US3900322A

US3900322A - Diffusion transfer color photographic material having developement inhibitor precursor

Info

Publication number: US3900322A
Application number: US296698A
Authority: US
Inventors: Yasushi Oishi; Jun Hayashi; Yoshinobu Yoshida
Original assignee: Fuji Photo Film Co Ltd
Current assignee: Fujifilm Holdings Corp
Priority date: 1971-10-12
Filing date: 1972-10-11
Publication date: 1975-08-19
Anticipated expiration: 1992-08-19
Also published as: GB1363040A; JPS4846331A; DE2250064A1; JPS5423581B2

Abstract

A diffusion transfer color photographic material having improved color separating power and giving transferred color images having improved density comprising a support having thereon at least two layers each containing a dye developer and at least two silver halide photographic emulsion layers, at least one of which contains a compound represented by general formula

WHEREIN Q represents an atomic group necessary for forming an unsubstituted or substituted heterocyclic ring and R represents an unsubstituted or substituted alkyl group, an unsubstituted or substituted aryl group, or a heterocyclic group.

Description

United States Patent 1 1 Oishi et a1.

[ Aug. 19, 1975 [75] Inventors: Yasushi Oishi; Jun Hayashi;

Yoshinobu Yoshida, all of Kanagawa. Japan [73] Assignee: Fuji Photo Film Co., Ltd., Minami- Ashigara. Japan [22] Filed: Oct. 11, 1972 [21 1 Appl. No.: 296,698

[30] Foreign Application Priority Data Oct. 12. 1971 Japan 46-80393 [52] [1.5. CI. 96/77; 96/3; 96/29 D; 96/76 R [51 I Int. CL G03C U40; 603C 7/00; GOZC 5/54; GO3C 1/48 [58] Field of Search 96/109 R, 3, 76 R, 29 D, 96/663. 77, 95

[56} References Cited UNITED STATES PATENTS 3.114.637 12/1963 Jeffrey's 96/109 3.202.512 8/1965 Williams v 96/3 3.260.597 7/1966 Weyerts et all. 96/3 3.265.498 8/1966 Rogers ct 111...... 96/3 3.330.657 7/1967 Roth 96/3 3.674.478 12/1970 Grasshoff ct a1 v 96/3 3.698.898 10/1972 Grasshoff et al..... 96/109 3.723.125 3/1973 Hayashi et a1. 96/22 CD 2 LL] Q 5/1973 Danhauser et a1 96/109 1/1974 Rickter 96/3 Primary Iiraminer-Norman G. Torchin Assistant liraminer-Richard L. Schilling Attorney. Agent, or FirmSughrue, Rothwell, Mion, Zinn and Macpeak 5 7 ABSTRACT A diffusion transfer color photographic material hav ing improved color separating power and giving trans ferred color images having improved density compris' ing a support having thereon at least two layers each containing a dye developer and at least two silver halide photographic emulsion layers, at least one of which contains a compound represented by general formula wherein Q represents an atomic group necessary for forming an unsubstituted or substituted heterocyclic ring and R represents an unsubstituted or substituted alkyl group. an unsubstituted or substituted aryl group, or a heterocyclic group.

13 Claims, 2 Drawing Figures RELATIVE EXPOSURE AMOUNT PATENT B AUG 1 9 I975 OPTICAL DENSITY OPTICAL DENSITY HG. l

RELATIVE EXPOSURE AMOUNT RELATIVE EXPOSURE AMOUNT DIFFUSION TRANSFER COLOR PHOTOGRAPHIC -MATERIAL HAVING DEVELDPEWNT INHIBITOR PRECURSOR BACKGROUND OF THE INVEN'HON 1. Field of the Invention The present invention is generally directed to diffusion transfer color photography and more particularly to a diffusion transfer color photographic material having multilayers containing dye developers capable of providing transferred color positive images by development.

2. Description of the Prior Art A diffusion transfer color photographic process of forming color images using a dye developer which is both a dye and a developing agent for silver halides is disclosed in the specification of US. Pat. No. 2,893,606. As set forth in the specification of this U.S. patent, as the exposed photosensitive silver halide emulsion is developed in the presence of dye developers, an imagewise distribution of unreacted and unoxidized dye developers is formed as a function of development.

The unreacted and unoxidized dye developers are mobile in a processing composition and at least a part of the imagewise-distributed dye developers is transferred to an image-receiving layer positioned in superposed relationship with the photosensitive emulsion to form positive dye images thereon. in a particularly useful example of the diffusion transfer process, a lightscnsitive material having a silver halide emulsion layer and a layer of dye developer is exposed and treated with a liquid processing composition in the dark by, for example, immersion, coating, spraying, etc.

The exposed light-sensitive material is brought into superposed relationship with an image receiving layer capable of mordanting the dye before, during, or after the application of the liquid processing composition. In a preferred practical embodiment, the light-sensitive material contains a dye developer in a layer disposed behind the silver halide emulsion layer with respect to the incident direction of light, and a liquid processing composition is supplied between the light-sensitive ma terial and the image receiving sheet by spreading processing composition therebetween in a thin layer as the emulsion layer of the light-sensitive material is brought into a superposed relationship with the image-receiving layer of the image receiving sheet.

Diffusion transfer color photographic materials providing multicolor images by using multilayer type negatives are described in detail in Japanese Pat. Nos. 179/1959, 182/1959, l0240/I959, and 4839/1960. In the specification of the aforementioned U.S. Pat. No. 2,983,606, there is also described a process of forming multi-color images using dye developers contained in a multilayer negative.

Now, returning to the abovementioned diffusion transfer process, the liquid processing composition thus supplied diffuses into the emulsion layer causing the development of the developable silver halide in the emulsion layer. The dye developer to be combined with the silver halide emulsion is immobilized in the developed areas as a result of development and the immobi lization is apparently due, at least in part, to a decrease in the mobility and solubility of the oxidation product of the dye developer as compared to the unoxidized dye developer. The immobilization is considered to be also due, in part, to a local decrease in alkali density as a function of development. Because the unreacted dye developer in the undeveloped areas of the emulsion layer is diffusible, the imagewise distribution of the mobile unoxidized dye developer is formed as a function of the exposure and development of the silver halide emulsion. The imagewise distribution of the diffusible unoxidized dye developer is, at least in part, transferred to the image-receiving layer positioned in superposed relationship with the light sensitive material by imbibition. This transfer is clearly distinguished from the lessdiffusible oxidation type dye developer and forms a visible transfer image on the image-receiving layer.

In a process of this type using a multilayer negative, the unoxidized dye developer which diffuses into the superposed image-receiving layer from the inside emulsion layer must pass through at least one other outside silver halide emulsion layer, and when the unoxidized dye developer diffused from the inside emulsion layer reaches the outside emulsion layer containing the developable silver halide it reacts with the developable silver halide grains in the outside emulsion layer and then is immobilized therein. Also, it is believed that not only does the unoxidized dye developer diffuse from the position of the negative layer to the imagereeeivin g layer through the outside emulsion layer, but also a part of the dye developer diffuses into the inside photosensitive emulsion layer which is not combined with the dye developer to cause the reaction with the emulsion, whereby the dye developer is immobilized.

