Light-sensitive silver halide photographic material

We claim:

1. A light-sensitive silver halide photographic material having at least one light-sensitive layer constituted of a plural number of silver halide emulsions which are substantially the same in color sensitiveness but different in light sensitivity and containing a diffusion resistant coupler for photography capable of forming a diffusion resistant color forming dye through the reaction with the oxidized product of a color developing agent provided on a support, which comprises a non-light-sensitive intermediate layer provided at least adjacent to the silver halide emulsion layer with the highest light sensitivity among said plural number of silver halide emulsion layers on its support side, said non-light-sensitive intermediate layer containing a diffusion resistant coupler capable of forming a migratable color forming dye which can be color formed to substantially the same hue as the said diffusion resistant color forming dye through the coupling reaction with the oxidized product of a color developing agent or a compound capable of forming a flow-out type coupling product through the coupling reaction with the oxidized product of a color developing agent.

2. A light-sensitive silver halide photographic material according to claim 1, wherein the diffusion resistant coupler is represented by the following formula [I]: ##STR16## wherein Coup is a coupler mother nucleus capable of forming a color forming dye through the coupling reaction with the oxidized product of a color developing agent; Ballast group is a group which is bonded to the coupling position of said coupler and can be eliminated from Coup during the coupling reaction between said coupler and the oxidized product of a color developing agent, said Ballast such that the coupler is non-diffusive; and Control group is a group bonded to Coup at the non-coupling position for controlling the color forming dye formed through the coupling reaction between the coupler and the oxidized product of a color developing agent so that it may be mobile.

3. A light-sensitive silver halide photographic material according to claim 2, wherein the diffusion resistant coupler is contained in the intermediate layer in an amount of 1.times.10.sup.-7 mole/m.sup.2 to 8.times.10.sup.-4 mole/m.sup.2.

4. A light-sensitive silver halide photographic material according to claim 2, wherein the diffusion resistant coupler is a yellow coupler represented by the following formula [II]: ##STR17## wherein R.sup.1 is an aryl group or an alkyl group; R.sup.2 is the ballast group as defined above; R.sup.3 is the control group; and R.sup.4 is a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or the control group as defined above.

5. A light-sensitive silver halide photographic material according to claim 2, wherein the diffusion resistant coupler is a cyan coupler represented by the following formula [III] or [IV]: ##STR18## wherein R.sup.2 is the ballast group as defined above; at least one of R.sup.5 is the control group as defined above, and the remainder representing either identical or different hydrogen atoms, halogen atoms, alkyl groups, alkoxy groups, alkylamino groups or acylamide groups; l is an integer of 1 to 3; and R.sup.6 represents the control group as defined above.

6. A light-sensitive silver halide photographic material according to claim 2, wherein the diffusion resistant coupler is a magenta coupler represented by the following formula [V] or [VI]: ##STR19## wherein R.sup.2 is the ballast group as defined above; R.sup.7 represents the control group as defined above; Ar is a phenyl group which may have at least one of a substituent selected from the group consisting of a halogen atom, an alkyl group, an alkoxy group and an amino group, and said phenyl group may have the control group; one of R.sup.8 and R.sup.9 represents the control group and the other represents a hydrogen atom, halogen atom, alkyl group, alkoxy group, aryl group, amino group or acylamide group.

7. A light-sensitive silver halide photographic material according to claim 1, wherein the compound capable of forming a flow-out type coupling product is represented by the following formula [VII]: ##STR20## wherein COUP is a coupler mother nucleus having a coupling site (asterisk *); BALL is a group which is bonded to the coupling site of COUP and can be eliminated from COUP during the reaction between said COUP and the oxidized product of a color developing agent, said BALL being a Ballast group having a size and a shape such that the compound of the formula [VII] is diffusion resistant; and SOL is a solubilizing group, which is bonded to COUP at the non-coupling position and imparts mobility to the coupling product formed by coupling between COUP and the oxidized product of a color developing agent so as to be flown out of the system from within the light-sensitive material during or after color developing processing.

8. A light-sensitive silver halide photographic material according to claim 7, wherein the compound capable of forming a flow-out type coupling product is contained in the intermediate layer in an amount of 1.times.10.sup.-7 mole/m.sup.2 to 8.times.10.sup.-4 mole/m.sup.2.

