US2331326A - Production of colored photographic images - Google Patents
Production of colored photographic images Download PDFInfo
- Publication number
- US2331326A US2331326A US345008A US34500840A US2331326A US 2331326 A US2331326 A US 2331326A US 345008 A US345008 A US 345008A US 34500840 A US34500840 A US 34500840A US 2331326 A US2331326 A US 2331326A
- Authority
- US
- United States
- Prior art keywords
- color
- image
- silver
- photographic
- coumarilyl
- 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
- 238000004519 manufacturing process Methods 0.000 title description 5
- -1 silver halide Chemical class 0.000 description 42
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 35
- 229910052709 silver Inorganic materials 0.000 description 34
- 239000004332 silver Substances 0.000 description 34
- 239000000839 emulsion Substances 0.000 description 32
- 239000000243 solution Substances 0.000 description 21
- 238000000034 method Methods 0.000 description 16
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 14
- 150000001408 amides Chemical class 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 12
- 125000003277 amino group Chemical group 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- 150000002148 esters Chemical class 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 8
- 239000008096 xylene Substances 0.000 description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 7
- 238000011161 development Methods 0.000 description 7
- 125000004494 ethyl ester group Chemical group 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000000975 dye Substances 0.000 description 6
- 150000002430 hydrocarbons Chemical group 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 5
- 239000001048 orange dye Substances 0.000 description 5
- 239000001044 red dye Substances 0.000 description 5
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000000987 azo dye Substances 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 3
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 2
- JRBJSXQPQWSCCF-UHFFFAOYSA-N 3,3'-Dimethoxybenzidine Chemical compound C1=C(N)C(OC)=CC(C=2C=C(OC)C(N)=CC=2)=C1 JRBJSXQPQWSCCF-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- OJGMBLNIHDZDGS-UHFFFAOYSA-N N-Ethylaniline Chemical compound CCNC1=CC=CC=C1 OJGMBLNIHDZDGS-UHFFFAOYSA-N 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
- 239000007844 bleaching agent Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- AJDUTMFFZHIJEM-UHFFFAOYSA-N n-(9,10-dioxoanthracen-1-yl)-4-[4-[[4-[4-[(9,10-dioxoanthracen-1-yl)carbamoyl]phenyl]phenyl]diazenyl]phenyl]benzamide Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2NC(=O)C(C=C1)=CC=C1C(C=C1)=CC=C1N=NC(C=C1)=CC=C1C(C=C1)=CC=C1C(=O)NC1=CC=CC2=C1C(=O)C1=CC=CC=C1C2=O AJDUTMFFZHIJEM-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 125000005429 oxyalkyl group Chemical group 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000001043 yellow dye Substances 0.000 description 2
- ODIRBFFBCSTPTO-UHFFFAOYSA-N 1,3-selenazole Chemical compound C1=C[se]C=N1 ODIRBFFBCSTPTO-UHFFFAOYSA-N 0.000 description 1
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 1
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- 241000577218 Phenes Species 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- SYKNUAWMBRIEKB-UHFFFAOYSA-N [Cl].[Br] Chemical compound [Cl].[Br] SYKNUAWMBRIEKB-UHFFFAOYSA-N 0.000 description 1
- 229960001413 acetanilide Drugs 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- ZEUDGVUWMXAXEF-UHFFFAOYSA-L bromo(chloro)silver Chemical compound Cl[Ag]Br ZEUDGVUWMXAXEF-UHFFFAOYSA-L 0.000 description 1
- OIPQUBBCOVJSNS-UHFFFAOYSA-L bromo(iodo)silver Chemical compound Br[Ag]I OIPQUBBCOVJSNS-UHFFFAOYSA-L 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000005265 dialkylamine group Chemical group 0.000 description 1
- 150000008049 diazo compounds Chemical class 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- DFWADNXPAGGDKQ-UHFFFAOYSA-N ethyl 4-amino-3-oxobutanoate Chemical compound CCOC(=O)CC(=O)CN DFWADNXPAGGDKQ-UHFFFAOYSA-N 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 1
- 150000003840 hydrochlorides Chemical class 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 125000006178 methyl benzyl group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- GTWJETSWSUWSEJ-UHFFFAOYSA-N n-benzylaniline Chemical compound C=1C=CC=CC=1CNC1=CC=CC=C1 GTWJETSWSUWSEJ-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 150000005002 naphthylamines Chemical class 0.000 description 1
- 125000004923 naphthylmethyl group Chemical group C1(=CC=CC2=CC=CC=C12)C* 0.000 description 1
- VMPITZXILSNTON-UHFFFAOYSA-N o-anisidine Chemical compound COC1=CC=CC=C1N VMPITZXILSNTON-UHFFFAOYSA-N 0.000 description 1
- 150000002916 oxazoles Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003230 pyrimidines Chemical class 0.000 description 1
- 125000002294 quinazolinyl group Chemical class N1=C(N=CC2=CC=CC=C12)* 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001629 stilbenes Chemical class 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- NQRYJNQNLNOLGT-UHFFFAOYSA-N tetrahydropyridine hydrochloride Natural products C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 125000001806 thionaphthenyl group Chemical group 0.000 description 1
- 238000011282 treatment Methods 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
- G03C7/32—Colour coupling substances
- G03C7/36—Couplers containing compounds with active methylene groups
Definitions
- a colored image may be formed simultaneously with the silver image obtained by developing a silver halide emulsion with an aromatic amino developing agent, if a substance known as a color former is present, for
- the colored-image may be revealed by bleaching out the silver image with farmers Reducer or other photographic bleaching agent.