As an example of one process which includes those problems indicated above, there is illustrated a mul tilayer-type lightsensitive material composed of a support having thereon a red-sensitive emulsion layer, a greensensitive emulsion layer and a blue-sensitive emulsion layer, in that order. These silver halide emulsion layers have a cyan dye developer, a magenta dye developer, and a yellow dye developer, respectively, in layers disposed behind the silver halide emulsion layers or in the silver halide emulsion layers themselves. Now, if only the green-sensitive emulsion layer of the negative light-sensitive material is exposed, the unoxidized cyan developer will diffuse by development and will pass through the green-sensitive emulsion layer before it reaches a superposed image-received layer. In this case, if the magenta dye developer has substantially finished the development of the developable greensensitive silver halide before the unoxidized cyan dye developer reaches the green-sensitive emulsion layer, no trouble will occur. However, if the cyan dye developer diffuses into the green-sensitive silver halide emulsion layer while developable silver halide which has not yet been developed is present in the emulsion layer, the cyan dye developer causes a reaction with the diffusible silver halide having a different color sensitivity without discriminating as to portions of such silver halide to be immobilized.

On the other hand, a part of the unoxidized yellow dye developer will reach the green sensitive emulsion layer by diffusion. If a developable silver halide is present in the green-sensitive emulsion layer, the yellow dye developer will also be immobilized in the greensensitive emulsion layer as in the case of the cyan dye developer. Therefore, the transfer image obtained on the image-receiving layer will show a cyan density and yellow density somewhat lower than those actually due to the exposure.

Although the above explanation relates to the case of exposing only the green-sensitive emulsion layer, then two or three layers of the blue-sensitive emulsion layer, the red-sensitive emulsion layer, and the photosensitive emulsion layer are exposed, it is believed that similar undesirable reactions in the silver halide emulsions will occur as in the aforesaid case. in this case, a transfer image having lowered transfer densities and reduced color separation will be formed.

A phenomenon as mentioned above appears when a multilayer type negative photographic material is developed, and it is called the entangled phenomenon" in this specification. The reduction in transfer density and color separation due to the engangled phenomenon of the dye developers can be improved to some extent by using a superposed effect as defined below.

The superposed effect is based on the phenomenon that in the development of a multilayer photographic material for diffusion transfer color photography, the development of one photosensitive emulsion layer by a dye developer has an influence on the development of the other photosensitive emulsion layer or layers by a developer or developers, and further the density of a dye developer transferred to an image-receiving layer has substantially no relationship to the development in other emulsion layer or layers.

The superposed effect can be explained more practically by the following example. A film support was coated with a cyan dye developer, a red-sensitive emulsion, a magenta dye developer, and a green-sensitive emulsion, in that order. The sample thus prepared was cut into two segments, one of which (sample I) was exposed uniformly to only green light with a middle intensity, while the other (sample H) was exposed uniformly to green light with a middle intensity as for sample l and then subjected to a wedge exposure by red light. After development, the density of the magenta dye transferred to the image-receiving layers was measured for samples l and ll.

Sample i showed the same magenta transfer density throughout all portions of the sample, while sample ll gave a transfer image having reduced magenta transfer density in proportion to the exposure amount of red light. This was clearly based on the occurence of the entangled phenomenon. In this case, the superposed effect is the effect of preventing the reduction in ma genta transfer density and the phenomenon that the magenta transfer density becomes constant regardless of the amount of red light exposure. Accordingly, it may be concluded that if the superposed effect is too high, density increases.

it is known in conventional photographic materials to use a material having the action of releasing a development inhibitor at development and, for example, there is known a process of using a coupler releasing a development inhibitor, such as benzotriazole or a mercapto compound, at coupling (see, US. Pat. Nos. 3,227,554 and 3,227,55l), and a process of using hydroquinone which is capable of releasing an inhibiting material such as an iodide ion or a mercapto compound (see; US. Pat. No. 3,297,445 British iat. No. 1,958,606). Further, the uses of 4-thiazoline-2-thion and an apomerocyanine compound are described in Japanese patent application Nos. 70,687/l9tfl and 28, l 72/ N 76. However, the above patents or patent applications teach no ex amples of using diffusion transfer color photographic materials containing dye developers.

SUMMARY OF THE lNVENTlON The inventors have discovered that the superposed effect can be obtained by imagewise releasing a mate rial capable of controlling development from the areas which have been developed.

in greater detail, as the result of various investigations, the inventors have discovered that in a multilayer-type diffusion transfer color photographic material having at least two silver halide photographic emulsion layers, the superposed effect occurs quite remarkably when a compound represented by the following general formula I is present in at least one of the siver halide photographic emulsion layers:

wherein Q represents an atomic group necessary for forming a heterocyclic ring which may be substituted, and R represents an unsubstituted or substituted alkyl group, an unsubstituted or substituted aryl group, or a heterocyclic ring.

The effect of using a compound which releases a development inhibitor is believed to be partially as follows: in an emulsion layer in which development is started, a developing inhibitor accumulates around the emulsion to inhibit the occurence of development during subsequent periods. Accordingly, when a dye developer which is not combined with said emulsion layer diffuses into said emulsion layer at development, the emulsion layer is essentially in such a state that the development thereof is stopped or inhibited. Furthermore, the development inhibitor diffuses imagewise into the adjacent emulsion layer and also inhibits the development of said emulsion. Therefore, unoxidized dye developer combined with the adjacent emulsion layer is released to too great of a degree, and thus a dye developer immobilized by the entangled phenomenon will be compensated for by the aforesaid dye developer in amount.

An object of the invention is to provide a new photographic material for use in a diffusion transfer process.

Another object of this invention is to provide a color photographic material providing a transfer image having improved density by a diffusion transfer process.

Still another object of this invention is to provide a processfor improving the color separation of multi color transfer images and for increasing the color reproducing power of transfer images formed by a diffusion transfer process.

Further objects and the advantages of the present invention will become apparent from the following detailed explanation of this invention.

BRlEF DESCRlPTlON OF THE DRAWlNGS H05. 1 and 2 are plots of relative exposure vs optical density for certain compounds of the present invention as compared to certain prior art compounds.

The compounds of general formula I used in the present invention are essentially colorless compounds and insoluble in water, They are also insoluble but diffusible in an aqueous alkali.