9. A light-sensitive silver halide photographic material according to claim 7, wherein the compounds capable of forming a flow-out type coupling product is a yellow dye forming compound represented by the following formula [VIII]: ##STR21## wherein R.sup.10 is an aryl group or an alkyl group; R.sup.11 is the ballast group as defined above (BALL); R.sup.12 is the control group or the solubilizing group (SOL) as defined above; R.sup.13 is a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group; and n and m are integers satisfing the relation of n+m=5 provided that each n and m are not zero, and when n and m are 2 or more, the plural groups may be either identical or different.

10. A light-sensitive silver halide photographic material according to claim 7, wherein the compound capable of forming a flow-out type coupling product is a cyan dye forming compound represented by the following formula [IX] or [X]: ##STR22## wherein R.sup.11 is the ballast group (BALL) as defined above; at least one of R.sup.14 and R.sup.15 is the solubilizing group (SOL) as defined above, and the remainder representing either identical or different hydrogen atoms, halogen atoms, alkyl groups, alkoxy groups or alkylamide groups; p is an integer of 1 to 3; and R.sup.16 represents the solubiliaing group (SOL) as defined above.

11. A light-sensitive silver halide photographic material according to claim 7, wherein the compound capable of forming a flow-out type coupling product is a magenta dye forming compound represented by the following formula [XI] or [XII]: ##STR23## wherein R.sup.11 is the ballast group (BALL) as defined above; R.sup.17 represents the solubilizing group (SOL) as defined above; R.sup.18 represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or an amino group; q is an integer of 1 to 5 provided that when q is 2 or more, the plural groups may be either idential or different; and one of R.sup.19 and R.sup.20 represents the solubilizing group (SOL) as defined above and the other represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or an amino group.

12. A light-sensitive silver halide photographic material according to claim 2, wherein the Control group is an alkyl group having 1 to 20 carbon atoms and an aryl group having 6 to 20 carbon atoms.

13. A light-sensitive silver halide photographic material according to claim 12, wherein the Control group is further connected with a divalent group selected from the group consisting of --O--, --S--, --CO--, --COO--, --NR--, --CONR--, --NRCO--, --SO.sub.2 NR--, --NRSO.sub.2 --and --NRCONR--

wherein R is a hydrogen atom, an alkyl group or an aryl group.

14. A light-sensitive silver halide photographic material according to claim 2, wherein the Ballast group is an alkyl group or an aryl group having 8 to 32 carbon atoms.

15. A light-sensitive silver halide photographic material according to claim 14, wherein the Ballast group is further connected with a divalent group selected from the group consisting of --O--, --S--, --N.dbd.N--and ##STR24## wherein Z is a group of atoms necessary for forming a 5- to 7-membered heterocyclic ring.

16. A light-sensitive silver halide photographic material according to claim 7, wherein the SOL is a group selected from the group consisting of an ionizable hydroxyl group, carboxyl group, sulfo group and aminosulfonyl group and ionizable salts thereof or a group having these group.

17. A light-sensitive silver halide photographic material according to claim 7, wherein the SOL is a group of an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms containing one or two or more hydroxyl group, sulfo group or ionizable salt thereof.

18. A light-sensitive silver halide photographic material according to claim 17, wherein the SOL is further connected with a divalent group selected from the group consisting of an oxy (--O--), thio (--S--), carbonyl group, carboxyl group, oxycarbonyl group, amino group, carbamoyl group, aminocarbonyl group, ureido group, sulfamoyl group and aminosulfonyl group.

19. A light-sensitive silver halide photographic material according to claim 17, wherein the SOL is further connected with an amino group and/or a carbonyl group.

20. A light-sensitive silver halide photographic material according to claim 7, wherein the BALL is an alkyl group or an aryl group having 8 to 32 carbon atoms.

21. A light-sensitive silver halide photographic material according to claim 20, wherein the BALL is further connected with a divalent group selected from the group consisting of --O--, --S--, --N.dbd.N--and ##STR25## wherein Z is a group of atoms necessary for forming a 5- to 7-membered heterocyclic ring.

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BACKGROUND OF THE INVENTION

This invention relates to a light-sensitive silver halide photographic material, more particularly to a light-sensitive silver halide photographic material improved in photographic characteristics such as sensitivity, graininess, sharpness, storability and gradation.

Heretofore, as the light-sensitive silver halide photographic material (hereinafter abbreviated as light-sensitive material), development of a light-sensitive material having high sensitivity and finely micropulverized grains has been desired, and a number of improved light-sensitive materials, particularly color light-sensitive materials, have been proposed.

As one of the light-sensitive materials suited for the above object, for example, U.K. Pat. No. 923,045 states that sensitivity can be enhanced without deterioration by applying the same color sensitive silver halide emulsion in separated layers in a high sensitivity silver halide emulsion layer (hereinafter called as high sensitivity emulsion layer) and a low sensitivity silver halide emulsion layer (hereinafter called as low sensitivity emulsion layer) and further by controlling the maximum color forming density at a low level.

In recent years, however, particularly the color light-sensitive material for photography is required progressively to be higher in sensitivity, whereby it is obliged to use coarse silver halide inferior in graininess and/or a coupler with greater coupling speed in the silver halide emulsion layer. For this reason, in the method described in the above U.K. Pat. No. 923,045, the degree of improvement became insufficient, and further elaborations have been done for improvement of graininess.

For example, in Japanese Patent Publication No. 15495/1974, the graininess is stated to be improved by provision of a gelatin layer between the high sensitivity emulsion layer and the low sensitivity emulsion layer. In this method, while graininess at lower density regions can be improved, bad influences on gradation are markedly observed. On the other hand, for restoration of gradation, if sensitivity of the low sensitivity emulsion layer enhanced according to the prior art, for example, by increasing the grain size of silver halide, the graininess in the medium density region which is important particularly in practical technique will unfavorably be deteriorated. Further, in the multi-layer color light-sensitive material having the above constitution, there is also involved the drawback that the color formed image density will be deteriorated in its stability depending on the changes in the developing processing conditions such as pH value, temperature and time.

As another example, Japanese Provisional Patent Publication No. 155536/1982 states that both graininess and gradation can be improved by providing a non-light-sensitive hydrophilic colloid layer between the high sensitivity emulsion layer and the low sensitivity emulsion layer, containing a diffusion resistant coupler for photography which is color formed to substantially the same hue as the diffusion resistant coupler for photography contained in the high sensitivity and low sensitivity emulsion layers, and has a coupling speed not greater than that of the diffusion resistant coupler for photography contained in the high sensitivity emulsion layer. This method involves no failure in gradation and is improved in graininess, but it is not yet satisfactory in improvement in graininess at the regions from low density to medium density. For example, in the above Japanese Patent Publication No. 15495/1974 and Japanese Provisional Patent Publication No. 7230/1978, there is described a method in which a medium sensitivity emulsion layer is provided between the high sensitivity emulsion layer and the low sensitivity emulsion layer and a compound capable of releasing a diffusive developing inhibiting compound (hereinafter called as DIR compound) through the reaction with the oxidized product of a color developing agent is incorporated in said layer. However, these methods have the drawbacks of increased fog accompanying the increased amount of silver halide as well as increase in amounts of valuable silver resources.

Also, in a light-sensitive material having two or more layers of silver halide emulsion layers sensitive to the same color, it is a general practice to improve graininess by making the silver halide emulsion layer having higher sensitivity lower in coupler density (in this case, it appears that the oxidized product of a developing agent formed in the developing reaction will be diffused in a wide scope searching for partners for coupling reaction, thereby forming an unfocused dye cloud with low density without worsening graininess). However, the oxidized product of the developing agent formed by development of the silver halide in said silver halide emulsion layer having higher light sensitivity does not exist only within the layer formed, but will be diffused even to the siler halide emulsion layer having lower light sensitivity to form a dye cloud with conspicuous graininess therein. As the result, when viewing the light-sensitive material, the influence of the developed silver grains in the silver halide emulsion having higher sensitivity will reach even the density (or light-sensitive) region under question, thus ensuing the problem of deterioation of graininess.

Accordingly, an object of this invention is to provide a light-sensitive material having high sensitivity as well as good gradation, further improved in sharpness, image storability and graininess, requiring only a small amount of silver to be employed.

SUMMARY OF THE INVENTION

As the result of various studies made by the present inventors, it has been found that the above object can be accomplished by a light-sensitive silver halide photographic material having at least one light-sensitive layer constituted of a plural number of silver halide emulsions which are substantially the same in color sensitiveness but different in light sensitivity and containing a diffusion resistant coupler for photography capable of forming a diffusion resistant color forming dye through the reaction with the oxidized product of a color developing agent provided on a support, which comprises a non-light-sensitive intermediate layer provided at least adjacent to the silver halide emulsion layer with the highest light sensitivity among said plural number of silver halide emulsion layers on its support side, said non-light-sensitive intermediate layer containing a diffusion resistant coupler capable of forming a mobile color forming dye which can be color formed to substantially the same hue as the said diffusion resistant color forming dye through the coupling reaction with the oxidized product of a color developing agent or a compound capable of forming a flow-out type coupling product through the coupling reaction with the oxidized product of a color developing agent.

In short, this invention proposes a novel improved light-sensitive material as a trial for overcoming the above-mentioned task.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

This invention is to be described in detail below by referring primarily to one embodiment of this invention. For example, in this invention, the light-sensitive material comprises light-sensitive layers different in light sensitivity, namely a high sensitivity emulsion layer and a low sensitivity emulsion layer with an intermediate layer according to this invention therebetween.

In this case, each of the high sensitivity emulsion layer and the low sensitivity emulsion may be constituted of one layer, or preferably two or more layers, since the effect of the method described in U.K. Pat. No. 923,045 as cited above can additively be added further to the effect of this invention. Also, in this invention it is preferable to provide the high sensitivity layer region apart farther from the support than the low sensitivity emulsion layer, and when each of the high sensitivity emulsion layer and the low sensitivity emulsion layer is constituted of two or more layers, it is preferable to provide a layer with lower sensitivity nearer to the support.

The sensitivity difference between the high sensitivity emulsion layer and the low sensitivity emulsion layer may be determined optimally according to the known method with considerations about gradation and graininess, but may preferably be approximately 0.1 to 1.0 log E (E: dosage of exposure).

Further, the high sensitivity emulsion layer and the low sensitivity emulsion layer have substantially the same color sensitiveness, and after the color developing processing, both of the emulsion layers should preferably contain diffusion resistant couplers for photography capable of forming color forming dyes having substantially the same hue. In this case, it is preferred that the contents of the diffusion resistant couplers for photography contained in the respective high sensitivity and low sensitivity emulsion layers should be such that the color forming density of the color forming dye formed as the result of the coupling reaction with the oxidized product of a color developing agent is higher in the low sensitivity emulsion layer than in the high sensitivity emulsion layer.

It is also possible to incorporate in the intermediate layer according to this invention the diffusion resistant coupler for photography to be contained in both of the emulsion layers.

The intermediate layer according to this invention should be provided by coating at a dry film thickness, ranging preferably from 0.2.mu. to 2.0.mu..

And, the intermediate layer according to this invention contains a diffusion resistant coupler capable of forming a mobile color forming dye which can be color formed to substantially the same hue as the said diffusion resistant color forming dye through the coupling reaction with the oxidized product of a color developing agent or a compound capable of forming a flow-out type coupling product through the coupling reaction with the oxidized product of a color developing agent.

Now, the diffusion resistant coupler according to this invention will be explained in the following:

The term "diffusion resistant" herein used has a meaning ordinarily applied in light-sensitive materials, and for all practical purposes, it means the property such that the coupler will not be moved or drifted through an organic colloid layer such as gelatin layer, when the light-sensitive layer of this invention is treated in an alkali atmosphere, preferably in a medium of pH 10 or higher.

The coupler of this invention has a ballast group at the coupling position which immobilizes the coupler to make it diffusion resistant, and also a control group at the non-coupling position for controlling the mobility of the color forming dye formed by the coupling reaction with the oxidized product of a color developing agent. When the coupler couples with the oxidized product of a color developing agent, the ballast group will be eliminated, whereby the color forming dye formed becomes mobile.

The "mobility" of "the diffusion resistant coupler capable of forming a mobile color forming dye" according to this invention means a mobility to the extent that the color forming dye formed by the coupling reaction with the oxidized product of a color developing agent can be moved within the layer containing the diffusion resistant coupler. Such a mobility can be controlled by the above-mentioned control group of the coupler. The control group depends on the coupler mother nucleus to which this groups is bonded, other substituents introduced into the coupler and the color developing agent employed.

The light-sensitive material of this invention, as described above, has at least one light-sensitive layer constituted of a plural number of silver halide emulsions which are substantially the same in color sensitiveness but different in light sensitivity and containing a diffusion resistant coupler for photography capable of forming a diffusion resistant color forming dye through the reaction with the oxidized product of a color developing agent provided on a support, and further a non-light-sensitive intermediate layer is provided at least adjacent to the silver halide emulsion layer with the highest light sensitivity among said plural number of silver halide emulsion layers on its support side, and further said non-light-sensitive intermediate layer contains a diffusion resistant coupler capable of forming a migratable color forming dye which can be color formed to substantially the same hue as the said diffusion resistant color forming dye through the coupling reaction with the oxidized product of a color developing agent.

The effect of this invention can be exhibited by such a light-sensitive material, and this effect, although not clearly understood, may be considered to be due to the fact that deterioration of sharpness and graininess in the adjacent silver halide emulsion layer with lower sensitivity caused by the oxidized product of a color developing agent formed excessively in the silver halide emulsion having the highest sensitivity during color development of the light-sensitive material after exposure can be prevented and also gradation can be controlled, and further at the same time due to marked improvement of graininess at leg portion by formation of a mobile color forming dye within the intermediate layer according to this invention through the coupling reaction of the "diffusion resistant coupler capable of forming a mobile color forming dye" according to this invention with the oxidized product of a color developing agent.

The diffusion resistant coupler capable of forming a mobile color forming dye according to this invention as mentioned above may be represented by the following formula [I]: ##STR1## wherein Coup is a coupler mother nucleus capable of forming a color forming dye through the coupling reaction with the oxidized product of a color developing agent; Ballast group is a group which is bonded to the coupling position of said coupler and can be eliminated from Coup during the coupling reaction between said coupler and the oxidized product of a color developing agent, said Ballast group having a size and a shape of molecule enough to make the coupler non-diffusive; and Control group is a group bonded to Coup at the non-coupling position for controlling the color forming dye formed through the coupling reaction between the coupler and the oxidized product of a color developing agent so that it may be mobile.

The above Coup, which represents a coupler mother nucleus, may be any of the coupler mother nuclei which is known or used in this field of the art for forming a color forming dye by the coupling reaction with the oxidized product of a color developing agent.

For example, as the yellow couplers, there may be employed benzoylacetanilide type yellow couplers or pivaloylacetanilide type yellow couplers as disclosed in U.S. Pat. Nos. 2,298,448, 2,407,210, 2,875,057, 3,408,194, 3,265,506 and 3,447,928; and "Farb-Kuppler-eine-Literaturubersicht" Agfa Mitteilung, Vol. 2, pp. 112-126, 1961. As for magenta couplers, it is possible to use various kinds of magenta couplers such as pyrazolone type magenta couplers, indazolone type magenta couplers, pyrazolotriazole type magenta couplers and pyrazolobenzimidazole type magenta couplers as disclosed in U.S. Pat. Nos. 2,369,489, 2,343,703, 2,311,082, 2,600,788, 2,908,573, 3,152,896 and 3,519,429 and the report of Agfa AG. as cited above, pp. 126-156. Further, in the case of cyan couplers, naphthol type or phenol type couplers, as disclosed in U.S. Pat. Nos. 2,367,531, 2,433,730, 2,474,293, 2,772,162, 2,895,826, 3,002,836, 3,034,892 and 3,041,236; and the report of Agfa AG. as cited above, pp. 156-175, may be used.

Next, the ballast group indicated in the formula [I] has a size and a shape of molecule enough to make the coupler non diffusive. Useful ballast groups of this kind are groups having an alkyl moiety or an aryl moiety with 8 or more carbon atoms, preferably 8 to 32 carbon atoms, said alkyl moiety and aryl moiety being bonded at the coupling position to the coupler mother nucleus directly or through a connecting group [e.g. --O--, --S--, --N.dbd.N--, ##STR2## (wherein Z is a group of atoms necessary for forming a 5- to 7-membered heterocyclic ring)]. Preferably, the ballast group may be one bonded through a connecting group, such as alkoxy, aryloxy, alkylthio, arylthio and nitrogen-containing heterocyclic ring.

The control group in this invention is a group having a size and a shape of molecule suitable for imparting mobility to the color forming dye formed as described above.

As the group suitable for imparting mobility to the color forming dye as described above, it is preferred to use an alkyl group having 1 to 20 carbon atoms and an aryl group having 6 to 20 atoms. These groups may also be substituted with a group for changing the spectral characteristics or mobility of the color forming dye. These control groups may also have connecting groups for bonding said control group to the coupler mother nucleus. Such connecting groups may include, for example, --O--, --S--, --CO--, --COO--, --NR--, --CONR--, --NRCO--, --SO.sub.2 NR--, --NRSO.sub.2 --, --NRCONR-- (wherein R is a hydrogen atom, an alkyl group or an aryl group) and the like.

Of the diffusion resistant couplers for forming mobile color forming dyes in this invention, the couplers preferable as the yellow coupler may be represented by the following formula [II]: ##STR3## wherein R.sup.1 is an aryl group (e.g. a phenyl group) or an alkyl group (e.g. a tertiary alkyl group such as t-butyl); R.sup.2 is the ballast group as defined above; R.sup.3 is the control group as defined above; and R.sup.4 is a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or the control group as defined above.

Next, preferable cyan couplers may be represented by the following formulae [III] and [IV]: ##STR4##

In the formulae [III] and [IV], R.sup.2 has the same meaning as defined in the formula [II]; at least one of R.sup.5 is the control group as defined above, and the remainder representing either identical or different hydrogen atoms, halogen atoms, alkyl groups, alkoxy groups, alkylamino groups or acylamide groups; l is an integer of 1 to 3, preferably 3; and R.sup.6 represents the control group as defined above.

Further, preferably magenta couplers can be represented by the following formulae [V] and [VI]: ##STR5##

In the formulae [V] and [VI], R.sup.2 is the same as defined defined above; R.sup.7 is the control group as defined above; Ar is a phenyl group which may have at least one of a substituent selected from the group of a halogen atom, an alkyl group, an alkoxy group and an amino group, and said phenyl group may have the control group; one of R.sup.8 and R.sup.9 represents the control group and the other represents a hydrogen atom, halogen atom, alkyl group, alkoxy group, aryl group, amino group or acylamide group.

In the above couplers, unless otherwise specifically noted, the alkyl group, the alkoxy group and the alkylamide group each contains 1 to 8 carbon atoms, the aryl group contains 6 to 10 carbon atoms, and the amino group is inclusive of primary, secondary and tertiary amino groups. These substituents and ballast groups also include those substitued with the groups such as halogen atom, hydroxy, carboxy, amino, amide, carbamoyl, sulfamoyl, sulfonamide, alkyl, alkoxy and aryl.

In the following, typical specific examples of the diffusion resistant couplers capable of forming mobile color forming dyes in this invention are enumerated, but this invention is not lilmited thereto. ##STR6##

Having thus enumerated specific examples of the couplers of this invention, the couplers, including both of those as enumerated above and other couplers of this invention, may be used either singly or as a combination of two or more kinds.

In the following, representative synthesis examples about these couplers according to this invention are described, but other couplers can also easily be synthesized according to the procedures similar to these synthetic methods.

SYNTHESIS EXAMPLE 1

(Synthesis of example compound [I-1]) ##STR7##

To a solution of 8.2 g of .alpha.-pivaloyl-.alpha.-bromo-2-chloro-5-(2-methoxycarbonyl)ethoxycarbony l-acetanilide and 8.7 g of 3-phenyl-4-(4-dodecylbenzyl)urazole dissolved in 100 ml of ethyl acetate, 1.4 g of anhydrous potassium carbonate was added and the mixture was refluxed for 5 hours. The reaction mixture was washed with addition of 200 ml of water, then dried over magnesium sulfate, followed by evaporation of ethyl acetate under reduced pressure. The oily product obtained was dissolved by heating in 10 ml of n-hexane, and left to stand, whereby white powdery crystals were precipitated. Yield: 10.7 g.

SYNTHESIS EXAMPLE 2

(Synthesis of example compound [I-6]) ##STR8##

To 50 ml of chloroform was added 6.5 g of 3-octadecylcarbamoylthiophenol, and under room temperature chlorine gas was passed through the mixture for 30 minutes to obtain a yellow solution. The chloroform was evaporated under reduced pressure to give sulphenyl chloride as an yellow oily product. The sulphenyl chloride was dissolved without purification in 100 ml of chloroform, and 7.4 g of 1-(2,4,6-trichlorophenyl)-3-(2-chloro-5-butanesulfonamido)aniline-5-pyrazo lone, followed by refluxing for 2 hours. Then, chloroform was evaporated under reduced pressure, and the residue obtained was chromatographed on a silica gel column with a solvent mixture of n-hexane and ethyl acetate (mixing ratio 2:1) as the eluant, to obtain the title compound.

This was recrystallized from acetonitrile to give pale yellow crystals. Yield: 5.2 g.

The title compound obtained according to the above synthetic method was confirmed to be identical with the example compound by NMR and Mass spectrum.

The coupler of this invention is to be incorporated in the intermediate layer according to this invention which is provided more adjacent to the support side than the silver halide emulsion layer having the highest light sensitivity among the plural number of silver halide emulsion layers with different light sensitivities, as described above. In this case, the amount of the coupler of this invention may generally range from 1.times.10.sup.-7 to 8.times.10.sup.-4 mole/m.sup.2, preferably from 4.times.10.sup.-7 to 3.times.10.sup.-4 mole/m.sup.2. However, the color formed density in the non-sensitive intermediate layer by the amount of the coupler added as specified above should be 0.02 to 0.7, preferably 0.05 to 0.6, particularly 0.05 to 0.2. Here, color fomation of the coupler in the non-sensitive intermediate layer may be considered to be due to the reaction with the oxidized product of a developing agent formed during development of the high sensitivity emulsion layer and the low sensitivity emulsion layer.

Also, in the above-mentioned embodiment, it is also possible to use in combination with the coupler of this invention, a diffusion resistant coupler capable of forming a diffusion resistant color forming dye after the coupling reaction with the oxidized product of a color developing agent in the above intermediate layer. In this case, at least one of said diffusion resistant couplers should preferably have a coupling speed which is equal to or greater than the greatest coupling speed among the diffusion resistant couplers contained in the high sensitivity emulsion layer.

Next, the compound according to this invention will be explained in the following:

The compound according to this invention is capable of forming a flow-out type coupling product through the coupling reaction with the oxidized product of a color developing agent. The "flow-out type" herein mentioned means that the coupling product formed by the coupling reaction of the compound according to this invention with the oxidized product of a color developing agent has mobility within the light-sensitive material during developing processing, namely at the time of color developing processing or thereafter, and is flown out of the system of said light-sensitive material substantially without remaining within said light-sensitive material.

The compound according to this invention, which forms a flow-out type coupling product through the reaction with the oxidized product of a color developing agent as described above, may preferably a compound capable of providing the coupling product which is a color forming dye or colorless.

The compound according to this invention has a ballast group at the coupling site for immobilizing the compound according to this invention and a solubilizing group at the non-coupling site for imparting mobility of the coupling product after the coupling reaction with the oxidized product of a color developing agent. When the coupling occurs with the oxidized product of a color developing agent, the stabilizing group will be eliminated. As the result, the coupling product has mobility.

The compound according to this invention forms a coupling product having mobility through the reaction with the oxidized product of a color developing agent. The mobility in this case may be imparted to the extent as mentioned above such that it may be flown out of the system of the light-sensitive material.

The compound according to this invention can be represented by the following formula [VII]: ##STR9## wherein COUP is a coupler mother nucleus having a coupling site (asterisk *); BALL is a group which is bonded to the coupling site of COUP and can be eliminated from COUP during the reaction between said COUP and the oxidized product of a color developing agent, said BALL being a Ballast group having a size and a shape enough to make the compound of the formula [VII] diffusion resistant; and SOL is a solubilizing group, which is bonded to COUP at the non-coupling position and imparts mobility to the coupling product formed by coupling between COUP and the oxidized product of a color developing agent so as to be flown out of the system from within the light-sensitive material during or after color developing processing.

As the coupler mother nucleus represented by COUP, there may be included any of coupler mother nuclei, which are known or used in this field for forming a reaction product, having a hue or no color, through the coupling reaction with the oxidized product of a color developing agent. For example, the coupler mother nucleus for forming yellow dye may be acylacetanilide such as acetoacetanilides and benzoylacetanilides; the coupler mother nucleus for forming magenta coupler may be pyrazolones, pyrazolotriazoles, pyrazolobenzimidazoles and indazolones; and the coupler mother nucleus for forming cyan dye may be phenols and naphthols.

BALL is a ballast group having a size and a shape of molecule which will make the compound of the formula [VII] diffusion resistant and it is not particularly limited, so long as it can impart diffusion resistance to the compound of the formula [VII]. Useful groups represented by BALL may include alkyl groups, aryl groups and heterocyclic groups having 8 to 32 carbon atoms. These groups may be either unsubstituted or subsituted. As substituents, there may be included those which will icrease diffusion resistance of the compound of the formula [VII], change the reactivity of the compound of the formula [VII] or undergo coupling reaction to increase diffusibility of BALL after elimination. Further, BALL may preferably be bonded at the coupling site of COUP through a connecting group. Typical connecting groups are oxy (--O--) and thio (--S--).

The solubilizing group represented by SOL is a group for imparting mobility to the coupling product formed by the coupling reaction to the extent such that it can be flown out of the system of the light-sensitive material, as exemplified by ionizable hydroxyl group, carboxyl group, sulfo group and aminosulfonyl group and ionizable salts thereof. One or two or more groups of these groups may be preferably bonded to COUP at the non-coupling sites. Alternatively, there may also advantageously be employed compounds in which solubilizing groups of an appropriate size, such as alkyl groups having 1 to 10 carbon atoms or aryl groups having 6 to 12 groups, which has one or two or more inoizable groups as defined above, are bonded to COUP at the non-coupling sites.

Compounds, in which SOL is bonded to COUP at the non-coupling site through a connecting group, are also preferred. Typical connecting groups may include oxy (--O--), thio (--S--), carbonyl group, carboxyl group, oxycarbonyl group, amino group, carbamoyl group, aminocarbonyl group, ureido group, sulfamoyl group and aminosulfonyl group.

Among the useful solubilizing groups as set forth above, particularly preferable solubilizing groups may include carboxyl group, sulfo group or ionizable salts thereof bonded directly to COUP at the non-coupling site, or alkyl group having 1 to 10 carbon atoms or aryl group having 6 to 12 carbon atoms containing one or two or more carboxyl group, sulfo group or ionizable salts thereof bonded directly or through amino group or carbonyl group to COUP at the non-coupling site.

Further, the compound according to this invention capable of forming yellow, magenta and cyan dyes preferably used in this invention can be represented by the formulae [VIII]-[XII] as shown below.

Of the compounds capable of forming a flow-out type coupling product in this invention, the compounds preferable as the yellow dye forming compound may be represented by the following formula [VIII]: ##STR10## wherein R.sup.10 is an aryl group (e.g. a phenyl group) or an alkyl group (e.g. a tertiary alkyl group such as t-butyl); R.sup.11 is the ballast group as defined above (BALL); R.sup.12 is the control group or the solubilizing group (SOL) as defined above; R.sup.13 is a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group; and n and m are integers satisfing the relation of n+m=5 (provided that each n and m are not zero, and when n and m are 2 or more, the plural groups may be either indentical or different).

Next, preferable cyan dye forming compounds may be represented by the following formulae [IX] and [X]: ##STR11##

In the formulae [IX] and [X], R.sup.11 has the same meaning as defined in the formula [VIII]; at least one of R.sup.14 and R.sup.15 is the solubilizing group (SOL) as defined above, the remainder representing either identical or different hydrogen atoms, halogen atoms, alkyl groups, alkoxy groups or alkylamide groups; p is an integer of 1 to 3; and R.sup.16 represents the solubilizing group (SOL) as defined above.

Further, preferable magneta dye forming compounds can be represented by the following formulae [XI] and [XII]: ##STR12##

In the formulae [XI] and [XII], R.sup.11 is the same as defined in the formula [VIII]; R.sup.17 represents the solubilizing group (SOL) as defined above; R.sup.18 represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or an amino group; q is an integer of 1 to 5 (provided that when q is 2 or more, the plural groups may be either idential or different); and one of R.sup.19 and R.sup.20 represents the solubilizing group (SOL) as defined above and the other represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or an amino group.

In the above compounds, unless otherwise specifically noted, the alkyl group, the alkoxy group and the alkylamide group each contains 1 to 8 carbon atoms, the aryl group contains 6 to 10 carbon atoms, and the amino group is inclusive of primary, secondary and tertiary amino groups. These substituents and ballast groups (BALL) also include those substitued with the groups such as halogen atom, hydroxy, carboxy, amino, amide, carbamoyl, sulfamoyl, sulfonamide, alkyl, alkoxy and aryl.

In the following, typical specific examples of the compounds according to this invention are enumerated, but these are not limitative of this invention. ##STR13##

Having thus enumerated specific examples of the compounds of this invention, the compounds, including both of those as enumerated above and other compounds of this invention, may be used either singly or as a combination of two or more kinds.

In the following, representative synthesis examples about these compounds according to this invention are described, but other compounds can also easily be synthisized according to the procedures similar to these synthetic methods.

SYNTHESIS EXAMPLE 3

(Synthesis of example compound [VII - 2]) ##STR14##

(a) Synthesis of the above [1]

To a solution of 7.4 g (0.018 mol) of .alpha.-pivalyl-.alpha.-bromo-2-chloro-5-ethoxycarbonylacetanilide and 8.0 g (0.018 mol)