US2113330A - Color-forming developers - Google Patents
Color-forming developers Download PDFInfo
- Publication number
- US2113330A US2113330A US8519A US851935A US2113330A US 2113330 A US2113330 A US 2113330A US 8519 A US8519 A US 8519A US 851935 A US851935 A US 851935A US 2113330 A US2113330 A US 2113330A
- Authority
- US
- United States
- Prior art keywords
- color
- compounds
- group
- forming
- compound
- 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
- 150000001875 compounds Chemical class 0.000 description 26
- 239000000975 dye Substances 0.000 description 12
- 229910052709 silver Inorganic materials 0.000 description 11
- 239000004332 silver Substances 0.000 description 11
- -1 silver halide Chemical class 0.000 description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 7
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 230000008878 coupling Effects 0.000 description 6
- 238000010168 coupling process Methods 0.000 description 6
- 238000005859 coupling reaction Methods 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- CVBUKMMMRLOKQR-UHFFFAOYSA-N 1-phenylbutane-1,3-dione Chemical compound CC(=O)CC(=O)C1=CC=CC=C1 CVBUKMMMRLOKQR-UHFFFAOYSA-N 0.000 description 3
- DYRDKSSFIWVSNM-UHFFFAOYSA-N acetoacetanilide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1 DYRDKSSFIWVSNM-UHFFFAOYSA-N 0.000 description 3
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 108010010803 Gelatin Proteins 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- 229910021653 sulphate ion Inorganic materials 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- OJHDELQFIANLQR-UHFFFAOYSA-N 4,4-dichloro-3-oxo-n-phenylbutanamide Chemical compound ClC(Cl)C(=O)CC(=O)NC1=CC=CC=C1 OJHDELQFIANLQR-UHFFFAOYSA-N 0.000 description 1
- 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 1
- JGXZCIFCMVTCEU-UHFFFAOYSA-N 4-nitro-3-oxo-n-phenylbutanamide Chemical compound [O-][N+](=O)CC(=O)CC(=O)NC1=CC=CC=C1 JGXZCIFCMVTCEU-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 125000004674 methylcarbonyl group Chemical group CC(=O)* 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 150000003839 salts Chemical group 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
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 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
- G03C7/36—Couplers containing compounds with active methylene groups
Definitions
- This invention relates to dyes and more particularly to dyes formed by coupling during photographic development.
- colored photographic images may be formed by using a developer which forms a colored compound on development.
- the colored compound thus formed is depositedadjacent the silver image during the development.
- a colored image may be formed by adding to the developer solution a compound which combines with the oxidation product of the developer and forms a coloring substance.
- the aromatic amino compounds which may be used as developers in our process include the mono-, di-, and tri-amino aryl compounds and compounds formed therefrom by substitution in the amino group as well as in the ring, such as alkyl phenylene diamines and alkyl toluylene diamines. These compounds are usually used in the salt form, such as the hydrochloride or' the sulphate which are more stable than the amines themselves. Examples are diethylparaphenylene diamine hydrochloride, monomethylparaphenylene diamine hydrochloride, and dimethylparaphenylene diamine sulphate.
- the coupling or color-forming compounds which are used according to our invention are certain compounds containing a substituted acetyl group which includes a reactive methylene group.
- These include acetoacetanilide and substituted acetoacetanilides, such as the halogen and alkylsubstituted compounds. Among these are parabromo acetoacetanilide, dichloro acetoacetanilide, and 4-nitro acetoacetanilide.
- Other compounds containing this group are benzoyl acetone and acetyl acetone.
- acetyl group is substituted with an aceto group, CH3CO-, but it may also be substituted with a cyano, CN, or with any substituent group which will produce a reactive methylene group.
- R an alkyl or an aryl group.
- the group represented by Y must be such that the methylene group to which it is attached is reactive in the dye-forming reaction.
- the acetyl group may contain sulfur instead of oxygen atoms, thus forming thioacetyl groups of the formula s s CHa-- -CH1 l-R Among the color-forming compounds used.
- Our process may be used form colored photographic images in films as well as in plates, and the dyes formed will attach to gelatin or other carrier for the silver halide, such as collodion.
- the emulsion treated may be on one side or on both sides of a film support and may be in one layer or a plurality of differently sensitized layers.
- the dyes formed may be bleached by an oxidizing agent, such as chromic acid, and colorless soluble compounds thereby formed. The bleaching of the dye in this manner does not destroy the silver image and a silver image may be colored, bleached, and recolored a number of times.
- an oxidizing agent such as chromic acid
- a color-forming photographic developer comprising an aromatic amino developing compound and a coupler compound having the termula where R is a group selected from the group consistlng of alkyl and aryl groups.
- a color-forming photographic developer comprising an aromatic amino developing compound and acetyl acetone.
- a color-forming photographic developer comprising an aromatic amino developing comp und and benzoyl acetone.
- a color-forming photographic developer comprising a paraphenylenediamine developing compound and a coupler compound having the formula II II where R is a group selected from the group consisting of alkyl and aryl groups.
Description
Patented Apr. 5, 1938 UNITED STATES COLOR-FORMING DEVELOPERS Leopold D. Mannes and Leopold Godowsky, Jr.,
Rochester, N. Y., assignors, by mesne assignments, to Eastman Kodak Company, Jersey City, N. J., a corporation of New Jersey No Drawing. Application February 27, 1935, Serial No. 8,519
4 Claims.
This invention relates to dyes and more particularly to dyes formed by coupling during photographic development.
It is known that colored photographic images may be formed by using a developer which forms a colored compound on development. The colored compound thus formed is depositedadjacent the silver image during the development. It is also known that a colored image may be formed by adding to the developer solution a compound which combines with the oxidation product of the developer and forms a coloring substance.
It is an object of the present invention to provide a developer which produces a dye simultaneously and in situ with photographic development. It is a further object to produce novel dyes in color-forming photographic development.
These objects are accomplished by the present invention by the use of aromatic diamino developers together with certain specific coupling compounds hereinafter disclosed.
When a silver halide emulsion containing a latent photographic image is developed, the silver halide is reduced to metallic silver and the developing agent is oxidized. The aromatic diamino compounds which have been used as developers form on oxidation, products which will react with coupling compounds to form dyes. If such coupling compounds are added to the developer solution or incorporated in the emulsion layer, a dye is formed by the coupling of this compound with the oxidation product of the arcmatic diamino compound and is deposited in the gelatin or other silver halide carrier adjacent to the metallic silver grain. The dyes thus formed do not readily wander from the place of formation. They may be soluble or insoluble in water, but the water-soluble dyes are preferably used. They are not physically attached to the silver grain, so that the silver may be subsequently washed out of the carrier layer leaving a pure dye image.
The aromatic amino compounds which may be used as developers in our process include the mono-, di-, and tri-amino aryl compounds and compounds formed therefrom by substitution in the amino group as well as in the ring, such as alkyl phenylene diamines and alkyl toluylene diamines. These compounds are usually used in the salt form, such as the hydrochloride or' the sulphate which are more stable than the amines themselves. Examples are diethylparaphenylene diamine hydrochloride, monomethylparaphenylene diamine hydrochloride, and dimethylparaphenylene diamine sulphate.
The coupling or color-forming compounds which are used according to our invention are certain compounds containing a substituted acetyl group which includes a reactive methylene group. These include acetoacetanilide and substituted acetoacetanilides, such as the halogen and alkylsubstituted compounds. Among these are parabromo acetoacetanilide, dichloro acetoacetanilide, and 4-nitro acetoacetanilide. Other compounds containing this group are benzoyl acetone and acetyl acetone. In these compounds the acetyl group is substituted with an aceto group, CH3CO-, but it may also be substituted with a cyano, CN, or with any substituent group which will produce a reactive methylene group. The compounds which we contemplate using as colorformers have the general formula i Y -CHI'C-R where Y=an aceto, cyano, sulfonyl, carbonyl, or
equivalent group, and R=an alkyl or an aryl group. The group represented by Y must be such that the methylene group to which it is attached is reactive in the dye-forming reaction. The acetyl group may contain sulfur instead of oxygen atoms, thus forming thioacetyl groups of the formula s s CHa-- -CH1 l-R Among the color-forming compounds used. where Y=aceto and R=alkyl, a typical compound is acetyl acetone:
CHaC O-GHzC CH:
When Y=aceto and R=aryl, a typical compound is benzoyl acetone:
CHiO 04:11.00
The following are examples of developer solutions which may be used according to our process:
Our process may be used form colored photographic images in films as well as in plates, and the dyes formed will attach to gelatin or other carrier for the silver halide, such as collodion. The emulsion treated may be on one side or on both sides of a film support and may be in one layer or a plurality of differently sensitized layers. The dyes formed may be bleached by an oxidizing agent, such as chromic acid, and colorless soluble compounds thereby formed. The bleaching of the dye in this manner does not destroy the silver image and a silver image may be colored, bleached, and recolored a number of times. Such a process is disclosed in our application, Serial No. 8,516, filed February 2'7, 1935.
-What we claim is:
i. A color-forming photographic developer comprising an aromatic amino developing compound and a coupler compound having the termula where R is a group selected from the group consistlng of alkyl and aryl groups.
2. A color-forming photographic developer comprising an aromatic amino developing compound and acetyl acetone.
3. A color-forming photographic developer comprising an aromatic amino developing comp und and benzoyl acetone.
4. A color-forming photographic developer comprising a paraphenylenediamine developing compound and a coupler compound having the formula II II where R is a group selected from the group consisting of alkyl and aryl groups.
LEOPOLD D. MANNES.
LEOPOLD GODOWSKY, Ja.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US8519A US2113330A (en) | 1935-02-27 | 1935-02-27 | Color-forming developers |
| FR804472D FR804472A (en) | 1935-02-27 | 1936-02-27 | Chromogenic developers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US8519A US2113330A (en) | 1935-02-27 | 1935-02-27 | Color-forming developers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2113330A true US2113330A (en) | 1938-04-05 |
Family
ID=21732052
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US8519A Expired - Lifetime US2113330A (en) | 1935-02-27 | 1935-02-27 | Color-forming developers |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US2113330A (en) |
| FR (1) | FR804472A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2520293A (en) * | 1947-01-30 | 1950-08-29 | Endo Products Inc | Mercaptoacetanilide derivatives |
| US2531004A (en) * | 1947-11-26 | 1950-11-21 | Gen Aniline & Film Corp | Acetonitriles as azo components in diazotypes |
| US2552355A (en) * | 1947-08-06 | 1951-05-08 | Gen Aniline & Film Corp | Diazotype layers having organic esters and nitriles containing an active methylene group as azo components |
| DE1124356B (en) * | 1960-04-28 | 1962-02-22 | Eastman Kodak Co | Process for photographic color developing |
| US3506389A (en) * | 1963-08-01 | 1970-04-14 | Oreal | Hair dyeing with couplers and a 1-amino-4-substituted-alkylaminobenzene |
| US4278750A (en) * | 1979-09-06 | 1981-07-14 | Eastman Kodak Company | Novel electron donor precursors and photographic elements containing them |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE743536C (en) * | 1937-10-21 | 1944-01-06 | Ig Farbenindustrie Ag | Process for the color development of photographic silver halide emulsions |
-
1935
- 1935-02-27 US US8519A patent/US2113330A/en not_active Expired - Lifetime
-
1936
- 1936-02-27 FR FR804472D patent/FR804472A/en not_active Expired
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2520293A (en) * | 1947-01-30 | 1950-08-29 | Endo Products Inc | Mercaptoacetanilide derivatives |
| US2552355A (en) * | 1947-08-06 | 1951-05-08 | Gen Aniline & Film Corp | Diazotype layers having organic esters and nitriles containing an active methylene group as azo components |
| US2531004A (en) * | 1947-11-26 | 1950-11-21 | Gen Aniline & Film Corp | Acetonitriles as azo components in diazotypes |
| DE1124356B (en) * | 1960-04-28 | 1962-02-22 | Eastman Kodak Co | Process for photographic color developing |
| US3506389A (en) * | 1963-08-01 | 1970-04-14 | Oreal | Hair dyeing with couplers and a 1-amino-4-substituted-alkylaminobenzene |
| US4278750A (en) * | 1979-09-06 | 1981-07-14 | Eastman Kodak Company | Novel electron donor precursors and photographic elements containing them |
Also Published As
| Publication number | Publication date |
|---|---|
| FR804472A (en) | 1936-10-24 |
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