US3841880A

US3841880A - Silver halide emulsion containing ketomethylene photographic color-forming couplers

Info

Publication number: US3841880A
Application number: US00347609A
Authority: US
Inventors: S Kertel
Original assignee: Eastman Kodak Co
Current assignee: Eastman Kodak Co
Priority date: 1973-04-03
Filing date: 1973-04-03
Publication date: 1974-10-15
Anticipated expiration: 1991-10-15

Abstract

This invention relates to photographic elements and to photographic emulsions and photographic color developer compositions that container certain color-forming couplers of the 1,2,4-benzothiadiazine-1,1-dioxide class having an open chain ketomethylene group on the carbon atom in the 3-position.

Description

United States Patent [191 Kertel SILVER I-IALIDE EMULSION CONTAINING KETOMETI-IYLENE PI-IOTOGRAPHIC COLOR-FORMING COUPLERS [75] Inventor: Stanley S. Kertel, Webster, NY.

[73] Assignee: Eastman Kodak Company,

Rochester, NY.

[22] Filed: Apr. 3, 1973 [21] Appl. No.: 347,609

[52] US. Cl 96/100, 96/563, 96/565,

96/82, 260/250 [51] Int. Cl G03c 1/40 [58] Field of Search 96/100, 56.2, 56.3, 56.6

[56] References Cited UNITED STATES PATENTS 2,435,l73 l/l948 Bavley .i 96/100 [111 3,841,880 [4 1 Oct. 15, 1974 ll/l96l .laeken 96/100 5/1973 lnoue et al 96/563 Primary Examiner-J. Travis Brown Attorney, Agent, or Firm-John Tv Lewis [5 7] ABSTRACT 21 Claims, No Drawings SILVER HALIDE EMULSION CONTAINING KETOMETHYLENE PHOTOGRAPI-IIC COLOR-FORMING COUPLERS This invention relates to a new class of cyclic ketomethylene color coupler compounds. The color couplers of this invention are readily synthesized benzothiazine compounds whichcan be efficiently reacted with an oxidized color developing agent to obtain sta-' ble, yellow photographic dyes.

BACKGROUND for instance on pages 822-823 of Kirk-Othmer, ENCY- CLOPEDIA OF CHEMICAL TECHNOLOGY, Volume 5, Copyright 1964 and in the Barr et al. US. Pat. No. 3,701,783. Open-chain ketomethylene couplers couple at the carbon atom forming the methylene moiety adjacent the carbonyl group 0 (e.g., C gHz--,

* 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 posses 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 characteristics of the emulsion layer, or the unity of an emulsion layer during modern high-speed multilayer coatmg. g

Several separate layers may be applied to a film base to obtain a colorphotographic 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 a new class of color-forming couplers which will satisfy the numerous requirements for a commercially acceptable colorforming photographic coupler.

It is a further object of this invention to provide new compounds which will readily and efficiently react with oxidized color developer to produce dyes having acceptable stability under normal photographic use conditions. I

It is a still further object of this invention to provide novel photographic elements in whichthe 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 obtained 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 l) or (2):-

N-R O 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 l-5 carbon atoms; R 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 1-18 carbon atoms; and n is 0-2. Preferred color coupler compounds of this invention are those in which, in formula l or (2) above, R is hydrogen or an alkyl group containing up to 5 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 alkyl-substituted aryloxy group containing up to 20 carbon atoms (such as chlorophenoxy and decylphenoxy); R is hydrogen; R" is alkyl containing l-22 carbon atoms or aryl such as a monoor di-substituted phenyl group wherein the substituent(s) on the phenyl group is preferably halo,

