US2295009A - Photographic color forming compound - Google Patents
Photographic color forming compound Download PDFInfo
- Publication number
- US2295009A US2295009A US382747A US38274741A US2295009A US 2295009 A US2295009 A US 2295009A US 382747 A US382747 A US 382747A US 38274741 A US38274741 A US 38274741A US 2295009 A US2295009 A US 2295009A
- Authority
- US
- United States
- Prior art keywords
- photographic
- compounds
- image
- developing
- development
- 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.)
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- 150000001875 compounds Chemical class 0.000 title description 28
- 239000000839 emulsion Substances 0.000 description 17
- -1 cinnamoyl substituent groups Chemical group 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 12
- 230000008878 coupling Effects 0.000 description 12
- 238000010168 coupling process Methods 0.000 description 12
- 238000005859 coupling reaction Methods 0.000 description 12
- 229910052709 silver Inorganic materials 0.000 description 12
- 239000004332 silver Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 125000003774 valeryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical class NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- XMTQHQNLBMWCCB-UHFFFAOYSA-N 1-N,4-N-dimethylbenzene-1,4-diamine sulfuric acid Chemical compound S(=O)(=O)(O)O.CNC1=CC=C(C=C1)NC XMTQHQNLBMWCCB-UHFFFAOYSA-N 0.000 description 1
- HRBLHUVHOWWBEN-UHFFFAOYSA-N 1-n,4-n-diethylbenzene-1,4-diamine;hydrochloride Chemical compound Cl.CCNC1=CC=C(NCC)C=C1 HRBLHUVHOWWBEN-UHFFFAOYSA-N 0.000 description 1
- MOMFXATYAINJML-UHFFFAOYSA-N 2-Acetylthiazole Chemical group CC(=O)C1=NC=CS1 MOMFXATYAINJML-UHFFFAOYSA-N 0.000 description 1
- IJJSFSXLZYFTKV-UHFFFAOYSA-N 4-n-methylbenzene-1,4-diamine;hydrochloride Chemical compound Cl.CNC1=CC=C(N)C=C1 IJJSFSXLZYFTKV-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012461 cellulose resin Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 150000002148 esters Chemical class 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
- 239000011521 glass Substances 0.000 description 1
- 239000001046 green dye Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002895 organic esters Chemical class 0.000 description 1
- 235000020004 porter Nutrition 0.000 description 1
- 150000003839 salts Chemical group 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent 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
- G03C7/34—Couplers containing phenols
- G03C7/344—Naphtholic couplers
Definitions
- This invention relates to color photography and more particularly to compounds which form dyes by coupling with the developing compound on photographic development.
- Dyes formed in this way are insoluble in water and in the ordinary photographic developing and fixing baths, although the silver images formed simultaneously with them during photographic development may be removed from the photographic layer to leave pure dye images in the layer.
- Compounds employed in conjunction with the developing agent for the silver and which couple with the development product of the developer during photographic development are referred to herein as coupling components or couplers. Depending upon their solubility or diffusion characteristics, these compounds may be incorporated in the emulsion layer prior to exposure or may be dissolved in the developing solution.
- these coupling components When these coupling components are incorporated in the photographic layer prior to exposure, they do not affect the exposure and development of the layer in the usual way, but when the development is carried out with a suit- ;able developing agent, they combine with the oxidation product of the developer to form a colored image in situ with the silver image.
- the developing agents used in color forming development of the type contemplated by our invention comprise aromatic amino developers including the mono-, diand triaminoaryl com pounds and their derivatives formed by substitution in the amino group as well as in the ring, suchas alkylphenylenediamines, alkyltoluenendiamines and p-aminophenols.
- aromatic amino developers including the mono-, diand triaminoaryl com pounds and their derivatives formed by substitution in the amino group as well as in the ring, suchas alkylphenylenediamines, alkyltoluenendiamines and p-aminophenols.
- These compounds are ordinarily used in the salt form such as the hydrochloride or the sulfate which are more Suitable compounds are diethyl-p-phenylenediamine hydrochloride, monomethyl-p-phenylene-diamine hydrochloride and dimethyl-p-phenylenediamine sulfate.
- valerylsubstituted a-naphthols, compounds 1 and3 are suitable for use in the developing solution and the cinnamoyl substituted a-naphthols, compounds 2 and 4, may be used in the emulsion layer. These compounds form blue-green dyes on photographic development.
- a developing formula which may be used is the following:
- the developing agent and the proportions of the ingredients used in the above formula may, of course, be varied. Solvents other than acetone, such as alcohols, may also be used.
- the coupler which are used in the emulsion layer may be incorporated in various ways but we prefer to form a solution of the sodium salt of the coupler in alcohol and add this to the emulsion.
- 3 grams of coupler may be dissolved or suspended in 50 cc. of ethyl alcohol and sodium hydroxide added in the amount of 1 equivalent weights of the coupler.
- the sodium hydroxide may be added as solid or as a concentrated solution.
