US3723125A - Process for the formation of color photographic images - Google Patents

Abstract

A PROCESS FOR THE FORMATION OF COLOR PHOTOGRAPHIC IMAGES BY PROCESS A MULTI-LAYER TYPE COLOR PHOTOGRAPHIC LIGHT-SENSITIVE MATERIAL HAING AT LEAST TWO SILVER HALIDE EMULSION LAYERS ON A SUPPORT, WHICH COMPRISES DEVELOPING SAID LIGHT-SENSITIVE MATERIAL IN THE PRESENCE OF A COMPOUND HAVING THE FOLLOWING GENERAL FORMULA 1

R-N<(-Q-C(=S)-)

WHEREIN Q REPRESENTS AN ATOMIC GROUP NECESSARY TO COMPLETE A HETEROCYCLIC RING WHICH MAY BE SUBSTITUTED, AND WHEREIN R IS SELECTED FROM THE GROUP, AN ARYL GROUP, A SUBGROUP, A SUBSTITUTED ALKYL GROUP, AN ARYL GROUP, A SUBSTITUTED ARYL GROUP, AND A HETEROCYCLIC GROUP, IS DISCLOSED.

Description

nited States Patent 3,723,125 PROCESS FOR THE FORMATION OF COLOR PHOTOGRAPHIC IMAGES Jun Hayashi, Reiichi Ohi, Tadao Shishido, and Tokiharu Kondo, Kanagawa, Japan, assignors to Fuji Photo Film Co., Ltd., Kanagawa, Japan No Drawing. Filed Sept. 8, 1970, Ser. No. 70,555

Claims priority, application Japan, Sept. 5, 1969,

44/ 7,068; Apr. 2, 1970, 45/28,712 Int. Cl. G03c 7/00 US. Cl. 9656.2 17 Claims ABSTRACT OF THE DISCLOSURE A process for the formation of color photographic images by processing a multi-layer type color photographic light-sensitive material having at least two silver halide emulsion layers on a support, which comprises developing said light-sensitive material in the presence of a compound having the following general Formula I IL (I) wherein Q represents an atomic group necessary to complete a heterocyclic ring which may be substituted, and wherein R is selected from the group consisting of an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, and a heterocyclic group, is disclosed.

BACKGROUND OF THE INVENTION (1) Field of the invention The present invention relates generally to color photography. More particularly, the present invention relates to a process for increasing the color contrast of multi-layer type color photographic light-sensitive materials by the interimage effect.

(2) Description of the prior art In a multi-layer type color photographic light-sensitive material having on a support a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer, the dye formed by the reaction of the oxidation product of an aromatic amino photographic developing agent and a color former or a coupler generally has the property of absorbing to some extent other light than the light to be absorbed.

For instance, a magenta dye absorbs blue light and red light to some extent besides the green light to be absorbed. Similarly, a yellow dye and a cyan dye absorb to some extent light other than the blue light and the red light respectively to be absorbed.

Such undesirable and unnecessary absorption by the dyes reduces the color contrast. Hence, the color obtained tends to become dark and also the saturation tends to decrease.

The reduction of the saturation of color by the unnecessary absorption by the dye can be improved to some extent by the interimageeffect. The interimage effect is a phenomenon occurring in a multi-layer type color photographic light-sensitive material, wherein the formation of a dye image in one emulsion layer influences the formation of the dye image in other emulsion layers. With the interimage effect the color contrast can be increased.

The interimage effect which increases the color contrast can be defined as follows: A silver halide emulsion layer "ice having red sensitivity and being coupled forming a cyan dye after development is formed on a film base and a silver halide emulsion layer having blue sensitivity and being coupled forming a cyan dye after development is formed on a film base and a silver halide emulsion layer having blue sensitivity and being coupled forming a yellow dye after development is formed on the red-sensitive emulsion layer. The sample thus obtained is cut into two samples and one (Sample I) of them is wedge exposed to red light only, while the other sample (Sample II) is exposed to the same amount of red light and also to blue light capable of causing the same photographic effect as that due to the red light exposure. Thus, the lowermost red-sensitive emulsion layer only is exposed to the wedge image in Sample I, whereas the blue-sensitive emulsion layer and the red-sensitive emulsion layer are exposed to the wedge image in Sample II. After development, the image density of Samples I and II is measured to observe the contrast of the cyan dye image formed in the redsensitive emulsion layer. In this case, the interimage effect is said to have occurred if the contrast of the cyan dye image in Sample I is higher than the contrast of the cyan dye image in Sample II. Furthermore, with a multilayer type color photographic light-sensitive material having on a support a red-sensitive emulsion layer, a greensensitive emulsion layer, and a blue-sensitive emulsion layer, it is possible using this interimage effect to increase the contrast of the yellow dye image and the magenta dye image. The term interimage effect as used in the specification is intended to encompass this interimage effect capable of increasing the color contrast.

This interimage effect is well known in color photography. For instance, W. T. Hanson and C. A. Horton, in Journal of the Optical Society of America, 42, 663-669 (1952) and A. Thiels, in Zeitschrift fiir Wissenschaftliche Photographie, Photophysik and Photochemie, 47, 106-118 and 246-255 (1952), describe that the color contrast of a multi-layer type color photographic light-sensitive material is higher when it is exposed to monochromatic light than when it is exposed to white light. The results thereof are that the saturation of the color is increased.

It is known that this interimage effect is important for increasing the color contrast but the manner of increasing this interimage effect is not well known. For instance, it is known that the interimage effect can be caused by using a coupler capable of releasing a development inhibitor, such as benzotriazole, a mercapto compound, and the like, at coupling or a compound such as hydroquinone, and the like, which can release an inhibitor such as iodine ion, a mercapto compound, and the like, at development. However, since such compounds are unstable and are readily decomposed or since such compounds greatly reduce the sensitivity of the light-sensitive material, the use of these compounds is limited. Accordingly, hitherto increasing the color contrast by the interimage effect using such known compounds without adversely affecting the other photographic properties has been diflicult.

Therefore, an object of the present invention is to provide a color photographic image in which unnecessary absorption by dyes is corrected by the interimage effect.

Another object of this invention is to provide a color photographic image having a high saturation unaccompanied with a reduction in sensitivity.