- the present invention has for an object the production of new color formers which are useful in color photography.
- a further object is the preparation of photographic emulsions which contain new and improved color formers which are substantially water insoluble and which yield dyes by coupling with the oxidation products of I aromatic amino developing agents.
- a further object is the provision of new photographic developing processes.
- a still further object is the preparation of photographic elements bearing an emulsion which contains one or more of the new color formers, which do not migrate; another object is the preparation of multi-layer photographic fllms containing color formers which do notmigrate from layer to layer or into the processing baths.
- Yet another object is the preparation of finished photographs which contain stable dyed images whiehare formed of water-insoluble dyes.
- Other objects include the preparation of color photographs and color forming emulsions upon opaque or transparent supports. Still other objects .will appear hereinafter.
- any of the pairs of groups R1 and R2, R2 and R: and R3 and R4 may together form a further cyclic nucleus fused to the benzene nucleus of the formula.
- D is the residue of any substituted or unsubstituted aromatic nucleus
- X is an oxygen atom or a sulphur atom
- R3 is a hydrogen atom or a hydrocarbon group
- A is an ester, amide or substituted amide group.
- the general formula includes coumarilylacetic esters, substituted coumarilyl-acetic esters. thionaphthenyl-m-acetic acid esters and substituted thionaphthenyl-a-acetic acid esters, and the amides and substituted amides which correv spond to them.
- the groups R1, R2, R3, R4, R5, Rs, R7 and Rs in the general formula (I) may be hydrocarbon groups. Thus they may be straight or branched chain primary, secondary, tertiary or iso alkyl groups of 1 to 18 or more carbon atoms (e. g. methyl, ethyl, propyl, butyl or higher alkyl groups, e. g. dodecyl, octadecyl etc., cycloalkyl groups, e. g. cyclohexyl, methyl cyclohexyl, dodecyl-cyclohexyl etc., aryl groups (e.
- phenyl or naphthyl groups phenyl or naphthyl groups
- aralkyl groups e. g. benzyl, methylbenzyl or naphthylmethyl groups.
- Such groups may themselves be substituted, for example, aryl groups may be substituted'with hydroxy, alkoxy, oxyalkyl, amino or nitro groups or with halogen atoms.
- Suitable groups include methoxy, ethoxy, hydroxyethyl,
- heterocyclic group Suitable heterocyclic nuclei are, for example, pyridine, quinoline, thiaaole, benzthiazole, naphthathiazole, oxazole, benzoxasole, selenazole. pyrimidine, quinanoline, thio-.
- R1, Ra, Rs, Ra, Re and X having the significance indicated above, and Z being a halogen atom, e. g. chlorine bromine or iodine.
- Color formers-of the type in which 2 is an group may be prepared by reacting a compound of the above general formula where Z is -OR0 with ammonia or a primary or secondary amin of the formula
- suitable amines are monoor dialkylamines e. g. ethylamine, diethylamine and higher homologues, aliphatic diamines e. g.
- ethylene diamine hexylenediamine etc. mono-'- and di-arylamines, e. g. aniline, diphenylamine and naphthylamines, monoand di-aralkylamines, e. g. benzylamine, alkyl arylamines, e. g. N-ethylaniline, alkyl aralkyl amines, e. g. N-ethyl bensylamine, aralkyl arylamines, e. g. benzyl aniline, heterocyclic amines, e. g.
- pyridine piperldine, methyl piperidine, quinoline, thiazoles, oxazoles, pyrimidines, quinazolines and the like and aromatic diamineae. g. oand p-phenylenediamine, benzidine, dianisidine, diamino stilbenes and dinaphthylamines.
- Aryl nuclei present in the amines may themselves be substituted, e. 8. by alkyl nitro, halogen, alkoxy or oxyalkyl groups. Where .the amine employed is a diamine, reaction may take place at both amino groups so that the final product contains two coumarilyl or thicnaphthenoyl nuclei.
- the new color formers ma solutions or in photographic silver halide emulsions.