- the sodium salt of the coupler is thereby generated in a solution of 50 cc. of alcohol and this solution is added to one liter of a gelatino silver halide.
- the pH of the emulsion may be adjusted if desired by adding a suitable-acid such as acetic or sulfuric acid to neutralize all or part of the sodium hydroxide used to form the sodium salt of the coupler.
- the coupling compounds may be incorporated either in gelatin or in other colloidal materials such as collodion, organic esters of cellulose or synthetic resins.
- the coupler is incorporated in the emulsion or is used in the developing solution, the-emulsion may be carried by a transparent medium such as glass, cellulose ester or synthetic resin or a non-transparent reflecting medium such as paper or an opaque cellulose ester.
- the emulsion may be coated as a single .layer on the support or superposed layers containing the couplers may be coated on one or both sides of the support.
- the superposed layers may be differentially sensitized for the formation of 'a neutral color image in the well known manner.
- . x inwhichonexisa x is an acyl group selected from the class consisting of valeryl and cinnamoyl groups.
- one X is a hydrogen atom and the other X is a valeryl group.
- the method of. producing a colored photographic image in a. silver halide emulsion layer which comprises simultaneously developing an image therein and coupling the development product of an aromatic amino developing agent containing a primary amino group with a compound having the formula:
- a color forming photographic developer comprising an aromatic amino developing agent containinga primary amino group and a coupling compound having the formula:
- a color forming photographic developer comprising an aromatic amino developing agent containing a primary amino group and a coupling compound having the formula:
- a photographic emulsion for forming colored images comprising a colloidal carrier containing a sensitive silver halide and a coupler compound having the formula:
- one X is a hydrogen atom and the other X is a cinnamoyl group.
- a photographic emulsion for forming colored images comprising a gelatino-silver halide emulsion containing a coupler compound having the formula:
Description
. stable than the amines themselves.
Patented 'Sept. 8, 1942 PHOTOGRAPHIC C COMP OL(I JR FORMING OUN Henry D. Porter and Arnold Weissberger, Rochv ester, N. Y.,
assignors to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey No Drawing.- Application March 11, 1941, Serial in Great Britain March 12, 1940 11 Claims.
This invention relates to color photography and more particularly to compounds which form dyes by coupling with the developing compound on photographic development.
The method of forming colored photographic images by depositing a colored compound in the photographic layer adjacent the silver image on development has been described in numerous.
prior patents. Dyes formed in this way are insoluble in water and in the ordinary photographic developing and fixing baths, although the silver images formed simultaneously with them during photographic development may be removed from the photographic layer to leave pure dye images in the layer. Compounds employed in conjunction with the developing agent for the silver and which couple with the development product of the developer during photographic development are referred to herein as coupling components or couplers. Depending upon their solubility or diffusion characteristics, these compounds may be incorporated in the emulsion layer prior to exposure or may be dissolved in the developing solution. When these coupling components are incorporated in the photographic layer prior to exposure, they do not affect the exposure and development of the layer in the usual way, but when the development is carried out with a suit- ;able developing agent, they combine with the oxidation product of the developer to form a colored image in situ with the silver image.
The developing agents used in color forming development of the type contemplated by our invention comprise aromatic amino developers including the mono-, diand triaminoaryl com pounds and their derivatives formed by substitution in the amino group as well as in the ring, suchas alkylphenylenediamines, alkyltoluenendiamines and p-aminophenols. These compounds are ordinarily used in the salt form such as the hydrochloride or the sulfate which are more Suitable compounds are diethyl-p-phenylenediamine hydrochloride, monomethyl-p-phenylene-diamine hydrochloride and dimethyl-p-phenylenediamine sulfate. The p-aminophenols and their substitution products may also be used where the amino group is unsubstituted. All of these compounds have an unsubstituted amino group which enables the oxidation products of the developer to .2;
couple with the color-forming compounds to form a dye image.
We have found that a-naphthols having valeryl or cinnamoyl substituent groups in the 2 or 4 position are useful as coupler compounds in photo- (|)H (3) I m 4 graphic developers and emulsipn layers. These compounds have the following. general formula:
X in which one X is a hydrogen atom, and the other X is a valeryl or cinnamoyl group.-
The following compounds illustrate couplers of this class:
Z-n-valeryl-l-nainhthol Prepared by the method given for the 2-acetyl derivative. Ber. 47, 3216 (1914.)
2pinnamoyl-l-naphthol Prepared as in Ber. 31, 706 (1898) Prepared by the method given for t; e 4-acety1 derivative. Ber. 47, 3228 (1914) Prepared by the method as given for Example 2.
4-cinnemoyl-l-naphthol In the compounds listed above, the valerylsubstituted a-naphthols, compounds 1 and3, are suitable for use in the developing solution and the cinnamoyl substituted a-naphthols, compounds 2 and 4, may be used in the emulsion layer. These compounds form blue-green dyes on photographic development.
A developing formula which may be used is the following:
The developing agent and the proportions of the ingredients used in the above formula may, of course, be varied. Solvents other than acetone, such as alcohols, may also be used.
The coupler which are used in the emulsion layer may be incorporated in various ways but we prefer to form a solution of the sodium salt of the coupler in alcohol and add this to the emulsion. For example, 3 grams of coupler may be dissolved or suspended in 50 cc. of ethyl alcohol and sodium hydroxide added in the amount of 1 equivalent weights of the coupler. The sodium hydroxide may be added as solid or as a concentrated solution. The sodium salt of the coupler is thereby generated in a solution of 50 cc. of alcohol and this solution is added to one liter of a gelatino silver halide. The pH of the emulsion may be adjusted if desired by adding a suitable-acid such as acetic or sulfuric acid to neutralize all or part of the sodium hydroxide used to form the sodium salt of the coupler.
The coupling compounds may be incorporated either in gelatin or in other colloidal materials such as collodion, organic esters of cellulose or synthetic resins. In case the coupler is incorporated in the emulsion or is used in the developing solution, the-emulsion may be carried by a transparent medium such as glass, cellulose ester or synthetic resin or a non-transparent reflecting medium such as paper or an opaque cellulose ester. The emulsion may be coated as a single .layer on the support or superposed layers containing the couplers may be coated on one or both sides of the support. The superposed layers may be differentially sensitized for the formation of 'a neutral color image in the well known manner.
The examples and compounds set forth in the present specification are illustrative only and it is to be understood that our invention should be taken as limited only by the scope of the appended claims.
We claim:
1. The method of producing a colored photo'- graphic image in a silver-halide emulsion layer which comprises simultaneously developing an image therein and coupling the development product of-an aromatic amino developing agent containing a primary amino group with a compoimdhavingzthe formula: on
. x inwhichonexisa x is an acyl group selected from the class consisting of valeryl and cinnamoyl groups.
2. The method of producing a colored photographic image in a silver halide emulsion layer which comprises simultaneously developing an image therein and coupling the development productof an aromatic amino developing agent containing a primary amino group with a compound having the formula:
in which one X is a hydrogen atom and the other X is a valeryl group.
3. The method of producing a colored photographic image in a silver halide emulsion layer which comprises simultaneously developing an image therein and. coupling the development product of an aromatic amino developing agent containing a primary amino group with'a compound having the formula:
0 PI-CHzCHzCHsCHa 4. The method of. producing a colored photographic image in a. silver halide emulsion layer which comprises simultaneously developing an image therein and coupling the development product of an aromatic amino developing agent containing a primary amino group with a compound having the formula:
5. The method of producing a colored photographic image in a silver halide emulsion layer which comprises simultaneously developing an image therein and coupling the development product of an aromatic amino developing agent containing a primary .amino group with a compound having the formula:
in which one X is a hydrogen atom and the other X is a cinnamoyl group. v
6; The method of producing a colored photographic image in a silver halide emulsion layer which comprises simultaneously developing an image therein and coupling the development product of an aromatic amino developing agent containing a primary amino group with a compound having the formula:
7. A color forming photographic developer comprising an aromatic amino developing agent containinga primary amino group and a coupling compound having the formula:
in which one X is a hydrogen atom and the other 9. A color forming photographic developer comprising an aromatic amino developing agent containing a primary amino group and a coupling compound having the formula:
o= -omcmomcm 10. A photographic emulsion for forming colored images comprising a colloidal carrier containing a sensitive silver halide and a coupler compound having the formula:
in which one X is a hydrogen atom and the other X is a cinnamoyl group.
11. A photographic emulsion for forming colored images comprising a gelatino-silver halide emulsion containing a coupler compound having the formula:
ARNOLD WEISSBERGER. HENRY D. PORTER.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB2295009X | 1940-03-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2295009A true US2295009A (en) | 1942-09-08 |
Family
ID=10903265
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US382747A Expired - Lifetime US2295009A (en) | 1940-03-12 | 1941-03-11 | Photographic color forming compound |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2295009A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2436007A (en) * | 1944-05-12 | 1948-02-17 | Ilford Ltd | Dye intermediates for colour photography |
| US2453661A (en) * | 1944-05-03 | 1948-11-09 | Eastman Kodak Co | Colored couplers |
| US2455169A (en) * | 1944-05-03 | 1948-11-30 | Eastman Kodak Co | Colored couplers |
| US3542552A (en) * | 1966-12-28 | 1970-11-24 | Fuji Photo Film Co Ltd | Color developer for color photography |
-
1941
- 1941-03-11 US US382747A patent/US2295009A/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2453661A (en) * | 1944-05-03 | 1948-11-09 | Eastman Kodak Co | Colored couplers |
| US2455169A (en) * | 1944-05-03 | 1948-11-30 | Eastman Kodak Co | Colored couplers |
| US2436007A (en) * | 1944-05-12 | 1948-02-17 | Ilford Ltd | Dye intermediates for colour photography |
| US3542552A (en) * | 1966-12-28 | 1970-11-24 | Fuji Photo Film Co Ltd | Color developer for color photography |
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