Silver halide color developer containing ketomethylene photographic color-forming couplers
United States Patent 1 1 1111 3,874,948 Kertel 5] Apr. 1, 1975 l l SILVER HALIDE COLOR DEVELOPER [56] References Cited CONTAINING KETOMETHYLENE UNITED STATES PATENTS PHOTOGRAPHIC COLOR-FORMING 2,184,303 12/1939 Jennings et&#39;al. 96/100 COUPLERS 2.359.274 9/1944 Wilson 96/100 2,403,040 7/1946 Bauley 96/l00 [73] memo&#34; Slam Kerk! Webster 2,668,112 2 1954 deCat et a]. 96/100 Asgignee; Eastman Kodak Company, 3,730,722 5/1973 lnoue et al Rochester. NY. B  
  Primary Examiner-J. Travis rown [22] Flled: May 1974 Attorney, Agent, or Fir/11J. T. Lewis [21] Appl. No.: 465,982  
  Related US Application Data elm i p 2p eleme t and t I 1s1nven1on r es 0 0 ogr 10 n s 0 [62] 3231a? 1973 photographic emulsions and photographic color developer compositions that contain certain color-forming IV] S Cl 96/56 3 96/56 5 couplers of the l,2,4-benzothiadiazine-l,l-dioxide 5 m&#39; 66 class having an open chain ketomethylene group on [gm the carbon atom in the 3 position.  
 Field of Search 96/563, 56.5, 100  
 4 Claims, N0 Drawings SILVER HALIDE COLOR DEVELOPER CONTAINING KETOMETHYLENE PHOTOGRAPI-IIC COLOR-FORMING COUPLERS BACKGROUND Colored photographic images are typically obtained in the photographic art by coupling a by-product from the silver image development process (i.e., an oxidized primary aromatic amino developing agent) with a color-forming coupler compound. The subtractive process of color formation is ordinarily employed. Coupler compounds employed to produce yellow or magenta photographic dyes. for instance, are generally of the socalled open chain ketomethylene type, as described for instance on pages 822-823 of Kirk-Othmer, ENCY- CLOPEDIA OF CHEMICAL TECHNOLOGY, Volume 5, Copyright I964 and in the Barr et al U.S. Pat. No. 3,701,783. Open-chain ketomethylene couplers couple at the carbon atom forming the methylene moiety adjacent the carbonyl group (e.g.,  
  ll (r(H- denoting the coupling position). The majority of such couplers are characterized in requiring the development of four silver halide molecules in order to ultimately produce one molecule of dye.  
  The suitability of an organic compound as a colorforming coupler depends upon more than general reactivity. Consideration must also be given to the color balance. contrast. grain size and general sharpness of the dye images obtained. A coupler should also be stable and produce stable photographic dyes having precise spectral absorption characteristics upon reaction with oxidized developer.  
  Successful couplers must also possess a number of important ancillary characteristics. It is often desirable, for instance. to utilize non-diffusible couplers. These usually require only minimal amounts of high-boiling coupler solvents and thereby enable the use of thinner and more durable photographic elements. Nondiffusible couplers should also be capable of precise incorporation into a silver halide emulsion without adversely affecting emulsion viscosity. adhesion characteristies of the emulsion layer, or the unity of an emulsion layer during modern high-speed multilayer coating.  
  Several separate layers may be applied to a film base to obtain a color photographic element. For this reason. coupler-induced changes in the physical properties of the coating can be as important as coupler reactivity with oxidized developer.  
 OBJECTS It is an object of this invention to provide anew class of color-forming couplers which will satisfy the numerous requirements for a commercially acceptable color forming photographic coupler.  
  It is a further object of this invention to provide new compounds which will readily and efficiently re act with oxidized color developer to produce dyes having acceptable stability under normal photographic use conditions.  
  It is a still further object of this invention to provide novel photographic elements in which the couplers of this invention can be used advantageously.  
  It is still another object of this invention to provide novel photographic emulsion compositions that contain such yellow dye-forming couplers; said emulsion compositions being useful in the manufacture of photographic elements containing at least one layer in which such color couplers are present in a non-diffusible form.  
