US2179239A - Color photography - Google Patents
Color photography Download PDFInfo
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- US2179239A US2179239A US174350A US17435037A US2179239A US 2179239 A US2179239 A US 2179239A US 174350 A US174350 A US 174350A US 17435037 A US17435037 A US 17435037A US 2179239 A US2179239 A US 2179239A
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- 150000001875 compounds Chemical class 0.000 description 15
- 239000000839 emulsion Substances 0.000 description 10
- 150000002148 esters Chemical class 0.000 description 8
- 150000003254 radicals Chemical class 0.000 description 8
- 125000004429 atom Chemical group 0.000 description 7
- 238000009792 diffusion process Methods 0.000 description 7
- 239000000975 dye Substances 0.000 description 6
- 229920000159 gelatin Polymers 0.000 description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- -1 amino, carboxyl Chemical group 0.000 description 4
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 235000019322 gelatine Nutrition 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 4
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 3
- QPKNFEVLZVJGBM-UHFFFAOYSA-N 2-aminonaphthalen-1-ol Chemical class C1=CC=CC2=C(O)C(N)=CC=C21 QPKNFEVLZVJGBM-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 108010010803 Gelatin Proteins 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical class C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000008273 gelatin Substances 0.000 description 3
- 235000011852 gelatine desserts Nutrition 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000009877 rendering Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- XRTJYEIMLZALBD-UHFFFAOYSA-N 4-(6-methyl-1,3-benzothiazol-2-yl)aniline Chemical compound S1C2=CC(C)=CC=C2N=C1C1=CC=C(N)C=C1 XRTJYEIMLZALBD-UHFFFAOYSA-N 0.000 description 2
- QNGVNLMMEQUVQK-UHFFFAOYSA-N 4-n,4-n-diethylbenzene-1,4-diamine Chemical compound CCN(CC)C1=CC=C(N)C=C1 QNGVNLMMEQUVQK-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000001828 Gelatine Substances 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 229940051880 analgesics and antipyretics pyrazolones Drugs 0.000 description 2
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 2
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 125000006267 biphenyl group Chemical group 0.000 description 2
- 235000013877 carbamide Nutrition 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000004780 naphthols Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical class O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 2
- 235000021286 stilbenes Nutrition 0.000 description 2
- TXVWTOBHDDIASC-UHFFFAOYSA-N 1,2-diphenylethene-1,2-diamine Chemical compound C=1C=CC=CC=1C(N)=C(N)C1=CC=CC=C1 TXVWTOBHDDIASC-UHFFFAOYSA-N 0.000 description 1
- HONMCSLFRKBQHG-UHFFFAOYSA-N 1,3-diamino-1,3-diphenylurea Chemical compound C=1C=CC=CC=1N(N)C(=O)N(N)C1=CC=CC=C1 HONMCSLFRKBQHG-UHFFFAOYSA-N 0.000 description 1
- KXIMTVJJKCWVRG-UHFFFAOYSA-N 1-N-ethoxy-4-N,4-N-dimethylbenzene-1,4-diamine Chemical compound C(C)ONC1=CC=C(C=C1)N(C)C KXIMTVJJKCWVRG-UHFFFAOYSA-N 0.000 description 1
- BGNYDUHQASPIML-UHFFFAOYSA-N 2,4-diamino-3-benzamidobenzenesulfonic acid Chemical compound NC1=C(C(=C(C=C1)S(=O)(=O)O)N)NC(C1=CC=CC=C1)=O BGNYDUHQASPIML-UHFFFAOYSA-N 0.000 description 1
- WONRDHPFOHAWOG-UHFFFAOYSA-N 2-chloronaphthalen-1-ol Chemical compound C1=CC=C2C(O)=C(Cl)C=CC2=C1 WONRDHPFOHAWOG-UHFFFAOYSA-N 0.000 description 1