alkyl, carboxyl, sulfonamido, or alkoxy; and Z is prefer- Still further preferred are the following coupler comreflux conditions at atmospheric pressure in the presence of a low boiling aliphaticalcohol (i.e., methyl, ethyl and/or isopropyl alcohol) as reaction solvent. If desired, however, the reaction can also be successfully P 5 carried out with an excess (i.e., more than theoretical 3-( a xy)m hyl-l,2,4- nzothiadiazine-1,1 amount) of sulfonamide reactant and/or in the absence dioxide of a reaction solvent and at a temperature up to about b. 3-[(4-ethoxyphenyl)carbamyl1methyl-l ,2,4- 170 C. The reaction is often aided by the presence of benZOthiadiaZine-Udioxide acetic acid as catlayst in the reaction mixture. 0 3-(carbethoxy)methyl--chloro-1,2,4- 10 Lower alkoxy acrylates such as the ethoxy acrylate benzothiadiazine-l,l-dioxide reactants useful in the manufacture of compounds of d. 3-(phenylcarbarnyl)inethyL-chloro-l ,2,4- formula (1), above are readily obtainable from the corbenzothi'adiazine-l,l-dioxide' l responding known alkoxy-ester of cyanoacetic acid, e. 3-{(2-chloro 5-methylphenyl)carbamyl1methyl-6- ama gam benzene sulfonaniidere ctants are oh-- chloro-l,2,4-benzothiadiazine-l,l-dioxide. f tainable commercially (ref. cpd. No. A4543-2; Aldrich This invention relates to the aforementioned coupler Chemical Co., Catalog No. 15, 1970). compounds, to color developer and photographic Compounds having the structure of formula (2 emulsion compositions containing them, and tophotoabove, can be prepared via the following general reacgraphic elements in which such coupler compounds are tion: contained in layers which also contain photosensitive V V W silver halide. Q}f Methods of Manufacture v Compounds having the structure of formula (1), (3 i p cymene above can be prepared via the following general reac- H'C tion: l i i D a N-R 0 (2) I n HOCIHE CHzC-NRR" DNHR A A .C=CH(JJY (2),, (Compoung'oi Formula. 2) B O NH:

ovan A wherein D is a sulfo (S0 group and R, R, Z and n H have the same meaning as in formula (2) above,

F Y ln carrying out reaction (ll) set out above to convert 0- an intermediate alkyl ester reactant to the correspond- D\ ing desired 'amido product (formula 2), the alkyl ester NR 0 reactant is preferably contacted and heated with about (Zln II HOB 40 an equimolar amount of an amine compound of the for- \N// CH2C Y mula NHR'R as above defined, the reaction can be optionally carried out in an inert organic solvent such wherein R, Y, Z and n have th sa e a i s i as xylene or p-isopropyltoluene under reflux conditions formula l above, D is a sulfo (SO?) group, and A and nd mp r re p {0 a ut 60C- B are referabl lower alk 'l such as eth l.

Gen rally, the? initial read tion'to obtain an alkyl ester Detalls Concemmg the lnvemlon of formula I) can be most conveniently effected by Typical, nonlimiting examples of the valuable color contacting and heating an alkoxyacrylate with a subf rming pler ompo nd Of this invention are exstantial amount of an appropriate benzene sulfonemplified with respect t fo 'm aeQ) d in Table amide, preferably in aboutequimolar amounts under be (a) n a H 0 z' JCH|- O-Y N 4 o o .a o Z CHr-(ll-IL' N RI! main 1 Coupler number B. R Y R Z Z" I H -G:Hs H H II H H H 7 Table I-Continued Coupler number R R Y R" z z" III H C:H5 01 H w H H 01 H v H H n o1 H 2H: v1 H H Q 01 H 00H vn"; H H Q 01 H SOzNHz P ":Qm BL to H9 7 r E? H 3H, 01 'H --s one-calm x H H or 01 H CrHn-t NHoowmno- Oran-t x1 H H or H CtHs 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 canine initially incorporated into one 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 artrecognized techniques as 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 described, for instance, in .Glafkides Photographic I a suitable support. Suitable solvents and techniques for of PRODUCT LICENSING INDEX, Volume 92, Publication 9232 (December, 1971). One or more silver chlride, si1ver 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 mglft being generally preferred.