SUMMARY OF THE INVENTION As the results of various studies, the inventors have discovered that at the development of a multi-layer type color photographic light-sensitive material having at least two silver halide photographic emulsion layers, the interimage eifect occurs markedly if the light sensitive material is developed in the presence of a compound represented by the general Formula I wherein Q represents an atomic group necessary for forming a heterocyclic ring, which may be substituted, and R represents an unsubstituted or a substituted alkyl group, an unsubstituted or a substituted aryl group, or a heterocyclic ring group.

DESCRIPTION OF THE INVENTION In general Formula I, Q represents the necessary atomic group for forming a heterocyclic ring, which may be substituted. For example, the thiazolidine-Z-thion ring series, such as thiazolidine-Z-thion ring, 4-methyl-thiazolidine-2- thion ring, and the like; the imidazolidine-Z-thion ring series, such as 1,3-dimethylimidazolidine-Z-thion ring, a 1,3- dimethylimidazolidine-2-thion ring, and the like; the selenazolidine-Z-thion ring series, such as a selenazoline-Z- thion ring, a 4-methylselenazolidine-Z-thion ring, and the like, the 1,3,4-thiadiazoline-2-thion ring series, such as a l,3,4-thiadiaZoline-2-thion ring, a 5-methyl-l,3,4-thiadiazoline 2-thion ring a S-ethylthio-1,3,4-thiadiazoline-2- thion ring, a 5-[2-(4-phenyl-5-thio-1,3,4-thiadiazoline-2- yl) mercaptoethylthio] 1,3,4-thiadiazoline-2-thion ring, and the like; the l,3,4-selenadiazoline-Z-thion ring series, such as a 1,3,4-selenadiazoline-Z-thion ring, 5-ethyl-1,3,4- selenadiazoline-Z-thion ring and the like; the 4-thiazoline- 2-thion ring series, such as a 4 methyl-4-thiazoline-2- thion ring, a 4-phenyl-4-thiazoline2-thion ring, a 4-methyl 5-ethoxycarbonyl-4-thiazoline-2-thion ring, a 4,5-trimethylenethiazoline 2-thion ring, a 4,5-tetramethylenethiazoline-Z-thion ring, and the like; the 4-selenazoline-2- thion ring series, such as a 4-selenazoline-2-thion ring, a 4-methyl-4-selenazoline-2-thion ring, a 4-phenyl-4-selenazoline 2-thion ring, a 5-ethylthio- 1,3,4-thiadiazoline-2- 2-thion ring series such as a 1,Z-dihydropyridine-Z-thion ring, a 6-ethyl-1,2-dihydropyridine-2-thion ring, and the like, the benzthiazoline-Z-thion ring series, such as a benzthiazoline-Z-thion ring, a 6-methyl-benzthiazoline-Z-thion ring, a 6-ethylbenzthiazoline-Z-thion ring, a 6-methoxybenzthiazoline 2 thion ring, a 6-chlorobenzthiazoline-2- thion ring, a S-methylbenzthiazoline-Z-thion ring, and the like; the benzoxazole-Z-thion ring series, such as benzoxazoline-2-thion ring, a 6ethylbenzoxazoline-2-thion ring, a 6-methoxybenzoxazoline-Z-thion ring, a S-methylbenzoxazoline-Z-thion ring, and the like; the benzimidazoline-Z- thion ring series, such as 1,3-dimethylbenzimidazoline-2- thion ring a 1,3-di-n-propylbenzimidazoline2-thion ring, a 1,3-di-n-deeylbenzimidazoline-Z-thion ring, a 1,3-dibenzylbenzimidazoline-Z-thion ring, a 5-chloro-1,3-dimethylbenzimidazoline 2-thion ring, a 5-methyl-1,3-di-benzylbenzimidazoline-Z-thion ring, and the like; the benzselenazoline Z-thion ring series, such as a berlzselenazoline-Z- thion ring, a 6 ethylbenzselenazoline-2-thion ring, a 6- methoxybenzselenazoline-Z-thion ring, a -chloro-benzselenazoline-Z-thion ring, and the like; and the 1,2-dihydroquinoline-Z-thion ring series, such as a 1,2-dihydroquinoline-2-thion ring, a 6-methyl-1,2-dihydroquinoline-Z-thion i'ing, a 6-chloro-l,Z-dihydroquinoline-Z-thion ring, and the ike.

R in general Formula I represents an unsubstituted alkyl group or a hydroxyl group-, an aryl group-, or a morpholino group-substitued alkyl group having from 1 to 6 carbon atoms, 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, and the like; an unsubstituted aryl group or an alkyl group, an alkoxyl group-, or a halogen atom-substituted aryl group, such as a phenyl group, a 2-methylphenyl group, a 4-methoxyphenyl group, a 4-chlorophenyl group, and the 4 like; or a heterocyclic ring group such as a 2-pyridyl group, and the like.

When R in general Formula I is a hydrogen atom, the hydrogen atom is enolated to provide a mercapto type compound. Such compounds having the mercapto group generally strongly inhibit the development of silver halide and frequently causes a reduction in sensitivity.

On the other hand, when the N-position is substituted as in the compound of this invention shown by general Formula I, no mercapto-type group is formed. Hence, a high interimage effect can be obtained without greatly reducing the sensitivity.

Although the mechanism of obtaining the interimage effect by the compound of this invention is not clearly understood, it is believed that the following explanation is applicable. The compound of this invention can diffuse through a hydrophilic colloid and hence it is considered that the compound can diffuse between each emulsion layer of a multi-layer type photographic light-sensitive material. Thus, when the compound is added, for instance, to the emulsion, it is first adsorbed by the silver halide crystals where it is fixed and hence it is impossible for it to diffuse freely into adjacent emulsion layers. However, the compound is released at the development of the silver halide and diffuses into the adjacent emulsion layers, inhibiting the development there. Accordingly, if a compound is strongly adsorbed on the silver halide particles (for example, a compound of the general Formula I in which, however, R is a hydrogen atom), a desensitization occurs severely, whereas when the adsorption of a compound by the silver halide particles is too weak, no interimage elfect is obtained.

Therefore, the compound of this invention is believed to have excellent characteristics in that an effective interimage effect can be obtained without seriously causing desensitization.

