US2570116A - Color developers for the production of azine dye images - Google Patents

Color developers for the production of azine dye images Download PDF

Info

Publication number
US2570116A
US2570116A US101913A US10191349A US2570116A US 2570116 A US2570116 A US 2570116A US 101913 A US101913 A US 101913A US 10191349 A US10191349 A US 10191349A US 2570116 A US2570116 A US 2570116A
Authority
US
United States
Prior art keywords
acid
images
color
alkyl
developer
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
Application number
US101913A
Inventor
Robert C Gunther
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
GAF Chemicals Corp
Original Assignee
General Aniline and Film Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by General Aniline and Film Corp filed Critical General Aniline and Film Corp
Application granted granted Critical
Publication of US2570116A publication Critical patent/US2570116A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • G03C7/3244—Couplers forming azinic dyes; Specific developers therefor

Definitions

  • the present invention relates to the production of azine dye images by color forming development while employing as the color forming developer derivatives of ZA-diamino aniline in which the amino group in the 2-position is substituted by an. aliphatically linked hydrophilic group.
  • magenta images rather than yellow images ensue.
  • the emagenta: images may besubsequently converted-into yellow images but only by a separate step involving a treatmentwith an alkali.
  • R is hydrogen or alkyl, i. e., methyl, ethyl, propyl, butyl, amyl or the like and R1 is an aliphatic radical such as alkyl as above, carboxy alkyl, such as carboxy methyl, carboxy ethyl, and the like; hydroxy alkyl, such as hydroxy ethyl, hydroxypropyl, andthe like, aryl, such asphenyl, toluyl and the like; carboxy alkyl aryl, such as oarboxy methyl phenyl, carboxy ethyl phenyl, and the like, carboxy alkoxy aryl, such as carboxy methoxy phenyl, carboxy ethoxyphenyl; hydroxy alkyl aryl, such as hydroxy methyl phenyl, hydroxy ethyl phenyl, and the like; and hydroxy alkoxy aryl, such as hydroxy.
  • R2 is an alkyl group substitutedby a hydrophilic group such as carboxy alkyl, such as carboxy methyl, carboxy ethyl and the like; hydroxy alkyl, such as hydroxy ethyl, hydroxy propyl, and the like; sulfo alkyl such as, sulfomethyl, sulfoethyl, sulfop-ropyl, sulfobutyl and the like and X and Y are hydrogen, alkyl as above, sulfo orcarboxy, or together represent the atoms necessary to complete a sixmembered isocyclic ring system such as benzo and the like.
  • a hydrophilic group such as carboxy alkyl, such as carboxy methyl, carboxy ethyl and the like
  • hydroxy alkyl such as hydroxy ethyl, hydroxy propyl, and the like
  • sulfo alkyl such as, sulfomethyl,
  • the preparation of the compound by the aforesaid method is made possible by the fact that the chlorine atom in the 4-position is more easily replaced by an amino group than the chlorine atom in 2-position.
  • the chlorine atom in 4- position is selectively replaced by such amine.
  • the chlorine atom in Z-position is replaced by the amine.
  • a glass interliner for an Aminco shaking-type bomb was charged with 95.6 parts of the 2-chlorol-(p-hydroxyethylamino)-5 nitro benzene sodium sulfonate (prepared as above), 30 parts of aniline and 34 parts of sodium carbonate dissolved in 200 parts of water.
  • the liner was sealed in the bomb and the bomb shaken at C. for 15 hours.
  • the bomb was cooled and the solid removed from the interliner with small amounts of hot water. .250 cc. of 30% sodium chloride solution were added with vigorous stirring of the mixture and the whole was then cooled in an ice bath for several hours.
  • the precipitated solid was collected by filtration, washed with 50 parts of water, and then digested with 200 parts of ethanol.
  • the product was again collected on a filter and dried overnight at 60 C. in a vacuum oven.
  • amines containing an aliphatically bound hydrophilic group different from that described in the above example.
  • Such other amines are for instance B-sulfoethyl amine (taurine) m-amino-phenoxy-acetic acid, amino acetic acid, p-amino phenyl ethyl alcohol, 10- amino phenyl acetic acid, 2-amino-2-methyl- LB-propanediol and the like.
  • the aforementioned derivatives of 2,4-diamino aniline are characterized by their marked ability to effect reduction of silver halides, i. e., latent images, reverse images, bleached images, and the like, without formation of ob-.
  • jectionable stain As a consequence of the reducing power they may be employed for development of black and white images or for the production of color images.
  • yellow dyes obtained by color development with my developers appear to be true azines. Thus "they withstand treatment with an acid bisulfite whereas yellow azomethines do not. Furthermore they are not split by strong mineral acids as happens with the yellow azomethines. Such yellow dye images have excellent lightfastness and brilliance and they adequately complement the magenta and cyan dyes produced by the mine methods.
