910006069 SO3H Inorganic materials 0.000 claims description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 4
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 125000004442 acylamino group Chemical group 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims 1
- 239000010410 layer Substances 0.000 description 39
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 27
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 108010010803 Gelatin Proteins 0.000 description 17
- 239000002253 acid Substances 0.000 description 17
- 229920000159 gelatin Polymers 0.000 description 17
- 239000008273 gelatin Substances 0.000 description 17
- 235000019322 gelatine Nutrition 0.000 description 17
- 235000011852 gelatine desserts Nutrition 0.000 description 17
- 238000012545 processing Methods 0.000 description 15
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 239000008139 complexing agent Substances 0.000 description 8
- 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 7
- 239000011241 protective layer Substances 0.000 description 7
- QVLXDGDLLZYJAM-UHFFFAOYSA-N 2,5-dioctylbenzene-1,4-diol Chemical compound CCCCCCCCC1=CC(O)=C(CCCCCCCC)C=C1O QVLXDGDLLZYJAM-UHFFFAOYSA-N 0.000 description 6
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
- 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 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 5
- 235000010323 ascorbic acid Nutrition 0.000 description 5
- 229960005070 ascorbic acid Drugs 0.000 description 5
- 239000011668 ascorbic acid Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 5
- 235000019796 monopotassium phosphate Nutrition 0.000 description 5
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 5
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 5
- 230000002441 reversible effect Effects 0.000 description 5
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000004061 bleaching Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 238000010979 pH adjustment Methods 0.000 description 4
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 4
- 235000019252 potassium sulphite Nutrition 0.000 description 4
- 235000011149 sulphuric acid Nutrition 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 3
- 150000007513 acids Chemical class 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
- 239000011575 calcium Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 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
- 230000002829 reductive effect Effects 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- AFBBKYQYNPNMAT-UHFFFAOYSA-N 1h-1,2,4-triazol-1-ium-3-thiolate Chemical compound SC=1N=CNN=1 AFBBKYQYNPNMAT-UHFFFAOYSA-N 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 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- 229920001174 Diethylhydroxylamine Polymers 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 description 2
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 150000004682 monohydrates Chemical class 0.000 description 2
- WMBCUXKYKVTJRF-UHFFFAOYSA-N n-methyl-1-(oxan-4-yl)methanamine Chemical compound CNCC1CCOCC1 WMBCUXKYKVTJRF-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 125000006290 2-hydroxybenzyl group Chemical group [H]OC1=C(C([H])=C([H])C([H])=C1[H])C([H])([H])* 0.000 description 1
- KRTDQDCPEZRVGC-UHFFFAOYSA-N 2-nitro-1h-benzimidazole Chemical compound C1=CC=C2NC([N+](=O)[O-])=NC2=C1 KRTDQDCPEZRVGC-UHFFFAOYSA-N 0.000 description 1
- BGNGWHSBYQYVRX-UHFFFAOYSA-N 4-(dimethylamino)benzaldehyde Chemical compound CN(C)C1=CC=C(C=O)C=C1 BGNGWHSBYQYVRX-UHFFFAOYSA-N 0.000 description 1
- ZVNPWFOVUDMGRP-UHFFFAOYSA-N 4-methylaminophenol sulfate Chemical compound OS(O)(=O)=O.CNC1=CC=C(O)C=C1.CNC1=CC=C(O)C=C1 ZVNPWFOVUDMGRP-UHFFFAOYSA-N 0.000 description 1
- XTBFKMDOQMQYPP-UHFFFAOYSA-N 4-n,4-n-diethylbenzene-1,4-diamine;hydron;chloride Chemical compound Cl.CCN(CC)C1=CC=C(N)C=C1 XTBFKMDOQMQYPP-UHFFFAOYSA-N 0.000 description 1
- QTFFUUQJZHEORK-UHFFFAOYSA-N 5,6-dihydroxybenzene-1,2,4-trisulfonic acid Chemical compound OC1=C(O)C(S(O)(=O)=O)=C(S(O)(=O)=O)C=C1S(O)(=O)=O QTFFUUQJZHEORK-UHFFFAOYSA-N 0.000 description 1
- 241001136792 Alle Species 0.000 description 1