In general formula I, Q is an atomic group necessary for forming a heterocyclic ring which may be substituted, as mentioned above. Examples of such heterocyclic rings and substituted heterocyclic rings are a thiazolidine-2-thion ring (such as a thiazolidine-Z-thion ring, a 4-methylthiazolidine-2-thion ring, etc.), an imidazolidine-Z-thion ring (such as a 1,3-dimethylimidazolidine-Z-thion ring, a 1,3-diethylimidazolidine-2-thion ring, etc.), a selenazolidine-2thion ring (such as a selenazolidine-Z-thion ring, a 4-methylselenazolidine-Z-thion ring, etc.), a 1,3,4-thiadiazoline- Z-thion ring (such as a l,3,4-thiadiazoline-2-thion ring, a S-methyl-l,3,4-thiadiazoline-2-thion ring, a 5- ethylthio1,3,4-thiadiazoline2-thion ring, a 5{2-(4- phenyl-S-thio-l ,3,4-thiadiazoline2-yl mercaptoethylthio 1,3,4thiadiazoline-2-thion ring, etc.), a l,3,4-selenadiazoline-2-thion ring (such as a l,3,4-selenadiazoline-Z-thion ring, a 5-ethyl-l,3,4- selenadiazoline-Z-thion ring, etc.), a 4-thiazoline-2- thion ring (such as a 4-methyl-4-thiazoline-Z-thion ring, a 4-phenyl-4-thiazoIine-Z-thion ring, a 4-methyl- S-ethoxy-carbonyl-4-thiazoline-2-thion ring, a 4,5- trimcthylenethiazoline-Z-thion ring, a 4,5- tetramethylenethiazoline-2-thion ring, etc.) a 4- selenazolinc-Z-thion ring (such as a 4-selenazoline-2- thion ring, a 4-methyl-4-selenazoline-2-thion ring, a 4- phenyl-4-selenazoline-Z-thion ring, etc.), a l,2-dihydropyridine-Z-thion ring (such as a l,2-dihydropyri dine-Z-thion ring, a 6-ethyl-l,Z-dihydropyridine-L thion ring, etc.), a benzthiazoline-2thion ring (such as a bcnzthiazolineQ-thion ring, a o-methylbenzthiazolinc-Z-thion ring, a o-ethylbenzthiazoline-Z-thion ring, a 6-methoxybenzthiazoline-Z-thion ring, a 6- chlorobenzthiazoline-Z-thion ring, a S-methylbenzthiazoline-Z-thion ring, etc.), a benzXazoline-2-thion ring (such as a benzoxazoline-Z-thion ring, a 6-cthylbenzoxazoline-Z-ring, a o-methylbenzoxazoline- 2-thion ring, a -methylbenzoxazoline-Z-thion ring, etc), a benzimidazoline2-thion ring (such as a 1,3- dimethylbenzimidazoline-Z-thion ring, a 1,3-di-npropylbenzimidazoline-Z-thion ring, a 1,3-di-ndecylbenzimidazoline-Z-thion ring, a 1,3-di-benzylbenzimidazoline-Z-thion ring, a 5-chloro-l,3-dimethylimidazoline-Z-thion ring, a 5-methyl-l,3-dibenzylbenzimida2oline-2-thion ring, etc.), a benzselenazolinc-Z-thion ring (such as a benzselenazoline- Z-thion ring, a 6-ethylbenzselenazoline-Z-thion ring, a 6-methoxybenzselenazoline-2-thion ring, a 6- chlorobenzselenazoline-2-thion ring, etc.), a 1,2-dihydroquinolinc-Z-thion ring (such as a l,2-dihydroquinoline-Z-thion ring, a o-methyl-l,2,-dihydroquinoline-2 thion ring, a o-chloro-l,2-dihydroquinoline-Z-thion ring, etc.), and the like.

R in the general formula is an alkyl group, preferably having l-6 carbon atoms, or such an alkyl group substituted by, e.g., a hydroxyl group, an aryl group, a morpholino group, etc, e.g., such as a methyl group, an ethyl group, a propyl group, a hexyl group, a decyl group, a hydroxyethyl group, a benzyl group, a morpholinoethyl group, etc; an aryl group or an aryl group substituted by, e.g., an alkyl group, an alkoxyl group,

a halogen atom, etc, e.g., such as an phenyl group, a Z-methylphenyl group, a 4-methoxyphenyl group, a 4- chlorophenyl group, etc; or a heterocyclic group such as a 2-pyridyl, tetrazolyl, thiazolyl and triazolyl group.

Among the compounds represented by general formula I, the compounds represented by the general formulae Ila, llb, and [is shown below form a most preferred grouping providing superior results.

c s (Ila) B N H2 X\ H C 5 (11b) c s l (TIC) N-- N In general formulae Ila, IIb, and He, X represents a sulfur atom, an oxygen atom, a selenium atom, an l\l-R" group, or a -CH=CH group; A and B each represents a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted aryl group, an alkoxycarbonyl group, or the atomic groups necessary to form, together, a saturated or unsaturated ring having 5-6 carbon atoms, which may have been substituted, such as cyclohexadiene, benzene and cyclopentadiene; and R and R have the same meaning as R in general formula I.

Preferably, A and B in the general formula Ila each represents a hydrogen atom; an alkyl group having 1-6 carbon atoms or such as alkyl group substituted by a hydroxyl group, a halogen atom, etc., e.g., such as a methyl group, an ethyl group, a butyl group, a hydroxyethyl group, and a 2-chloroethyl group; an aryl group or an aryl group substituted by, e.g., an alkyl group, a hydroxyl group, a halogen atom, etc., e.g., such as alkoxyl phenyl group, a 4-methylphenyl group, a 4- hydroxyphenyl group, a 3-chlorophenyl group, etc; an alkoxycarbonyl group such as. a propanoyloxy group, etc.; the groups necessary for forming, together, an un saturated ring having 5-6 carbon atoms, such as a trimethylene group to form a pentacyclic ring, a tetramethylene group to form a hexacyclic ring, etc.; the groups necessary for forming, together, a benzene ring or a benzene ring substituted by an alkyl group (such as a methyl group, an ethyl group, etc.), an aryl group (such as a phenyl group, etc.), an alkoxy group (such a methoxy group, an ethoxy group, etc.), or a halogen atom (such as a chlorine atom or a bromine atom); and Y represents an alkyl group such as a methyl group, an ethyl group, a n-butyl group, a n-hexyl group, etc; an alkoxyl group such as a mcthoxy group, an eth oxy group, etc; or an alkylthio group such as a methylthio group, an ethylthio group, a 2-(4-phenyl-5-thionyl and cthoxycarbonyl.

Compound 1:

Cmzayounu' (L 1-:

Compound (6):

Practical examples of the aforesaid compounds useful in this invention are illustrated below:

m. p. 149 C m. p. 190C.

Compound (18):

Compound (1 Compound E) z COTIlpOUld Compour;d (23) m. p. 133C.

liquid 1: Ollid Cozxpouzii (2U Germ-101.211 (P5) Compound (26):

0 s m. p. 143C. N/

Compound (27) Compound (25 IN s CH.

Corzpouz'x Ccmpound (30) Compound (31) m. p. 46 C.

Cornpou'fl (33) 1 21 The compounds illustrated above may be prepared by well known processes. For instance, processes of producing the above compounds are described in the specifications of Japanese patent application Nos.

70,682/1969 and 28,172/1970. The afore-mentioned compounds may also be readily prepared by referring to the descriptions of F. M. Hamer; The Cyanine Dyes and Related Compounds; page 51 1, published by John Wiley & Sons Co. or to the specifications of U.S.

Pat. Nos. 2,493,748 and 2,519,001. 11

Compounds 1-8 shown above can be prepared by the 15 process described in the Journal of the Chemical Society; pages 473476( 1939) using 2- mercaptobenzthiazole as the staring material. Synthesis example 2 (Compounds 9-17):

bromide, or silver chloroiodo-bromide, containing 1-10 mole percent of iodine.

The silver halide photographic emulsion used in this invention may also have been chemically sensitized by any method well known in the art, such as by adding a compound having unstable sulfur, e.g., sodium thiosulfate, allylthiocarbazide, etc.; a gold compound, e.g., a gold complex salt of thiocyarnic acid as disclosed in U.S. Pat. Nos. 2,526,632, 2,503,776, 2,493,748 and 3,384,486; a reducing agent, e.g., stannous chloride; at polyalkyleneoxide derivative; or a combination thereof. Furthermore, the silver halide emulsion used in this invention may have been sensitized by cyanine dyes such as 1,1 -diethylcyanine iodide, 1,1-diethyl-9- methylcarbocyanine bromide, anhydro-5,5-diphenyl- 9-ethyl-3 ,3 '-di( 2-sulfoethyl -benzoxazolocarbocyanine hydroxide, etc., individually or as combinations thereof.

Representative dye developers effectively used in the Compounds 9-17 can be prepared by the process depresent invention are described in the specifications of scribed in the Journal of the Chemical Society; pages l5031509( 1949), i.e., by the reaction of a dithiocarbamate and a compound containing a halogen.