- color coupling amino developing agents the diam'ino aryl compounds such as p-phenylene diamine and its substitution products are preferred. These developers may be substituted in the amino groups as well as in the ring.
- the developing compounds must, of course, have one free or unsubstituted amino group which enables the oxidation product-of the; developer to couple with the color formers.
- developers which may be emthere may be mentioned the following: p-phenylene diamine, mono ethyl-p-phenylene diamine; di ethyl ortho phenylene diamine, chloro-p-phenylene d'iamine, amino-p-phenylene diamine Lab-toluene diamine, 2-amino-5-diethylamine toluene, p-amino phenylene piperidine, methyl oxyethyl p phenylene diamine,
- Developing solution A containing a color-former in accordance with the present invention may be made up as follows:
- Exalrts 1 a-coumadlylacetic acid ethyl ester (L-C O-GHr-C 0-0 can oi 63 gms. ofethylacetoacetate were added to a solution of 11.2 gms. of sodium in 197 cos. of ethyl alcohol contained in' a 3-litre, 3-necked flask fitted with a mercury seal, a double surface condenser, a mechanical stirrer and a dropping funnel.
- 84 gms. of coumarilyl chloride were slowly added to the resulting solution by means of the dropping funnel, the addition being effected over a period of two hours and the temperature being maintained at 0 C. to -5 C. The temperature was then raised to 15 C. for
- the resulting thick suspension of green copper salt was then cooled to 10 C. with stirring over a period of one hour, and filtered.
- The'solid residue was then washed with water and ethyl alcohol, dried, pulverised and then suspended in 300 ccs.-of water.
- the suspension was rendered acid with 22 cos. of'24% hydrochloric acid and stirred for half an hour, care. being taken not to add an excess of acid.
- An oil separated which was extracted with ether, dried over sodium sulphate and distilled at 15 m. m. pressure.
- the resulting liquid had a boiling point of 200-220 C. and was a-coumarilyl-acetic acid ethyl ester.
- This compound was included in Developing solution A and used for the development of an exposed silver halide photographic emulsion and yielded a red image together with the silver image.
- the corresponding nitro oz coumarilyl acetic acid ethyl ester may besimilarly produced by starting with the corresponding 5-nitrocoumarilyl chloride.
- EXAMPLE 2 a-Coumarilylaceto-o-anisidide 2.32 of u-coumarilyl acetic acid ethyl ester prepared as in Example 1 were dissolved in' ccs. of xylene containing three drops of pyridine, in a 100 cc. distilling flask fitted with a dropping funnel. The solution was gently boiled on a sand bath and then a solution of 1.23 grams of 'o-anisidine in 10 ccs. of xylene was run in slowly over a period of ten minutes. 'At the end of. this time the solution was boiled for fifteen minutes during which time some of the xylene was (distilled off.
- This compound was prepared by a method similar to that of Example 2, but using 1.16 1
- EXAMPLE 4 a-C'oumarilyl-acet-anilide (L i 10 -.o O--'CHT-G 0-NH-C/ This compound was prepared by a method similar to Example 2 using 1.16 grams of acoumarilylacetic acid ethyl ester dissolved in 10 and 0.45 gram of aniline dissolved in 10 cos. of xylene. The recrystallised product had a melting point of 150 C. When included in Developing solution A and used for the development of an exposed silver halide emulsion it yielded an orange-red image in addition to the silver image.
- EXAMPLE 5 a-CoumarilyZ-acet-o-chloranilide
- EXAMPLE 6 a-CoumariZylacet-pmitmnilide coo-onrod-NnONo'z l k s on 4 v 1.16 grams of acoumarilyl acetic acid ethyl esterdissolved in' 10; cos. of xylene and containing three drops of py ridine were gently boiled and then 2.69 grams of p-m'traniline dissolved in 50 cos. of ,xylene were added slowly.
- the color-formers may be employed to iorm-such azo dyes and the dyes then a-Thionaphthenoylacetic acid ethyl ester, boiling point 220-228 C./25 mm., yielding a red dye image a-Thionaphthenoylacet-o-anlsidide, M. pt. 144
- the process of development employing the color-iormers in accordance with the present invention may be applied'to a latent image in an emulsion 01 silver halide which has been exposed to the action of light, for example, in a camera or behind a photographic negative image.
- the process may also be applied to a silver salt image which has been obtained by dissolving away an initial reduced silver image and exposing to light the residual unaltered silver salt, for example, in the reversal process of development.
- the process may also be applied to a developable silver salt image obtained by removingthe unaldiiferentially bleached by known processes to yield azo dye images.
- the new color formers of this invention possess many advantages. As indicated above they do not migrate from one emulsion layer to another and they do not tend to diffuse from the emulsion layers during processing treatments. Moreover, the new color formers are strongly resistant to the bleaching action of the sulphite commonly contained in photographic developing solutions; that is, they yield dye images oi! satisfactory depth even though sulphite is present in the developer employed. Moreover, the. dye
- a photographic element comprising a light sensitive silver halide emulsion containing as a color former an ester of an a -coumarilyl acetic acid.