Among the compounds represented by general Formula I, the compound represented by the general Formulae Ia, Ib, and Ic shown below give particularly less desensitization and better results;

A C=s ,l

wherein X represents a sulfur atom, an oxygen atom, a selenium atom, a NR" group, or a CH=CH group; wherein A and B each represents a hydrogen atom, an unsubstituted or a substituted alkyl group, an unsubstituted or a substituted aryl group, an alkoxycarbonyl group, an acyloxy group, or an atomic group necessary to complete a saturated or unsaturated ring having from 5 to 6 carbon atoms, which may be substituted, by the combination of the groups A and B; wherein Y represents an alkyl group, an alkoxyl group, or an alkylthio group; and wherein R and R" have the same meanings as R described above in regard to general Formula I.

Each of the groups A and B in general Formula Ia represents a hydrogen atom; an unsubstituted or a hydroxyl groupor a halogen atom-substituted alkyl group having from 1 to 6 carbon atoms, such as a methyl group,

an ethyl group, a butyl group, a hydroxyethyl group, a 2-chloroethyl group, and the like; an unsubstituted or an alkyl group-, a hydroxyl group or a halogen atom-substituted group, a '3-chlorophenyl group, and the like; an

group, such as a phenyl group, and the like; an alkoxyl group such as a methoxy group, an ethoxy group, and the like; or a halogen atom, such as a chlorine atom, a bromine atom, and the like, and vice versa.

alkoxycarbonyl group such as an ethoxycanbonyl group; 5 Moreover, Y in the general Formula Ic represents an aryloxy group such as a propanoyloxy group, and the an alkyl group, such as a methyl group, an ethyl group, like; and group A combined with group B represents an an n-butyl group, an n-hexyl group, and the like, an atomic group necessary to complete an unsaturated ring alkoxyl group, such as a methoxy group, an ethoxy group, having from 5 to 6carbon atoms, .such asa trimethylene and the like, or an alkylthio group such as a methylthio group, a tetramethylene group, and the like; or an atomic 10 group, an ethylthio group, a 2-(4-phenyl 5 thi0-1,3,4- group necessary to complete an unsubstituted benzene ring thiadiazoline-Z-yl) mercaptoethylthio group, and the like. or a benzene ring substituted with an alkyl group, such Examples of the compounds which can be employed in as a methyl group, an ethyl group, and the like; an aryl this invention are shown below:

Compound 1...- S\ M.P. 90 0.

0:8 N (EH1 Compound 2.; S\ M.P. 76 C.

. C=S hHl Compound 3... S\ M.P. 74 C.

/C=S \N nzHr Compound 4... 8 MP. 55 C.

:8 N lso-hHu Compound 5-.. S\ M.P. 149 C.

Compound 6- S M. P. 190 C.

CHI

/C=S N Compound 7-.. 8 MP. 87 C.

/C=S N 6H3 Compound 8-.. S M.P. 130 0.

Compound 9..- H: 8 M1. 81-82 C.

H C=s Compound 10-- H: 3 MP. 102 0.

C=S H: H:

Compound 11: S\ M.P. 96 C.

Compound 12..- S\ M.P. 114 C.

1 c=s OH;

Compound 13.; S M.P. 162 C.

HECIOOC I CH3 Compound 14.: 8 MP. 82 C C=S CH1 Compound 15.. S\ MP. 119 C:

Compound 16.. S MsP. 166 0.

OCH:

Compound 17..

Compound 18.. 0

Compound 19... 0

Compound 20... Se

Compound 23... nCnHn Com ound 24.:

Com und 25..

M.P. 113 C;

M.P. 133 C;

M.P. 92 C:

M.P. 80 Cu IVLP: 151 C;

Llquldl Compound 26..- c G M1. 143 C.

Compound 27.. Ml. 118 C.

S N (5H;

Compound 28.. O1 1 MP. 184 C.

Compound 29.. MP. 94 C.

Compound 30.- Ml. 90 C.

N (EH3 Compound 31-- M. P. 46 C.

N hHu Compound 32.. 8 MP. 123 C.

Compound 33.. (311: MP. 62.5 C.

Compound 34..

Compound 35-. M.P. 108 C.

s mots-IE \C S Compound 36-.

Compound 37..

H.C L AH.

Compound 38... S

Eho/ Tsomoms-f \c=s M.P. 66 C.

M-P; 152 C.

M.P. 145 C.

The compounds illustrated above can be prepared by well known methods. Hereinafter, examples of the synthesis of the compounds shown above are as follows:

Synthesis-1 (Compounds 1-8) Compounds 1-8 illustrated above can be prepared by the method described in Journal of The Chemical Society, 473-476 (1939), using Z-mercaptobenzthiazole as the starting material.

Synthesis-2 (Compounds 9-17) Compounds 9-17 shown above can be prepared by the method shown in Journal of The Chemical Society, 1503- 1509 (1949), by the reaction of a dithiocarbamate and an alpha haloketone.

Synthesis-3 (Compounds 18 and 19) Compounds 18 and 19 illustrated above can be prepared by the method described in Journal of The Chemical Society, 143-151 (1939).

Synthesis-4 (Compound 20) Compound 20 can be prepared by the method described in Journal of The Chemical Society, 1762-1766 (1939).

Synthesis-5 (Compound 21) Compound 21 can be prepared by the method described in Nippon Yakugaku Zasshi (Journal of Pharmaceutical Society of Japan), 1865-1369 (1954).

Synthesis-6- (Compound 22) The 2-propylthiobenzimidazole, obtained by refluxing under heating for 6 hours Z-mercaptobenzimidazole and an equimolar amount of propyl iodide in ethanol, is refluxed under heating for 12 hours together with an equimolar amount of propyl iodide in dioxane. After distil1-' Analysis as C H N S. Found (percent): C, 66.75; H, 7.63; N, 11.42. Calculated (percent): C, 66.64; H, 7.74; N, 11.96.

Synthesis-7 (Compounds 23-26) Compounds 23-26 can also be prepared by procedures similar to the procedure described in Synthesis-6.

Synthesis-8 (Compounds 27-29) Compounds 2 7-29 can be prepared according to the method shown in Berichte der Deutschen Chemischen Gesellschaft, 33, page 3359 and ibid, 35, page 3682.

Synthesis-9 (Compound 30) Compound 30 can be prepared by the method shown in Justus Lierbigs Annalen der Chemie, 331, page 245.

Synthesis-10 (Compounds 31 and 33) Compounds 31 and 33 can be prepared by the method shown in Journal of Organic Chemistry, 14, page 946.

Synthesis-11 (Compound 32) 6.5 g. of thiazoline-Z-thion is mixed with 4.5 cc. of 37% formalin at 50 C. and then an alcohol solution of 5 g. of morpholine is added gradually to the mixture, whereby white crystals are formed. By recrystallizing the crystals from alcohol, 9 g. of the crystals of Compound 32 having a melting point of 123 C. is obtained.

Synthesis-12 (Compounds 34, 36 and 38) Compounds 34, 36 and 37 can be prepared according to the methods taught in Journal fiir Praktische Chemie, 60, page 53 and ibid, 60, pages 187-188.

Synthesis-13 (Compound 35) Compound 35 can be prepared by the method described in Berichte der Deutschen Chemischen Gesellschaft, 27, page 2513.

Synthesis-14 (Compound 37) Compound 37 shown above can be prepared according to the method described in Chemical Abstracts, 33, page 25 18.

By incorporating the compound of this invention represented by general Formula I in a multi-layer type color photographic light-sensitive material, it can be incorporated in at least one of the layers consisting of the silver halide emulsion layers of a multi-layer type color photographic light-sensitive material and the layers adjacent to the silver halide emulsion layers, such as a yellow filter layer, an antihalation layer, intermediate layers, and a protective layer. Furthermore, the compound can be incorporated in a developer solution for the multi-layer type color photographic light-sensitive material. Still further, the above two modes of the addition of the compound can be used in combination.

The amount of the compound used in this invention varies depending to the nature of the mult-i-layer type color photographic light-sensitive material to be employed and also the manner of development but the amount generally ranges from 0.006 to 1.5 g. per mole of silver halide when the compound is incorporated in the silver halide emulsion layer of a multi-layer type color photographic light-sensitive material, from 0.006 to 1.5 g. per 100 g. of gelatin when it is incorporated in a layer adjacent to the above-mentioned silver halide emulsion layer, and further, from 0.1 mg. to 1 g., preferably from mg. to 500 mg. per liter of developer solution when the compound is added to the developer solution. However, the ranges set forth above for this compound are not to be interpreted as limiting.

As a solvent for incorporating the compound of this invention a solvent which does not adversely affect the silver halide photographic emulsion, such as water, methanol, and acetone, can be used.

In incorporating the compound of this invention in a developer solution, any developer solutions which can reduce silver halide particles to silver can be employed. For instance, in case of black and white development, a developer solution containing polyhydroxybenzenes, N-alkylaminophenols, 1-phenyl-3-pyrazolidones, or a mixture thereof, as the developing agent, can be used. As the polyhydroxybenzene, suitable ones are, for example, hydroquinone, pyrocatechol, pyrogallol, and the like; as the N- monoalkylaminophenol, suitable ones are N-methylaminophenol, N-ethylaminophenol, and the like; and as the 1- phenyl-3-pyrazolidone, suitable ones are l-phenyl-3-pyrafclxilidone, 1-pheny1-4,4-dimethyl-3-pyrazolidone, and the Moreover, in case of color development, the compound of this invention can be added to a developer solution containing, as a developing agent, a p-phenylenediamine derivative, such as 4-amino-N,N-diethylaniline, 4-amino- S-methyI-N-methyl-N-(beta methylsulfone amidoethyl) aniline, 4-amino-3-methyl-N-ethyl-N-(beta-hydroxyethyl) aniline, and the like.

In increasing the interimage effect by the present invention, the multi-layer type color photographic light-sensitive material can be processed at ordinary processing temperatures, i.e., at from to C. but can be processed at higher temperatures, i.e., at 30 to 80 C. or at an even higher temperature, if desired.

The compound of this invention can be used in any processes capable of forming color photographic images, that is to say, in processes for developing multi-layer type color photographic light-sensitive materials having at least two photographic silver halide emulsion layers containing silver halide dispersions in hydrophilic colloids to form dye images according to the reduced ratio of silver halide into silver. For instance, better results are obtained when the compound of this invention is used in the so-called reversal color photographic process, i.e., a process wherein, after exposing a multi-layer color photographic lightsensitive material having at least two silver halide photographic emulsion layers sensitized to different wavelength regions, respectively, the light-sensitive material is first developed in a black and white developer solution to provide a negative silver image and then the silver ha- 16 lide particles in the areas which have not been developed in the black and white development are developed by a color developer solution to provide positive dye images.

AS the reversal color photographic process, there are the so-called coupler-in-developer type color system, wherein a dye image is formed by successively developing a multi-layer type color photographic light-sensitive material using color developer solutions each containing a diffusible coupler to be coupled in each difierent color, and the so-called coupler-in-emulsion layer color system wherein a dye image is obtained by incorporating each diffusion resisting coupler capable of being coupled in each different color in each silver halide emulsion layer of the multi-layer type color photographic light-sensitive material and processing the light-sensitive material by color developer solutions containing no couplers.

The compound of this invention can be used effectively in both systems of the reversal color photographic processes.

Moreover, the compound of the present invention can also be used in a system wherein a negative dye image is obtained by developing a multi-layer type color photographic light-sensitive material having at least two silver halide photographic emulsion sensitized to different Wavelength regions, each containing a diffusion resistant coupler, directly after exposure in a color developer solution.

Also, the compound of this invention can be used in the color diffusion transfer process, as described in the specifications of US. Pats. 2,559,643, 2,698,798, and 3,227,551, having the characteristics that a developer solution, a coupler, or a dye is diffused from a light-sensitive layer to a reception layer in contact with the lightsensitive layer in proportion to the images in the lightsensitive layer.

Still further, the compound of this invention can be used in the silver dye bleaching color photographic process, as described in the specifications of U8. Pats. 2,020,- 775 and 2,410,025, in which a dye image can be obtained by bleaching the dye in the areas containing silver.

In the multi-layer type color photographic light-sensitive material to be used in the present invention it is desirable to apply a red-sensitive silver halide photographic emulsion layer, a green-sensitive silver halide photographic emulsion layer and a blue-sensitive silver halide photographic light-sensitive emulsion layer to a support in this order.

Also, it is desirable that in the multi-layer type lightsensitive material used in this invention after development, cyan, magenta, and yellow images are formed in the red-sensitive, green-sensitive, and blue-sensitive silver halide photographic emulsion layers, respectively. However, other emulsion layer orders and other methods for forming dye images than those described above can be employed in this invention.

As the silver halide emulsion used in this invention, there are employed photographic emulsions containing silver halides such as silver bromide, silver iodide, silver chloride, silver chlorobromide, silver iodobromide, and silver chloroiodo bromide. In particular, better results are obtained in employing at least a photographic emulsion layer containing, silver chloroiodide, silver iodobromide, or silver chloroiodobromide having an iodine content of from 1 to 10 molar percent.

Furthermore, the silver halide photographic emulsion to be used in the present invention can be chemically sensitized by methods well known in this field, such as, by using a compound containing an unstable sulfur, such as sodium thiosulfate, allylthiocarbazide; a gold compound such as a gold (I) complex salt of thiocyanic acid; a reducing agent such as stannous chloride; or a polyalkylene oxide derivative. Also, the silver halide photographic emulsion to be used in the present invention can be spectrally sensitized using a cyanine dye, such as 1,1'-diethylcyanine iodide, 1,1'-diethyl-9-methylcarbocyanine bromide, anhydro-5,5'-dipl1enyl-9-ethyl-3,3'-di(2-sulfoethyl)- 'benzoxazolocarbocyanine hydroxide, and the like, used alone or in combinations thereof. Still further, the silver halide photographic emulsion to be used in this invention can contain a developing agent capable of releasing a developing inhibitor, such as 2-iodo-S-pentadecylhydroquinone or 2-methyl-5-(1-phenyl-5-tetrazolylthio)-hydroquinone; a stabilizer, such as 4-hydroxy- 6 -methyl- 1,-3,3a,7 tetraazaindene, benz'imidazole, or 1 phenyl-- mercaptotetrazole; a hardening agent, such as formaldehyde or mucobromic acid; and a wetting agent, such as saponin or sodium alkylbenzenesulfonate.

The invention now will be explained in greater detail by reference to the following examples. In the following examples, two types of color photographic processes are used. That is to say, the so-called coupler-in-developertype color system, wherein couplers are supplied from color developer solutions, and the so-called coupler-inemulsion layer type system wherein couplers are incorporated into the photographic emulsion layers of a color photographic light-sensitive material, are employed.

'In the following examples, in the coupler-in-developer type color system the multi-layer type color photographic light-sensitive material having the following composition is used.

Coupler-in-Developer Type Color System To a cellulose triacetate film base were applied successively the following different emulsion layers:

First layer-Red-sensitive silver halide emulsion layer: A layer formed by coating a high speed gelatino silver iodobromide emulsion having red sensitivity due to a sensitizing dye and containing no coupler so that the amount of silver is 15 mg./1'00 cm.

lSecond layerGreen-sensitive silver halide emulsion layer: A layer formed by coating a high speed silver iodobromide emulsion having green sensitivity due to a sensitizing dye and containing no coupler so that the amount of silver is 15 mg./ 100 cm.

Third layerYellow filter layer: A layer formed by coating a yellow colloidal silver dispersion containing colloidal silver in gelatin so that the amount of silver is 2.5 mg./100 cm.

Fourth layer--Blue-sensitive silver halide emulsion layer: A layer formed by coating a high speed silver iodobromide emulsion having blue sensitivity and containing no coupler so that the amount of silver is 20 mg./ 100 cm Also in the examples shown 'below relating to the coupler-in-developer type color system, the multi-layer type photographic light-sensitive material was processed using the following procedures:

Process: Time (min.) (1) Hardening bath 1 (2) Water washing 2 (3) Negative development 4 (4) Water washing 3 (5) Reversal red flash exposure (6) Cyan color development 4 (7) Water washing 3 (8) 'Reversal blue flash exposure (9) Yellow color development 4 (10) Water washing 3 (11) Reversal white exposure (12) Magenta color develpoment 4 (13) Water washing 3 (14) Silver bleaching 3 (15) Fixing 3 (16) Water washing and drying The temperatures of the processing baths in the above process were 27 C. The composition of the baths are as shown below:

18 Hardening bath Sodium hexametaphosphate g 2.0 Sodium bisulfite g 5.0 Sodium pyrophosphate (10H O) g 15.0 Sodium sulfate g 100.0 Potassium bromide g 2.0 Sodium hydroxide ..g 0.1 37% formaldehyde cc 17.0 Water added to make the total volume to 1000 cc.

Negative developer solution N-methyl-p-aminophenol sulfate g 5.0 Sodium sulfite a g 79.0 Hydroquinone g 2.0 Sodium hydroxide n. n g 1.0 Sodium carbonate (H O) g 41.0 0.1% potassium iodide cc 12.5 Potassium bromide g 3.6 Sodium hydroquinone monosulfonate g 4.0 Potassium thiocyanate g 2.0 0.5% 6-nitrobenzoindazole nitrate cc 5.0 Water added to make the total volume to 1000 cc.

Cyan color developer solution Potassium bromide g 2.9 1% -nitrobenzoimidabole nitrate cc 3.0 0.1% potassium iodide -..cc.... 11.0 Sodium sulfite g 10.0 Sodium sulfate g 60.0 Potassium thiocyanate g 1.2 4-amino-3-methyl-N ethyl-N-(betahydroxyethyl)- aniline sulfate 3 2.5 Sodium hydroxide g 3.4 1-hydroxy-N-(2 propionamidophenethyl)-2-naphthamide g 1.5 2,4-dichloro-1-naphthol -g 0.2 2-methyl-2,4-pentane diol cc 10.0 Polyoxyethylene-methylphenyl ether 0.5 Monobenzyl-p-aminophenol hydrochloride g 0.4 p-Aminophenol hydrochloride g 0.12 Water added to make the total volume to 1000 cc.

Yellow color developer solution Sodium sulfite g 10.0 Potassium bromide g 0.65 0.1% potassium iodide cc 29.0 1% 6-nitrobenzoimidazole nitrate cc 10.0 Sodium sulfate t cc 64.0 N,N diethyl p phenylenediamine hydrochloride g 3.0 Sodium hydroxide g 2.4 2-methyl-2,4-pentanediol cc 20.0 2-benzoyl-2-methoxyacetanilide g 1.8 Diethyl hydroxylamine cc 0.3 Polyoxyethylene-methylphenyl ether g 0.8 Water added to make the total volume to 1000 cc.

Magenta color developer solution Conc. sulfuric acid cc 2.0 Sodium phosphate (12H O) g 40.0 Sodium sulfite g-.. 5.0 Potassium thiocyanate g 1.2 0.1% potassium iodide cc 7.5 Potassium bromide g 0.6 4-amino-3-methyl-N-ethyl N (beta-methylsulfonamidoethyl)-aniline sulfate g 2.0 Ethylene diamine cc 6.0 Sodium hydroxide cc 0.3 1-(2,4,6 trichlorphenyl) 3 (4-nitroanilino)-5- pyrazolone g 1.7 2-methyl-2,4-pentanediol cc 10.0 Sodium sulfate g 50.0 Polyoxyethylene-methylphenyl ether g 0.5 Water added to make the total volume to 1000 cc.

19 Bleaching solution Potassium ferricyanide g 100.0 Potassium bromide g 30.0

Water added to make the total volume to 1000 cc.

Fixing solution Sodium thiosulfate g 125.0 Sodium sulfite g 9.0 Water added to make the total volume to 1000 cc.

Furthermore, in the following examples, in the couplerin-emulsion layer type color system, a multi-layer type color photographic light-sensitive material having the following composition is used.

Coupler-in-emulsion layer type color system To a cellulose triacetate film base are successively applied the following different emulsion layers.

First layer-Antihalation layer: A layer formed by coating a gray colloidal silver dispersion containing colloidal silver in gelatin so that the amount of silver is 3 mg./100 cm.

Second layer-Intermediate layer: A layer formed by coating gelatin in an amount of 13.4 mg./100 cm.

Third layer-Red-sensitive silver halide emulsion layer: A layer formed by coating a high speed gelatino silver iodo-bromide emulsion layer having red sensitivity due to a sensitizing dye and containing a cyan coupler, (a coupler emulsion prepared by dissolving a cyan coupler, 1-hydroxy-4-chloro-N-dodecyl-2-naphthamide in tricresyl phosphate and dispersing the solution in gelatin) so that the amount of silver is 10 mg./100 cm.

Fourth layer-Intermediate layer: A layer formed by coating gelatin in an amount of 13.4 mg./ 100 cmf Fifth layer-Green-sensitive silver halide emulsion layer: A layer formed by coating a high speed gelatino silver iodo-bromide emulsion having green sensitivity due to a sensitizing dye and containing a magenta coupler (a conpler emulsion prepared by dissolving a magenta coupler, 1-(2,6-dichloro-4-methoxyphenyl)-3-[3 {alpha-(2,4-ditert-amylphenoxy)propionamido}benzamido] 5 pyrazolone in dibutylphthalate and dispersing the solution in gelatin) so that the amount of silver is 15 mg./100 cm.

Sixth layerYellow filter layer: A layer formed by coating a yellow colloidal silver dispersion prepared by dispersing colloidal silver in gelatin so that the amount of silver is 2.5 mg./100 cm.

Seventh layerBlue-sensitive silver halide emulsion layer: A layer formed by coating a high speed gelatino silver iodobromide emulsion containing a yellow coupler (a coupler emulsion prepared by dissolving 2-benz0yl-2'- chloro 5 tridecanoyloxyacetanilide in dibutylphthalate and dispersing the solution in gelatin) so that the amount of silver in the coated layer is 15 mg./ 100 cm.

Eighth layer-Protective layer: A layer formed by coating :1 gelatin in an amount of 8.9 mg./100 cm.

In the coupler-in-emulsion layer type color system in the following examples, the multi-layer type color photographic light-sensitive material was processed using the following procedures:

The temperatures of the above-described processing baths in the procedure were 30 C. The compositions of the processing baths were as shown below:

20 Hardening bath Sulfuric acid (1:1) cc 5.4 Sodium sulfate g 150.0 Sodium acetate g 20.0 30% pyruvaldehyde cc 40.0 37% formaldehyde cc 20.0 Water added to make the total volume to 1000 cc.

First developer solution N-methyl-p-aminophenol sulfate g 2.0 Sodium sulfite g 90.0 Hydroquinone g 8.0 Sodium carbonate (1H O) g 52.5 Potassium bromide g 5.0 Potassium thiocyanate g 1.0 Water added to make the total volume to 1000 cc.

Secondary developer solution Benzyl alcohol cc 5.0 Sodium sulfite g 5.0 Hydroxylamine hydrochloride g 2.0 3-methyl 4 amino-N-ethyl-N-(beta-methylsulfonamidoethyl)aniline sulfate g 1.5 Potassium bromide g 1.0 Sodium phosphate g 30 Sodium hydroxide g 0.5 Ethylene diamine (70% aqueous solution) cc 7 Water added to make the total volume to 1000 cc.

Bleaching solution Ferricyanide g Sodium acetate g 40 Glacial acetic acid g 20 Potassium bromide g 30 Water added to make the total volume to 1000 cc.

Fixing solution Sodium thiosulfate g Sodium acetate g 70 Sodium sulfite t g 10 Potassium alum g 20 Water added to make the total volume to 1000 cc.

EXAMPLE 1 According to the above-described technique, two types of multilayer type color photographic light-sensitive materials for coupler-in-developer type color system were prepared.

One of them was prepared as a control sample and the second one has the same composition as the control sample except that Compound 2 described hereinbefore was incorporated in the first emulsion layer, the second emulsion layer, or the fourth emulsion layer of the lightsensitive material in an amount of 100 mg. per mol of silver halide.

Each of the multi-layer type color photographic lightsensitive materials thus prepared was subjected to the following two types of sensitometric exposure, i.e., red exposure alone and white exposure (red light+green light-l-blue light). In the two types of exposures the amount of red light in the former was controlled to be the same as the amount of red light in the latter and further the amount of each component of the green light and the blue light in the white light was controlled to provide the same photographic effect as that with the red light.

