Photographic developing agents, process for developing using same, and light-sensitive materials containing same

What is claimed is:

1. A silver halide photographic light-sensitive material comprising a support having thereon at least one light-sensitive silver halide emulsion layer, with a layer of the photographic material containing a photographic developing agent represented by the formula (I): ##STR7## wherein one of X and Y is a group which inhibits development on release immediately after a developing agent is oxidized at development and is connected to the benzene ring in the agent represented by formula (I) by a sulfur, selenium or nitrogen atom, and the other of X and Y is an --NH--SO.sub.2 --Z group wherein Z is an alkyl group, an aryl group, or a heterocyclic group; A is a hydrogen atom or a group hydrolyzable under alkaline conditions; R.sub.1, R.sub.2 and R.sub.3, which can be the same or different, each is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an --S--Z' group wherein Z' is an alkyl group, an aryl group or a heterocyclic group, an --NH--SO.sub.2 --Z" group wherein Z" is an alkyl group, an aryl group or a heterocyclic group, an acylamido group, an amino group, a halogen atom, a hydroxy group, or an acyloxy group; and R.sub.1 and R.sub.2 further may combine to form a ring.

2. A silver halide photographic light-sensitive material as claimed in claim 1, wherein said photographic developing agent represented by the formula (I) has the formula (II): ##STR8## wherein R.sub.4, R.sub.5, R.sub.6 and R.sub.7, which may be the same or different, each represents a hydrogen atom, a halogen atom, a straight or branched alkyl group containing 1 to 30 carbon atoms which may be substituted with one or more of a halogen atom, an alkoxy group, a hydroxy group, a carboxy group, a sulfo group, a heterocyclic group or an aryl group, a straight or branched alkoxy group containing 1 to 30 carbon atoms which may be substituted with one or more of the substituents as described above for the alkyl group, a phenyl group having from 6 to 36 carbon atoms which may be substituted with one or more of a halogen atom, an alkyl group, or an alkoxy group, a phenyloxy group, which may be substituted with one or more of the substituents as defined above for the phenyl group, a 5- or 6-membered heterocyclic group containing one or more of a nitrogen atom, an oxygen atom, or a sulfur atom as a hetero atom, which may be condensed with a benzene or naphthylene nucleus, an acylamino group, a sulfonamido group, a carbamoyl group, a sulfamyl group, an acyl group, an alkoxycarbonyl group or an alkylthio group, and wherein X, Y and A are as defined in claim 1.

3. A silver halide photographic light-sensitive material as claimed in claim 1, wherein said photographic developing agent represented by the formula (I) has the formula (III): ##STR9## wherein one of X and Y is a group capable of inhibiting development on release immediately after a developing agent is oxidized at development, and the other of X and Y is an --NHSO.sub.2 --Z group, wherein Z contains 1 to 30 carbon atoms and is an alkyl group, an aryl group, or a 5- or 6-membered heterocyclic group; A is a hydrogen atom or a group hydrolyzable under alkaline conditions; R.sub.1, R.sub.2 and R.sub.3, which may be the same or different, is a hydrogen atom, a halogen atom, an alkyl group containing 1 to 30 carbon atoms, an alkoxy group containing 1 to 30 carbon atoms, an aryl group, an aryloxy group, an amino group, an --SZ' group, or an --NHSO.sub.2 Z" group, wherein Z' and Z", which may be the same or different, each is as described above for Z, and R.sub.1 and R.sub.2 further may combine together to form a saturated or unsaturated ring.

4. A silver halide photographic light-sensitive material as claimed in claim 1, wherein said group capable of inhibiting development on release for X and Y is a group containing a sulfur atom or a nitrogen atom therein through which said group is bonded to the developing agent mother nucleus.

5. A silver halide photographic light-sensitive material as claimed in claim 4, wherein said group capable of inhibiting the development on release for X and Y is an arylthio group, a heterocyclic thio group, a group derived from a thioglycolic acid based compound, a group derived from a cystein based compound or a group derived from a glutathion based group.

6. A silver halide photographic light-sensitive material as claimed in claim 1, wherein said group capable of inhibiting development on release for X and Y is a triazolyl group.