  • the color formers employed for producing the dye images are those used in the production of color developed images, i. e., those containing aromatic-primary amino, phenolic hydroxyl or active methylene groups.
  • Examples of such compounds for producing the magenta images are: 3.6-d-isulfo-8-benzsulfonylamino naphthol-1; 8-benzsulfonylaminonaphthol-1; B-hydroxy quinoline; naphthsultam acid; 3-sulfo-7-phenylaminonaphthol-l; li8- bi's- (benzsulfonyl amino)-naphthalene; 6-bromo-8- hydroxy quinoline; 6-sulfo-8-hydroxy quinoline;
  • cyan color formers are: 3-sulfo- 6 aminonaphthol 1; 3 sulfo-S-phenyl-aminonaphthol 1; 3-sulfo-6-(4-methoxy-phenylami no) -naphthol-l; ethyl urethane of phenyl J acid; 6 (4' octadecoxy-phenylamino) -1-naphthol-B-sulfonic acid; 3-sulfo-6-oleylamino-naphthol-l, and the like.
  • yellow color forming components 7 8 13. 12 (m-benzoylacetamidophenyl) -1-octadecy1- 33. 'pCyanoacetyl-3-octadecenylsuccinialic acid. "5-benzimidazolesulionic acid. COOECN 14. o-Acetoacetaniside. v OH ZOOoH V V 15. 4.4"-methylenebis-a-benzoylacetanilide.
  • the processor employing the color developer QO0GHzCONHC CHz--ONHOOCH ⁇ Q 00' a l o Phenylacetoacetanilide. to produce the azine 'dye images may be effected in 17..
  • a color formingcom- 1 V ponent may. be added to the developer containing the 5 diamino aniline derivative.
  • a color former in non-diffusing form may be C COCHNH SOzNH located in the emulsion and the diamino aniline N derivative in the developer.
  • Multi-layer film 18. 5.5'-ureylenebis-N-benzoylacetyl anthranilic each layer containing a non-diffusing color acid.
  • the developer While the diamino aniline derivative and an 3 alkali, such as sodium carbonate, sodium hydroxllIH ide, or the like, are the essential components of the developer, it is .preferred that the developer also contain the usual adjuncts such as an alkali metal bromide, i. e.,. potassium bromide, sodium bromide, and the like, and an alkali metal sulfite,
  • OCOCHZGONHOOOOH i. e., sodium sulfite, and the like.
  • a coupling 7-b n y ph hoxyacetic acid aid injthe form of an inorganic or organic base 00112-000151 such as pyridine, quinoline, or ammonium hydroxide.
  • v Q0 0 oHzoo-NH The-following exampes will serve to illustrate 22.
  • Example II 31 a-Phenylsulfonylacetophenone. The procedure is the same as in Example I ex- 32. 2-(p benzoylacetamidophenyl)-1octadecylcepting that the 4-(p-hydroxyethylamino) -6- 5-benzimidazolesu1fonic acid. .75 phenylamino-metanilic acid is replaced by 4-(5- 28. 1.3-diphenyl-1.3-propanedione.
  • a photographic silver "bromide emulsion is exposed and color developed in a developer having the following composition:
  • Example IV The procedure 'is the same as "in Example III excepting that 'the B-hydroxyquinoline is replaced by the ethyl urethane of phenyl J -acid. 'By working up the emulsion as in Example III a cyan azine dye "image isobtained.
  • Example V photographic silver halide emulsion carrying a silver 'halide image was developed for 15 minutes in ar developer of the -following composition:
  • Example VJ An integral tripack ⁇ having as the bottom layer a red sensitive emulsion containing as a cyan color former 6-(4octadetsoxyphenylaniino? -'1- naphthOl-S-Sulfonicacid of the formula:
  • a photographic developer comprising an alkaline aqueous :solution of an alkali metal sulfite and .a compound selected rrom the class of the following constitution:
  • R is selected from .the class consisting of hydrogen and alkyl
  • R1 is selected from the class consisting of alkyl, carboxyalkyl, hydroxyalkyl, aryl, carboxyalkylaryl, carboxyalkoxyaryl, hydroxyalkylaryl and hydroxyalkoxyaryl
  • R2 is an alkyl group substituted by a hydroxyl roup
  • X and Y are selected from the class consisting of hydrogen, alkyl, sulfo and carboxy, and Z; represents the atoms necessary to complete a G-membered isocyclic ring.
  • a photographic developer for producing azine dyestuff images on color development comprising aqueous alkaline solution of a color former capable of reacting with the oxidation products of a primary aromatic amino developer to form a dye image and 4-(fl-hydroxyethylamino)-6-pheny1- aminometanilic acid.
  • composition as defined in claim 4 wherein the color former is S-hydroxyquinoline.
  • R' is selected from the class consistin of hydrogen and alkyl
  • R1 is selected from the class consisting of alkyl, carboxyalkyl, hydroxyalkyl, aryl, carboxyalkylaryl, carboxyalkoxyaryl, hydroxyalkylaryl and hydroxyalkoxyaryl
  • R2 is an alkyl group substituted by a hydroxyl group
  • X and Y are selected from the class consisting of hydrogen, alkyl, sulfo and carboxy
  • Z represents the atoms necessary to complete a G-membered isocyclic ring.
  • R is selected from the class consisting of hydrogen and alkyl
  • R1 is selected from the class of alkyl, carboxyalkyl, hydroxyallsylraryl; carboxyalkylaryl, carboxyalkoxyaryl, 'hydroxyalkylaryL'hydroxyalkoxyaryl, Rz'is an alkyl group substituted by a hydroxyl group
  • X and Y are selected from the class consisting of hydrogen, alkyl, sulfo and carboxy
  • Z represents the atoms necesbenzoylacet' radical with a 4.6 diamino'metanilic acid in which the nitrogen atom in the-G-position is substituted by aryl and the nitrogen atom in the 4-position by hydroxy alkyl.