  It is still another object of this invention to provide novel photographic color developer compositions which contain, dissolved therein, one or more of such yellow dye-forming color couplers.  
 DESCRIPTION OF THE INVENTION These and other objects of this invention are ob tained through the utilization of a class of colorforming coupler compounds capable of forming a dye when reacted with oxidized aromatic primary amino color developing agent and represented by formula (I or (2):  
  O O z v R O ll CH -C- O-Y O O 0 R N-R 2 ll 1 n cu -c-i&#39; N 1 wherein R is hydrogen, or an alkyl group containing up to 15 carbon atoms; Y is an alkyl or aryl radical; R is hydrogen or an alkyl group containing 1-5 carbon atoms;  
 R&#34; is an alkyl or aryl group; and  
 Z is individually defined at each occurrence as a halo group, an alkoxy group or an alkyl group containing ll8 carbon atoms; and  
 n is 0-2.  
  Preferred color coupler compounds of this invention are those in which, in formula I or (2) above, R is hydrogen or an alkyl group containing up to five carbon atoms (for example, methyl, isopropyl, or butyl); Y is an alkoxy group containing up to 25 carbon atoms (such as methoxy, isopropoxy, dodecyloxy), an aryloxy group containing up to 15 carbon atoms (such as phenoxy or naphthoxy), or a halo-. alkoxy-, or alkylsubstituted aryloxy group containing up to carbon atoms (such as chlorophenoxy and decylphenoxy); R is hydrogen; R&#34; is alkyl containing 1-22 carbon atoms or aryl such as a monoor disubstituted phenyl group wherein the substituent(s) on the phenyl group is preferably halo, alkyl, carboxyl, sulfonamido, or alkoxy; and Z is preferably chloro, alkoxy containing l5 carbon atoms or alkyl containing 1-5 carbon atoms when Z is present.  
  Still further preferred are the following coupler compounds:  
 a. 3-(carbethoxy)methyl-l ,2,4-benzothiadiazine-l ,1-  
 dioxide b. 3-[ (4-ethoxyphenyl )carbamyl ]methyl-l ,2,4-  
  benzothiadiazine-l l -dioxide. 3-( carbethoxy )methyl-6-ehlorol ,2,4-  
  benzothiadiazinel l -dioxide d. 3-(phenylcarbamyl)methyl-6-chloro-l ,2,4-  
  benzothiadiazine-l l -dioxide 2. 3-[(2-chloro-5-methylphenyl)carbamyl]methyl-6- chlorol ,2,4-benzothiadiazine-l l -dioxide.  
 This invention relates to the aforementioned coupler compounds, to color developer and photographic emulsion compositions containing them, and to photographic elements in which such coupler compounds are contained in layers which also contain photosensitive silver halide.  
 METHODS OF MANUFACTURE Compounds having the structure of formula (1), above can be prepared via the following general reaction:  
 wherein R, Y, Z, and n have the same meanings as in formula (1) above, D is sulfo (S0 group, and A and B are preferably lower alkyl such as ethyl.  
  Generally, the initial reaction to obtain an alkyl ester of formula (1) can be most conveniently effected by contacting and heating an alkoxyacrylate with a sub- 2 )n HOB stantial amount of an appropriate benzene sulfonamide, preferably in about equimolar amounts under reflux conditions at atmospheric pressure in the presence of low boiling aliphatic alcohol (i.e., methyl, ethyl and/or isopropyl alcohol) as reaction solvent. If desired, however, the reaction can also be successfully carried out with an excess (i.e., more than theoretical amount) of sulfonamide reactant and/or in the absence of a reaction solvent and at a temperature up to about 170 C. The reaction is often aided by the presence of acetic acid as catlayst in the reaction mixture.  
  Lower alkoxy acrylates such as the ethoxy acrylate reactants useful in the manufacture of compounds of formula 1), above are readily obtainable from the corresponding known alkoxy ester of cyanoacetic acid, and a-amino benzene sulfonamide reactants are obtainable commercially (ref. cpd. No. A4543-2; Aldrich Chemical Co., Catalog No. 15, 1970).  
