US 2353205 A
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Patented July 11,- 1944 UNITED STATES PATENT.OFFICE COLOR-FORMING COMPOUND CONTAINING SULPIIONAMIDE GROUPS Paul W. Vittum, Willard 1). Peterson, and Henry D. Porter, Rochester, N. Y., assignors to Eastman Kodak Company, Rochester, N. J., a corporation o! NewJersey No Drawing. Application July 26, 1941, Serial No. 404,236. In Great Britain March. 31, 1939 7 Claims.
' react with the development product of primary aromatic amino developing agents to form color images on photographic development is well known and has been the subject of numerous prior patents. The dyes formed in this way are insoluble in water and in the ordinary photographic development and fixing baths although the silver images formed simultaneously with them during the photographic development may be removed from the photographic layer to leave pure dye images in the layer. The coupler compounds used in this way may be added to the developing soluticn or in certain cases may be incorporated in the photographic layer prior to exposure. when the coupler compounds are incorporated in the developing solution, it is desirable that they be 'sufilciently soluble in the developing solution so that amounts may be used which produce sumciently high dye densities in the resulting photographic image. In many'cases the coupler compounds are not sumeiently soluble in the developer and steps must be taken to increase their solubility. In Schinzel application Serial No.'-263,945, filed March 2-1, 1939, a continuation-in-part of Serial No; 151,811, filed July 3, 1937, now Patent 2,306,410, granted December 29, 1942, phenolic and naphtholic coupler compounds are described which contain sulphonamide groups in which the sulphur of the sulphonamide is attached to the phenol or naphthol. ll'hese compounds are highly soluble in the developing solutions and produce dyes which are transparent and are not cloudy or opaque as is the case with many dyes produced in this way. These dyes are, however, subject to, decomposition by the action of heat and light and it is, therefore, desirable to produce dyes having the solubility and light transmission characteristics of the dyes described in-the Schinzel appllcation but which are more stable to'heat and light.
It is, therefore, an object of the present in= vention to provide novel photographic coupler compounds having desirable properties with respect to heat and light stability. A further object is to provide photographic couplers which are highly soluble in developing solutions, A still further object is to provide photographic couplers which produce transparent dyes on photographic development. A still further object is to provide coupler compounds which produce dyes of desir- (Cl. 9H)
able light transmission characteristics for multicolor photography. Other obiects will appear from the following description of our invention.
These objects are accomplished by the use of certain coupler compounds containing sulphonamide groups.
The color-forming compounds which we have found to be useful are compounds of the general structure:
where It represents a substituted or unsubstituted aryl radical or an alkyl radical and R represents an alkyl radical.
Compounds representing this generahclass are as follows:
-(Dt enzenesulphouamino)-phenyl)-3-msthyl+pyrazolone N= C-C HI M'O N l CO- HI CO- H:
p-(a-metbyl-fi-pyrasolonyl-l)-benzenesulphonauilide N=c --C 5111 ihenozybonnnosulphonamido)-phenyl]- p 3-n-amyl-5-pyramlone cum-O-sm-mr l-ip-n-psniancsulplionamidophenyl)s't-mothyls'i-pyrazolone 2 aasaaos I The coupler compounds having the general dimethyl-p-phenylenedisminehydrochioride and dimethyl-p-phenylenediaminesulphate. The pformula:
. rz-c-sx co m N c-a* contain a methylene group which is reactive with the oxidation product of primary aromatic amino photographic developers to produce magenta dyes.
The following example. which is illustrative I only, is a developing solution containing a coupler suitable for use according to our invention: A. p-Aminodimethylanillnesulpha te --grsms.... 3.5 Sodium sulphite (anhydrous) ..-.do 2 Sodium carbonate (anhydrous) do- 20 Potassium bromide do 1 Water to cc 1000 B. l-[p-(bensenesulphonaminol-ph' 'l-.
s-methyl-ll-pyrazolone grams-.. 2 Sodium hydroxidblo'lb solution -cc-- is is added to A.
In the foregoin'gexample, we have described adding the coupler compound to the developingsolution itself. Although it will usually be employed in this way, the coupler compound may also be incorporated in the photographic layer prior to exposure and the colored image formed by development of the layer in the primary arcmatic amino developing s lution. speclal dispersing agents may be used for incorporating the coupler compoundin the emulsion and in certain cases the couplerflmay be absorved or adsorbed to the sensitive salt or may be combined with theaminophenols and their substitution products mayslsobeusedwheretheaminogroupisimsubstituted. All of these compounds have an unsubstituted amino group which enables the oxidation products of the developer to couple with the color forming compounds to form a dye image.
Our development process may be employed for the production of colored photographic images in layers of gelatin or other carrier, such as collodi'on organic esters of cellulose, or synthetic resins. The carrier may be supported by a transsensitive salt as a chemical combination. In the ease of a multi-layer photographic illm in which color forming compounds may be incorporated in one or more of the layers, it may be necessary to take special precautions to prevent wandering of the coupler compound from the sensitive layer in which it is incorporated.- Certain of the coupler compounds described in the present-application are in themselves non-dimming and may be incorporated in the photographic layer without the use of additional agents to prevent diffusion.
The compound I- [p- (p'-sec.-amylbensenesulphonamidolphenyl] 3 n-pentadecyl-li-pyrazolone is an example of this type coupler.
The sulphonamlde group. because of its solubilizing eflect, has-"a very important advantage in'connection withmon-diflusing couplers in thatit makes dispersion of the couplers very much easier. Thus it is'- posslble to have a coupler of high molecular weight which is completely nondiflusing and yet which is simp y and easily disdue to the salt-forming properties of the The aromatic amino developing agents used with the couplerg'compounds or our invention include the mono-F, diand triamin'oaryl compounds and their derivatives formed by substitution in the aminclsr p as w l as in the m:-
such as .alkylphetiylenediamines and albitoluylenediamines, These compounds are usually used inthe salt such *as'the hydrochloride or the sulphate, which are more stable than the parent medium such as glass, a cellulose ester or a non-transparent reflecting medium such as paper or an opaq e cellulose ester. The emulsion may be coated as single layer on the support or foe superposed layers on one or both sides of the support. The superposed layers may be diiferentially sensitized and the dyes formed therein by .coupling may be bleached by an oxidizing a ent such as chromic acid to colorless soluble compounds. The destruction of the dye in this way does not destroy the silver image and a silver image may be developed, bleached and developed to color a number oi times, thus permitting the formation of natural color images in superposed layers as described, for example, in Mannes and Godowsky U. 8. Patent No. 2,113,329.
'The examples and compounds set forth in the present specification are illustrative only and it is to be understood that our invention is to be taken as limited only by the scope ofthe appended claims. Where we describe organic groups such as aryl, alkyi. and sulphonamide' in a-Nnsm-Q com where R isselected from the group consisting of and alkyl and aryl radicals and R is an alkyl radical.
2. A color-forming photographic developer comprising a primary aromatic amino developmg agent and a coupler compound having a V formula selected from the group consisting of radical.v
3. A' color-forming photographic developer -comprising a primary aromatic amino developing agent and l-lp-(bensenesulphonaminm- 4. A color-forming photographic developer comprising a, primary aromatic amino developing agent and p-(3-methyl-5-pyrazolonyl-1 )benzenesulphonanilide.
5. The method of producing a colored photographic image in a gelatino silver halide emulsion layer, which comprises exposing the layer and developing it with a primary aromatic amino developing agent in the presence oil a coupler compound having a formula selected from the group consisting of R-NHBOON l CO- H:
ored images comprising a colloidal carrier containing a sensitive silver halide and a coupler compound having a formula selected from the group consisting of where R is selected from the group consisting of alkyl and aryl radicals and R. is an alkyl radical; 7. A photographic emulsion for forming colored images comprising a, colloidal carrier containing a sensitive silver halide and 1-[p-(p'- secondary amylbenzenesulphonamido) -phenyl1- 3-n-pentadecyl-5-pyrazolone as a coupler.
PAUL W. VITI'UM.
WILLARD D. PETERSON.
HENRY D. PORTER.