Landscapes

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

Description

Patented Oct. 2, 1951 COLOR DEVELOPERS FOR THE PRODUC- TION OF AZINE DYE IMAGES Robert C. Gunther, Easton, Pa., assignor toGeneral Aniline & Film Corporation, New York, N; Y., a corporation of Delaware No Drawing. Application June 28, 1949, Serial No. 101,913
The present invention relates to the production of azine dye images by color forming development while employing as the color forming developer derivatives of ZA-diamino aniline in which the amino group in the 2-position is substituted by an. aliphatically linked hydrophilic group.
This application. is. a continuation-in-part of my application SeriaLNo. 793,532, filed December 23,. 1947,, now abandoned, entitled Color Developers for the Production of Phenazonium Dye;- stufilmages.
Inthe copending application Serial No. 640,382, filed on January 10, 1946, by Willy A. Schmidt and Vsevolod Tulagin, now U. S. P.. 2,486,440, there is described, the production of azine dye images by color forming development while utilizing inter alia as the color developer derivatives f, 2,4'-diamino-aniline. While these color developershave been found to be effective-inproducing the desired dyestuff images in the presence of the usual color forming componentsit is noted that they have atendency tobe. adsorbed to silver halide. grains. of the photographic emulsions, thereby making it difficult 110: efiectthe complete removal thereof from the emulsion by washing after development. Furthermore, saidv compounds have been observed-to cause stainin thereduction of silver halides, particularly when such. reduction takes place in the absenceoi a color former.
Difiiculties have also been encountered in the production of yellow dye images by the utilization of the. aforestated developers. Experience has shown that when using'such developers with color formers generally employed for the production of. yellow azomethine images, i. e., open chain;
keto methylene compounds, magenta images rather than yellow images ensue. The emagenta: images may besubsequently converted-into yellow images but only by a separate step involving a treatmentwith an alkali.
It has now been-discovered that the production of azine dye images can be effectively carried out without the aforenotedobjectionsif there be employed as color developers derivatives'of 2,4-diamino anilinesin which the amino group in the 2.-po'sition is; substituted. by an aliphatically linked hydrophilics group such: as; hydroxyj, car
boxy or sulfo. Inasmuch as said compounds are:
capableofi effecting the reduction of silver halides including; latent images without the formation of 13 Claims. (Cl. 9588) stain, they may also be employed as developers for black and White images.
These developers also havethe unique property of yielding yellow dye images directly when employed to develop a developable silver halide emulsion in the presence of an open chain keto methylene compound. They are therefore admirably suited for the production in one development step of azine dye images in the three subtractive colors.
Developers utilizing such compounds and their employment particularly in the production of azine dye images constitutethe purposes and object of the present invention.
The derivative of 2,4-diamino aniline contemplated for use herein as developers are typified by the following structural formula:
NR R
wherein R is hydrogen or alkyl, i. e., methyl, ethyl, propyl, butyl, amyl or the like and R1 is an aliphatic radical such as alkyl as above, carboxy alkyl, such as carboxy methyl, carboxy ethyl, and the like; hydroxy alkyl, such as hydroxy ethyl, hydroxypropyl, andthe like, aryl, such asphenyl, toluyl and the like; carboxy alkyl aryl, such as oarboxy methyl phenyl, carboxy ethyl phenyl, and the like, carboxy alkoxy aryl, such as carboxy methoxy phenyl, carboxy ethoxyphenyl; hydroxy alkyl aryl, such as hydroxy methyl phenyl, hydroxy ethyl phenyl, and the like; and hydroxy alkoxy aryl, such as hydroxy. methoxy phenyl, hydroxy ethoxy phenyl and the like, R2 is an alkyl group substitutedby a hydrophilic group such as carboxy alkyl, such as carboxy methyl, carboxy ethyl and the like; hydroxy alkyl, such as hydroxy ethyl, hydroxy propyl, and the like; sulfo alkyl such as, sulfomethyl, sulfoethyl, sulfop-ropyl, sulfobutyl and the like and X and Y are hydrogen, alkyl as above, sulfo orcarboxy, or together represent the atoms necessary to complete a sixmembered isocyclic ring system such as benzo and the like. It is to be observed that in the above compounds the substituent groups repre- HNGO c1110 OH N-CHzCHaOH 4- (B-hydroxyethylamino -6- (4' -carboz zy-methoxy phenylamino) metamlic acid Nil-@OCHa 4-( carbpxymethylamino) -6- (4-methoxy phenylamino metanilic acid l qHz 2- (B-sulfoethylamino) -4-phenylamino aniline NH C Hz 0 H2 0 H NHCHQOHZOH 4, G-di (B-hydroxyethylamino )-metanilic acid 2- B-hydroxyethyiamino) 4- (B-sulfoethylamino) --methyl aniline HOzS NHCHr-HOH 4 B-hydroxy-f:-methyl-ethylamino) -6-phenylaminometanilic acid 8 0 CaHs CHIOH 4- (a-di (hydroxymethyl ethylamino -6- (3'-ethoay phenylamino)-metanilic acid 9 NHCHI NHCHaCHaOH l THz 4- (B-hydroxy ethylaniino) -6-methylamino-metanilic acid moms 03H 4-(sulfomethylamino)-6-(metl1gl phenyl amino)-metanilic aci The aforementioned compounds are prepared by reacting in the proper sequence 2,4-dichloro- 5-nitro benzene sodium sulfonate with the amines desired to be introduced into the 2- and 4-positions of the benzene ring, and then effecting reduction of the nitro group to an amino group. The preparation of the compound by the aforesaid method is made possible by the fact that the chlorine atom in the 4-position is more easily replaced by an amino group than the chlorine atom in 2-position. Thus by refluxing the 2,4-dichloro-5-nitro benzene sodium sulfonate with an equivalent of an amine, the chlorine atom in 4- position is selectively replaced by such amine. By subsequently treating the resulting compound with the same or a different amine under more elevated temperatures, i. e., temperature ranging from to 150 C., the chlorine atom in Z-position is replaced by the amine.
The following is a specific illustration of the application of the foregoing general method in the production of l-(p-hydroxyethylamino) -6- phenyl amino metanilic acid.
Into a 1-liter, 3-necked round-bottom flask equipped with a mechanical stirrer and a reflux condenser was placed 147 parts of the sodium salt of 2,4-dichloro-5-nitro benzene sulfonic acid, 31 parts of ethanolamine and 54 parts of sodium carbonate dissolved in 250 parts of water. After the stirrer was started, the contents of the flask were gently refluxed for 10 hours. 200 cc. of 30% sodium chloride solution were added to the hot reaction mixture and the flask was then cooled in an ice bath. The precipitated orange solid was collected by filtration, washed with a small amount of water, and dried overnight at 80-90 C.
A glass interliner for an Aminco shaking-type bomb was charged with 95.6 parts of the 2-chlorol-(p-hydroxyethylamino)-5 nitro benzene sodium sulfonate (prepared as above), 30 parts of aniline and 34 parts of sodium carbonate dissolved in 200 parts of water. The liner was sealed in the bomb and the bomb shaken at C. for 15 hours. The bomb was cooled and the solid removed from the interliner with small amounts of hot water. .250 cc. of 30% sodium chloride solution were added with vigorous stirring of the mixture and the whole was then cooled in an ice bath for several hours. The precipitated solid was collected by filtration, washed with 50 parts of water, and then digested with 200 parts of ethanol. The product was again collected on a filter and dried overnight at 60 C. in a vacuum oven.
10 parts of 2-phenylamino-4-(fi-hydroxyethylamino) -5-nitro benzene sulfonic acid (prepared as above) were added portion-wise to a boiling solution of 40 parts of sodium hydrosulfite in 200 cc. of sodium hydroxide. After reduction is complete, a small amount of decolorizing carbon is added to the solution. The mixture is boiled vigorously for several minutes and then filtered rapidly through a fluted filter. Thecompound was then isolated from the clear filtrate as the inner salt by acidification with glacial acetic acid. The mixture was cooled in an ice bath for several hours, the inner salt collected on a filter and washed with water. The product was then dried six hours at 65 C. in a vacuum oven and constituted the 4-(B-hydroxyethylamino)-6-phenyl amino-metanili'c acid.
The same procedure may also be utilized in the preparation of the other compounds noted above while employing amines containing an aliphatically bound hydrophilic group different from that described in the above example. Such other amines are for instance B-sulfoethyl amine (taurine) m-amino-phenoxy-acetic acid, amino acetic acid, p-amino phenyl ethyl alcohol, 10- amino phenyl acetic acid, 2-amino-2-methyl- LB-propanediol and the like.
As stated, the aforementioned derivatives of 2,4-diamino aniline are characterized by their marked ability to effect reduction of silver halides, i. e., latent images, reverse images, bleached images, and the like, without formation of ob-.
jectionable stain. As a consequence of the reducing power they may be employed for development of black and white images or for the production of color images.
One of the mst notable properties of the aforementioned derivatives of 2,4-diamino aniline, however, is, as stated, their ability to directly yield yellow dyeimages. This result is achieved when employin the developers to develop a developable silver halide emulsion in the presence of an open chain keto methylene compound even though the emulsion during a, subsequent processing step be treated with an acidic bleach bath as is usual in the processing of film to azine dye images. In other words, whereas the formerly employed, ZA-diamino anilines only yielded yellow images, as the result of a subsequent alkaline 6. consequence such developers very materially contribute to the utilization on a commercial scale of the azine method for processing film in the three subtractive colors.
The yellow dyes obtained by color development with my developers appear to be true azines. Thus "they withstand treatment with an acid bisulfite whereas yellow azomethines do not. Furthermore they are not split by strong mineral acids as happens with the yellow azomethines. Such yellow dye images have excellent lightfastness and brilliance and they adequately complement the magenta and cyan dyes produced by the mine methods.
The color formers employed for producing the dye images are those used in the production of color developed images, i. e., those containing aromatic-primary amino, phenolic hydroxyl or active methylene groups.
Examples of such compounds for producing the magenta images are: 3.6-d-isulfo-8-benzsulfonylamino naphthol-1; 8-benzsulfonylaminonaphthol-1; B-hydroxy quinoline; naphthsultam acid; 3-sulfo-7-phenylaminonaphthol-l; li8- bi's- (benzsulfonyl amino)-naphthalene; 6-bromo-8- hydroxy quinoline; 6-sulfo-8-hydroxy quinoline;
Z-phenyl-6-bromo-8-hydroxy cinchoninic acid; 6-bromo-8-hydroxy quinaldine; G-stearoylamino 2 (2-phenyl-6'-bromo-8-hydroxy cinchoninoyl) -amino to'luene-4-sulfonic acid; 2-phenyl- G-chloro-S-hydroxy cinchoninoyl octadecyl taurine, and the like.
Examples of cyan color formers are: 3-sulfo- 6 aminonaphthol 1; 3 sulfo-S-phenyl-aminonaphthol 1; 3-sulfo-6-(4-methoxy-phenylami no) -naphthol-l; ethyl urethane of phenyl J acid; 6 (4' octadecoxy-phenylamino) -1-naphthol-B-sulfonic acid; 3-sulfo-6-oleylamino-naphthol-l, and the like.
are:
j 4. N,N'-ethylenebisacetoacetamide CHaCOCHzCO NH' CH2CH2NHCOCH2COCH3 5. N .N '-ethylenebis-a-benzoylacetamide. 6. p.p'-Bi-o-acetoacetaniside QQNHGOGmOO 0H.
CHsO O CHzC ONH I a '7. N-2-naphthylbenzoylacetamide. 8. p.p-Biacetoacetanilide.
9. p.p-Bi-a-benzoylacetanilide.
10. and 'I'erephthaloylbis-(3chloro-4.6dimethoxy-acetanilide) treatment, the developers contemplated herein yield such images directly and Without such subon, OlQNH-C o c1120 oQ-co-omc OHN sequent processing with an alkaline bath. As a,
11. a4! Terephthaloylbis (4-chloro-5-methylo-acetaniside) on. p
12. a-Benzoylacetanilide.
Examples of yellow color forming components 7 8 13. 12 (m-benzoylacetamidophenyl) -1-octadecy1- 33. 'pCyanoacetyl-3-octadecenylsuccinialic acid. "5-benzimidazolesulionic acid. COOECN 14. o-Acetoacetaniside. v OH ZOOoH V V 15. 4.4"-methylenebis-a-benzoylacetanilide. The processor employing the color developer QO0GHzCONHC CHz--ONHOOCH}Q 00' a l o Phenylacetoacetanilide. to produce the azine 'dye images may be effected in 17.. 4'-2-pyridylsulfamyl-a-benzoylacetanilide. various ways. For instance, a color formingcom- 1 V ponent may. be added to the developer containing the 5 diamino aniline derivative. On the other hand; a color former in non-diffusing form may be C COCHNH SOzNH located in the emulsion and the diamino aniline N derivative in the developer. Multi-layer film, 18. 5.5'-ureylenebis-N-benzoylacetyl anthranilic each layer containing a non-diffusing color acid. former, may be used and the entire film color OOOCHzOONH-O-NHCONHQNHCOClEizCO eoon (300E V r g 19. 3.3 -ureylenebis 6 p benzoylacetamidodeveloped to. the desired subtractive dyestufi benzamide-benzene sulfonic acid. images in a single color forming development step using the diamino aniline derivatives as the de- -oooH2 o ONHOOONHQ I veloperu. V V
S0311 NH While the diamino aniline derivative and an 3 alkali, such as sodium carbonate, sodium hydroxllIH ide, or the like, are the essential components of the developer, it is .preferred that the developer also contain the usual adjuncts such as an alkali metal bromide, i. e.,. potassium bromide, sodium bromide, and the like, and an alkali metal sulfite,
O0 0 011,0 ONE-O0 ONE-O- 403E 20.1 p-Benzoylacetamidobenzoic acid.
5 the invention, but it is to be understood that the invention is not limited thereto:
OCOCHZGONHOOOOH i. e., sodium sulfite, and the like. If desired there may also be present in thedeveloper a coupling 7-b n y ph hoxyacetic acid. aid injthe form of an inorganic or organic base 00112-000151 such as pyridine, quinoline, or ammonium hydroxide. v Q0 0 oHzoo-NH The-following exampes will serve to illustrate 22. 2-p-benzoylacetamidobenzamido-6 stearoyl- Example I amino-p-toluenesulfonic acid- A photographic silver bromide emulsion con- CHQ NHCOCwHsfi taining per kilo of emulsion .5 part of 3-stearoy1- amino-5-sulfo-acetoacetanilide as the color O O formeris exposed, the latent image developed in a Metol-I-Iydr'oquinone Developer, re-exposed Tere hthaloylbisa etanilide and the residual silver halide developed for 10 24. 4.4methy1enebisacetoacetanilide, minutes in a solution of the following composition: omooomoorrn-O-omQ-vnoo0112000113 V 7 p Potassium carbonate grams 20 25. p-Sulfamylbenzoylacetanlllde. sodium COCHzCONHC -SO:NH2 w Ethylene diamine 30 4-(p-hydroxyethylamino) 6 phenylami- 26. N,N-l-methylethylenebisaceto-acetamide H no-metam'lic acid grams 3 onaooc1120oNHoH oHz-NHoooH2o0oH3 f 1000 H, V The developed silver images are bleached with 27. 2.4-pentanedione 55 potassium ferricyanide and fixed in an acid CHdCOCHzCOCHS hardening hypo solution. There is thus obtained a yellow dyestufi" image which is stable to acids and alkali oxidizing agents. No difficulty is inlgegfgygggggfiggile. volved in efiecting removal of the developer from y the emulsion by the usual washing procedure.
CNCHzCO-NH-O V Example II 31. a-Phenylsulfonylacetophenone. The procedure is the same as in Example I ex- 32. 2-(p benzoylacetamidophenyl)-1octadecylcepting that the 4-(p-hydroxyethylamino) -6- 5-benzimidazolesu1fonic acid. .75 phenylamino-metanilic acid is replaced by 4-(5- 28. 1.3-diphenyl-1.3-propanedione.
A photographic silver "bromide emulsion is exposed and color developed in a developer having the following composition:
After bleaching with rerricyanide bleach and 'iixing in an 'acidhardening fixer, there is obtained a magenta azine dye "image. No staining is observed, nor is any diiliculty met with in the complete removal or the developer from the emulsion by the usual water washing.
Example IV The procedure 'is the same as "in Example III excepting that 'the B-hydroxyquinoline is replaced by the ethyl urethane of phenyl J -acid. 'By working up the emulsion as in Example III a cyan azine dye "image isobtained.
Example V photographic silver halide emulsion carrying a silver 'halide image was developed for 15 minutes in ar developer of the -following composition:
fi-phenylamino 4 .(p hydroxyethylamino) -metanilic acid grams 4 Benzoylacet-2maphthylamine "5 sulronamide "grams" 3 Sodium sulfite do 60 Potassium carbonate do 20 Ethylene diamine d0 30 Water to cc 1000 The film, after washing, was bleached in ferricyanide-bleach and fixed in acid hardening hypo. There was directly obtained a yellow dye image, no alkaline treatment being necessary.
Example VJ An integral tripack \having as the bottom layer a red sensitive emulsion containing as a cyan color former 6-(4octadetsoxyphenylaniino? -'1- naphthOl-S-Sulfonicacid of the formula:
CpHyO-O-NH -so,H
as the middle layer a green sensitive emulsion containing as the magenta'color former 2-stearoylamino 6 (8 hydroxycinchoninylamino)- toluenei-sulfonie acid acid of the formula:
| CONH NC 0 CnHas SOaH and as the outermost layer a blue sensitive emulsion containing as the yellow color former 2 (benzoylacetamidophenyl) 1 octa'decyl 5- benz'imidazole sulfonic acid was exposed, developed in black and white, re-exposed and the residual silver halide developed for 12 minutes in a developer of the following composition:
G-phenylamino --4 (,6, hydroxyethylam'ino) -metanilic acid grams 8 Potassium carbonate do 20 sodium sulfite do 60 Potassium bromide do 10 Benzylamine do 5 Water to cc 1000 The film after development is washed, bleached in ferricyanide bleach, and fixed in an acid hardening hypo. There was thus obtained a positive dyestufi image in each of the three 1ayers-a cyan dye image in the bottom layer, a magenta dye image in the middle layer, and a brilliant yellow dye image in the top layer.
Similar results are obtained by replacing the metanilic acid derivatives of the above examples by other developers listed hereinabove.
Various modifications of the invention will occur to operators in this field, and I accordingly do not intend to be limited in the patent granted except 'as necessitated by the appended claims.
I claim:
1. A photographic developer comprising an alkaline aqueous :solution of an alkali metal sulfite and .a compound selected rrom the class of the following constitution:
and
NHR:
wherein R is selected from .the class consisting of hydrogen and alkyl, R1 is selected from the class consisting of alkyl, carboxyalkyl, hydroxyalkyl, aryl, carboxyalkylaryl, carboxyalkoxyaryl, hydroxyalkylaryl and hydroxyalkoxyaryl, R2 is an alkyl group substituted by a hydroxyl roup, X and Y are selected from the class consisting of hydrogen, alkyl, sulfo and carboxy, and Z; represents the atoms necessary to complete a G-membered isocyclic ring.
2. The composition as defined in claim 1 wherein Y is hydrogen and X is sulfo.
3. A photographic developer as defined in claim 1 wherein Y is hydrogen and X is sulfo and wherein the developer contains a color former capable of reacting with the oxidation products of a primary aromatic amino developer to form a dye image.
4. A photographic developer for producing azine dyestuff images on color development comprising aqueous alkaline solution of a color former capable of reacting with the oxidation products of a primary aromatic amino developer to form a dye image and 4-(fl-hydroxyethylamino)-6-pheny1- aminometanilic acid.
5. The composition as defined in claim 4 wherein the color former is S-hydroxyquinoline.
and
wherein R'is selected from the class consistin of hydrogen and alkyl, R1 is selected from the class consisting of alkyl, carboxyalkyl, hydroxyalkyl, aryl, carboxyalkylaryl, carboxyalkoxyaryl, hydroxyalkylaryl and hydroxyalkoxyaryl, R2 is an alkyl group substituted by a hydroxyl group, X and Y are selected from the class consisting of hydrogen, alkyl, sulfo and carboxy, and Z represents the atoms necessary to complete a G-membered isocyclic ring.
'7. The process as defined in. claim 6 wherein Y is hydrogen and X is sulfo.
8. The process of directlyproducing yellow dye images resistant to splitting by strong mineral acids which comprises developing a developable silver halide emulsion in the presence of an open chain keto methylene compound with a photographic developer containing as the active developing agent a compound of the following formula:
NR-R
r a Y 2 3 4 NH-Rz azine dyestuff images on color developmentcomand NH: 7 or wherein R is selected from the class consisting of hydrogen and alkyl, R1 is selected from the class of alkyl, carboxyalkyl, hydroxyallsylraryl; carboxyalkylaryl, carboxyalkoxyaryl, 'hydroxyalkylaryL'hydroxyalkoxyaryl, Rz'is an alkyl group substituted by a hydroxyl group, X and Y are selected from the class consisting of hydrogen, alkyl, sulfo and carboxy, and Z represents the atoms necesbenzoylacet' radical with a 4.6 diamino'metanilic acid in which the nitrogen atom in the-G-position is substituted by aryl and the nitrogen atom in the 4-position by hydroxy alkyl.
12. The process as definedin claim 11 wherein the 4.6-diaminometanilic acid is fi-phenylamino- 4 (fl-hydroxyethylaminoi metam'lic acid. y
13. A photographic developer for producing prising an aqueous alkaline solutionof 4- (/3-;hy droxyethylamino) -6-phenylaminometaniiic, P acid,
and an alkali metal sulfite:
, RTGI fr Ea 7 REFERENCES-CITED H The following references are of; record in the file ofthis'patent: T TES P T NTS UNITED Number Name Date 2,304,953 Peterson Dec. 15, 1942 2,489,440 Schmidt et a1. NOV. 1, 1949 FOREIGN PATENTS. '1 Number Country Date {$3,064 Great Britain May 6, 1943

Claims (1)

1. A PHOTOGRAPHIC DEVELOPER COMPRISING AN ALKALINE AQUEOUS SOLUTION OF AN ALKALINE METAL SULFITE AND A COMPOUND SELECTED FROM THE CLASS OF THE FOLLOWING CONSTITUTION:
US101913A 1946-01-10 1949-06-28 Color developers for the production of azine dye images Expired - Lifetime US2570116A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US640382A US2486440A (en) 1946-01-10 1946-01-10 Production of phenazonium dyestuff images

Publications (1)

Publication Number Publication Date
US2570116A true US2570116A (en) 1951-10-02

Family

ID=41210569

Family Applications (6)

Application Number Title Priority Date Filing Date
US640382A Expired - Lifetime US2486440A (en) 1946-01-10 1946-01-10 Production of phenazonium dyestuff images
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
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
US101913A Expired - Lifetime US2570116A (en) 1946-01-10 1949-06-28 Color developers for the production of azine dye images

Family Applications Before (5)

Application Number Title Priority Date Filing Date
US640382A Expired - Lifetime US2486440A (en) 1946-01-10 1946-01-10 Production of phenazonium dyestuff images
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
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

Country Status (6)

Country Link
US (6) US2486440A (en)
BE (6) BE470459A (en)
CH (5) CH280516A (en)
DE (6) DE817554C (en)
FR (6) FR939497A (en)
GB (5) GB644863A (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2611785A (en) * 1952-09-23 N-substituted x
US2687431A (en) * 1950-12-20 1954-08-24 Gen Aniline & Film Corp Process of preparing nitro phenylenediamines
US2695234A (en) * 1951-01-26 1954-11-23 Gevaert Photo Prod Nv Photographic development
US2700037A (en) * 1949-05-03 1955-01-18 Ciba Ltd Process for the manufacture of monoacyl acetyl compounds of primary amines
US2945761A (en) * 1957-07-29 1960-07-19 Eastman Kodak Co Reactivity of couplers incorporated in photographic emulsions
US3077403A (en) * 1960-05-31 1963-02-12 Gen Aniline & Film Corp Color former containing bis coupling functions
US3099559A (en) * 1959-08-31 1963-07-30 Gen Aniline & Film Corp Silver-free color reproduction process and composition therefor

Families Citing this family (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2575027A (en) * 1949-10-29 1951-11-13 Gen Aniline & Film Corp N-substituted 4, 6-diamino metanilic acids
US2594917A (en) * 1949-12-16 1952-04-29 Gen Aniline & Film Corp Suppression of proximity development with azine color developers
US2596926A (en) * 1949-12-16 1952-05-13 Gen Aniline & Film Corp Preparation of azine dye images
US2618559A (en) * 1950-03-21 1952-11-18 Gen Aniline & Film Corp Stain preventing shortstop bath for photographic azine dye images
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
US2691588A (en) * 1952-03-14 1954-10-12 Eastman Kodak Co Photographic developers containing 8-hydroxyquinolines
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
BE526742A (en) * 1953-02-24
GB802553A (en) * 1955-11-18 1958-10-08 Gen Aniline & Film Corp Improvements in or relating to colour photographic materials and processes
BE576817A (en) * 1958-04-03
NL255792A (en) * 1959-09-11
US3050394A (en) * 1959-09-30 1962-08-21 Gen Aniline & Film Corp Method of incorporating color couplers in hydrophlic colloids
US4511569A (en) * 1982-08-26 1985-04-16 Schering Corporation Tricyclic lactams and derivatives useful in increasing cardiac contractility
JPS59177554A (en) * 1983-03-28 1984-10-08 Fuji Photo Film Co Ltd Silver halide color photosensitive material
SE8302361D0 (en) * 1983-04-27 1983-04-27 Astra Laekemedel Ab NEW TRICYCLIC AMINES
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
US4847381A (en) * 1987-08-31 1989-07-11 American Cyanamid Company 2-Phenyl-4-quinoline carboxylic acids
US5260177A (en) * 1988-03-16 1993-11-09 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive material
US5223386A (en) * 1989-03-04 1993-06-29 Konica Corporation Cyan coupler
EP0386931A1 (en) * 1989-03-04 1990-09-12 Konica Corporation A novel cyan coupler
US4990436A (en) * 1990-01-23 1991-02-05 Eastman Kodak Company Cyan dye-forming couplers and photographic recording materials containing same

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2304953A (en) * 1941-08-08 1942-12-15 Eastman Kodak Co Photographic developer
GB553064A (en) * 1941-09-25 1943-05-06 Eastman Kodak Co Improvements in photographic developers
US2489440A (en) * 1945-05-03 1949-11-29 Naylor Brothers Ltd Conveyer

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB178986A (en) * 1921-02-11 1922-05-04 John Augustus Ward Improvements in and relating to advertising apparatus
US1782356A (en) * 1927-11-14 1930-11-18 Firm J R Geigy S A Manufacture of acid dyestuffs of the phenonaphthosafranine series
US1886809A (en) * 1929-09-04 1932-11-08 Gen Aniline Works Inc Arylated safranines and process of preparing them
BE369421A (en) * 1929-09-09
GB458664A (en) * 1935-03-21 1936-12-21 Eastman Kodak Co Improvements in and relating to colour forming developers and processes of colour development
DE767652C (en) * 1936-05-27 1953-03-02 Ig Farbenindustrie Ag Process for the color development of halogen silver emulsions
US2356475A (en) * 1936-07-07 1944-08-22 Eastman Kodak Co Phenolic and naphtholic couplers containing sulphonamide groups
US2306410A (en) * 1936-07-07 1942-12-29 Eastman Kodak Co Color development
US2196739A (en) * 1938-09-23 1940-04-09 Eastman Kodak Co Photographic developer for color photography
GB531312A (en) * 1939-03-31 1941-01-01 Eastman Kodak Co Improvements in and relating to colour forming developers and processes of colour development
US2193015A (en) * 1939-05-24 1940-03-12 Eastman Kodak Co Developer containing sulphonamide groups
GB536939A (en) * 1939-08-24 1941-06-03 Eastman Kodak Co Improvements in and relating to photographic colour development
BE442586A (en) * 1940-07-31
FR956698A (en) * 1941-09-11 1950-02-02
US2364350A (en) * 1941-11-06 1944-12-05 Eastman Kodak Co Photographic developer
US2400872A (en) * 1942-09-01 1946-05-28 Eastman Kodak Co Diamino-nu-alkyl phenazinium salts
US2394527A (en) * 1942-11-04 1946-02-05 Du Pont Color photography
GB576891A (en) * 1944-05-12 1946-04-25 John David Kendall Improvements in or relating to colour photography
BE465025A (en) * 1945-01-27
US2445252A (en) * 1947-04-10 1948-07-13 Gen Aniline & Film Corp Photographic elements containing urethanes of nu-substituted j acids as color formers

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2304953A (en) * 1941-08-08 1942-12-15 Eastman Kodak Co Photographic developer
GB553064A (en) * 1941-09-25 1943-05-06 Eastman Kodak Co Improvements in photographic developers
US2489440A (en) * 1945-05-03 1949-11-29 Naylor Brothers Ltd Conveyer

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2611785A (en) * 1952-09-23 N-substituted x
US2700037A (en) * 1949-05-03 1955-01-18 Ciba Ltd Process for the manufacture of monoacyl acetyl compounds of primary amines
US2687431A (en) * 1950-12-20 1954-08-24 Gen Aniline & Film Corp Process of preparing nitro phenylenediamines
US2695234A (en) * 1951-01-26 1954-11-23 Gevaert Photo Prod Nv Photographic development
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
US3077403A (en) * 1960-05-31 1963-02-12 Gen Aniline & Film Corp Color former containing bis coupling functions

Also Published As

Publication number Publication date
GB647638A (en) 1950-12-20
BE486433A (en) 1949-01-15
BE486432A (en) 1949-01-15
US2524741A (en) 1950-10-03
DE850385C (en) 1952-09-25
CH283787A (en) 1952-06-30
FR939497A (en) 1948-11-16
FR61004E (en) 1955-03-23
CH283788A (en) 1952-06-30
CH280517A (en) 1952-01-31
US2524725A (en) 1950-10-03
US2525503A (en) 1950-10-10
DE848155C (en) 1952-11-04
DE854889C (en) 1952-11-06
BE486434A (en) 1949-01-15
FR61006E (en) 1955-03-23
GB644863A (en) 1950-10-18
DE851163C (en) 1952-10-02
FR58855E (en) 1954-04-06
BE486431A (en) 1948-12-21
BE486430A (en) 1949-01-16
FR61005E (en) 1955-03-23
CH280516A (en) 1952-01-31
BE470459A (en) 1947-02-28
GB646348A (en) 1950-11-22
DE817554C (en) 1951-10-18
GB646490A (en) 1950-11-22
FR61007E (en) 1955-03-23
US2525502A (en) 1950-10-10
DE837959C (en) 1952-05-05
US2486440A (en) 1949-11-01
CH280518A (en) 1952-01-31
GB649811A (en) 1951-01-31

Similar Documents

Publication Publication Date Title
US2570116A (en) Color developers for the production of azine dye images
US3061432A (en) Pyrazolino benzimidazole color coupler
US2414491A (en) Photographic developer
US2424256A (en) Color developers comprising arylsulfonhydrazides and methods of developing with same
US2619419A (en) Production of color photographic images
US2672417A (en) Production of color photographic images
US2937089A (en) Supersensitized photographic emulsions containing sulfonated compounds
US2899305A (en) Colour photography
US2331326A (en) Production of colored photographic images
US3556796A (en) Silver halide emulsion containing naphthol colour couplers for cyan
US2333106A (en) Color photography
US2376679A (en) Production of color photographic images
CA1213891A (en) Color-forming sulfonamidodiphenylamine dye precursor that produces phenazine dye
US2886436A (en) 5-amino-8-hydroxyquinolines as coupling components for azine dye images
US2823998A (en) Process and material for producing photographic multi-color images
CA1158473A (en) Production of coloured photographic images by the silver dye-bleach process using a cinnoline derivative as the dye-bleach catalyst
US2575027A (en) N-substituted 4, 6-diamino metanilic acids
US2555127A (en) Production of azine dyestuff images
US3318700A (en) Application of dyestuff bleaching catalysts in the silver dyestuff bleaching process
US3038802A (en) Photographic color element with novel cyan dye
US2694636A (en) Light-sensitive element for color photography
US2269481A (en) Production of colored photographic images
US2163820A (en) Photographic developer
US2500487A (en) Yellow diffusion-fast color formers of the benzimidazole class
US2611785A (en) N-substituted x