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Publication numberUS3288778 A
Publication typeGrant
Publication dateNov 29, 1966
Filing dateOct 5, 1964
Priority dateOct 5, 1964
Publication numberUS 3288778 A, US 3288778A, US-A-3288778, US3288778 A, US3288778A
InventorsBlout Elkan R, Cohen Saul G, Rogers Howard G, Simon Myron S, Woodward Robert B
Original AssigneePolaroid Corp
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Azo and anthraquinone dye developers
US 3288778 A
Abstract  available in
Images(38)
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Claims  available in
Description  (OCR text may contain errors)

United States Patent 3,288,778 AZO AND ANTHRAQUINONE DYE DEVELOPERS Elkan R. Blout, Belmont, Saul'G. Cohen, Lexington, Milton Green, Newton Center, Howard G. Rogers, Weston, Myron S. Simon, Newton Center, and Robert B. Woodward, Belmont, Mass., assignors to Polaroid Corporation, Cambridge, Mass., acorporation of Delaware No Drawing. Filed Oct. 5, 1964, Ser. N0. 401,714 13 Claims. (Cl. 260-163) This invention relates to photography and more particularly to products, compositions and processes for the development of photosensitive silver halide elements.

This application is'in part a continuation of our copending U.S. application Serial No. 1,442, filed January 11, 1960 (now abandoned) which in turn is in part a continuation of application Serial No. 471,542, filed November 26, 1954 (now abandoned).

It is one object of-the present invention to provide novel processes and compositions for the development of silver halide emulsions, in which colored developing agents are used to develop a-latent image.

Another object is to provide novel processes and compositions for the development of silver halide emulsions, in which the novel developing agent is capable of developing a latent image and imparting a reversed or positive colored image of said latent image to a superposed image-receiving material.

Still another object is to provide novel products, processes and compositions suitable for use in preparing monochromatic and multichromatic photographic images.

A further object is to provide novel compounds which are useful as photographic color-providing materials.

Other objects of the invention will in part be obvious and will in part appear hereinafter.

The invention accordingly comprises the processes 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.

The novel photographic developing agents employed in this invention possess the properties of both dye and a developing agent; thus they may be referred to as dye developers. The nature of these dye developers will be described hereinafter.

The photographic processes and compositions disclosed herein are particularly useful in the treatment of a latent image present in a photosensitive element, such as an exposed silver halide emulsion, whereby a positive dye image thereof may be imparted to another element, herein referred to as an image-carrying or image-receiving element.

U.S. Patent No. 2,983,606, issued to Howard G. Rogers on May 9, 1961, discloses difiusion-transfer reversal processes wherein a photographic negative material, such as a photographic element comprising an exposed silver halide emulsion, is developed in the presence of a dye developer to impart to an image-receiving layer a reversed or positive dye image of the developed image by permeating into said emulsion layer a suitable liquid processing composition and bringing said emulsion into superposed relationship with an appropriate image-receiving layer. The inventive concepts herein set forth provide novel dye developers for use in such processes.

In carrying out the process of this invention, a photosensitive element containing a silver halide emulsion is exposed and Wetted with a liquid processing composi tion, for example, by immersing, coating, spraying, flowing, etc., in the dark, and the photosensitive element superposed, prior to, during or after wetting, on an image-receiving element. In a preferred embodiment, the photosensitive element contains a layer of dye developer, and the liquid processing'cornposition is applied to the photosensitive element'in a uniform layer as-the photosensitive element is brought into superposed position with an image-receiving element. It is also within the scope of this invention to apply the liquid processing composition prior to exposure, in accordance with the disclosure in U.S.- Patent No. 3,087,816. The liquid processing composition permeates the emulsion to provide a solution of dye developer substantially uniformly distributed therein. As the exposed silver halide emulsion is developed, the oxidation product of the dye developer is immobilized or precipitated in situ with the developed silver, thereby providing an imagewise distribution of unoxidized dye developer dissolved in the liquid processing composition. This immobilization is apparently due, at least in part, to a change in the solubility characteristics of the dye developer upon oxidation, and especially as regards its'solubility in alkaline solutions. It may also be due, in part, to a tanning effect on the emulsion by the oxidized developing agent. At

least part of this imagewise distribution of unoxidized unoxidized dye developer Without appreciably disturbing the imagewise distribution thereof to provide a reversed or positive, colored image of the developed image. The

image-receiving element may contain agents adapted to mordant or otherwise fix the diffused, unoxidized dye developer. If the color of the diffused dye developer is affected by changes in the pH of the image-receiving element, this pH may be adjusted in accordance with well-known techniques to provide a pH affording the desired color. Imbibi-tion periods of approximately one minute have been found to give good results, but this contact period may be adjusted'where necessary to compensate for variations in temperature or other conditions. The desired positive image is revealed-by stripping the image-receiving layer from the silver halide emulsion at the end of the imbibition period.

The dye developers of this invention may be utilized in the photosensitive element, for example, in, on or behind the silver halide emulsion, or they may be utilized in the image-receiving element or in the liquid processing composition. In a preferred embodiment, a coating or layer of the dye developer is placed behind the silver halide emulsion, i.e., on the side of the emulsion adapted to be located most distant from the photographed subject when the emulsion is exposed and preferably also adapted to be most distant from the imagereceiving element when in superposed relationship there wit-h. Placing the dye developer behind the emulsion layer, as in the preferred embodiment, has the advantage of providing increased contrast in the positive image, and also minimizes any light-filtering action by the colored dye developer. In this preferred embodiment, the layer of dye developer may be applied by using a coating solution containing about 0.5 to -8%, by weight,.of' the dye developer. Similar concentrations may be used if the dye developer is utilized as a component of the liquid processing composition. In an especially useful mode of dispersing the dye developers in the photosensitive elements,.the dye developer is dissolved in a Water-immiscible solvent and then dispersed ina gelatin coating solution.

The liquid processing which is used in the process Patented Nov. 29, 1966 herein disclosed comprises at least an aqueous solution of an alkaline compound, for example, diethylamine, sodium hydroxide or sodium carbonate, and may contain the dye developer. In some instances, it may contain an additional silver halide developing agent. If the liquid processing composition is to be applied to the emulsion by being spread thereon, preferably in a relatively thin, uniform layer, it may also include a viscosityincreasing compound constituting film-forming material of the type which, when spread over a water-absorbent base, will form a relatively firm and relatively stable film. A preferred film-forming material is a high molecular weight polymer such as a polymeric, water-soluble ether inert to an alkali solution, as, for example, a hydroxyethyl cellulose or sodium carboxymethyl cellulose. Other filmforming materials or thickening agents whose ability to increase viscosity is substantially unaffected when left in solution for a long period of time may also be used.

The novel compounds of the present invention comprise dyes, preferably azo, anthraquinone, indophenol, indoaniline, and azomethine dyes, characterized in that they contain at least one and preferably not more than two groups of the formula:

(1) I ll NC (alkylene) n1 Z wherein n is a positive integer from 1 to 2; R represents hydrogen or an alkyl group, preferably a lower alkyl group comprising from 1 to 5 carbon atoms, inclusive, for example, methyl, ethyl, etc.; and Z is a benzenoid developing group, preferably comprising an aryl nucleus selected from the group consisting of benzene and naphthalene nuclei so substituted by at least two groups selected from the group consisting of hydroxyl and amino groups as to be capable of developing an exposed silver halide emulsion. In addition to the substituents which provide the silver halide developing function, the aromatic nucleus of Z may contain other substituents, e.g., halo, lower alkyl, lower alkoxy, etc.

The preferred compounds may be represented by the formula: v

i i D [N(] (alkyleue) n1 Z wherein n and R have the same significance as set forth in regard to Formula 1; a is 1 or 2; and D represents the radical of a dye molecule D-[N-H],

wherein a has the same significance as previously noted and most preferably wherein D comprises an anthraquinone or azo system; and Z is a benzene nucleus substituted by hydroxyl or amino groups ortho or para to one another, e.g., 0- or p-dihydroxyphenyl, 0- or p-hydroxyanilino, etc., and halo, lower alkyl and lower alkoxy derivatives thereof.

' One preferred group of compounds comprises azo and anthraquinone dyes having one or two groups of the formula:

wherein the lower alkylene moiety comprises 1-6 carbon atoms, e.g.,

'Depending upon whether an azo or an anthraquinone dye developer is contemplated, the group of Formula 3 is preferably bonded to a carbon atom of an azo dye molecule or contained in a substituent bonded directly to a nuclear carbon atom of an anthraquinone dye nucleus. In the latter case, the group may comprise the entire substituent so bonded to the anthraquinone nucleus, or it may be but a part of the said substituent, as exemplified in the illustrative compounds recited hereinafter.

The novel compounds of this invention, as noted above, are dye developers which contain not less than one and not more than two benzenoid developing groups. A preferred silver halide developing group comprises a hydroquinonyl group. Other suitable developing groups include orthodihydroxyphenyl and orthoand para-amino substituted hydroxyphenyl groups. In general, the developing group comprises a benzenoid developing configuration, that is, an aromatic developing group which forms quinonoid or quinone products upon oxidation. Preferred aromatic developing groups which form quinonoid 01' quinone oxidation products comprise aryl nuclei selected from the group consisting of benzene and naphthalene nuclei substituted by at least two groups selected from the group consisting of hydroxyl and amino groups so as to be capable of developing an exposed silver halide emul- Experience has indicated that in the most useful dye developers the term alkylene represents lower alkylene groups such as a methylene group, and preferably a lower alkylene group comprising from 1 to 5 carbon atoms. It should be noted that the alkylene group may possess either a branched or straight chain configuration and that the number of carbon atoms possessed by the alkylene group is only restricted by the proviso that the resulting dye developer is capable of being dissolved in the liquid processing composition and its oxidation product rendered immobile in the developed emulsion layer.

Although the dye preferably contains not in excess of two groups of Formula 1, it will be recognized that the number of such groups is only limited by the operational functionability of the resultant dye developer. In that the designated groups generally impart increased solubility to the dye molecule, it will be recognized that employment of more than two of such groups may be desirable where increased solubility of the resultant dye developer molecule is intended. For example, a dye molecule which is initially insoluble in the fluid processing composition may be made soluble therein by the employment of a sufiicient number of the designated groups. It must be noted, however, that the number of groups employed must be so balanced as to provide a dye developer soluble in the fluid processing composition, the oxidation product of which is rendered immobile in the exposed areas of the photosensitive element.

The term amino, as used above, is intended to include substituted amino groups, for example, alkylamino and arylamino groups. It will be recognized that the substituents on the amino groups preferably comprise radicals which provide little or no decrease in the silver halide developing function of the amino groups.

As examples of dye developers within the scope of the present invention, mention may be made of:

l-fi-aminoethylamino-et-fi-(homogentisamido) -ethylamino anthraquinone phenyl) -methane 75 pyrazolone 2- 4-homogen-tisamido-2 ,5 -dimethoxy) A-aceto-l-naphtlrol One method of preparing the novel dye developers of this invention, designated throughout the specification as procedure (A), comprises reacting a dye, preferably an azo, anthraquinone, indophenol, indoaniline, or ammethine dye, having not less than one and preferably not more than two reactive primary or secondary amino groups with a suitable derivative of a compound such as set forth in the formula:

as, for example, the corresponding lactone or acid halide, preferably the acid chloride. In this formula Z and n have the same significance as previously set forth. However, where a dye has more than two available reactive hydroxyl or primary or secondary amino groups, reaction may occur at two or more of such groups.

As examples of suitable compounds, within Formula 4, from which Z-(alkylene) n1-( 1 may be derived, mention may be made of the following: gentisic acid, homogentisic acid, 2,5-dihydroxyhydrocinnamic acid, homogentisic acid lactone, 2,3-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3-amino-2-hydroxybenzoic acid, S-arnino-Z-hydroxybenzoic acid, 2,3- dihydroxybenzoic acid, B-Z,5-dihydroxyphenylpropionic acid, ,3-2,S-dihydroxyphenylpropionic acid lactone, etc.

When reacting some of the above compounds with amino-substituted dyes, it is preferred to protect the hydroxyl or amino groups in Z which provide the developing function in order to avoid undesirable side reactions; this may be accomplished by acylation, for example, by reaction with an alkyl or aryl chloroformate to form carboalkoxyl deivatives.

As examples of alkyl and aryl chloroformates available to provide suitable protection, mention may be made of: methyl chloroformate, ethyl chloroformate, nfpropyl chloroformate, n-butyl chloroformate, benzyl chloroformate, phenyl chloroformate, etc.

After reaction, and prior to photographic use, the protective groups are removed, as for example, by hydrolysis in the presence of alkali.

Examples of protected compounds include homogentisic acid chloride dibenzoate and 2,5-dicarbomethoxygentisyl chloride. It will be apparent that one advantage of using homogentisic acid lactone is that it is unnecessary to further protect the hydroxyl groups and hence no hydrolysis step is necessary.

The preferred protected derivatives comprise compounds of the general formula: I

l (fl y eHe) n-l' 0 -Halogen wherein each R is an alkyl group, preferably a lower alkyl group such as methyl, ethyl, etc.; n has-the same significance as previously noted; and the halogen radical comprises preferably a chlorine radical.

A second method of preparing the compounds of Formula 5 comprises reacting a compound of the formula:

II (alkylene) 11-1 O NH;

wherein n has the same significance as in Formula 1; for example, gentisamide, homogentisamide, etc., with an alkyl chloroformate, such as for example, one of the aforementioned chloroformates, to form the carboalkoxyl derivatives of said compound.

Treatment of the aforementioned carboalkoxylated amido derivatives with nitrous acid results in the formation of the corresponding free acid.

The acid halide derivatives of the carboalkoxylated free acid, prepared by either of the aforementioned procedures, comprises replacing the hydoxyl group of the free acids carboxyl group with a suitable halogen radical, such as a chlorine radical, for example, by reacting the free acid with phosphorous trichloride, phosphorous pentachloride, thionyl chloride, etc.

As examples of dyes possessing not less than one and not more than two reactive primary and secondary amino groups, mention may be made of:

1,4-bisfi-aminoethylamino -anthraquinone;

l-amino-4-(p-aminoanilino -2-anthraquinone;

4-amino-azobenzene;

1,4-bis- (p-aminoanilino -anthraquinone;

1,4-diamino-anthraquin one;

1,4-bis- (p-aminobenzylamino -anthraquinone;

l-amino-anthraquinone;

l-amino-Z -methyl-anthra quinone;

1-N-methylamino-anthraquinone;

1-amino-4-bromo-anthraquinone;

1 -methylamino-4-p-amino anilino-anthraquinone;

1,4-bis-methylamino-anthraquinone;

1-amino-4-acetamido-anthraquinone;

1-amino-4-N-methyl amino-anthraquinone;

l ,4-diamino-5-nitro-anthraquinone;

1,4-diamino-2-methoXy-anthraquinone 1,5-diamino-anthraquinone;

1,4-bis-(B-aminoethylamino) -anthraquinone;

3 '-amino-quinaphthalone;

3 -amino-1-phenyl-4-phenylazo-5-pyrazolone;

3-amino-4- (2,5 '-dichlorophenylazo) 1-phenyl-5- pyrazolone;

3-amino-4-(4'[phenylazo1-phenylazo) -l-phenyl-5- pyrazolone;

3 -amino-4- 2',5-dichlorophenyl) -1- 2',4',6'-trichl0rophenylazo) -5-pyrazolone;

3 -amino-4- (o-hydroxyphenylazo -1-phenyl-5-pyrazolone;

1- 2',5-dimethoxy-4- [N-methylamino] -phenylazo -2- methoxy-naphthalene;

3-amino-4- (4'-N-ethyl-N-B-methylsulfonamidoethylamino-2-methoxyphenylimino -1-phenyl-5-pyrazolone;

1- (2,4',6'-trichlorophenyl) -4- (4'- [N,N-diethylamino] 2'-rnethyl-phenylimino -5-pyrazolone;

l- (4'-amino-2',5'-dimethoxy-phenylazo) -2-methoxynaphthalene;

3-amino-4-biphenylazo-l- (2,4',6'-trichlorophenyl) -5- pyrazolone;

tetramethylamino-anthraquinone; and

4,8-diarnino-anthrarufin.

As previously noted, it will be recognized that where a dye has more than two available reactive primary and/or secondary amino groups, reaction may take place at two or more of such amino groups.

13 Synthetic procedure (A) will be illustrated in greater detail in conjunction with the following specific example which sets out a representative application of this procedure, which, however, is not limited to the details therein set forth and is intended to be illustrative only.

Example (a) 2.00 g. of 4,8-diamino-anthrarufin is dissolved in 100 cc. of o-dichlorobenzene in a flask equipped with an air reflux condenser, a nitrogen gas inlet tube and protected from moisture by a tube of Drierite. The solution is deaerated with nitrogen, brought to a boil and 3.00 g. 1:1 mole ratio) of 2,5-dicarbethoxyhomogentisyl chloride is added under nitrogen. After 20 minutes at the boiling point, the solution is cooled, the product collected, washed with acetone and hexane, and dried. The resultant product comprises 2.50 g. of -amino-l-(2',5'- dicarbethoxy-homogentisarnido)-4,8-dihydroxy anthraquinone, blue-black crystals with a bronze reflex. A second crop provided 0.45 g. of the same product.

The first crop above, 2.50 g., is finely ground, added under nitrogen to 110 cc. of hot deaerated water containing 5.0 g. of potassium hydroxide, 2-3 cc. of methanol, and kept at approximately 90 C. for 60 seconds. The mixture is filtered, under nitrogen, into excess dilute acetic acid. The precipitated product is then filtered and washed with water. The product, a deep blue powder, 5 amino 4,8 dihydroxy 1 homogentisamido anthraquinone, Formula XVII, is moderately soluble in acetone and ethanol; very soluble in pyridine and 2% aqueous alkali. The product exhibits a spectral absorption curve which shows a hmaxv at 612 m 20,000.

Analysis for C H N O containing 22.3 wt. percent sodium acetate.Calculated: 7, 55.4; H, 3.9; N, 5.2; Ash, 10.6. Found: C, 55.1; H, 4.4; N, 5.2; Ash, 10.6.

A second synthetic procedure, designated throughout the specification as procedure (B), is concerned with the preparation of specified dye developers within generic Formulae l and 2; specifically monoand diazo dye developers wherein the phrase wherein R has the same significance as previously noted; W is a primary amino, a secondary amino, a tertiary amino, or a hydroxyl group in ortho or para position with regard to the azo group; Ar is an aryl group which may be substituted as for example by alkyl, halogen, alkoxy, acid (e.g., carboxyl, sulfo, etc.), sulfonyl, acyl, nitro, or amino groups or a heterocyclic group; p is 0 or 1; and A and A are each the nucleus of a diazotizable aromatic primary amine, e.g., a benzene, naphthalene, diphenyl or heterocyclic nucleus, which nucleus may be the same or different.

As illustrations of suitable aromatic primary amines from which A and A may be derived, mention may be made of any cyclic amine of the benzene, naphthalene, diphenyl or heterocyclic series, which is capable of diazotization. Where a disazo compound is desired, i.e., where p is 1 in the above formula, any cyclic amine of the azobenzene, azonaphthalene, or azoheterocyclic series, as well as azo compounds containing dissimilar nuclei, may be employed in the practice of this invention. The nucleus may be unsubstituted or it may be substituted in any or all positions by any monovalent group, such as for example, hydroxy, alkyl, aryl, aryloxy, halogen, nitro, sulfonyl, acid, acyl, cyano and others. As representative of the many diazotizable amines which can be used as the diazo component in the process of this invention, mention may be made of: 3-nitro-4-chloro-aniline, 2-nitro-4- amino-toluene, 2-chloro-4-aminophenetole, 2-nitro-benzidine, dianisidine, thioaniline, 4,4'-diamino-benzophcnone, benzidine-sulfone, beta-amino-anthraquinone, 2- amino-methyl-thiazole, 2-amino-benzothiazole, 2-amino- 6-ethoxy-benzothiazole, 5-amino-quinoline, 6-amino-quinoline, ortho-, meta and para-toluidines, -xylidines, -anisidines and -phenetidines, ortho-, metaand para-chloro (and -bromo-) anilines, 4-chloro-2-amino-toluene, chloroanisidines and -phenetidines, nitro-toluidines and anisidines such as 2-nitro-4-aminotoluene and 2-nitro-4-aminoanisol, amino-phenyl sulfones such as 4-amino-phenylmethyl-sulfone, 3-amino-phenyl-ethyl-sulfone and 4- amino-diphenyl-sulfone, mand p-amino-acetanilide, 2-, 3- and 4-amino-diphenyl, 2-, 3- and 4-amino-diphenyl ether, 0-, mand p-amino-phenyl-sulfon-dimethyl-amide, o-, mand p-amirimbenzamide, p-amino-acetanilide, 2,5- dimethoxy-aniline, p-an'isidine, o-anisidine, alpha-naphthylamine, m-nitro-acetanilide, aniline, m-anisidine, 1namino-acetanilide, 5-amino-1,2,4-triazol, 2-phenyl-4,5-diamino-tetrazol, 1-phenyl-S-amino-triazol, S-amino-tetrazol, 4,4-diaminoazobenzene, and 4-amino-1,1'-azobenzene.

We have discovered that these dye developers may be prepared by coupling an appropriate diazoniurn salt into a compound of the general formula:

II I L Z -(a1]eylene)ni-O-N 2 wherein n, R, W, and Ar have the same significance as previously noted; and Z represents the protected derivative of a benzenoid developing group, preferably the acylated derivative thereof, more preferably an o-bis-acyloxyphenyl or a p-bis-acyloxyphenyl group. The protecting or insulating groups areremoved prior to photographic utilization of the dye developers, for example, removal of the acyloxy protective groups of Z to effect thereby reconstitution of hydroxyl groups, the removal being accomplished, for example, by hydrolysis in the presence of alkali.

The compounds of Formula 8 are disclosed and claimed in the copending US. application of Milton Green, Helen P. Husek and Sidney Kasman, Serial No. 200,639, filed June 7, 1962, and now US. Patent No. 3,214,469, a continuation-in-part of Serial No. 709,001, filed January 15, 1958 (now abandoned).

Synthetic procedures of the last-mentioned type are disclosed and claimed in the copending US. application of Sidney Kasman and Helen P. Husek, Serial No. 339,615, filed January 23, 1964, a continuation-in-part of Serial No. 75,127, filed December 12, 1960, and now abandoned, which in turn is a continuation-in-part of Serial No. 709,005, filed January 15, 1958, and now abandoned.

The term acyloxy is meant to signify the grouping wherein Y is an aryl, alkyl, aryloxy, or alkoxy group. The terms alkyl and aryl are intended to signify also substituted aryl and alkyl groups, for example, aralkyl and alkaryl groups.

As examples of compounds within the scope of Formula 8, mention may be made of:

5 2',5 '-bis-carbethoxyphenylacetamido -2-methoxy- N,N-diethylaniline;

p- 2,5 -bis-carbethoxyphenylacetamido -aniline;

4- 2',5 -bis-canbethoxyphenylacetamido -2,5-diethoxy- I aniline;

3- 2',5 '-bis-carbethoxyphenylacetamido -N,N-diethylaniline;

3 2',5 -bis-carbethoxyphenethylcarboximido -N,N-

diethylaniline;

3- 2',5 '-bis-carbethoxyphenylacetamido -N,N-diethylnaphthylamine;

3-( acetamido-6- 2',5 '-bis-carbethoxyphenylacetamido N,N-diethylaniline;

One method of preparing the compounds of Formula 8 comprises reacting a compound of the formula:

W ArNR wherein R and Ar have the same significance as noted in Formula 8 and W is a hydroxyl, a nitro, a tertiary amino or, Where R is hydrogen, a secondary amino group; with a compound of the formula:

ll Z (alkylene) n-1G halogen wherein n and Z have the same significance as noted in Formula 8.

The product of the aforementioned reaction wherein W is a nitro group may be directly reduced to yield a compound where W is a primary amino group.

The preferred halogen component of Formula is chlorine.

The preferred hydroxyl-protected derivatives of the orthoand para-dihydroxyphenyl groups represented by the term Z in Formula 10 may be prepared by esterification of the orthoor para-dihydroxyphenyl group. After reaction, and prior to use in a photographic developing process, the protective groups may be removed by deesterification, such as for example, by hydrolysis in the presence of alkali.

In a preferred embodiment of this synthesis, compounds of the general formula:

wherein Z n, R, W and M have the same significance as previously noted, said coupling occurring on the aryl nucleus at an unsubstituted position para in respect to W; and removing the acyloxy groups of Z for example, by hydrolysis in the presence of an alkali subsequent to completion of the coupling reaction.

Where both the ortho and para positions are unsubstituted on the nucleus, coupling occurs almost exclusively in the para position. However, although there is a marked preference for para substitution, coupling occurs in the unsubstituted ortho position if said para position is substituted.

Where it is desired to separate respective ortho and para coupled products, this may be accomplished by suitable methods knownto the art, such as for example, their differential solubilities in alkaline media, steam distillation, etc. For many, purposes, separation of a mixture or ortho and para coupled products may be unnecessary.

id The diazonium salts utilized in the practice of this invention may be represented by the formula:

wherein A and ,0 have the same significance as previously noted. The preferred halogen is a chlorine.

It must be noted that coupling of a diazotizable cyclic amine into the compounds of Formula 8 wherein W is an amino group is preferably performed in an acid medium; however, Where W is a hydroxyl group and coupling is preferably performed in an alkaline medium, care must be observed that the pH of the reaction mixture does not at tain a concentration such that the acyloxy protective derivatives of the dihydroxyphenyl group may be hydrolyzed prior to the coupling reaction.

Synthetic procedure (B) will be illustrated in greater detail in conjunction with the following specific example which sets out a representative application of this procedure, which, however, is not limited to the details therein set forth and is intended to be illustrative only.

Example (b) 0.59 g. of p-cyanoaniline (0.005 mole) is dissolved in 7.5 cc. of water and 1.5 cc. of concentrated hydrochloric acid (0.018 mole). The p-cyanoaniline is diazotized at 5 C. by the addition with constant stirring of 0.35 g. of sodium nitrite (0.005 mole) in 2 cc. of water. The resultant diazo solution is then added at 5 to 10 C. with constant stirring to a solution of 2.49 g. of 5-(2,5'-biscarbethoxyphenylacetamido) 2 methoxy N,N-diethylaniline hydrochloride (0.0047 mole) in 10 cc. of pyridine. The resultant solution is stirred for 10 minutes at 5 C. and 50 cc. of water is added dropwise. A crystalline precipitate forms which is filtered, washed with water and dried under vacuum. The crystalline product, 5-(2'-,5'-biscarbethoxyphenylacetamido) 4 (p-cyanophenylazo)-2- methoxy-N,N-diethylaniline, a brick red solid, MP. to 102 C., forms a scarlet colored solution in acetone, the spectral absorption curve of which exhibits a x,,,,,,, at 515 I'll a; 25,800.

205 g. of 5-(2,5-bis-carbethoxyphenylacetamido)-4- (p-cyanophenylazo)-2-methoxy-N,N-diethylaniline is suspended in 30 cc. of 95% ethanol. 2 g. of potassium hydroxide (0.0357 mole) is dissolved in 7.5 cc. of water, deaerated, added to the alcohol suspension, warmed, and agitated for 10 minutes. 2.05 cc. of acetic acid (0.037 mole) is added, the mixture cooled and resultant precipitate filtered, washed with water and dried. The product, 4-(p-cyanophenylazo) 5 hornogentisamido-Z-methoxy- N,N-diethylaniline, Formula (IV), a brownish-red solid, MP. 183 to 185 C., exhibits a spectral absorption curve which shows a A at 515 my in acetone; e=28,400.

A third synthetic procedure, designated throughout the specification as procedure (C), is concerned with the preparation of specified dye developers within generic Formulae 1 and 2; specifically monoand disazo dye developers wherein the phrase set forth in Formula 2represents the residue of a dye molecule:

wherein R has the same significance as previously noted; Ar is an aryl group which may be substituted by alkyl, halogen, alkoxy, acid, sulfonyl, acyl, nitro, amino, or amino groups; A and A are each the residue of an azo coupling component, which coupling component may be the same or different.

As illustrations of suitable azo coupling components or couplers from which A. and A may be derived, mention may be made of phenols and aromatic amines having a free position ortho or para to the hydroxyl or amino group, e.g., phenols, anilines, naphthols, anthrols, naphthylamines, etc.; heterocyclic aromatic compounds containing hydroxyl or amino groups, such as pyrazolones or pyrroles; aliphatic or alicyclic activated methylene couplers, i.e., compounds having an aliphatic or alicyclic methylene group activated by two adjacent keto, aldehyde, ester or nitrile groups, which may be the same or different, or a keto, aldehyde, ester or nitrile group in combination with an amide group, e.g., 1,3-diketones or fi-ketonic acid arylamides; etc.; and substituted derivatives thereof. Examples of groups which may be present in such substituted derivatives include alkyl, sulfo, alkoxy, aryl, aryloxy, amino, keto, alkylarnino, arylamino, hydroxyl, cyano, alkylamido, arylamido, carbalkoxy, carboxamido, sulfonarnido, etc.

As used herein with reference to A and A the expression residue of a phenolic coupler is intended to refer to hydroxyphenyl, hydroxynaphthyl, hydroxyanthryl, etc. radicals, and substituted derivatives thereof; the expression residue of an aromatic amino coupler is intended to refer to aminophenyl, aminonaphthyl, etc. radicals, and substituted derivatives thereof; and the expressions residue of a heterocyclic aromatic coupler, residue of an aliphatic activated methylene coupler and residue of an alicyclic activated methylene coupler are to be similarly construed.

It has been discovered that certain dye developers, within Formula 1, may be prepared by diazotizing a compound of the formula:

wherein Z Ar n, and R have the same significance as previously noted; coupling the diazonium compound into the desired coupling component A and removing the protective groups of Z to effect thereby reconstitution of the Z, said removal being accomplished, for example, by hydrolysis of acyl groups in the presence of alkali.

The compounds of Formula 15 are disclosed and claimed in the previously cited copending US. application Serial No. 200,639, now US. Patent No. 3,214,469.

Synthetic procedures of the last-mentioned type are disclosed and claimed in the copending US. application of Milton Green and Helen P. Husek, Serial No. 75,128, filed December 12, 1960, and now US. Patent No. 3,- 158,595, a continuation-in-part of Serial No. 709,002, filed January 15, 1959, and now abandoned.

The coupling component employed to provide the residue A may be a coupler containing a diazotizable amino group. It is to be understood, however, that one may employ a coupler having a group convertible to a diazotizable amino group, e.g., a nitro group, and that the diazotizable amino group may be on a nucleus other than the nucleus substituted by the azo grouping. Thus, Where a disazo compound is desired, that is, where p is 1 in Formula 14, the monoazo intermediates may be employed, in subsequent diazotization and coupling steps, prior to removal of the protective groups of Z For example, the initial coupling may be into 2,5-dimethoxyaniline and the resulting monoazo product diazotized and coupled into the desired second coupler.

The coupling is generally performed at a pH which is preferably not greater than about 9.

By the use of two moles of the diazonium salt to each mole of the coupling component, one may couple twice into certain of the coupling components which provide the residue A as, for example, phenols and aromatic amines which have two directing groups and two free coupling positions, such as 1,6-dihydroxy naphthalene and 1,5-diaminonaphthalene.

Where the coupling component is a phenolic coupler, and particularly a naphthol, it has been found that coupling ortho to the hydroxyl group gives a dye developer of superior color properties. It has also been found that such ortho-coupled dye developers exhibit essentially no pH sensitivity over a fairly wide range on either side of neutral.

As examples of additional coupling components which may be employed to provide A and A mention may be made of:

4-benzyl-1-naphthol 4-methy1-1-napthol 4-methoxy-a-naphthylamine 4-acetamido-a-naphthylamine Phenol Aniline 1 ,5 -naphthalene,diamine p-Cresol l-hydroxyanthracene 1-hydroxy-2-naphthanilide Diketohydrindene Malonitrile Acetoacetanilide Synthetic procedure (C) will be illustrated in greater detail in conjunction with the following specific example which sets out a representative application of this procedure, which, however, is not limited to the details therein set forth and is intended to be illustrative only.

Example (0) 0.011 mole of p-(2,5-bis-carbethoxyphenylacetamido)- aniline hydrochloride is dissolved in 0.033 mole of concentrated hydrochloric acid and cc. of water. The mixture is cooled in an ice bath and diazotized at 0 to 5 C. with sodium nitrite. The resultant diazo solution is clarified and added, with constant stirring over a twentyminute interval, to a mixture of 0.01 mole of 4-methoxyl-naphthol, 100 cc. of acetone, cc. of saturated sodium bircarbouate solution, and 50 cc. of Water. The resulting slurry is stirred, filtered and the filter cake subjected to a water wash. The resultant product, 2-(p-[2', 5 bis-carbethoxyphenylacetemido]-phenylazo)-4-methoxy-l-naphthol, is a magenta dye.

This product is treated in vacuo with a solution containing 5 g. of potassium hydroxide in 15 cc. of water and 70 cc. of alcohol. The mixture is intermittently warmed in a steam bath for three minutes and the desired product precipitated from the mixture with dilute hydrochloric acid. Purification of the product is accomplished by dissolving the product in methyl Cellosolve and reprecipitating with a 1% solution of hydrochloric acid. The resultant product, 2-(p-homogentisamido-phenylazo)-4-methoxy-l-naphthol, Formula V, a magenta dye, exhibits a spectral absorption curve which displays a km x 'at 534 me in ethanol; e=24,000.

A fourth synthetic procedure, designated throughout the specification as procedure (D), is concerned with the preparation of specified dye developers within generic Formulae 1 and 2; specifically monoand disazo dye developers wherein the phrase O R N-Ar 1 9 wherein n, R and Ar have the same significance as previously noted; and Z represents the protected derivative of a hydroquinonyl group, preferably the acylated derivative thereof; and effecting removal of the protecting 20 toluene. The product, 3.2 g. of N-ethyl-N-(B-[LS-diacetoxyphenylacetamido] ethyl) 3 methyl 4 (pnitro-phenylazo)-aniline, melting at 162 to 165 C., exhibits a spectral absorption curve which shows a h at groups from Z to provide a hydroquinonyl group as Z. 5 502 m in methyl Cellosolve; E=34,400

The compounds of Formula 17 may be prepared by Analysis for C H N O .Ca1culated: N, 12.5%. reacting homogentisic lactone with a compound of the Pound: N, 12.4%. formula: 0.56 g. (0.001 mole) of the product is dissolved in 15 (18) 02116 cc. of 95% aqueous ethanol in a nitrogen atmosphere. Y 0.23 g. (0.004 mole) of potassium hydroxide is dissolved AIL! in 4 cc. of ethanol, deaerated with nitrogen and added to C2H4NH2 the product solution. The mixture is maintained at 5.0 such as N-(2-aminoethyl)-N-ethyl-m-toluidine and formto Q two hours, ecldlfiflid With y ing the protecetive derivative of the products hydroquiacld- The resultant Preclpltate ls l"emoved y none group as by acylation. filtratlon and the resultant product crystallized from an Synthetic procedure (D) will be illustrated in greater akohol'water mixture The P P the 3' detail in conjunction with the following specific example 10W dye develop? 5' Q P Y which sets out a representative application of this procei j P Formula F dure, which, however, is not limited to the details therein men-mg f 190 to 191 exhlblts spectral absorptlon set forth and is intended to be illustrative only. 20 curve whlfih shows a )\maxat 492 111 ethanol; 6:335000- Analysis for C H N O .Calculated: C, 62.88%; H, Example (4) 5.70%; N, 14.67%. Found: 0, 62.83%; H, 6.17%; N, 2.76 g. (0.02 mole) of p-nitroaniline is dissolved at 35 C. indil te hydrochloric id, Th oluti i o l d The invention Wlll be illustrated 1n greater detail in to approximately 5 C. and diazotized With 1.4 g. (0.02 25 COHlImCfiOH With the following Specific examples Which mole) of sodium nitrate. 8.25 g. (0.02 mole) of N-(fifepfesentatlve Preparation "F f p pi [2,5 diacetoxyphenylacetamido] ethyl) N ethyl utihzatron of the novel compounds of this invention, WhlCh toluidine is dissolved in 20 cc. of acetic acid and added however are not limited to the details therein set forth to the diazoniurn solution. The resultant mixture is and are lIlteflded to be 1111 1StfatlVe ystirred for approximately minutes, poured into a mix- 30 i lndlcated y Intermediates, developer Interture of ice and water, and neutralized. The solid pre- 11164121165, synthetlc Procedure, resultant P and cipitate is separated and crystallized fro a water-alcohol characterization thereof are hereinafter set forth in tabular mixture. The resultant product is recrystallized from forminthe interest of clarity.

TABLE I Dye Dlg veloper Dye Intermediate Developer Intermediate Synthetic Procedure Dye Color I 1,4-bis-(Baminoethylamin0)-anthrahomogentisiclactone- A Cyan.

qumone. II. .do do A Do. III 3-z1imino1-phenyl-4-phenylazo-5-pyrazo- 2,5-dibenzoyl-homogentisyl chloride A Yellow.

one. IV p-Cyanoaniline hydrochloride 5-(2,5-dicarbethoxy-phenylacetamido)- B Magenta.

Z-methoxy-N ,N-diethyl-aniline. V 4-methoxy-l-naphthol p-(2,5-dicarbethoxy-phenylacetamidoy C Do.

aniline hydrochloride. fi-anilino-l-naphthol-3-sulphonic acid 4-(2' -dicarbethoxy-phenylacetamido)- C Do.

2,5-diethoxy-aniline hydrochloride. 4-acetamido-1-mnh hnl ,fln 0... Purple. 3-methyl-l-phenyl-5-pyrazolone 4-(2,5-diacetoxygentisamido)-ani1ine C Yellow.

hydrochloride. 1-(2',5-dimethoxy-4'-[N-methy1amino]- 2,5-dicarbethoxy-homogentisyl chloride. A Magenta.

phenylazo)-2-methoxy-naphthalene. 4-(4-[N,N-diethylamino]-phenylazo)- A..- Yellow.

3-amino-1-pheny1-5-pyrazolone. 3-ammu l-(4-N-ethyl-N-fl-methylsulfondn A" Magenta.

amjdoethylamino-2'-methoxyphenylimino)-1-phenyl-5-pyrazolone. 2,5-dimethoxyanilinehydrochloride 4-(2,Siglficarbethoxyhomogentisamido)-l- Do.

nap o 1-(2',4 6'-trichloropheny1)-4-(4-[N,N-di- 2,5-dicarbethoxyhomogentisyl ehlon'de Do.

ethy amin0]-2-methylphenylimino)-5- pyrazolone. l-(4-amino-2,5-dimethoxyphenylazo)-2- -do Do.

methoxy-naphthalene. 3-amino-4-biphenylazo-1-(2',4',6-trichloro- 2,5-dibenzoylhomogentisyl chloride Yellow.

phenyl)-5-pyrazolone. 3-amino-4-(5'-chloro-2-hydroxyphenyl- 2,o-dicarbethoxy-homogentisyl chloride--. Do.

azo)-1 phenyl-5-pyrazolone. 4,8-diamh1oanthramfin dn Blue. p,p-Methylenedianiline 3-(2,5-dicarbethoxyhomogentisamido)1- Yellow.

phenyl-fi-pyrazolone. 4,8-diaminoanthrarufin 2,5-dicarbethoxyhomogentisyl chloride Magenta, l,5-diaminoanthraquinone 2,5-dibenzoylhomogentisyl chloride A Salmon. 3-amino-4-(2-hydroxyphenylazo)-1- 2,5-dicarbethoxy-homogeutisyl chloride.-. Yellow.

phenyl-fi-pyrazolone. 3-amjno-4-(2,5-diehloro-phcnylazo)-1- do Do.

(2 ,4 ,6-trichlorophenyl) -5-pyra-zolone. 3-amino-4-(p-[phenylazo]-phenylazo)-1- 2,5-dibenzoyl-homogentisyl chloride Do.

phenyl-5-pyrazolone. 3-amitio-4-(2,6-dichlorophenylazo)-1- fi Do.

phenvl-5-pyrazolone. lA-diamino-anthraquinnne dn Purple. l-amino-anthraquinone do Yellow-orange. 4-cyano-2,5-dimethoxy-aniline hydro- 8-(2,5'-dicarbethoxy-homogentisarnido)- Magenta.

chloride. 2-naphthol. 4-methoxy-1-naphthol 4-(2',5'-dicarbethoxy-homogentisamido)- Do.

. 2,5-dichloroani1ine hydrochloride. XXIX Z-amino--methyl-5-acetyl-thiazole N-(B-[2,5-diacetoxy-phenylacetamido]- De.

ethyl)-N-ethyl-m-toluidine.

TABLE ICont1nued Dye Developer Dye Intermediate Developer Intermediate Synthetic Procedure Dye Color XXX 8-acetamido-2-naphthol 4-(2,5-dicarbethoxy-homogentisamido)-2- Do.

methoxy-aniline hydrochloride.

XXXI 4-(N,N-dimethyl-sulfamyl)-1-naphtho1- do Do.

XXXII 3'-amino-quinaphthalone 2,5-dicarbethoxyhomogentisyl chloride- Yellow.

XXXIII p-Nitroaniline hydrochloride N-(B-[2,5-diacetoxyphenylacetamido} o.

ethyl)-N-ethyl-m-toluidine.

XXXIV Tetramethylamino-anthraquinone 2,5-dicarbethoxy-homogentisyl chloride A Magenta.

XXXV 2-amino-4-methy1-5-carbethoxy-thiazole N -fl-[2,5-diacetoxy-phenylacetamido} D Do.

ethyl)-N-ethyl-m-toluidine.

XXXVI 4-aceto-1-naphthol 4-(2,5-dicarbethoxy-homogentisamido)- C Do.

2,5dimethoxy-aniline hydrochloride.

As previously mentioned, the novel compounds of this invention are useful dye developers. In the following eX- 20 amples, all parts are given by weight except where otherwise noted, and all operations involving light-sensitive materials are carried out in the absence of actinic radiation. These examples are intended to be illustrative only of the photographic use of the dye developers and should 25 not be construed as limiting the invention in any Way.

Each of the photographic examples set forth in Table II was effected as follows: a photosensitive element is prepared by coating a gelatin-coated film base with the dye layer coating solution set :forthin the table, when 0 a dye layer is employed. After this coating has dried,

TABLE II Dye De- Concen- 4 Inhibition Image Image-Receiving veloper tration Disposition Emulsion Processing Composition Time Color Layer Coating N o. Composition 1 3.0 grams In a dye layer formed Silver iodobro Sodium hydroxide 2.5 1 minute Cyan.

from a coating compom e. grams; metol 0.1 sition comprising 4.0 gram; potassium brograms of cellulose acemide 0.1 gram; urea tate hydrogen phthal- 1.0 gram; sodium carate; 80 cc. of acetone; boxymethyl cellulose and 20 cc. of methanol. 5.0 grams; and 100 cc.

of water. I 1.0% In processing comdo Sodium hydroxide Conventional Nega- None.

position. 1.5%; sodium sulfite developtive: 1.0%; and potassium ment 1 graybromide 0.1%. minute. ishblue image.

111 2.0 grams" In a dye layer formed do Water 100 cc.; sodium 1 minute Yellow... 4.0 grams of N-methfrom a coating compocarboxymethyl celluoxymethyl polysition comprising 4.0 lose 4.5 grams; sodium hexamethylene grams of cellulose hydroxide 1.5 grams; adipamide; 80 cc. acetate hydrogen and Inetol 0.1 gram. of isopropanol; and phthalate in 100 cc. 20 cc. of water. of methyl Cellosolve.

IV 4.0% In a dye layer formed do Sodium carboxymethyl do Magenta. 4.0% N -methoxyfrom a coating comcellulose 5.0%; lmethyl polyhexaposition comprising a phenyl-3-pyrazolidone methylene adip. 4% solution of cellu- 0.6%; sodium hydroxamide in 80% lose acetate hydrogen ide 3.0%; fi-nitroaqueous ethanol. phthalate in a 50:50 benzimidazole 0.08%; mixture, by volume, and 2,5-bis-ethyleneof acetone and tetraimlno-hydroquinone hydrofuran. 0.4%.

V 3.0% do do Sodium hydroxide .do do Do.

1.25%; potassium bromide 0.2%; 1- phenyLS-pyrazolidone 0.2%; and sodium carboxymethyl cellulose 4.25%.

VII 3.0% do do Sodium hydroxide2.0%; do Purple. Do.

potassium bromide 0.2%; 1-phenyl-3- pyrazolidone 0.2%; and sodium carboxymethyl cellulose 4.5%.

VIII. 3.0% In a dye layer formed do Sodium hydroxide 1.5%; do Orange- Do.

from a coating compotassium bromide yellow. position comprising a 0.2%; 1-phenyl-3- 4% solution of cellupyrazolidone 0.2%; lose acetate hydrogen and sodium carboxyphthalate in a 80:20 methyl cellulose 4.5%. mixture, by volume.

of acetone and methanol.

See footnote at end of table.

Dye De- Concen- Inhibition Image Image-Receiv ng veloper tretion Disposition Emulsion Processing Composition Time Color Layer Coating No. Composition IX 3.0% In a dye layer formed do Sodium carboxymethyl do Magenta Do.

from a coating compocellulose 4.5%; l-

sition comprising a phenyl-3-pyrazolidone 4% solution of cellu- 0.2%; sodium hylose acetate hydrogen droxide 1.5%; and phthalate in a 50:50 potassium bromide mixture, by volume, 0.2%. of acetone and tetrahydroiuran.

X 2.5% do d0 d0 Do.

XI 3.0% do d0 Sodium carboxyrnethyl Do.

' cellulose 4.5%; l-

phenyLB-pyrazolidone 0.2%; sodium hydroxide 2.0%; and pgigssium bromide 0.

XII 4.0% do do Sodium hydroxide 2.0%; do Magenta- Do.

potassium bromide 0.2%; 1-phenyl-3- pyrazolidone 0.2%; and sodium carboxymethyl cellulose 4.5%. XIII 1.5% In a dye layer formed do Sodium carboxymethyl do do 6% aqueous poly from a coating compocellulose 4.5%; 1- vinyl alcohol. sition comprising a phenyl-3-pyrazolidone 4% solution of cellu- 0.2%; sodium hylose acetate hydrogen droxide 1.5%; and phthalate in a 80: 20 potassium bromide mixture, by volume, 0.2%. of acetone and tetrahydroiuran. XIV 3.0% In a dye layer formed -do Sodium carboxyrnethyl --do -do Do.

from a coating compocellulose 4.5%; 1- sition comprising a phenyl-3-pyrazolidone 4% solution of cellu- 0.2%; sodium hylose acetate hydrogen droxide 2.5%; and phthalate in a 80:20 potassium bromide mixture, by volume, 0.2%. of acetone and methanol. XV 3.0% do do Sodium hydroxide 2.0%; .do Yellow-.. 4.0% N-methoxypotassium bromide methyl polyhexa- 0.2%; 1-phenyl-3- methylene adipapyrazolidone 0.2%; sodimide in 80% aqueous um carbonate2.0%; and alcohol. sodium carboxymethyl cellulose 4.5%.

XVI 3.0% --do --do Sodium hydroxide 1.5%; do. Orange... 6% aqueous polyvinyl potassium bromide alcohol. 0.2%; l-phenyl-S-pyraz olidone 0.2%; and sodium carboxymethyl cellulose 4.5%.

XVIL- 3.0% In a dye layer formed do Sodium carboxy'methyl do Blue 4.0% N-methoxyfrom a coating compocellulose 4.5%; 1- methyl polyhexasition comprising a phenyl-3-pyrazolidone methylene adipa- 4% solution of cellu- 0.2%; sodium hydroxmide in 80% aqueous lose acetate hydrogen ide 2.0%; and potasethanol. phthalate in a 80:20 slum bromide 0.2%. mixture, by volume of acetone and tetrahydroiuran.

XVIL do -do --do do .do. 6.0% aqueouspolyvinyl alcohol.

XVIII. In a dye layer formed --.do Sodium carboxymethyl -do- Yellow 40% N -methoxyfrom a coating compocellulose 4.5%; 1- methyl polyhexasition comprising a phenyl-B-pyrazolidone methylene adipa- 4% solution of cellu- 0.2%; sodium hydroxmide in 80% aqueous lose acetate hydrogen ide 3.0% and potesethanol. phthalate in a 50:50 slum bromide 0.5%. mixture, by volume, of acetone and tetrahydrofuran.

XVIII 1.2 grams In emulsion 1.2 grams of dye do --do do... Do.

developer is ground in 3 cc. of Water and 4 drops of Antarox D-l00. The mixture is added to 30 cc. of a silver iodobromide emulsion and coated on a support.

XIX 2.75% In a dye layer formed Silver iodobro Sodium carboxymethyl do Magenta- 6% aqueous polyvinyl from a coating compomide. cellulose 4.5%; 1- alcohol. sition comprising a phenyl-3pyrazolidone 4% solution of cellu- 0.2%; sodium hydroxlose acetate hydrogen ide 1.5%; and potasphthalate in a 50:50 slum bromide 0.2%. mixture, by volume, of acetone and tetrahydroiuran.

irom a coating composition comprising a 2% solution of cellulose acetate hydrogen phthalate in methyl Cellosolve.

3.0%; 1-phenyl-3- pyrazolidone 1.2%; 2,5-bis-ethyleneimino-hydroquinone 0.9%; 6-nitrobenzlmidazole 0.12%; and sodium carboxymethyl cellulose 5.0%.

TABLE II-Continued Dye De- Concen- Inbibition Image Image-Receiving veloper tration Disposition Emulsion Processing Composition Time Color Layer Coating No. Composition XX 3.00% In a. dye layer formed do .do .do Salmon. 4% N-methoxymethyl from a coating compopolyhexamethylene sition comprising a adipamide in 80% 4% solution of celluaqueous ethanol. lose acetate hydrogen phthalate in a 80:20 mixture, by volume, of 1acetone and methano XXI 2.0% do do Sodium hydroxide 1.5%; do Yellow 4.0% N-methoxymeth l potassium bromide polyhexamethylene 0.2%; 1-phenyl-3-pyradipamide in 80% ezolidone 0.2%; and aqueous alcohol. sodium carboxymethyl cellulose 4.5%.

XXII 3.0% In a dye layer formed .do Sodium hydroxide 2.0%; .do do Do.

from a coating compometol 0.2%; potassium sition comprising a bromide 0.2%; and 4% solution of cellusodium carboxylose acetate hydrogen methyl cellulose 4.5%. phthalate in a 80:20 mixture, by volume, of acetone and tetrahydrofuran.

XXIII 3.0% In a dye layer formed .do Sodium hydroxide 2.0%; do Orange 6% aqueous polyvinyl from a coating compometol 0.2%; potassium alcohol. sition comprising a bromide 0.2%; sodium 4% solution of cellucarbonate 2.0%; and lose acetate hydrogen sodium carboxyphthalate in tctramethyl cellulose 4.5%. hydroiuran.

XXIV 2.5% do do do ..do Yellow 4.0% N-methoxymethyl polyhexamethylene adipamide in 85% aqueous A I ethanol and 15% iurfural alcohol. XXV 2.5% In a dye layer formed .do. Sodium carboxymethyl do Purple... Do. from a coating compocellulose 4.5%; metol sition comprising a 0.1%; and sodium 4% solution of celluhydroxide 1.5%. lose acetate hydrogen phthalate in a 80:20 mixture, by volume, of acetone and methano XXV II 3.0% In a dye layer formed do Sodium carboxymethyl .do Magenta- 4.0% N-methoxyfrom a coating compocellulose 5.0%; 1- methyl polyhexasition comprising a phenyl-3-pyrazolidone methylene adipa- 4% solution of cellu- 0.8%; sodium hydroxmide in 80% aqueous lose acetate hydrogen ide 3.0%; Potassium ethanol. phthalate in a 50:50 o ide 0 nd mixture, by volume, 2,5-bis-ethylene-iminoof acetone and tetrahydroquinone 0.6%. hydrofuran. v

XXV III 3.0% do do 1-phenyl-3-pyrazolidone .do do Do.

0.6%; sodium hydroxide 2.0%; G-nitrobenzimidazole 0.08%; 2,5- bis-ethyleneiminohydroquinone 0.4%; and sodium carboxymethyl cellulose 4.5%.

XXIX 3.0% do do Sodium hydroxide 1.5%; .do do Do.

1-phenyl-3-pyrazolldone 0.4%; 2,5-bisethyleneimino-hydroquinone 0.2%; 6- nitrobenzimidazole 0.08%; and sodium carboxymethyl cellulose 4.5%.

XXX 3.0% In a dye layer formed .do Sodium hydroxide 2 minutes, do Do.

from a coating com- 3.0%; sodium carposition comprising a boxy-methyl cellulose 2% solution of cellu- 5.0%; l-phenyl-3- lose acetate hydrogen pyra olidone 1.2%; phthalate in tetra- 2,5-b1s-ethyleneiminohydrofuran. hydroquinone 0.9%;

and 6-nitrobenzlmidazole 0.12%.

XXXI 3.5% In a dye layer formed .do Sodium hydroxide 1 minute -..do Do.

from a coating com- 1.0%; sodium carposition comprising a boxymethyl cellulose 2% solution oi cellu- 4.25%; 4,4-dimethyllose acetate hydrogen l-phenyl-3-pyrazoliphthalate in a 50:50 done 0.6%; xylohymixture, by volume, droquinone 0.4%; and of acetone and tetrafi-nitrobenzimidazole hydrofuran. 0.06%.

XXXII 3.0% In a dye layer formed .do Sodium hydroxide .do Ye11 w D0.

TABLE III-Continued Dye De- Concen- Inhibition Image Image-Receiving veloper tration Disposition Emulsion Processing Composition Time Color Layer Coating N 0. Composition XXXIIL. 1.5% In a dye layer formed do Sodium hydroxide 3 minutes Magenta, Do.

irom a coating com- 2.5%; l-phenyl-Z? position comprising a pyrazolidone 1.0%; 2% solution of cellut-butyl-hydroquinone lose acetate hydrogen 0.45%; fi-nitrobenzphthalate in a 50:50 imidazole 0.2%; and mixture, by volume, sodium carboxyof acetone and tetramethyl cellulose hydroi'uran. 4.5%. XXXIV 4.5% do do Sodium hydroxide 1 minute do Do.

1.0%; Lphenyl-Iipyrazolidone 0.8%; 2,5'bis-ethyleneiInino-hydroquinone 0.6%; o-nitrobenzimidazole 0.08%; and sodium carboxy methyl cellulose 4.25%. XXXV 3.0% In a dye layer formed do Sodium hydroxide do .do. Do.

from a coating corn- 1.5%; 1-phenyl-3- position comprising a pyrazolidone 0.6%; 4% solution of cellu- 2,5-bis-ethy1enelose acetate hydrogen imino-hydroquinone phthalate in tetra 0.4%; 6nitrobenzimhydroiuran. idazole 0.08%; and

sodium carboxy insehyl cellulose XXXVI 5.2% In a dye layer formed do Sodium hydroxide do do Do.

from a coating com- 1.0%; sodium carposition comprising a boxymethyl cellulose 2% solution of cellu- 4.25%; 4,4-dimethyllose acetate hydrogen l-phenyl-S-pyrazoliphthalate in a 50:50 done 0.6%; xylohymixture, by volume, droquinone 0.4%;aud of acetone and tetra,- fi-nitrobenzimidazole hydrofuran. 0.06%.

1 The image-receiving element was prepared by coating a polyvinyl Benzoic anhydride g 1.5 butyral-coated baryta paper with a solution comprising: Diethyl male 2 7. 5

Partially hydrolyzed polyvinyl acetate (sold under the name of "Vinylite MA28-18 -.g Stearto-chromic chloride (hardening agent sold in isopropanol under the name of Quilon") g 1. 5

In addition to the aforementioned illustrative dye developers (I to XXVI) disclosed in the parent application, Serial No. 1,442, the following additional dye developers followed by coating with a solution of 50 g. of silica suspension and 25 cc. of water, after which a coating was a plied comprising 6 g. of polyvinyl alcohol and 0.375 g. of phosphoric aci in 100 cc. of water.

2 Trade name for an aliphatic polyglycol ether non-ionic emulsifier and disperser.

useful in photographic processes such as disclosed in Table H also have been prepared:

LXVI

LXVIII

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Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3533788 *Aug 25, 1967Oct 13, 1970Minnesota Mining & MfgImage recording sheet
US4013633 *Jun 27, 1975Mar 22, 1977Eastman Kodak CompanyYellow azopyrazoline dye releasing redox compounds for photographic color transfer
US6689828 *Jul 24, 2001Feb 10, 2004Eastman Chemical CompanyThermally stable, anthraquinone colorants containing copolymerizable vinyl groups
US6787658 *Nov 21, 2003Sep 7, 2004Eastman Chemical CompanyThermally stable, anthraquinone colorants containing copolymerizable vinyl groups
US6870062 *Nov 21, 2003Mar 22, 2005Eastman Chemical CompanyThermally stable, anthraquinone colorants containing copolymerizable vinyl groups
US6870063 *Nov 21, 2003Mar 22, 2005Eastman Chemical CompanyThermally stable, anthraquinone colorants containing copolymerizable vinyl groups
US7141685 *Dec 12, 2003Nov 28, 2006Eastman Chemical CompanyThermally stable, anthraquinone colorants containing copolymerizable vinyl groups
US20040102637 *Nov 21, 2003May 27, 2004Cyr Michael JonhThermally stable, anthraquinone colorants containing copolymerizable vinyl groups
US20040110812 *Nov 21, 2003Jun 10, 2004Cyr Michael JohnThermally stable, anthraquinone colorants containing copolymerizable vinyl groups
US20040122072 *Nov 21, 2003Jun 24, 2004Michael John CyrThermally stable, anthraquinone colorants containing copolymerizable vinyl groups
US20070032598 *Oct 6, 2006Feb 8, 2007Cyr Michael JThermally stable, anthraquinone colorants containing copolymerizable vinyl groups
Classifications
U.S. Classification534/682, 552/241, 534/599, 534/595, 552/255, 552/260, 430/464, 558/268, 552/237, 430/225, 552/235, 552/248, 558/269
International ClassificationG03C8/18, G03C8/02
Cooperative ClassificationG03C8/18
European ClassificationG03C8/18