To use the compound represented by general formula l in a multilayer type diffusion transfer color pho- 25 tographic material, the compound is added to a silver halide emulsion layer of the multilayer diffusion transfer color photographic material. The compound may also be incorporated into a layer adjacent a photosensitive emulsion layer whereby the compound may act on the emulsion grains at the surface side of the emulsion layer utilizing the diffusion of the compound, but in such a case the effect of the compound is less. This is because while the compound may diffuse in a wet layer,

diffusion is minimal in a dry layer.

The compound of this invention is suitably incorporated into a silver halide emulsion in an amount of from 0.006 to 1.5 g, preferably from 0.1 to 0.01 g, per mole of silver halide therein but the amount of the compound is not necessarily limited to above values. How ever, much lesser amounts generally will not produce the desired effect and greater amounts may inhibit the development of the emulsion layer to which the compound has been added.

A solvent is preferably used to add the compound to the silver halide emulsion, and solvents having no harmful influence on the silver halide emulsion, such as water, methanol, and ethanol, should be used.

If desired, a yellow filter layer, an antihalation layer,

intermediate layers, and a protective layer may also be formed.

As the silver halide emulsion used in this invention, there are photographic emulsions containing silver halides such as silver bromide, silver iodide, silver chloride, silver chlorobromidc, silver iodobromide, and silver chloroiodo-bromide. but particularly superior results are obtained when at least one photographic emulsion layer contains silver chloroiodide, silver iodo- U.S. Pat. Nos. 3,255,001; 3,320,063; 2,992,106; 3,297,441; 3,134,762; 3,236,643; 3,134,763; 3,134,764; 3,134,672; 3,134,765; 3,183,089; 3,135,734; 3,135,604; 3,173,906; 3,222,169; 3,183,090; 3,201,384; 3,246,955; 3,208,991; 3,142,565; 2,983,605; 3,047,386; 3,076,820;

3,173,929; and 3,230,083.

Examples of particularly useful dye developers used in this invention are illustrated below:

4 p-( 2,5 -dihydroxyphenyl )-pheny1azo]-5- acetamidol-naphthol,

4[p-(2',5'-dihydroxyphenethyl)-phenylazo]-5-ben- .zamidol -naphthol,

l-phenyl-3-methyl-4- p-( 2 ',5 'dihydroxyphenethyl)- phenylazo -5-benzamidol-naphthol,

1-phenyl-3-methy1-4-[ p-( 2 ',5 'dihydroxyphenethyl phenylazol-S-pyrazolone,

2- p-( 2 ',5 dihydroxyphenlethyl phenylazo ]-4- acetamidol-naphthol,

2-[p-( 2 ',5 -dihydroxyphenethyl )-phenylazo]-4- -amino 1 -naphthol,

2- p-( 2 ',5 -dihydroxyphen.ethyl )-phenylazo]-4- methoxyl -naphthol,

2- p-( 2 ',5 -dihydroxyphenyl )-phenylazo l-4-ethoxyl-naphthol,

1-phenyl-3-N-n-butyl-carb-oxyamido-4-[p-2 ',5 dihydroxy-phenethyl )-phenylazo]-5-pyrazolone,

l-phenyl-3N-n-hexylcarboxyamido-4-[p-( 2 ',5 dihydroxy-phenethyl )-phenylazo]-5-pyrazolone,

l-phenyl-3 N-cyclohexylcarboxyamido-4-[ p-( 2 ',5 dihydroxy-phenethyl)-phenylazo]-5-pyrazolone,

l-phenyl-3-amino-4-(4 -[p-( 2 ',5 dihydroxyphenethyl )-phenylazo]-2 ',5 -diethoxyphenylazo )-5-pyrazolone,

l-acetoxy-2-[ p-( B-hydroquinonylethyl )-phenylazo l- 4-methoxynaphthalene,

4-isopropoxy-2-I p-( B-hydr-oquinonylethyl phenylazo]- l-naphthol,

1-acetoxy-2-[ p-( Bhydroquinonylethyl )-phenylazo]- 4-propoxynaphthalene,

l,4-bis( 2 '5 '-dihydroxyanilino)-4,8dihydroxyanthraquinone,

l,5-bis( 2 ',5 -dihydroxyanilino)-4,8-dihydroxyanthraquinone,

l,4-bis[ B4 2',5 '-dihydroxyphenyl )-isopropylamin0 anthraquinone,

1,4-bis [B-2',5 '-dihydroxyphenyl )-ethylamino anthraquinone,

l-chloro-4-[B-(2,5-dihydroxyphenyl)-ethylaminojanthraquinone,

N-monobenzoyl-l ,4-bis[,B-( 2,5 -dihydroxyphenyl ethylamino l-anthraquinone, and

5,8-dihydroxyl ,4-bis[ (B-hydroquinonyl-a-methyl ethylaminol-anthraquinone.

However, the dye developers in this invention are not limited to those compounds.

It is preferred that the dye developer be dissolved in a high boiling solvent, the resulting solution be finely dispersed by emulsification in a gelatin solution, and the resulting dispersion be applied as a layer of photographic material.

ln the case of preparing an emulsified dispersion of the dye developer, an organic solvent substantially immiscible with water having a boiling point above 175C. is used alone or together with a solvent aid. Typical examples of high boiling solvents suitably used for this purpose are described in the specification of U.S. Pat. No. 2,322,027.

In the diffusion transfer color photographic material a compound called a subsidiary developer may also be used, if desired. As examples of suitable subsidiary developers there are benzenoid-type silver halide developing agents, i.e., silver halide developing agents each having a benzene or naphthalene nucleus substituted by at least two of the following groups; hydroxyl groups, amino groups and/or alkylamino groups, which can form a quinoid oxidation product by developing a A silver halide. Examples of such are hydroxyphenylhydroquinone. phenylhydroquinone, and 4'methylphenylhydroquinone. Examples of other preferred subsidiary developers are the 3-pyrazolidones, preferably l-phenyl-3-pyrazolidone or l-phenyl-4,4-dimethyl3 pyrazolidone. Other subsidiary developers which may be used in this invention include catechol compounds as disclosed in British Pat. No. 1,243,539, hydroquinone compounds as disclosed in U.S. Pat. No 3,253,915 and 3-pyrazo1idones as disclosed in U.S. Pat. Nos. 3,351,465 and 3,039,869, etc. The subsidiary developer in this invention is not limited to those recited, however.

The subsidiary developer is preferably incorporated in at least one layer of a negative photographic mate rial, such as a protective layer, a silver halide emulsion layer, a dye developer-containing layer, or an intermediate layer. Furthermore, the subsidiary developer may be used by the method described in Japanese Pat. publication Nos. 17,383/1960 and 393/1964 in which addi tional practical examples of subsidiary developers are described.

Furthermore, the negative color photographic material of this invention may contain a stabilizer such as 4- hydroxy-6-methyl-1 ,3,3a,7-tetraazaindenc, benzimidazole, benzotriazole, and l-phenyl-S- mercaptotetrazole; a hardening agent such as formaldehyde, mucobromic acid, and dichlorotriazine; and a wetting agent such as saponin, and sodium alkylbenzene sulfonate.

The image-receiving sheet for receiving the dye developers from the negative color photographic material described above can be selected in a wide range of materials. As a mordant material suitably used in the image-receiving layer of the image-receiving sheet, there are illustrated gelatin, polyvinyl pyrrolidone, poly-4- vinyl-pyridine, polyvinyl acetate, polyvinyl alcohol, cel lulose acetate, polyvinyl salicyloyl, partially hydrolyzed polyvinyl acetate, methyl cellulose, and mixtures thereof. The support used for the image-receiving sheet may also be selected from the wide range of supports as are now used for negative color photographic materials, e.g., cellulose nitrate films, cellulose acetate films, polyvinyl acetal films, polystyrene films, polyethylene terephthalate films, polyethylene films, polypropylene films, papers, polyethylene-coated papers, and glass sheets. Also, as the support for the image-receiving sheet, a negative photographic material having a coated multilayer structure may be used. The support may be opaque or transparent, according to the desired use.