7. A silver halide photographic light-sensitive material as claimed in claim 1, wherein Z is a straight or branched alkyl group containing 1 to 30 carbon atoms which may be substituted with one or more of a halogen atom, an alkenyl group, an alkoxy group, a hydroxy group, an aryloxy group, a carboxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfo group, a heterocyclic group, or an aryl group, an aryl group which may be substituted with one or more of a halogen atom, an alkyl group, an alkoxy group, a nitro group, a cyano group, an acyl group, a carboxy group, an alkoxycarbonyl group, an acylamino group, a carbamoyl group, a sulfamoyl group, or a sulfo group, a 5- or 6-membered heterocyclic group containing one or more of a nitrogen atom, an oxygen atom, or a sulfur atom as a hetero atom, which may be condensed with a benzene or naphthylene nucleus; wherein R.sub.1, R.sub.2 and R.sub.3, which can the same or different, each is a hydrogen atom, a halogen atom, a straight or branched alkyl group having 1 to 30 carbon atoms which may be substituted with one or more of a halogen atom, an alkoxy group, a hydroxy group, a carboxy group, a sulfo group, a heterocyclic group or an aryl group, a straight or branched alkoxy group containing 1 to 30 carbon atoms in which the alkyl moiety thereof may be substituted with one or more of a halogen atom, an alkoxy group, a hydroxy group, a carboxy group, a sulfo group, a heterocyclic group or an aryl group, an acylamino group, an aryl group containing 6 to 36 carbon atoms which may be substituted with one or more of a halogen atom, an alkyl group, or an alkoxy group. an aryloxy group containing 6 to 36 carbon atoms in which the aryl moiety thereof may be substituted with one or more of a halogen atom, an alkyl group, or an alkoxy group, a 5- or 6-membered heterocyclic group containing one or more of a nitrogen atom, an oxygen atom, or a sulfur atom as a hetero atom, which may be condensed with a benzene nucleus or naphthylene nucleus, an amino group, which may be substituted with one or more of an alkyl group, an aryl group or a heterocyclic group containing up to 30 carbon atoms as substituents, an --SZ' group or an --NHSO.sub.2 Z" group wherein Z' and Z", which may be the same or different, each is as defined for Z and wherein the ring formed when R.sub.1 and R.sub.2 combine is a saturated or unsaturated ring which may be substituted with those groups as defined above for R.sub.1, R.sub.2 and R.sub.3 as substituents.

8. A multi-layer color light-sensitive material comprising a support having thereon a blue-sensitive emulsion layer comprising at least one blue-sensitive silver halide emulsion layer containing a yellow image-forming coupler, a green-sensitive emulsion layer comprising at least one green-sensitive silver halide emulsion layer containing a magenta image-forming coupler, and a red-sensitive emulsion layer comprising at least one red-sensitive silver halide emulsion layer containing a cyan image-forming coupler, said light-sensitive material further containing a photographic developing agent in at least one of said emulsion layers or an intermediate layer additionally present, wherein said photographic developing agent is represented by the formula (I): ##STR10## wherein one of X and Y is a group which inhibits development on release immediately after a developing agent is oxidized at development and is connected to the benzene ring in the agent represented by formula (I) by a sulfur, selenium or nitrogen atom, and the other of X and Y is an --NH--SO.sub.2 --Z group wherein Z is an alkyl group, an aryl group, or a heterocyclic group; A is a hydrogen atom or a group hydrolyzable under alkaline conditions; R.sub.1, R.sub.2 and R.sub.3, which can be the same or different, each is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an --S--Z' group wherein Z' is an alkyl group, an aryl group or a heterocyclic group, an --NH--SO.sub.2 --Z" group wherein Z" is an alkyl group, an aryl group or a heterocyclic group, an acylamido group, an amino group, a halogen atom, a hydroxy group, or an acyloxy group; and R.sub.1 and R.sub.2 further may combine to form a ring.

9. A multi-layer color light-sensitive material as claimed in claim 8, wherein said photographic developing agent represented by the formula (I) has the formula (II): ##STR11## wherein R.sub.4, R.sub.5, R.sub.6 and R.sub.7, which may be the same or different, each represents a hydrogen atom, a halogen atom, a straight or branched alkyl group containing 1 to 30 carbon atoms which may be substituted with one or more of a halogen atom, an alkoxy group, a hydroxy group, a carboxy group, a sulfo group, a heterocyclic group or an aryl group, a straight or branched alkoxy group containing 1 to 30 carbon atoms which may be substituted with one or more of the substituents as described above for the alkyl group, a phenyl group having from 6 to 36 carbon atoms which may be substituted with one or more of a halogen atom, an alkyl group, or an alkoxy group, a phenyloxy group, which may be substituted with one or more of the substituents as defined above for the phenyl group, a 5- or 6-membered heterocyclic group containing one or more of a nitrogen atom, an oxygen atom, or a sulfur atom as a hetero atom, which may be condensed with a benzene or naphthylene nucleus, an acylamino group, a sulfonamido group, a carbamoyl group, a sulfamyl group, an acyl group, an alkoxycarbonyl group or an alkylthio group, and wherein X, Y and A are as defined in claim 8.