Photographic elements suitable according to the present invention comprise:

l. a support such as described in Section X of PROD- UCT LICENSING INDEX, Vol. 92, Publication 9232 (December, 1971). Included among the possible supports are layers or films comprising hydrophobic resins which have been electron bombarded as described, for instance, in British Pat. Nos. 971,058; 1,060,526 and U.S. 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 self-supporting or may be coated over another support layer. Specific supports having useful hydrophobic surfaces include poly(ethylene terephthalate) films electronbombarded to have a contact angle less than 45 (U.S. Pat. No. 3,220,842), an electron-bombarded surface comprising a chromium halide (U.S. 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 7 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

Chemistry, Volume 1, pages 470-471, Arrowsmith Ltd. 1958;

3. one or more, and preferably three or more, lightsensitive and differently sensitized silver halide emul-' sion 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, (1964); (b) a green-sensitized layer containing at least one 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 comsensitization 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 chlorobromidc, silver bromolodide, 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. U.S.

Pat. No. 2,833,650), cellulose ethers and esters alkali soluble poly( vinyl phthalate) (ref. U.S. 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 copolymers and interpolymers exemplified by copoly (methyl vinyl ether/maleic anhydride), copoly(acrylic acid/methacrylic acid, ethyl ester maleic anhydride) and copopound 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 PROD- UCT LICENSING INDEX, Volume 92, (December, 1971).

Suitable light-sensitive silver halide emulsions and references describing their preparation and chemical pages 108-1 10 5 ly(maleic anhydride/acrylic acid/vinyl acetate). The overcoat layer(s) may conveniently contain an aldehyde scavenger sh desa ted 9! i s an tal -,5: PatfNos: 3.236552531241135; 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, 4,4Y-dimethoxybenzophenone, 4,4- diazidostilbene-2,2'-disulfonic acid sodium salt, and qs ism-tsrphesylhyd szon 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 in Sections XIV, XV and XVI of PRODUCT LICENSING INDEX, Volume 92 (December, 1971). H

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 I, above) Into a 1 liter three-necked flask, equipped with a mechanical stirrer and a steam-heated condenser, were placed 0.1 mole of ethyI-,l3,B-diethoxyacrylate and 0.1 mole of 2-amino-4-chlorobenzenesulfonamide. The reaction mixture was heated in an oil bath at 120C-130C for about 1% hours until distillation of ethanol was completed. The resulting product was recrystallized from methanol to obtain a compound iden tified as coupler III (M.P. l4l-l43C.) in Table I. Preparation B (Coupler I in Table I, above) By utilizing 0.1 mole of Z-aminobenzenesulfonamide and 0.1 mole ethyl-B,B-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 IX in Table I, above) A mixture of 0.01 mole of coupler No. III, 0.01 mole 4-(N-methyl-N-octadecylsulfonamido)aniline and 30 ml vp-cymene were placed in a 100 ml flask equipped with a steam-heated condenser and heated to reflux until the distillation of ethanol was completed. After the reaction mixture had cooled, the resulting solid residue was collected with suction then washed with hexane and with acetonitrile. The resulting product was identified as coupler IX (M.P. l68-1 70C) in Table I.

Preparation D (Coupler XI in Table I, above) A mixture of 0.01 mole of coupler No. III, 0.01 mole 4-ethoxyaniline and 30 ml p-cymene were reacted as in Preparation C to obtain a product identified as coupler XI(M. P 2o8j- 2 7 C)in Table I.

Preparation E (Coupler V in Table I, above) Example 1 A 1% solution of coupler IX (see Table 1, above) in butyl alcohol was added in equal volume to a 5% sodium carbonate solution and then admixed with 50 ml of a color developing composition A (described below) and an oxidant (K S O to obtain a yellow dye extract-' able in the organic phase and with a A max absorption at 475 nm. Acidification with dilute HCl caused a reversible bathochromic dye shift to obtain an orange-red solution. I