- XXAXVMUWHZHZMJ-UHFFFAOYSA-N Chymopapain Chemical compound OC1=CC(S(O)(=O)=O)=CC(S(O)(=O)=O)=C1O XXAXVMUWHZHZMJ-UHFFFAOYSA-N 0.000 description 1
- 229940120146 EDTMP Drugs 0.000 description 1
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 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
- 230000002378 acidificating effect Effects 0.000 description 1
- JINBYESILADKFW-UHFFFAOYSA-N aminomalonic acid Chemical compound OC(=O)C(N)C(O)=O JINBYESILADKFW-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229940051880 analgesics and antipyretics pyrazolones Drugs 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- UMEAURNTRYCPNR-UHFFFAOYSA-N azane;iron(2+) Chemical compound N.[Fe+2] UMEAURNTRYCPNR-UHFFFAOYSA-N 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- DGJMPUGMZIKDRO-UHFFFAOYSA-N cyanoacetamide Chemical class NC(=O)CC#N DGJMPUGMZIKDRO-UHFFFAOYSA-N 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-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
- 229940083761 high-ceiling diuretics pyrazolone derivative Drugs 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000004989 p-phenylenediamines Chemical class 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- CMCWWLVWPDLCRM-UHFFFAOYSA-N phenidone Chemical compound N1C(=O)CCN1C1=CC=CC=C1 CMCWWLVWPDLCRM-UHFFFAOYSA-N 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 229920000141 poly(maleic anhydride) Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 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 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- QYSXJUFSXHHAJI-YRZJJWOYSA-N vitamin D3 Chemical compound C1(/[C@@H]2CC[C@@H]([C@]2(CCC1)C)[C@H](C)CCCC(C)C)=C\C=C1\C[C@@H](O)CCC1=C QYSXJUFSXHHAJI-YRZJJWOYSA-N 0.000 description 1
- 239000000080 wetting agent Substances 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
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
- G03C5/50—Reversal development; Contact processes
Definitions
- the invention relates to a method for processing photographic reversal materials, in which washing between the black-and-white and color developing bath is essentially dispensed with.
- a positive color image is formed by exposing a negative working color reversal paper through a special reversal development.
- the color reversal paper has at least one blue-sensitive silver-halide layer containing a yellow coupler, at least one green-sensitive layer containing green-sensitive couplers and at least one red-sensitive silver-halide layer containing a cyan coupler.
- the current state of the art is characterized by the Kodak R3 process.
- the total processing time for this process is 600 seconds. Of this, 75 seconds are allotted to the initial development; 90 seconds for the absolutely necessary two-stage cascade watering between first and color developer and 135 seconds for color development.
- the remaining time is taken up by bleaching and washing.
- Postponement of the first developer would, however, be of minor importance if it were comparable to the structure of the color developer and would not cause any side reactions in the color development bath.
- DE-OS 2 249 857 describes a process for reverse development in which black-and-white developer substances as well as color developer substances which are impaired in color coupling activities are used simultaneously in the first development bath.
- the clutch inhibiting effects e.g. canceled by sulfite, ascorbic acid etc.
- the color coupling can take place.
- a disadvantage of this process is the competing presence of two types of developers and the resulting coordination and process problems.
- the object of the invention was to develop a reverse development process in which washing between the first and color development baths can be dispensed with without the disadvantages mentioned above occurring.
- Hydrophilizing groups are understood to mean the radicals -OH, -COOH and -SO3H.
- Preferred compounds of the formula (I) are listed below:
- N, N-diethylhydroxylamine can be mentioned as an example of a hydroxylamine derivative according to formula II.
- Citrazinic acid is described by E. Klingsberg in The Chemistry of Heteryclic Compounds "Pyridine and Derivates Part one", p. 293, Interscience Publications Inc., New York.