As set forth in the specification of U.S. Pat. No. 2,584,030, it is particularly useful to use an acid polymer or a derivative of an acid compound which is capable of releasing an acid material at a definite rate. In typical examples of the layer structure in the case of using an acid releasing material, the layer containing the material is disposed under the image-receiving layer for the dye developers. Such an acid material contributes to neutralize alkali in the liquid processing composition on the imagereceiving layer. Furthermore, a spacer layer may be inserted between the image-receiving layer and the layer containing the material capable of releasing an acid which spacer layer controls the release of the acid material.

Still further, the image-receiving sheet may contain a development inhibitor such as a mercaptotetrazole and iodine.

Materials for such image-receiving layers and the layer structures thereof are disclosed in the specifica tions of Japanese Pat. publication Nos. 8274/1963; 8449/1963; U.S. Pat. Nos. 3,003,872; 3,043,689; 3,065,074; 3,148,061; 3,239,337; 3,353,956; 3,362,819; and Japanese Pat. publication No. 29,756/1961.

The liquid processing composition for developing the exposed areas of the negative photographic material is a strong alkaline solution having, generally, a pH of higher than 12 or containing more than 0.0] normal of hydroxide ions. In the liquid processing composition, an alkali metal hydroxide such as potassium hydroxide, sodium hydroxide, etc., or sodium carbonate is usually used. In the case of applying the liquid processing composition as a thin uniform layer to the emulsion layer by spreading, it is preferable to incorporate in the aforesaid alkaline processing composition a viscosityincreasing compound, thereby providing a film-forming material capable of forming a comparatively solid and stable film when the processing composition is spread and dried. The preferred film-forming materials are inactive to the alkaline solution. Examples of such filmforming materials include water-soluble polymers such as hydroxyethyl cellulose and carboxymethyl cellulose. Other film-forming materials whose function of increasing the viscosity is not substantially influenced when the material is placed in an alkaline solution for a long period of time may be also used. Suitable examples of alkaline processing compositions are described in the examples.

It is preferred that the diffusion transfer color photographic material of this invention be subjected to development processing in the presence of a diffusible onium compound. As examples of such onium compounds, there are quaternary ammonium compounds, quaternary phosphate compounds and quaternary sulfonium compounds. Particularly useful examples of such onium compounds are l-benzyl-2-picolinium bromide, l-( 3-brornopropyl )-2-picoliniump-toluenesulfonic acid, l-phenethyl-2-picolinium bromide, 2,4- dimethyl-1-phenethylpyridinium bromide, a-picoline-B-naphthoylmethyl bromide, N,N- diethylpiperidinium bromide, phenethyltrimethyl phosphonium bromide, and dodecyldimethylsulfonium-ptoluene sulfonium. It is preferred that the onium compound be contained in the alkaline processing composition. The most preferred amount of the onium compound is 2-15 percent by weight, based on the total amount of the processing composition. By conducting development in the presence of the onium compound,

the quality of the transfer image obtained is remarkably improved. Other onium compounds are described together with the procedures of using them in the specifcations of US. Pat. Nos. 3,41 1,904 and 3,173,786.

A development inhibitor such as benzotriazole may be incorporated in the liquid processing composition. Further, the subsidiary developer described above may also be incorporated in the liquid processing composition. At least a part of the dye developers oxidized during development are oxidized and immobilized as a result of reaction with the oxidation product of the subsidiary developer. The subsidiary developer is oxidized by the development of the exposed silver halide and it is believed that the reaction of the oxidized subsidiary developer and the unoxidized dye developers regenerates the subsidiary developer to cause additional reac' tion with the exposed silver halide.

The aforementioned compound of this invention represented by general formula 1 has the property that when it is incorporated in an emulsion layer of a diffusion transfer color photographic material it is released imagewise with the progress of development of the photographic material. The compound of this invention may be said to be a compound having a development inhibiting action but the behavior thereof differs completcly from the case when a conventional developing inhibitor well known in the field of photography is incorporated in light-sensitive materials. That is to say, when such a conventional development inhibitor is employed, the above-mentioned superposed effect is not obtained and the overall sensitivity of the lightsensitive material containing it is reduced, while when the compound of this invention is employed, almost no reduction in sensitivity of light-sensitive material occurs and further a remarkable superposed effect is obtained.

The compound of this invention exhibits its effect when it is incorporated not only in a photographic emulsion layer of a multilayer color photographic material of the type wherein the dye developer is incorporated in the light-sensitive layer adjacent to the photographic emulsion layer but also in a multilayer color photographic material of the type wherein the dye developer is incorporated in the photographic emulsion layer.

The invention will now be explained more partically and in more in detail based on the following nonlimitative examples.

EXAMPLE 1 1. Preparation of Sample A (Comparison Sample):

A multilayer diffusion transfer color photographic film was prepared by successively coating a cellulose triacetate support with the following layers.

1. cyan dye developer layer:

g of a cyan dye developer, 5,8-dihydroxy-L4- bis[ (B-hydroquinonyl-a-methyl )ethylamino anthraquinone, was dissolved in a mixed solvent of 10 cc of N-n-butyl-acetanilide and 20 cc of ethyl acetate and the solution was dispersed by emulsification in 50 cc of a 10% aqueous gelatin solution containing 3 cc of sodium n-dodecylbenzenesulfonate. 2 cc of a 2% aqueous solution of 2-hydroxy-4,6- dichloro-S-triazine sodium salt was added to the emulsion and then the volume of the mixture was adjusted to cc by adding water. The emulsion was coated onto the support to give a dry thickness of 5 microns.

2. Red-sensitive emulsion layer:

1.0 g of 4-methylphenylhydroquinone was dissolved in a mixed solvent of 2 cc of N-n-butyl-acetanilide and 2 cc of ethyl acetate and the solution was dispersed by emulsification in 10 cc of a 10% aqueous gelatin solution containing 1 cc of an aqueous solution of 5% sodium n-dodecylbenzene sulfonate. A mixture of 10 g of the emulsion thus prepared and a red-sensitive silver iodobromide emulsion containing 5.3 X 10 mole of silver halide per 100g of the silver halide emulsion and 5.3 g of gelatin was coated on the cyan dye developer layer so that the dry thickness of the coated layer was 2.5 microns.

3. Intermediate layer:

100 cc of a 5% aqueous gelatin solution containing 1.5 cc of a 5% aqueous solution of sodium ndodecylbenzene sulfonate was coated on the redsensitive emulsion layer so that the dry thickness of the layer was 2.5 microns.

4. Magenta dye developer layer:

3 g of a magenta dye developer, 4-isopropoxy-2-[p- (B-hydroxynonylethyl)-phenylazo]- l-naphthol was dissolved in a mixture of 6 cc of N,N-diethyl laurylamide and 10 cc of ethyl acetate and this solution was dispersed by emulsification in 50 cc of a 10% aqueous gelatin solution containing 3 cc of' a 5% aqueous solution of sodium n-dodecylbenzene sulfonate. Then, 2 cc of a 2% aqueous solution of mucochloric acid was added to the emulsion thus prepared and the emulsion was diluted to 100 cc with water. The resultant emulsion was coated on the intermediate layer so that the dry thickness of the layer was 3 microns.

5. Green-sensitive emulsion layer:

1 g of 4-methylphenyl hydroquinone was dissolved in a mixture of 2 cc of l\ln-butyl-acetanilide and 2 cc of ethyl acetate, and the solution was dispersed by emulsification in 10 cc of a 10% aqueous solution of gelatin containing 1 cc of a 5% aqueous solution of sodium n-dodecylbenzene sulfonate. Then, a mixture of 10 g of the emulsion thus prepared and a greensensitive silver iodobromide emulsion containing 4.7 X 10 mole of silver halide/100 g of emulsion and 6.2 g of gelatin was coated on the magenta dye developer layer so that the dry thickness of the layer was 1.8 microns.

6. Protective layer:

100 cc of a 5% aqueous gelatin solution containing 1.5 cc of a 5% aqueous solution of sodium ndodecylbenzcne sulfonate and 1 cc ofa 2% aqueous solution of 2-hydroxy-4,6-dichloroS-triazine sodium salt was coated on the green-sensitive emulsion layer so that the dry thickness of the layer was 1 micron.

2. Preparation of Sample B:

A diffusion transfer color photographic material of this invention was prepared by following the same pro cedure as in the case of preparing Sample A except that 3 cc of a 1% methanol solution of N-methyl-benzmordant and 0.5

thiazoline-2-thion (Compound I) was incorporated in each of the green-sensitive emulsion layer and the redsensitive emulsion layer.

3. Formation of images on the samples:

Each of samples A and B was subjected to stage exposure, i.e., the film samples were exposed for 1/20 second with a 500 watt tungsten lamp using a green wedge filterand then exposed over all for l/200 second with the same lamp but using a red filter at a distance of 30 cm. on an intensity scale sensitometer. The exposed film was processed using a liquid processing composition having the following formula while in superposed relationship with an image-receiving sheet prepared as described below.

Liquid processing composition:

Highly viscous hydroxyethyl cellulose 3.5 g sufficient to make the final viscosity of the composition about 1000 centipoises) Image receiving sheet:

The image-receiving sheet was prepared by coating a baryta-coated support with a gelatin layer containing a mixture of 100 grams of poly-4-vinylpyridine as a grams of l-phenyl-5- mereaptotetrazole to a dry thickness of microns.

4. Density measurement and consideration:

After an imbibition period of about 1 minute, the reflection densities of the color image transferred onto the image-receiving sheet in the case of using a red fil ter and a green filter were measured. The results are shown in FIG. 1 of the accompanying drawing, which shows the relationship between the relative exposure amount and the optical density of the image on the image-receiving sheet. In FIG. 1, AG and AR are the curves resulting from Sample A when green light and red light were employed, respectively, while BG and BR are the curves resulting from Sample B when green light and red light were employed, respectively. From the results shown in FIG. 1, it will be understood that the variation of density measured using a red filter was less in Sample B than in Sample A. This shows that the development and transfer of the cyan dye developer were less influenced by the amount of green light exposure and further that an improved transfer density and a high color separation power were obtained.

EXAMPLE 2 1. Preparation of Sample C (Comparison Sample):

A cellulose tn'acetate support was successively coated with the following layers to provide a diffusion transfer color photographic material.

1. Cyan dye developer layer:

g of l,4 bis (a-methyl-B- hydroxynonylpropylamine)-5,8-dihydroxyanthraquinone was dissolved in a mixture of 25 cc of N,N-diethyl laurylamide and 25 cc of methylcyclohexanone at 70C. This solution was dispersed by emulsification in 160 cc of an aqueous 10% gelatin solution containing l0 cc of a 5% aqueous solution of sodium dodecylbenzenesulfonatc, and after further adding water to the emulsion to make the volume 500 cc, the resultant emulsion was coated on the support so that the dry thickness of the layer was 5 microns.

2. Red-sensitive emulsion layer:

A red-sensitive silver iodobromide emulsion contain ing 5.5 X 10" mole of silver halide/ g of the silver halide emulsion and 5.0 g of gelatin was coated on the cyan developer layer so that the dry thickness of the layer was 3.5 microns.

3. Intermediate layer:

100 cc of an aqueous 5% gelatin solution containing 1.5 cc of a 5% aqueous solution of sodium ndodecylbenzene sulfonate was coated on the redsensitive emulsion layer so that the dry thickness of the layer was l.5 microns.

4. Magenta dye developer layer:

10 g of a magenta dye developer, 4-propoxy-2-[p-(B- hydroxyquinonylethyl )-phenylazo l -naphthol, was dissolved by heating in a mixture of 20 cc of N-nbutylacetanilide and 25 cc of methylcyclohexanone, and the solution thus prepared was dispersed by emulsification in cc of a 10% aqueous gelatin solution containing 8 cc of a 5% aqueous solution of sodium ndodecylbenzene sulfonate and after adding water to make the total value 400 cc, the resultant emulsion was coated on the intermediate layer so that the dry thickness of the layer was 3.5 microns.

5. Green-sensitive emulsion layer:

A green-sensitive silver iodobromide emulsion containing 4.7 X 10 mole of silver halide/100 g of emulsion and 6.2 g of gelatin was coated on the magenta developer layer so that the dry thickness of the layer was 1.8 microns.

6. Intermediate layer:

100 cc of a 5% aqueous gelatin solution containing 1.5 cc of a 5% aqueous solution of sodium ndodecylbenzene sulfonate was coated on the greensensitive emulsion layer so that, the dry thickness of the layer became 1.0 micron.

7. Yellow dye developer layer:

10 g of a yellow dye developer, l-phenyl-3-N-nhexylcarboxy-amid04-[ p-2 ',5 '-dihydroxyphenethyl phenylazo]-5-pyrazolone was dissolved by heating in a mixture of 10 cc of N-n-butylacctanilide and 25 cc of cyclohexanone. The solution was dispersed by emulsification in 100 cc ofa 10% aqueous gelatin solution containing 8 cc of a 5% aqueous solution of sodium ndodecylbenzene sulfonate, and after adding to the emulsion 5 cc of a 2% aqueous solution of 2-hydroxy- 4,6-dichloro-S-triazine and water to make the total vol ume 300 cc, the resultant emulsion was coated on the intermediate layer so that the dry thickness of the layer was 1.5 microns.

8. Blue-sensitive emulsion layer:

A blue-sensitive silver iodobromide emulsion containing 3.5 X 10 mole of silver halide/l00 g of emulsion and 6.5 g of gelatin was coated on the yellow dye developer layer so that the dry thickness of the layer was 1.5 microns.

9. Protective layer:

5 g of ,4-inethylphenyl hydroquinone was dissolved in a mixture of 10 cc of tri-o-cresylphosphate and 10 cc of ethyl acetate, and the solution was dispersed by emulsification in l0 cc of a 10% aqueous gelatin solution containing 2 cc of a 5% aqueous solution of sodium n-dodecylbenzenesulfonate. The, l0 g of the emulsion thus prepared was mixed with 100 cc ofa 5% aqueous gelatin solution containing 5 cc ofa 2% aqueous solution of mucochloric acid, and the mixture was coated on the blue-sensitive emulsion layer so that the dry thickness of the layer was 1 micron.

2. Preparation of Sample D:

A diffusion transfer color photographic material of this invention was prepared by following the same procedure as the case of preparing Sample C except that cc of a 171 methanol solution of N-benzylbehzthiazoline-2-thion (Compound 5) was incorporated in the blue-sensitive emulsion layer and 2 cc of the same methanol solution was incorporated in the greensensitive emulsion layer.

