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US2525503A - Production of phenazonium dyestuff images - Google Patents

Production of phenazonium dyestuff images Download PDF

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Publication number
US2525503A
US2525503A US793535A US79353547A US2525503A US 2525503 A US2525503 A US 2525503A US 793535 A US793535 A US 793535A US 79353547 A US79353547 A US 79353547A US 2525503 A US2525503 A US 2525503A
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Prior art keywords
naphthol
phenazonium
color
images
developer
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Expired - Lifetime
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US793535A
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Tulagin Vsevolod
Willy A Schmidt
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GAF Chemicals Corp
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General Aniline and Film Corp
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/32Colour coupling substances
    • G03C7/3244Couplers forming azinic dyes; Specific developers therefor

Definitions

  • Patented Oct. 10, 1950 PRODUCTION OF PHENAZONIUM DYESTUFF IMAGES Vsevolod Tulagin, Phillipsburg, N. a, and Willy A. Schmidt, Easton, Pa, assignors to General Aniline & Film Corporation, New York, N. Y., a
  • the present invention relates to the production of blue to reddish-blue phenazonium dyestuff images by color development of an exposed silver halide emulsion with an orthophenylenediamine type developer in the presence of a color former which is a B-naphthol derivative.
  • magenta As a matter of fact, it may be said that these are the only shades Which areobtainable from phenols or naphthols when the coupling reaction takes place para to the phenolic hydroxyl group. This limitation on the shades of the dyestuffs produced according to the method of said application imposes a restriction on its use in three-color photography.
  • Z is an alkyl radical as above or halogen, i. e., chlorine, bromine, or the like, a sulfonic acid group, or hydrogen.
  • the color formers may be employed either in the emulsion or in the developer. However, where they contain a group preventing diffusion, in which case they are preferably used in the emulsion. Examples of compounds falling within such category are those in which the nitrogen atom is substituted by an aliphatic radical containing at least locarbon atoms, i. e., stearyl, and the like i
  • the color developers which are employed are, as stated, of the ortho-phenylenediamine type, anumber of examples of which are referred to in the aforesaid Schmidt and Tulagin application.. Suitable developers of this class are; 7
  • the invention may be effectuated so as to use the color developing method for producing colored negatives, colored positives, or reverse images.
  • These general methods are conventional in the art, being dependent for their efficacy upon the point at which color development takes place.
  • Example 1 A photographic silver bromide emulsion is exposed and color developed in the following developer:
  • Example 2 The developer is the same as in Example 1 excepting that there is used 'l-acetamido-2- naphthol in lieu of the 'l-amino-2-naphthol.
  • Example 3 A silver halide emulsion is exposed, developed in a black and white M-Q developer, re-exposed, and developed in a developer of the following composition:
  • Example 4 4-;6"-dianilino .metanilic' acid. grams Sodium sulfite do 60 Potassium carbonate do.. .40 Pyridine cubic centimeters 12 Water do 1000 The film is then washed, bleached and fixed the conventional manner to yield a blue phenazonium dyestuif image.
  • R is a member selected from the class consisting of'hydrogen, alkyl and aromatic radicals
  • R1 is selected from the class consisting of hydrogen and acylamino
  • Z is a member selected from the class consisting of hydrogen, halogen, alkyl and sulfo groups Z being in the ring 'fused to that containing the phenolic hydroxyl group.
  • R is a member selected from the class consisting of hydrogen, alkyl and aromatic radicals
  • R1 is selected from the class'consisting of hydrogen and acylamino
  • Z is a member selected from the class consisting of h'ydrogen, halogen, alkyl and sulfo groups .Z'Sblllgill the ring fused to that containing the phenolic hydroxyl group.
  • a photographic developer containing an ortho-phenylenediamine compound and as a color former capable of yielding'bluish phenazonium dyestuif images a compound of the following formula 5 6 wherein R is a member selected from the class oped with an ortho-phenylenediamine type deconsisting of hydrogen, alkyl and aromatic radiveloper 7-stearoylamino-2-naphthol.
  • R1 is selected from the class consisting of hydrogen and acylamino
  • Z is a member selected from the class consisting of hydrogen, 5 halogen, alkyl and sulfo groups Z being in the ring fused to that containing the phenolic hy- REFERENCES CITED .droxyl gr up, S Compound being e from The following references are of record in the groups rendering said compound non-diffusing in m f this patent; photographic emulsions. 10
  • a photographic developer capable of yield- UNITED STATES PATENTS ing bluish phenazonium dyestuff images compris- Number Name Date ing 4.6-dianilino metanilic acid and 'I-amino-Z- 2,356,475 Schinzel Aug. 22, 1944 naphthol. 2,394,527 Woodward Feb. 5, 1945 7.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
  • Quinoline Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Description

