US3785829A

US3785829A - Novel cyan-dye forming coupler

Info

Publication number: US3785829A
Application number: US00259065A
Authority: US
Inventors: J Fernandez
Original assignee: Eastman Kodak Co
Current assignee: Eastman Kodak Co
Priority date: 1972-06-02
Filing date: 1972-06-02
Publication date: 1974-01-15
Anticipated expiration: 1991-01-15

Abstract

A class of cyan-dye-forming Alpha -naptholic couplers having an alkylthio, an alkysulfinyl, or an alkysulfonyl ballasting group attached onto the Beta -naptholic ring; elements and emulsions containing said couplers and a method for improving color photographic images by utilizing said couplers.

Description

United States Patent [191 Fernandez Jan. 15, 1974 1 NOVEL CYAN-DYE FORMING COUPLER [75] Inventor: Jose M. Fernandez, Rochester, NY.

[73] Assignee: Eastman Kodak Company,

Rochester, NY.

[22] Filed: June 2, 1972 [21] Appl. No.: 259,065

[52] US. Cl 96/100, 96/3, 96/74 [51] Int. Cl G03c H40 [58] Field of Search 96/100, 56.6, 55,

[56] References Cited UNITED STATES PATENTS 2,356,475 8/1944 Schinzel 96/100 2,362,598 11/1944 Vittum et a1, 96/100 3,458,315 7/1969 Loria 96/55 3,620,745 11/1971 Seymour 96/55 Primary Examiner-Norman G. Torchin Assistant ExaminerRichard L. Schilling Attorney-Robert W. Hampton et a1.

[57] ABSTRACT 28 Claims, N0 Drawings The present invention relates to a new class of -naphtholic compounds, particularly {3 ringsubstituted a-naphtholic couplers capable of reacting with oxidized color developing agent to form a photographic dye, silver halide emulsions containing such compounds, corresponding color photographic elements and a method for obtaining improved color photographic images.

By way of background, colored photographic images are generally obtained in the art by coupling a silver image development by-product (i.e., oxidized aromatic primary amino developing agent) with a color-forming coupler compound. The subtractive process of color formation is ordinarily employed and the usual resulting cyan, magenta or yellow image dyes are complementary to the primary colors. Coupler compounds employed to produce cyan photographic dyes, for instance, are generally of the phenolic or a-naphtholic type. A majority of such couplers are known and described as four-equivalent couplers, and are characterized in requiring the development of four lightexposed silver halide molecules in order to obtain one molecule of dye. Also widely used are so-called twoequivalent couplers having a non-chromophoric coupling off group substituted in'coupling position and requiring the development of only two exposed silver halide molecules during development to obtain one molecule of dye. Known two-equivalent couplers and method for their utilization are disclosed, for instance, in US. Pats. Nos. 3,458,315 and 3,227,155 of Loria and Loria et al. respectively.

Suitability of an organic compound as 'a color photographic coupler, however, 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 also must possess a number of important ancillary characteristics. It is-desirable, for instance, to utilize non-diffusible couplers which require minimal amounts, or no high-boiling coupler solvent in order to obtain thinner and more durable photographic elements and betterimage resolution. Itis also important that non-diffusible couplers be capable of precise incorporation into a silver halide emulsion without adverse effects on emulsion viscosity, adhesion characteristics, or unity of the emulsion during modern high-speed multilayer application onto a film backing.

Including antihalation and gelatin interlayers, up to eight or more separate layers may be-applied to afilm base to obtain a modern color photographic element (ref. KirbOthmer, Vol. 5', pages 812-845, Encyclopedia of Chemical Technology (1950). For this reason, coupler-induced changes in the physical properties of a coatingmay well be as important as coupler reactivity with oxidized developer.

Undesirable changes in viscosity are sometimes traceable to particular couplers or additives such as wetting agents etc., and these changes are capable of directly affecting thecoating characteristics of the photographic emulsion. This fact is indicated, for instance, on page 250 of the test by Zelikman and Levi, entitled Making and Coating Photographic Emulsionsi" The Focal Press (1964).

A still further need exists in the art for non-diffusible,

coupler-type intermediate or precursor compounds to which it is possible to releasibly attach various functionally useful groups such as diffusible photographic dyes suitable for a diffusion transfer system.

The above-listed features are not necessarily complete and are sometimes incompatible since the color photographic technology of recent years is complex and functionally interrelated. In fact, some coupler characteristics considered advantageous in earlier photographic art may now even be considered undesirable.

For the above reasons, it is necessary to discover new compounds having utility as couplers, and new color photographic elements efficiently utilizing such compounds for color photographic purposes.

Generally speaking, the prior art fails to recognize particular functional significance in the available B- ring positions of a-naphtholic cyan dye-forming couplers as a class. As a result, the amount and direction of chromatographic shift, the solubility and stability of such substituted couplers and of their corresponding dyes are essentially unpredictable, at best.

It is an object of the present invention to obtain a new class of compounds suitable as cyan dye-forming couplers for color photographic purposes and as precursors for obtaining non-diffusible, diffusible-dyecarrying coupler-type compounds suitable for color diffusion transfer systems.

It is another object of the present invention to provide new compounds which readily and efficiently react with oxidized color developer to produce heatand light-stable cyan dyes suitable for modern color photographic purposes in photographic emulsions and elements.

his a still further object to obtain a new class of ballasted a-naphtholic cyan dye-forming couplers which are easily incorporated into a color photographic element, particularly into a color photographic emulsion thereof while usingminimal amounts, or optionally, no high-boiling coupler solvent at all.

These and other objects of the invention are obtained by utilizing a class comprising a non-diffusible a-naphtholic cyan dye-forming coupler with an alkylthio, alkylsulfonyl, or alkylsulfinyl substituent having at least 12 carbon atoms substituted in the [3 ring of the a-na'phtholic coupler.

Compounds of the above type are further conveniently described in the following formula:

wherein -(NAOL) is an unballasted or lightly ballasted a-naphtholic cyan dye-forming coupler moiety; R is an alkyl group, inclusive of straight and branched chain alkyls, having 12-22 carbon atoms and preferably 13-18 carbon atoms (e.g. S-pentyl-heptyl, ntridecyl, n-octadecyl, and docosyl); and -(L) represents S-,

wherein R, and L are defined as above;

R is a hydrogen atom, a halo group such as a chloro, an amino group, including an alkylamino group having one to 12 carbon atoms in the alkyl moiety (e.g., N-methylamine, N-dodecylamine); an alkyl carbonyl group of 2-l 2 carbon atoms (e.g. methylcarbonyl, n-butyl carbonyl and nundecylcarbonyl); an arylcarbonyl group such as an unsubstitutedor a substituted-phenylcarbonyl or a naphthylcarbonyl group in which ring substituent groups total zero to 12 carbon atoms, including a chlorophenylcarbonyl group, an alkoxyphenylcarbonyl group having 1-2 alkoxy substituent totaling zero to 12 carbon atoms or an alkylphenylcarbonyl group having 1-2 alkyl substituents totaling -12 carbon atoms (e.g. dimethylphenylcarbonyl, chlorophenylcarbonyl and di-t-amylphenylcarboy R is also defined as a carbamyl group of the formula in which R is defined as a hydrogen atom or an alkyl group not exceeding three carbon atoms and preferably one to two carbon atoms (e.g. methyl, n-propyl) and R is defined as a hydrogen atom; an alkyl group not exceeding 18 carbon atoms and preferably one to 12 carbons; an aryloxy alkyl group such as a phenoxy alkylor a naphthoxyalkyl group, an arylalkyl group such as a phenylalkyl-or a naphthyalkyl group, in which the alkyl moieties contain one to four carbon atoms (e.g., methyl, n-octadecyl, ndodecyl, 2,4-di-t-amylphenoxy-methyl, 2- methylcarbonamidophenyl butyl and 2-methylcarbonamidophenylethyl);

R is also defined as an aryl group such as phenyl, naphthyl including a substituted aryl group such as a phenyl group or a naphthyl group having as substituents a member of not more than 16 carbon atoms and preferably totaling less than 12 carbon atoms such as one or more carboxy, alkoxy or alkyl-sulfonyl group (e.g., n-hexadecylsulfonylphenyl, 3,5-dicarboxyphenyl, n-hexadecyloxphenyl, n-decyloxyphenyl); also defined as a carboncontaining heterocyclic group having a 5-6 membered heterocyclic ring nucleus with at least one hetero-nitrogen, oxygen or sulfur atom in the nucleus such as a pyridinyl, a pyrimidyl, or a quinolinyl group;

R is defined as a hydrogen atom;

an amino group, including an N-alkylamine group in which the alkyl moiety contains not more than 10 carbon atoms as a coupling off group such as a halo group (e.g. chloro or fluoro), a thiocyano group, an acyloxy group such as an alkoyloxy group of two to 10 carbon atoms, or an aroyloxy group such as a phenylcarbonyloxy group; e.g.

an alkoxy group or its sulfur analog having an alkyl moiety of one to 10 carbon atoms (e.g. decyloxy, decylthio); as an aryloxy or an arylthio group (e.g. phenoxy, naphthoxy, phenylthio, n-decylcarbamylphenylthio, methylcarbamylphenoxy); as a heterocycloxy group or its thioanalog in which the heterocyclic moiety has a 5-6 membered heterocyclic ring nucleus with at least one hetero-nitrogen, oxygen or sulfur atoms, and preferably containing 1-4 hetero-nitrogen atoms (e.g. a tetrazoyloxy, a triazinyloxy, a triazolyloxy, a tetrazolylthio, a benzothiazolylthio etc.);

as a sulfo group;

as an aryl azo radical of the formula in which R is defined as an aryl group such as a phenyl group,

or a naphthyl group including substituted aryl such as an alkylcarbonylphenyl, an alkoxycarbonylnaphthyl or an alkoxyphenyl group in which the alkyl and alkoxy moieties contain one to 13 carbon atoms (e.g. p-butoxyphenyl, 2-n-propylcarbonylphenyl, and 3-octyloxycarbonylphenyl); R being further defined as a carbon-containing heterocyclic group having 5-6 membered heterocyclic ring nucleus with at least one hetero-nitrogen, oxygen or sulfur atoms, and preferably containing 1 to 4 hetero-nitrogen atoms. Such groups include, for instance, a l-phenyl tetrazolyl, a triazinyl, a triazolyl, a thiadiazolyl, a benzoxazolyl, a benzotriazolyl, a benzothiazolyl, a pyrimidyl, a pyridinyl and a quinolinyl group;

R as a coupling-off group also includes a sulfonamido group such as a radical of the formula which is wholly or partly displaceable upon reaction with oxidized color developing agent; also included within the above definition are radicals of formula III in which R represents a dye or dye precursor inclusive of an azo, an azomethine, an indoaniline, an indophenol, or an anthioquinone dye moiety; also included are leuco dyes or shifted dyes which will shift hypsochromically or bathochromically when subject to a different environment such as a change in pH. Such groups are exemplified, for instance, in copending US. Ser. No. 176,751 filed Aug. 31, 1971 and U. S. Ser. No. 176,752 also filed Aug. 31, 1971 and now abandoned. R is also more specifically defined as an alkyl group, inclusive of straight or branched alkyls of one to carbon atoms exemplfied by methyl, isopropyl, and ndecyl, also as an aryl group such as a phenyl or a naphthyl group, inclusive of phenyl, naphthyl, and substituted phenyl or substituted naphthyl groups in which the substituted aryl ring has at least one substituent such as an alkyl group of one to 10 carbon atoms, an alkoxy group of one to 10 carbon atoms, an amino, a nitro, a carboxy, a halo, an arylazo group such as a phenylazo or naphthylazo group, a heterocycloazo such as a pyrazolino group, carbamyl group such as an N-phenyl carbamyl, a N-heterocyclocarbamyl such as a N-triazinyl-or an N-pyrazolino-carbamyl, and an alkyl-substituted carbamyl of two to 10 carbon atoms (e.g. N-propyl carbamylphenyl, p-aminophenyl, p-nitrophenyl, 4-amino naphthyl, 3-methyl-4-nitrophenyl, 2- nitrophenyl, S-carbamylphenyl etc.).

Suitable diffusible a-naphtholic cyan dye-forming coupler moieties falling within the above general definition of -(NAOL) are described, for instance, in US.

Pats. Nos. 2,113,329 and 2,252,718 of Mannes et a1.,

3,002,836 of Vittum et al., US. Pat. No. 3,253,924, US. Pat. No. 3,458,315 (e.g. couplers 1, 4-7, 19-23, 25-29 and 39) and in US. Pat. No. 3,311,476 of Loria (coupler 6). Such patents, however, are not limitative, but merely exemplify some of the unballasted or lightly ballasted coupler moieties of the type to which the [3 ring substituent (ref. formula 1) may be attached.

For purposes of describing the present invention, it is understood that the term coupling-off group defines a substituent group attached at the No. 4-coupling position of an a-naphtholic cyan dye-forming coupler, said substituent group being split off or released for instance, upon coupler reaction with oxidized developing agent.

The term lightly ballasted a-naphtholic cyan dyeforming coupler moiety defines a color photographic coupler group having at least one additional ballasting substituent group other than a [3 ring substituent, said additional ballasting group or groups favoring non-diffusibility of the coupler in a gelatino silver halide emulsion or contiguous gelatin layer without causing substantial loss in solubility in the corresponding fully ballasted non-diffusible coupler (i.e., the fl-ring substituted coupler) in the usual coupler solvents (ref.

infra). I

Substituted compounds of interest are obtainable, fo instance, by reaction of commercially available 1,7- dihydroxy naphthalene with an alkyl mercaptan in the presence of p-toluenesulfonic acid to obtain a desired 7-alkylthio derivative. This compound, in turn, can be converted to the l-acetoxynaphthalene by reacting, with acetic acid anhydride, then oxidized to the corresponding alkylsulfo or alkyl sulfinyl. The l-acetoxy derivative is then subjected to a Fries rearrangement to obtain a corresponding l-hydroxy 7-a1kylsulfonaphthyl derivative. The general reaction mechanism is demonstrated as follows:

1) 0 1r OH HO nolulasn HCXBHIYS 5 p-toluenesuHonic acid n C s cm-b-o--cm 0 C OCH:

2O (3) O OCOCH: (I)COCHJ 11 1sHa1- S n C isHuSO 3 0 II l 0 ll- The produce of equation (3) (pag. 11) can be rearranged as follows:

(refljbur. Pli arm. Soc. of Japan 74, pg 154-6 (1954)).

Corresponding 1,5 and 1,6 isomers of the above compounds are also obtainable to form the corresponding dihydroxy naphthylene precursors (ref. Richter Lexikon Der Kohlenstoffe Vubindungenz, 3rd ed.; Vol.11, page 1411 (1911) Z-Equivalent 4-sulfonamido substituted couplers included within the present invention are conveniently obtained, for instance, by reacting the corresponding a-naphthol 4-amine with the desired aryl sulfonyl halide.

The following compounds are listed in Table 1 with respect to Formula 11 to illustrate a group falling within the scope of the present invention:

(In OH (IV) on TABLE II Compound number R L L R R3 25. CH3(CHz) S H H 26 CHa(CH2)11 (H) H H 27 CHa(CH2)u I H H 28 r CIIz(CHz')n- -S- H -N=N- -OCH3 2U CH3(CHz)11 s- H H 30 CHa(CHz)n- 4') H ll -N=N OCH3 31. CH3(CHZ)11 -S CzHs COOH H C O-N- OOH 32. CHa(CHz)11 S C O-NH-CHzs n( l lsHuflil 33 CH3(CHz)11 -S Sameasabove H 34 CHa(CHz)n ('3' CzHs COOH H JOOH 35. CH3(CH2)12 1; g H

H O CCH3 311.. (,llzflllldlz C1-- The ballasted non-diffusible type cyan couplers of the present invention can be usefully incorporated into a photographic element as part of a photographic silver halide emulsion layer or contiguous thereto. This is most conveniently accomplished by initially dissolving the coupler into a high-boiling and/or one or more lowboiling organic solvents. The resulting solution is then dispersed into a gelatin solution with the aid of an emulsifier, and this coupler dispersion is 'set, noodled, washed and then melted and dispersed into a lightsensitive silver halide gelatin dispersion and thereafter coated onto a film support. Suitable solvents and techniques for this purpose are disclosed, for instance, in US Pats. Nos. 2,949,360, 2,801,171, 2,322,827 and 2,304,939 and on page 107 (Section 11) of Product Licensing Index, Vol. 92, Publication 9232; (Dec. 1971).

Suitable light-sensitive silver halide gelatin emulsions and references describing their preparation and sensitization, .which are suitable for use in preparing photographic elements within the present invention, are summarized on page 107 (Section 1 and Ill) and pages 108-9 (Section XV) of Product Licensing Index, Vol.

92, Publication 9232 (Dec. 197] Such emulsions can 1. A support layer including cellulose acetate film, polystyrene film, polyethylene film, polypropylene film, poly (ethylene) terephthalate film, etc. or as otherwise described, for instance, on page 108, Section X of Product Licensing Index, Vol 92, Publication 9232 (Dec. 1971). Such supports can optionally be electronbombarded at a contact angle of less than 45 or otherwise treated (ref. U.S. Pats. Nos. 3,220,842, 3,117,865 and Belgian Patent 671,661);

2. An antihalation layer attached to the support layer such as a dye-containing gelatin starch, etc., as described, for instance, in Glafkides Photographic Chemistry, Vol. 1, pages 470-471, Arrowsmith Ltd. 1958;

3. One or more, preferably three types of lightsensitive differently sensitized silver halide emulsion layers coated onto the support; the layers comprise (a) a single or double coated red-sensitized layer containing at least one cyan dye-forming coupler of the type defined in formulae l-II (supra). (b) A green-sensitized emulsion layer containing at least one S-pyrazolonemagenta-dye-forming coupler (ref. 823-4, Volume 5, Kirk-Othmer, Encyclopedia of Chemical Technology (1964), also U.S. Pats. Nos. 2,600,788, 2,908,573, 2,895,826, 3,519,429, 3,227,554, 3,062,653 and 2,983,608); and (c) a blue-sensitized layer containing an open-chain yellow dye-forming ketomethylene coupler (ref. pages 822-23, Volume 5, Kirk-Othmer, Encyclopedia of Chemical Technology (1964), also U.S. Pats. Nos. 2,875,057, 2,895,826, 2,908,573, 3,265,506, 3,384,657, 3,408,194 and 3,447,928); a Carey-Lea filter layer is optionally interposed between the blueand greensensitized layers.

Suitable light-sensitive silver halide emulsion and references describing their preparation and chemical sensitization thereof are summarized, for instance, on page 107 in Section I and III of Product Licensing Index, V0. 92, Publication 9232 (Dec., 1971 and include emulsions of silver chloride, silver bromide, silver chlorobromide, silver bromoiodide, silver chlorobromiodide 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 polyvinyl phthalate (ref. U.S. Pat. No. 2,798,004); also water-soluble polymers having varying degrees of solubility, such as polyvinyl alcohol (optimally with surfactant), polyvinyl pyrrolidone polyalkylene oxides, polyvinyl alcohol and its derivatives such as partial esters, ethers and acetals exemplified by hydrolizyed polyvinylacetate, polyvinyl acetaldehyde acetal, polyvinyl butyraldehyde acetal, polyvinyl osulfobenzaldehyde acetal. polyvinyl 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 may conveniently contain an aldehyde scavenger such as described, for instance, in U.S. Pat. Nos. 3,236,652, 3,287,135, 3,220,839, 2,403,927 and British Patent 623,448, and other ingredients such as buffering agents (e.g., an acidic or basic material), and ultra-violet light absorbers such as 2,2'-d-hydroxy 4,4'-dimethoxybenzophenone, 4,4'-diazidostilbene- 2,2-disulfonic acid sodium salt, and sodium -(a-phenylhydrazone).

In addition, photographic materials and elements utilizing the present cyan 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 in sections XIV, XV and XVI of Product Licensing Index Volume 92 (Dec. 1971 Suitable light-sensitive emulsions for purposes of the present invention can also contain speed-increasing compounds of the quaternary ammonium and polyethylene gylcol type as found, for instance, in U.S. Pat. Nos. 2,271,623, 2,288,226, 2,334,864 and 2,708,162.

This invention is further described, although not limited, by the following examples:

EXAMPLE I (COMPOUND NO. 1)

grams (.5 mole) of 1,7-dihydroxynaphthylene is refluxed for 48 hours in a-xylene with 126 grams of noctadecyl mercaptan in the presence of a catalytic amount of p-toluenesulfonic acid. The water byproduct is then removed from a Dean-Stark tube and the naphtholic product removed and identified as 1 hydroxy-7-octadecylthio-naphthylene. m.p. 7072C..

EXAMPLE ll (COMPOUND NO. 8)

A. 140 ml of acetic anhydride is slowly added to 70 grams of 1 hydroxy-7-octadecylthio naphthylene (Example I) with stirring at 120C for 4 hours. After cooling, the 1-acetoxy-7-octadecylthio naphthylene product is separated out (ref. reaction 2 supra).

B. To .2 mole of the 1-acetoxy-7-octadecylthio intermediate product of (A) dissolved in acetic acid is added .4 mole of H 0 and the reaction mixture agitated at -100C. for about 1 hour to obtain the corresponding 7-alkylsulfonyl derivative (m.p. 92-93.5C); this compound is then hydrolyzed with 10 percent KOl-I-ethyl alcohol solution at 45C. to obtain the 7-octadecylsulfonyl-l-naphthol product; m.p. 90.5C.-9l .5C.

EXAMPLE lll (COMPOUND NO. 7)

To .2 mole of the 1-acetoxy-7-octadecylthio naphthol of Example II (A) dissolved in acetic acid is added .2 mole of H 0, and the mixture agitated at 50-55C. for 1 hour to obtain the corresponding 7-alkylsulfinyl derivative (m.p. 81C82C); the derivative is then hydrolyzed with 10 percent KOH-ethyl alcohol solution at 45C as in Example 11 to obtain the corresponding 7- octadecylsulfinyl- 1 -naphthol product; mp. 94-95.5C.

EXAMPLE IV (COMPOUNDS NO. 25-27) Starting with .5 mole of 1,6 dihydroxynaphthylene and reacting with n-octadecyl mercaptan in the presence of p-toluenesulfonic acid as in Example I, a compound identified as compound 25 (i.e. l-hydroxy-6- octadecylthio naphthylene; m.p. 7078C) is obtained. 70 Grams of this compound is converted into the corresponding l-acetoxy-6-octadecylthio naphthylene derivative by reacting with acetic anhydride, and .4 mole of this product is dissolved in acetic acid and reacted with .4 mole H 0 as in Example-11(8) to obtain a compound identified as compound 27. By reacting .2 mole of acetic acid solution of 1-acetoxy-6-octadecylthio naphthylene with .2 mole of H 0 and then hydrolyzing in the manner of Example 111, there is obtained the corresponding 1-hydroxy-6-octadecyl sulfinyl naphthylene derivative identified as compound 26.

EXAMPLE v (COMPOUND N0.

.1 Mole of compound No. l of Example I in a basic solution of tetrahydrofuran and methanol (m.p. 70-72C.) is slowly added to with an equimolar amount of p-methoxy benzenediazonium chloride obtained from p-methoxyaniline diazotized in acidic solution with sodium nitrite to obtain a product identified as compound No. 5 (m.p. l1l114C.).

EXAMPLE VI (COMPOUND NO. 22)

.1 Mole of compound No. 2 of Example 11 is reacted with .1 mole of diazotized p-methoxyaniline as in Example V to obtain a product identified as Compound 22 (m.p. 118-l20C.).

EXAMPLE VII (COMPOUND NO. 23)

.1 Mole of compound No. 7 of Example III is reacted with .1 mole of diazotized p-methoxyaniline as in Example V to obtain a product identified as Compoun No. 23 (m.p. 9699C.).

EXAMPLE VIII (COMPOUND NO. 24)

.l Mole of 1-hydroxy-2-acetyl-7- octadecylthionaphthylene is reacted with .1 mole of diazotized p-methoxyaniline as in Example V to obtain a product identified as Compound 24 (m.p. 12l-l23C.).

EXAMPLE IX (COMPOUND NO. 28)

By utilizing .1 mole of the corresponding l-hydroxy- 6-octadecylthio naphthylene of Example IV and reacting this compound with an equimolar amount of diazotized p-methoxy-aniline as in Example V, there is obtainable a compound identified as Compound No. 28.

EXAMPLE X Eight test film strips are prepared, comprising a support layer having a single gelatino-silver bromoiodide emulsion layer coated thereon which contains 75 mg/ft of one of the following couplers: 2-(2,5-di-tamylphenoxy)-butyl 1 carbamyl-I-naphthol (control: U.S. Pat. No. 2,474,293), compound 1, compound 7, or compound 8 (ref. Table I supra). The emulsion is prepared by dissolving one of these couplers into di-nbutylphthalate (39 mg/ft), the solution then being einulsified with a percent aqueous gelatin solution in the presence of an emulsifying agent and the emulsion dispersed into a light-sensitive gelatino-silver bromoiodide emulsion containing 450 mg/ft gelatin and 136 mg/ft silver. The emulsion coated test strips are sensitometrically exposed and processed by using either developing solution A or B (described below), stop fixed, washed, silver bleached, washed, fixed, washed, and dried in the conventional manner. The test 14 strips are subjected to the usual light fading and heat fading tests to determine the stability characteristics of unreacted coupler and of the corresponding image dyes. The results obtained are recorded in Table I be- 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 is termed Light Fade and is recorded in terms of density units in Table I below.

b. 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 mp.) of a Dmin area of the coating. This increase is termed Printout and is recorded in terms of percent density increase in Table I 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 1 week to a temperature of 140F at a relative humidity of 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 Table I 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 in 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 Table I below.

TABLE I Light Heat Fade Fade Print YELL Compound Developer (LF (HF 2 Out Dens. No. Solution Dmax max 21 days) weeks) (PO) Increase) Control A 3 .00 699 .05 l 2 16% 8 a 2.78 688 .05 +93 15% 10 1 A 1.78 650 .11 +.l0 B 1.35 625 .08 +.09 7 A 1.81 648 .11 +.02 9% 9 B 1.85 638 .09 +.04 9% 9 8 A 3.08 653 .09 01 8% 10 B 2.21 s10 .05 +16 8% 13 This invention has been described in detail with particular reference to a preferred 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:

I. A photographic silver halide emulsion containing a non-diffusible a-naphtholic cyan dye-forming coupler with an alkylthio, alkylsulfonyl, or alkylsulfinyl substituent having at least 12 carbon atoms substituted in the B ring of the a-naphtholic coupler.

2. A photographic silver halide emulsion containing at least one a-naphtholic cyan dye-forming coupler of the formula R(L)(NAOL) wherein (NAOL) is an unballasted or lightly ballasted a-naphtholic cyan dye-forming coupler moiety;

R is an alkyl group having 12-22 carbon atoms;

L represents S-,

the R'(L)- radical being attached to -(NAOL) at the B ring.

3. A photographic silver halide emulsion containing at least one cyan dye-forming coupler of the formula wherein R' is an alkyl group of l2-22 carbon atoms;

L represents -S,

R is a hydrogen atom; a halo group; an amino group; an alkyl carbonyl group of two to 12 carbon atoms; an arylcarbonyl group in which ring substituent groups total zero-l 2 carbon atoms; or a carbamyl group of the formula in which R is defined as a hydrogen atom or an alkyl R is defined as a hydrogen atom or as a coupling off group.

4. An emulsion of claim 3 wherein R' is an alkyl group of 13-18 carbon atoms; and

R is a hydrogen atom or a carbamyl group defining R as hydrogen and R as an alkyl group of one to 18 carbon atoms. 5. An emulsion of claim 3 wherein R is a hydrogen atom, a sulfonamido group or an arylazo group.

6. A photographic silver halide emulsion containing at least one cyan dye-forming coupler of the formula H OH R S wherein R is defined as an alkyl group having I2 22 carbon atoms;

R is a hydrogen atom, a halo group, or an alkyl carbonyl group having two to 12 carbon atoms;

R is a hydrogen atom; a halo group; a sulfo group or salt thereof; a thiocyano group; an alkoyloxy group of two to 10 carbon atoms; a phenyloxy group; a naphthoxy group; a phenylthio group; a naphthylthio group; a heterocycloxy group or its thioanalog in which the heterocycloxy group or its thioanalog has a 5-6 membered heterocyclic ring nucleus;

N=NR in which R is defined as a phenyl group, a naphthyl group, a carbon-containing heterocyclic group having 56 membered heterocyclic ring nucleus; or NHSO R in which R is defined as an alkyl group, a phenyl group, or a naphthyl group.

7. A photographic silver halide emulsion containing at least one cyan dye-forming coupler of the formula 0 at OH wherein R is defined as an alkyl group having l2-22 carbon atoms;

R is a hydrogen atom, a halo group, or an alkyl carbonyl group having two to l2 carbon atoms;

N=NR in which R is defined as a phenyl group, a naphthyl group, a carbon-containing heterocyclic group having 5-6 membered heterocyclic ring nu- 17 cleus; or -NHSO R" in which R is defined as an alkyl group, a phenyl group, or a naphthyl group. 8. A photographic silver halide emulsion containing at least one cyan dye-forming coupler of the formula wherein R is defined as an alkyl group having 12-22 carbon atoms; I

R is a hydrogen atom; a halo group; a sulfo group or salt thereof; a thiocyano group; an alkoyloxy group of two to 10 carbon atoms; a phenyloxy group; a naphthoxy group; a phenylthio group; a naphthylthio group; a heterocycloxy group or its thioanalog in which the heterocycloxy group or its thioanalog has a 5-6 membered heterocyclic ring nucleus; N=N-R in which R is defined as a phenyl group, a naphthyl group, a carboncontaining heterocyclic group having 5-6 membered heterocyclic ring nucleus; or NHSO -R in which R" is defined as an alkyl group, a phenyl group, or a naphthyl group.

9. A color photographic silver halide emulsion of claim 3 wherein R is defined as a p-alkoxy phenyl azo group in which the alkoxy moiety contains one to 10 carbon atoms.

10. A color photographic silver halide emulsion containing 7-octadecylthio-l-naphthol as a coupler.

l l. A color photographic silver halide emulsion containing 7-octadecylsulfinyl-l-naphthol as a coupler.

12. A color photographic silver halide emulsion containing 7-octadecylsulfonyl-l-naphthol as a coupler.

13. A color photographic silver halide emulsion containing 2-acetyl-7-octadecylsulfony1-l-naphthol as a 4 coupler.

14. A color photographic silver halide emulsion containing 2-(Abutylcarbamyl 7-hexadecylthio-l-naphthol as a coupler.

15. A color photographic element comprising a support layer having coated thereon at least one gelatino- 5 wherein -(NAOL) is an unballasted or lightly ballasted a-naphtholic cyan dye-forming coupler moiety; R is an alkyl group having 12-22 carbon atoms; L represents :S-,

wherein R is an alkyl group of 12-22 carbon atoms; L represents -S-,

O 0 II 11 SO or S-;

R is a hydrogen atom; a halo group; an amino group; an alkyl group; an alkyl carbonyl group of two to 12 carbon atoms; an arylcarbonyl group in which ring substituent groups total zero-12 carbon atoms; or a carbamyl group of the formula in which R is defined as a hydrogen atom or an alkyl group not exceeding three carbon atoms; and

R is defined as a hydrogen atom; an alkyl group not exceeding 18 carbon atoms; an aryloxy alkyl group or an arylalkyl group in which the alkyl moieties contain one to four carbon atoms; an aryl group having as substituents a member of not more than 16 carbon atoms selected from the group consisting of a carboxy, an alkoxy and an alkyl sulfonyl group; or

a carbon-containing heterocyclic group having a 5-6 membered heterocyclic ring nucleus with at least one heteronitrogen, oxygen or sulfur atom in the nucleus; and

R is defined as a hydrogen atom or as a coupling off group.

18. A color photographic element of claim 17 in which the cyan dye-forming coupler is characterized by defining R as an alkyl group of 13-18 carbon atoms; and R as a hydrogen atom or a carbamyl group defining R as hydrogen and R as an alkyl group of one to 18 carbon atoms.

19. A color photographic element of claim 17 in which the cyan dye-forming coupler is characterized by defining R as a hydrogen atom or a sulfonamido group.

20. A color photographic element comprising a support layer,-at least one gelatino-silver halide emulsion and at least one cyan dye-forming coupler of the formula I V RLS OH wherein R is defined as an alkyl group having 12-22 carbon atoms;

R is a hydrogen atoms, a halo group, or an alkyl carbonyl group having two to 12 carbon atoms;

R is a hydrogen atom; a halo group; a sulfo group or salt thereof; a thiocyano group; an alkoyloxy group of two to l carbon atoms; a phenyloxy group; a naphthoxy group; a phenylthio group; a naphthylthio group; a heterocycloxy group or its thioanalog in which the heterocycloxy group or its thioanalog has a 5-6 membered heterocyclic ring nucleus;

N=NR in which R is defined as a phenyl group,

a naphthyl group, a carbon-containing heterocyclic group having 5-6 membered heterocyclic ring nucleus; or ---Nl-lSO R in which R is defined as an alkyl group, a phenyl group, or a naphthyl group.

21. A color photographic element comprising a support layer, at least one gelatino-silver halide emulsion and at least one cyan dye-forming coupler of the formula 0H R S RI I Hi wherein R is defined as an alkyl group having 12-22 carbon atoms;

R is a hydrogen atom; a halo group; a sulfo group or salt thereof; a thiocyano group; an alkoyloxy group of two to carbon atoms; a phenyloxy group; a naphthoxy group; a phenylthio group; a naphthylthio group; a heterocycloxy group or its thioanalog in which the heterocycloxy group or its thioanalog has a 5-6 membered heterocyclic ring nucleus;

---N=N-R in which R is defined as a phenyl group, a naphthyl group, a carbon-containing heterocyclic group having 5-6 membered heterocyclic ring nucleus; or -NH--SO R in which R is defined as an alkyl group, a phenyl group, or a naphthyl group.

22. A color photographic element comprising a support layer, at least one gelatino-silver halide emulsion and at least one cyan dye-forming coupler of the formula II 0H R1S wherein R is defined as an alkyl group having 12-22 carbon atoms;

N=NR in which R is defined as a phenyl group,

a naphthyl group, a carbon-containing heterocyclic group having 5-6 membered heterocyclic ring nucleus; or --Nl-lSO R in which R is defined as an alkyl group, a phenyl group, or a naphthyl group.

23. A color photographic element of claim 17 wherein R is defined as a p-alkoxy phenyl azo group in which the alkoxy moiety contains one to 10 carbon atoms.

24. A color photographic element comprising a support layer, at least one gelatino-silver halide emulsion and 7-octadecylthio-l-naphthol as a coupler.

25. A color photographic element comprising a support layer, at least one gelatino-silver halide emulsion and 7-octadecylthio-l-naphthol as a coupler.

26. A color photographic element comprising a sup port layer, at least one gelatino-silver halide emulsion and 7-octadecylsulfonyl-l-naphthol as a coupler.

27. A color photographic element comprising a support layer, at least one gelatino-silver halide emulsion and 2-acetyl-7-octadecylsulfonyl-l-naphthol as a coupler.

28. A color photographic element comprising a support layer, at least one gelatino-silver halide emulsion and 2-(A butylcarbamyl 7-hexadecyl-l-naphthol as a coupler.

Claims

2. A photographic silver halide emulsion containing at least one Alpha -naphtholic cyan dye-forming coupler of the formula R1-(L)-(NAOL) wherein -(NAOL) is an unballasted or lightly ballasted Alpha -naphtholic cyan dye-forming coupler moiety; R1 is an alkyl group having 12-22 carbon atoms; L represents -S-,
3. A photographic silver halide emulsion containing at least one cyan dye-forming coupler of the formula
4. An emulsion of claim 3 wherein R1 is an alkyl group of 13-18 carbon atoms; and R2 is a hydrogen atom or a carbamyl group defining R4 as hydrogen and R5 as an alkyl group of one to 18 carbon atoms.
5. An emulsion of claim 3 wherein R3 is a hydrogen atom, a sulfonamido group or an arylazo group.
6. A photographic silver halide emulsion containing at least one cyan dye-forming coupler of the formula
7. A photographic silver halide emulsion containing at least one cyan dye-forming coupler of the formula
8. A photographic silver halide emulsion containing at least one cyan dye-forming coupler of the formula
9. A color photographic silver halide emulsion of claim 3 wherein R3 is defined as a p-alkoxy phenyl azo group in which the alkoxy moiety contains one to 10 carbon atoms.
10. A color photographic silver halide emulsion containing 7-octadecylthio-1-naphthol as a coupler.
11. A color photographic silver halide emulsion containing 7-octadecylsulfinyl-1-naphthol as a coupler.
12. A color photographic silver halide emulsion containing 7-octadecylsulfonyl-1-naphthol as a coupler.
13. A color photographic silver halide emulsion containing 2-acetyl-7-octadecylsulfonyl-1-naphthol as a coupler.
14. A color photographic silver halide emulsion containing 2-( Delta butylcarbamyl 7-hexadecylthio-1-naphthol as a coupler.
15. A color photographic element comprising a support layer having coated thereon at least one gelatino-silver halide emulsion layer containing a non-diffusible Alpha -naphtholic cyan dye-forming coupler with an alkylthio, alkylsulfonyl, or alkylsulfinyl substituent having at least 12 carbon atoms substituted in the Beta ring of the Alpha naphtholic coupler.
16. A color photographic element comprising a support layer having coated thereon at least one gelatino-silver halide emulsion layer containing at least one Alpha -naphtholic cyan dye-forming coupler of the formula R1-(L)-(NAOL) wherein -(NAOL) is an unballasted or lightly ballasted Alpha -naphtholic cyan dye-forming coupler moiety; R1 is an alkyl group having 12-22 carbon atoms; L represents -S-,
17. A color photographic element comprising a support layer, at least one gelatino-silver halide emulsion layer applied thereto, and at least one cyan dye-forming coupler of the formula
18. A color photographic element of claim 17 in which the cyan dye-forming coupler is characterized by defining R1 as an alkyl group of 13-18 carbon atoms; and R2 as a hydrogen atom or a carbamyl group defining R4 as hydrogen and R5 as an alkyl group of one to 18 carbon atoms.
19. A color photographic element of claim 17 in which the cyan dye-forming coupler is characterized by defining R3 as a hydrogen atom or a sulfonamido group.
20. A color photographic element comprising a support layer, at least one gelatino-silver halide emulsion and at least one cyan dye-forming coupler of the formula
21. A color photographic element comprising a support layer, at least one gelatino-silver halide emulsion and at least one cyan dye-forming coupler of the formula
22. A color photographic element comprising a support layer, at least one gelatino-silver halide emulsion and at least one cyan dye-forming coupler of the formula
23. A color photographic element of claim 17 wherein R3 is defined as a p-alkoxy phenyl azo group in which the alkoxy moiety contains one to 10 carbon atoms.
24. A color photographic element comprising a support layer, at least one gelatino-silver halide emulsion and 7-octadecylthio-1-naphthol as a coupler.
25. A color photographic element comprising a support layer, at least one gelatino-silver halide emulsion and 7-octadecylthio-1-naphthol as a coupler.
26. A color photographic element comprising a support layer, at least one gelatino-silver halide emulsion and 7-octadecylsulfonyl-1-naphthol as a coupler.
27. A color photographic element comprising a support layer, at least one gelatino-silver halide emulsion and 2-acetyl-7-octadecylsulfonyl-1-naphthol as a coupler.
28. A color photographic element comprising a support layer, at least one gelatino-silver halide emulsion and 2-( Delta butylcarbamyl 7-hexadecyl-1-naphthol as a coupler.