  Compounds having the structure of formula (2), above, can be prepared via the following general reaction:  
 (Compound of Formula 2) wherein D is a sulfo (S0 group and R, R, Z and n have the same meaning as in formula (2) above.  
  In carrying out reaction (11) set out above to convert an intermediate alkyl ester reactant to the corresponding desired amido product (formula 2), the alkyl ester reactant is preferably contacted and heated with about an equimolar amount of an amine compound of the formula NHR&#39;R&#34; as above defined, the reaction can be optionally out in an inert organic solvent such as xylene or p-isopropyltoluene under reflux conditions and at a temperature up to about C.  
 DETAILS CONCERNING THE INVENTION Typical, non-limiting examples of the valuable color forming coupler compounds of this invention are exemplified with respect to formulae (3) and (4) in Table 1, below:  
  Included in Table I are examples of both diffusible and non-diffusible couplers. Thus, it can be appreciated that the non-ballasted coupler materials of this invention can be utilized as part of a color developing solution. The ballasted coupler materials of this invention can be initially incorporated into one or more of the silver halide emulsion layers of a photographic element by known solution and emulsification techniques. Upon reaction of such compounds with oxidized developing agent, either diffusible or non-diffusible dyes can be produced depending upon the attached ballasting and/or solubilizing groups. In addition, the presence of certain substituent groups (such as an alkyl, chloro or bromo) on the benzothiazine nucleus will generally favor a bathochromic shift in maximum light absorption of the resulting dye to a lower wavelength.  
  Diffusible coupler compounds are illustrated in Table I by couplers I-VII. This type of compound is generally introduced into a color photographic element by inclusion within a developer solution in accordance with arti&#39;ecognized techniques is summarized, for instance, on  
 lines 50-65 of Section XXII of PRODUCT LICENS- ING INDEX, Volume 92, Publication 9232 (December, 1971). An effective amount of diffusible couplers for color photographic purposes can preferably range from about 0.5 grams per liter to 1.9 grams per liter of developer solution. Varying concentrations outside of this range are useful, however, depending upon the desired image processing conditions and the like.  
  Ballasted, non-diffusible hydrophobic coupler compounds encompassed by this invention (such as, for example, couplers VIII-X in Table I) can be conveniently incorporated into a photographic element either as part of a photographic silver halide emulsion layer or as part of a layer contiguous thereto. This is most conveniently accomplished by initially dissolving the coupler into a high-boiling and/or one or more low-boiling organic solvents. The resulting solution is then dispersed into an aqueous gelatin solution with the aid of an emulsifier, and this coupler dispersion is set, noddled, washed and then melted and dispersed into a light sensitive silver halide gelatin dispersion and thereafter coated onto a suitable support. Suitable solvents and techniques for this purpose are disclosed, for instance, in US. Pat. Nos. 2,949,360; 2,801,171; 2,322,827; and 2,304,939. See, for instance, in section XXII, page 1 10, lines 1-50 of PRODUCT LICENSING INDEX, Volume 92, Publication 9232 (December, 1971). One or more silver chloride, silver bromide, silver chlorobromide, silver bromoiodide, silver chlorobromoiodide, and silver chloroiodide salts are usually included in photographic elements in which the present couplers are utilized. An effective amount of non-diffusible coupler for color photographic purposes can range from about 25-200 mg/ft of coated material, a concentration of 30-50 mg/ft being generally preferred.  
  Photographic elements suitable according to the present invention comprise:  
  1. a support such as described in Section X of PROD- UCT LICENSING INDEX, Vol. 92, Publication 9232 (December, 1971). Included among the possible sup ports are layers or films comprising hydrophobic resins which have been electron bombarded as described, for instance, in British Pat. Nos. 971,058 and 1,060,526 and US. Pat. Nos. 2,864,755 and 2,864,756 to improve adhesion of hydrophilic colloid layers coated over them. Such resin layers or films may be either selfsupporting or may be coated over another support layer. Specific supports having useful hydrophobic surfaces include poly(ethylene terephthalate) films electron-bombarded to have a contact angle less than 45 (US. Pat. No. 3,220,842), and electron-bombarded surface comprising a chromium halide (US. Pat. No. 3,117,865), or electron-bombarded hardened gelatin coated papers (Belgian Pat. No. 671,661), etc. The support layer can be overcoated, if desired, with an antistatic layer to prevent or minimize the build-up of static electricity to objectionable levels during the manufacture and/or processing of the photographic element. Some conventional antistatic layers are described in Section IX of PRODUCT LICENSING IN- DEX, Vol. 92, p. 108, Publication 9232 (December, 1971).  