10. A multi-layer color light-sensitive material as claimed in claim 8, wherein said photographic developing agent represented by the formula (I) has the formula (III): ##STR12## wherein one of X and Y is a group capable of inhibiting development on release immediately after the developing agent is oxidized at development, and the other of X and Y is an --NHSO.sub.2 --Z group, wherein Z contains 1 to 30 carbon atoms and is an alkyl group, an aryl group, or a 5- or 6-membered heterocyclic group; A is a hydrogen atom or a group hydrolyzable under alkaline conditions; R.sub.1, R.sub.2 and R.sub.3, which may be the same or different, is a hydrogen atom, a halogen atom, an alkyl group containing 1 to 30 carbon atoms, an alkoxy group containing 1 to 30 carbon atoms, an aryl group, an aryloxy group, an amino group, an --SZ' group, or an --NHSO.sub.2 Z" group, wherein Z' and Z", which may be the same or different, each is as described above for Z, and R.sub.1 and R.sub.2 further may combine together to form a saturated or unsaturated ring.

11. A method of forming an image comprising developing an imagewise exposed silver halide photographic light-sensitive material having thereon at least one light-sensitive silver halide emulsion layer in the presence of a photographic developing agent represented by the formula (I): ##STR13## wherein one of X and Y is a group which inhibits development on release immediately after a developing agent is oxidized at development and is connected to the benzene ring in the agent represented by formula (I) by a sulfur, selenium or nitrogen atom, and the other of X and Y is an --NH--SO.sub.2 --Z group wherein Z is an alkyl group, an aryl group, or a heterocyclic group; A is a hydrogen atom or a group hydrolyzable under alkaline conditions; R.sub.1, R.sub.2 and R.sub.3, which can be the same or different, each is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an --S--Z' group wherein Z' is an alkyl group, an aryl group or a heterocyclic group, an --NH--SO.sub.2 --Z" group wherein Z" is an alkyl group, an aryl group or a heterocyclic group, an acylamido group, an amino group, a halogen atom, a hydroxy group, or an acyloxy group; and R.sub.1 and R.sub.2 further may combine to form a ring.

12. The method of forming an image of claim 11, wherein the silver halide photographic light-sensitive material comprises a support having thereon a blue-sensitive silver halide emulsion layer containing a yellow image-forming coupler, a green-sensitive silver halide emulsion layer containing a magenta image-forming coupler and a red-sensitive silver halide emulsion layer containing a cyan image-forming coupler.

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BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a photographic developing agent and more particularly to a photographic developing agent capable of releasing a development inhibitor at the step of development; a silver halide photographic light-sensitive material which has a photographic layer containing the same; and a process for developing images by treating a photographic light-sensitive material with a developer containing the same.

2. Description of the Prior Art

Hitherto, hydroquinone derivatives releasing a development inhibitor depending upon the density of image at the time of development (so-called DIR hydroquinones) are known. Typical examples of known DIR hydroquinones are described in U.S. Pat. Nos. 3,379,529 and 3,620,746, and Japanese Patent Application (OPI) No. 129,536/1974, etc. These DIR hydroquinones are, as described in the above patents, used for the purpose of attaining the so-called DIR effect, e.g., control of image tone, an improvement in graininess, image sharpness and color reproduction, etc.

Although these DIR hydroquinones have desirable properties, they also have various defects. One defect is that a sufficient DIR effect cannot be obtained because of insufficient activity of the compounds. A second defect is that incorporation of the compound into a light-sensitive emulsion layer as a dispersion deteriorates the storage stability of the light-sensitive material. A third defect is that synthesis of the compounds is not easy. A fourth defect is that a reduction in storage stability with time of a coating solution containing the compound deteriorates the photographic properties.

SUMMARY OF THE INVENTION

It has now been found that the photographic developing agents of the present invention are free from the above defects, and have quite excellent properties.

An object of the present invention is to provide an advantageous photographic developing agent.

Another object of the present invention is to provide a photographic developing agent which releases a development inhibitor immediately after being oxidized at the step of development.

A further object of the present invention is to provide a photographic developing agent which does not reduce the storage stability of a light-sensitive material even though it is incorporated into the light-sensitive material.

Further another object of the present invention is to provide a silver halide photographic material contianing the photographic developing agent.

Another object of the present invention is to provide a photographic treating liquid containing the photographic developing agent.

A still further object of the present invention is to provide a process for developing images by effecting development in the presence of the photographic developing agent.

An even further object of the present invention is to provide a photographic developing agent which can be synthesized with ease.

These objects are attained with photographic developing agents which release a development inhibitor after being oxidized and which are represented by the following formula (I) ##STR2## wherein one of X and Y is a group capable of inhibiting development on release immediately after being oxidized at the step of development, and the other of X and Y is an --NH--SO.sub.2 --Z group (wherein Z is an alkyl group, an aryl group or a heterocyclic group); A is a hydrogen atom or a group capable of being hydrolyzed under alkaline conditions; R.sub.1, R.sub.2 and R.sub.3, which may be the same or different, each is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an --S--Z' group (wherein Z' is an alkyl group, an aryl group or a heterocyclic group), an --NH--SO.sub.2 --Z" group (wherein Z" is an alkyl group, an aryl group or a heterocyclic group), an acylamino group, an amino group, a halogen atom, a hydroxy group or an acyloxy group; and further R.sub.1 and R.sub.2 may combine to form a ring.

DETAILED DESCRIPTION OF THE INVENTION

In greater detail, in the formula (I), the group represented by X or Y, which exhibits a development inhibiting action is released immediately after the developing agent is oxidized at the step of development. This development inhibiting group represented by X or Y forms a compound which is strongly adsorbed on the silver halide grains when such is released from the developer nucleus. Such a group is preferably connected through a sulfur atom, a selenium atom or nitrogen atom therein, especially preferably a sulfur atom or a nitrogen atom, to the developing agent mother nucleus (i.e., the phenyl nucleus derived by the removal of X or Y from the formula (I)). Where X or Y is a group which is connected through a sulfur atom therein, an arylthio group, a heterocyclicthio group, a group derived from thioglycolic acid based compounds, and a group derived from cystein or glutathion based compounds are particularly useful and these contain groups, such as --SCH.sub.2 COOH, ##STR3##

Suitable examples of heterocyclicthio groups include a tetrazolylthio group (e.g., 1-phenyltetrazol-5-ylthio, 1-nitrophenyltetrazol-5-ylthio, 1-naphthyltetrazol-5-ylthio, etc.), a thiazolylthio group (e.g., 2-benzothiazolylthio, 2-naphthothiazolylthio, etc.), an oxadiazolylthio group (e.g., 1,2,4-oxadiazole-5-thio, etc.), a pyrimidinylthio group (e.g., pyrimidinylthio, etc.), a thiazolylthio group (e.g., 1,3,4-thiadiazole-2-thio, etc.), a triazinylthio group (e.g., 1,3,5-triazin-2-ylthio, etc.), triazolylthio group (e.g., 1,2,4-triazolylthio, etc.), and the like.

Suitable examples of the arylthio groups include a phenylthio group (e.g., 2-carboxyphenylthio, 2-nitrophenylthio, 3-heptanamidophenylthio, etc.), and the like. Of these groups, 1-phenyltetrazol-5-ylthio, and 1-nitrophenyltetrazole-5-thio are particularly excellent.

Where X or Y is a group which is connected through a nitrogen atom therein, a triazolyl group, especially a benzotriazolyl group which may be substituted, e.g., 5-methylbenzotriazol-1- or -2-yl, 5-bromobenzotriazol-1- or -2-yl, 5-octanamidobenzotriazol-1- or --2-yl, 5-benzyloxybenzotriazol-1-or --2-yl, 5-(3-methylbenzothiazolinilidene)aminobenzotriazol-1-or --2-yl, and the like are particularly useful.

Where X or Y is an --NHSO.sub.2 Z group, Z is preferably a straight or branched alkyl group containing 1 to 30 carbon atoms, a substituted alkyl group (with substituents including one or more halogen atoms and alkenyl, aryloxy, hydroxy, allyloxy, carboxy, alkoxycarbonyl, aryloxycarbonyl, sulfo, heterocyclic, aryl, and like groups), an aryl group, e.g., phenyl, and substituted phenyl (in which the number of carbon atoms can be 6 to 36) (with substituents including one or more halogen atoms or alkyl, alkoxy, nitro, cyano, acyl, carboxy, alkoxycarbonyl, acylamino, carbamoyl, sulfamoyl, sulfo, and like groups), a 5-or 6-membered heterocyclic group containing one or more hetero atoms, such as N, O, S, etc., (which group may be condensed with a benzene or naphthalene nucleus), or the like.

Suitable specific examples of Z include methyl, isopropyl, 2-methoxyethyl, octadecyl, benzyl, 3-(4-nitrophenoxy)propyl, 4-(2,4-di-t-pentylphenoxy)butyl, phenyl, 4-tolyl, 4-nonylphenyl, 3-nitrophenyl, 3-(2,4-di-t-pentylphenoxyacetamido)phenyl, 3-[3-(2,4-di-t-pentylphenoxy)propylsulfamoyl]phenyl, pyridyl, imidazolyl, and the like.

Preferred specific examples of groups represented by A, in addition to a hydrogen atom, which are hydrolyzable under alkaline conditions, e.g., at a pH of about 9 to 14, include chloroacetyl, dichloroacetyl, 4-nitrobenzoyl, phenoxycarbonyl, alkoxycarbonyl, alkoxyoxalyl, and the like.

R.sub.1, R.sub.2 and R.sub.3, which can be the same or different, each preferably is a hydrogen atom, a halogen atom, straight or branched substituted or unsubstituted alkyl or alkoxy group (with substituents including one or more halogen atoms and alkoxy, hydroxy, carboxy, sulfo, heterocyclic, aryl, and like groups) containing 1 to 30 carbon atoms, an acylamino group, a substituted or unsubstituted aryl or aryloxy group containing 6 to 36 carbon atoms (with substituents including one or more halogen atoms and alkyl, alkoxy, and like groups), a 5- or 6-membered heterocyclic group containing one or more hetero atoms such as N, O, S, etc., (which group may be condensed with a benzene or naphthalene nucleus), a substituted or unsubstituted amino group (with substituents including one or more alkyl, aryl, heterocyclic, and like groups containing 1 to 30 carbon atoms), an --SZ' group, and an --NHSO.sub.2 Z" group (where Z' and Z" are the same as Z defined for X or Y, and Z, Z' and Z" may be the same or different), and the like.

R.sub.1 and R.sub.2 may combine with each other to form a substituted or unsubstituted saturated or unsaturated ring (with substituents including those as described by R.sub.1, R.sub.2 and R.sub.3, and with typical developing agent mother nuclei being formed by the combination of R.sub.1 and R.sub.2 with each other, are saturated carbon rings and unsaturated carbon rings, such as a naphthalene nucleus, a tetralin nucleus, which are preferably used in the present invention). R.sub.1, R.sub.2 and R.sub.3 may be the same or different.

Preferred specific examples of R.sub.1, R.sub.2 and R.sub.3 are hydrogen, halogen, methyl, ethyl, isopropyl, 2-chloroethyl, t-octyl, dodecyl, octadecyl, methoxy, octoxy, benzyloxy, acetamido, trifluoroacetamido, tetradecanamido, benzamido, phenyl, 4-methylphenoxy, pyridyl, imidazolyl, and the like.

Further, with respect to the above described groups for X, Y and R.sub.1 -R.sub.3, the number of carbon atoms for the alkyl groups, the alkyl moieties present in the above described groups or the alkenyl groups can range from 1 to 30, preferably from 1 to 25. Further, the aryl groups or aryl moieties can be either monocyclic groups or moieties (e.g., phenyl) or polycyclic groups or moieties (e.g., naphthyl). Additionally, suitable heterocyclic groups include 5- or 6-membered rings containing at least one of a nitrogen atom, a sulfur atom or an oxygen atom as a hetero atom, which heterocyclic ring may be condensed with an aromatic ring (e.g., a benzene ring) and examples of halogen atoms or halogen substituents include a fluorine atom, a bromine atom and a chlorine atom.

Particularly useful photographic developing agents of the present invention are represented by the following formula (II): ##STR4## wherein R.sub.4 through R.sub.7 each represents a hydrogen atom, a halogen atom, an unsubstituted or substituted alkyl (straight or branched) group containing 1 to 30 carbon atoms (with substituents including one or more halogen atoms and alkoxy, hydroxy, carboxy, sulfo, heterocyclic, aryl and like groups), a straight or branched unsubstituted or substituted alkoxy group containing 1 to 30 carbon atoms (with substituents including the same as described for the above substituted alkyl group), an unsubstituted or substituted phenyl group whose total number of carbon atoms is 6 to 36 (with substituents including one or more halogen atoms and alkyl, alkoxy and like groups), an unsubstituted or substituted phenyloxy group (with substituents including the same as described for the substituted phenyl group), a 5- or 6-membered heterocyclic group containing one or more hetero atoms such as N, O, S, etc. (which may be condensed with a benzene or naphthalene nucleus), an acylamino group, a sulfonamido group, a carbamoyl group, a sulfamoyl group, an acyl group, an alkoxycarbonyl group, an alkylthio group, and the like. R.sub.4, R.sub.5, R.sub.6 and R.sub.7 may be the same or different. X, Y and A are the same as defined in the formula (I).

It is further particularly preferred for the developing agent of this invention to have the general formula (III): ##STR5## wherein one of X and Y is a group capable of inhibiting development on release immediately after the developing agent is oxidized at development, and the other of X and Y is an --NHSO.sub.2 --Z group, wherein Z contains 1 to 30 carbon atoms and is an alkyl group, an aryl group, or a 5- or 6-membered heterocyclic group; A is a hydrogen atom or a group hydrolyzable under alkaline conditions; R.sub.1, R.sub.2 and R.sub.3, which may be the same or different, is a hydrogen atom, a halogen atom, an alkyl group containing 1 to 30 carbon atoms, an alkoxy group containing 1 to 30 carbon atoms, an aryl group, an aryloxy group, an amino group, an --SZ' group, or an --NHSO.sub.2 Z" group, wherein Z' and Z", which may be the same or different, each is as described above for Z, and R.sub.1 and R.sub.2 further may combine together to form a saturated or unsaturated ring.

Typical examples of the photographic developing agents represented by the formula (I) are as follows: ##STR6##

Of the above compounds, those compounds in which the developing agent mother nucleus and the group exhibiting a development inhibiting action are bonded together through a sulfur atom in the development-inhibiting group can be easily prepared, for example, by reacting sulfenyl chloride, XCl or YCl, which have been prepared by reacting XH or YH (where X and Y are the same as defined in the formula (I)) with chlorine gas or sulfuryl chloride, with the developing agent mother nucleus at the active position thereof.

On the other hand, those compounds in which the developing agent mother nucleus and the group exhibiting a development inhibiting action are bonded together through a nitrogen atom in the development-inhibiting group can be easily prepared, for example, by a method which comprises coupling a substituted or unsubstituted o-nitrophenyl diazonium salt to the active position of the developing agent mother nucleus, and then reducing and closing the ring to thereby produce a triazole ring, as in the method described in U.S. Pat. No. 3,617,291.

A suitable temperature which can be used for the reactions described above ranges from about 0.degree. to 50.degree. C with a suitable molar ratio of reactants being about 1:1. In general, the reaction takes about 2 to 3 hours and is generally conducted in a solvent such as chloroform, carbon tetrachloride, dimethylformamide, or the like.

Typical methods of synthesizing the compounds of the present invention are shown below. Other compounds can be produced in an analogous way to the following examples.

PREPARATION EXAMPLE 1

Compound (7)

In 100 ml of carbon tetrachloride was dispersed 68 g (0.038 mol) of 1-phenyl-5-mercaptotetrazole. A sulfenyl chloride compound was produced by feeding chlorine gas until the contents became uniform. This compound was added to 13.4 g (0.038 mol) of 4-(3-nitrobenzenesulfonamido)-1-naphthol dissolved in 70 ml of dimethylformamide, which was then stirred at room temperature (about 25.degree. C) for 2 hours. The reaction mixture was poured onto ice water and extracted with ethyl acetate. The solvent was distilled away from the extract and the residue so obtained was recrystallized from a mixed solvent of methanol and ethanol (2:1 by volume). Thus, 16.5 g of Compound (7) having a melting point of 170.degree. C was obtained. Yield 89%.

PREPARATION EXAMPLE 2

Compound (1)

Compound (1) having a melting point of 206.degree. to 207.degree. C was produced in the same manner as used in Preparation Example 1 except that 4-(p-toluenesulfonamido)-1-naphthol was used in place of 4-(3-nitrobenzenesulfonamido)-1-naphthol. Acetonitrile was used as the recrystallization solvent. Yield 94%.

PREPARATION EXAMPLE 3

Compound (2)

Compound (2) having a melting point of 130.degree. to 132.degree. C was produced in the same manner as used in Preparation Example 1 except that 4-[3-(2,4-di-tert-pentylphenoxyacetamido)benzenesulfonamido]-1-naphthol was used in place of 4-(3-nitrobenzenesulfonamido)-1-naphthol. Benzene was used as the recrystallization solvent. Yield 87%.

PREPARATION EXAMPLE 4

Compound (9)

Compound (9) having a melting point of 108.degree. to 111.degree. C was produced in the same manner as used in Preparation Example 1 except that 4-{3-[.gamma.-(2,4-di-tert-pentylphenoxy)propylcarbamoyl]benzenesulfonamid o}-1-naphthol was used in place of 4-(3-nitrobenzenesulfonamido)-1-naphthol. Chloroform was used as the recrystallization solvent. Yield 91%.

The photographic developing agents of the present invention can be incorporated into either a photographic emulsion layer or a developer. Where the photographic developing agents of the present invention are incorporated into the photographic emulsion layer to provide anti-diffusion properties thereto, all of the known ballast groups can be used. These ballast groups are described in many patents, e.g., U.S. Pat. Nos. 2,920,961, 3,926,634 and 3,891,445.

Examples of suitable ballast groups which can be used include substituted or unsubstituted alkyl groups having at least 5 carbon atoms, substituted or unsubstituted alkoxy groups having at least 5 carbon atoms, sulfonamido groups having at least 5 carbon atoms, aryl or aryloxy groups having at least 6 carbon atoms, alkyl- or heterocyclic-thio groups having at least 5 carbon atoms, arylthio groups having at least 6 carbon atoms, acylamino or acyloxy groups having at least 5 carbon atoms, and heterocyclic groups having at least 4 carbon atoms. The number of carbon atoms in the ballast group can range from about 6 to 30 and the alkyl group or moiety of the ballast group can either be straight or branched chain.

It is anticipated that the developing agents of the present invention are, as are the DIR hydroquinones described in U.S. Pat. No. 3,379,529, etc., subjected to cross-oxidation through a redox reaction thereof and the developing agent oxidants are imagewise produced at the time of color development, thereby imagewise releasing development inhibiting materials and being converted into colorless oxidants. Herein, the development inhibiting materials imagewise released cause intra-image effect and inter-image effect in the light-sensitive material, and exhibit DIR effects, e.g., an improvement in graininess, a softening of image tone, an improvement in image sharpness and an improvement in color reproduction, etc. It is quite surprising that the developing agents of the present invention are highly active and that almost no reduction in sensitivity with time occurs, as compared with the conventional DIR hydroquinones. Since the developing agents of the present invention are substantially colorless or are only very slightly pale blue, from a practical standpoint they have substantially no influence.

The photographic developing agents of the present invention can be dispersed and incorporated into a photographic layer using known methods. In this case, they can be used individually or in admixture with each other. The photographic developing agents of the present invention can be used in combination with couplers and added to the same emulsion layer as the coupler, or added to auxiliary photographic layers such as an intermediate layer and the like as independent emulsions.

The photographic developing agent of the present invention when incorporated in the photographic element is used in an amount of 0.1 to 50 mol%, preferably 0.3 to 15 mol%, based upon the coupler(s) contained in each of the light-sensitive layers in which the developing agent is incorporated: yellow coupler in the blue-sensitive layer, magenta coupler in the green-sensitive layer, or cyan coupler in the red-sensitive layer.

Color-forming couplers which can be used in the present invention include those compounds listed below. These couplers may be either four-equivalent or two-equivalent. Also, they can be either colored couplers for color correction or couplers (DIR couplers) releasing development inhibiting agents.

As yellow image-forming couplers, known open-chain ketomethylene based couplers can be used. Of these couplers, benzoylacetanilide based and pivaloylacetanilide based compounds are particularly useful. Representative examples of the yellow image-forming couplers which can be used in the present invention are described in U.S. Pat. Nos. 2,875,057, 3,265,506, 3,341,331, 3,369,895, 3,408,194, 3,551,155, 3,582,322, 3,725,072, West German Patent Publication No. 1,547,868, West German Patent Application (OLS) Nos. 2,057,941, 2,162,899, 2,213,461, 2,219,917, 2,261,361, 2,263,875, etc.

As the magenta image-forming couplers, pyrazolone based compounds, indazolone based compounds, cyanoacetyl compounds, and the like can be used. Of these compounds, the pyrazolone based compounds are useful. Representative examples of the magenta image-forming couplers which can be used in the present invention are described in U.S. Pat. Nos. 2,439,098, 2,600,788, 2,983,608, 3,311,476, 3,419,391, 3,519,429, 3,558,319, 3,582,322, 3,615,506, British Pat. No. 956,261, West German Patent No. 1,810,464, West German Patent Application (OLS) Nos. 2,408,665, 2,418,959, 2,424,467, Japanese Patent Publication No. 2016/1969, etc.

As the cyan image-forming couplers, phenol derivatives, naphthol derivatives, and the like can be used. Representative examples of these compounds are described in U.S. Pat. Nos. 2,369,924, 2,434,272, 2,474,293, 2,600,788, 2,698,794, 2,706,684, 2,895,826, 3,034,892, 3,214,437, 3,253,924, 3,311,476, 3,386,830, 3,458,315, 3,560,212, 3,582,322, 3,583,971, 3,591,383, West German Patent Application (OLS) Nos. 2,163,811, 2,414,006, Japanese Patent Publication Nos. 6031/1965, 28836/1970, etc.

Those image forming couplers which can be used in the present invention are described in Japanese Patent Publication No. 2016/1969, U.S. Pat. Nos. 2,434,272, 3,476,560, 3,476,564, West German Patent Application (OLS) No. 2,418,959 (magenta image-forming); and Japanese Patent Publication Nos. 22335/1963, 20591/1966, 11304/1967, 32461/1969, U.S. Pat. Nos. 3,034,892, 3,386,830 (cyan image-forming), etc.

As the DIR couplers, those compounds having groups which form development inhibiting agents as coupling releasable groups can be used. These compounds are described in U.S. Pat. Nos. 3,148,062, 3,214,437, 3,227,554, 3,253,924, 3,617,291, 3,622,328, 3,639,417, 3,701,783, 3,705,201, 3,770,436, 3,790,384, Japanese Patent Publication No. 28836/1970, West German Patent Application (OLS) Nos. 2,414,006, 2,417,914, etc.

The above couplers, etc., can be incorporated into a single layer in admixture with each other in order to satisfy the properties required for a light-sensitive material, and alternatively one compound can be incorporated into two or more different layers.

Incorporation of the coupler can be carried out using known methods, for example, the method described in U.S. Pat. No. 2,322,027. That is to say, the coupler is dissolved in an organic solvent having a boiling point of not less than about 180.degree. C, such as phthalic acid alkyl esters (e.g., dibutyl phthalate, dioctyl phthalate, and the like), trimellitic acid esters (e.g., tri-tert-octyl trimellitate), phosphoric acid esters (e.g., diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate, and the like), citric acid esters (e.g., tributyl acetylcitrate), alkylamides (e.g., N,N-diethyllaurylamide, and the like), etc., or in an organic solvent having a boiling point of about 30.degree. to 150.degree. C, such as lower alkyl acetates, e.g., ethyl acetate, butyl acetate, ethyl propionate, sec-butyl alcohol, methyl isobutyl ketone, .beta.-ethoxyethyl acetate, methyl Cellosolve acetate, and the like, and then dispersed in a hydrophilic colloid. The high boiling organic solvents and low boiling organic solvents can be used in admixture with each other.

Where the coupler has an acid group, such as a carboxylic acid group, a sulfonic acid group, or the like, the coupler can be incorporated into a hydrophilic colloid as an alkaline aqueous solution.

The color-image forming coupler is generally employed in an amount of about 2 .times. 10.sup.-3 mol to about 5 .times. 10.sup.-1 mol, preferably 1 .times. 10.sup.-2 mol to 5 .times. 10.sup.-1 mol, per mol of silver in the emulsion layer.

The color development processing used in treating a color light-sensitive material in the presence of the developing agent of the present invention comprises fundamentally the steps of color development, bleaching, and fixing. Each step can be carried out independently, or two or more steps can be carried out at the same time by using a treating solution capable of simultaneously achieving each of the steps combined. For example, a one-bath bleaching and fixing solution can be employed. Also, each step can be divided into two or more steps as necessary, and carried out. Alternatively, a combination of color development, first fixing, and bleaching-fixing can be employed. In combination with the step of development, various steps such as pre-hardening, neutralizing, first development (black-and-white development), image stabilizing, washing, etc., can be carried out, if necessary. The preferred processing temperature range will be dependent upon the light-sensitive material and processing involved. Sometimes the temperature employed is below about 18.degree. C, but usually the temperature is above about 18.degree. C. The processing temperature especially often used is about 20.degree. C to about 60.degree. C, and recently it is particularly within the range of about 30.degree. C to about 60.degree. C. It is not always necessary that the series of processing steps be carried out at the same temperature.

A color developer is an alkaline aqueous solution containing a developing agent and having a pH of 8 or more, preferably 9 to 12.

The above developing agent designates a compound having a primary amino group at the aromatic nucleus thereof and capable of developing silver halide, or a precursor of such a compound. Preferred developing agents include 4-amino-N,N-diethylaniline, 3-methyl-4-amino-N,N-diethylaniline, 4-amino-N-ethyl-N-.beta.-hydroxyethyl aniline, 3-methyl-4-amino-N-ethyl-N-.beta.-hydroxyethyl aniline, 4-amino-3-methyl-N-ethyl-N-.beta.-methanesulfonamidoethyl aniline, 4-amino-N,N-dimethyl aniline, 4-amino-3-methoxy-N,N-diethyl aniline, 4-amino-3-methyl-N-ethyl-N-.beta.-methoxyethyl aniline, 4-amino-3-methoxy-N-ethyl-N-.beta.-methoxyethyl aniline, 4-amino-3-.beta.-methanesulfonamidoethyl-N,N-diethyl aniline, and the salts (for example, sulfates, hydrochlorides, sulfites, p-toluenesulfonic acid salts, and the like) thereof. In addition, those compounds described in U.S. Pat. Nos. 2,193,015, 2,592,364, Japanese Patent Application (OPI) No. 64933/1973, and L. F. A. Mason, Photographic Processing Chemistry, pp. 226 to 229, Focal Press-London Edition (1966), etc., can be used. Also, the above compounds can be used in combination with 3-pyrazolidones. To the color developer is added various kinds of additives, if necessary.

Typical additives include alkali agents (e.g., the hydroxides, carbonates, and phosphates of alkali metals or ammonia); pH controlling agents or buffers (e.g., weak acids such as acetic acid, boric acid, weak bases, and the salts thereof); development accelerating agents (e.g., those described in U.S. Pat. Nos. 2,648,604, 3,671,247, 2,533,990, 2,577,127, 2,950,970, British Pat. Nos. 1,020,033, 1,020,032, U.S. Pat. No. 3,068,097, etc.); anti-fogging agents, (e.g., alkali metal bromides, alkali metal iodides, nitrobenzoimidazoles described in U.S. Pat. Nos. 2,496,940, 2,656,271, mercaptobe