US2163166A - Photographic developer - Google Patents
Photographic developer Download PDFInfo
- Publication number
- US2163166A US2163166A US143724A US14372437A US2163166A US 2163166 A US2163166 A US 2163166A US 143724 A US143724 A US 143724A US 14372437 A US14372437 A US 14372437A US 2163166 A US2163166 A US 2163166A
- Authority
- US
- United States
- Prior art keywords
- mol
- phenylenediamine
- photographic developer
- following formula
- developers
- 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
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical class NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 5
- 229940117927 ethylene oxide Drugs 0.000 description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- 239000007859 condensation product Substances 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- VEXDRERIMPLZLU-UHFFFAOYSA-N 3-hydroxy-2-methylbutanoic acid Chemical compound CC(O)C(C)C(O)=O VEXDRERIMPLZLU-UHFFFAOYSA-N 0.000 description 2
- UEUIKXVPXLWUDU-UHFFFAOYSA-N 4-diazoniobenzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=C([N+]#N)C=C1 UEUIKXVPXLWUDU-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OJGMBLNIHDZDGS-UHFFFAOYSA-N N-Ethylaniline Chemical compound CCNC1=CC=CC=C1 OJGMBLNIHDZDGS-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- GIQSVAVNCBQEEB-UHFFFAOYSA-N 3-methyl-N-(nitromethyl)aniline Chemical compound [N+](=O)([O-])CNC1=CC(=CC=C1)C GIQSVAVNCBQEEB-UHFFFAOYSA-N 0.000 description 1
- 241001479434 Agfa Species 0.000 description 1
- 201000004624 Dermatitis Diseases 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000001668 ameliorated effect Effects 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 208000010668 atopic eczema Diseases 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 150000004985 diamines Chemical group 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 230000003211 malignant effect Effects 0.000 description 1
- GUYMMHOQXYZMJQ-UHFFFAOYSA-N n-ethyl-3-methylaniline Chemical compound CCNC1=CC=CC(C)=C1 GUYMMHOQXYZMJQ-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- -1 silver halide Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005406 washing 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
- G03C7/407—Development processes or agents therefor
- G03C7/413—Developers
- G03C7/4136—Developers p-Phenylenediamine or derivatives thereof
Definitions
- One of-its objects is to provide new photographic developers of the para-phenylenediamine series. Further objects will be seen-from the detailed specification following hereafter.
- Para-phenylenediamine is a known developer for silver halide emulsions. It is also known that wthe substitution products of developers of this class form, with suitable dyestuif "components, color pictures in the development. Substances suitable are described in UJS. Patent, 1 ,'102,028, dated June 30, 1914. Hitherto only'thederivatives of para-phenylenediamine whi'cii'are alkylated at the nitrogen atom have been used as color developers. All these bodies and especially the most suitable of them are, however, of only limited solubility in water or in a sodium carbonate solution.
- This invention is based on the observation that valuable developing agents, particularly suitable for development in colors, may be obtained by introducing a sulfonlc or carboxylic group into a positive radical 'attachedto the nitrogen, so as to produce for example, paraamino-N-methyl-aniline-omega-sulfonic a c i d, para-amino-N-ethylaniline-omega-sulfonic acid. 4-amino-N-benzyl-aniline-4'-sulfonic acid, and so on.
- a formula for the developers of this invention is the following:
- the two groups of' developers may be. combined in accordance with the following formula:
- NHI-HCI (7) 1 mol of the condensation product from 1 mol monoethyl-m-toluidine and 2 mols ethyleneoxide is treated in the same manner as described in Example 1. A compound of the following formula is obtained:
- n is a whole number.
- n is a whole number and a member selected from the group consisting of hydrogen.
- alkyl aryl and aralkyl.
- NHI-HCI 4 A photographic developer containing a p-phenyienediamine corresponding with the following formula CHEN-Clix.0H
- NHsHCl 5 A photographic developer containing a p-phenylenediamine corresponding with the following formula NHaHCl GUSTAV WILMANNS.
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Description
Patent ed June 193$ "UNITED s'r res PATENT. OFFICE 2,188,166 I PHOTOGRAPHIODEVELOPER v, Gustav Wilmanns, Woll'en, Bitterfeld, and Wilhelm Schneider and Bruno Wendt, Dessau, Anhalt, Germany, assignors, by mesne assignments, to Agfa Ansco Corporation, Bingham ton, N. Y., a. corporation of Delaware 1 I No Drawing. Application May 20,1937. Serial No; 143,724. In Germany May. 26, 1936 5 Claims. (Cl. 95'-88) Our present invention relates to photographic developers and more particularly to developers for development in colors.
One of-its objects is to provide new photographic developers of the para-phenylenediamine series. Further objects will be seen-from the detailed specification following hereafter.
Para-phenylenediamine is a known developer for silver halide emulsions. It is also known that wthe substitution products of developers of this class form, with suitable dyestuif "components, color pictures in the development. Substances suitable are described in UJS. Patent, 1 ,'102,028, dated June 30, 1914. Hitherto only'thederivatives of para-phenylenediamine whi'cii'are alkylated at the nitrogen atom have been used as color developers. All these bodies and especially the most suitable of them are, however, of only limited solubility in water or in a sodium carbonate solution. This fact is a drawback in that the developer is removed only withd'ifliculty by washing after the development, so that in sub- "sequent ly bleaching the silver picture with an oxidizing agent such as potassiumferricyanide undesired color is apt to be developed, particularly when suitable components are present;
Moreover, these substances are freely absorbed by the skin and give rise to malignant eczema and like troubles. All these disadvantages would be considerably ameliorated if the solubility of the compounds could be increased. It has been found that the introduction of 'carboxylic groups or sulfonic groups for increasing'the solubility is not satisfactory in this caseifl'the group enters the nucleus of the para-phenylenediamine, because then. the developing power is at the least strongly diminished.
This invention is based on the observation that valuable developing agents, particularly suitable for development in colors, may be obtained by introducing a sulfonlc or carboxylic group into a positive radical 'attachedto the nitrogen, so as to produce for example, paraamino-N-methyl-aniline-omega-sulfonic a c i d, para-amino-N-ethylaniline-omega-sulfonic acid. 4-amino-N-benzyl-aniline-4'-sulfonic acid, and so on. A formula for the developers of this invention is the following:
R Y R =alkylene arylene 1 ii=coonfsoan the para-phenylenediamine is unsubstituted or contains a further substituent in the free orthoor meta-position, a radical which contains several oxy-groups. It has already been proposed in U. S. Patent 2,108,243 dated February 15, 1938 to introduce hydroxyethyl-groups in the paraphenylenediamine. It has been shown, however,
that the solubility is not-sumcient to render the base easily soluble in water. The solubility is attained, however, if the paraphenylenediamine is caused to react with ethylene-oxide, for instance with 3 --to 5mol-ethylene-oxide. This ex- R X R=any positive groups, for instance hydrogen, alkyl aryl or hydroxyalkyl Nv X=[CH.OH1.O],.-CHMJHLOH n=a whole number These developers are well suited for black and white and also for color development, and their superior solubility and physiological harmlessness distinguish them from known phenylene= diamines. f
The two groups of' developers may be. combined in accordance with the following formula:
The following examples illustrate the invention: (1) 1 mol methylphenylamino-benzyl-2-propicnic acid is coupled with 1 mol of diazotized sulfanilic acid in the usual manner. The dye is precipitated and is filtered off and split by reducing with tin and hydrochloric acid. The tin is precipitated from the solution of the double-salt by means of sulfuretted hydrogen and the resulting developing agent is obtained by evaporating (2)1 mol"'of p-sulfobenzylaniiine is. coupled with l'molof diazotized sulfa'nilic acid, the dye is isolated and split in the same manner as disclosed in Example 1 with tin and hydrochloric acid. The hydrochloride of p-sulfobenzylamino-4-aniline is obtained from the tin double-salt and corresponds to the following formula:
W t rm Nm (3) 1 mol of di-(p -sulfobenzyD-aniline is coupled with 1 mol of diazotized sulfanilic acid and further treated in a manner analogous to that of Example 1. Di'-(p-su1fobenzyl)-aminoanilinehydrochloride which has the following formula:
(5) 1 mol of a condensation product obtained from 1 mol nitromethyl-m-toluidine and 2 mols ethyleneoxide yields after reduction with tin and hydrochloric acid. a product of the following formula:
CHr-N-JJHpOHnOJIHaCHLOH NHLHCI (6) 1 mol of a condensation product produced by the known method from 1 mol of ethylaniline and 2 mols of ethyleneoxide yields if treated according to the method of Example 1 a developer of the following formula:
NHI-HCI (7) 1 mol of the condensation product from 1 mol monoethyl-m-toluidine and 2 mols ethyleneoxide is treated in the same manner as described in Example 1. A compound of the following formula is obtained:
4 'OsHr-N-CHaCHaQCHaOHaOH I Name! What we claim is: g 1. A photographic developer containing a p-phenylenediamine having attached to one of the nitrogen atoms the radicle (CH2.CH2.O) a.CH:.CHs.OH,
wherein n is a whole number.
2. A photographic developer containing a p-phenylenediamine having attached to one of the nitrogen atoms the radicle (CHz.CH:.0) .CH:.CH:.OH,
wherein n is a whole number and a member selected from the group consisting of hydrogen.
alkyl, aryl and aralkyl.
3. A photographic developer containing a p-phenylenediamine corresponding with the following formula cmt-N-cmcmocm.0n,.o .cm.cm.on
NHI-HCI 4. A photographic developer containing a p-phenyienediamine corresponding with the following formula CHEN-Clix.0H|.0.CH1.CH1.0H
NHsHCl 5. A photographic developer containing a p-phenylenediamine corresponding with the following formula NHaHCl GUSTAV WILMANNS.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEI55101D DE767652C (en) | 1936-05-27 | 1936-05-27 | Process for the color development of halogen silver emulsions |
| GB15966/36A GB481275A (en) | 1936-05-27 | 1936-06-08 | Improvements relating to photographic developers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2163166A true US2163166A (en) | 1939-06-20 |
Family
ID=25981935
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US143724A Expired - Lifetime US2163166A (en) | 1936-05-27 | 1937-05-20 | Photographic developer |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US2163166A (en) |
| DE (1) | DE767652C (en) |
| FR (1) | FR822269A (en) |
| GB (1) | GB481275A (en) |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2449919A (en) * | 1947-07-05 | 1948-09-21 | Eastman Kodak Co | 3-methylsulfonamido-4-amino dimethyl aniline photographic developer |
| US2486440A (en) * | 1946-01-10 | 1949-11-01 | Gen Aniline & Film Corp | Production of phenazonium dyestuff images |
| US2575027A (en) * | 1949-10-29 | 1951-11-13 | Gen Aniline & Film Corp | N-substituted 4, 6-diamino metanilic acids |
| US2603659A (en) * | 1950-06-16 | 1952-07-15 | Du Pont | Photographic developers |
| US2603656A (en) * | 1951-02-27 | 1952-07-15 | Du Pont | Photographic developing agents |
| US2604399A (en) * | 1949-07-07 | 1952-07-22 | Eastman Kodak Co | Photographic developers comprising bis-(di-hydroxyalkyl aminomethyl)-hydroquinones |
| US2611785A (en) * | 1952-09-23 | N-substituted x | ||
| US2695234A (en) * | 1951-01-26 | 1954-11-23 | Gevaert Photo Prod Nv | Photographic development |
| US2716132A (en) * | 1952-10-22 | 1955-08-23 | Du Pont | N-substituted amino anilines |
| US3113124A (en) * | 1959-11-27 | 1963-12-03 | Pennsalt Chemicals Corp | Novel antiozonants for elastomers |
| US3181942A (en) * | 1961-11-15 | 1965-05-04 | Pennsalt Chemicals Corp | Method of controlling plant growth |
| US3656950A (en) * | 1970-12-03 | 1972-04-18 | Eastman Kodak Co | Color photographic processes |
| US3658525A (en) * | 1970-12-03 | 1972-04-25 | Eastman Kodak Co | Reversal color photographic processes |
| US3661587A (en) * | 1968-04-01 | 1972-05-09 | Itek Corp | Photographic media |
| US4066457A (en) * | 1974-12-10 | 1978-01-03 | Gaf Corporation | Color developer for diffusion transfer |
| US4066456A (en) * | 1974-12-10 | 1978-01-03 | Gaf Corporation | Incorporated carboxy substituted p-phenylenediamine color developer |
| US4113491A (en) * | 1975-02-10 | 1978-09-12 | Konishiroku Photo Industry Co., Ltd. | Color photographic developing composition |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102755C (en) * | ||||
| DE253335C (en) * | 1912-02-06 |
-
1936
- 1936-05-27 DE DEI55101D patent/DE767652C/en not_active Expired
- 1936-06-08 GB GB15966/36A patent/GB481275A/en not_active Expired
-
1937
- 1937-05-20 US US143724A patent/US2163166A/en not_active Expired - Lifetime
- 1937-05-26 FR FR822269D patent/FR822269A/en not_active Expired
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2611785A (en) * | 1952-09-23 | N-substituted x | ||
| US2486440A (en) * | 1946-01-10 | 1949-11-01 | Gen Aniline & Film Corp | Production of phenazonium dyestuff images |
| US2449919A (en) * | 1947-07-05 | 1948-09-21 | Eastman Kodak Co | 3-methylsulfonamido-4-amino dimethyl aniline photographic developer |
| US2604399A (en) * | 1949-07-07 | 1952-07-22 | Eastman Kodak Co | Photographic developers comprising bis-(di-hydroxyalkyl aminomethyl)-hydroquinones |
| US2575027A (en) * | 1949-10-29 | 1951-11-13 | Gen Aniline & Film Corp | N-substituted 4, 6-diamino metanilic acids |
| US2603659A (en) * | 1950-06-16 | 1952-07-15 | Du Pont | Photographic developers |
| US2695234A (en) * | 1951-01-26 | 1954-11-23 | Gevaert Photo Prod Nv | Photographic development |
| US2603656A (en) * | 1951-02-27 | 1952-07-15 | Du Pont | Photographic developing agents |
| US2716132A (en) * | 1952-10-22 | 1955-08-23 | Du Pont | N-substituted amino anilines |
| US3113124A (en) * | 1959-11-27 | 1963-12-03 | Pennsalt Chemicals Corp | Novel antiozonants for elastomers |
| US3181942A (en) * | 1961-11-15 | 1965-05-04 | Pennsalt Chemicals Corp | Method of controlling plant growth |
| US3661587A (en) * | 1968-04-01 | 1972-05-09 | Itek Corp | Photographic media |
| US3656950A (en) * | 1970-12-03 | 1972-04-18 | Eastman Kodak Co | Color photographic processes |
| US3658525A (en) * | 1970-12-03 | 1972-04-25 | Eastman Kodak Co | Reversal color photographic processes |
| US4066457A (en) * | 1974-12-10 | 1978-01-03 | Gaf Corporation | Color developer for diffusion transfer |
| US4066456A (en) * | 1974-12-10 | 1978-01-03 | Gaf Corporation | Incorporated carboxy substituted p-phenylenediamine color developer |
| US4113491A (en) * | 1975-02-10 | 1978-09-12 | Konishiroku Photo Industry Co., Ltd. | Color photographic developing composition |
Also Published As
| Publication number | Publication date |
|---|---|
| FR822269A (en) | 1937-12-24 |
| DE767652C (en) | 1953-03-02 |
| GB481275A (en) | 1938-03-08 |
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