3. Formation of images on the samples:

Each of samples C and D was subjected to a stage exposure using green light and then uniformly exposed using blue light and red light of an intermediate intensity. The exposed film was subjected to a diffusion transfer using a liquid processing composition and image-receiving sheet the same as those in Example 1.

4. Density measurement and consideration:

After an imbibition period of one minute, the reflection density of the color image transferred onto the image-receiving sheet was measured using a blue filter, a green filter, or a red filter, the results of which are shown in FIG. 2 of the accompanying drawing (FIG. 2 shows the same relationships as FIG. 1). From the results shown, it will be understood that the variation of the density measured by using the blue filter and red filter was less in Sample D than in Sample C. This shows that the development and image transfer of the yellow dye developer and the cyan dye developer were less influenced by the amount of green light exposure and also an improved transfer density and a high color separation power were obtained.

Furthermore, when each of samples C and D was subjected to a stage exposure using blue light, uniformly exposed to green light and red light of an intermediate intensity, subjected to developing processing and then the reflection density of the transfer image was measured using a green filter and a red filter, it was confirmed that the variation of density was less in Sample D than in Sample C. This shows that an improved transfer density and a high color separation power were obtained.

EXAMPLE 3 1. Preparation of Sample E (Comparison Sample):

A cellulose triacetate support was coated successively with the following layers to provide a multilayer diffusion transfer color photographic material for comparison purposes.

1. Cyan dye developer layer:

5 g of a cyan dye developer, 5,8-dihydroxy-1-4- bix (B-hydroquinonyl-amethyl )ethylamino] anthraquinone, was dissolved in a mixture of cc of N-n-butyl-acetanilide and cc of methylcyclohexanone, and the solution was dispersed by emulsification in 50 cc of a 10% aqueous gelatin solution. After adding to the solution water and a wetting agent, sodium ndodecylbenzene sulfonate, to make the total volume I00 cc, the resultant mixture was coated on the support so that the dry thickness of the layer was 6 microns.

2. Red-sensitive emulsion layer:

A red-sensitive silver iodobromide emulsion containing 4.8 X 10 mole of silver halide/100 g of emulsion and 6.2 g of gelatin was coated onto the cyan dye developer layer so that the dry thickness of the layer was 3.0 microns.

3. Intermediate layer:

A 5% aqueous gelatin solution containing 2.5 cc of a 5% aqueous solution of sodium n-dodecylbenzenesulfonate was coated onto the red-sensitive emulsion layer so that the dry thickness of the layer was 1.8 microns.

4. Yellow dye developer layer:

3 g of a yellow dye developer, l-phenyl-3-N-nhexylcarboxyamido'4- p-( 2 ,5 '-dihydroxyphenethyl phenylazol-S-hydroxypyrazole, was dissolved in a mixture of 3 cc of N-n-butylacetanilide and 8 cc of methylcyclohexanone and the solution was dispersed by emulsification in 30 cc of a 10% aqueous gelatin solution. After adding to the solution a wetting agent and water to make the total volume cc, the resultant mixture was coated on the intermediate layer so that the dry thickness of the layer was 2.0 microns.

5. Blue-sensitive emulsion layer:

A blue-sensitive silver iodobromide emulsion containing 4.8 X 10" mole of silver halide/ g of emulsion and 6.2 g of gelatin was coated on the yellow dye developer layer so that the dry thickness of the layer was 1.8 microns.

6. Protective layer:

5 g of 4'-methylphenyl hydroquinone was dissolved in a mixture of 10 cc of tri-o-cresylphosphate and 10 cc of ethyl acetate, and the solution was dispersed by emulsification in 10 cc of a 10% aqueous gelatin solution containing 2 cc of a 5% aqueous solution of sodium n-dodecylbenzene sulfonate. Then, 10 g of the emulsion thus prepared was mixed with 100 cc of a 5'% aqueous gelatin solution containing 5 cc of 2% mucochloric acid, and the mixture was coated on the blue-sensitive emulsion layer so that the dry thickness of the layer was 1.2 microns.

2. Preparation of Samples F-Y:

Diffusion transfer color photographic materials of this invention were prepared following the procedure described above except that 3 cc of a 1% methanol solution of each of various compounds shown in the Table below was incorporated in the blue-sensitive emulsion layer.

3. Each of the samples was exposed uniformly to red light of an intermediate intensity and then subjected to a stage exposure using blue light. The exposed film was subjected to diffusion transfer processing using a liquid processing composition and an image-receiving sheet the same as those used in Example 1.

4. Density measurement and consideration:

After an imbibition period of 1 minute, the reflection density of the color image transferred onto the image receiving sheet was measured using a blue filter and a red filter and the results from samples containing the compounds of this invention were compared with the results from Sample E containing no compound of this invention. The results of measuring the differences between the red density of Sample E and those of Samples F-Y containing the compounds of this invention at the exposure amount at which the blue density was minimized are shown in the following table as AD The larger the numerical value the more remarkable the superposed effect becomes. The results below indicate that Samples F to S containing the compounds of this invention exhibit remarkable multilayer affects and less variation in red density relative to the variation of blue density in comparison with variations in Sample E which does not contain the compounds of this inventionv Thus, Samples F to S have an improved transfer density and high color resolution.

While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modification can be made therein without departing from the spirit and scope thereof.

What is claimed is:

1. A diffusion transfer color photographic material comprising a support having thereon at least two layers each containing a dye developer, and having thereon at least two silver halide photographic emulsion layers, at least one of said silver halide photographic emulsion layers containing a compound represented by general formula l wherein Q represents an atomic group necessary for forming a heterocyclic ring, and R represents an unsubstituted alkyl group, an alkyl group substituted by a hydroxyl group, an aryl group or a morpholino group, an unsubstituted aryl group, an aryl group substituted by an alkyl group, an alkoxy group or a halogen atom or a heterocyclic group, said compound being capable of releasing a diffusible development inhibitor upon development of exposed silver halide by said dye developer, thereby causing imagewise release of said inhibitor upon development of said emulsion layers subsequent to exposure thereof,

2. The diffusion transfer color photographic material as set forth in claim 1 wherein said compound is a compound represented by the general formula la wherein X represents a sulfur atom, an oxygen atom. a selenium atom, a N-R group, or a CH=CH group; A and B each represents a hydrogen atom, an unsubstituted alkyl group or an alkyl group substituted by a hydroxyl group or a halogen atom, an unsubstituted aryl group, an aryl group substituted by an alkyl group, a hydroxyl group or a halogen atom, an alkoxycarbonyl group, or an atomic group necessary for forming a saturated or unsaturated ring having 5-6 carbon atoms which may be substituted by an alkyl group, an aryl group, an alkoxy group or a halogen atom; and R and R" are independently the same as R of claim 1.

3. The diffusion transfer color photographic material as set forth in claim 1 wherein said compound of general formula I is a compound represented by general formula lb wherein Y represents an alkyl group, an alkoxyl group or an alkylthio group and Ris the same as R of claim 1.

5. The diffusion transfer color photographic material as set forth in claim 1 wherein said compound of general formula I is contained in an amount of 0.006-2.5 g per mole of silver halide in said silver halide emulsion layer.

6. The diffusion transfer color photographic material as set forth in claim 1 wherein said layers containing dye developers are a layer containing cyan dye developer, a layer containing a magenta dye developer, and a layer containing a yellow dye developer; said silver halide photographic emulsion layers are a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer, said red-sensitive emulsion layer being the lowermost silver halide emulsion layer; said cyan developer layer is disposed adjacent to the red-sensitive emulsion layer at the support side, said magenta dye developer layer adjacent to the green-sensitive emulsion layer at the support side, and said yellow dye developer layer adjacent to said bluesensitive emulsion layer at the support side.

7. The diffusion transfer color photographic material as set forth in claim 1 wherein said heterocyclic ring represented by group O of general formula l is a thiazolidine-Z-thion ring, an imidazolidineQ-thion ring, a selenazolidine-Z-thion ring, a 1,3,4-thidiazoline-2 thion ring, a 1,3,4-selenadiazoline-2-thion ring, a 4- thiazoline-Z-thion ring, a 4-selenazoline-2-thion ring, a 1,Z-dihydropyridine-2-thion ring, a benzthiazoline-Z- thion ring, a benzoxazoline2-thion ring, :1 benzimidazoline2thion ring, a benzselenazolineQ-thion ring, or a l,Z-dihydroquinoline-Z-thion ring and R is an alkyl group having 1-6 carbon atoms, an alkyl group having l-6 carbon atoms substituted by a hydroxyl group, an aryl group, a morpholino group; an aryl group substituted by an alkyl group, an alkoxyl group, a halogen atom, or a 2-pyridyl, tetrazolyl, thiazolyl or triazolyl group.

8. The diffusion transfer color photographic material as set forth in claim 1 wherein said dye developer is 5,8- dihydroxyl ,4-bis[ B-hydroquinonyl-amethyl ethylamino l-anthraquinone, 4-propoxy-2-l p( B- hydroxyquinonylethyl )phenylazo]-l-naphthol, or N-nhexylcarboxyamido-4- p-( 2 ,5 dihydroxyphenylethyl)phenylazol-5-pyrazolone,

9. The diffusion transfer color photographic material of claim 2 wherein A and B are selected from the group consisting of methyl, phenyl and ethoxycarbonyl,

10. The diffusion transfer color photographic mate rial of claim 2 wherein R and R represent an alkyl group having 1-6 carbon atoms, an alkyl group having l-6 carbon atoms substituted by a hydroxyl group, an aryl group, a morpholino group; an aryl group substituted by an alkyl group, an alkoxyl group, a halogen atom, or a Z-pyridyl, tetrazolyl, thiazolyl or triazolyl group.

11. The diffusion transfer color photographic material of claim 3 wherein R and R" represent an alkyl group having 1-6 carbon atoms, an alkyl group having l6 carbon atoms substituted by a hydroxyl group, an aryl group, a morpholino group; an aryl group substituted by an alkyl group, an aljkoxyl group, a halogen atom, or a 2-pyridyl, tetrazolyl, thiazolyl or triazolyl group.

12. The diffusion transfer color photographic material of claim 4 where R represents an alkyl group having 16 carbon atoms, an alkyl group having 16 carbon atoms substituted by a hydroxyl group, an aryl group, a morpholino group; an aryl group substituted by an alkyl group, an alkoxyl group, a halogen atom, or a 2-pyridyl, tetrazolyl, thiazolyl or triazolyl group.

13. The diffusion transfer color photographic material as set forth in claim 1 wherein said compound of general formula 1 is contained in an amount of 0.01 to 0.1 per mole of silver halide in said silver halide emulsion layer.

Claims

1. A DIFFUSION TRANSFER COLOR PHOTOGRAPHIC MATERIAL COMPRISING A SUPPORT HAVING THEREON AT LEAST TWO LAYERS EACH CONTAINING A DYE DEVELOPER, AND HAVING THEREON AT LEAST TWO SILVER HALIDE PHOTOGRAPHIC EMULSION LAYER, AT LEAST ONE OF SAID SLIVER HALIDE PHOTOGRAPHIC EMULSION LAYERS CONTAINING A COMPOUND REPRESENTED BY GENERAL FORMULA I

2. The diffusion transfer color photographic material as set forth in claim 1 wherein said compound is a compound represented by the general formula Ia

3. The diffusion transfer color photographic material as set forth in claim 1 wherein said compoUnd of general formula I is a compound represented by general formula Ib

4. The diffusion transfer color photographic material as set forth in claim 1 wherein said compound of general formula I is a compound represented by general formula Ic

6. The diffusion transfer color photographic material as set forth in claim 1 wherein said layers containing dye developers are a layer containing cyan dye developer, a layer containing a magenta dye developer, and a layer containing a yellow dye developer; said silver halide photographic emulsion layers are a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer, said red-sensitive emulsion layer being the lowermost silver halide emulsion layer; said cyan developer layer is disposed adjacent to the red-sensitive emulsion layer at the support side, said magenta dye developer layer adjacent to the green-sensitive emulsion layer at the support side, and said yellow dye developer layer adjacent to said blue-sensitive emulsion layer at the support side.

7. The diffusion transfer color photographic material as set forth in claim 1 wherein said heterocyclic ring represented by group Q of general formula I is a thiazolidine-2-thion ring, an imidazolidine-2-thion ring, a selenazolidine-2-thion ring, a 1,3, 4-thidiazoline-2-thion ring, a 1,3,4-selenadiazoline-2-thion ring, a 4-thiazoline-2-thion ring, a 4-selenazoline-2-thion ring, a 1,2-dihydropyridine-2-thion ring, a benzthiazoline-2-thion ring, a benzoxazoline-2-thion ring, a benzimidazoline-2-thion ring, a benzselenazoline-2-thion ring, or a 1,2-dihydroquinoline-2-thion ring and R is an alkyl group having 1-6 carbon atoms, an alkyl group having 1-6 carbon atoms substituted by a hydroxyl group, an aryl group, a morpholino group; an aryl group substituted by an alkyl group, an alkoxyl group, a halogen atom, or a 2-pyridyl, tetrazolyl, thiazolyl or triazolyl group.

8. The diffusion transfer color photographic material as set forth in claim 1 wherein said dye developer is 5,8-dihydroxy-1,4-bis( Beta -hydroquinonyl- Alpha -methyl)-ethylamino)-anthraquinone, 4-propoxy-2-(p-( Beta -hydroxyquinonylethyl)phenylazo)-1-naphthol, or N-n-hexylcarboxyamido-4-(p-(2'',5''-dihydroxyphenylethyl)phenylazo)-5 -pyrazolone.

9. The diffusion transfer color photographic material of claim 2 wherein A and B are selected from the group consisting of methyl, phenyl and ethoxycarbonyl.

10. The diffusion transfer color photographic material of claim 2 wherein R'' and R'''' represent an alkyl group having 1-6 carbon atoms, an alkyl group having 1-6 carbon atoms substituted by a hydroxyl group, an aryl group, a morpholino group; an aryl group substituted by an alkyl group, an alkoxyl group, a halogen atom, or a 2-pyridyl, tetrazolyl, thiazolyl or triazolyl group.

11. The diffusion transfer color photographic material of claim 3 wherein R'' and R'''' represent an alkyl group having 1-6 carbon atoms, an alkyl group having 1-6 carbon atoms substituted by a hydroxyl group, an aryl group, a morpholino group; an aryl group substituted by an alkyl group, an alkoxyl group, a halogen atom, or a 2-pyridyl, tetrazolyl, thiazolyl or triazolyl group.

12. The diffusion transfer color photographic material of claim 4 where R'' represents an alkyl group having 1-6 carbon atoms, an alkyl group having 1-6 carbon atoms substituted by a hydroxyl group, an aryl group, a morpholino group; an aryl group substituted by an alkyl group, an alkoxyl group, a halogen atom, or a 2-pyridyl, tetrazolyl, thiazolyl or triazolyl group.

13. The diffusion transfer color photographic material as set forth in claim 1 wherein said compound of general formula I is contained in an amount of 0.01 to 0.1 per mole of silver halide in said silver halide emulsion layer.