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Home , Methine group

Patented Sept. 14, 1948 2,449,244

UNITED STATES PATENT OFFICE 2,449,244 THIoINDoxYL couPLERs FoR COLOR PHOTOGRAPHY Fritz W. H. Mueller and Abraham Bavley, Bing hamton, N.Y., assignors to General Aniline & - Film Corporation, New York, N. Y., a corpora tion of Delaware No Drawing. Application January 25, 1945, Serial No. 574,619 6. Claims. (CI, 95-6) 1. 2 This invention relates to the production of col the following specification in which its preferred ored photographic images by color-forming de details and embodiments are described. velopment, and more particularly to arylaldehyde This invention is based on the discovery that derivatives bridged by a single methine chain as arylaldehyde derivatives which are linked to color-forming couplers therefor. gether by a single methine (-CHF) chain in It is known that compounds containing meth the reactive coupling position normally occupied ylene groups whose are activated by by the arylimino group during azomethine dye other in the molecule, such as car formation will react in color-forming develop bonyl (CO) or (CN), readily combine di ment with the oxidation product of the developer rectly with arylnitroso compounds or indirectly 0 in the absence of sodium sulfite or sodium bisul with primary aromatic in the presence of fite, in the usual manner, to form dye images. It an oxidizing agent, through intermediate oxidiza has been found that the methine group of the tion products, to form. azomethine dyes. For ex color-former is displaced by the arylamino group ample, l-phenyl-3-methyl-5-pyrazolone reacts during dye image formation. This discovery is with p--dimethylaniline to form the azo 5 surprising and wholly unexpected since, ingen methine dye, -phenyl-4-dimethyl-aminophenyl eral, methine linkages are not readily displaced imino-3-methyl-5-pyrazolone. Alternatively, the by other groups in the absence of a reducing same dye results from the reaction of the above agent. mentioned pyrazolone with p-aminodimethylani The arylaldehyde derivatives bridged by a single line in the presence of an oxidizing agent such as, "20 methine chain of the present invention, are rep for example, potassium persulfate. resented by the following general formula: . . The ability of these so-called coupling com pounds to react with primary aromatic amines in C the presence of oxidizing agents forms the basis Yo-on of color development in photographic subtractive i Six color processes, in which the developing wherein R represents a grouping of atoms nece agent becomes oxidized locally with the forma essary to complete a five-membered or six-mem tion of the silver image and immediately reacts bered heterocyclic nucleus, e. g., oxythionaph with the coupling compound to form an azo 30 thene, methyloxythionaphthene, coumaranon, methine dye image in situ with the developed sil oxyselenonaphthene, thiobarbituric acid, barbi verimage...... turic acid, oxindole, homophthalimide thioox Arylaldehyde derivatives which are linked to azoledione, isohydantoin, rhodanine, selenazo gether by a single methine group and employed lonethione and the like, R1 represents an aro as filter and anti-halation dyes are already 35 matic group such as aryl, e.g., phenylnaphthyl, known. Compounds of this category are illus anthryl and the like. Said aryl group may be trated, for example, in United States Patent substituted by a radical such as an group, 2,036,546. It will be noted that the arylaldehyde e.g., methyl,ethyl, propyl, butyl, octyl, decyl, octa derivatives referred to in this patent are em decyl, stearyl, or any other, alkyl or alkylamino ployed as filter and anti-halation dyes which can 40 radical containing up to 24 atoms, amino be completely and permanently decolorized with groups, e. g., primary amino, secondary amino, in a short time in photographic developing solu such as methylamino, phenylamino and the like, tions containing sodium sulfite or sodium bisulfite. or tertiary amino such as dimethylamino, di It is an object of the present invention to pro phenylamino, etc., sulfamino or solubilizing wide a new class of color-formers for the produc 45 groups such as sulfonic or groups, tion of cyan and magenta, images by color-form and X represents either sulfur, oxygen, selenium, ing development. - benzo or a carbonyl radical. : A further object is to provide photographic These compounds are readily prepared by con emulsions and developer solutions which contain densing molecular proportions of an aromatic or a new class of color-formers for producing cyan cyclic with a five-membered or six and magenta, images in situ with photographic membered heterocyclic compound containing a imageS. . capable of reacting as described A still further object is to provide finished in United States Patent 2,036,546. photographs which contain stable dye images. In general, the compounds of the present in Other objects Will be apparent by reference to 55 vention are water insoluble. Their solubility in 2,449,244 3 4. water, however, is accomplished by the introduc AS examples of suitable aromatic primary lion of suitable solubilizing groups, e. g. sulfonic amino developing agents which may be employed or carboxylic acid groups into the aryl or hetero With the color coupling compound of the present cyclic nuclei of the above general formula. invention, there may be mentioned p-phenylene The compounds of the present invention when diamine, mono ethyl-p-phenylene diamine, di imployed as color-formers may ba added to the ethyl-O-phenylene diamine, 4,4'-diamino-di developer, providing they are not fast, to dif phenylamine, p-amino-dialkyl anilines, e. g., fusion in gelatin. Or to the silver-halide emul p-amino-dimethyl aniline and p-amino-di Sion in the form of a solution or a suspension in ethyl aniline. These compounds are prefer a suitable solvent. Such as 1 N-alcoholic sodium 10 ably used in the form of their salts such as or potassium hydroxide, acetone, ethyl , the hydrochloride or sulfate, since they are more isopropyl alcohol. etc. Dispersing agents. Such as Soluble and stable than the free base. The isopropylnaphthalene or any of the p-amino-phenols and their substitution products dispersing agents disclosed in United States may also be used where the amino group is un Patent 2,186,717 may be used in preparing the 15 substituted. All of these compounds are char Suspension of the Water insoll be color-formers acterized by the presence of a primary amino for incorporation into developers or silver-halide group in the phenyl nucleus which enables its emulsions. Instead of gelatin the color-formers oxidation product in the developer to couple with may be incorporated in other colioidal materials, the color-forming compound to form a dye image Such as, organic of cellulose, super-poly 20 in the emulsion adjacent to the individual par , polyesters or synthetic resins. The emul ticles of the silver image. The silver image may sion may be carried by a transparent medium be removed by bleaching in the Well-known man such as cellulose esters, super-polyamides. Syn ner to leave the color image in the gelatin layer. thetic resins or a non-transparent refiecting The following example is illustrative of a suit medium such as paper, or an opaque cellulose 25 able color developing solution to which the color . The emulsion may be coated as a single formers may be added either as such or in the layer on the Support, or superposed layers con form of a Solution in a suitable solvent, such as taining the couplers may be coated on one or ethyl alcohol, 0.1. Nealcoholic potassium hydrox both sides of the support. The superposed layers ide, acetone and the like, or they may be dissolved may be differentially sensitized for the formation 30 in dilute sodium carbonate, sodium or potassium of a color image in the well-known manner. hydroxide solution, etc., and, added to the de When incorporating the color-formers into veloper prior to color development: photographic silver-halide emulsions, it is essen tial that the substitution of the aryl or the five p-Amino-diethylaniline HCl -----grams. 2.0 membered or six-membered heterocyclic nucleus 35 Sodium earbonate (anhydrous)---do---- 50.0 in the above general formula be such that it will Potassium bromide------do---- 0.2 prevent the color-formers from migrating from Water to make------liter- 1. One layer to another, otherwise color distortion From the above example, it will be seen that will result upon color-forming development. the developing solution does not contain sodium Several methods have been proposed to prevent 40 Sulfite. The presence of this compound is not migration of color-formers from silver-halide necessary, Since azomethine dye formation takes emulsion layers by rendering such color-formers place in its absence during color-forming -de “fast to diffusion in gelatin.' This result may velopment. However, in order to retard the de be accomplished in several ways, as for example, veloping solution from deterioration by absorp. by substituting the aryl, or the five-membered or 45 tion of oxygen from the atmosphere, a quantity six-membered heterocyclic nucleus with suitable ranging from 2 to 5 grams may be added as a groups which impart substantive characteristics preservative, - to the color-formers which combine permanently During the course of the color-forming develop With the gelatin and other colloidal materials of ment, the reaction between the arylaldehyde de the silver-halide emulsion, or by enlarging the 50 rivative and an oxidized primary amine develop group of the color-former with a long ing agent, the arylaldehyde derivative splits at chain alkyl radical so that, the color-formaer is the methine chain and is replaced by the nitro incapable of diffusing from the gelatin or other gen of the oxidized aromatic primary amine. The colloidal material. Examples of such methods reaction with p-dialkyl amino aniline to form an which render color-formers fast to diffusion by 55 azomethine dye may be pictured in the following imparting substantive characteristics thereto are manner: disclosed in United States Patent 2,179,228. Ex amples of color-formers which are rendered fast to diffusion by enlarging the substituent group g - are disclosed in United States Patants 2.178 612; 60 C \ /"CH to 2,179.244; 2,179.234; 2.179.238-9; 2.179344; 2.186 (45; 2,186,719: 2,186,732-3-4; 2,186 849; R x/ C=CH-R, +HN-Krear-e- X N CH seen 2,186,851-2; 2.200.306: 2,280.722; 2.292.575: 2,303,928 and 2.307399. By reference to the lat ter patents, it will be noted that the color-formers 65 are inodified by the inclusion of radicals of resins. polypeptides, hydrogenated ring systems, ()--N-(D-x carbohydrates, leng alkyl chains. and by having x/ sees CHs. the Substituent radical recur a number of times Many Specific objects, features and advantages in the final molecule. It is to be understood that O of this invention will become apparent to those the substituent group of the color-formers of the skilled in the art from the specific examples ap present invention, in addition to those previously pearing below. The following examples are not mentioned, include Substantive groups or molecul to be considered as limiting the invention, but lar enlarging groups for the purpose of render are merely illustrative of methods of carrying it ing the arylaldehyde derivatives fast to diffusion. 5 Out. 2,449,244 5 6 Eacample I Equimolar quantities of oxythionaphthene and 2-benza-5-methyl-thioindoxyl 4-sulfo-5-stearylaminobenzaldehyde were added to a quantity of aqueous ethanol sufficient to O effect solution. To this was added 3.5 cc. of con centrated CH1 and the whole allowed to stand for \ 2 days. Sufficient KOH was added to neutralize c-ch-( ) the hydrochloric acid and the whole evaporated and recrystallized from ethanol. Equimolar quantities of methyloxythionaph One gram of the above product was dissolved thene and benzaldehyde were dissolved in hot 0 in 2.0 cc. of 1 N-alcoholic KOH and added with ethanol to which was added several cc. of concen thorough mixing to 100 cc. of gelatin silver bro trated HCl. This was allowed to stand overnight. mide-iodide emulsion. After coating the emul The crystalline substance formed was filtered and Sion containing the color former onto a suitable recrystallized from glacial acetic acid, and again support and drying, the film was exposed and from ethanol. A yellow crystalline substance 15 color developed to yield a magenta dye image to readily soluble in alcoholic KOH was obtained. gether with the silver image. The latter was re One gram of the above product was dissolved moved by bleaching in the well-known manner. in 20 cc. of ethyl alcohol. 2 cc. of the solution was Eacample V - then added to the color developing solution and used for the development of exposed silver-halide 20 2-(4'-dimethylamino-6'-sulfobenzal) -thiobarbituric acid emulsion. An excellent magneta dye image was B obtained together with the silver image. The N-CO C latter was readily removed by bleaching. Eacample II Y-c o/De-ch-K X-NCYor, 25 SOH kiss; 2-benzal-thioindoxyl One gram of the above compound obtained ac O cording to Example WI of United States Patent /C 2,036,546 was dissolved in a small quantity of a N 5% sodium carbonate solution. This Solution 30 was added to the color developing solution of an exposed silver halide emulsion. An excellent >-el-KD cyan dye image was obtained together With the Equimolar quantities of oxythionaphthene and silver image. The silver image was removed by benzaldehyde were dissolved in hot absolute etha beaching in the Well-known manner. nol. To this solution 3 cc. of concentrated HC 35 While We have disclosed the preferred embodi were added. On standing 14 hours, yellow crys ments of Our invention and the preferred modes tals formed which were filtered off and recrystal of carrying the same into effect, it will be readily lized from ethanol. apparent to those skilled in the art that many One gram of the above product was dissolved variations may be made therein without depart in 20 cc. of ethyl alcohol. 2 cc. of the solution 40 ing from the spirit and scope thereof. Accord was then added to the color developing solution ingly, the scope of our invention is to be limited and used for the developement of exposed silver only by the following claims. halide emulsion. An excellent magenta dye im We claim: age was obtained together with the silver image. 1. A color-forming photographic developer The silver image was removed by bleaching. 45 comprising an aromatic primary amino develop Eacample III ing agent and a coupler compound of the for 2-(3'-sulfobenzal)-thioindoxy mula: SOs O /8O-on-O 50 (N Equimolar quantities of oxythionaphthene and wherein R represents the atoms necessary to m-sulfobenzaldehyde were added to a quantity 55 complete a six-membered isocyclic ring, and R1 of aqueous ethanol sufficient to effect solution. represents an aromatic radical. To this was added 3.5 cc. of concentrated HCl 2. A method of producing a dye image in a ge and the whole allowed to stand for 2 days. Sufi latino silver halide emulsion which comprises ex cient KOH was added to neutralize the hydro posing the emulsion and developing it with an chloric acid and the whole evaporated and re 60 aromatic primary amino developing agent in the crystallized from ethanol. presence of a coupler compound of the formula: One gram of the above product was dissolved O in 20 cc. of ethyl alcohol. 2cc. of the Solution was I then added to the color developing solution and used for the development of exposed silver halide 65 R CecCE-R emulsion. An excellent magenta dye image was A. obtained together with the silver image. The lat OS ter was removed by bleaching. wherein R represents the atoms necessary to com Eacample IV plete a six-membered isocyclic ring, and R1 rep 2-(4-sulfo-5'-stearylaminobenzal)-thioindoxy 70 resents an aromatic radical. 3. A color-forming photographic developer o O comprising an aromatic primary amino develop ing agent and 2- (3'-sulfobenzal) -thioindoxyl. )-on-O-son 4. A color-forming photographic developer S / NaCOCH 5 comprising an aromatic primary amino develop 2,449,244 7 8 ing agent and 2-(4'-sulfo-5'-stearylaminoben Zal) -thioindoxyl. . . . UNITED STATES PATENTS 5. The method of producing a dye image in a Number Name Date gelatino silver-halide emulsion layer which com 2,036,546 Schneider ------Apr. 7, 1936 prises exposing the layer and developing it with is 2,133,937 Middleton et al. ----- Oct. 18, 1938 an aromatic primary amino deveolping agent in 2,186,849 Wiemanns et al. ------Jan. 9, 1940 the presence of 2-(3'-sulfobenzal) -thioindoxyl. 2,213,986 Kendall ------Sept. 10, 1940 6. The method of producing a dye image in a 2,220,123 Schwarc ------Nov. 5, 1940 gelatino Silver-halide emulsion layer which com 2,274,782 Gaspar ------Mar. 3, 1942 prises exposing the layer and developing it with 0 2,397,865 Jennings ------Apr. 2, 1946 an aromatic primary amino developing agent in 2,397,867 Jennings ------Apr. 2, 1946 the presence of 2-(4'-sulfo-5'-Stearylaminoben Zal) -thioindoxyl. FOREIGN PATENTS Number Country Date FRITZ W. H. MUELLER. 5 481,274 Great Britain ------Mar. 8, 1938 ABRAHAM BAWLEY. . 513,596 Great Britain ------Oct. 17, 1939 REFERENCES CITED OTHER REFERENCES Beilstein, Handbuch der Organischen Chemie, The following references are of record in the 4th edition, vol. XXVI/XXVII, first supplement file of this patent: 1938.page 3olicited.