- a photographic element comprising a light sensitive silver halide emulsion containing as a color i'ormer an amide of a ha oge S st ted a-coumarilyl acetic acid.
- a photographic color forming developer which comprises an aromatic amino developing agent containing an unsubstituted amino group and a color former which is an ester of anoccoumarilyl acetic acid.
- a photographic color forming developer which comprises an aromatic amino developing agent containing an unsubstituted amino group and a color former which is an amideof an a-coumarilyl acetic acid.
- a photographic color forming developer which comprise an aromatic amino developing agent containing an unsubstituted amino group and a color former which is an amide of a halogen substituted a-coumarilyl acetic acid.
- a method 'of producing a colored image in a silver halide emulsion which has a latent image formed in it which comprises developing the emulsion in the presence of an amide of aha-0011- marilyl acetic acid in the presence of an aromatic 'amino developing agent containing an unsubstituted amino group.
- a method of producing a colored image in a silver halide emulsion which has a latent image formed in it which comprises developing the emulsion in the presence of an amide of a halogen 5 substituted a-coumarilyl acetic acid in the presence of an aromatic amino developing agent containing an unsubstituted amino group.
- a method of producinga color image in a photographic element bearing a silver halide emulsion layer having a latent image formed in it which comprises color developing said element an aromatic amino color developing agent havthe presence of alpha-coumarilyl-acet-ortho-- chloranilide withan aromatic amino color developing agent having an unsubstituted amino group.
Description
Patented on. 12, 1943 PRDDUGTION OF COLORED PHOTO- GRAPHIC IMAGES John David Kendall and Ronald Bernard Collins, lJford, England, assignors to lli'ord Limited, Ilford, England, a British company No Drawing. Application July 11, 1940, Serial N 0. 345,008. In Great Britain July 22, 1939 18 Claims. (Cl. 95-6) This invention relates to the production of colored photographic images by color development.
It is known that a colored image may be formed simultaneously with the silver image obtained by developing a silver halide emulsion with an aromatic amino developing agent, if a substance known as a color former is present, for
example, in the developing solution or in the silver halide emulsion. The colored-image may be revealed by bleaching out the silver image with Farmers Reducer or other photographic bleaching agent.
The present invention has for an object the production of new color formers which are useful in color photography. A further object is the preparation of photographic emulsions which contain new and improved color formers which are substantially water insoluble and which yield dyes by coupling with the oxidation products of I aromatic amino developing agents. A further object is the provision of new photographic developing processes. A still further object is the preparation of photographic elements bearing an emulsion which contains one or more of the new color formers, which do not migrate; another object is the preparation of multi-layer photographic fllms containing color formers which do notmigrate from layer to layer or into the processing baths. Yet another object is the preparation of finished photographs which contain stable dyed images whiehare formed of water-insoluble dyes. Other objects include the preparation of color photographs and color forming emulsions upon opaque or transparent supports. Still other objects .will appear hereinafter.
The above and other objects are accomplished by the preparation and use in photographic processes and emulsions of color formers which are esters, amides and substituted amides of the genwhere R1, R2, R3 and R4 are the same or different and are hydrogen atoms or substituent groups, e. g. hydrocarbon groups, halogen atoms, nitro groups, amino groups,'hydroxy groups and alkoxy groups, R5 is a hydrogen atom or a hydrocarbon group, X is an oxygen atom or a sulphur atom and Y is an OR@ group or a Ra group where Re is a hydrocarbon group and R1 and Rs are the same or different and are hydrogen atoms or hydrocarbon groups or together form a heterocyclic residue.
Any of the pairs of groups R1 and R2, R2 and R: and R3 and R4 may together form a further cyclic nucleus fused to the benzene nucleus of the formula.
For simplicity these compounds may be defined as compounds of the general formula:
where D is the residue of any substituted or unsubstituted aromatic nucleus, X is an oxygen atom or a sulphur atom, R3 is a hydrogen atom or a hydrocarbon group and A is an ester, amide or substituted amide group.
The general formula includes coumarilylacetic esters, substituted coumarilyl-acetic esters. thionaphthenyl-m-acetic acid esters and substituted thionaphthenyl-a-acetic acid esters, and the amides and substituted amides which correv spond to them.
As indicated above, the groups R1, R2, R3, R4, R5, Rs, R7 and Rs in the general formula (I) may be hydrocarbon groups. Thus they may be straight or branched chain primary, secondary, tertiary or iso alkyl groups of 1 to 18 or more carbon atoms (e. g. methyl, ethyl, propyl, butyl or higher alkyl groups, e. g. dodecyl, octadecyl etc., cycloalkyl groups, e. g. cyclohexyl, methyl cyclohexyl, dodecyl-cyclohexyl etc., aryl groups (e. 'g, phenyl or naphthyl groups), or aralkyl groups (e. g. benzyl, methylbenzyl or naphthylmethyl groups). Such groups may themselves be substituted, for example, aryl groups may be substituted'with hydroxy, alkoxy, oxyalkyl, amino or nitro groups or with halogen atoms. Suitable groups include methoxy, ethoxy, hydroxyethyl,
heterocyclic group. Suitable heterocyclic nuclei are, for example, pyridine, quinoline, thiaaole, benzthiazole, naphthathiazole, oxazole, benzoxasole, selenazole. pyrimidine, quinanoline, thio-.
phene, coumarane and other heteroc'yclic nuclei.
The color-formers of the type where Y in the above general formula is an ORs group may be 7 prepared by condensing an acylacetic ester'with a substituted or unsubstituted coumarilyl chloride or a substituted orunsubstituted thionaphc-xn I -on=o with a 'y-halogen aceto-acetic ester of the general formula:
the groups R1, Ra, Rs, Ra, Re and X having the significance indicated above, and Z being a halogen atom, e. g. chlorine bromine or iodine.
Color formers-of the type in which 2 is an group may be prepared by reacting a compound of the above general formula where Z is -OR0 with ammonia or a primary or secondary amin of the formula Examples of suitable amines are monoor dialkylamines e. g. ethylamine, diethylamine and higher homologues, aliphatic diamines e. g.
ethylene diamine hexylenediamine etc., mono-'- and di-arylamines, e. g. aniline, diphenylamine and naphthylamines, monoand di-aralkylamines, e. g. benzylamine, alkyl arylamines, e. g. N-ethylaniline, alkyl aralkyl amines, e. g. N-ethyl bensylamine, aralkyl arylamines, e. g. benzyl aniline, heterocyclic amines, e. g. pyridine, piperldine, methyl piperidine, quinoline, thiazoles, oxazoles, pyrimidines, quinazolines and the like and aromatic diamineae. g. oand p-phenylenediamine, benzidine, dianisidine, diamino stilbenes and dinaphthylamines. Aryl nuclei present in the amines may themselves be substituted, e. 8. by alkyl nitro, halogen, alkoxy or oxyalkyl groups. Where .the amine employed is a diamine, reaction may take place at both amino groups so that the final product contains two coumarilyl or thicnaphthenoyl nuclei.
The new color formers ma solutions or in photographic silver halide emulsions. As color coupling amino developing agents the diam'ino aryl compounds such as p-phenylene diamine and its substitution products are preferred. These developers may be substituted in the amino groups as well as in the ring. Preferbe incorporated in'color-coupling or Jorming amino developing' assua e ably the former, to constitute compounds such as the monoand di-alkyl aryl e-diamines including the monoand di-alkyl naphthylene diamines, alkyl phenylene diamines and alkyl toluylene. diamines. The developing compounds must, of course, have one free or unsubstituted amino group which enables the oxidation product-of the; developer to couple with the color formers.
As examples of developers which may be emthere may be mentioned the following: p-phenylene diamine, mono ethyl-p-phenylene diamine; di ethyl ortho phenylene diamine, chloro-p-phenylene d'iamine, amino-p-phenylene diamine Lab-toluene diamine, 2-amino-5-diethylamine toluene, p-amino phenylene piperidine, methyl oxyethyl p phenylene diamine,
ethyl-oxyethyl-p-phenylene diamine, butyl-oxyethyl-p-phenylene diamine, 2-amino-5-oxyethyli-butylaminotoluene and its dihydrochloride, 'y dioxypropyl p phenylene diamine, 4:4'-diamino diphenylamine and a aminoacetoacetic acid ethyl ester. These compounds are preferably used in the form of their salts either of organic or inorganic type, since the salts are more soluble and stable than the free bases. The hydrochlorides, sulphates and acetates are examples of suitable salts.
By way of example a suitable developing solution (referred to for convenience in the subsequent examples as "Developing solution A") containing a color-former in accordance with the present invention may be made up as follows:
The solution sulphite may be omitted if desired. The following examples illustrate the so method of production of the color-formers of the invention:
Exalrts 1 a-coumadlylacetic acid ethyl ester (L-C O-GHr-C 0-0 can oi 63 gms. ofethylacetoacetate were added to a solution of 11.2 gms. of sodium in 197 cos. of ethyl alcohol contained in' a 3-litre, 3-necked flask fitted with a mercury seal, a double surface condenser, a mechanical stirrer and a dropping funnel. 84 gms. of coumarilyl chloride were slowly added to the resulting solution by means of the dropping funnel, the addition being effected over a period of two hours and the temperature being maintained at 0 C. to -5 C. The temperature was then raised to 15 C. for
one hour and maintained at 10-15" C for a further two hours. At the end of this period 102 cos. of ammonia solution (S. G. 0.920) were added rapidly and the temperature raised to C. The solution was maintained at this temperature for'flfteen minutes and then cooled to 20 C. A
200 cos. of water were then added to. the
cooled solution (which had set solid) and a solution of 66.1 grams of copper sulphate in181 ccs. of water then run in, the temperature not being allowed to exceed 35 C.