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 I and a strip of mordanted receiver immersed in the dye solution for 1 minute. After washing and drying, it was determined Example 3 Four test film strips identified respectively as Tl,'

were then exposed to a graduated-density test and de- 40 o i veloped at 20 C 1n the usual way in Developlng Com- A mlxture of 0.01 mole of coupler No. III, 0.01 mole position A (Example I) or in Developing composition 2-chloro-5-methylan1l1ne, and 30 ml xylene were re- B as described below: acted as in Preparation C to obtain a product identified D l C I B as coupler v (M.P. 180C) in Table I. eve P .-a w... Preparation F (Coupler IV m Table I, above) Benz alcohol 40 ml A mixture of 0.01 mole of coupler No. III, 0.01 mole Sodium hexametaphosphate 0.5 g aniline, and 30 ml cymene were reacted as in Prepara- Z EQZ Solution g tion'C to obtain a product identified as coupler IV Na,co,.-H,o 20.0 g M -l-- .8 9 lIali il- N-diethyl ml Preparation G (Coupler XVII in Table I, above) hydrochloride 3- t By utilizing 0.1 mole of ethyl-B,/3-diethylacrylate and 2, 0.1 mole of 2-amino-4,5-dichlorobenzenesulfonamido in accordance with the process of Preparation A there The test strips were then bleached, fixed, washed and is obtainable a coupler identified as coupler XVII in dried in the usual manner and the results evaluated m Table I. .Tablel l- Table 11 Developing Strip Coupler Amax' Dmax Fog Composition amma 'r-l 1x 504 1.92 .06 1.21 A (Invention) Control 445 1.90 .10 l .46 A Coupler T-3 IX 514 2.47 .07 1.60 B (Invention) T-4 Control 450 2.30 .12 1.49 B

Coupler wavelength at absorption maximum CsHu-t N HCO (CH1) s-O In Table lll is shown data resulting from a photographic test performed on the resulting test strips.

Table III Developing Strip Coupler A max Composition amma Control Control X ww Giana: Oneness l A 2 A 3 B 4 B wavelength at absorption maximum wherein R is defined as hydrogen, or an alkyl group containing up to 15 carbon atoms; Y is defined as an alkyl or an aryl group; I R is hydrogen or an alkyl group containing l-5 carbon atoms; R" is an alkyl or an aryl group; and v Z is individually defined at each occurrence as a halo group, an alkoxy group or an alkyl group containing l-l8 carbon atoms; and n is 0-2. 2. A light-scnsitive photographic element comprising a photographic support having coated thereon at least one photosensitive silver halide emulsion layer containing atleast one color coupler capable of formipg a yellow dye when reacted with oxidized primary amino color developing agent; said color coupler being represented by the formula:

R is hydrogen or alkyl containing l-S carbon atoms;

Y is an alkyl or an aryl group containing 1 to 15 carbon atoms, or a halo-, alkoxyor alkyl-substituted aryloxy group containing 1 to 15 carbon atoms;

R is hydrogen;

R is an alkyl group containing 1-22 carbon atoms or an aryl or monoor di-substituted phenyl group in which the substituents are halo, alkyl, carboxyl, aikoxyl or sulfonamido groups;

Z is chloro, an alkoxy group containing l-5 carbon atoms or an alkyl group containing l-5 carbon atoms; and

n is 0-2.

3. A photographic element as in claim 2, wherein said element has the structure of formula (1 and Z is hydrogen, R is hydrogen and Y is an alkyl group.

4. A photographic element as in claim 2, wherein said element has the structure of formula (2) and Z is H or chlorine, R is H, R is H and R is a substituted phenyl group.

5. A photographic element as in claim 2, wherein said element has the structure of formula (2) and n is O, R is H, R is H and R" is alkyl.

6. A photographic light-sensitive element comprising a photographic support having coated thereon at least one photosensitive silver halide emulsion layer containing 3-(carbethoxy) methyl- 1 ,2,4-benzothiadiazine-l ldioxide.

7. A photographic light-sensitive element comprising a photographic support having coated thereon at least one photosensitive silver halide emulsion layer containing 3-( 4-ethoxyphenyl )carbamyl methyl-l ,2,4- benzothiadiazinel l-dioxide.

8. A photographic light-sensitive element comprising a photographic support having coated thereon at least one photosensitive silver halide emulsion layer containing 3-(carbethoxy)methyl-o-chloro-l ,2,4- benzothiadiazinel 1 -dioxide.