  2. an antihalation layer (attached to the support either directly or indirectly by means of a subbing layer) such as dye-containing gelatin, starch, or the like, as described, for instance, in Glafkides Photographic Chemistry, Volume 1, pages 470-471, Arrowsmith Ltd. 1958.  
  3. one or more, and preferably three or more, lightsensitive and differently sensitized silver halide emulsion layers coated onto the support; the layers conveniently comprising a. a red-sensitized layer containing at least one phenolic or a-naphtholic cyan-dye-forming coupler, (ref. Kirk-Othmer Encyclopedia of Chemical Technology, Vol. 5, pages 825-826, (1946);  
 b. a green-sensitized layer containing at least one 5- pyrazolone magenta dye-forming coupler (ref. Kirk- Othmer Encyclopedia of Chemical Technology, Vol. 5, pages 823-824 (1964); and  
 c. a blue-sensitized layer containing at least one coupler compound of the present invention. A Carey-Lea filter layer is preferably interposed between the blueand green-sensitized layers. See also Sections XV (spectral sensitization) and XXII (Color materials) of PRODUCT LICENSING INDEX, Volume 92, pages 108-110 (December, 1971).  
  Suitable light-sensitive silver halide emulsions and references describing their preparation and chemical sensitization thereof are summarized, for instance, on page 107 in Section I and III of PRODUCT LICENS- ING INDEX, Volume 92, Publication 9232 (December, 1971), and includes emulsions of silver chloride, silver bromide, silver chlorobromide, silver bromoiodide, silver chlorobromoiodide, and silver chloroiodide.  
  4. One or more gelatin spacer layers between the light-sensitive emulsion layers or the emulsion layers and Carey-Lea filter layer as above described; and  
  5. a protective, water-permeable overcoat layer, such as gelatin, poly(N-vinyl lactam), gum arabic, hydrophilic copolymer of N-acrylamidoalkyl betain (ref. US. Pat. No. 2,833,650), cellulose ethers and esters alkali soluble poly(vinyl phthalate) (ref. US. Pat. No. 2,798,004); also water-soluble polymers having varying degrees of solubility, such as poly(vinyl alcohol) (optimally with surfactant), poly(vinyl pyrrolidone), poly- (alkylene oxides), poly(vinyl alcohol) and its derivatives such as its partial esters, ethers and acetals exemplified by hydrolyzed and partially hydrolyzed poly(vinylacetate). poly(vinyl acetaldehyde acetal), poly(vinyl butyraldehyde) acetal, poly(vinyl sodium 0- sulfobenzaldehyde acetal), poly(vinyl disodium 2,4-  
 disulfobenzaldehyde acetal); and water-soluble copolymcrs and interpolymers exemplified by copoly (methyl vinyl cther/maleic anhydride), copoly(acry1ic acid/methacrylic acid, ethyl ester maleic anhydride) and copoly(maleic anhydride/acrylic acid/vinyl acetate). The overcoat layer(s) may conveniently contain an aidehyde scavenger such as described, for instance, in US. Pat. Nos. 3,236,652; 3,287,135; 3,220,839; 2,403,927 and British Pat. No. 623,448, and other ingredients such as buffering agents (e.g., an acidic or basic material), lubricating agents, matting agents, and ultraviolet light absorbers such as 2,2-di-hydroxy 4,4-dimethoxybenzophenone, 4,4&#39;-dimethoxybenzophenone, 4,4- diazidostilbene-2,2&#39;-disulfonic acid sodium salt, and sodium-( a-phenylhydrazone In addition, photographic materials and elements utilizing the present dye-forming couplers can usefully contain brightners, such as stilbenes, triazines etc. spectral sensitizing dyes, supersensitizing addenda, and also absorbing and filter dyes as summarized, for instance, on page 109-1 10 Sections XIV, XV and XVI of PRODUCT LICENSING INDEX, Volume 92 (December, 1971).  
  A still further embodiment of the present invention includes photographic elements such as x-ray films which can contain at least one fluorescing screen (such as those described in U.S. Pat. Nos. 3,300,311 and 3,617,285 and one or more silver halide emulsion layers applied directly or indirectly to a support layer. One or more couplers of the present invention can be used in optional combination with one or more cyan dyeforming couplers in one or more layers of an x-ray element. Thus, when an element containing such a combination of couplers plus photosensitive silver halide is exposed and then developed with an aromatic primary amino oxidizable color developer, neutral silver and dye images having increased maximum densities will be produced. This density increase permits the use of a lower silver halide concentration without sacrificing the quality or amount of information obtained from the resulting x-ray picture.  
  The following preparations and examples are included to provide a better understanding of the invention. Preparations A through G, below, illustrate methods of preparing some of the preferred coupler compounds of this invention. Some of the valuable end uses and properties of the coupler compounds of this invention are set out in Examples 1 through 3.  
 Preparation A (Coupler III in Table 1, above) Into a 1 liter three-necked flask, equipped with a mechanical stirrer and a steam-heated condenser, were placed .1 mole of ethyl-B,B-diethoxyacrylate and .1 mole of 2-amino-4-chlorobenzenesulfonamide. The reaction mixture was heated in an oil bath at ll30 C for about 1 /2 hours until distillation of ethanol was completed. The resulting product was recrystallized from methanol to obtain a compound identified as couplcr 111 (MP l4l143 C.) in Table 1.  
 Preparation B (Coupler I in Table 1, above) By utilizing .1 mole of 2-aminobenzenesulfonamide and .1 mole ethyl-,Bfi-diethoxyacrylate in accordance with the process described in Preparation A there is obtainable a compound identified as coupler I in Table 1. Preparation C (Coupler lX in Table 1, above) A mixture of .01 mole of coupler No.1&#34;. .01 mole 4- (N-methyl-N-octadecylsulfonamido)aniline and ml p-cymene were placed in a 100 ml flask equipped with a steam-heated condenser and heated to reflux until the distillation of ethanolwas completed. After the reaction mixture had cooled, thelresulting solid residue was collected with suction then washed with hexane and with acetonitrile. The resulting product was identified as coupler IX (M.P. 168-l70 C) in Table 1.  
 Preparation D (Coupler X1 in Table 1, above) A mixture of .01 mole of coupler No. III, .01 mole 4- ethoxyaniline and 30 m1 p-cymene were reacted as in Preparation C to obtain a product identified as coupler XI (M.P. 268270 C) in Table 1.  
 Preparation E (Coupler V in Table 1, above) A mixture of .01 mole of coupler No. 111, .01 mole 2- chloro-5-methylaniline, and 30 ml xylene were reacted as in Preparation C to obtain a product identified as coupler V (M.P. 180 C) in Table 1.  
 Preparation F (Coupler IV in Table 1, above) A mixture of .01 mole of coupler No. 111, .01 mole aniline, and 30 ml cymene were reacted as in Preparation C to obtain a product identified as coupler IV (M.P. 285 C) in Table 1.  
 Preparation G (Coupler XVII in Table 1, above) By utilizing .1 mole of ethyl-B,B-diethylacrylate and .1 mole of 2-amino-4,5-dichlorobenzenesulfonamido in accordance with the process of Preparation A there is obtainable a coupler identified as coupler XVII in Table 1.  
 EXAMPLE 1 Developing Composition A Benzyl alcohol 4.0 ml Sodium hexametaphosphate 0.5 g Na SO 2.0 g 40% NaOH solution 0.4 ml Na CO -H O 50.0 g 50% NaBr solution 1.72 ml 4-Amino-3-methyl-N-ethyl-N-B- (methanesulfonamide)ethylaniline 5.0 g Water to 1000 ml pH adjusted to 10.75  
 EXAMPLE 2 A 1% solution of coupler IV (product of Preparation F) in methanol was converted to the corresponding dye solution in accordance with Example 1 and a strip of mordanted receiver immersed in the dye solution for one minute. After washing and drying, it was determined that the captured dye has a )t max of 420 mu.  
 EXAMPLE 3 Four test film strips identified respectively as T-l, T-2, T-3 and T-4 were prepared by coating a film support with a single gelatin-silver bromoiodide emulsion containing silver (206 mg/ft gelatin (685 mg/ft&#39; din-butyl phthalate mg/ft and coupler IX (I61 mg/ft or an equivalent amount of a-[3-{a-(2,4-ditert-amylphenoxy)butyramido}-benzoyl]-2- 1 1 methoxyacetanilide as a control coupler. The test strips were then exposed to a graduated-density test and developed at in the usual way in Developing Composition A (Example 1) or in Developing Composition B as described below:  
 Developing Composition B Benzyl alcohol The test strips were then bleached, fixed, washed and dried in the usual manner and the results evaluated in 20 Table II.  
 Table 11 Develo ing Strip Coupler A max* Dmax Fog Corhp.  
 amma  
 1:1 IX 504 1.92 .06 1.21 A n vention) T-2 Control 445 1.90 .10 1.46  
  Coupler T-3 1X 514 2.47 .07 1.60 (Invention) T4 Control 450 2.30 .12 1.49 B  
 Coupler wavelength at absorption maximum EXAMPLE 4 Example 3 was repeated, except that Coupler X (Table l) was used in place of Coupler IX. The structure of Coupler X is:  
 In Table 111 is shown data resulting from a photographic test performed on the resulting test strips.  
 Table 111 Developing Strip Coupler A max* Dmax Fog Comp.  
 amma  
 1 Control 445 2.08 0.1 l 1.30 A 2 X 473 2.58 0.12 1.46 A 3 Control 451 2662 0.12 1.75 B 4 X 473 3.66 0.12 2.21 B  
 *warelcngth alt absorption maximum The invention has been described in detail with particular reference to preferred embodiments thereof, but, it will be understood that variations and modifications can be effected within the spirit and scope of the invention.  
 What is claimed is:  
  l. A color developing composition comprising a silver halide color developing agent and diffusible colorforming coupler represented by the formula:  
 wherein R is hydrogen or an alkyl containing l-5 carbon atoms;  
 Y is an alkyl group containing 1-5 carbon atoms or an aryl group;  
 R is hydrogen or alkyl containing 1-5 carbon atoms;  
 R&#34; is an alkyl containing l-5 carbon atoms, phenyl,  
 halo-substituted phenyl, alkyl-substituted phenyl or alkoxy-substituted phenyl group;  
 Z is halo, a lower alkoxy group or a lower alkyl group; and  
  n is 0-2; said coupler being soluble in a water solution of said color developing composition.  
  2. A color developing composition as in claim I, wherein said diffusible color-forming coupler is 3- (carbethoxy)methyl-l ,2,4-benzothiadiazine-l ,1- dioxide.  
  3. A color developing composition as in claim 1, wherein said diffusible color-forming coupler is 3-[(4- ethoxyphenyl) carbamyl]methyl-1,2,4-benzothiadiazine-1,1-dioxide.  
  4. A color developing composition as in claim 1, wherein said diffusible color-forming coupler is 3- (carbethoxy) methyl-6-chlorol ,2,4-benzothiadiazine- 1,1-dioxide.  
 UNITED STATES PATENT AND TRADEMARK OFFICE rrmrr or PATENT NO. 1 3,874,948  
 DATED 1 April 1, 1975 INVENTOR(S) Stanley S. Kertel It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:  
 Column 7, line 40, &#34;noddled&#34; should read ---noodled.  
 Column 8, line 5, &#34;and&#34; should read an-.  
 Column 8, line 31, &#34;(1946)&#34; should read (l964)-.  
 Column 12, line 4, &#34;amma&#34; should read -Gamma-.  
  eaied of August 1975 [SEAL] Attesr: