US 4,345,017 AGrant
Photographic Products and Processes With a pH Sensitive Xanthene Light Screening Dye
Issue Date:1982-08-17
•66 Claims
•1 Drawing Sheets
Abstract
The present invention is concerned with photographic products and processes employing certain pH-sensitive xanthene compounds as light-screening dyes, which compounds may be represented by the formulae ##STR1## wherein A and A', the same or different, are selected from ##STR2## each R is hydrogen or an electron-withdrawing group; each R.sup.1 is hydrogen or alkyl; each R.sup.2 is hydrogen, alkyl or an electron-withdrawing group; R.sup.3 is hydrogen or alkyl; R.sup.4 is alkyl; and n is 0 or 1 and which compounds in their colored, i.e., ring-opened form may be represented by the formulae ##STR3## wherein A, A', R.sup.3, R.sup.4 and n have the same meaning given above and Z is an anion.
Metadata
Assignee
- Polaroid Corporation
Inventors
- Richard L. Cournoyer
- James W. Foley
Application Information
Application Number:US 1944681
Filing Date:1980-10-06
Priority Date:1980-10-06
Art Unit:166
Classifications
IPC:
G03C 700G03C 1400G03C 184G03C 554
Field of Search:
430221;503;504;513;543;376;955
Patent Drawings (1 sheets)
Description
Background of the Invention
1. Field of the Invention
This invention relates to photography, and more particularly, it relates to the use of certain xanthene compounds in photographic products and processes.
2. Description of the Prior Art
It is well known that photographic film, and especially multicolor films, may and generally do vary from lot to lot, notwithstanding efforts to "repeat" previous films. Manufacturers of multicolor photographic films have developed a number of procedures to minimize the effects upon the final multicolor image of unavoidable variations in the manufacturing operations. These variations are reflected primarily in shifts in color balance as reflected in mismatching of the D log E curves of the individual red, green and blue exposures. Equipment used to coat multicolor films is highly precise but variations between intended coverage of silver halide and/or the dye image-forming material do occur. Repeat batches of silver halide emulsions may, and usually do, vary in their photographic response. Individual layers may be dried to slightly different degrees. Films are stored for a period of time after coating to allow the films to "age", so that changes in sensitometry following coating have an opportunity to reach a plateau prior to sale. If the film is designed to be developed by a photofinisher or in a darkroom, processing of the exposed multicolor film is controlled within very narrow limits, typically within plus or minus a half degree of a prescribed temperature, in order to minimize sensitometric variations from film to film. Where the multicolor film is of the negative type, an opportunity to adjust the sensitometry occurs in printing the desired final positive image, during which operation the printing exposure may be appropriately color filtered.
The basic sources of sensitometric variations noted above exist also in multicolor diffusion transfer films, with the added complication that once the film is shipped, the sensitometric properties are essentially fixed. The opportunity for adjustment provided in darkroom processing, practically speaking, is unavailable for users of self-developing films. While professional and advanced amateur photographers may be skillful enough to utilize color correction filters to at least partially "rebalance" the color balance, ordinary users of the film would only be confused by such additional operations.
It is well known to use light-screening dyes in photographic elements. Such a dye may be incorporated as a filter dye in a light-sensitive emulsion layer(s) or in a layer coated over one or more light-sensitive emulsion layers or between two differently color-sensitized emulsion layers to modify the light record in the emulsion layer or to control the spectral composition of light falling on the underlying light-sensitive layer, or it may be incorporated as an antihalation dye in a non-light-sensitive layer positioned on either side of a support carrying the light-sensitive layer(s).
The dyes employed for these purposes, in addition to having the requisite spectral absorption characteristics for their intended use should not have any adverse effect on the properties of the light-sensitive emulsion layer(s), and also, should be capable of being decolorized or removed during photographic processing so as not to leave stain in the processed photographic element. In photographic processes where the dye is removed by being dissolved in a processing solution, it is usually preferred that the dye also decolorize in order to avoid contamination of the processing solution and to prevent staining from residual dye in the processed light-sensitive element.
Though various classes of dyes have been proposed for use in antihalation and color correction filter layers, the dyes heretofore employed have not been altogether satisfactory. Some of the dyes tend to reduce sensitivity, fog or exert other adverse effect on the light-sensitive material. However, the major drawback of previously employed dyes is their tendency to cause stain due to incomplete decolorization or reversal of some of the decolorized form to the original colored form. For example, some classes of dyes rely on the presence of a reagent, such as, a sulfite for "bleaching", i.e., decolorization and unless the dyes are removed from the light-sensitive material during or after processing, their color may reappear in time.
Among the classes of light-screening dyes used previously are the triarylmethanes. For example, U.S. Pat. Nos. 1,879,537; 1,994,876; 2,350,090 and 3,005,711 disclose the use of fuchsone-type dyes in antihalation layers, and U.S. Pat. Nos. 3,406,069 and 3,615,548 are concerned with the metal chelates of fuchsone dyes as antihalation dyes. These and other types of triarylmethane dyes suffer from one or more of the drawbacks discussed above, and in particular, prior dyes of this type have been difficult to keep decolorized at the pH's normally encountered during processing subsequent to "bleaching" and in the final product. Xanthenes have been employed in antihalation layers that are removed during photographic processing. For example, U.S. Pat. Nos. 2,182,794; 2,203,767 and 2,203,768 disclose the use of rhodamine dyes in certain antihalation layers that are removed during processing in an acid bath or a plain water rinse bath depending upon the solubility characteristics of the particular layer.
Copending U.S. Patent Application Ser. No. 169,843 of Richard L. Cournoyer and James W. Foley filed July 17, 1980 (now U.S. Pat. No. 4,304,834), a continuation-in-part of abandoned U.S. Patent Application Ser. No. 106,901 filed Dec. 26, 1979; U.S. Patent Application Ser. No. 106,905 of James W. Foley, Louis Locatell, Jr. and Charles M. Zepp filed Dec. 26, 1979 (now U.S. Pat. No. 4,258,118); and U.S. Patent Application Ser. No. 106,938 of Richard L. Cournoyer and James W. Foley also filed Dec. 26, 1979 (now U.S. Pat. No. 4,258,119), are concerned with certain 3,6-disubstituted-xanthene compounds possessing a phenyl moiety in the 9-position which is substituted in the position ortho to the 9-carbon atom with a group that undergoes an irreversible cleavage reaction in base to provide a moiety that adds to the 9-carbon atom to form a new ring-closed compound which is colorless. As disclosed and claimed therein, these compounds are useful as photographic light-screening dyes which offer advantages over prior light-screening dyes because of their ability to decolorize completely and irreversibly to a substantially inert colorless product.
The present invention is concerned with a different class of xanthene compounds useful as photographic light-screening dyes which do not undergo an irreversible cleavage reaction but decolorize in response to a change in pH. However, like the xanthene dyes of the aforementioned patent applications, they are free from the deficiencies associated with previous light-screening dyes. The subject pH-sensitive dyes are initially colored, i.e., capable of absorbing visible radiation at a given pH, usually about pH 6 or below and are converted to a colorless or non-light-absorbing form above said pH. Because of their ability to decolorize completely in base without requiring an additional reagent, such as, a sulfite for the "bleaching" reaction and because they remain colorless in aqueous solution above said given pH to pH 14, compounds may be selected for use in a given photographic process on the basis of final pH so that they may be retained in the photographic light-sensitive element without the possibility of color reappearing in time. Besides being non-staining, the compounds usually are substantially inert with respect to the light-sensitive material and thus, may be positioned, for example, in a layer adjacent to a silver halide emulsion layer without having any adverse effect on the properties of the emulsion.
Summary of the Invention
It is therefore the primary object of the present invention to provide photographic products and processes which employ certain colored xanthene compounds which are rendered colorless when contacted with an alkaline photographic processing composition.
It is another object of the present invention to provide photographic multicolor diffusion transfer film units which contain a layer of said xanthene dye(s) so positioned that photoexposure is effected therethrough to correct imbalances in the color sensitometry of the multicolor photosensitive element of said film units.
Other objects of this invention will in part be obvious and will in part appear hereinafter.
This invention accordingly comprises the process involving the several steps and the relation and order of one or more of such steps with respect to each of the others and the products and compositions possessing the features, properties and the relation of elements which are exemplified in the following detailed disclosure, and the scope of the application of which will be indicated in the claims.
For a fuller understanding of the nature and objects of the present invention, reference should be had to the following detailed description taken in conjunction with the accompanying drawings.
Brief Description of the Drawing
FIG. 1 is a diagrammatic, enlarged cross-sectional view of a diffusion transfer film unit incorporating a dye of the present invention as a bleachable antihalation dye layer; and
FIG. 2 is a diagrammatic, enlarged cross-sectional view of another diffusion transfer film unit incorporating a dye of the present invention as a color correction filter dye.
Detailed Description of the Invention
Specifically, the compounds employed in accordance with the present invention may be represented by the formulae ##STR4## wherein A and A', the same or different, are selected from ##STR5## each R is hydrogen or an electron-withdrawing group; each R.sup.1 is hydrogen or alkyl; each R.sup.2 is hydrogen, alkyl or an electron-withdrawing group; R.sup.3 is hydrogen or alkyl; R.sup.4 is alkyl; and n is 0 or 1. When R is an electron-withdrawing group, it may be substituted on any of the available carbon atoms of said indolinyl moiety, and when R.sup.2 is an electron-withdrawing group, it may be ortho, meta or para to said N atom. By an electron-withdrawing group is meant a group having a positive sigma value as defined by Hammett's Equation.
Typically, said R.sup.1, R.sup.2 groups, when alkyl, contain 1 to 7 carbon atoms, e.g., methyl, ethyl, n-propyl, n-butyl, s-butyl, n-hexyl and benzyl, and said R.sup.3 and R.sup.4 groups are lower alkyl containing 1 to 4 carbon atoms, and preferably, methyl. Though any electron-withdrawing group is suitable, where it is desirable that the light-screening dye be in its colorless form at a pH in the neighborhood of 4 to 5, the R.sup.2 group(s) should be electron-withdrawing group(s) which have a positive sigma value (.sigma..sup.-) greater than 0.6. Such electron-withdrawing groups include nitro; cyano; ##STR6## --SO.sub.2 N(CH.sub.2 Ph).sub.2 ; and --SO.sub.2 N(CH.sub.3).sub.2. The sigma values for these and other groups, such as, --CHO, --COOH, --COOC.sub.2 H.sub.5 and --CONH.sub.2 have been reported by Eugen Muller, Methoden Der Organischen Chemie, Georg Thieme Verlag, Stuttgart, 1970, p. 78 in terms of .sigma..sup.- values based on the ionization of p-substituted phenols.
As noted above, the subject xanthene compounds are pH-sensitive dyes and are colored, i.e., capable of absorbing visible radiation at a given pH of about pH 6 or below and have a colorless or non-light-absorbing form above said given pH. The subject compounds, of course, are in their light-absorbing or ring-opened form as initially disposed in a processing composition permeable layer of a photographic film unit and upon application of an aqueous alkaline processing composition, they are converted to their non-light-absorbing or ring-closed form. Their ring-opened form is illustrated below: ##STR7## wherein A, A', R.sup.3, R.sup.4 and n have the same meaning given above and Z is an anion.
Specific examples of compounds within the scope of the present invention are as follows: ##STR8##
The subject light-screening dyes may be prepared in a known manner, for example,
(a) by reacting a 3,6-disubstituted compound of the formula ##STR9## wherein A and A' have the same meaning given above with phosphorus pentachloride or thionyl chloride to give the corresponding sulfonyl chloride of the formula ##STR10##
(b) reacting said sulfonyl chloride with ammonia to give the corresponding cyclic sulfonamide of the formula ##STR11##
(c) and, optionally, reacting said cyclic sulfonamide with an alkylating agent to give the corresponding N--R.sup.3 sulfonamide of the formula ##STR12##
The starting material used in step (a) may be prepared in a known manner by replacing one of the chloro groups of sulfonefluorescein dichloride with the selected indoline or aniline compound and then reacting this intermediate with another equivalent of the selected indoline or aniline compound to replace the remaining chloro group. Where the 3,6-substituents are the same, the starting material also may be prepared by reacting sulfone-fluorescein dichloride with two equivalents of the selected indoline or aniline compound to give the corresponding disubstituted compound. If one or both of the 3,6-substituents is anilino, the compound may be reacted with an alkylating agent to substitute the N atom of said anilino group(s). Where both 3,6-substituents are anilino, they may be alkylated in a stepwise fashion and the alkyl groups may be the same or different.
Starting materials useful in the synthesis of the compounds of the present invention are disclosed and claimed in copending U.S. Patent Application Ser. No. 106,898 of Louis Locatell, Jr. and Charles M. Zepp filed Dec. 26, 1979.
The sulfo-substituted compounds may be prepared by reducing the compounds of step (c), reacting with chlorosulfonic acid in a solvent, such as, methylene chloride to give mainly monosulfonated compound or in a more polar solvent, such as, acetic anhydride to give essentially disulfonated compound, and then oxidizing to the product. Alternatively, the sulfonated compounds may be prepared by treating the sulfo-substituted xanthene light-screening dyes of aforementioned U.S. Patent Applications Ser. Nos. 106,901 and 106,938 with aqueous alkali.
The following examples are given to further illustrate the present invention and are not intended to limit the scope thereof.
Example 1
Preparation of the compound having the formula ##STR13##
(a) A mixture of 81 g (0.2 M) of sulfonefluorescein dichloride (3,6-dichlorosulfofluorescein) ##STR14## and 100 g (0.84 M) of indoline in 3300 ml absolute methanol was heated at reflux for three hours. After a short time, the product began to precipitate from solution. The product was filtered hot, washed with ethanol (2.times.500 ml), diethyl ether (2.times.500 ml), air dried overnight and then dried in vacuo to give 107.4 g of the compound ##STR15##
(b) The compound of step (a) 100 g (0.175 M) in 1500 ml of chloroform was treated with 73 g (0.35 M) of phosphorus pentachloride. The stirred mixture was heated at reflux for approximately 5 hours, then allowed to stir overnight while cooling to room temperature. The mixture was treated with 500 ml water (no exotherm was observed at this stage) and then allowed to stir for 10 minutes. The mixture was transferred to a 4000 ml separatory funnel and the chloroform layer separated. The chloroform layer was washed with water (2.times.1000 ml) and dried over anhydrous magnesium sulfate. The magnesium sulfate was filtered, and the filtrate containing the corresponding sulfonylchloride compound ##STR16## was cooled to 0.degree. C. (dry ice-acetone bath).
(c) The filtrate of step (b) was then saturated with anhydrous ammonia. The mixture was filtered to remove the NH.sub.4 Cl and the solvent evaporated under reduced pressure. The residue was continuously extracted with methanol by the use of a Soxhlet extractor over the weekend. The light blue solid which remained was dried in vacuo to give 71.8 g of the title compound. This material was essentially single spot on TLC (chloroform) R.sub.f =0.41; a minor component was observed at the origin (starting material). Melting range 258.degree.-61.degree. C. (d).
Example 2
Preparation of the compound having the formula ##STR17##
A slurry of the compound of Example 1 60 g (0.11 M) in 750 ml diglyme (previously dried over 4 A molecular sieves) was treated with 14.8 g (0.132 M) of potassium t-butoxide and allowed to stir at room temperature for about 45 minutes during which time solution takes place. The dark-brown solution was cooled in an ice-bath and treated with 12.5 ml (16.65 g; 0.132 M) of dimethyl sulfate all at once. The resulting mixture was allowed to warm to room temperature with stirring overnight.
The mixture was worked up in two portions. Approximately one half of the reaction mixture was poured into 3500 ml water containing 175 g of sodium chloride with stirring. After stirring for about 15 minutes, the product was filtered, washed voluminously with water and dried in vacuo. The other half of the reaction mixture was worked up in the same manner to yield 59.6 g of the title compound. This material was essentially single spot by TLC (chloroform); however, there was a minor component at the origin.
Example 3
Preparation of the compound having the formula ##STR18##
The compound having the formula ##STR19## was treated with aqueous 1 N sodium hydroxide to give the title compound.
Example 4
Preparation of the compound having the formula ##STR20##
The compound having the formula ##STR21## was treated with aqueous 1 N sodium hydroxide to give the title compound.
Example 5
Preparation of the compound having the formula ##STR22##
(a) A mixture of 10.0 g (0.05 M) of sulfonefluorescein dichloride ##STR23## and 20.26 g (0.05 M) of p-(N,N-dimethylsulfonamido)aniline in 160 ml of 2-methoxyethyl ether were stirred together for 24 hours, filtered, washed with a small amount of 2-methoxyethyl ether, then with ether and dried in vacuo to give 18.53 g of the compound ##STR24##
(b) The above compound, 20.0 g (35.1 mM) and 14.1 g (70.3 mM) of p-(N,N-dimethylsulfonamido)aniline and 20 ml 1-methyl-2-pyrrolidinone were heated in an oil bath at 170.degree. C. under an atmosphere of nitrogen for 4 hours. The deep magenta mixture was then treated with 100 ml 1-methyl-2-pyrrolidinone, cooled to room temperature and poured into a solution of 200 ml conc. HCl and 1400 ml water. This mixture was centrifuged, and the residue was washed with saturated sodium chloride solution and placed in a crystallizing dish to air dry over the weekend. The residue, which contained a considerable amount of sodium chloride, was then dried under vacuum at (70.degree. C.) for 4 hours to give 25.4 g of crude material comprising the compound ##STR25##
(c) The compound prepared in step (b), 25.4 g, (34.7 mM) was dissolved in 300 ml dry dimethylsulfoxide. (Some solid material was observed floating in the solution which was probably sodium chloride.) A 50% sodium hydride dispersion, 6.72 g, was added to the above solution all at once and then allowed to stir at room temperature for 11/2 hours. The green solution was cooled in an ice bath and iodomethane (300 g) was added dropwise over a period of about one hour. The mixture was allowed to warm to room temperature overnight with stirring. The mixture was poured into three liters of water containing 200 ml conc. HCl and extracted with methylene chloride (6.times.200 ml). The combined methylene chloride extracts were washed with a 2 N HCl solution (5.times.1000 ml) and dried over sodium sulfate. The solvent was removed in vacuo to give 10.41 g of the compound ##STR26##
(d) The compound prepared in step (c), 10.4 g (about 13.7 mM), was dissolved in 150 ml of chloroform and treated with 6.25 g (30 mM) of phosphorus pentachloride. The resulting mixture was heated at reflux for 5 hours and then allowed to stir at room temperature overnight. The purple solution was transferred to a separatory funnel, washed with water (2.times.75 ml) and then dried over magnesium sulfate. The mixture was filtered to remove the magnesium sulfate and the filtrate cooled in an ice bath. The filtrate comprised the sulfonyl chloride of the formula ##STR27##
(e) Ammonia gas was bubbled into the filtrate obtained in step (d) until saturated. It was then allowed to come to room temperature and stirred overnight. (The purple color of the solution became much less intense.) The mixture was filtered to remove the salts, and the solvent removed from the filtrate in vacuo leaving 10.67 g of residue. The residue was taken up in 25 ml chloroform:methanol (100:1), applied to medium pressure liquid chromatography column and eluted with 1000 ml chloroform:methanol (100:1), then with chloroform:methanol (50:1). Fractions 2 to 7 were combined and the separation repeated eluting with chloroform:methanol (100:1) to give 5.0 g (90-95% purity) of the title compound.
Example 6
Preparation of the compound having the formula ##STR28##
The compound prepared in Example 5, 4.85 g (6.4 mM) was dissolved in 60 ml of dry 2-methoxyethyl ether. To this solution, 0.88 g (7.9 mM) of potassium-t-butoxide was added all at once and the resulting solution allowed to stir at room temperature for one hour. The dark mixture was cooled in an ice bath and 0.75 ml (1.0 g; 7.9 mM) of dimethylsulfate was added all at once. The mixture was allowed to come to room temperature overnight and then was poured into 600 ml of water containing 30 g of sodium chloride. The mixture was stirred for about 15 minutes, filtered and the product washed with water. The product was taken up in about 100 ml of methylene chloride, washed with saturated sodium chloride solution (2.times.75 ml) and dried over sodium sulfate. Methylation did not go to completion so the methylation was repeated on the dried material which was dissolved in 60 ml dry 2-methoxyethyl ether and then treated with 0.95 g (8.47 mM) of potassium t-butoxide. This mixture was heated for one hour at 50.degree., then cooled in an ice bath. The mixture was then treated with 0.80 ml (1.068 g; 8.47 mM) of dimethyl sulfate. The resulting reaction mixture was allowed to come to room temperature and stirred for 5 days. The mixture was poured into 600 ml water containing 30 g of sodium chloride and allowed to stir for 15 minutes. The reaction product was filtered, washed with water and dissolved in approximately 100 ml of methylene chloride. The methylene chloride solution was washed with saturated sodium chloride solution and then dried over sodium sulfate. The solvent was removed to give 3.7 g of the title compound.
Example 7
Preparation of the compound having the formula ##STR29##
(a) A mixture of 68.9 g (0.17 M) of sulfonefluorescein dichloride, 50 g (0.36 M) 2-methylthioaniline and 7.26 g (0.18 M) magnesium oxide in 135 ml of dimethyl sulfoxide was heated at 140.degree.-145.degree. C. under nitrogen with stirring for 2.5 hours and then poured into 1500 ml of 2 N hydrochloric acid with vigorous stirring. The mixture was stirred for about one hour, the crude reaction product filtered, washed voluminously with water and dried in vacuo overnight to give 94.9 g of solid comprising the compound of the formula ##STR30##
(b) To a mixture of 50 g (0.082 M) of the compound prepared in step (a) in 500 ml of dimethyl sulfoxide under an atmosphere of nitrogen was added 19.65 g of 50% sodium hydride (previously washed with hexane; .ident.9.82 g, 0.41 M). The resulting mixture was allowed to stir at room temperature for two hours, and then 100 g (0.70 M) of iodomethane was added dropwise to the green solution. The mixture turned magenta in color within minutes. The mixture was allowed to stir at room temperature over the weekend, then poured into 6000 ml 2 N hydrochloric acid, stirred for approximately one-half hour and filtered. The filter cake was treated with approximately 1200 ml of methylene chloride, washed with 1 N hydrochloric acid (4.times.500 ml), 1/2-saturated sodium chloride solution (1.times.500 ml) and then dried over magnesium sulfate. The solvent was evaporated under reduced pressure leaving 57.67 g of crude reaction product. High pressure liquid chromatography of the crude product gave 20.47 g of the compound having the formula ##STR31## Overall yield from sulfonefluorescein was 35% by weight.
A 1.0 g sample was dissolved in a minimum amount of methylene chloride, precipitated in about 100 ml of ether, and the precipitate filtered and dried in vacuo. (Ethanol: .lambda.max 543 nm-Epsilon 98,000).
(c) A solution of 10.0 g (15.7 mM) of the compound of step (b) in 75 ml methylene chloride was added dropwise to a solution of 20.2 g of 80-90% m-chloroperoxybenzoic acid (equivalent to 16.2-18.2 g) in 400 ml methylene chloride. The temperature increased from 18.degree. to 32.degree. C. The mixture was allowed to stir at room temperature overnight. The mixture was then filtered to remove a small amount of m-chlorobenzoic acid. The filtrate was washed with 10% aqueous sodium hydrogen sulfite (3.times.250 ml), 5% aqueous sodium bicarbonate (3.times.250 ml), 1/2-saturated sodium chloride solution (2.times.250 ml) and dried over magnesium sulfate. The solvent was evaporated under reduced pressure, and the residue dried under high vacuum for about one hour to give 9.7 g of the compound of the formula ##STR32## (Ethanol: .lambda.max 534 nm-Epsilon 105,000)
(d) To a solution of 17.89 g (24.45 mM) of the compound of step (c) dissolved in 400 ml of chloroform was added 10.6 g (50.9 mM) of phosphorus pentachloride. The resulting mixture was heated at reflux for 6 hours, then allowed to come to room temperature overnight. The reaction product comprising the compound of the formula ##STR33## was used directly in the next step without isolation from the reaction mixture.
(e) The reaction mixture of step (d) was cooled to about 5.degree. C. in an ice-bath. Then anhydrous NH.sub.3 gas was bubbled into the mixture until it was saturated. The temperature rose from 5.degree. to 22.degree. C. The ice-bath was removed and the reaction mixture allowed to warm to room temperature. After 6 hours of stirring, the mixture was filtered to remove the salts. The filtrate was washed with water containing a little sodium chloride (3.times.200 ml) and then dried over anhydrous sodium sulfate. The solvent was evaporated under reduced pressure to give 18.58 g of crude product, which was further purified by high pressure liquid chromatography to yield 15.27 g of the title compound as a light pink solid. A 1.0 g sample of this compound was crystallized from ethanol containing a little NH.sub.3 gas to give 0.45 g of light pink solid.
Example 8
Preparation of the compound having the formula ##STR34##
To a mixture of 0.50 g (0.71 mM) of the compound of Example 7 in 10 ml methylene chloride and 0.75 ml of 1.0 N sodium hydroxide (0.75 mM) in 10 ml water was added 232 mg (.ident.197.3 mg; 0.71 mM) of 85% tetra-n-butylammonium chloride and 0.25 ml (.ident.568; 4.0 mM) of iodomethane. After about 45 minutes the reaction appeared to be essentially complete. (TLC showed no starting material.) The reaction was allowed to stir overnight, and the TLC looked the same. The methylene chloride layer was separated and washed with water (5.times.25 ml), dried over sodium sulfate and the solvent evaporated leaving 0.57 g of the reaction product which was crystallized from about 5 ml of ethanol to give the title compound.
Example 9
Preparation of the compound having the formula ##STR35##
The compound having the formula ##STR36## was treated with aqueous 1 N NaOH to give the title compound.
Example 10
Preparation of the compound having the formula ##STR37##
The compound having the formula ##STR38## was treated with aqueous 1 N NaOH to give the title compound.
Example 11
Preparation of the compound having the formula ##STR39##
(a) One gram (1.76 mM) of the compound having the formula ##STR40## in 4 ml dry 1-methyl-2-pyrrolidinone and 0.345 ml (0.350 g; 3.75 mM) of aniline were heated together in an oil bath at 150.degree. C. for 30 minutes. TLC with chloroform/methanol (9:1) indicated a single magenta spot with no starting material present. The mixture was stirred with 40 ml water, filtered, washed with water and dried in vacuo overnight to give 1.09 g of the compound having the formula ##STR41##
(b) 1.09 g (1.74 mM) of the compound prepared in step (a) was dissolved in 20 ml dry dimethylsulfoxide under an atmosphere of nitrogen. 312 mg of 50% sodium hydride (.ident.186 mg or 7.75 mM), previously washed with hexane, was added and the resulting mixture stirred for 11/2 hours. The mixture was cooled in an ice bath and then 8 ml of methyliodide was added dropwise. The mixture was then allowed to warm to room temperature over the weekend. The mixture was poured into 250 ml of ice-cold water which contained 30 ml conc. HCl. The mixture was extracted with methylene chloride (4.times.50 ml). The combined methylene chloride extracts were washed with 2 N HCl (3.times.100 ml) dried over magnesium sulfate, and the solvent removed in vacuo to give 1.18 g of the compound ##STR42##
(c) 1.18 g (.about.1.74 mM) of the compound prepared in step (b) in 25 ml chloroform was treated with 1.5 g phosphorous pentachloride. The mixture was heated at reflux for 4 hours and then allowed to stir at room temperature overnight. The dark mixture was washed with water (3.times.25 ml), dried over magnesium sulfate and the solvent removed in vacuo. The residue was taken up in methylene chloride and added to 40 ml ice-cold methylene chloride saturated with ammonia (g). The mixture was allowed to stir overnight. The next morning the mixture was filtered and the filtrate stripped in vacuo leaving the crude product. This crude material was taken up in about 50 ml of methylene chloride. 15 g silica gel was added and after evaporation to dryness, the material was treated by medium pressure liquid chromatography to yield 0.26 g of the title compound.
Example 12
Preparation of the compound having the formula ##STR43##
A mixture of 18.3 g (0.1 M) of saccharin, 37.0 g (0.2 M) of 3-hydroxydiphenylamine and 2.2 g (16.5 mM) of anhydrous aluminum chloride was heated in an oil bath at 200.degree.-220.degree. C. for 8 hours. The dark purple mass was cooled to room temperature. The flask was broken and the brittle mass comprising the crude product was removed. 10 g of crude material was treated with 13.8 g (100 mM) of potassium carbonate in 100 ml water and 100 ml chloroform. The mixture was stirred at room temperature overnight. The chloroform layer was separated, filtered and dried over sodium sulfate. The chloroform was evaporated to give 6.0 g of amorphous solid. This solid was taken up in 50 ml of isopropanol and allowed to stir over the weekend. A gummy oil came out. The combined filtrates were evaporated in vacuo, taken up in 60 ml chloroform, seeded with authentic product and placed in the freezer to give 1.7 g of the title compound as crude crystalline material.
Sulfonefluorescein dichloride was prepared as follows:
In a 5 liter 3-necked round-bottom flask equipped with a paddle stirrer, a reflux condenser and a thermometer was placed 1.5 liters of ethyl acetate which was then cooled to 0.degree. C. using an ice bath. Sulfonefluorescein (250 g) was added followed by 200 ml of thionyl chloride. The temperature rose slightly. The temperature was allowed to fall back to 0.degree. C. 750 ml of N,N-dimethylformamide (DMF) was then added all at once. The temperature rose to about 30.degree. C. After the additions were completed, the mixture was stirred for 1 hour. The ice bath was removed to allow the temperature of the reaction mixture to rise to room temperature after which the mixture was placed on a steam bath and heated to reflux with stirring. During heating the mixture became lighter in color and thicker. (The color was brown.) After refluxing 10 to 15 minutes the reaction mixture was placed in an ice bath and cooled to 0.degree. C. with stirring continuing. The cold reaction mixture was filtered and washed with cooled 15% DMF/ethyl acetate solution until the color of the precipitate became as light as possible, then washed with ether. After sucking under a rubber dam, the sulfonefluorescein dichloride was air dried. Yield 184.3 g (68%); 99.7% pure by L.C.
Methanolic solutions of the compounds prepared in Examples 1, 2, 5-8, 11 and 12 were added to a series of buffered solutions having a pH of 4, 5, 6 and 7, respectively, in order to determine the approximate pH at which these compounds become colored as the pH drops below alkaline values. As a comparison, the following compound disclosed in Beilstein's Handbuch der Organischen Chemis, Vol. 27, p. 544, also was added as a methanolic solution to a series of buffers. ##STR44## The results are set forth in the Table below.
As discussed previously, the subject light-screening compounds are pH-sensitive dyes that are in their colored form at a given pH of about 6 or below and are converted to their colorless form above said pH when contacted with aqueous base. In their colored form, the sulfamphthalein ring is open, for example, ##STR45## wherein R.sup.3 is hydrogen or alkyl, and in their colorless form, the sulfamphthalein ring is closed ##STR46##
It will be appreciated that the compounds of formula II possessing one or two sulfo substituents function in the same manner.
Because compounds may be selected from those herein that remain colorless at the pH's normally encountered in a given photographic process during processing subsequent to being converted to their colorless form, they may be retained in a photographic film unit, e.g., a photosensitive element without the possibility of color reappearing in time. Typically, dyes may be selected for use as antihalation dyes, e.g., in a non-light-sensitive layer positioned intermediate a photosensitive silver halide emulsion layer and the support. Also, dyes may be selected for use as color correction filter dyes where absorption of light within a particular wavelength range during exposure is desirable for achieving appropriate color balance.
Whether used for antihalation, color correction or other photographic light-screening applications, the subject compounds, of course, should be in their colored or light-absorbing form initially, and thus, they should be incorporated in a layer having sufficient acidity to render the compounds colored. Useful layers include polymers which contain acid groups, e.g., carboxylic acid and sulfonic acid groups and polymeric acid or other polymeric layers containing polymeric or monomeric organic acids added in the amount necessary to give the level of acidity required for the selected dye compound. The amount of additional acid needed, if any, may be readily determined empirically.
Illustrative film units in which the dyes of the present invention may be advantageously used as antihalation dyes are described, for example, in British Pat. No. 1,482,156. These film units comprise, in the order in which incident light passes therethrough, an additive multicolor screen, a photosensitive silver halide emulsion layer, an antihalation layer in which the selected compound may be disposed, and preferably, an image-receiving layer. As described therein, exposure of the silver halide layer is accomplished through the screen which possesses optical filter elements selectively transmitting predetermined portions of incident radiation, e.g., red, green and blue light, to the underlying photosensitive silver halide layer. Upon photographic processing with an aqueous alkaline processing composition, soluble silver complex is transferred by diffusion and deposited in a superposed image-receiving layer as a function of the degree of exposure of silver halide behind each filter element. The silver image thus formed may then serve to modulate the quantity of light passing through the filter elements in the reverse direction during projection through a transparent support.
In a preferred embodiment, the image-receiving layer is intermediate the photosensitive silver halide emulsion layer and the additive multicolor screen and remains in position as part of an integral film unit prior to, during and after formation of the image. The antihalation dye is disposed in a processing composition permeable layer adjacent to the photosensitive layer on the side opposite the screen and serves to prevent the reflection or back-scattering of incident light which has passed through the photosensitive layer thereby eliminating the exposure of silver halide grains in the photosensitive layer other than those within the intended photoexposure path.
As noted above, the dyes of the present invention also are useful as color correction filter dyes in photographic film units comprising multilayered, multicolor photosensitive elements employing a blue-, a green-, and a red-sensitive silver halide layer, and particularly in integral negative-positive diffusion transfer film units wherein the image-receiving layer carrying the color transfer image is not separated from the developed photosensitive layers after processing but both components are retained together as a permanent laminate. Included as part of the laminate is a layer of light-reflecting material, preferably titanium dioxide, positioned between the image-carrying layer and the developed photosensitive layer(s). The light-reflecting layer separating the image-carrying and photosensitive components provides a white background for the transfer image and masks the developed photosensitive layer(s). In addition to these layers, the laminate usually includes dimensionally stable outer layers or supports, at least one of which is transparent so that the resulting transfer image may be viewed by reflection against the background provided by the light-reflecting layer.
Illustrative of patents describing such film units are U.S. Pat. No. 2,983,606 issued Mar. 9, 1961 to Howard G. Rogers, U.S. Pat. Nos. 3,415,644, 3,415,645 and 3,415,646 issued Dec. 10, 1968 to Edwin H. Land, U.S. Pat. Nos. 3,594,164 and 3,594,165 issued July 20, 1971 to Howard G. Rogers, and U.S. Pat. No. 3,647,437 issued Mar. 7, 1972 to Edwin H. Land. Copending U.S. patent application Ser. No. 134,424 of Edwin H. Land filed Mar. 21, 1980, a continuation-in-part of abandoned U.S. patent application Ser. No. 537,124 filed Dec. 30, 1974 is concerned with multicolor diffusion transfer film units, wherein a layer of a dye, preferably a dye bleachable by the processing composition, is so positioned that photoexposure is effected therethrough, whereby said dye layer is effective as a color correction filter. For convenience, the specification of this application is specifically incorporated herein.
The dyes of the present invention may be incorporated into the appropriate layer of the photographic film unit using any of the techniques known in the art. For instance, the selected compound can be dissolved in the appropriate solvent and then dispersed, in the presence of a wetting agent if desired, in a coating solution of, e.g., an acid polymer and the resulting coating solution applied as the desired layer, for example, coated on a transparent support to provide an antihalation layer, or coated over the outermost photosensitive layer of a multilayered, multicolor photosensitive element to provide a color correction filter layer through which photoexposure is made. The concentration of compound in the layer will vary depending upon the product in which the filter layer is to be used and may be readily determined empirically to provide the optical density necessary for the specific use. It will be appreciated that the dyes of the present invention may be used in combination with each other and also may be used in combination with other classes of dyes previously employed in antihalation, color correction and other filter layers.
FIG. 1 of the accompanying drawing, which illustrates one embodiment of the present invention, is an enlarged cross-sectional view of an integral diffusion transfer film unit comprising a transparent film base or support 1 carrying on one surface, in order, additive multicolor screen 3 comprising a plurality of primary red color filter elements, a plurality of primary green color filter elements and a plurality of blue color filter elements arranged in a geometrically repetitive distribution in side-by-side relationship in substantially a single plane, photoinsensitive layer 5 carrying silver precipitating nuclei, photosensitive layer 7 containing silver halide crystals and antihalation layer 9 comprising a processing composition permeable layer containing one or more light-screening dyes of the present invention in their colored form.
As discussed in aforementioned British Pat. No. 1,482,156, the degree of light absorption of the antihalation layer in such film units can vary over a relatively wide range, but usually, the antihalation layer possesses a transmission density range from about 0.4 to 1.4. Preferably, the transmission density is greater than 0.6 so that in the event a plurality of film units is employed in a stacked relationship during photoexposure, the antihalation layer will have sufficient density, i.e., light-absorbing capacity to substantially prevent reflectance as well as prevent exposure of underlying film units.
In determining the appropriate light-absorbing capacity for cyan, magenta and yellow for color correction purposes, "color compensating" filters as conventionally used in front of the camera lens may be employed in the usual manner as a convenient method of approximating the type and quantity of filtration which it would be desirable to provide. A layer containing the appropriate color correction dye(s) in a corresponding density may then be provided as a layer through which photoexposure is to be made.
Multicolor diffusion transfer images may be obtained using a variety of arrangements of the image-receiving layer and the silver halide emulsions. Thus, these layers may be carried by a common support brought into suspension after photoexposure. A particularly advantageous film structure is shown in U.S. Pat. No. 3,415,644 wherein the requisite layers are in superposed relationship prior to and during photoexposure, and these layers are maintained in superposed relationship as a permanent laminate after processing and image formation. Such film units typically contain an outer transparent layer or support through which photoexposure is effected and the final multicolor image viewed, and another outer layer or support carrying at least the photosensitive layers, the latter support being opaque. While these supports or sheet-like elements may simply be held in superposed relationship, e.g., by a binding tape around the edges, in the preferred embodiment these elements are laminated together prior to photoexposure. This prelamination provides a number of benefits, both during manufacture and in photoexposure. Following exposure, the elements are delaminated by the distribution of a fluid processing composition which, upon solidification, bonds the elements together to form the desired permanent laminate. Procedures for forming such prelaminated film units wherein the two elements are temporarily laminated together prior to exposure are described, for example, in U.S. Pat. No. 3,625,231 to Albert J. Bachelder and Frederick J. Binda, and U.S. Pat. No. 3,652,282 to Edwin H. Land, both issued Mar. 28, 1972 and in U.S. Pat. No. 3,793,023 issued to Edwin H. Land on Feb. 19, 1974.
Further description of this embodiment of the present invention may be facilitated by reference to FIG. 2 of the accompanying drawing which illustrates a diffusion transfer film unit adapted to provide integral negative-positive reflection prints and employing dye developers as the image dyes.
FIG. 2 illustrates a diffusion transfer film unit comprising a photosensitive element or component 2, a rupturable container 30, and an image-receiving element or component 4. The photosensitive element 2 comprises an opaque support 10 carrying, in turn, a cyan dye developer layer 12, a red-sensitive silver halide emulsion layer 14, an interlayer 16, a magenta dye developer layer 18, a green-sensitive silver halide emulsion layer 20, an interlayer 22, a yellow dye developer layer 24, a blue-sensitive silver halide emulsion layer 26, and an auxiliary layer 28. The positive or image-receiving element 4 comprises a transparent support 40 carrying, in turn, a polymeric acid layer 42, a timing layer 44, an image-receiving layer 46, and a processing composition permeable layer 48 having dispersed therein a dye of this invention in its colored form as a color correction filter dye. The two elements are held in superposed, registered relationship, e.g., by a binding tape (not shown), so that photoexposure of the silver halide emulsion layers is effected through layer 48 containing the filter dye. The rupturable container 30 contains a processing composition and is so positioned that, upon rupture the processing composition is distributed between the superposed elements 2 and 4. By including in the processing composition a light-reflecting pigment, preferably titanium dioxide, a light-reflecting layer may be provided against which the transfer image formed in the image-receiving layer 46 may be viewed. The developed photosensitive layers are masked from view by the light-reflecting layer and remain with the receiving layer 46 as part of a permanent laminate. The rupturable container 30 is of the type shown in U.S. Pat. No. 2,543,181 and is positioned adjacent the leading edge of the film unit.
In the processing of the film unit, the film unit is advanced relative to and between a pair of pressure-applying members which apply compressive pressure to the rupturable container 30 to eject its liquid contents between the photosensitive and image-receiving components 2 and 4 and then distribute the mass of liquid between the sheets toward the trailing ends thereof to form a layer of substantially uniform, predetermined thickness at least co-extensive with the image area. In order to insure sufficient processing liquid to form a layer of the required area and thickness between the sheets, excess processing liquid may be provided in container 30 and trapping means (not shown) provided for collecting and retaining excess processing liquid overrun. Details of the various layers of this and of the film unit of FIG. 1 may be found in the herein cited patents and applications and need not be recited here.
Processing of film units of the type described in FIG. 2 is initiated by distributing the processing composition between predetermined layers of the film unit. In exposed and developed areas, the dye developer will be immobilized as a function of development. In unexposed and undeveloped areas, the dye developer is unreacted and diffusible, and this provides an imagewise distribution of unoxidized dye developer, diffusible in the processing composition, as a function of the point-to-point degree of exposure of the silver halide layer. The desired transfer image is obtained by the diffusion transfer to the image-receiving layer of at least part of this imagewise distribution to unoxidized dye developer. In the illustrated embodiment, the pH of the photographic system is controlled and reduced by the neutralization of alkali after a predetermined interval, in accordance with the teachings of the above noted U.S. Pat. No. 3,615,644, to reduce the alkalinity to a pH at which the unoxidized dye developer is substantially insoluble and non-diffusible. As will be readily recognized, the details of such processes form no part of the present invention but are well known; the previously noted U.S. patents may be referred to for more specific discussion of such processes.
As noted above, one of the considerations in selecting the subject light-screening dyes for use in a given photographic system is the final pH subsequent to processing. Thus, it will be appreciated that the compounds selected for use as color correction filter dyes, antihalation dyes, etc., in integral photographic film units employing a neutralization or pH-reducing layer should be those compounds that remain colorless down to the lower pH's, for example, pH 5 to 6. The subject dyes may be disposed in any layer of the film unit including the neutralization layer (polymeric acid layer 42), depending upon the particular light-screening requirements. However, where practicable, the dyes preferably are disposed in a layer adjacent to the alkaline processing composition layer, for example, in a layer coated over the outermost photosensitive layer of the negative or in a layer coated over the image-receiving layer. Where the image-receiving layer carries an optical filter agent decolorizing layer, the compounds selected for color correction purposes may be disposed in said decolorizing layer. Photographic products and processes employing an optical filter agent decolorizing layer are disclosed and claimed in copending U.S. Patent Application Ser. No. 143,293 of Edwin H. Land et al filed Apr. 24, 1980 (now U.S. Pat. No. 4,298,674), a continuation-in-part of application Ser. No. 33,001, filed Apr. 24, 1979, now abandoned.
Multicolor images may be obtained by providing the requisite number of differentially exposable silver halide emulsions, and said silver halide emulsions are most commonly provided as individual layers coated in superposed relationship. Film units intended to provide multicolor images comprise two or more selectively sensitized silver halide layers each having associated therewith an appropriate image dye-providing material providing an image dye having spectral absorption characteristics substantially complementary to the light by which the associated silver halide is exposed. The most commonly employed negative components for forming multicolor images are of the "tripack" structure and contain blue-, green-, and red-sensitive silver halide layers each having associated therewith in the same or in a contiguous layer a yellow, a magenta and a cyan image dye-providing material respectively. Interlayers or spacer layers may, if desired, be provided between the respective silver halide layers and associated image dye-providing materials or between other layers. Integral multicolor photosensitive elements of this general type are disclosed in U.S. Pat. No. 3,345,163 issued Oct. 3, 1967 to Edwin H. Land and Howard G. Rogers as well as in the previously noted U.S. patents, e.g., in FIG. 9 of the aforementioned U.S. Pat. No. 2,983,606.
A number of modifications to the structures described in connection with FIG. 2 will readily suggest themselves to one skilled in the art. Thus, for example, the multicolor multilayer negative may be replaced by a screen-type negative as illustrated in U.S. Pat. No. 2,968,554 issued Jan. 17, 1961 to Edwin H. Land and in the aforementioned U.S. Pat. No. 2,983,606 particularly with respect to FIG. 3 thereof.
The image dye-providing materials which may be employed in such processes generally may be characterized as either (1) initially soluble or diffusible in the processing composition but are selectively rendered non-diffusible in an imagewise pattern as a function of development; or (2) initially insoluble or non-diffusible in the processing composition but which are selectively rendered diffusible or provide a diffusible product in an imagewise pattern as a function of development. These materials may be complete dyes or dye intermediates, e.g., color couplers. The requisite differential in mobility or solubility may, for example, be obtained by a chemical action such as a redox reaction or a coupling reaction.
As examples of initially soluble or diffusible materials and their application in color diffusion transfer, mention may be made of those disclosed, for example, in U.S. Pat. Nos. 2,774,668; 2,968,554; 2,983,606; 3,087,817; 3,185,567; 3,230,082; 3,345,163; and 3,443,943. As examples of initially non-diffusible materials and their use in color transfer systems, mention may be made of the materials and systems disclosed in U.S. Pat. Nos. 3,185,567; 3,719,489; 3,443,939; 3,443,940; 3,227,550; 3,227,552; and 4,076,529. Many types of image dye-providing substances and film units useful therewith also are discussed in the aforementioned U.S. Pat. No. 3,647,437 to which reference may be made.
It is also to be understood that "direct positive" silver halide emulsions may also be used, depending upon the particular image dye-providing substances employed and whether a positive or negative color transfer image is desired.
A preferred opacification system to be contained in the processing composition to effect processing outside of a camera is that described in the above-mentioned U.S. Pat. No. 3,647,437, and comprises a dispersion of an inorganic light-reflecting pigment which also contains at least one light-absorbing agent, i.e., optical filter agent, at a pH above the pKa of the optical filter agent in a concentration effective when the processing composition is applied, to provide a layer exhibiting optical transmission density>than about 6.0 density units with respect to incident radiation actinic to the photosensitive silver halide and optical reflection density<than about 1.0 density units with respect to incident visible radiation.
In lieu of having the light-reflecting pigment in the processing composition, the light-reflecting pigment used to mask the photosensitive strata and to provide the background for viewing the color transfer image formed in the receiving layer may be present initially in whole or in part as a preformed layer in the film unit. As an example of such a preformed layer, mention may be made of that disclosed in U.S. Pat. No. 3,615,421 issued Oct. 26, 1971 and in U.S. Pat. No. 3,620,724 issued Nov. 16, 1971, both in the name of Edwin H. Land. The reflecting agent may be generated in situ as is disclosed in U.S. Pat. Nos. 3,647,437 and 3,647,435, both issued Mar. 7, 1972 to Edwin H. Land.
The dye developers (or other image dye-providing substances) are preferably selected for their ability to provide colors that are useful in carrying out subtractive color photography, that is, the previously mentioned cyan, magenta and yellow. They may be incorporated in the respective silver halide emulsion or, in the preferred embodiment, in a separate layer behind the respective silver halide emulsion. Thus, a dye developer may, for example, be in a coating or layer behind the respective silver halide emulsion and such a layer of dye developer may be applied by use of a coating solution containing the respective dye developer distributed, in a concentration calculated to give the desired coverage of dye developer per unit area, in a film-forming natural, or synthetic, polymer, for example, gelatin, polyvinyl alcohol, and the like, adapted to be permeated by the processing composition.
Dye developers, as noted above, are compounds which contain the chromophoric system of a dye and also a silver halide developing function. By "a silver halide developing function" is meant a grouping adapted to develop exposed silver halide. A preferred silver halide development function is a hydroquinonyl group. Other suitable developing functions include ortho-dihydroxyphenyl and ortho- and paraamino substituted hydroxyphenyl groups. In general, the development function includes a benzenoid developing function, that is, an aromatic developing group which forms quinonoid or quinone substances when oxidized.
The image-receiving layer may comprise one of the materials known in the art, such as polyvinyl alcohol, gelatin, etc. It may contain agents adapted to mordant or otherwise fix the transferred image dye(s). Preferred materials comprise polyvinyl alcohol or gelatin containing a dye mordant such as poly-4-vinylpyridine, as disclosed in U.S. Pat. No. 3,148,061 and graft copolymers containing 4-vinylpyridine as disclosed in U.S. Pat. No. 3,756,814.
In the various color diffusion transfer systems which have previously been described and which employ an aqueous alkaline processing fluid, it is well known to employ an acid-reacting reagent in a layer of the film unit to lower the environmental pH following substantial dye transfer in order to increase the image stability and/or to adjust the pH from the first pH at which the image dyes are diffusible to a second (lower) pH at which they are not. For example, the previously mentioned U.S. Pat. No. 3,415,644 discloses systems wherein the desired pH reduction may be effected by providing a polymeric acid layer adjacent the dyeable stratum, which layer may contain a dye of the present invention as a color correction filter dye by adjusting the acidity of the polymeric acid layer, if necessary. These polymeric acids may be polymers which contain acid groups, e.g., carboxylic acid and sulfonic acid groups, which are capable of forming salts with alkali metals or with organic bases; or potentially acid-yielding groups such as anhydrides or lactones. Preferably the acid polymer contains free carboxyl groups. Alternatively, the acid-reacting reagent may be in a layer adjacent to the silver halide most distant from the image-receiving layer, as disclosed in U.S. Pat. No. 3,573,043 issued Mar. 30, 1971 to Edwin H. Land. Another system for providing an acid-reacting reagent is disclosed in U.S. Pat. No. 3,576,625 issued Apr. 27, 1971 to Edwin H. Land.
An inert interlayer or spacer layer may be and is preferably disposed between the polymeric acid layer and the dyeable stratum in order to control or "time" the pH reduction so that it is not premature and interferes with the development process. Suitable spacer or "timing" layers for this purpose are described with particularity in U.S. Pat. Nos. 3,362,819; 3,419,389; 3,421,893; 3,455,686; and 3,575,701.
While the acid-reacting layer and associated spacer layer are preferably contained in the positive component employed in systems wherein the dyeable stratum and photosensitive strata are contained on separate supports, e.g., between the support for the receiving element and the dyeable stratum; or associated with the dyeable stratum in those integral film units, e.g., on the side of the dyeable stratum opposed from the negative components, they may, if desired, be associated with the photosensitive strata, as is disclosed, for example, in U.S. Pat. Nos. 3,362,821 and 3,573,043. In film units such as those described in the aforementioned U.S. Pat. Nos. 3,594,164 and 3,594,165, they also may be contained on the spreader sheet employed to facilitate application of the processing fluid.
As is now well known and illustrated, for example, in the previously cited patents, the liquid processing composition referred to for effecting multicolor diffusion transfer processes comprises at least an aqueous solution of an alkaline material, for example sodium hydroxide, potassium hydroxide, and the like, and preferably possessing a pH in excess of 12, and most preferably includes a viscosity-increasing compound constituting a film-forming material of the type which, when the composition is spread and dried, forms a relatively firm and relatively stable film. The preferred film-forming materials comprise high molecular weight polymers such as polymeric, water-soluble ethers which are inert to an alkaline solution such as, for example, a hydroxyethyl cellulose or sodium carboxymethyl cellulose. Other film-forming materials or thickening agents whose ability to increase viscosity is substantially unaffected if left in solution for a long period of time also are capable of utilization. The film-forming material is preferably contained in the processing composition in such suitable quantities as to impart to the composition a viscosity in excess of 100 cps, at a temperature of approximately 24.degree. C. and preferably in the order of 100,000 cps to 200,000 cps at that temperature.
In particularly useful embodiments, the transparent polymeric support contains a small quantity of a pigment, e.g., carbon black, to prevent fog formation due to light-piping by internal reflection within the transparent support, and subsequent exiting from the support surface carrying the photographic layers, of actinic light incident upon the edge thereof; such elements are described in Belgian Pat. No. 777,407. The transparent support advantageously may include an ultraviolet light absorber.
For purposes of illustrating the invention, samples of the compounds prepared in Examples 1, 2, 6, 7 and 8 were incorporated into different polymeric compositions by admixing a solvent solution of each compound with a solution of the selected polymer(s) with the aid of a dispersing agent. The resulting coating solutions were then applied to a layer of gelatin carried on a transparent polyethylene terephthalate support, and then the resulting layer was dried.
The six coatings designated A through F were prepared and applied as follows.
Coating A
Poly(ethylene-maleic anhydride) (2.0 g) in 40 ml water was heated until the polymer dissolved. To 5 ml portions of this 5% polymer solution were added solutions of the compounds of Examples 1, 2, 6, 7 and 8 dissolved in ethanol or 2-methoxyethanol together with one drop of Triton X-100. The resulting clear mixtures were coated manually on polyethylene terephthalate base overcoated with a gelatin layer using a Meyer bar #24 and then dried.
Coating B
Poly(methoxyvinylmaleic anhydride) (1.5 g) was heated in 30 ml water until the polymer dissolved. To 5 ml portions of this 5% polymer solution were added solutions of the compounds of Examples 1, 2, 6, 7 and 8 dissolved in ethanol or 2-methoxyethanol together with one drop of Triton X-100. The resulting solutions were coated in the same manner described for Coating A.
Coating C
Poly(methoxyvinylmaleic anhydride) (4.0 g) in 96 ml water was heated at about 75.degree. C. until the polymer hydrolyzed and went into solution. This solution was cooled to room temperature and 0.67 ml of 30% polystyrene sulfonic acid was added. Approximately 1-2 mgs of each of the compounds of Examples 1, 2, 6, 7 and 8 were dissolved in either ethanol or 2-methoxyethanol together with one drop of Triton X-100, and the resulting solutions added to approximately 2 ml portions of the polymer solution. The resulting mixtures were coated and dried as described above.
Coating D
Polyvinylalcohol (43 ml; 7% solution), polystyrene sulfonic acid (0.5 ml; 30% solution) and 56.5 ml water were mixed together. About 1-2 mgs of each of the compounds of Examples 1, 2, 6, 7 and 8 were dissolved in ethanol or 2-methoxyethanol and the resulting solutions added to approximately 2 ml portions of the polymer solution. The mixtures were than coated and dried in the same manner described above.
Coating E
Poly(methoxyvinyl-maleic anhydride) (3.75 g) was heated in 75 ml water until solution took place. To 5 ml portions of this 5% polymer solution were added solutions of the compounds of Examples 1, 2, 6, 7 and 8 dissolved in ethanol or 2-methoxyethanol together with one drop of Triton X-100 and one drop of methanedisulfonic acid. The resulting mixtures were coated and dried as described above.
It was observed visually that the compounds of Examples 1 and 7 produced more intense color in coatings A, B, and C than the compounds of Examples 2, 6 and 8 which gave little or no color. However, all of the compounds gave color in coatings D and E with the compound of Example 7 giving the most intense color. Also, it was observed that all of the compounds were decolorized in coatings A through E when the coatings were treated with aqueous 1 N sodium hydroxide solution.
It will be appreciated that in utilizing the subject dyes to correct color balance, for example, in multicolor diffusion transfer photographic film units that a photosensitive element may be exposed to a suitable multicolor step-wedge and diffusion transfer processed with a given processing composition and image-receiving element. The blue, green and red D log E curves of the resulting multicolor transfer image (sample image) are then prepared. Examination of these D log E curves will indicate to one skilled in color photographic sensitometry the manner and extent to which the individual D log E curves depart from the desired curve shape. From this examination, one may determine by routine analysis and experimentation how much filtration would be required of what wavelength range or ranges to obtain a more desirable color balance. The photosensitive element of another film unit, having the identical photosensitive element, image-receiving element and processing composition as used in obtaining the sample image, is then given the same exposure through a conventional color correction filter(s) of the color and density estimated to be necessary to provide the desired changes in the D log E curves of the sample image. The blue, green and red D log E curves of the resulting test multicolor transfer image are then prepared and compared with the sample. While more than one "test" may be required to determine the color filtration most effective to give the desired D log E curve shape changes, such tests may be performed rapidly and easily. When the appropriate color filtration has been determined, a layer containing a color correction dye or dyes absorbing light in appropriate wavelength range(s) is coated on a transparent support at a coverage calculated to provide the requisite density. This "test" color correction dye layer is placed in the exposure path and the previous exposure test repeated. Analysis of the D log E curves of the resulting multicolor transfer image will indicate what changes, if any, should be made in the spectral absorption range and density prior to incorporating a corresponding color correction dye layer into the diffusion transfer film unit.
It will be recognized that effecting photoexposure through a layer containing the subject dye(s) is effective to "filter", i.e., decrease the exposure given to the silver halide layer(s) exposable by light absorbed by said color correction dye(s) and that one or more dyes of the present invention may be used in conjunction with other filter dyes for effecting changes in one, two or all three of the individual red, green and blue H and D curves to achieve the desired color balance. Though the subject dyes find particular utility in diffusion transfer and other photographic film units where it is desired to bleach, i.e., decolorize the dye(s) during processing subsequent to photoexposure through the dye layer(s), the subject dyes also may be employed in diffusion transfer and other film units where the dye is so positioned as not to contribute dye density to the transfer or final image. Where the filter dye layer through which photoexposure has been made is not part of the transfer image, or where the final image is masked from view as in certain integral negative-positive reflection print structures, the "unbleached" filter dye should be non-diffusible to the image-receiving layer containing the transfer image. The requisite non-diffusion character may be provided by the use of a suitable mordant, by the use of long chain "ballast" or "anchor" substituents and/or other art known techniques.
Besides final pH, in integral diffusion transfer film units, the choice of location of the color correction dye(s) also will depend upon what stage of the manufacturing process the determination is made to incorporate such a color correction dye. As will be readily apparent, provision of the color correction dye(s) in a separate layer has the advantage of permitting modification after the components have fully "matured" and also permits different modification of portions of the same lot of the positive component. In addition, coating the dye in a separate layer over the negative and/or positive has the advantage of more rapid "bleaching" and ensuring complete decolorization.
The supports for the various layers may be any of the types known in the art to be useful. In the preferred embodiments wherein an integral negative-positive reflection print is obtained, the supports should be dimensionally stable and may be polyethylene terephthalate or other polymeric film base, as disclosed in the cross-reference patents.
It will be recognized that the transfer image formed following exposure and processing of film units of the type illustrated in FIG. 2 will be a geometrically reversed image of the subject. Accordingly, to provide geometrically non-reversed transfer images, exposure of such film units should be accomplished through an image reversing optical system, such as in a camera possessing an image reversing optical system utilizing mirror optics, e.g., as described in U.S. Pat. No. 3,447,437 issued June 3, 1969 to Douglas B. Tiffany.
Where the expression "positive image" has been used, this expression should not be interpreted in a restrictive sense since it is used primarily for purposes of illustration, in that it defines the image produced on the image-carrying layer as being reversed, in the positive-negative sense, with respect to the image in the photosensitive emulsion layers. As an example of an alternative meaning for "positive image", assume that the photosensitive element is exposed to actinic light through a negative transparency. In this case, the latent image in the photosensitive emulsion layers will be positive and the dye image produced on the image-carrying layer will be negative. The expression "positive image" is intended to cover such an image produced on the image-carrying layer, as well as transfer images obtained by use of direct positive silver halide emulsions to provide a "positive" image of the photographed subject.
While the usefulness of the subject dyes has been described as applied to integral diffusion transfer film units where the transfer image is retained with the developed photosensitive element as part of a permanent laminate, it will be understood that the dyes of this invention also may be used to provide antihalo, color correction or other light filtering layer(s) in diffusion transfer film units where the transfer image, either in silver or in dye, is separated from the developed photosensitive layer(s) subsequent to processing. Though the image dye-providing materials are preferably dye developers, it will be appreciated that other types of image dyes and dye intermediates may be employed to provide the dye transfer image.
Besides their usefulness in diffusion transfer photographic products and processes, the dyes of the present invention also may be used in filter layers of conventional photographic materials, for example, in antihalation or color correction layers in conventional negatives, and may be disposed in the appropriate layer(s) in an amount sufficient to provide the desired filtering effect. The selection and incorporation of the dyes for the desired filtering effect may be accomplished in a known manner using conventional techniques and is well within the skill of the art. For example, for color correction purposes, the dye(s) selected may absorb light within a specific wavelength range, e.g., blue, green or red light, or within a combination of several wavelength ranges and will be disposed in a layer through which photoexposure is made. Indeed, it may be desirable in a given instance to filter light of two different wavelength ranges in a ratio such that one silver halide emulsion receives more exposure filtration than does another. As in the diffusion transfer film units, the dye(s) selected for color correction are advantageously applied after the photosensitive element has aged to "maturity", i.e., the sensitometry of the photosensitive element as manufactured is no longer changing significantly with time. Where the subject dyes are employed for antihalation purposes, they may be incorporated, for example, in a layer on one or both sides of a support carrying the photosensitive layer(s) and where they are employed as optical filter agents, they will be so positioned as to prevent post-exposure fogging during processing in ambient light without, of course, interfering with imagewise exposure of the photosensitive layer(s) or with viewing of the final image.
Since certain changes may be made in the hereinafter defined subject matter without departing from the scope of the invention herein involved, it is intended that all matter contained in the above description and examples be interpreted as illustrative and not in a limiting sense.
Claims
What is claimed is:
1. A photographic product comprising a plurality of layers including a support and at least one photosensitive silver halide emulsion layer carried on said support, at least one of said layers containing a colored xanthene compound selected from those having the formulae ##STR47## wherein A and A', the same or different, are selected from ##STR48## each R is hydrogen or an electron-withdrawing group; each R.sup.1 is hydrogen or alkyl; each R.sup.2 is hydrogen, alkyl or an electron-withdrawing group; R.sup.3 is hydrogen or alkyl; R.sup.4 is alkyl; n is 0 or 1; and Z is an anion.
2. A photographic product as defined in claim 1 wherein said colored compound is disposed in a processing composition permeable layer on the same side of said support as said silver halide emulsion layer(s).
3. A photographic product as defined in claim 2 which comprises, in order, said support, said photosensitive silver halide emulsion layer and said layer containing said colored compound.
4. A photographic product as defined in claim 3 which includes a silver-precipitating layer carried on said support or on a second support and so positioned as to receive a silver diffusion transfer image upon application of an aqueous alkaline processing composition to provide a silver halide developing agent and a silver halide solvent.
5. A photographic product as defined in claim 4 which comprises, in order, said support, an additive multicolor screen, said silver-precipitating layer, said photosensitive silver halide emulsion layer and said layer of said colored compound, said support being transparent.
6. A photographic product as defined in claim 2 wherein said support is transparent and said colored compound is disposed in a layer between said support and said silver halide emulsion layer(s).
7. A photographic product as defined in claim 2 which additionally includes a layer of said colored compound coated over the photosensitive silver halide emulsion layer outermost from said support on the surface opposite said support.
8. A photographic product as defined in claim 2 wherein said silver halide emulsion layers are a red-sensitive silver halide emulsion, a green-sensitive silver halide emulsion and a blue-sensitive silver halide emulsion, each said emulsion layer having an image dye-providing substance associated therewith.
9. A photographic product as defined in claim 1 wherein said colored compound is a compound of said formula Ia.
10. A photographic product as defined in claim 1 wherein said colored compound is a compound of said formula IIa.
11. A photographic product as defined in claim 1 wherein said colored compound has the formula ##STR49## wherein Z is an anion.
12. A photographic product as defined in claim 1 wherein said colored compound has the formula ##STR50## wherein Z is an anion.
13. A photographic product as defined in claim 1 wherein said colored compound has the formula ##STR51## wherein Z is an anion.
14. A photographic product for forming a multicolor diffusion transfer image, said product comprising a first sheet-like element comprising a first support carrying a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer, said silver halide emulsion layers having associated therewith, respectively, a cyan image dye-providing material, a magenta image dye-providing material and a yellow image dye-providing material; a second sheet-like element comprising a second support; said first and second sheet-like elements being in superposed relationship, or adapted to be brought into superposed relationship, with said supports being outermost; at least one of said supports being transparent to permit photoexposure of said silver halide emulsions therethrough; a rupturable container releasably holding an aqueous alkaline processing composition, said rupturable container being so positioned as to be capable of discharging said processing composition between a pair of predetermined layers carried by said supports; an image-receiving layer carried by one of said supports; and a colored xanthene compound being disposed in a processing composition permeable layer carried by one of said supports, said xanthene compound selected from those having the formulae ##STR52## wherein A and A', the same or different, are selected from ##STR53## each R is hydrogen or an electron-withdrawing group; each R.sup.1 is hydrogen or alkyl; each R.sup.2 is hydrogen, alkyl or an electron-withdrawing group; R.sup.3 is hydrogen or alkyl; R.sup.4 is alkyl; n is 0 or 1; and Z is an anion.
15. A photographic product as defined in claim 14 wherein said colored compound is so positioned that photoexposure of said silver halide emulsion layers is effected therethrough.
16. A photographic product as defined in claim 15 wherein said second support is transparent and said image-receiving layer and said light-screening dye are carried by said transparent second support of said second sheet-like element.
17. A photographic product as defined in claim 14 wherein said product includes means providing a layer of a white pigment between said image-receiving layer and said silver halide emulsions.
18. A photographic product as defined in claim 17 wherein said means providing a layer of a white pigment comprises a white pigment dispersed in said processing composition.
19. A photographic product as defined in claim 17 wherein said means providing a layer of a white pigment comprises a preformed layer of a white pigment.
20. A photographic product as defined in claim 16 wherein said colored compound is disposed in said image-receiving layer.
21. A photographic product as defined in claim 19 wherein said colored compound is disposed in said preformed layer of a white pigment.
22. A photographic product as defined in claim 14 wherein each said image dye-providing materials is an image dye-providing material selected from image dyes and image dye intermediates.
23. A photographic product as defined in claim 22 wherein each said image dye-providing material is a dye.
24. A photographic product as defined in claim 23 wherein each said dye is a dye developer.
25. A photographic product as defined in claim 14 wherein said first and second sheet-like elements are in superposed relationship.
26. A photographic product as defined in claim 14 wherein said second sheet-like element is adapted to be superposed with said first sheet-like element.
27. A photographic product as defined in claim 16 wherein said first support is opaque.
28. A photographic product as defined in claim 15 wherein said first and second supports are transparent.
29. A photographic product as defined in claim 14 wherein said colored compound is a compound of said formula Ia.
30. A photographic product as defined in claim 14 wherein said colored compound is a compound of said formula IIa.
31. A photographic product as defined in claim 14 wherein said colored compound has the formula ##STR54## wherein Z is an anion.
32. A photographic product as defined in claim 14 wherein said colored compound has the formula ##STR55## wherein Z is an anion.
33. A photographic product as defined in claim 14 wherein said colored compound has the formula ##STR56## wherein Z is an anion.
34. A photographic process which comprises the steps of exposing a photosensitive film comprising a plurality of layers including at least one photosensitive silver halide emulsion layer carried on a support, at least one of said layers containing a colored xanthene compound having the formulae ##STR57## wherein A and A', the same or different, are selected from ##STR58## each R is hydrogen or an electron-withdrawing group; each R.sup.1 is hydrogen or alkyl; each R.sup.2 is hydrogen, alkyl or an electron-withdrawing group; R.sup.3 is hydrogen or alkyl; R.sup.4 is alkyl; n is 0 or 1 and Z is an anion and contacting said photosensitive silver halide emulsion layer(s) with an aqueous alkaline processing composition having an alkaline pH to effect development.
35. A photographic process as defined in claim 34 wherein said colored compound is disposed in a processing composition permeable layer on the same side of said support as said silver halide emulsion layer and said contacting with said alkaline processing composition also being effective to convert said colored compound to its colorless form.
36. A photographic process as defined in claim 35 wherein said support is transparent and said colored compound is disposed in a layer between said support and said silver halide emulsion layer(s).
37. A photographic process as defined in claim 35 wherein said film includes a layer of said colored compound coated over the silver halide emulsion layer outermost from said support on the surface opposite said support.
38. A photographic process as defined in claim 35 wherein said silver halide emulsion layers are a red-sensitive silver halide layer, a green-sensitive silver halide layer and a blue-sensitive silver halide layer, each said emulsion layer having an image dye-providing material associated therewith.
39. A photographic process as defined in claim 35 including the step of separating said processing composition from contact with said film unit subsequent to development.
40. A photographic process which comprises, in combination, the steps of: (a) exposing a photosensitive film unit comprising a plurality of layers including a support carrying at least one photosensitive silver halide emulsion layer having associated therewith an image-providing material, an image-receiving layer adapted to receive a solubilized image-providing material diffusing thereto, at least one of said layers on the same side of said support as said silver halide layer(s) containing a colored xanthene compound selected from those having the formulae ##STR59## wherein A and A', the same or different, are selected from ##STR60## each R is hydrogen or an electron-withdrawing group; each R.sup.1 is hydrogen or alkyl; each R.sup.2 is hydrogen, alkyl or an electron-withdrawing group; R.sup.3 is hydrogen or alkyl; R.sup.4 is alkyl; n is 0 or 1; and Z is an anion; (b) contacting said silver halide layer(s) and said colored compound with a processing composition having an alkaline pH; (c) effecting thereby development of said silver halide layer(s), contacting with said alkaline processing composition also being effective to convert said colored compound to its colorless form; (d) forming as a result of said development, an imagewise distribution of diffusible image-providing material; and (e) transferring, by diffusion, at least a portion of said imagewise distribution of diffusible image-providing material to said layer adapted to receive said material to provide a transfer image thereto.
41. A photographic process as defined in claim 40 which includes the step of maintaining said film unit intact subsequent to said processing.
42. A photographic process as defined in claim 41 wherein said processing composition includes a silver halide solvent and said transfer image is an image in silver.
43. A photographic process as defined in claim 42 wherein said photosensitive film unit comprises, in order, a transparent support, an additive multicolor screen, an image-receiving layer comprising a silver-precipitating layer, a photosensitive silver halide emulsion layer and a layer of said colored compound.
44. A photographic process as defined in claim 40 wherein said colored compound is a compound of said formula Ia.
45. A photographic process as defined in claim 40 wherein said colored compound is a compound of said formula IIa.
46. A photographic process as defined in claim 40 wherein said colored compound has the formula ##STR61## wherein Z is an anion.
47. A photographic process as defined in claim 40 wherein said colored compound has the formula ##STR62## wherein Z is an anion.
48. A photographic process as defined in claim 40 wherein said colored compound has the formula ##STR63## wherein Z is an anion.
49. A photographic process for forming a multicolor diffusion transfer image which comprises the steps of: (a) exposing a photosensitive film unit which includes, in combination, a first sheet-like element comprising a first support carrying a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer, said silver halide emulsion layers having associated therewith, respectively, a cyan image dye-providing material, a magenta image dye-providing material and a yellow image dye-providing material; a second sheet-like element comprising a second support; said first and second sheet-like elements being in superposed relationship, or adapted to be brought into superposed relationship, with said supports being outermost; at least one of said supports being transparent to permit photoexposure of said silver halide emulsions therethrough; a rupturable container releasably holding an aqueous alkaline processing composition, said rupturable container being so positioned as to be capable of discharging said processing composition between a pair of predetermined layers carried by said supports; an image-receiving layer carried by one of said supports; and a colored compound disposed in a processing composition permeable layer carried by one of said supports, said colored compound being a xanthene compound having the formulae ##STR64## wherein A and A', the same or different, are selected from ##STR65## each R is hydrogen or an electron-withdrawing group; each R.sup.1 is hydrogen or alkyl; each R.sup.2 is hydrogen, alkyl or an electron-withdrawing group; R.sup.3 is hydrogen or alkyl; R.sup.4 is alkyl; n is 0 or 1; and Z is an anion; (b) contacting said silver halide layer(s) and said colored compound with a processing composition having an alkaline pH; (c) effecting thereby development of said silver halide layer(s), said contacting with said alkaline processing composition also being effective to convert said colored compound to its colorless form; (d) forming as a result of said development, an imagewise distribution of diffusible image dye-providing material; and (e) transferring, by diffusion, at least a portion of said imagewise distribution of diffusible image dye-providing material to said image-receiving layer to provide a transfer image thereto.
50. A photographic process as defined in claim 49 wherein said colored compound is so positioned that exposure of said silver halide layer(s) is effected therethrough.
51. A photographic process as defined in claim 50 wherein said second support is transparent and said image-receiving layer and said colored compound are carried by said transparent second support of said second sheet-like element.
52. A photographic process as defined in claim 50 wherein said product includes means providing a layer of a white pigment between said image-receiving layer and said silver halide emulsions.
53. A photographic process as defined in claim 52 wherein said means providing a layer of a white pigment comprises a white pigment dispersed in said processing composition.
54. A photographic process as defined in claim 52 wherein said means providing a layer of a white pigment comprises a preformed layer of a white pigment.
55. A photographic process as defined in claim 51 wherein said light-screening dye is disposed in said image-receiving layer.
56. A photographic process as defined in claim 49 wherein each said image dye-providing materials is an image dye-providing material selected from image dyes and image dye intermediates.
57. A photographic process as defined in claim 56 wherein each said image dye-providing material is a dye.
58. A photographic process as defined in claim 57 wherein each said dye is a dye developer.
59. A photographic process as defined in claim 49 wherein said first and second sheet-like elements are in superposed relationship.
60. A photographic process as defined in claim 49 wherein said second sheet-like element is adapted to be superposed with said first sheet-like element.
61. A photographic process as defined in claim 51 wherein said first support is opaque.
62. A photographic process as defined in claim 49 wherein said colored compound is a compound of said formula Ia.
63. A photographic process as defined in claim 49 wherein said colored compound is a compound of said formula IIa.
64. A photographic process as defined in claim 49 wherein said colored compound has the formula ##STR66## wherein Z is an anion.
65. A photographic process as defined in claim 49 whrerein said colored compound has the formula ##STR67## wherein Z is an anion.
66. A photographic process as defined in claim 49 wherein said colored compound has the formula ##STR68## wherein Z is an anion.
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| Patent | Date | Inventor | Cited By |
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| US1879537 | 1932-09-01 | Schneider | |
| US1944876 | 1935-03-01 | Schneider et al. | |
| US2182794 | 1939-12-01 | Dawson | |
| US2203767 | 1940-06-01 | Baldsiefen | |
| US2203768 | 1940-06-01 | Baldsiefen | |
| US2350090 | 1944-05-01 | Beilenson | |
| US3005711 | 1961-10-01 | Burgardt | |
| US3406069 | 1968-10-01 | De Witt Overman | |
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