9. A photographic light-sensitive element comprising a photographic support having coated thereon at least one photosensitive silver halide emulsion layer containing 3-( phenylcarbamyl )methyl-6-ehloro-l ,2 ,4- benzothiadiazinel ,l-dioxide.

10. A photographic light-sensitive element comprising a photographic support having coated thereon at least one photosensitive silver halide emulsion layer containing 3-[(2-chloro-5- methylphenyl )carbamyllmethyl-G-chloro-l ,2,4- benz othiadia zine-l ,l-dioxide.

1 l. A light-sensitive silver halide emulsion containing a non-diffusible color coupler compound of the formula I atoms; Y is an alkyl group or an aryl group; 7 R is hydrogen or an alkyl group containing 1-5 carbon atoms; R" is an alkyl or an aryl group containing up to 20 carbon atoms; Z is a halo, an alkoxy group or an alkyl group; and n is -2. 12. A light-sensitive, photographic silver halide emulsion containing a non-diffusible color coupler compound of the formula:

R is hydrogen or alkyl containing 1-5 carbon atoms;

Y is an alkyl, aryl, or halo-substituted, alkoxysubstituted, or alkyl-substituted aryl group containing 1 to carbon atoms;

R is hydrogen;

R" is alkyl containing 1-22 carbon atoms; and

16. A light-sensitive, photographic silver halide emulsion as in claim 12, wherein'said color coupler is 3- (carbethoxy) methyl-1,2,4-benzothiadiazine-1,1- dioxide.

17. A light-sensitive, photographic silver halide emulsion as in claim 12, wherein said color coupler is 3-[(4- ethoxyphenyl)carbamyllmethyl-1 ,2,4-benzothiadiazine-1,1-dioxide.

18. A light-sensitive, photographic silver halide emulsion as in claim 12, wherein said color coupler is 3- (carbethoxy)methyl-6-chloro-1 ,2,4-benzothiadiazine- 1,1-dioxide.

19. A light-sensitive, photographic silver halide emulsion as in claim 12, wherein said color coupler is 3- (phenylcarbamyl)methyl-o-chloro-1,2,4-benzothiadiazine-1,1-dioxide.

20. A light-sensitive, photographic silver halide emulsion as in claim 12, wherein said color coupler is 3-[(2- chloro-S-methylphenyl)carbamyl]methyl-6-chloro- 1,2,4-benzothiadiazine-l l -dioxide.

21. A photographic element comprising a photographic support having coated thereon at least three emulsion layers containing photosensitive silver halide, each of said emulsion layers being sensitized to a different wavelength region of the visible spectrum, and one of said emulsion layers containing from about 25 to about 200 mg per square foot of said support of a ballasted, non-diffusible coupler compound capable of forming a yellow dye when reacted with 4-amino-3- methyl-N-B-(methane-sulfonamide) ethylaniline; said coupler compound being represented by the formula:

N H C Ha mg UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,8Ml,880- Dated October 15, 197A Inventofls) 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:

Title page, line 3 of the Abstract, "container," should read ---contain---5 Column 10, line 56, "III" should read ---II---;

Column 10, approximate columnar line I 60, in Table II, "amma" should read --Gamma---; and 4 Column 11, line 20, "amma" should read ---Gamma---.

Signed and sealed this 4th day of February 1975.

,SEAL) Ittest: v

IcCOY M. GIBSON JR. C. MARSHALL DANN kttesting Officer Commissioner of Patents

Claims

1. A LIGHT-SENSITIVE PHOTOGRAPHIC ELEMENT COMPRISING A PHOTOGRAPHIC SUPPORT HAVING COATED THEREON AT LEAST ONE PHOTOSENSITIVE SILVER HALIDE EMULSION LAYER CONTAINING AT LEAST ONE COLOR COUPLER CAPABLE OF FORMING A YELLOW DYE WHEN REACTED WITH OXIDIZED PRIMARY AMINO COLOR DEVELOPING AGENT, SAID COLOR COUPLER BEING REPRESENTED BY THE FORMULA:

2. A light-sensitive photographic element comprising a photographic support having coated thereon at least one photosensitive silver halide emulsion layer containing at least one color coupler capable of forming a yellow dye when reacted with oxidized primary amino color developing agent; said color coupler being represented by the formula:

3. A photographic element as in claim 2, wherein said element has the structure of formula (1) and Z is hydrogen, R is hydrogen and Y is an alkyl group.

4. A photographic element as in claim 2, wherein said element has the structure of formula (2) and Z is H or chlorine, R is H, R'' is H and R'''' is a substituted phenyl group.

5. A photographic element as in claim 2, wherein said element has the structure of formula (2) and n is O, R is H, R'' is H and R'''' is alkyl.

6. A photographic light-sensitive element comprising a photographic support having coated thereon at least one photosensitive silver halide emulsion layer containing 3-(carbethoxy) methyl-1,2,4-benzothiadiazine-1,1-dioxide.

7. A photographic light-sensitive element comprising a photographic support having coated thereon at least one photosensitive silver halide emulsion layer containing 3-((4-ethoxyphenyl)carbamyl)methyl-1,2,4-benzothiadiazine-1,1-dioxide.

8. A photographic light-sensitive element comprising a photographic support having coated thereon at least one photosensitive silver halide emulsion layer containing 3-(carbethoxy)methyl-6-chloro-1,2,4-benzothiadiazine-1,1-dioxide.

9. A photographic light-sensitive element comprising a photographic support having coated thereon at least one photosensitive silver halide emulsion layer containing 3-(phenylcarbamyl)methyl-6-chloro-1,2,4-benzothiadiazine-1,1-dioxide.

10. A photographic light-sensitive element comprising a photographic support having coated thereon at least one photosensitive silver halide emulsion layer containing 3-((2-chloro-5-methylphenyl)carbamyl)methyl-6-chloro-1,2,4-benzothiadiazine -1,1-dioxide.

11. A light-sensitive silver halide emulsion containing a non-diffusible color coupler compound of the formula

12. A light-sensitive, photographic silver halide emulsion containing a non-diffusible color coupler compound of the formula:

13. A light-sensitive, photographic silver halide emulsion as in claim 12, wherein said R'''' is a mono-substituted phenyl group or a di-substituted phenyl group in which the substituents are halo, alkyl, carboxyl or sulfonamido radicals.

14. A light-sensitive, photographic silver halide emulsion as in claim 12, wherein said R'''' is phenyl.

15. A light-sensitive, photographic silver halide emulsion as in claim 12, wherein said R'''' is an alkoxy group.

16. A light-sensitive, photographic silver halide emulsion as in claim 12, wherein said color coupler is 3-(carbethoxy) methyl-1, 2,4-benzothiadiazine-1,1-dioxide.

17. A light-sensitive, photographic silver halide emulsion as in claim 12, wherein said color coupler is 3-((4-ethoxyphenyl)carbamyl)methyl-1,2,4-benzothiadiazine-1,1-dioxide.

18. A light-sensitive, photographic silver halide emulsion as in claim 12, wherein said color coupler is 3-(carbethoxy)methyl-6-chloro-1,2,4-benzothiadiazine-1,1-dioxide.

19. A light-sensitIve, photographic silver halide emulsion as in claim 12, wherein said color coupler is 3-(phenylcarbamyl)methyl-6-chloro-1,2,4-benzothiadiazine-1,1-dioxide.

20. A light-sensitive, photographic silver halide emulsion as in claim 12, wherein said color coupler is 3-((2-chloro-5-methylphenyl)carbamyl)methyl-6-chloro-1,2,4-benzothiadiazine -1,1-dioxide.

21. A photographic element comprising a photographic support having coated thereon at least three emulsion layers containing photosensitive silver halide, each of said emulsion layers being sensitized to a different wavelength region of the visible spectrum, and one of said emulsion layers containing from about 25 to about 200 mg per square foot of said support of a ballasted, non-diffusible coupler compound capable of forming a yellow dye when reacted with 4-amino-3-methyl-N- Beta -(methane-sulfonamide) ethylaniline; said coupler compound being represented by the formula: