Photographic element comprising a dir coupler and a barc coupler containing an acid solubilizing group

Description

Technical Field

[0001] This invention relates to new photographic couplers, such as naphtholic and acylanilide couplers, that are capable of forming washout dyes and releasing bleach accelerator groups in a photographic material upon photographic processing for formation of an improved image and to a photographic material and process using such compounds.

Prior Art

[0002] Various ways are known in the photographic art for release of a photographically useful group (PUG) from a compound, such as a photographic coupler, in a photographic material and process. For example, U.S. Patents 4,248,962; 4,409,323 and 4,861,701 describes groups that enable timed release of a photographically useful group. Bleach accelerator groups have also been used as coupling-off groups, such as described in European Patent Specification No. 193389 and U.S. Patents 4,861,701; 4,959,299 and 4,912,024.

[0003] The part of the compound that remains in the photographic material after release of the coupling-off groups and the dye that is formed in the material from the reaction with oxidized developer often provide undesired properties in the photographic material during or after photographic processing. For example, the dye formed from a coupler upon release of the coupling-off group often adversely affects the desired image. One answer to this problem has been to provide a water-solubilizing group on the parent coupler to enable the dye formed from the coupler to be washed out of the photographic element upon photographic processing. Such couplers are described in, for example, U.S. Patents 4,482,629 and 5,026,628.

[0004] A class of washout couplers (couplers capable of forming dyes that may be washed out of photographic materials containing such couplers upon photographic processing) that are especially useful is the naphtholic class of couplers, such as described in U.S. Patents 4,482,629 and 5,026,628.

[0005] EP-A-0443530 describes a photographic naphtholic coupler moiety comprising a ballast free naptholic coupler moiety containing a -CONH₂ group in the 2- position and a ballasted coupling-off group in the 4- position enables good wash out of dye formed upon oxidative coupling from a photographic material during processing of such a photographic material. Such a naphtholic coupler is useful in photographic silver halide materials and processes.

[0006] EP-A-0485965 describes a photographic silver halide element comprising a combination of a first coupler that is capable of releasing a development inhibitor moiety during photographic processing that enhances development inhibition and a second coupler that enables release of a bleach accelerator group upon processing. The photographic silver halide element is useful in photographic imaging.

Assessment of the Art

[0007] However, such couplers have not provided both enabling of washout of the dye formed and bleach acceleration upon processing of the photographic material containing such a coupler. Thus, there exists a need to provide photographic elements comprising such couplers, as well as, to provide photographic elements comprising such couplers and development inhibitor releasing couplers (DIR's).

Disclosure of the Invention

[0008] The present invention solves these problems by providing A color photographic element comprising a support bearing at least one photographic silver halide emulsion layer, an image dye-forming coupler, and a combination of a development inhibitor releasing coupler and a wash-out coupler, the wash-out coupler (A) being distinct from the development inhibitor releasing coupler, and

(i) capable of forming a compound upon reaction with oxidized developer that is washed out of the photographic element upon processing or forms a compound which washes out after further reaction and

(ii)capable of releasing a bleach accelerator group, and

(iii) is represented by the formula:

wherein

R³

is hydrogen;

R⁴

is selected from hydrogen -Cl, -NO₂, -OCH₃, -NHSO₂R⁵, NHCOR⁵, -SO₂NHR⁵, -CONHR⁵, -CO₂R⁵, and -COR⁵;

R⁵

is selected from the group consisting of hydrogen, substituted or unsubstituted alkyl containing 1-5 carbon atoms and substituted or unsubstituted aryl containing 6-8 carbon atoms wherein the substituted or unsubstituted alkyl or aryl is a solubilizing group or contains a solubilizing group;

R¹⁰

is selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, nitro, substituted or unsubstituted amino, carboxylic acid, sulfonic acid, methoxy, chloro, bromo, ester groups, keto groups, -NHCOCH₃, -CONHCH₃, -NHSO₂CH₃, and -SO₂NHCH₃;

R¹¹ and R¹²

are selected from hydrogen, substituted or unsubstituted alkyl, and substituted or unsubstituted aryl;

Z¹

represents the atoms necessary to complete a 6 member aryl or a 5 or 6 member heterocyclic ring;

Q

is selected from oxygen, sulfur or nitrogen;

W

is 0, 1, 2, or 3;

at least one of R¹⁰, R¹¹, and R¹² contains a photographic ballast; and
BLEACH is represented by the formula

        -S-R¹³-COOH

wherein R¹³ is an unsubstituted or substituted alkylene containing 1 to 8 carbon atoms.

[0009] The development inhibitor releasing coupler is selected from a timed and non-timed development inhibitor releasing coupler (B).

[0010] Such couplers enable not only the washout of dyes formed from the coupler during photographic processing but also the acceleration of bleaching of the silver formed during processing. Couplers used in the invention can be coated in imaging layers, non-imaging layers or interlayers. Non-imaging layers or interlayers can contain interlayer scavengers, filter dyes of any type known in the photographic art including solid particle dispersion, conventional oil-in water dispersed filter dyes and washout filter dyes, non-imaging silver emulsions such as fine particle Carey-Lea or Lippmann emulsion containing layers, or yellow colored silver emulsions which are non-imaging layers. The interlayers can be located between imaging layers, between non-imaging layers, between an imaging and an non-imaging layer, between an antihalation layer and an interlayer or between an antihalation and an imaging layer. In addition to releasing a bleach accelerator group, said couplers behave as photographic scavengers, forming washout dyes, and preventing excess oxidized color developer from diffusing to another imaging layer. Further, when coated in an imaging or non-imaging layer, these couplers can affect the development inhibition of the silver halide in not only the layer in which it is coated but also in adjacent layers thus allowing for the use of increased amounts of development inhibiting releasing compounds in photographic elements, resulting in increased sharpness. Further, one particular advantage of locating said couplers in an interlayer is to minimize any speed loss due to direct competition of oxidized color developer for said couplers over the imaging couplers. A Detailed Description of the Invention

[0011] The washout coupler (A) utilized in this invention is represented by the formula:

wherein

R³

is hydrogen;

R⁴

is selected from hydrogen -Cl, -NO₂, -OCH₃, -NHSO₂R⁵, NHCOR⁵, -SO₂NHR⁵, -CONHR⁵, -CO₂R⁵, and -COR⁵;

R⁵

is selected from the group consisting of hydrogen, substituted or unsubstituted alkyl containing 1-5 carbon atoms and substituted or unsubstituted aryl containing 6-8 carbon atoms wherein the substituted or unsubstituted alkyl or aryl is a solubilizing group or contains a solubilizing group;

R¹⁰

is selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, nitro, substituted or unsubstituted amino, carboxylic acid, sulfonic acid, methoxy, chloro, bromo, ester groups, keto groups, -NHCOCH₃, -CONHCH₃, -NHSO₂CH₃, and -SO₂NHCH₃;

R¹¹ and R¹²

are selected from hydrogen, substituted or unsubstituted alkyl, and substituted or unsubstituted aryl;

Z¹

represents the atoms necessary to complete a 6 member aryl or a 5 or 6 member heterocyclic ring;

Q

is selected from oxygen, sulfur or nitrogen;

W

is 0, 1, 2, or 3;
at least one of R¹⁰, R¹¹, and R¹² contains a photographic ballast; and
BLEACH is represented by the formula

        -S-R¹³-COOH

wherein R¹³ is an unsubstituted or substituted alkylene containing 1 to 8 carbon atoms.

[0012] The following are useful examples of R¹³ groups:

[0013] The development inhibiting releasing coupler (B) may be selected from:

wherein:

INH is a photographic development inhibiting group;

COUP is a coupler moiety;

BALLAST is a photographic ballast;

Q is selected from O (oxygen), S (sulfur), or N (nitrogen);

R⁶ and R¹⁰ is hydrogen or a substituent selected from substituted or unsubstituted alkyl and substituted or unsubstituted aryl, nitro, amino, substituted amino, carboxylic acid, sulfonic acid, methoxy, chloro, bromo, ester groups such as - CO₂CH₃, keto groups such as -COCH₃, or -NHCOCH₃, - CONHCH₃, -NHSO₂CH₃, or -SO₂NHCH₃;

R⁷, R⁸, R¹¹, and R¹² are selected from hydrogen, substituted or unsubstituted alkyl, and substituted or unsubstituted aryl;

R⁹ is unsubstituted or substituted alkyl or substituted or unsubstituted aryl;

Z¹ represents the atoms necessary to complete a 6 member aryl or a 5 or 6 member heterocyclic group; R^2b is a timing group;

p and m are individually 0 or 1;

n is 0, 1 or 2; and

at least one of R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹ and R¹² contains a photographic ballast when m is 0.

[0014] U. S. Patent 4,886,736 discloses timing groups at Col. 16, line 50 through Col. 21 useful for DIR couplers (B) and such groups may contain a ballast.

[0015] INH can be any releasable development inhibitor group. Typical INH groups are described in, for example U.S. Patents 4,477,563; 4,782,012; 4,886,736; 4,912,024; 4,959,299; and 5,026,628. Preferred development inhibitor groups are heterocyclic inhibitor groups which for example, include mercaptotetrazoles, mercaptoxadiazoles, mercaptothiadiazoles and benzotriazoles. Structures A-1 through A-8 as follows, represent typical releasable development inhibitor groups.



wherein:

R_b, R_e, R_h, and R_i are individually hydrogen, substituted or unsubstituted alkyl of 1 to 8 carbon atoms such as methyl, ethyl, propyl, butyl, 1-ethylpentyl, 2-ethoxyethyl, substituted phenyl, unsubstituted phenyl; substituted or unsubstituted phenyl of 6 to 10 carbon atoms; alkylthio, such as methyl, ethyl, propyl, butyl or octylthio; or alkyl esters such as -CO₂CH₃, -CO₂C₂H₅, -CO₂C₃H₇, -CO₂C₄H₉, -CH₂CO₂CH₃, -CH₂CO₂C₂H₅, -CH₂CO₂C₃H₇, -CH₂CO₂C₄H₉, -CH₂CH₂CO₂CH₃, -CH₂CH₂CO₂C₂H₅, -CH₂CH₂CO₂C₃H₇, and -CH₂CH₂CO₂C₄H₉; or aryl esters such as -CO₂R_j, -CH₂CO₂R_j, -CH₂CH₂CO₂R_j, wherein R_j is substituted or unsubstituted aryl;
wherein:

R_c, R_d, R_f, and R_g are as described for R_b, R_e, R_h, and R_i; or, are individually one or more halogen such as chloro, fluoro, or bromo; carboxyl, esters or other substituents such as -NHCOCH₃, -SO₂OCH₃, -OCH₂CH₂SO₂CH₃, -OCOCH₂CH₃, -NHCOCH₃ or nitro groups.

[0016] The photographic couplers used in the invention can be incorporated in photographic elements by means and processes known in the photographic art. In a photographic element prior to exposure and processing the photographic coupler should be of such size and configuration that it will not diffuse through the photographic layers.

[0017] During photographic processing, the reaction of coupler (A) with oxidized color developing agent cleaves the bond between the coupling-off group and the coupler moiety of the coupler (A). Tailoring of the particular parts of the releasing groups and timing groups as required for a given releasable bleach accelerator group allows control over the timing and rate of the release of the bleach accelerator group.

[0018] The releasing group and/or timing groups can contain a ballast group, BALLAST, if desired. As used herein BALLAST is a ballast group that is known in the photographic art. The ballast group as described is an organic group of such size and configuration as to confer on the molecule sufficient bulk to render the molecule substantially non-diffusible from the layer in which it is coated in a photographic element. Representative ballast groups include substituted or unsubstituted alkyl or aryl groups typically containing 8 to 40 carbon atoms. A process of forming an image having the described advantages comprises developing an exposed photographic element by means of a color developing agent in the presence of described coupler (A).

[0019] The naphtholic coupler moiety can be ballasted or unballasted provided that the dye formed upon oxidative coupling is capable of being washed out of the photographic element.

[0020] The photographic element can comprise other couplers known in the photographic art. The photographic element can, for example comprise at least one photographic coupler that is capable of release during photographic processing a reagent or a photographic dye. A photographic reagent herein is a moiety that upon release further reacts with components in the photographic element, such as a development inhibitor, a development accelerator, a bleach inhibitor, a bleach accelerator, a coupler (for example, a competing coupler, a dye-forming coupler, or a development inhibitor releasing coupler (DIR coupler), a dye precursor, a dye, a developing agent (for example, a competing developing agent, a dye-forming developing agent, or a silver halide developing agent), a silver complexing agent, a fixing agent, an image toner, a stabilizer, a hardener, a tanning agent, a fogging agent, an ultraviolet radiation absorber, an antifoggant, a nucleator, a chemical or spectral sensitizer or desensitizer.

[0021] The bleach accelerator group can be present in the coupling-off group as a preformed species or it can be present in a blocked form or as a precursor. The bleach accelerator group can be for example a preformed bleach accelerator group or the bleach accelerator function can be blocked.

[0022] There follows a listing of patents and publications that describe representative couplers useful in the photographic element of the invention:

I. Couplers

[0023] 

A. Couplers which form cyan dyes upon reaction with oxidized color developing agents are described in such representative patents and publications as: U.S. Patent Nos. 2,772,162; 2,895,826; 3,002,836; 3,034,892; 2,474,293; 2,423,730; 2,367,531; 3,041,236; 4,333,999 and "Farbkuppler-eine Literaturübersicht," published in Agfa Mitteilungen, Band III, pp. 156-175 (1961).
Preferably such couplers are phenols and naphthols which form cyan dyes on reaction with oxidized color developing agent.

B. Couplers which form magenta dyes upon reaction with oxidized color developing agent are publications as: U.S. Patent Nos. 2,600,788; 2,369,489; 2,343,703; 2,311,082; 3,152,896; 3,519,429; 3,062,653; 2,908,573 and "Farbkuppler-eine Mitteilungen, Band III, pp. 126-156 (1961).
Preferably such magenta dye-forming couplers are pyrazolones or pyrazolotriazole couplers.

C. Couplers which form yellow dyes upon reaction with oxidized and color developing agent are described in such representative patents and publications as: U.S. Patent Nos. 2,875,057; 2,407,210; 3,265,506; 2,298,443; 3,048,194; 3,447,928 and "Farbkuppler-eine Mitteilungen, Band III, pp. 112-126 (1961). Preferably such yellow dye-forming couplers are acylacetamides, such as benzoylacetamides and pivaloylacetamides.

D. Couplers which form colorless products upon reaction with oxidized color developing agent are described in such representative patents as: U.K. Patent No. 861,138; U.S. Patent Nos. 3,632,345; 3,928,041; 3,958,993 and 3,961,959.

[0024] The naphtholic couplers used in the invention are especially useful in combination with at least one development inhibitor releasing coupler (DIR couplers) known in the photographic art.

[0025] The photographic couplers used in the invention can be incorporated in photographic elements by means and processes known in the photographic art. In a photographic element prior to exposure and processing the photographic coupler should be of such size and configuration that it will not diffuse through the photographic layers.

[0026] Photographic elements of this invention can be processed by conventional techniques in which color forming couplers and color developing agents are incorporated in separate processing solutions or compositions or in the element.

[0027] Photographic elements in which the compounds used in this invention are incorporated can be a simple element comprising a support and a single silver halide emulsion layer or they can be multilayer, multicolor elements. The compounds used in this invention can be incorporated in at least one of the silver halide emulsion layers and/or in at least one other layer, such as an adjacent layer, where they will come into reactive association with oxidized color developing agent which has developed silver halide in the emulsion layer. The silver halide emulsion layer can contain or have associated with it, other photographic coupler compounds, such as dye-forming couplers, colored masking couplers, and/or competing couplers. These other photographic couplers can form dyes of the same or different color and hue as the photographic couplers used in this invention. Additionally, the silver halide emulsion layers and other layers of the photographic element can contain addenda conventionally contained in such layers.

[0028] A typical multilayer, multicolor photographic element can comprise a support having thereon a red-sensitive silver halide emulsion unit having associated therewith a cyan dye image-providing material, a green-sensitive silver halide emulsion unit having associated therewith a magenta dye image-providing material and a blue-sensitive silver halide emulsion unit having associated therewith a yellow dye image-providing material, at least one of the silver halide emulsion units having associated there with a photographic coupler used in the invention. Each silver halide emulsion unit can be composed of one or more layers and the various units and layers can be arranged in different locations with respect to one another.

[0029] The light sensitive silver halide emulsions can include coarse, regular or fine grain silver halide crystals or mixtures thereof and can be comprised of such silver halides as silver chloride, silver bromide, silver bromoiodide, silver chlorobromide, silver chloroiodide, silver chlorobromoiodide and mixtures thereof. The emulsions can be negative-working or direct-positive emulsions. They can form, latent images predominantly on the surface of the silver halide grains or predominantly on the interior of the silver halide grains. They can be chemically and spectrally sensitized. The emulsions typically will be gelatin emulsions although other hydrophilic colloids are useful. Tabular grain light sensitive silver halides are particularly useful such as described in Research Disclosure, January 1983, Item No. 22534, and U.S. Patent 4,434,226.

[0030] The support can be any support used with photographic elements. Typical supports include cellulose nitrate film, cellulose acetate film, polyvinylacetal film, polyethylene terephthalate film, polycarbonate film and related films or resinous materials as well as glass, paper, metal. Typically, a flexible support is employed, such as a polymeric film or paper support. Paper supports can be acetylated or coated with baryta and/or an a-olefin polymer, particularly a polymer of an a-olefin containing 2 to 10 carbon atoms such as polyethylene, polypropylene, ethylene-butene copolymers.

[0031] The coupler (A) can be used in photographic elements in the same way as photographic couplers which release bleach accelerator groups have previously been used in photographic elements.

[0032] Depending upon the nature of the particular PUG, the couplers can be incorporated in a photographic element for different purposes and in different locations.

[0033] In the following discussion of suitable materials for use in the emulsions used in the elements of this invention, reference will be made to Research Disclosure, December 1978, Item 17643, published by Industrial Opportunities Ltd., Homewell Havant, Hampshire, P09 1EF, U.K. This publication will be identified hereafter by the term "Research Disclosure".

[0034] The photographic elements can be coated on a variety of supports as described in Research Disclosure Section XVII and the references described therein.

[0035] Photographic elements can be exposed to actinic radiation, typically in the visible region of the spectrum, to form a latent image as described in Research Disclosure Section XVIII and then processed to form a visible dye image as described in Research Disclosure Section XIX. Processing to form a visible dye image includes the step of contacting the element with a color developing agent to reduce developable silver halide and oxidize the color developing agent. Oxidized color developing agent in turn reacts with the coupler to yield a dye.

[0036] Preferred color developing agents useful in the invention are p-phenylene diamines. Especially preferred are 4-amino-N,N-diethylaniline hydrochloride; 4-amino-3-methyl-N,N-diethylaniline hydrochloride; 4-amino-3-methyl-N-ethyl-N-β-(methanesulfonamido)ethylaniline sulfate hydrate; 4-amino-3-methyl-N-ethyl-N-β-hydroxyethylaniline sulfate; 4-amino-3-β-(methanesulfonamido)-ethyl-N,N-diethlaniline hydrochloride; and 4-amino-N-ethyl-N-(2-methoxyethyl)-m-toluidine di-p-toluenesulfonic acid.

[0037] The described photographic materials and processes can be used with photographic silver halide emulsions and addenda known to be useful in the photographic art, as described in, for example, Research Disclosure, December 1989, Item No. 308,119.

[0038] With negative working silver halide the processing step described above gives a negative image. To obtain a positive (or reversal) image, this step can be preceded by development with a non-chromogenic developing agent to develop exposed silver halide, but not form a dye, and then uniformly fogging the element to render unexposed silver halide developable. Alternatively, a direct positive emulsion can be employed to obtain a positive image.

[0039] Development is followed by the conventional steps of bleaching, fixing, or bleach-fixing, to remove silver and silver halide, washing and drying.

[0040] The following examples and data further illustrate the invention. Photographic elements were prepared comprising the bleach accelerating releasing couplers (BARCs) forming washout dyes as described. Example 1

[0041] Illustrative example wherein compounds used in the invention are located within an emulsion layer. On a cellulose triacetate film support subbed with gelatin, were coated the following layers: (amounts are in grams per meter squared).

Emulsion layer 1

Gelatin - 3.2; red sensitized silver bromoiodide (as Ag) - 1.61; cyan image forming coupler C-1 - 0.75, dispersed in di-n-butylphthalate, (1:0.75, by weight); cyan dye forming DIR coupler (Development Inhibiting Releasing Coupler) DC-1 - 0.05, dispersed in N-butylacetanilide, (1:2 by weight); BARC(s), as described in Table 1, dispersed in N,N-diethyldodecanamide, (1:2 by weight); and saponin - 1.5% of melt volume.

Protective Overcoat

Gelatin - 5.4; bisvinylsulfonylmethyl ether - 2% of total gelatin; and saponin surfactant - 1.5% of melt volume.

[0042] Structures of the couplers are as follows:

[0043] Strips of each element were exposed to red light through a graduated density step tablet and then developed 3.25 minutes at 40°C in color developer solution CDs1, stopped, washed, bleached using bleach solutions Bls1, Bls1 modified as described, or Bls2, fixed, washed and dried. Bleach solutions referred to should not be confused with the earlier BLEACH which is a fragment released from coupler (A). The residual silver levels were measured by X-ray fluoresence.

Color Developer, CDs1:
Distilled Water	800mL
Sodium Metabisulfite	2.78 g
Sodium Sulfite, anhydrous	0.38 g
Kodak CD-4 (color developer)*	4.52 g
Potassium Carbonate, anhyd.	34.3 g
Potassium Bicarbonate	2.32 g
Sodium Bromide	1.31 g
Potassium Iodoide	1.20 mg
Hydroxylamine Sulfate (HAS)	2.41 g
Diethylenetriaminepentacetic acid, pentasodium salt (40% Soln.)	8.43 g
Distilled Water	to 1 L
Adjust pH to 10.0.

*CD-4 is 4-amino-3-methyl-N-ethyl-N-beta-hydroxyethylaniline sulfate.

Bleach Solution, Bls1
Distilled water	600mL
Ammonium bromide	150g
Ammonium Ferric EDTA (1.56M, pH 7.05, 44% by weight.	175mL
Contains 10% molar excess EDTA, 3.5% by weight
Glacial acetic acid	9.5mL
Sodium nitrate	35g
Distilled water	to 1L
pH at 26.7°C 6.00 +/-0.05 Adjusted with NH4OH or HNO3.

Bleach Solution, Bls2
Gelatin	0.5g
Sodium persulfate	33.0g
Sodium chloride	15.0g
Sodium dihydrogen phosphate (anhydrous)	9.0g
Distilled water	to 1L

[0044] Structures of the couplers are as follows:

[0045] Compounds used in the Invention

[0046] In Example 1, Table 1, it can be seen that compound B-2 used in the invention, releases a bleaching fragment which gives desired bleaching and contrast increases without undesired large speed increases observed with comparison compound Cm-1. The large speed increase associated with Cm-1 is due to the formation of cyan dye which does not wash out of the element.

[0047] Table 1 also shows two variations in bleaching fragment both of which contain a carboxylic acid group, released from B-3 and B-4. Both give the desired increases in contrast and bleaching performance similar to B-2. They do not show the large speed increases associated with the comparison compound Cm-1. Example 2

[0048] Illustrative example wherein compounds used in the invention are located in an interlayer, (between imaging layers).

[0049] On a cellulose triacetate film support subbed with gelatin, were coated the following layers: (amounts are in grams per meter squared, unless noted).

Antihalation layer

Gelatin - 2.44; and grey collodal silver - 0.32.

Interlayer B

Gelatin - 0.65; and S-1 - 0.108 Mol/m² or BARC(s) - 0.108 Mole/m² as described in Table 2, dispersed in N,N-diethyldodecanamide, (1:2).

Emulsion layer 1:

Gelatin - 2.15; green sensitized

(Green Record)

silver bromoiodide (as Ag) - 1.07; magenta image forming coupler M-1 - 0.32, dispersed in dibutylphthalate, (1:1/2); and magenta dye forming DIR coupler (Development Inhibiting Releasing Coupler) DM-1 - 0.02, dispersed in dibutylphthalate, (1:2).

Interlayer A

Gelatin - 0.65; and S-1 - 0.108Mol/m² or BARC(s) - 0.108 Mole/m², as described in Table 2, dispersed in N,N-diethyldodecanamide, (1:2).

Emulsion layer 2

Gelatin - 2.42; blue sensitized

(Blue Record)

silver bromoiodide (as Ag) - 0.91; yellow image forming coupler Y-1 - 0.75, dispersed in dibutylphthalate, (1:1/3); and yellow dye forming DIAR coupler (Development Inhibiting Releasing Coupler) DY-1 - 0.05, dispersed in dibutylphthalate, (1:1/2).

Overcoat Gelatin -.2.7;

and bisvinylsulfonylmethyl ether - 1.75% total gelatin.

[0050] Structures of the couplers, not already described in Example 1, are as follows:

[0051] Strips of each element were exposed to white light through a graduated density step tablet and then developed 3.25 minutes at 40°C in the color developer solution CDs1, described, stopped, washed, bleached using bleach solutions, Bls2, Bls3, and modified bleach solutions Bls1 and Bls3 as described, fixed, washed and dried.

Bleach Solution, Bls3
Distilled water	600mL
Ammonium bromide	50.0g
1,3-Propanediaminetetraacetic acid	30.27g
Ammonium hydroxide (28% ammonia)	35.20g
Ferric nitrate nonahydrate	36.40g
Glacial acetic acid	26.50g
1,3-Diamino-2-propanoltetraacetic acid (Rexpronol Acid, Grace)	1.0g
Ammonmium ferric EDTA (1.56M, pH 7.05, 44% wgt.) (contains 10% molar excess EDTA, 3.5% wgt.)	149.0g
Distilled water to make	1.0L
pH at 26.7°C 5.25 +/- 0.10 Adjusted pH with NH4OH or HNO3.

[0052] From Table 2 it can be seen that the photographic element containing compound B-2 used in the invention has less red density at D_max, than the comparison Cm-1, showing that during processing, the dye formed from the compound used in the invention, is washing out of the photographic element. This is not the case for Cm-1.

[0053] Table 2 also shows that the photographic element containing compound B-2 used in the invention has lower D_min values than those containing S-1. This shows that the compound used in the invention is very effective scavanger of oxidized color developer.

[0054] Changes in speed and contrast were generally less with compounds used in the invention or comparison compounds when they were coated in interlayers, see Table 1, compared with emulsion containing layers.

[0055] Compounds used in the invention give excellent bleaching when coated in interlayers.

Claims

1. A color photographic element comprising a support bearing at least one photographic silver halide emulsion layer, an image dye-forming coupler, and a combination of a development inhibitor releasing coupler and a wash-out coupler,the wash-out coupler (A) being distinct from the development inhibitor releasing coupler, and

(i) capable of forming a compound upon reaction with oxidized developer that is washed out of the photographic element upon processing or forms a compound which washes out after further reaction and

(ii)capable of releasing a bleach accelerator group, and

(iii) is represented by the formula:

wherein

R³   is hydrogen;

R⁴   is selected from hydrogen -Cl, -NO₂, -OCH₃, -NHSO₂R⁵, NHCOR⁵, -SO₂NHR⁵, -CONHR⁵, -CO₂R⁵, and -COR⁵;

R⁵   is selected from the group consisting of hydrogen, substituted or unsubstituted alkyl containing 1-5 carbon atoms and substituted or unsubstituted aryl containing 6-8 carbon atoms wherein the substituted or unsubstituted alkyl or aryl is a solubilizing group or contains a solubilizing group;

R¹⁰   is selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, nitro, substituted or unsubstituted amino, carboxylic acid, sulfonic acid, methoxy, chloro, bromo, ester groups, keto groups, -NHCOCH₃, -CONHCH₃, -NHSO₂CH₃, and -SO₂NHCH₃;

R¹¹ and R¹²   are selected from hydrogen, substituted or unsubstituted alkyl, and substituted or unsubstituted aryl;

Z¹   represents the atoms necessary to complete a 6 member aryl or a 5 or 6 member heterocyclic ring;

Q   is selected from oxygen, sulfur or nitrogen;

W   is 0, 1, 2, or 3;

at least one of R¹⁰, R¹¹, and R¹² contains a photographic ballast; and
BLEACH is represented by the formula

        -S-R¹³-COOH

wherein R¹³ is an unsubstituted or substituted alkylene containing 1 to 8 carbon atoms.

2. A color photographic element as in claim 1 wherein the coupler (A) is represented by the formulae:

3. A color photographic element as in claims 1 & 2 comprising a support bearing in sequence

at least one red sensitive photographic silver halide emulsion layer comprising at least one cyan image dye-forming coupler;

at least one green sensitive photographic silver halide emulsion layer comprising a least one magenta image dye-forming coupler; and

at least one blue sensitive photographic silver halide emulsion layer comprising at least one yellow image dye-forming coupler; and

at least one of the layers comprises at least one wash out coupler (A) as defined in claims 1 and 2 and at least one development inhibiting releasing coupler.

4. The photographic element in accordance with any one of claims 1 to 3 wherein the wash out coupler (A) is located in an imaging layer.

5. The photographic element in accordance with any one of claims 1 to 3 wherein the wash out coupler (A) is located in an interlayer between two imaging layers.

6. A color photographic element as in claims 1 through 5 wherein the development inhibiting releasing coupler is selected from:

wherein:

INH is a photographic development inhibiting group;

COUP is a coupler moiety;

BALLAST is a photographic ballast;

Q is selected from O (oxygen), S (sulfur), or N (nitrogen);

R⁶ and R¹⁰ are hydrogen or a substituent selected from substituted or unsubstituted alkyl, substituted or unsubstituted aryl, nitro, amino, substituted amino, carboxylic acid, sulfonic acid, methoxy, chloro, bromo, ester groups, keto groups, -NHCOCH₃, -CONHCH₃, -NHSO₂CH₃, or -SO₂NHCH₃;

R⁷, R⁸, R¹¹, and R¹² are selected from hydrogen, substituted or unsubstituted alkyl, and substituted or unsubstituted aryl;

R⁹ is unsubstituted or substituted alkyl or substituted or unsubstituted aryl;

Z¹ represents the atoms necessary to complete a 6 member aryl or a 5 or 6 member heterocyclic group;

R^2b is a timing group;

p and m are individually 0 or 1;

n is 0, 1 or 2; and

at least one of R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹ and R¹² contains a photographic ballast when m is 0.

7. A process of forming an image in an exposed photographic element as defined in claims 1-6 comprising developing the photographic element with a color developer.

Ansprüche

1. Farbfotografisches Element mit einem Träger, auf dem sich mindestens eine fotografische Silberhalogenid-Emulsionsschicht befindet, ein bildfarbstoffbildender Kuppler und eine Kombination eines einen Entwicklungsinhibitor freisetzenden Kupplers ("DIR-Kuppler") und eines Auswaschkupplers (A), der sich vom DIR-Kuppler unterscheidet, wobei das Element

(i) durch Reaktion mit oxidiertem Entwickler eine Verbindung bilden kann, die bei der Verarbeitung aus dem fotografischen Element ausgewaschen wird oder eine Verbindung bildet, die nach Weiterreaktion ausgewaschen wird und

(ii) eine Bleichbeschleunigungsgruppe freisetzen kann und

(iii) durch folgende Formel wiedergegeben wird:

wobei

R³   Wasserstoff ist;

R⁴   aus der Gruppe Wasserstoff, -Cl, -NO₂, -OCH₃, -NHSO₂R⁵, NHCOR⁵, -SO₂NHR⁵, -CONHR⁵, -CO₂R⁵ und -COR⁵ ausgewählt wird;

R⁵   aus der Gruppe Wasserstoff, substituiertes oder unsubstituiertes Alkyl mit 1-5 Kohlenstoffatomen und substituiertes oder unsubstituiertes Aryl mit 6-8 Kohlenstoffatomen ausgewählt wird, und die substituierte oder unsubstituierte Alkyl- oder Arylgruppe eine solubilisierende Gruppe ist oder eine solubilisierende Gruppe enthält;

R¹⁰   aus der Gruppe Wasserstoff, substituiertes oder unsubstituiertes Alkyl, substituiertes oder unsubstituiertes Aryl, Nitro, substituiertes oder unsubstituiertes Amino, Carbonsäure, Sulfonsäure, Methoxy, Chlor, Brom, Estergruppen, Ketogruppen, -NHCOCH₃, -CONHCH₃, -NHSO₂CH₃ und -SO₂NHCH₃ ausgewählt wird;

R¹¹ und R¹²   aus der Gruppe Wasserstoff, substituiertes oder unsubstituiertes Alkyl und substituiertes oder unsubstituiertes Aryl ausgewählt werden;

Z¹   die Atome sind, die für die Ausbildung eines 6-gliedrigen Aryl- oder eines 5- oder 6-gliedrigen heterocyclischen Rings benötigt werden;

Q   Sauerstoff, Schwefel oder Stickstoff ist;

W   0, 1, 2 oder 3 ist;

mindestens eine der Gruppen R¹⁰, R¹¹ und R¹² eine fotografische Ballastgruppe enthält, und
BLEICHE für die Formel steht

        -S-R¹³-COOH,

wobei R¹³ eine unsubstituierte oder substituierte Alkylengruppe mit 1 bis 8 Kohlenstoffatomen darstellt.

2. Farbfotografisches Element nach Anspruch 1, dadurch gekennzeichnet, dass der Kuppler (A) durch folgende Formeln dargestellt wird:

3. Farbfotografisches Element nach Anspruch 1 und 2 mit einem Träger, auf dem sich in der Reihenfolge

- mindestens eine rotempfindliche fotografische Silberhalogenid-Emulsionsschicht mit mindestens einem farbstoffbildenden Kuppler für das Blaugrünbild,

- mindestens eine grünempfindliche fotografische Silberhalogenid-Emulsionsschicht mit mindestens einem farbstoffbildenden Kuppler für das Purpurbild,

- mindestens eine blauempfindliche fotografische Silberhalogenid-Emulsionsschicht mit mindestens einem farbstoffbildenden Kuppler für das Gelbbild befindet und

- mindestens eine der Schichten mindestens einen wie in Anspruch 1 und 2 definierten Auswaschkuppler (A) und mindestens einen DIR-Kuppler enthält.

4. Fotografisches Element nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass sich der Auswaschkuppler (A) in einer bilderzeugenden Schicht befindet.

5. Fotografisches Element nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass sich der Auswaschkuppler (A) in einer Zwischenschicht zwischen zwei bilderzeugenden Schichten befindet.

6. Farbfotografisches Element nach Anspruch 1 bis 5, dadurch gekennzeichnet, dass der DIR-Kuppler eine der folgenden Verbindungen ist:

wobei

- INH eine die fotografische Entwicklung inhibierende Gruppe ist;

- KUPPLER eine Kuppler-Komponente ist;

- BALLAST eine fotografische Ballastgruppe ist;

- Q entweder O (Sauerstoff), S (Schwefel) oder N (Stickstoff) ist;

- R⁶ und R¹⁰ Wasserstoff oder Substituenten sind, die aus der Gruppe substituiertes oder unsubstituiertes Alkyl, substituiertes oder unsubstituiertes Aryl, Nitro, Amino, substituiertes Amino, Carbonsäure, Sulfonsäure, Methoxy, Chlor, Brom, Estergruppen, Ketogruppen, -NHCOCH₃, -CONHCH₃, -NHSO₂CH₃ oder -SO₂NHCH₃ ausgewählt werden;

- R⁷, R⁸, R¹¹ und R¹² Substituenten sind, die aus der Gruppe Wasserstoff, substituiertes oder unsubstituiertes Alkyl und substituiertes oder unsubstituiertes Aryl ausgewählt werden;

- R⁹ substituiertes oder unsubstituiertes Alkyl oder substituiertes oder unsubstituiertes Aryl ist;

- Z¹ die Atome sind, die für die Ausbildung eines 6-gliedrigen Aryl- oder eines 5- oder 6-gliedrigen heterocyclischen Rings benötigt werden;

- R^2b eine Zeitgebergruppe ist;

- p und m jeweils 0 oder 1 sind;

- n 0, 1 oder 2 ist, und

- mindestens eine der Gruppen R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹ und R¹² eine fotografische Ballastgruppe enthält, wenn m gleich 0 ist.

7. Verfahren zur Bilderzeugung in einem belichteten, in Anspruch 1 - 6 definierten fotografischen Element, das die Entwicklung des fotografischen Elements mit einem Farbentwickler umfasst.

Revendications

1. Elément photographique couleur comprenant un support portant au moins une couche d'émulsion photographique aux halogénures d'argent, un coupleur formateur de colorant d'image et une combinaison d'un coupleur libérant un inhibiteur de développement et d'un coupleur pouvant être éliminé par lavage, le coupleur (A) pouvant être éliminé par lavage étant différent du coupleur libérant un inhibiteur de développement et

(i) capable de former, lors de sa réaction avec un développateur oxydé, un composé qui est éliminé de l'élément photographique par lavage lors du traitement ou qui forme un composé qui est éliminé par lavage après une réaction ultérieure et

(ii) capable de libérer un groupe accélérateur de blanchiment, et

(iii) étant représenté par la formule :

dans laquelle

R³ représente un hydrogène ;

R⁴ est choisi parmi l'hydrogène, -Cl, -NO₂, -OCH₃, -NHSO₂R⁵, NHCOR⁵, -SO₂NHR⁵, -CONHR⁵, -CO₂R⁵ et -COR⁵;

R⁵ est choisi dans le groupe constitué de l'hydrogène, d'un groupe alkyle substitué ou non contenant 1 à 5 atomes de carbone et d'un groupe aryle substitué ou non contenant 6 à 8 atomes de carbone, dans lequel le groupe alkyle ou aryle substitué ou non est un groupe solubilisant ou contient un groupe solubilisant ;

R¹⁰ est choisi dans le groupe constitué de l'hydrogène, d'un groupe alkyle substitué ou non, d'un groupe aryle substitué ou non, d'un groupe nitro, d'un groupe amino substitué ou non, d'un acide carboxylique, d'un acide sulfonique, d'un groupe méthoxy, d'un groupe chloro, d'un groupe bromo, de groupes esters, de groupes céto, de -NHCOCH₃, -CONHCH₃, -NHSO₂CH₃ et -SO₂NHCH₃ ;

R¹¹ et R¹² sont choisis parmi l'hydrogène, un groupe alkyle substitué ou non et un groupe aryle substitué ou non ;

Z¹ représente les atomes nécessaires pour compléter un noyau aryle à 6 membres ou un hétérocycle à 5 ou 6 membres ;

Q est choisi parmi l'oxygène, le soufre et l'azote ;

W est égal à 0, 1, 2 ou 3 ;

au moins l'un des groupes R¹⁰, R¹¹ et R¹² contient un groupe ballast photographique, et
BLEACH est représenté par la formule

        -S-R¹³-COOH

dans laquelle R¹³ représente un groupe alkylène substitué ou non contenant 1 à 8 atomes de carbone.

2. Elément photographique couleur selon la revendication 1, dans lequel le coupleur (A) est représenté par les formules :

et

3. Elément photographique couleur selon les revendications 1 et 2, comprenant un support portant, dans l'ordre :

au moins une couche d'émulsion photographique aux halogénures d'argent sensible au rouge comprenant au moins un coupleur formateur de colorant d'image cyan ;

au moins une couche d'émulsion photographique aux halogénures d'argent sensible au vert comprenant au moins un coupleur formateur de colorant d'image magenta ; et

au moins une couche d'émulsion photographique aux halogénures d'argent sensible au bleu comprenant au moins un coupleur formateur de colorant d'image jaune ;

au moins l'une des couches comprenant au moins un coupleur (A) pouvant être éliminé par lavage, tel que défini dans les revendications 1 et 2, et au moins un coupleur libérant un inhibiteur de développement.

4. Elément photographique selon l'une quelconque des revendications 1 à 3, dans lequel le coupleur (A) pouvant être éliminé par lavage est incorporé dans une couche formatrice d'image.

5. Elément photographique selon l'une quelconque des revendications 1 à 3, dans lequel le coupleur (A) pouvant être éliminé par lavage est incorporé dans une couche intermédiaire entre deux couches formatrices d'image.

6. Elément photographique couleur selon les revendications 1 à 5, dans lequel le coupleur libérant un inhibiteur de développement est choisi parmi :

dans lesquelles :

INH est un groupe inhibant le développement photographique ;

COUP est un groupe coupleur ;

BALLAST est un groupe ballast photographique ;

Q est choisi parmi O (oxygène), S (soufre) et N (azote) ;

R⁶ et R¹⁰ représentent un hydrogène ou un substituant choisi parmi un groupe alkyle substitué ou non, un groupe aryle substitué ou non, un groupe nitro, un groupe amino, un groupe amino substitué, un acide carboxylique, un acide sulfonique, un groupe méthoxy, un groupe chloro, un groupe bromo, des groupes esters, des groupes céto, -NHCOCH₃, -CONHCH₃, -NHSO₂CH₃ et -SO₂NHCH₃ ;

R⁷, R⁸, R¹¹ et R¹² sont choisis parmi l'hydrogène, un groupe alkyle substitué ou non et un groupe aryle substitué ou non ;

R⁹ est un groupe alkyle substitué ou non ou un groupe aryle substitué ou non ;

Z¹ représente les atomes nécessaires pour compléter un noyau aryle à 6 membres ou un hétérocycle à 5 ou 6 membres ;

R^2b est un groupe retardateur ;

p et m sont individuellement égaux à 0 ou 1 ;

n est égal à 0, 1 ou 2 ; et

au moins l'un des groupes R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹ et R¹² contient un groupe ballast photographique lorsque m est égal à 0.

7. Procédé de formation d'une image dans un élément photographique exposé, tel que défini dans les revendications 1 à 6, comprenant le développement de l'élément photographique par un révélateur chromogène.