Patented Oct. 10, 1950 PRODUCTION OF PHENAZONIUM DYESTUFF IMAGES Vsevolod Tulagin, Phillipsburg, N. a, and Willy A. Schmidt, Easton, Pa, assignors to General Aniline & Film Corporation, New York, N. Y., a
corporation of Delaware No Drawing. Application December 23, 1947, Serial No. 793,535
8 Claims.
The present invention relates to the production of blue to reddish-blue phenazonium dyestuff images by color development of an exposed silver halide emulsion with an orthophenylenediamine type developer in the presence of a color former which is a B-naphthol derivative.
Our copending application Serial Number 640,382, filed January 10, 1946, now Patent No. 2,486,440, of which the present application is a continuation in part describes the production of phenazonium dyestufi images by color developing an exposed silver halide emulsion with a color developer comprising an ortho-phenylenediamine type developer in the presence of various color formers. Among the color formers mentioned are those containing a phenolic hydroxyl group which couples in para. position to such group. It has been observed that with such color formers, the most common color of the dyestuff images obtained is either red or that shade of red known in the photographic artas.
magenta. As a matter of fact, it may be said that these are the only shades Which areobtainable from phenols or naphthols when the coupling reaction takes place para to the phenolic hydroxyl group. This limitation on the shades of the dyestuffs produced according to the method of said application imposes a restriction on its use in three-color photography.
It has now been discovered that phenazonium dyestufi images having a bluish shade, i. e., a
shade ranging from blue to reddish-blue are obtained by color developing an exposed silver halide emulsion with an ortho-phenylenediamine type developer in the presence of a fl-naphthol containing an amino Qrsubstituted amino group. 2 i The production of phenazonium dyestuif images by the utilization of such color formers and silver halide emulsions and color developers containing such color formers constitutes the purposes and objects of the present invention.
The ,B-naphthol compounds contemplated for employment herein may be represented by the following structural formula:
sulfonyl, and the like, and Z is an alkyl radical as above or halogen, i. e., chlorine, bromine, or the like, a sulfonic acid group, or hydrogen.
Examples of compounds embraced by this formula and which we have found to be eminently suitable in yielding the desirable blue images by color development with an orthophenylenediamine type developer are the following:
. 7-amino-2-naphthol.
. 7 -acetamido-2-naphthol.
. 7-benzoylamido-2-naphthol.
. 7-benzene sulfonylamido-2-naphthol. 7-methanesulfonylamino-2-naphthol. 7-anilino-2-naphthol.
. 7 -anisidino-2-naphthol.
. S-amino-Z-naphthol.
. B-acetamido-Z-naphthol.
10. 8-N-benzyl-benzoylamido-2-naphthol. ll. 5-acetamido-2-naphthol.
12. 3-anilino-2-naphthol.
13. 7-ethylamino-2-naphthol.
S-stearoyl sulfonylamido-2-naphthol. 8-amino-2-naphthol5sulfonic acid. 5-amino-2-naphthol-7-sulfonic acid. .17. 5-chloro-8amino-2-naphthol.
'18. 7-stearoylamido-2-naphthol.
These compounds are, for'the most part, known in the literature, and in any casecan be made by simple and well known chemical reactions, such as amidation, alkylation, halogenation, and the like. A description of the method of preparing the compounds is accordingly deemed to be unnecessary.
The color formers may be employed either in the emulsion or in the developer. However, where they contain a group preventing diffusion, in which case they are preferably used in the emulsion. Examples of compounds falling within such category are those in which the nitrogen atom is substituted by an aliphatic radical containing at least locarbon atoms, i. e., stearyl, and the like i The color developers which are employed are, as stated, of the ortho-phenylenediamine type, anumber of examples of which are referred to in the aforesaid Schmidt and Tulagin application.. Suitable developers of this class are; 7
4i-6-dia1iilino metanilic acid 4.6 bis (p methoxy phenylamino) met anilic acid 4 (o methoxy phenylamino) 6 (pmethoxy-phenylamino) metanilic acid I 4.6-bis-(o-methoxy phenylamino) metanilic acid 4 (p sulfo phenylamino) 6 dimethylamino metanilic acid, and the like.
The invention may be effectuated so as to use the color developing method for producing colored negatives, colored positives, or reverse images. These general methods are conventional in the art, being dependent for their efficacy upon the point at which color development takes place.
The invention is further illustrated by the following examples, but it is to be understood that the invention is not restricted thereto.
Example 1 A photographic silver bromide emulsion is exposed and color developed in the following developer:
4.6-dianilino metanilic acid grams 1.5 Sodium sulfite (anhydrous) do 60 Potassium carbonate (anhydrous) do 40 Pyridine cubic centimeters 12 7-amino-2-naphthol grams 1 Water cubic centimeters 1000 After development the film is washed for 15 minutes, the silver removed by the conventional ferricyanide bleach, and then fixed and washed. There is thus obtained a brilliant blue phenazonium dyestuff image.
Example 2 The developer is the same as in Example 1 excepting that there is used 'l-acetamido-2- naphthol in lieu of the 'l-amino-2-naphthol.
By processing the exposed silver halide emulsion as in Example 1 a blue phenazonium dyestufif image is obtained.
Example 3 A silver halide emulsion is exposed, developed in a black and white M-Q developer, re-exposed, and developed in a developer of the following composition:
4.6-dianilino metanilic acid grams Sodium sulfite (anhydrous) do 60 Potassium carbonate (anhydrous) do 40 Pyridine cubic centimeters 12 'l benzoylamido-2-naphthol grams 1 Water cubic centimeterse- 1000 The film is washed for 15 minutes, the silver bleached with a'ferricyanide bleach, fixed and washed. A blue phenazonium dyestufl image is thereby produced.
Example 4 4-;6"-dianilino .metanilic' acid. grams Sodium sulfite do 60 Potassium carbonate do.. .40 Pyridine cubic centimeters 12 Water do 1000 The film is then washed, bleached and fixed the conventional manner to yield a blue phenazonium dyestuif image.
The following table lists the color of the phenazonium dyestufi' images obtained when employing the developer of Example 4 with other color forming components of the fi-naphthol class here involved:
Table .1
Color of Formed Coupler Dye 7-benzenesulionylamido-2-napthol Bluish violet. 7-auilino-2-naphthol B 7-anisidino-2-naphth0l Do. S-amino-Z-naphthol. Do. S-acetamido-Z-naphthol. Do. S-N-benzyl-benzoylamido-2-napl1tho Do. S-acetamido-Z-napht Do. 3-anilino-2-naphthol Do.
Various modifications of the invention will occur to persons skilled in the art, and we therefore do not intend to be limited in the patent granted except as necessitated by the prior art wherein R is a member selected from the class consisting of'hydrogen, alkyl and aromatic radicals, R1 is selected from the class consisting of hydrogen and acylamino, and Z is a member selected from the class consisting of hydrogen, halogen, alkyl and sulfo groups Z being in the ring 'fused to that containing the phenolic hydroxyl group.
2 The process as defined in claim 1 wherein the color former is 'l-amino-Z-naphthol.
3. The process as defined in claim 1 wherein the color former is 'l-benzoylamido-Z-naphthol.
4. A photographic silver halide emulsion containing as a color former capable of yielding bluish phenazonium dyestuff images when color developed with an ortho-phenylenediamine type developer a compound of .the followin formula:
wherein R is a member selected from the class consisting of hydrogen, alkyl and aromatic radicals, R1 is selected from the class'consisting of hydrogen and acylamino, and Z is a member selected from the class consisting of h'ydrogen, halogen, alkyl and sulfo groups .Z'Sblllgill the ring fused to that containing the phenolic hydroxyl group.
5. A photographic developer containing an ortho-phenylenediamine compound and as a color former capable of yielding'bluish phenazonium dyestuif images a compound of the following formula 5 6 wherein R is a member selected from the class oped with an ortho-phenylenediamine type deconsisting of hydrogen, alkyl and aromatic radiveloper 7-stearoylamino-2-naphthol. cals, R1 is selected from the class consisting of hydrogen and acylamino, and Z isa member selected from the class consisting of hydrogen, 5 halogen, alkyl and sulfo groups Z being in the ring fused to that containing the phenolic hy- REFERENCES CITED .droxyl gr up, S Compound being e from The following references are of record in the groups rendering said compound non-diffusing in m f this patent; photographic emulsions. 10
6. A photographic developer capable of yield- UNITED STATES PATENTS ing bluish phenazonium dyestuff images compris- Number Name Date ing 4.6-dianilino metanilic acid and 'I-amino-Z- 2,356,475 Schinzel Aug. 22, 1944 naphthol. 2,394,527 Woodward Feb. 5, 1945 7. A photographic developer capable of yielding 15 2,441,491 Kendall et a1. May 11, 1948 bluish phenazonium dyestufl images comprising 2,445,252 Tulagin July 13, 1948 4.6-dianilino metanilic acid and 7-benzoylamido- 2 naphtho1 FOREIGN PATENTS 8. A photographic silver halide emulsion con- Number Country Date taining as a, color former capable of yielding bluish 531,312 Great Britain Jan. 1, 1941 phenazonium dyestutf images when color devel- 536,939 Great Britain June 3, 1941

Claims (1)

1. THE PROCESS OF PRODUCING BLUISH PHENAZONIUM DYESTUFF IMAGES BY COLOR FORMING DEVELOPMENT WHICH COMPRISES EXPOSING A SILVER HALIDE EMULSION AND DEVELOPING THE SAME WITH AN ORTHOPHENYLENEDIAMINE TYPE DEVELOPER IN THE PRESENCE OF A COLOR FORMER HAVING THE FOLLOWING FORMULA:
US793535A 1946-01-10 1947-12-23 Production of phenazonium dyestuff images Expired - Lifetime US2525503A (en)

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US640382A Expired - Lifetime US2486440A (en) 1946-01-10 1946-01-10 Production of phenazonium dyestuff images
US793534A Expired - Lifetime US2525502A (en) 1946-01-10 1947-12-23 Production of phenazonium dyestuff images
US793533A Expired - Lifetime US2524741A (en) 1946-01-10 1947-12-23 Magenta phenazonium dyestuff images from 6-substituted-8-hydroxyquinoline couplers
US793536A Expired - Lifetime US2524725A (en) 1946-01-10 1947-12-23 Magenta phenazonium dyestuff images from 8-hydroxyquinoline couplers
US793535A Expired - Lifetime US2525503A (en) 1946-01-10 1947-12-23 Production of phenazonium dyestuff images
US101913A Expired - Lifetime US2570116A (en) 1946-01-10 1949-06-28 Color developers for the production of azine dye images

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US793534A Expired - Lifetime US2525502A (en) 1946-01-10 1947-12-23 Production of phenazonium dyestuff images
US793533A Expired - Lifetime US2524741A (en) 1946-01-10 1947-12-23 Magenta phenazonium dyestuff images from 6-substituted-8-hydroxyquinoline couplers
US793536A Expired - Lifetime US2524725A (en) 1946-01-10 1947-12-23 Magenta phenazonium dyestuff images from 8-hydroxyquinoline couplers

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BE (6) BE470459A (en)
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DE (6) DE851163C (en)
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US2921851A (en) * 1958-04-03 1960-01-19 Gen Aniline & Film Corp Production of yellow dye images by color development
US3174862A (en) * 1959-09-11 1965-03-23 Agfa Ag Process for improving the color reproduction in color photographic material

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US2596926A (en) * 1949-12-16 1952-05-13 Gen Aniline & Film Corp Preparation of azine dye images
US2594917A (en) * 1949-12-16 1952-04-29 Gen Aniline & Film Corp Suppression of proximity development with azine color developers
US2623823A (en) * 1950-03-21 1952-12-30 Gen Aniline & Film Corp Energizers for aromatic triamino developing agents and suppression of proximity development in azine color developers
US2618559A (en) * 1950-03-21 1952-11-18 Gen Aniline & Film Corp Stain preventing shortstop bath for photographic azine dye images
US2687431A (en) * 1950-12-20 1954-08-24 Gen Aniline & Film Corp Process of preparing nitro phenylenediamines
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US2701766A (en) * 1952-06-14 1955-02-08 Gen Aniline & Film Corp Developers for and method of producing phenazonium dyestuff images with p-dialkylaminoaniline developing agents
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US2945761A (en) * 1957-07-29 1960-07-19 Eastman Kodak Co Reactivity of couplers incorporated in photographic emulsions
US3099559A (en) * 1959-08-31 1963-07-30 Gen Aniline & Film Corp Silver-free color reproduction process and composition therefor
US3050394A (en) * 1959-09-30 1962-08-21 Gen Aniline & Film Corp Method of incorporating color couplers in hydrophlic colloids
US3077403A (en) * 1960-05-31 1963-02-12 Gen Aniline & Film Corp Color former containing bis coupling functions
US4511569A (en) * 1982-08-26 1985-04-16 Schering Corporation Tricyclic lactams and derivatives useful in increasing cardiac contractility
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US4680299A (en) * 1984-04-30 1987-07-14 E.I. Du Pont De Nemours And Company 2-phenyl-4-quinolinecarboxylic acids and pharmaceutical compositions thereof
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Publication number Priority date Publication date Assignee Title
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US2921851A (en) * 1958-04-03 1960-01-19 Gen Aniline & Film Corp Production of yellow dye images by color development
US3174862A (en) * 1959-09-11 1965-03-23 Agfa Ag Process for improving the color reproduction in color photographic material

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US2486440A (en) 1949-11-01
BE486432A (en) 1949-01-15
US2524741A (en) 1950-10-03
CH280518A (en) 1952-01-31
CH280517A (en) 1952-01-31
CH283787A (en) 1952-06-30
US2524725A (en) 1950-10-03
GB646490A (en) 1950-11-22
BE486434A (en) 1949-01-15
FR58855E (en) 1954-04-06
DE851163C (en) 1952-10-02
DE817554C (en) 1951-10-18
DE850385C (en) 1952-09-25
CH283788A (en) 1952-06-30
DE854889C (en) 1952-11-06
US2525502A (en) 1950-10-10
CH280516A (en) 1952-01-31
GB644863A (en) 1950-10-18
FR61005E (en) 1955-03-23
FR939497A (en) 1948-11-16
GB646348A (en) 1950-11-22
BE486431A (en) 1948-12-21
GB649811A (en) 1951-01-31
BE486433A (en) 1949-01-15
GB647638A (en) 1950-12-20
DE848155C (en) 1952-11-04
BE486430A (en) 1949-01-16
FR61007E (en) 1955-03-23
DE837959C (en) 1952-05-05
BE470459A (en) 1947-02-28
FR61006E (en) 1955-03-23
US2570116A (en) 1951-10-02
FR61004E (en) 1955-03-23

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