US3839044A - Silver halide emulsions containing 2-equivalent color couplers - Google Patents

Abstract

4-(1-Phenyl-5-tetrazolyloxy) substituted aryl alcohols suitable as modern cyan dye-forming photographic coupler compounds.

Description

United States Patent 11 1 Salminen et a1. Get. 1, 1974 1 SILVER HALIDE EMULSIONS CONTAINING Z-EQUIVALENT COLOR [56] References Cited COUPLERS UNITED STATES PATENTS [75] Inventors: Ilmari F. Salminen; Anthony Loria, 3,148,062 9/ 1964 Whitmore et a1 96/100 both of Rochester, NY. 3,617,291 11/1971 Sawdey 96/ 100 3,620,747 1l/197l Marchant et al. 96/100 [73] Assgneei Eastman Kodak P Y 3,632,373 1/1972 OConnell et a1 96/100 Rochester, NY 3,647,452 3/1972 Hendess et al 96/100 [22] Filed: Apr. 2, 1973 Primary Examiner-J. Travls Brown PP NOJ 347,315 Attorney, Agent, or FirmJohn T. Lewis Related US. Application Data I [63] Continuation-impart of Ser. No. 128,112, March 25, ABSTRACT 1971, abandoned- 4-(l-Phenyl-S-tetrazolyloxy) substituted aryl alcohols suitable as modern cyan dye-forming photographic 52 US. Cl 915/565, 96/100, 260/241 boupler compounds [51] Int. Cl G03c 7/00, G036 l/4O 58] Field of Search 96/100, 56.5 17 Clams, N0 Drawmgs SILVER HALIDF EMULSIONS CONTAINING Z-EQUIVALENT COLOR COUPLERS This application is a continuation-in-part of U.S. Pat. Application Ser. No. 128,112, filed Mar. 25, 1971, now abandoned.

This invention relates to a group of 4-(l-phenyltetrazolyloxy) substituted phenolic or naphtholic compounds and their utilization in the color photographic art.

BACKGROUND Colored photographic images are obtained in the photographic art by coupling the development product (i.e., an oxidized primary aromatic amino developing agent) with a dye-forming or coupling compound. Coupler compounds employed to produce cyan dyes generally contain color-forming groups of the phenolic or naphtholic hydroxyl class, which coupler compounds are capable of reacting with the above-described oxidation product of a primary aromatic amino developing agent. I

A majority of color photographic couplers of the above types are generically described as 4- equivalent couplers and require the development of four light-exposed silver halide molecules in order to ultimately produce one molecule of dye by coupler reaction with oxidized developer. I

There are also other classes of coupler compounds, including Z-equ'ivalent couplers, in which nonchromophoric coupling-off groups are substituted onto a 4-equivalent coupler in coupling position. Such couplers are characterized by requiring the development of only two exposed silver halide molecules to obtain one molecule of dye. Compounds'of the 2-equivalent type vary substantially in overall structure, depending upon the particular dye product desired. Some Z-equivalent couplers and methods for their utilization are disclosed, for instance, in U.S. Pat Nos. 3,458,315 and 3,277,155

of Loria. I

Modern photographic products and the underlying technology continue to utilize 4-equivalent couplers, howerver, however, despite the known advantages of the 2-equivalent type. This is so because present day photographic couplers require a number of important ancillary characteristics. It is desirable, for instance, to obtain thinner and more durable photographic elements as well as stable couplers which produce stable photographic dyes having precise spectral absorption characteristics. It is also important that a coupler be precisely and homogeneously incorporated into a silver halide emulsion without adversely affecting viscosity, adhesion,'or the unity of any particular emulsion layerduring high speed multilayer application onto a film support.

Undesired changes in viscosity of a melted gelatin photographic emulsion may be caused by additives such as wetting agents, color components, etc., and

such changes will directly affect the coating character istics of the photographic emulsion. This fact is indicated, for instance, on page 250 of the text by Zelikman and Levi, entitled Making and Coating Photographic Emu|sions; The Focal Press. Including antihalation and gelatin interlayers, several separate layers may be applied to a film base to obtain a modern color photographic element. For this reason, major coupler-' induced changes in the adhesion or coating characteristics of a photographic layer may be unacceptable.

The above-listed characteristics are not all necessarily obtainable in a single photographic element. In fact. some couplerv characteristics considered advantageous in earlier photographic art may now be considered undesirable. Moreover, with few exceptions, it is not possible to predict a particular desirable combination of functional coupler characteristics from molecular structure alone.

Objects It is an object of the present invention to'obtain a group of can dye-producing color coupler compounds which will readily and efficiently convert into stable non-diffusible dyes having a precise, desirable light absorption spectrum upon exposure to small amounts of oxidized aryl diamines, such as phenylene diamine color photographic developer compounds.

It is a further object to obtain new highly reactive cyan dye-producing coupler compounds without the sacrifice of coupler or dye stability, diffusibility of resulting emulsion, image definition, resolution characteristics of the resulting photographic element, or effect undesirable viscosity changes prior to or during application onto a film base.