The resulting thick suspension of green copper salt was then cooled to 10 C. with stirring over a period of one hour, and filtered. -The'solid residue was then washed with water and ethyl alcohol, dried, pulverised and then suspended in 300 ccs.-of water. The suspension was rendered acid with 22 cos. of'24% hydrochloric acid and stirred for half an hour, care. being taken not to add an excess of acid.- An oil separated which was extracted with ether, dried over sodium sulphate and distilled at 15 m. m. pressure. The resulting liquid had a boiling point of 200-220 C. and was a-coumarilyl-acetic acid ethyl ester.
This compound was included in Developing solution A and used for the development of an exposed silver halide photographic emulsion and yielded a red image together with the silver image. A
The corresponding nitro oz coumarilyl acetic acid ethyl ester may besimilarly produced by starting with the corresponding 5-nitrocoumarilyl chloride. When included in- Developing solution A and used as above it yields a magneta image together with the silver image.
EXAMPLE 2 a-Coumarilylaceto-o-anisidide 2.32 of u-coumarilyl acetic acid ethyl ester prepared as in Example 1 were dissolved in' ccs. of xylene containing three drops of pyridine, in a 100 cc. distilling flask fitted with a dropping funnel. The solution was gently boiled on a sand bath and then a solution of 1.23 grams of 'o-anisidine in 10 ccs. of xylene was run in slowly over a period of ten minutes. 'At the end of. this time the solution was boiled for fifteen minutes during which time some of the xylene was (distilled off. .The residual solution was cooled and diluted with petroleum ether when a-coumarilyl-acetic acid-o-anisidide separated as a yellow solid having a melting point of 100 -C. This product when included in Developing solutionA and used for developing an exposed silver halide photographic emulsion yielded a yellow image together with the silver image.
This compound was prepared by a method similar to that of Example 2, but using 1.16 1
"photographic emulsion it yielded an orange-re image together with the silver image.
EXAMPLE 4 a-C'oumarilyl-acet-anilide (L i 10 -.o O--'CHT-G 0-NH-C/ This compound was prepared by a method similar to Example 2 using 1.16 grams of acoumarilylacetic acid ethyl ester dissolved in 10 and 0.45 gram of aniline dissolved in 10 cos. of xylene. The recrystallised product had a melting point of 150 C. When included in Developing solution A and used for the development of an exposed silver halide emulsion it yielded an orange-red image in addition to the silver image.
EXAMPLE 5 a-CoumarilyZ-acet-o-chloranilide EXAMPLE 6 a-CoumariZylacet-pmitmnilide coo-onrod-NnONo'z l k s on 4 v 1.16 grams of acoumarilyl acetic acid ethyl esterdissolved in' 10; cos. of xylene and containing three drops of py ridine were gently boiled and then 2.69 grams of p-m'traniline dissolved in 50 cos. of ,xylene were added slowly. I
At the same time the xylene was steadily dis tilled-oil so that the bulk of the reaction mixture at no time exceeded 1045 cc. Finally the mixture was boiled for fifteen minutes, cooled and filtered. The produpt, separated by filtration, was recrystallised from ethyl alcohol solution and had a melting point of 193 0: When included in Developing solutlum A? and used for the development of an exposed silver halide photographic emulsion it yielded a brown image together with the silver image.
05 In the foregoing examples the tests were effected using silver chloride emulsions. How-.
ever, other tests show that similar colors are obtained using emulsions of 'any other silver and silver ohloro bromide.
Exmpm '7 This example illustrates the incorporation of the color-formers of this invention in emulsion layers. 20 cos. of a 1% solution in ethylene glyccs. of xylene containing three drops of pyridine halides, e. g. silver bromide, silver iodobromide col monomethyl ether of a-coumarilylacetic acid ethyl ester were added to 25 cos. of a 10% aqueous solution of gelatin and the mixture added to .50 cos. of a melted photographic Gaslight ylether. l A red image was produced together with the silver image.
In addition to the color formers specifically referred to above, the following specific color formers which can be prepared in like manner from the reactants described may be instanced as yielding dye images 01 especial value according to this invention:
4:6 dibrom-a coumarilylacetic acid ethyl ester, )6. pt. 210 C., yielding a bright red dye image 6 brorno-a-coumarilylacetic acid ethyl ester,
M. pt. 110 C., yielding a bright red dye image 4 brom-a-coumarilylacetanilide, M. pt. 180 C.,
yielding an orange dye image 6 brom-a-coumarilylacet-o-anisidide,-M. pt. 179
C., yielding an orange dye image 6 brom-a-coumarilyl acet-p-nitranilide, M. pt.
227 C., yielding a red dye image 4:6 dibrom-a-coumarilylacet-o-anisidide, M. pt.
220-230 C., yielding an orange dye image 3:4 benz-a-coumarilylacetic acid ethyl ester,
M. pt. 100 C., yielding a red dye image 3:4 benz-a-coumarilylacet-o-anisidide, M. pt.
160 C., yielding a yellow dye image tered silver halide by means oi solvents from a developed photographic image in metallic silver and then converting the metallic silver to a developable silver salt by means of known photographic bleaching agents. The process may also be applied to the development of silver halide photographic emulsions which have been rendered developable by means other than exposure to light, for example, by chemical means. The color formers and processes'are not limited to any one type or reducible silver salt. Any developable silver halide may be used. Thus, as indicated above, simple and mixed silver halides such as silver chloride, silver bromide, silver-chloride bromide, silver bromide iodide etc., may be employed.
As a modification, the production of colored images by means of the color-formers of this inprocesses :0! color photography, wherein azo dye images are formed. The color formers couple with the usual types of diazo compound, e. g. di-
. azotized p-nitroaniline, tetrozotised dianisidine solutions etc. Thus, the color-formers may be employed to iorm-such azo dyes and the dyes then a-Thionaphthenoylacetic acid ethyl ester, boiling point 220-228 C./25 mm., yielding a red dye image a-Thionaphthenoylacet-o-anlsidide, M. pt. 144
C., yielding a yellow dye image a-Thionaphthenoylacetanllide, M. pt. 166 C.,
yielding an orange brown image a-Thionaphthenoyl-p-chlor-anilide, M. pt., 210
C., yielding an orange brown image Di (a thionaphthenoylacetamino) diphenyl,
M. pt. above 305 C., yielding a red image p.p'-Di-(coumarilyl-acetamino) -diphenyl, M. pt.
228 C., yielding an orange dye image p.p'-Di- (coumarilyl-acetamlno) -benzene, M. pt.
227 C., yielding an orange dye image (In naming the above. compounds the coumarilyl nucleus is numbered as follows:
The process of development employing the color-iormers in accordance with the present invention may be applied'to a latent image in an emulsion 01 silver halide which has been exposed to the action of light, for example, in a camera or behind a photographic negative image.
The process may also be applied to a silver salt image which has been obtained by dissolving away an initial reduced silver image and exposing to light the residual unaltered silver salt, for example, in the reversal process of development. The process may also be applied to a developable silver salt image obtained by removingthe unaldiiferentially bleached by known processes to yield azo dye images.
The new color formers of this invention possess many advantages. As indicated above they do not migrate from one emulsion layer to another and they do not tend to diffuse from the emulsion layers during processing treatments. Moreover, the new color formers are strongly resistant to the bleaching action of the sulphite commonly contained in photographic developing solutions; that is, they yield dye images oi! satisfactory depth even though sulphite is present in the developer employed. Moreover, the. dye
images produced are very stable.
We claim:
1. A light sensitive photographic emulsion taken from the group consisting of silver halide and bichromate emulsions containing as a color former a compound selected from the class consisting of esters, amides and substituted amides oi a-coumarilyl acetic acid, substituted-a-coumarilyl acetic acid, thionaphthenyl s-acetic acid and substituted thio-naphthenyl-a-acetic acid.
2. A photographic element comprising a light sensitive silver halide emulsion containing as a color former an ester of an a -coumarilyl acetic acid. 3. A photographic element containing at least one colloid layer )mprising a light sensitive silver halide emulsion containing as a color former an amide of an a-coumarilyl acetic'acid.
4. A photographic element comprising a light sensitive silver halide emulsion containing as a color i'ormer an amide of a ha oge S st ted a-coumarilyl acetic acid.
6. A photographic color forming developer which comprises an aromatic amino developing agent containing an unsubstituted amino group and a color former which is an ester of anoccoumarilyl acetic acid.
7. A photographic color forming developer which comprises an aromatic amino developing agent containing an unsubstituted amino group and a color former which is an amideof an a-coumarilyl acetic acid.
8. A photographic color forming developer which comprise an aromatic amino developing agent containing an unsubstituted amino group and a color former which is an amide of a halogen substituted a-coumarilyl acetic acid.
9. A method of producing a colored imag in a silver halide emulsion which has a latent image formed in itwhich COmDrises color developing the emulsion in the presence of a compound selected from the class consisting of esters, amides and Y substituted amides of a-coumarilyl acetic acid,
emulsion in thepresence of an ester of an a- -coumarilyl acetic acid in the presence of an aromatic amino developing agent containing an unsubstituted amino group.
11. A method 'of producing a colored image in a silver halide emulsion which has a latent image formed in it which comprises developing the emulsion in the presence of an amide of aha-0011- marilyl acetic acid in the presence of an aromatic 'amino developing agent containing an unsubstituted amino group.
12. A method of producing a colored image in a silver halide emulsion which has a latent image formed in it which comprises developing the emulsion in the presence of an amide of a halogen 5 substituted a-coumarilyl acetic acid in the presence of an aromatic amino developing agent containing an unsubstituted amino group.
13. A method of producinga color image in a photographic element bearing a silver halide emulsion layer having a latent image formed in it which comprises color developing said element an aromatic amino color developing agent havthe presence of alpha-coumarilyl-acet-ortho-- chloranilide withan aromatic amino color developing agent having an unsubstituted amino group.
JOHN DAVID KENDALL. RONALD BERNARD COLLINS.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB21331/39A GB532804A (en) | 1939-07-22 | 1939-07-22 | Improvements in or relating to colour photography |
Publications (1)
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US2331326A true US2331326A (en) | 1943-10-12 |
Family
ID=10161075
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US345008A Expired - Lifetime US2331326A (en) | 1939-07-22 | 1940-07-11 | Production of colored photographic images |
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US (1) | US2331326A (en) |
GB (1) | GB532804A (en) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2434272A (en) * | 1944-05-03 | 1948-01-13 | Eastman Kodak Co | Color photography with azosubstituted couplers |
US2531091A (en) * | 1945-08-03 | 1950-11-21 | Gevaert Photo Prod Nv | N-acetonyl-pyridinium chloride as an azo coupling component in diazotypes |
US2533185A (en) * | 1947-10-22 | 1950-12-05 | Gen Aniline & Film Corp | Alkyl malonamates as azo coupling components in diazotype layers |
US2541727A (en) * | 1947-12-17 | 1951-02-13 | Gen Analine & Film Corp | Diazotypes containing aldehyde reaction products of dihydroxy aryl compounds |
US2846307A (en) * | 1954-10-22 | 1958-08-05 | Ici Ltd | Isoxazolone couplers in color photography |
DE1074976B (en) * | 1960-02-04 | Imperial Chemical Industries Limited, London | Process for the production of tarbphotographic images by the color development process | |
EP0751427A1 (en) * | 1995-06-28 | 1997-01-02 | Kodak Limited | Image-dye-forming couplers and photographic elements containing them |
EP0953871A1 (en) * | 1998-04-29 | 1999-11-03 | Eastman Kodak Company | Photographic element containing yellow dye-forming photographic coupler |
US6221573B1 (en) | 1999-10-27 | 2001-04-24 | Eastman Kodak Company | Yellow coupler, photographic element, and process |
-
1939
- 1939-07-22 GB GB21331/39A patent/GB532804A/en not_active Expired
-
1940
- 1940-07-11 US US345008A patent/US2331326A/en not_active Expired - Lifetime
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1074976B (en) * | 1960-02-04 | Imperial Chemical Industries Limited, London | Process for the production of tarbphotographic images by the color development process | |
US2434272A (en) * | 1944-05-03 | 1948-01-13 | Eastman Kodak Co | Color photography with azosubstituted couplers |
US2531091A (en) * | 1945-08-03 | 1950-11-21 | Gevaert Photo Prod Nv | N-acetonyl-pyridinium chloride as an azo coupling component in diazotypes |
US2533185A (en) * | 1947-10-22 | 1950-12-05 | Gen Aniline & Film Corp | Alkyl malonamates as azo coupling components in diazotype layers |
US2541727A (en) * | 1947-12-17 | 1951-02-13 | Gen Analine & Film Corp | Diazotypes containing aldehyde reaction products of dihydroxy aryl compounds |
US2846307A (en) * | 1954-10-22 | 1958-08-05 | Ici Ltd | Isoxazolone couplers in color photography |
EP0751427A1 (en) * | 1995-06-28 | 1997-01-02 | Kodak Limited | Image-dye-forming couplers and photographic elements containing them |
US5693458A (en) * | 1995-06-28 | 1997-12-02 | Eastman Kodak Company | Photographic elements containing certain yellow dye-forming couplers |
EP0953871A1 (en) * | 1998-04-29 | 1999-11-03 | Eastman Kodak Company | Photographic element containing yellow dye-forming photographic coupler |
US6083677A (en) * | 1998-04-29 | 2000-07-04 | Eastman Kodak Company | Photographic element containing yellow dye-forming photographic coupler |
US6221573B1 (en) | 1999-10-27 | 2001-04-24 | Eastman Kodak Company | Yellow coupler, photographic element, and process |
Also Published As
Publication number | Publication date |
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GB532804A (en) | 1941-01-31 |
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