- the photographic material can be immediately transferred to the following color development bath without watering, in which the diffuse post-exposure also takes place, or the watering can be greatly shortened.
- the watering times are 1 to 30 seconds, preferably 15 seconds, and can be used for the second exposure.
- the oxidation protection is carried out by means of hydroxylamines, diketones or ⁇ -hydroxyketones instead of sulfite, rhodanide can be added to the first developer to increase sensitivity, preferably in amounts of 2 ⁇ 10 -3 to 1 ⁇ 10 ⁇ 2 mol / l.
- Primary aromatic amino developer substances which are particularly suitable for the first and color development bath are p-phenylenediamines and in particular N, N-dialkyl-p-phenylenediamines, in which the alkyl groups and the aromatic nucleus are substituted or unsubstituted.
- Examples of such compounds are N, N-diethyl-p-phenylenediamine hydrochloride, 4-N, N-diethyl-2-methylphenylenediamine hydrochloride, 4- (N-ethyl-N-2-methanesulfonylaminoethyl) -2-methylphenylenediamine sesquisulfate monohydrate, 4- (N-ethyl-N-2-hydroxyethyl) -2-methylphenylenediamine sulfate and 4-N, N-diethyl-2,2'-methanesulfonylamino-ethylphenylenediamine hydrochloride.
- CD 3 and CD 4 are preferred.
- the content of ascorbic acid or its derivatives in the first development bath is 0.3 to 30 g / l, preferably 2 to 15 g / l.
- Sulfite is used in an amount of 2 to 15 g / l in the first development bath.
- the concentration of citrazinic acid is in the range from 1 to 25 g / l, preferably 5 to 15 g / l.
- Colorless coupling compounds are present in amounts of 1 to 25 g / l in the initial development bath, preferably 2 to 15 g / l.
- the concentrations of the hydroxylamine derivatives are in the range from 3 to 25 g / l, preferably 5 to 15 g / l.
- the substances can also be combined.
- the pH in the initial development bath is in the range from 6.5 to 7.5.
- the concentrations of the developer substances in the first development bath are in the range from 1 to 20 g / l, preferably 4 to 12 g / l.
- the bromide content of the first development bath is between 0 and 1 g / l, preferably 0-0.5 g / l.
- the chloride content can vary between 0.3 and 6 g / l, preferably 0.5 to 5 g / l.
- the black and white development of photographic reversal material performed in the first development bath is completed in less than 60 seconds, preferably in less than 30 seconds.
- wetting agents and complexing agents to the two developer solutions, which accelerate the penetration of the solutions into the emulsion layers or bind calcium ions from the gelatin and the water.
- Suitable complexing agents for complexing calcium ions are, for example, aminopolycarboxylic acids, which are well known per se.
- aminopolycarboxylic acids are nitrilotriacetic acid, ethylenediaminetetraacetic acid (EDTA), 1,3-diamino-2-hydroxypropyltetraacetic acid, diethylenetriaminepentaacetic acid, N, N'-bis- (2-hydroxybenzyl) -ethylenediamine-N, N'-diesiacetic acid, hydroxysethyldiacetic acid, hydroxyethyldiacetic acid, hydroxyethyldiacetic acid, hydroxyethyldiacetic acid, hydroxyethyldiacetic acid, hydroxyethyldiacetic acid, hydroxyethyldiacetic acid, hydroxyethyldiacetic acid, hydroxyethyldiacetic acid, hydroxyethyldiacetamic
- calcium complexing agents are polyphosphates, phosphonic acids, aminopolyphosphonic acids and hydrolyzed polymaleic anhydride, e.g. Sodium hexametaphosphate, 1-hydroxyethane-1,1-diphosphonic acid, aminotrismethylenephosphonic acid, ethylenediaminetetramethylenephosphonic acid. 1-hydroxyethane-1,1-diphosphonic acid also acts as an iron complexing agent.
- Special iron complexing agents are e.g. 4,5-dihydroxy-1,3-benzenedisulfonic acid, 5,6-dihydroxy-1,2,4-benzenetrisulfonic acid and 3,4,5-trihydroxybenzoic acid.
- the iron complexing agent is used in amounts of about 0.02 to about 0.2 moles per mole of developer substance.
- Optical brighteners e.g. Polyalkylene glycols, surfactants, stabilizers, e.g. heterocyclic mercapto compounds or nitrobenzimidazole and means for adjusting the desired pH in question.
- the developer solution may also contain less than 5 g / l benzyl alcohol; it is preferably free of benzyl alcohol.
- the ready-to-use solutions can be prepared from the individual components or from so-called concentrates, the individual components being dissolved in the concentrates in a much higher concentration.
- the concentrates are adjusted so that they can be used to produce a so-called regenerator, ie a solution that has slightly higher concentrations of the individual components than the ready-to-use solution has, on the one hand, by further dilution and addition of a starter, preferably KCI, a ready-to-use solution and, on the other hand, is constantly added to a developer solution in use in order to replace the chemicals consumed during development or removed from the developer solution by overflow or by the developed material.
- a starter preferably KCI
- Chloride ions usually do not need to be added except for the freshly prepared developer, since chloride ions are released from the photographic material by the development.
- the diffuse second exposure takes effect no earlier than 1 second after the material has entered the color development bath, since particularly good maximum densities are then achieved.
- the diffuse second exposure takes place 2 to 15 seconds after the material enters the color development bath.
- the delayed exposure can take place with the aid of a light slot or a division of the second development bath into a dark and a light part.
- the light slit and light / dark separation are applied in such a way that the color developing bath acts on the non-diffusively exposed material for at least 1 second in the dark.
- bleaching and fixing can be combined for bleach-fixing, and the washing can be replaced by a stabilizing bath. If the bleaching or bleach-fixing bath is sufficiently acidic, the stop bath can also be dispensed with.
- a color photographic recording material which is suitable for the processing method according to the invention was produced by applying the following layers in the order given to a layer support on paper coated on both sides with polyethylene.
- the quantities given relate to 1 m2.
- the corresponding amounts of AgNO3 are given.
- samples were watered fluently for 15 seconds or immediately added to the color developer (examples a).
- CD 4 can also be used.
- the development time in the color developer was 30 seconds at room temperature.
- color wedges were developed with the first developers described in the examples for comparison and testing to determine to what extent an undesired color coupling takes place, then rinsed and fixed for 5 minutes in a commercially available fixing bath based on ammonium thiosulfate and finally rinsed. Negative images are obtained and these can be evaluated with regard to maximum densities and the undesired color coupling.
- the desired suppression of the color coupling in the first developer is adequately achieved by adding antioxidants or competitive couplers at pH values of 6.5-7.5 by adding sulfite, white coupler and citrazinic acid. This ensures a good reversal with good D-Min, D-Max, clean colors and sufficient development.
- a color photographic recording material which is suitable for the processing method according to the invention was produced by applying the following layers in the order given to a layer support on paper coated on both sides with polyethylene.
- the quantities given relate to 1 m2.
- the corresponding amounts of AgNO3 are given.
- the couplers used were the same as in Examples 1 to 10.
- This example shows the sensitometric effects that result from the direct transition of the exposed photographic recording material from the first developer to the second developer in comparison to a processing sequence in which intermediate washing is carried out after the first development in order to wash out the first developer components.
- the processing is as follows:
- the processing baths had the following composition:
- pH adjustment to pH 9 with KOH or H2SO4 fill up to 1 liter with water.
- the following example shows the sensitometric effect that results from the direct transition of the exposed photographic reversal material from a first developer according to the invention to the second developer compared to a processing sequence in which washing is carried out between the first and second developer.
- a step wedge is exposed on a photographic material described in Example 11.
- the processing sequence corresponds to that from Example 11.
- Test sequence A is carried out with intermediate washing; the test sequence B without intermediate washing.
- the individual baths have the following composition
- Table 6 shows the sensitometric results of the densitometer measurements:
- a color photographic material according to Example 1 is processed according to the following processing variants I, II and III.
- the maximum densities show that it is advantageous not to carry out the diffuse second exposure immediately after entering the color developer, but only after a delay of 5 seconds.
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3835661 | 1988-10-20 | ||
DE3835661 | 1988-10-20 | ||
DE3843264 | 1988-12-22 | ||
DE3843264 | 1988-12-22 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0364845A2 EP0364845A2 (de) | 1990-04-25 |
EP0364845A3 EP0364845A3 (de) | 1991-09-25 |
EP0364845B1 true EP0364845B1 (de) | 1995-01-04 |
Family
ID=25873412
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP89118691A Expired - Lifetime EP0364845B1 (de) | 1988-10-20 | 1989-10-07 | Fotografisches Umkehrverfahren |
Country Status (4)
Country | Link |
---|---|
US (1) | US5110715A (ja) |
EP (1) | EP0364845B1 (ja) |
JP (1) | JPH02170158A (ja) |
DE (1) | DE58908850D1 (ja) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3920084A1 (de) * | 1989-06-20 | 1991-01-10 | Agfa Gevaert Ag | Verfahren zur herstellung von farbfotografischen kopien |
DE4104292A1 (de) * | 1991-02-13 | 1992-08-20 | Agfa Gevaert Ag | Bleichbad fuer fotografisches material |
JP2802695B2 (ja) * | 1991-11-20 | 1998-09-24 | 富士写真フイルム株式会社 | カラー反転画像形成方法 |
DE4217022A1 (de) * | 1992-05-22 | 1993-11-25 | Agfa Gevaert Ag | Verarbeitung von Umkehrmaterialien |
US5695914A (en) * | 1995-09-15 | 1997-12-09 | Eastman Kodak Company | Process of forming a dye image |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2449919A (en) * | 1947-07-05 | 1948-09-21 | Eastman Kodak Co | 3-methylsulfonamido-4-amino dimethyl aniline photographic developer |
BE560907A (ja) * | 1956-09-18 | |||
BE637358A (ja) * | 1962-09-15 | |||
BE789928A (fr) * | 1971-10-12 | 1973-02-01 | Minnesota Mining & Mfg | Procede et revelateur d'inversion des couleurs |
US4194911A (en) * | 1973-01-22 | 1980-03-25 | Minnesota Mining And Manufacturing Company | Inhibitor removing bath for direct positive color photographic development |
US4258117A (en) * | 1979-02-09 | 1981-03-24 | Eastman Kodak Company | Dye image reversal processes and image transfer film units |
JPH07117712B2 (ja) * | 1985-11-18 | 1995-12-18 | コニカ株式会社 | カラ−リバ−サル写真感光材料の処理方法 |
JPS63129341A (ja) * | 1986-11-19 | 1988-06-01 | Fuji Photo Film Co Ltd | ハロゲン化銀カラ−反転写真感光材料の処理方法 |
JPH07109497B2 (ja) * | 1987-04-06 | 1995-11-22 | コニカ株式会社 | ハロゲン化銀カラ−感光材料の処理方法 |
EP0370348A1 (de) * | 1988-11-24 | 1990-05-30 | Agfa-Gevaert AG | Fotografisches Umkehrverfahren |
-
1989
- 1989-10-07 EP EP89118691A patent/EP0364845B1/de not_active Expired - Lifetime
- 1989-10-07 DE DE58908850T patent/DE58908850D1/de not_active Expired - Fee Related
- 1989-10-10 US US07/419,584 patent/US5110715A/en not_active Expired - Fee Related
- 1989-10-19 JP JP1270515A patent/JPH02170158A/ja active Pending
Also Published As
Publication number | Publication date |
---|---|
DE58908850D1 (de) | 1995-02-16 |
US5110715A (en) | 1992-05-05 |
EP0364845A2 (de) | 1990-04-25 |
JPH02170158A (ja) | 1990-06-29 |
EP0364845A3 (de) | 1991-09-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
DE3333227C2 (ja) | ||
DE3412684C2 (ja) | ||
DE68918067T2 (de) | Bleichbeschleunigungszusammensetzungen, die ein Farbstoffstabilisierungsmittel enthalten und deren Verwendubg in der farbphotographischen Verarbeitung. | |
DE3302741A1 (de) | Farbbilderzeugungsverfahren | |
DE3687398T2 (de) | Verfahren zur behandlung farbphotographischer silberhalogenidmaterialien. | |
DE3248359C2 (ja) | ||
DE69029927T2 (de) | Verfahren zur Stabilisierung photographischer Elemente | |
DE3423100A1 (de) | Behandlungsbad mit bleichfaehigkeit gegenueber lichtempfindlichen (farb-)photographischen silberhalogenid-aufzeichnungsmaterialien | |
DE3412857C2 (ja) | ||
DE2942339A1 (de) | Verfahren zur behandlung eines farbphotographischen silberhalogenidmaterials | |
DE2707989C2 (de) | Farbentwickler und dessen Verwendung zum Entwickeln eines belichteten farbphotographischen Silberhalogenidmaterials | |
DE3412712A1 (de) | Farbentwickler und verfahren fuer die behandlung eines farbphotographischen silberhalogenidmaterials unter verwendung des farbentwicklers | |
DE3516417C2 (de) | Verfahren zur Verarbeitung eines farbphotographischen Silberhalogenidmaterials | |
DE3444091A1 (de) | Photographische farbbildner-zusammensetzung | |
EP0364845B1 (de) | Fotografisches Umkehrverfahren | |
DE69224867T2 (de) | Bleichlösung für farbfotografisches Verfahren | |
DE68926357T2 (de) | Verfahren zur Herstellung von farbphotographischen Bildern | |
DE3810348C2 (de) | Verfahren zur Schnellentwicklung von Colormaterialien | |
DE2411249A1 (de) | Verfahren zur behandlung von farbphotographischen materialien | |
DE69130091T2 (de) | Verfahren zur Verarbeitung farbphotographischer lichtempfindlicher Silberhalogenidmaterialien | |
DE69426851T2 (de) | Fotografische Entwicklungs-Lösung, die ternäre Ferri-Komplexsalze enthält | |
DE3687009T2 (de) | Verfahren zur behandlung eines farbphotographischen lichtempfindlichen silberhalogenidmaterials. | |
EP0358037A2 (de) | Verfahren zur Verarbeitung eines farbfotografischen Materials | |
EP0370348A1 (de) | Fotografisches Umkehrverfahren | |
DE69305728T2 (de) | Verfahren zum Bleichen und zum Fixieren eines farbphotographischen Elements |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 19891007 |
|
AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): BE DE FR GB IT NL |
|
PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
AK | Designated contracting states |
Kind code of ref document: A3 Designated state(s): BE DE FR GB IT NL |
|
17Q | First examination report despatched |
Effective date: 19940322 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): BE DE FR GB IT NL |
|
REF | Corresponds to: |
Ref document number: 58908850 Country of ref document: DE Date of ref document: 19950216 |
|
ITF | It: translation for a ep patent filed | ||
ET | Fr: translation filed | ||
GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) |
Effective date: 19950323 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 19960912 Year of fee payment: 8 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 19960930 Year of fee payment: 8 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 19961016 Year of fee payment: 8 Ref country code: BE Payment date: 19961016 Year of fee payment: 8 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 19961031 Year of fee payment: 8 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19971007 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY Effective date: 19971031 Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19971031 |
|
BERE | Be: lapsed |
Owner name: AGFA-GEVAERT A.G. Effective date: 19971031 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19980501 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 19971007 |
|
NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 19980501 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19980701 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED. Effective date: 20051007 |