It is a still further object to find new stable cyan dyeproducing coupler compounds which can, if desired, be successfully incorporated into a silver halide emulsion and applied to a film base, using minimal amounts or substantially no coupler solvent.

DESCRIPTION OF THE INVENTION These and other objects are accomplished by utilizing in a photographic emulsion or incorporating into a photographic element at least one coupler compound represented by the formulae:

C ON-(CHz) r-Ra wherein X is defined as hydrogen or halo radical such as a chloro group; Y is defined as a hydrogen, an alkyl containing 1-15 carbon atoms such as methyl, octyl or octadecyl and particularly lower alkyl group having lcarbon atoms, alkoxy or alkylthio, where the alkyl moiety therein contains lcarbon atoms, and preferably is an alkyl group containing l-8 carbon atoms such as methyl, isopropy] and octyl; R is a hydrogen or alkyl containing l-15 carbon atoms such as methyl, isobutyl and octyl;

n is 0-6 and m is 0-1; R is defined as a hydrogen or aryloxy such as phenoxy, including substituted aryloxy groups exemplified by an alkyl substituted phenoxy, wherein one or more alkyl substitutent groups may contain l-l 5 carbon atoms, including a branched alkyl group such as di-tertiary alkyl phenoxy wherein the alkyl groups each contain 3-8carbon atoms; R may be a hydrogen or alkyl containing 1-15 carbon atoms; preferably an alkyl of l-8 carbon atoms; R is defined as an alkyl radical having lvcarbon atoms, including cycloalkyls of 4-6 carbon atoms such as cyclobutyl and cyclohexyl, an aryl radical such as a phenyl or naphthyl group, including an alkyl-carbonamido phenyl such as a phenoxy lower alkyl carbonamido-phenyl, a di-lower alkylphenoxy lower alkyl carbonamido-phenyl, an alkoxyphenyl and dialkoxyphenyl wherein the alkyl moieties have from 1 to 20 carbon atoms, a carboxyphenyl, including dicarboxy phenyl, also mixed substituted aryl radicals exemplified by an alkoxy-alkyl phenyl, an aryloxy radical such as a phenoxy group including an alkyl substituted phenoxy, or di-alkyl phenoxy in which the alkyl moiety thereof contains up to 20 carbon atoms and may include both branched and unbranched alkyls; lower alkyl in each instance containing l-5 carbon atoms; Z is a nitro, amino, chloro, bromo or fiuoro group, an alkyl group containing l-20 carbon atoms, an aryl group, an alkylamido group containing l-20 carbon atoms such as methyl or butyl carbonamido, an alkylcarbonamido phenyl, including phenoxyalkyl carbonamido groups in which each alkyl moiety contains lcarbon atoms (such as meta, pentadecyl, phenoxyethyl), an alkoxy group containing l-ZO carbon atoms, and an alkylsulfonamido or an alkylcarbamyl group wherein the alkyl moiety contains l-20 carbon atoms; p is an integer of 0-2; and

3-Methylthio-4-( l '-phenyl-5 '-tet- 5 N-Ca a I I- .--N

Coupler No. 2: 6-Acetamido-2-chloro-3-methyl-4-( l phenyl-5 '-tetrazolyloxy )phenol 01 NHCOCHs Coupler N0. 3: 6-[oz-(2.4-di-amyl-phenoxy) propylcarbonamidwhzllsav s ii 01- NHCfHO 051111-11 CzHa r n-n Coupler No: 45 i'-ayarmay 2: n- 232mmaarsyrsha noxy )butyl 4-( l-phenyl-S '-tetrazolyloxy)-2- naphthamide Coupler No. 5; l;Hydroxy-2[l$l-(2-acetamidophenyl)- carbonamido)phenyl]-tetrazolyloxy-2naphthamide Coupler 5 Coupler No. 6: 4-{l-{2-[a(2,4-di-tert-amylphenoxy) butyramidolphenyl}-5-tetrazolyloxy}- l -hydroxy-2- l6-0fiwmm w ene mlnanh ha dq.w

Nncocm C ONHCHaCHz Q nncocgnoQmm-u G 2 5 aHu-t Coupler No. 7: 4-{l-{2-[a-(2,4-di-n-arnylphenoxy) butyramidolphenyl}-5-tetrazolyloxy}-hydroxy-2-[/3- (2-acetamido)phenethyl]naphthamide NH C CH3 O ONHCHzCHa (U Q NHC 0 CH0 --CH 1n B2B: tHirn Coupler No. 8: 4-{1-[2-(2-carboxyheneicosylamido;-

phenyl]-5-tetrazolyloxy}1-hydroxy-2-[B-(2-acetamido)phenethyl]naphthamide Nnooci n 0 NHCOCHICHCIBHM-II A Coupler No. 9: 4-{l-[2-(2-carboxy-A -heneic0sylamido)phenyl1-5-tetrazolyloxy}-l -hydroxy-2-[B-(2- acetamido)phenethyl]naphthamide NHCOCH:

No. 10: 4-[1-(2- pentadecylsulfonamido)phenyl-S-tetrazolyoxy]- l hydrOXy- Z -[B-(Z-acetamido)phenethyllnaphthamide NHCOCH;

on WONHGIQCHO Coupler No. 11: 4-{1 {2-[a-(2,4-di-tert-amylphenoxy) acetamidolphenyl} -5 -tetrazolyloxy} l -hydroxy-2- g-2;-2 tceE1 mido)p henethyl]naphthamide NHCOCH:

OH @comromomfi NHCOCHzO iii sHai-t Additional coupler compounds within the scope of the present invention include, for instance,

12. 1-Hydroxy-N-[-(2-acetamid0)phenethyl- 4-2'-[3''-(2-carb oxy)-3-eicosenylamido]phenyl tetrazolyloxy-Z-naphthamide (m.p. l45l48C) phen yltetrazolyloxy}-2-naphthamide (m.p. l8() conditions illustrated in the scheme shown below with the appropriate heterocyclic chloro compound, C1-

( Het), in dimethylformamide, to obtain the intermediate (B). Intermediate (B) is reacted with phenol as shown to obtain intermediate (C), which is combined 5 with the appropriate amine (D) and heated to yield the desired coupler.

OH OH 00,11 DMF 0,11 s r NaOH OI-(Het) y l\ I I (Est) (B) B HO ioxane 00.0.11. r l

(Hat) A ONR1R2 (0) NH Y i I v (Bet) V Coupler wherein Y represents elements or groups required for completion of a polycyclic system such as a naphthol or quinolinol when such is desired. PREPARATION OF COUPLER NO. 2 40 OCHgCaHa 01 I 1 NHCOCH C N/\NCQH5 moo.

CH: N=N Acetone OCHzCeHs 011 C1 NHCOCH; PM 01 NHCOCH:

H: CH3 THF CH:

lI III-C5115 Ail-(35H: N=N v- Preparation of Coupler 4 0 ooiH N-N DMF ZNaOH 01% l N-N lsHg (A) H 0 II/ IIICaH5 (B) N =N To a solution of 20.4 g (0.1 mole) of the acid (A) in 250 ml DMF and 28 ml 40% NaOH (0.2 mole) were added with stirring 18 g (0.1 mole) of 5-chl0ro-1- phenyltetrazole. The mixture was stirred for 6 hours, poured into 600 ml of cold water and acidified with concentrated l-lCl. The solid obtained, i.e., intermediate (B), was collected and slurried in 600 ml of cold water, collected again, washed with cold water, and crystallized from acetonitrile. 1t decomposed at 215C.

Intermediate (B) -6 Dioxane P 0 C13 ozCeHs A mixture of 22 g (0.063 mole) of the intermediate (B), ml of dioxane (dry), 7 g of phenol, and 5 ml of POC1 was refluxed for 3 hours and allowed to stand for 48 hours. Upon the addition of 10 ml H O, a precipitate, i.e., intermediate (C) was obtained which was collected, washed with water, air-dried, and crystallized from acetonitrile; (m.p. 153155C.)

N N (Coupler No. 4)

A mixture of 11.88 g (0.028 mole) of lnterrnediate (C) and 9.42 g (0.0308 mole) of the amine (D) was heated to C. The phenol generated was removed by distillation. The preparation was cooled, dissolved in 250 ml of hot ethylacetate, and washed twice with 11 0. The organic phase was dried over MgSO,, concentrated to dryness, dissolved in hot ethanol, cooled, and crystallized. The solid product, i.e., coupler N0. 4, was collected and sparingly washed with ethanol. Yield 12.5 g (70.25 percent m.p. l30132C.

By reacting the desired 5-chloro tetrazole with a 1,4 dihydroxy 2-naphthoic acid and, thereafter, reacting the resulting intermediate with phenol and 2 acetamidophenyl ethyl amine in the above manner, Coupler No. 5 (mp. l83-185C.) was also obtained. Such a compound can also be obtained, for instance, by reducing the corresponding 1-nitrophenyl-4-chlorotetrazolyl reactant and then reacting the resulting amine with a suitable acid chloride.

The above-described and exempmlified compounds represent a group which possesses a desirable combination of characteristics wholly surprising in view of known properties of structurally distinguishable but similar compounds in the art. Such art is exemplified, for instance, in U.S. Pat. Nos. 2,474,273, 2,275,292, 2,895,826, 2,908,573, 3,148,062, 3,311,476, 3,227,551 and 3,227,554 and herein incorporated by reference.

Based on such knowledge in the art, it is clearly not possible to accurately predict the sizeable combination of functional properties required for a modern color photographic coupler based on chemical structure alone.

Compounds of the present invention, however, are found to produce stable cyan dyes having a useful and precise spectral absorption range for color photo graphic purposes.

In addition, the amount of print-out or breakdown of unreacted coupler residue in the finished photograph is found to at least favorably compare with known 2-equivalent couplers without the usual need for relatively high concentrations of development reaction inhibitors.

Photographic elements utilizing coupler compounds V of the present invention may comprise, for instance, an emulsion support layer or film base; an antihalation layer; one or more light-sensitive silver halide emulsion layers utilizing gelatin or other carriers for the silver halide; interlayers, usually of gelatin; and a protective water permeable overcoat, such as a 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 watersoluble polymers having varying degrees of solubility, poly(vinyl pyrrolidone), poly(alkylene oxides), poly(vinyl alcohol) (optimally with surfactant) and its derivatives such as partial esters, ethers and acetals exemplified by hydrolyzed poly(vinlyacetate), poly(vinyl acetaldehyde acetal), poly(vinyl butyraldehyde acetal), poly(vinyl sodium o-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 copoly(maleic anhydride/acrylic acid/vinyl acetate).

The overcoat or topcoat may also contain other ingredients such as a lubricant, a buffering agent (e.g., an acidic or basic material), or an ultraviolet light absorber such as 2,2'-di-hydroxy-4,4-dimethoxybenzophenone, 4,4'-diazidostilbene-2,2'-disulfonic acid sodium salt, and sodium -(a-phenylhydrazone).

The compounds of interest in the present invention may be incorporated within one or more of the emulsion or interlayers in the manner described, for instance, in U.S. Pat. Nos. 2,367,531, 2,474,293, and the above-cited U.S. Pats. of Julian, Marines, Jelley and Fierke. Alternatively, some may be subsequently introduced as diffusible-type couplers in a standard color developer solution.

The term emulsion support or film base as here used includes known photographic support layers such as cellulose acetate, polyterephthalate, etc., bases, as disclosed, for instance, in chapter 3, pages 47-56 of Emulsion Chemistry by Duffm (1966), and herein incorporated by reference. The term as defined includes paper or other fibrous material coated with a hydrophobic film or surface which repels and does not absorb or adsorb water.

Supports having a hydrophobic surface used to advantage in the present invention include hydrophobic resins which may be electron bombarded as described, for instance, in British Pat. Nos. 971,058 and 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 films are either selfsupporting or may be coated over another support layer. Specific supports having useful hydrophobic surfaces include electron-bombarded supports exposed so as to have a contact angle less than 45 (U.S. Pat. No. 3,220,842), a corona-treated surface comprising a chromium halide (US. Pat. No. 3,1 17,865), or coronatreated hardened gelatin coated papers (Belgian Pat. No. 61,661 etc. The support layer may also contain various functional additives such as titanium dioxide, zinc oxide, and silica as suggested in U.S. Pat. Nos. 2,992,101 and 2,701,245, and anti-static agents as described, for instance, in U.S. Pat. No. 3,253,922.

The emulsions used in the photographic element of the present invention can be chemically sensitized by any of the accepted procedures. The emulsions can be digested with naturally active gelatin, or sulfur compounds can be added, such as those described in Sheppard U.S. Pat. No. 1,574,944, issued Mar. 2, 1926; Sheppard et al, U.S. Pat. No. 1,623,499, issued Apr. 5, 1927; and Sheppard et a1. U.S. Pat. No. 2,410,689, issued Nov. 5, 1946.

The emulsions can also be treated with salts of the noble metals, such as ruthenium, rhodium, palladium, iridium and platinum, as described in Smith et al, U.S. Pat. No. 2,448,060, issued Aug. 31, 1948 and as described in Trivelli et al, U.S. Pat. Nos. 2,566,245 and 2,566,263, both issued Aug. 28, 1951.

Emulsions of this invention can also be optically sensitized with cyanine and merocyanine dyes, such as those described in Brooker U.S. Pat. Nos. 1,846,301 and 1,846,302, both issued Feb. 23, 1932; and 1,942,854, issued Jan. 9, 1934; White U.S. Pat. No. 1,990,507, issued Feb. 12, 1935; Brooker and White U.S. Pat. No. 2,112,140, issued Mar. 22, 1938; 2,165,338, issued July 11, 1939; 2,493,747, issued Jan. 10, 1950; and 2,739,964, issued Mar. 27, 1956; Brooker et al, U.S. Pat. No. 2,493,748, issued Jan. 10, 1950; Sprague U.S. Pat. No. 2,503,776, issued Apr. 11, 1950, and 2,519,001, issued Aug. 15, 1950; Heseltine et al, U.S. Pat. No. 2,666,761, issued Jan. 19, 1954; Heseltine U.S. Pat. No. 2,734,900, issued Feb. 14, 1956;

.VanLare U.S. Pat. No. 2,739,149, issued Mar. 20,

1956; and Kodak Limited British 450,958, accepted July 15, 1936.

Emulsions of this invention may also contain speedincreasing compounds of the quaternary ammonium type of Carroll U.S. Pat. No. 2,271,623, issued Feb. 3, 1942; Carroll et al, U.S. Pat. No. 2,288,226, issued June 30, 1942; and Carroll et a1, U.S. Pat. No.

2,334,864, issued Nov. 23, 1943', and the polyethylene glycol type of Carroll et al, US. Pat. No. 2,708,162, issued May 10, 1955.

The emulsions can also be chemically sensitized with gold salts as described in Waller et al, US. Pat. No. 2,399,803, issued Apr. 23, 1946, or stabilized with gold salts as described in Damschroder US. Pat. No. 2,597,856, issued May 27, 1952; and Yutzy et al, US.

Pat. No. 2,597,915, issued May 27, 1942. Suitable compounds are potassium chloroaurite, potassium aurithiocyanate, potassium chloroaurate, auric trichloride and 2-aurosulfobenzothiazole methochloride.

Color developing agents suitable for use in processing photographic elements of the present invention include the usual N, N-dialkyl-p-phenylenediamines. These compounds may, if desired, contain various electrondonating substituent groups such as alkyl, alkoxy, alkylamino or other groups in a position ortho to the primary amino groups.

Among the useful developing agents are included, for instance:

4-amine-3-methyl-N-ethyl-N-B- (methanesulfonamido)ethyl aniline sesquisulfate hydrate, 4-amino-3-methyl-N-ethyl-N-hydroxyethyl sulfate, 4-amino-N-ethyl-N-B-hydroxyethylaniline sulfate, 4-amino-3-methyl '-N,N-diethylaniline hydrochoride,

and p amino-N,N-diethylaniline hydrochloride.

EXAMPLE I Coupler No. 2 supra and its 6-acetamido-2,4- dichloro-3-methyl phenol analog of the formula Coupler No. 2 A

aniline Cl NH O CH3 were comparatively tested for reactivity with oxidized developer by measuring the relative amount of deamination vs. dye formation with oxidized developer as described, for instance, in the articles by Tong and Gleasman in .I.A.C.S. 79 583 (1957), and J.A.C.S. 82 1988 (1960). Five coupler solutions were prepared in concentration varying from .002 molar to 0.004 molar at pH 1 l in a phosphate buffer (u-0.75 The solution was admixed with K Fe(CN) and 4-amino-3-methyl-N-B- sulfoethylaniline at 25C, and the )tmax density determined immediately thereafter as well as the pH of the reaction mixture. Allowing for the relative ionization of each coupler, a plot of l/D vs l/(C),,, wherein D is the dye density and Co is coupler concentration, was then run to determine the slope and 'y intercept values. This information, plus the relationship of deamination rateto-pH of the reaction mixture (ref. .1 .A.C.S. 82 Supra), were utilized in the formula 1 K Kd Slope X intercept wherein K, is the coupling rate constant and K, is the deamination rate constant, to determine coupling reac-' tivity in mole/second as indicated below.

TABLE 1 Compound Rate (Liter/Mole second) Coupler 2 EXAMPLE 2 Two samples of each of eighteen supported singlelayer gelatinous silver bromoiodide emulsion coatings, containing/ft of film, mg coupler, 39 mg di-n-butyl phthalate as coupler solvent, 450 mg gelatin and 136 mg silver were sensitometrically exposed, developed in Solution A (ref. infra), stop fixed, washed, silver bleached, washed, fixed, washed and dried in conventional manner and subjected to Light Fading and Heat Fading tests as hereinafter described.

Light Fading Tests:

a. The extent to which the image dyes faded under the influence of light was determined by subjecting several processed coatings to a simulated 21-day North skylight exposure (SANS) and recording the resulting decrease in dye density in an area of the coating having had an initial dye density of approximately 1.2. This decrease in dye density was termed Light Fade and is recorded in terms of density units in the table below.

bl The extent to which unreacted coupler caused unwanted stain under the influence of light was determined by exposing several processed coatings by the procedure described under (a) above and recording the resulting increase in density to blue light (420 mu) of a D-min area of the coating. This increase was termed Printout and is recorded in terms of percent density increase in the table below.

Heat Fading Tests:

a. The extent to which the image dyes faded under the influence of heat and humidity was determined by subjecting several processed coatings for one week to a temperature of l40F at a relative humidity of 70 percent. The decrease in image dye density, termed Heat Fade," was measured by the method described in section (a) under Light Fading Tests. It is recorded in terms of density units in the table below.

b. The effect of heat on unreacted coupler was determined by subjecting several coatings to the heat and humidity conditions cited above and determining the increase of density, termed Yellowing, by the method described in section (b) under Light Fading Tests. The obtained values are recorded in terms of percent density increase in the table below.

Color Developing Solution A 1 liter (pH 10.86) Color Developing Solution B 80 Benzyl alcohol Calgon Na SO,

40% NaOH solution ever- -Continued 4-amino-B-methyl-N-ethyl-N-l3- (methanesulfon-amido)-ethylaniline 5 sesquisulfate hydrate 50% NaBr solution 1.72 ml H2O to 1 liter For purposes of comparison the following structurally similar compounds of the prior art were tested along with invention couplers 3, 4, and 5.

OONH(CHa)4O--C5Hu(t) 05 11 R Coupler number I R=H II Chs ai C2115 l R-O- NHoooHo- III... 31%

IV (13F:

vI R=0C4Hn VII. R=0CH3 v1II m IIIHOOCHa @UoonnomombQ-NHCOCHQ- ('JzHs is ai Ix.--.- OH

I /CHa o ONH-S OzN CxsHar CONH C1rHa1 CHa The resulting sensitometric results are recorded in Table ll below, the headings being defined as L.F. Light fade (21 days SANS) of dye derived from coupler H.F. Heat fade (1 week, l40F-70% RH) of dye derived from coupler P0. Printout (21 days SANS) of unreacted coupler Yell, Yellowing (1 week, F70% RH) of unreacted coupler TABLE 11 Cplr. No.* Dev. Soln. D-max )l-max L.F. H.F. P.O. Yell.

6 A 2.68 700+ 0.06 0.02 7% 6% B 2.40 695 0.04 0.05 7% 6% 7 A 2.54 657 0.05 0.01 2% 5% B 2.03 652 0.06 0.02 2% 5% l A 3.06 700+ 0.05 0.05 17% 7% B 2.80 691 0.06 0.02 16% 7% 11 A 3.17 700+ 0.10 15% 9% B 3.04 695 0.07 0.03 15% 8% 111 A 2.62 7000+ 0.26 0.06 29% 17% B 2.30 697 0.20 0.04 32% 16% IV A 2.39 700+ 0.32 0.28 21% 7% B 2.20 691 0.32 0.22 23% 7.5% V A 2.70 700+ 0.24 0.04 39% 14% .B 2.33 697 0.20 0.02 38% 15% V1 A 3.50 700 0.30 0.16 15% 9% B 2.50 695 0.25 0.10 12.5% 7% V11 A 3.20 700 0.26 0.14 12.5% 7% B 2.94 690 0.19 0.10 12.5% 7% VIII A 2.23 678 0.06 0 11% 9% B 1.85 660 0.06 0.03 11% 9% 1X A 2.90 700+ 0.20 0.34 14% 49% B 1.48 700+ 0.12 0.10 13% 47% X A 324 700+ 0.04 0 12% 40% B 2.68 700+ 0.08 0.06 15% 36% X1 A 1.60 700 0.12 0.08 11.5%

B 2.60 690 0.20 0.04 12% X11. A 1.78 694 0.21 0.05 13.5% 28.5%

Xlll A No Values Recorded B 1.34 696 0.12 0.16 2% 3% XIV A ,6 70 9-9 9-98. E 5% B 1.36 698 0.04 0.00 1% 3.5% XV A 1.34 700 0.08 0.11 2% 3.5% B No Values Recorded Roman number-uls represent couplers structurally described above in Table II.

The comparative results confirm that representative compounds of this invention (Couplers 5, 6 and 7 in Table 11) exhibit a surprising, relatively high stability and that the resulting photographic dyes also have excellent stability and an acceptable, high density level for photographic purposes.

EXAMPLE 111 Diethyl-p-phenylene diamine-HCl 3 g Sodium sulflte 5 g Sodium Carbonate 50 g Potassium Thiocyanate .5 g Boiled distilled water to 1000 cc Coupler No. 1 2.5 g Methanol 100 cc After bleaching, washing and drying, the resulting cyan dye images were exposed to the standard lightfading test (SANS) described in Example 11 and the results evaluated and compiled in Table 111.

B. Two coated film strips were treated as in Example 111(A) but with a color developer solution containing Coupler No. 2 in place of Coupler No. l.

The fully processed film strips were then tested as in Example 111(A) and tabulated as follows:

TABLE 111 Test Strip SANS (FL) The invention has been described in detail with particular reference to a referred embodiment thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention as described hereinabove and as defined in the appended claims.

We claim:

1. A photographic silver halide emulsion containing as cyan-dye-forming color coupler a compound of the fo mula C 0IIT (CH2)nR6 wherein X is a hydrogen or halo radical;

Y is a hydrogen, alkyl, alkoxy or alkylthio group containing one to carbon atoms;

R; is hydrogen or an alkyl group containing one-l5 carbon atoms;

R, is hydrogen or an aryloxy group;

R is hydrogen or an alkyl group containing one-l5 carbon atoms;

R, is an alkyl or aryl group containing onecarbon atoms;

n is an integer of zero-eight;

m is an integer of zero-one;

p is an integer of zero-two; Z is a nitro, amino, chloro, bromo, fluoro group, an alkyl, an alkylamido or an alkoxy group containing l-20 carbon atoms, an arly group, an alkylcarbonamido group, a phenoxyalkylcarbonamido group, an alkylcarbamyl group or an alkylsulfonamido group having an alkyl moiety containing 1-25 carbon atoms; and

is heterocyclic radicals containing 5-6 ring members.

2. A photographic silver halide emulsion containing as cyan-dye-forming color coupler a compound of the formula pb -P- TGTA color photographic element comprising a film atoms or an alkylthio group containing 1-5 carbon atoms; R is hydrogen or an alkyl group containing l-5 carbon atoms; R, is hydrogen or a phenoxy group; and R is hydrogen or an alkyl group containing l-5 carbon atoms; Z is an alkyl, halo, alkoxy or aryl group, and p is an integer of 0-2.

3. A silver halide emulsion of claim 1, wherein the cyan-dye-forming color coupler is incorporated in a high boiling organic coupler solvent.

4. A silver halide emulsion of claim 1 wherein the cyan-dye-forming color coupler as incorporated is substantially free of high-boiling organiccoupler solvent.

5. A silver halide emulsion containing as cyan-dyeforming-color coupler a compound of the formula R is dialkylphenoxy or alkylcarbonamidophenyl wherein each alkyl moiety contains l-S carbon atoms;

Z is an alkyl, halo, alkoxy or aryl group, and p is an integer of O-2.

6. A silver halide emulsion of claim 5, wherein n is 0-4;

R is a di-tertiary-alkylphenoxy group; and Z is a phenyl group.

7. A silver halide emulsion containing 6- acetamido2-chloro-3-methyl-4-( 1 -phenyl-5 tetrazolyloxy)-phenol as a cyan dye-forming coupler.

8. A silver halide emulsion containing l-hydroxy--2- [N-(2,4-di-(t)-amyl phenoxy)-butyl]-4-(l-phenyl-5- tetrazolyloxy)-2-naphthamide as a cyan dye-forming coupler. I

9. A silver halide emulsion containing l-hydroxy- 2-[N-(2-acetamidophenyl)-ethyl]-4-[1-(3-{a-{3- pentadecylphenoxy}-propyl}-carbonamido)phenyl]- tetrazolyloxy-Z-naphthamide as a cyan dye-forming base having incorporated thereon at least one lightsensitive silver halide emulsion layer containing a photographic dye-forming compound of the formula X is a hydrogen or halo radical;

Y is a hydrogen, alkyl, alkoxy or alkylthio group containing 1-15 carbon atoms;

R is hydrogen or an alkyl group containing l-l5 carbon atoms;

R is hydrogen or an aryloxy group;

R is hydrogen or an alkyl group containing 1-15 carbon atoms; 1

R is an alkyl or aryl group containing l-2O carbon atoms;

n is an integer of -8;

m is an integer of 0-1;

p is an integer of 0-2;

Z is a nitro, amino, chloro, bromo, fluoro group, an alkyl, an alkylamido or an alkoxy group containing l-2O carbon atoms, an aryl group, an alkylcarbonamido group, a phenoxyalkylcarbonamido group, an alkylcarbamyl group or an alkylsulfonamido group having an alkyl moiety containing 1-25 carbon atoms; and N Z is heterocyclic radicals containing -6 ring members.

11. A color photographic element comprising a film base having incorporated thereon at least one lightsensitive silver halide emulsion layer containing a photographic dye-forming compound of the formula OER 1500 'l i? L it w l O a wherein m is 0 or 1;

X is hydrogen or halo;

Y is hydrogen, an alkyl group containing l-5 carbon atoms or an alkylthio group containing l-5 carbon atoms;

R is hydrogen or an alkyl group containing l-5 carbon atoms;

R is hydrogen or a phenoxy group; and

R is hydrogen or an alkyl group containing l-5 carbon atoms;

Z is an alkyl, halo, alkoxy or aryl group, and

p is an integer of 0-2.

12. A color photographic element comprising a film base having incorporated thereon at least one lightsensitive silver halide emulsion layer containing a photographic dye-forming compound of the formula wherein 7 if n is O-6;

R is hydrogen; R is dialkylphenoxy or alkylcarbonamidophenyl wherein each alkyl moiety contains 1-5 carbon atoms;

Z is an alkyl, halo, alkoxy, or aryl group, and p is an integer of 0-2.

13. A color photographic element comprising a film base having incorporated thereon at least one lightsensitive silver halide emulsion as defined in claim 6.

14. A color photographic element comprising a film base having incorporated thereon at least one lightsensitive silver halide emulsion as defined in claim 7.

15. A color photographic element comprising a film base having incorporated thereon the light-sensitive silver halide emulsion of claim 8.

16. A color photographic element comprising a film base having incorporated thereon the light-sensitive silver halide emulsion of claim 9.

17. In a method for producing a cyan dye image by color development of an exposed photographic element containing a support and at least one lightsensitive silver halide emulsion coated thereon, the improvement comprising effecting development of said exposed photograhic element under alkaline conditions with a color developing solution containing a diffusible phenolic coupler of the formula l H LN-C 0-i-R4 wherein I X is a hydrogen or halo group; Y is hydrogen, an alkylgroup containing l-5 carbon 5 atoms or an alkylthio group containing l-5 carbon atoms;

m is 0 or 1; and

R and R, and R are hydrogen.

" UNITED S'KATES PATENT @FFXGE neurone Patent No. 3 83 ,I044 I Dated October 1 1974 H Ilmari Salminen and Anthony Loria It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 2, line 13, "can" should read --cyan---; Column 3, last line, "phenyl" should read -'-phenol---',

Column 4, lines 26-29, that partof the formula reading "carbonamid- -2chloro'. 3methyl4 (l' -phenyl-S' tetrazolyloxy)phenol" should read ---carbonamido]2-chlero-.3-methyl-4-(l'phenyl-5'- tetrazolyloxy)-phenol---; l

Column 5, last line, "tetrazolyoxy" should read -tetrazolyloXy--;

Column 6, line 13, that part of the formula reading:

" N N should read N N g I V Y Y N--N N N Column 6, line 30, that part of the formula reading:

I "t '-t C H should read (1 H Column 8', line 54, that part ofthe formula reading:

should read N N W105) I UNITED STATES PATENT @E-FECE @E or Patent No. 3 339 044 Dated October I, 1974 Inventor) Ilmari F. Salminen and Anthony Loria Page 2 It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

(Continued) Column 10, line 26, "61,661" should read 67l,66l;

Column 11, line 63, that part of the formula reading "K should read --K Column'l2, "-line 10,, "of" (first occurrence) should be-deleted;

Columns 15-16, Table II, under heading'h-max" for Cplr. No. III, Dev. Soln. A, "7000+" should read ---700+;

Columns 15-16, Table II, under heading "A-max", for Cplr. No. XV, Dev., Soln. A, "700" should read --7,00+---;

Column 16, line 48, "referred" should read ---preferred--;

Column 17, line 40 "arly" should read -aryl- Column 20, last line, "and" (first occurrence) should be deleted.

Signed and sealed this 28th day of January 19'25o (SEAL) Attest:

SHALL D MCCOY M. GIBSON JR 7 o,

Attesting Ofgieer Cssioner of Patents

Claims (17)

1. A PHOTOGRAPHIC SILVER HALIDE EMULSION CONTAINING AS CYAN-DYE-FORMING COLOR COUPLER A COMPOUND OF THE FORMULA

2. A photographic silver halide emulsion containing as cyan-dye-forming color coupler a compound of the formula

3. A silver halide emulsion of claim 1, wherein the cyan-dye-forming color coupler is incorporated in a high boiling organic coupler solvent.

4. A silver halide emulsion of claim 1 wherein the cyan-dye-forming color coupler as incorporated is substantially free of high-boiling organic coupler solvent.

5. A silver halide emulsion containing as cyan-dye-forming-color coupler a compound of the formula

6. A silver halide emulsion of claim 5, wherein n is 0-4; R6 is a di-tertiary-alkylphenoxy group; and Z is a phenyl group.

7. A silver halide emulsion containing 6-acetamido-2-chloro-3-methyl-4-(1''-phenyl-5''-tetrazolyloxy)-phenol as a cyan dye-forming coupler.

8. A silver halide emulsion containing 1-hydroxy-2-(N-(2'',4''-di-(t)-amyl phenoxy)-butyl)-4-(1-phenyl-5''-tetrazolyloxy)-2-naphthamide as a cyan dye-forming coupler.

9. A silver halide emulsion containing 1-hydroxy-2-(N-(2-acetamidodphenyl)-ethyl)-4-(1-(3-( Alpha -(3''-phentadecylphenoxy)-propyl)carbonamido)phenyl)-tetrazolyloxy-2 -naphthamide as a cyan dye-forming coupler.

10. A color photographic element comprising a film base having incorporated thereon at least one light-sensitive silver halide emulsion layer containing a photographic dye-forming compound of the formula

11. A color photographic element comprising a film base having incorporated thereon at least one light-sensitive silver halide emulsion layer containing a photographic dye-forming compound of the formula

12. A color photographic element comprising a film base having incorporated thereon at least one light-sensitive silver halide emulsion layer containing a photographic dye-forming compound of the formula

13. A color photographic element comprising a film base having incorporated thereon at least one light-sensitive silver halide emulsion as defined in claim 6.

14. A color photographic element comprising a film base having incorporated thereon at least one light-sensitive silver halide emulsion as defined in claim 7.

15. A color photographic element comprising a film base having incorporated thereon the light-sensitive silver halide emulsion of claim 8.

16. A color photographic element comprising a film base having incorporated thereon the light-sensitive silver halide emulsion of claim 9.

17. In a methoD for producing a cyan dye image by color development of an exposed photographic element containing a support and at least one light-sensitive silver halide emulsion coated thereon, the improvement comprising effecting development of said exposed photograhic element under alkaline conditions with a color developing solution containing a diffusible phenolic coupler of the formula