- UPHOPMSGKZNELG-UHFFFAOYSA-N 2-hydroxynaphthalene-1-carboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=C(O)C=CC2=C1 UPHOPMSGKZNELG-UHFFFAOYSA-N 0.000 description 1
- 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 1
- NOJXRHBIVBIMQY-UHFFFAOYSA-N 3-anilino-3-oxopropanoic acid Chemical compound OC(=O)CC(=O)NC1=CC=CC=C1 NOJXRHBIVBIMQY-UHFFFAOYSA-N 0.000 description 1
- HXUIDZOMTRMIOE-UHFFFAOYSA-N 3-oxo-3-phenylpropionic acid Chemical compound OC(=O)CC(=O)C1=CC=CC=C1 HXUIDZOMTRMIOE-UHFFFAOYSA-N 0.000 description 1
- XKVUYEYANWFIJX-UHFFFAOYSA-N 5-methyl-1h-pyrazole Chemical compound CC1=CC=NN1 XKVUYEYANWFIJX-UHFFFAOYSA-N 0.000 description 1
- KYARBIJYVGJZLB-UHFFFAOYSA-N 7-amino-4-hydroxy-2-naphthalenesulfonic acid Chemical compound OC1=CC(S(O)(=O)=O)=CC2=CC(N)=CC=C21 KYARBIJYVGJZLB-UHFFFAOYSA-N 0.000 description 1
- RMMXTBMQSGEXHJ-UHFFFAOYSA-N Aminophenazone Chemical compound O=C1C(N(C)C)=C(C)N(C)N1C1=CC=CC=C1 RMMXTBMQSGEXHJ-UHFFFAOYSA-N 0.000 description 1
- HUKHTHOZQTUTKC-UHFFFAOYSA-N C1(=CC=CC=C1)[ClH]C(=O)C1=CC=CC=C1 Chemical compound C1(=CC=CC=C1)[ClH]C(=O)C1=CC=CC=C1 HUKHTHOZQTUTKC-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BZORFPDSXLZWJF-UHFFFAOYSA-N N,N-dimethyl-1,4-phenylenediamine Chemical compound CN(C)C1=CC=C(N)C=C1 BZORFPDSXLZWJF-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 241001165766 Tetraoninae Species 0.000 description 1
- DYRDKSSFIWVSNM-UHFFFAOYSA-N acetoacetanilide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1 DYRDKSSFIWVSNM-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- GAUZCKBSTZFWCT-UHFFFAOYSA-N azoxybenzene Chemical compound C=1C=CC=CC=1[N+]([O-])=NC1=CC=CC=C1 GAUZCKBSTZFWCT-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- OQENBJBTQPIZKA-UHFFFAOYSA-N chrysen-1-amine Chemical compound C1=CC2=C3C=CC=CC3=CC=C2C2=C1C(N)=CC=C2 OQENBJBTQPIZKA-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- ZIUSEGSNTOUIPT-UHFFFAOYSA-N ethyl 2-cyanoacetate Chemical compound CCOC(=O)CC#N ZIUSEGSNTOUIPT-UHFFFAOYSA-N 0.000 description 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000003392 indanyl group Chemical group C1(CCC2=CC=CC=C12)* 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002916 oxazoles Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 150000007965 phenolic acids Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- FCJSHPDYVMKCHI-UHFFFAOYSA-N phenyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC1=CC=CC=C1 FCJSHPDYVMKCHI-UHFFFAOYSA-N 0.000 description 1
- 150000004986 phenylenediamines Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000001044 red dye Substances 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- G03C7/3212—Couplers characterised by a group not in coupling site, e.g. ballast group, as far as the coupling rest is not specific
Definitions
- Uur present invention relates to color photography and more particularly to a process and material in which color is produced in a colloidal emulsion layer by the action of an oxidation product of a photographic developer on a dyestuff component'incorporatedinsaid layer!
- This process of color forming development has first been disclosed in U. S. Patents 1,102,028 and i,055,155 to Fischer.
- a photographic emulsion layer containing these dyestuff components is developed by means of a developer containing free amino groups, for instance phenylene-diamines, especially the monoor unsymmetrically disubstituted ones like p-dimethylaminoaniline, ethoxy-p-dimethylaminoaniline, there is obtained a colored photographic picture.
- a developer containing free amino groups for instance phenylene-diamines, especially the monoor unsymmetrically disubstituted ones like p-dimethylaminoaniline, ethoxy-p-dimethylaminoaniline
- the color of the pictures depends upon the I dyestufi forming components applied to the layer. Pyrazolones for instance yield blue-red dyes, de-
- a further object is to'provide a process by which dyestufi components may be obtained which are soluble in aqueous liquids and which @DLOB.
- PHOTOGRAP Gustav Wilmanns, Wolfen, Kreis Eitterfeld, Wilhelm Schneider, Dessau, and Ernst Bauer, Hersbruck, Min, Germany assignors, by mesme assignments, to .dgfa Ansco Corporation, hinghamton, N. Y a corporation oi Welaware No brawing.
- a further object is to provide dyestuff cjo nents which will not be removed fronftheir spective photographic layers by the 'aeti aqueous alkaline liquids such as'for insta veloping solutions.
- a COlOr photographic multi-layer material prising a series of superposed emulsionf each layer containing a dyestuficompon the above described kind. 1
- the invention is based on the ob'servatio th by adding groups to the coupling compo having so large a number of atoms that the e their solubility in aqueous'liquids, do not to diffuse from the photographicemulsio or into the developing solution.
- i i As dyestufi components which maybes tuted by radicals which will increase'their ular size the following may be' namedby example: All compounds with an active methylene grou for instance acetoacetic ester, bromacetoac ester, acetoacetic anilide, cyanoacetic ester, b
- zoylacetoacetic ester benzoylacetic acid and terephthaloylacetic ester, 'hydrindenes such as for instance 1-phenyl-ii methyl pyrazol l phenyl-B -phenyl-pyrazolone, couniar'an malonic acid anilide-,omega-cyanoacetopheiioh hydroxythionaphthene etc.
- lhere are further used phenols such as for example meta-arn'n phenol, o-o'-dinaphthol, o-hydroirydiphenyl dihydroxydiphenyl, substituted naphthols instance e-naphthol, dinaphthol, 1,5-hydrdx naphthol, chloronaphthol and trichloronaphth substituted aminonaphthols, for instance aminonaphthol, phenolcarboxylic acids, tor stance salicylic acid, naphthol' carb'dxylicaci for instance a-hydroxynaphthoic acid.
- phenols such as for example meta-arn'n phenol, o-o'-dinaphthol, o-hydroirydiphenyl dihydroxydiphenyl, substituted naphthols instance e-naphthol, dinaphthol, 1,5-hydrdx naphthol, chlor
- Oil-t benzene and naphthalene derivativestho se droxy compounds are especiallysuitablewh in p-position to the hydroxy grous catalognejr n t substituent at all or a negativesubstituents as for instance chlorine, sulfonidacid. other substitution products of the above harried. 55
- the carbon atoms may be arranged in chain or nuclear formation and they may be linked to 20 hydrogen or other atoms, such as oxygen, sulfur, selenium, nitrogen and halogen etc.
- These radicals may in themselves have the structure of the aforementioned dyestufi components so that dyestufl components which are obtained by linkage of several molecules of coupling components are also within the scope of the present invention.
- the compounds obtained in this manner may be dissolved in alkali with perhaps an addition of alcohol or other organic solvents and may then be added to layer forming colloids without any precipitation.
- the fastness to diffusion of these components may further be increased by the introduction into their molecule of still fur- 8 grams of the resulting compound are dissolved in 3 cc. of sodium hydroxide of 40 per cent strength, 25 cc. of methanol, and 70 cc. of water and then added to 500 cc. of a gelatin emulsion of 5 per cent strength.
- Example 2 5 grams of this compound are dissolved as described in Example 1 and added to a 5 per cent gelatin emulsion. By developing with a color forming developer 2. blue picture is obtained.
- a ma HaC may be obtained from l-p aminophenyl -limethyloxazole and hydroxynaphtholc acid chloride.
- a compound of the formula yields when developed with color forming developers a yellow picture.
- the compound is obtained by heating 2 mols of benzoyl-acetic ester and di-p-aminophenylurea in boiling zylene while at the same time distilling off the formed alcohol.
- a dyestufi component yielding a red picture and having the formula:
- a photographic emulsion layer having incorporated therein a color forming development component having linked to an atom of its molecule the stilbene grouping, said grouping being capable of rendering said component fast to diffusion.
- A. photographic emulsion layer having incorporated therein a color forming development component having linked to an atom of its molecule the benzthiazole grouping, said grouping being capable of rendering said component fast to diffusion.
- a photographic silver halide-gelatine emulsion layer having incorporated therein a color forming development component having linked to an atom of its molecule a group of so large a diflusing in gelatine in any photographic treating number of atoms that the molecular size of said bath.
- compo- GUSTAV WILMANNS nent although soluble in aqueous photographic WILHELM SCHNEIDER. developing solutions being as a result of its mo- ERNST BAUER.
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Description
. 5 illllaims.
Uur present invention relates to color photography and more particularly to a process and material in which color is produced in a colloidal emulsion layer by the action of an oxidation product of a photographic developer on a dyestuff component'incorporatedinsaid layer! This process of color forming development has first been disclosed in U. S. Patents 1,102,028 and i,055,155 to Fischer.
If a photographic emulsion layer containing these dyestuff components is developed by means of a developer containing free amino groups, for instance phenylene-diamines, especially the monoor unsymmetrically disubstituted ones like p-dimethylaminoaniline, ethoxy-p-dimethylaminoaniline, there is obtained a colored photographic picture.
The color of the pictures depends upon the I dyestufi forming components applied to the layer. Pyrazolones for instance yield blue-red dyes, de-
rivatives of acetoacetic ester yield yellow colorings, and naphthols yield blue colors.
The dyestuff components of Fischer, however, merely lent themselves to the production of pictures in one single color., When dyestufi' components which yield various colors by development were incorporated in several superposed layers it became apparent after developing that the components had diffused into all the other layers, viz., that a separation of the color values of the photographed object had not been achieved. Even if components were selected from those listed in the aforementioned patents which are dimcultly soluble, i. e., which are capable of being incorporated in the layers in the form of an insoluble precipitate, these components did not show a satisfactory fastness to diflusion, unless they were entirely insoluble, in which case they did not react at all with the developers and merely a black silver picture was produced.
Even for the production of single-colored reversal pictures the dyestuff components were useless inasmuch as they were washed out of the layers during the black-and-white development, so that for the subsequent color development an insufficient amount of them remained in the layers, or at least they were apt to diffuse into the developer itself thereby soiling pictures which were simultaneously developed in another color. It is therefore an object of the present invention to provide a material in which all these disadvantages and drawbacks are overcome.-
A further object is to'provide a process by which dyestufi components may be obtained which are soluble in aqueous liquids and which @DLOB. PHOTOGRAP Gustav Wilmanns, Wolfen, Kreis Eitterfeld, Wilhelm Schneider, Dessau, and Ernst Bauer, Hersbruck, Min, Germany, assignors, by mesme assignments, to .dgfa Ansco Corporation, hinghamton, N. Y a corporation oi Welaware No brawing. Application November 13, 193i, Se-
rial No. W435i). in Germany April lit, 1935 for instance dik'etohydrindene; pyrazolones are fast to diffusion once theyareincorpora d in the photographic emulsion layers.
A further object is to provide dyestuff cjo nents which will not be removed fronftheir spective photographic layers by the 'aeti aqueous alkaline liquids such as'for insta veloping solutions. a COlOr photographic multi-layer material prising a series of superposed emulsionf each layer containing a dyestuficompon the above described kind. 1
Further objects will be apparentfroint tailed specification following hereafter.
This application is to be jregarded as 'a tinuation in part of our'cop'ending applicatf 1 Ser. No. 72,718 filed April 4, i936. x
The invention is based on the ob'servatio th by adding groups to the coupling compo having so large a number of atoms that the e their solubility in aqueous'liquids, do not to diffuse from the photographicemulsio or into the developing solution. i i As dyestufi components which maybes tuted by radicals which will increase'their ular size the following may be' namedby example: All compounds with an active methylene grou for instance acetoacetic ester, bromacetoac ester, acetoacetic anilide, cyanoacetic ester, b
zoylacetoacetic ester, benzoylacetic acid and terephthaloylacetic ester, 'hydrindenes such as for instance 1-phenyl-ii methyl pyrazol l phenyl-B -phenyl-pyrazolone, couniar'an malonic acid anilide-,omega-cyanoacetopheiioh hydroxythionaphthene etc. lhere are further used phenols such as for example meta-arn'n phenol, o-o'-dinaphthol, o-hydroirydiphenyl dihydroxydiphenyl, substituted naphthols instance e-naphthol, dinaphthol, 1,5-hydrdx naphthol, chloronaphthol and trichloronaphth substituted aminonaphthols, for instance aminonaphthol, phenolcarboxylic acids, tor stance salicylic acid, naphthol' carb'dxylicaci for instance a-hydroxynaphthoic acid. Oil-t benzene and naphthalene derivativestho se droxy compounds are especiallysuitablewh in p-position to the hydroxy grous aveanejr n t substituent at all or a negativesubstituents as for instance chlorine, sulfonidacid. other substitution products of the above harried. 55
compounds may "be used, such as for instance nitro derivatives.
It is impossible to define a general chemical structure of the radicals which are to be introduced into the molecule of the aforementioned coupling components. However, it should be generally stated that all organic radicals which produce a substantial increase in the molecular size of the dyestuif components are suitable for the purpose of the present invention. The exact size of the radicals which-are to be introduced depends largehr upon the tendency of diifusion which the substituted dyestuif component possesses. .Thus radicals from 5 carbon atoms upwards will be very useful in some cases, while in others radicals of at least 12 to 18 carbon atoms are required.
The carbon atoms may be arranged in chain or nuclear formation and they may be linked to 20 hydrogen or other atoms, such as oxygen, sulfur, selenium, nitrogen and halogen etc. These radicals may in themselves have the structure of the aforementioned dyestufi components so that dyestufl components which are obtained by linkage of several molecules of coupling components are also within the scope of the present invention.
For the synthesis of these compounds it is advisable to introduce the radicalswhich impart the fastness to diffusion to the molecule of the dyestufi forming component by means of an amino, carboxyl, or hydroxyl group in the form of an amide or an ester. However, a direct connection by means of C-C-linkage of coupling component and the radical to be introduced is also possible. Also Schifis bases may be formed. In order to increase the solubility of the compounds they may contain special groups imparting solubility to them as for instance carboxyl or sulfo-groups.
For the production of photographic layers, especially those dyestufi components will be suited which may be introduced into the layer in a dissolved state. It has been found that in the manner suggested above components may be obtained which possess a satisfactory fastness to diffusion in dilute alkaline solutions and which are soluble in aqueous liquids in some cases by addition of slight quantities of an organic solvent, so as to be easily incorporated in photographic layers in a dissolved state. Of course there always exists the possibility of introducing the undissolved dyestuff components into the layer, but such layers yield less clear pictures and pictures of coarser grain.
Of the great number of groups which come into question for the production of dyestufi components fast to difiusion some have been found to be especially suitable. Such groups are for instance the substantive groups with which direct cotton dyestuffs of good qualities of fastness could be obtained. Chemically these are groups which contain a comparatively long chain of conjugated double bonds, such as for instance diphenyl, dianisidine, tolidine, diphenyl-carboxylic acid, 3-hydroxy-4-diphenyl-carboxylic acid, diaminobenzoylaminodiphenyl, 2,2'-dihydroxy-4,4-diaminodiphenyl, stilbene, diaminostilbene, diaminobenzoylaminostilbene, azoxybenzene, hydroxynaphthoic acid, for instance 2,3-hydroxynaphthoic acid, 4,2',3'-hydroxynaphthoylaminoaniline, diaryl ureas, as for instance diaminodiphenylurea, diaminobenzoylaminodiphenylurea, the carbamide of aminobenzoylamino-o-sulfanilic acid, heterocyclic nuclei as for example triazines, thiazoles, benzthiazoles, dehydrothiotoluldines, oxazoles, nuclear cyanuric derivatives in which several dyestuif components are linked by means of the cyanuric nucleus and which may contain still further substantive groups, furthermore certain aminonaphthols as for instance 2-amino-5-naphthol-7-sulfonic acid and 2-aminobenzoylamino-5-naphthol-sulfonic acid, furthermore highly molecular compounds as terephthaloylbisacetic ester, 2,3-hydroxyanthracene carboxylic acid, 2,3-hydroxycarbazo1e carboxylic acid, aminochrysene, aminopyrene, aminonaphthyleneoxide.
The compounds obtained in this manner may be dissolved in alkali with perhaps an addition of alcohol or other organic solvents and may then be added to layer forming colloids without any precipitation. The fastness to diffusion of these components may further be increased by the introduction into their molecule of still fur- 8 grams of the resulting compound are dissolved in 3 cc. of sodium hydroxide of 40 per cent strength, 25 cc. of methanol, and 70 cc. of water and then added to 500 cc. of a gelatin emulsion of 5 per cent strength. By developing with p-di ethylaminoaniline a blue picture is obtained.
2. From salicyclic acid chloride and benzidine a dyestufi component of the following formula is obtained:
on on There are added to the component 9 grams of salicyclic acid chloride dissolved in the same manner as in Example 1 and 500 cc. of a 5 per cent emulsion. By developing with p-diethylaminoaniline a blue picture is obtained.
3. From dehydrothiotoluidine and a-hydrownaphthoic acid chloride the following component is obtained:
5 grams of this compound are dissolved as described in Example 1 and added to a 5 per cent gelatin emulsion. By developing with a color forming developer 2. blue picture is obtained.
4. From dehydrothiotoluidine and salicylic airmen acid chloride the following compound, which yields a blue icture. is obtained 5. A component yielding a blue picture and having the formula:
a ma HaC may be obtained from l-p aminophenyl -limethyloxazole and hydroxynaphtholc acid chloride.
6. A component yielding a red picture and having the formula:
S ONH-O 0 i0- l I N/ ll l is obtained from the hydrazine of the dehydro thiotoluidlne which is condensed with p-nitrobenzoylacetic ester, then reduced and again condensed with benzoylchloride. The compound is dissolved as described in Example 1.
l. A dyestuii component yielding a red picture and having the formula:
is obtained by heating 2 mols of benzoylacetlc ester and 1 mol of benzidine. 3 grams of the compound are dissolved according to the prescriptions given in Example 1 and added to 500 cc. of a 5 per cent gelatin emulsion.
10. A compound of the formula yields when developed with color forming developers a yellow picture. The compound is obtained by heating 2 mols of benzoyl-acetic ester and di-p-aminophenylurea in boiling zylene while at the same time distilling off the formed alcohol.
ii. A compound of the formula OH OH (ilH HJO- \vQN/ I N/ vi 0 Ha is'obtained in analogous manner as in the preceding example with the sole exception that the last process step consists in condensing with diphenylcarboxylic acid chloride instead of with benzoylchloride.
8. A dyestufi component yielding a red picture and having the formula:
is obtained from the hydrazine of the 2-p-amino- S-methylbenzoxazole which is condensed with pnitrobenzoylacetic ester, whereat the nitro group is reduced to the amino group and the latter reacted with diphenyl-dicarboxylic acid chloride.
9. A dyestuif component yielding a yellow picture and having the formula:
component having linked to an atom of its molecule the diphenyl grouping, said grouping being capable of rendering said component fast to diffusion.
3. A photographic emulsion layer having incorporated therein a color forming development component having linked to an atom of its molecule the stilbene grouping, said grouping being capable of rendering said component fast to diffusion.
i. A. photographic emulsion layer having incorporated therein a color forming development component having linked to an atom of its molecule the benzthiazole grouping, said grouping being capable of rendering said component fast to diffusion.
5. A photographic silver halide-gelatine emulsion layer having incorporated therein a color forming development component having linked to an atom of its molecule a group of so large a diflusing in gelatine in any photographic treating number of atoms that the molecular size of said bath.
component is more than doubled, said compo- GUSTAV WILMANNS. nent although soluble in aqueous photographic WILHELM SCHNEIDER. developing solutions being as a result of its mo- ERNST BAUER.
lecular size incapable in such dissolved form 01
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Cited By (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2418747A (en) * | 1944-05-20 | 1947-04-08 | Gen Aniline & Film Corp | Nondiffusing phenolic color couplers |
US2423730A (en) * | 1942-06-12 | 1947-07-08 | Eastman Kodak Co | Acylamino phenols |
US2435173A (en) * | 1944-06-07 | 1948-01-27 | Gen Aniline & Film Corp | Acetyl n-heterocyclic couplers for color photography |
US2437063A (en) * | 1940-08-08 | 1948-03-02 | Gen Aniline & Film Corp | Nondiffusing 1-phenyl-5-pyrazolone couplers for color photography |
US2463838A (en) * | 1943-02-18 | 1949-03-08 | Du Pont | Polymeric color couplers |
US2500487A (en) * | 1948-11-09 | 1950-03-14 | Gen Aniline & Film Corp | Yellow diffusion-fast color formers of the benzimidazole class |
US2550661A (en) * | 1947-03-27 | 1951-05-01 | Eastman Kodak Co | Color couplers containing terphenyl radicals |
US2575182A (en) * | 1946-08-21 | 1951-11-13 | Du Pont | Photographic silver halide emulsions and developers containing 5-acyloxypyrazole color formers |
US2584349A (en) * | 1944-11-10 | 1952-02-05 | Gen Aniline & Film Corp | Color forming development with an aromatic primary amino developer and alpha-[4-sulfophenylazo]-aceto-acet-2-4-dichloroanilide |
US2594537A (en) * | 1946-10-26 | 1952-04-29 | Universal Oil Prod Co | Resinous products from aromatic polyketones and polyamides |
US2619419A (en) * | 1947-12-24 | 1952-11-25 | Gevaert Photo Prod Nv | Production of color photographic images |
US2635536A (en) * | 1947-08-07 | 1953-04-21 | Du Pont | Mordanting |
US2635535A (en) * | 1946-01-31 | 1953-04-21 | Du Pont | Mordanting |
US2657134A (en) * | 1951-12-05 | 1953-10-27 | Eastman Kodak Co | Photographic emulsion with colored couplers containing isophthalic ester groups |
US2678884A (en) * | 1949-11-18 | 1954-05-18 | Du Pont | Photographic silver halide emulsions of synthetic polymers |
US2694635A (en) * | 1951-12-05 | 1954-11-16 | Eastman Kodak Co | Couplers for color photography |
US2718466A (en) * | 1950-05-02 | 1955-09-20 | Anken Chemical And Film Corp | Diffusion-fast color-formers in a silver halide emulsion |
US2754209A (en) * | 1952-06-10 | 1956-07-10 | Azoplate Corp | Light-sensitive para quinone diazides for making printing plates |
US2773096A (en) * | 1953-02-12 | 1956-12-04 | Cutter Lab | N-(4-hydroxyphenyl)-3-phenylsalicylamide |
US2773765A (en) * | 1952-08-16 | 1956-12-11 | Azoplate Corp | Light sensitive material for photomechanical reproduction |
DE970007C (en) * | 1953-09-30 | 1958-08-07 | Gevaert Photo Prod Nv | Process for the production of photographic color images by developing a reducible silver salt by means of an aromatic developing substance in the presence of a dye former |
DE972067C (en) * | 1941-02-18 | 1959-05-14 | Agfa Ag | Process for increasing the whiteness of photographic reflective images |
US20050181455A1 (en) * | 2000-04-03 | 2005-08-18 | Cerno Biosciences Llc | Generation of combinatorial synthetic libraries and screening for novel proadhesins and nonadhesins |
US20090124690A1 (en) * | 2000-04-03 | 2009-05-14 | Alberte Randall S | Generation of Combinatorial Synthetic Libraries and Screening for Novel Proadhesins and Nonadhesins |
-
1937
- 1937-11-13 US US174350A patent/US2179239A/en not_active Expired - Lifetime
Cited By (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2437063A (en) * | 1940-08-08 | 1948-03-02 | Gen Aniline & Film Corp | Nondiffusing 1-phenyl-5-pyrazolone couplers for color photography |
DE972067C (en) * | 1941-02-18 | 1959-05-14 | Agfa Ag | Process for increasing the whiteness of photographic reflective images |
US2423730A (en) * | 1942-06-12 | 1947-07-08 | Eastman Kodak Co | Acylamino phenols |
US2463838A (en) * | 1943-02-18 | 1949-03-08 | Du Pont | Polymeric color couplers |
US2418747A (en) * | 1944-05-20 | 1947-04-08 | Gen Aniline & Film Corp | Nondiffusing phenolic color couplers |
US2435173A (en) * | 1944-06-07 | 1948-01-27 | Gen Aniline & Film Corp | Acetyl n-heterocyclic couplers for color photography |
US2584349A (en) * | 1944-11-10 | 1952-02-05 | Gen Aniline & Film Corp | Color forming development with an aromatic primary amino developer and alpha-[4-sulfophenylazo]-aceto-acet-2-4-dichloroanilide |
US2635535A (en) * | 1946-01-31 | 1953-04-21 | Du Pont | Mordanting |
US2575182A (en) * | 1946-08-21 | 1951-11-13 | Du Pont | Photographic silver halide emulsions and developers containing 5-acyloxypyrazole color formers |
US2594537A (en) * | 1946-10-26 | 1952-04-29 | Universal Oil Prod Co | Resinous products from aromatic polyketones and polyamides |
US2550661A (en) * | 1947-03-27 | 1951-05-01 | Eastman Kodak Co | Color couplers containing terphenyl radicals |
US2635536A (en) * | 1947-08-07 | 1953-04-21 | Du Pont | Mordanting |
US2619419A (en) * | 1947-12-24 | 1952-11-25 | Gevaert Photo Prod Nv | Production of color photographic images |
US2500487A (en) * | 1948-11-09 | 1950-03-14 | Gen Aniline & Film Corp | Yellow diffusion-fast color formers of the benzimidazole class |
US2678884A (en) * | 1949-11-18 | 1954-05-18 | Du Pont | Photographic silver halide emulsions of synthetic polymers |
US2718466A (en) * | 1950-05-02 | 1955-09-20 | Anken Chemical And Film Corp | Diffusion-fast color-formers in a silver halide emulsion |
US2657134A (en) * | 1951-12-05 | 1953-10-27 | Eastman Kodak Co | Photographic emulsion with colored couplers containing isophthalic ester groups |
US2694635A (en) * | 1951-12-05 | 1954-11-16 | Eastman Kodak Co | Couplers for color photography |
US2754209A (en) * | 1952-06-10 | 1956-07-10 | Azoplate Corp | Light-sensitive para quinone diazides for making printing plates |
US2773765A (en) * | 1952-08-16 | 1956-12-11 | Azoplate Corp | Light sensitive material for photomechanical reproduction |
US2773096A (en) * | 1953-02-12 | 1956-12-04 | Cutter Lab | N-(4-hydroxyphenyl)-3-phenylsalicylamide |
DE970007C (en) * | 1953-09-30 | 1958-08-07 | Gevaert Photo Prod Nv | Process for the production of photographic color images by developing a reducible silver salt by means of an aromatic developing substance in the presence of a dye former |
US20050181455A1 (en) * | 2000-04-03 | 2005-08-18 | Cerno Biosciences Llc | Generation of combinatorial synthetic libraries and screening for novel proadhesins and nonadhesins |
US7479571B2 (en) * | 2000-04-03 | 2009-01-20 | Cernofina, Llc | Generation of combinatorial synthetic libraries and screening for novel proadhesins and nonadhesins |
US20090124690A1 (en) * | 2000-04-03 | 2009-05-14 | Alberte Randall S | Generation of Combinatorial Synthetic Libraries and Screening for Novel Proadhesins and Nonadhesins |
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