Each of the samples thus exposed was developed according to the developing procedure as described above for the coupler-in-developer type color system. After development the density of the cyan dye in each sample was measured and expressed as a function of the red exposure amount. The interimage effect of each sample can be evaluated using the ratio of gamma values of the characteristic curves of the cyan dye images exposed to red light alone and exposed to white light (7 /7 wherein 21 7 represents the gamma value of the cyan dye image when the sample is exposed to red light, while represents the gamma value of the cyan dye image when the sample is exposed to white light. Also, the interimage effeet can be evaluated by the difference in sensitivity obtained at the density value at D=0.6, i.e., A log E [A log E: (log E at D=0.6 of the cyan dye image when exposed to white light)-(log E at D=0.6 of the cyan dye image when exposed to red light)]. In other words, if the interimage effect to the cyan dye image is larger, the ratio 'y /'y is higher and also A log E becomes larger.

The results obtained are shown in Table 1.

1 MgJmol of silver halide.

The results in Table 1 show clearly that by incorporating Compound 2 in the emulsion layers, the values of /y and A log E are increased and hence the interimage effect is increased.

EXAMPLE 2 According to the abovedescribed procedure, 41 types of multi-layer type color photographic light-sensitive materials for coupler-in-developer type color systems were prepared. One of them was prepared as a control sample with the others having the same composition as the control sample except that each of the compounds of this invention, shown in Table 2, was incorporated in the bluesensitive silver halide photographic emulsion layer (the above-described fourth layer) of each of the samples in the amount shown in the same table. Each of the multilayer type color photographic light-sensitive materials thus obtained was exposed and developed using the same procedures as in Example 1 and also the ratio 'y /y was obtained by measuring the density.

On the other hand, in order to determine the influence of the compounds shown in Table 2 on the sensitivity of the blue-sensitive emulsion layer of the multi-layer type color photographic light-sensitive material, it was sensitometrically exposed to blue light and then processed according to the developing procedures of the coupler-indeveloper type color system, thereafter the density of the yellow dye image was measured. By the variation of the sensitivity value S (expressed as a relative value with the sensitivity value of the control sample being assumed to be 100) obtained at D=0.6, the extent of the compound reducing the sensitivity of the blue-sensitive emulsion layer can be determined. That is to say, a lower sensitivity value shows that the compound incorporated reduced the sensitivity of the blue-sensitive emulsion layer to a greater extent. The values of 'y /'y and the sensitivity values S thus obtained are shown in Table 2 in which the values are also shown at the same time, for the sake of comparison, for the two comparison compounds X and Y, shown below:

Compound X (for comparison) Compound Y (for comparison) In Table 2, shown below, the developing procedures were conducted separately in Experiments No. 1 to No. 4. To make it possible to compare Experiments No. l to 4, a control experiment was conducted in each experiment (the results of the control experiment are shown at the beginning of each experimental group). That is to say, each control experiment was so conducted that essentially the same results were obtained and hence the results of the experimental groups can be compared directly with each other.

TABLE 2 Compound Amount 1 'yR/'yw S 1 Experiment No. 1:

ontr 0 1. 14 100 6 1. 19 101 60 1. 48 110 600 2. 15 105 1500 1. 98 98 200 1.35 98 400 1.80 200 1.40 100 400 1. 89 98 200 1. 21 400 1. 39 89 Control 0 1. 12 100 200 1. 38 86 400 1. 68 66 200 l. 28 79 400 1. 48 61 200 1. 35 77 400 l. 48 60 200 1. 30 58 400 1. 49 30 200 1. 21 55 400 1. 28 38 1 Mg./mol of blue-sensitive silver halide. Relative. sensitivity of blue-sensitive layer.

From the results shown in Table 2, it can be seen that by incorporating Compounds 1-17 of this invention, the values of 'y /7 become markedly larger and hence the interimage effects are increased.

Also, from the results shown in Table 2,'it is clear that when the compound of general Formula I, wherein, however, R is a hydrogen atom, i.e., Compound X or Y which can assume a mercapto form on enolation, the value of 'y /v becomes larger but the sensitivity is greatly reduced.

As shown above the compounds of this invention have the advantages of increasing the interimage effect without causing desensitization to a great extent.

EXAMPLE 3 A multi-layer type color photographic light-sensitive material for the coupler-in-developer type color system was subjected to four types of sensitometric exposures, i.e., red light, green light, blue light, and white light (red light-l-green light+blue light) separately. The amount of each of the red light, the green light, and the blue light in the white light was same as that of the red light, the green light and the blue light respectively when the light-sensitive material was exposed to each component alone. Also, each of the red light, the green light and the blue light was controlled so that the same photographic effect was provided.

Several groups of the thus exposed four samples were prepared and each of the groups of the four samples was developed according to the above-described developing procedures for the coupler-in-developer type color system except that the negative developer solution contains Compound 3. After development, the ratio 'y /'y of the gamma values of the characteristic curves of the cyan dye images in the case of exposure to red light and in the case of exposure to white light, the ratio v /v of the gamma values of the characteristic curves of the magenta dye images in the case of exposure to green light and in the case of exposure to white light, and the ratio 'y /'y of the gamma values of the characteristic curves of the yellow dye images in the case of exposure to blue light and in the case of exposure to white light were obtained. The results obtained are shown in Table 3.

1 Mg./liter of developer solution.

From the results shown in the above table, it can be seen that by incorporating Compound 3 in the negative developer solution, the interimage effect was increased in the yellow dye layer, magenta dye layer and cyan dye layer.

EXAMPLE 4 According to the above-described procedures for the coupler-in-emulsion layer type color system, 11 types of multi-layer type color photographic light-sensitive materials were prepared. One of them was prepared as a control sample and the remaining ten had the same composition as the control sample except that Compound 1 was incorporated in either the protective layer (the eighth layer), the blue-sensitive silver halide emulsion layer (the seventh layer), the yellow filter layer (the sixth layer), or the intermediate layer (the fourth layer) as shown in Table 4 and in the amount shown in Table 4.

The multi-layer type color photographic light-sensitive materials thus obtained were exposed in the same manner as in Example 3 and then the light-sensitive materials thus exposed were developed according to the above described developing procedures for the coupler-in-emulsion layer type color system.

After development, the ratios 'y /y 'y /y and 'y /y were obtained by measuring the densities in the same manner as in Example 3. The results are shown in Table 4.

TABLE 4 Compound Amount of containing layer Compound 1 'y/rww 'YG/YW 'ynl'yw Control. 1. 28 1. 15 1. 06 6 mg./100 g. gelatin 1. 31 1. 19 1.07 60 mg./100 g. gelatin. 1. 68 1. 29 1. 10 600 mg./100 g. gelatin 2. 01 1. 54 1. 18 Do 1,500 mg./100 g. 1. 95 1. 55 1. 11

gelatin.

Blue-sensitive layer 200 mgJmol Ag 1. 45 1. 21 1. 09 o 400 mg./mol Ag 1. 89 1. 31 1. 11 Yellow filter lay 200/100 g gelatin- 1.38 1. 25 1. 07 Do 400/100 1;. gelatin 1. 75 1. 38 1. 12 Intermediate layer- 200/100 g. gelatin. 1. 35 1. 26 1. 08 Do 400/100 g. gelatin- 1. 49 1. 37 1. 09

As can be seen from the results shown in the able above, by incorporating Compound 1 in the above-described layers, the ratios 'y /'y /7 and 'y /q were markedly increased and thus the interimage effects were increased.

24 EXAMPLE 5 According to the above-described procedures, six types of multilayer type color photographic light-sensitive materials for the coupler-in-developer type color system were prepared.

One of them was prepared as a control sample and the other five have the same composition as that of the control sample except that each of the compounds shown in Table 5 was incorporated in the first layer, the second layer, and the fourth layer as described above in the amount shown in the table.

The multi-layer type color photographic light-sensitive materials thus obtained were exposed and developed as in Example 1 and also the densities were measured using the same procedure as in Example 1 to provide the ratio /y and A log E. The results are shown in Table 5.

As can be seen from the results shown in Table 5, the incorporation of each of Compounds 19, 21, 27, 32 and 35 of this invention, the values of 'y y and A log E were increased and accordingly the interimage eflect became larger.

EXAMPLE 6 According to the above-described procedures 31 types of multilayer type color photographic light-sensitive materials for coupler-in-developer type reversal color system were prepared. One of them was prepared as a control sample and the remaining thirty have the same composition as the control sample except that each of the compounds shown in Table 6 was incorporated in the bluesensitive silver halide emulsion layer (the fourth layer) in the amount shown in Table 6.

The multi-layer type color photographic light-sensitive materials thus prepared were exposed and developed in the same manner as in Example 2. The densities also were measured in the same manner as in Example 2 to obtain 'y /y and S.

The 'y /'y values and the sensitivity values S thus obtained are shown in Table 6, in which the results obtained using the following control Compounds A, B and C are shown for comparison:

Compound A (for comparison) Compound B (for comparison) E (I C=.

Compound 0 (for comparison) TABLE 6 Compound Amount 1 'yn/yw S 3 Experiment No. 1:

Control 1. 12 100 6 1. 20 101 60 1. 41 103 600 1. 95 110 1,500 1. 90 95 200 1. 39 98 400 1. 78 70 200 1. 28 100 400 1.50 98 200 1. 21 105 400 1. 48 102 l Mg./mol of blue-sensitive silver halide. 2 Relative sensitivity of hlue-sens1t1ve layer.

In Table 6, Experiment Nos. 1-3 were developed separately. In order that Experiments 1-3 could be compared with each other, the control sample was processed in each experiment and the results of the control experiment are shown at the top of each experimental group. Since each of the control experiments were so controlled providing essentially the same results, these experimental results can be compared directly with each other.

From the results shown in Table 6, it can be seen that by the incorporation of Compounds 18, 20, 22-24, 29-30. 33-34, and 37-38 of this invention, the value of 'y /q was markedly increased and hence the interimage efi'ect became larger.

Also, from the results shown in Table 6 it can be seen that when the compound of general Formula I, but where R is a hydrogen atom which is diiferent from the compound of this invention, that is to say Compound A, B or C, which can assume the corresponding mercapto form on enolation, the value 'y /y was increased but the sensitivity was greatly reduced.

As shown above, the compounds of this invention have the advantages that the interimage effect becomes larger when they are used unaccompanied with any desensitization.

EXAMPLE 7 The multi-layer type color photographic light-sensitive materials for the coupler-in-developer type color system were exposed in the same manner as in Example 3. The light-sensitive materials thus exposed were developed according to the above-described developing procedures for the coupler-in-developer type color system except that each of the compounds shown in Table 7 was incorporated in the negative developer solution in the amount shown in Table 7. After development, the values of 'y /y 'y /v and 7 /7 were obtained in the same manner as in Example 3. The results thus obtained are shown in Table 7,

1 Mg./liter of negative developer solution.

From the results shown in Table 7, it can be seen that incorporation of Compounds 18, 21 and 28 of this invention in the negative developer solution, the interimage effect occurred in each of the yellow dye-containing emulsion layer, magenta dye-containing layer, and cyan dyecontaining layer.

EXAMPLE 8 According to the above-described procedures, 11 types of the multi-layer type color photographic light-sensitive materials for the coupler-in-emulsiontype color system were prepared. One of them was prepared as a control sample and the remaining 10 had the same composition as that of the control sample except that Compound 21 was incorporated in the protective layer (the eighth layer), the blue-sensitive silver halide emulsion layer (the seventh layer), the yellow filter layer (the sixth layer), or the intermediate layer (the fourth layer) in the amount shown in Table 8.

The multi-layer type color photographic light-sensitive materials thus obtained were exposed and developed in the same manner as in Example 4 and the densities were measured in the same manner as in Example 4 to obtain the values of 'y y 'y and 'y The results obtained are shown in Table 8.

TABLE 8 Compound- Amount of containing layer Compound 21 ya/7w 'yolyw YB/7W Control 0 1.30 1. 18 1. 10 Protective layer: 6 rug/100 g. gelatin. 1. 33 1. 19 1. 11 Do 60 rug/100 g. gelatin 1. 69 1.31 1. 13 Do. 600 rug/100 g. gelatin 2. 05 1. 59 1. 20 Do 1,500 mg./l00 g. gelatin. 1. 1. 55 1. 19 Blue-sensitive layer 00 mg./mol Ag 1. 54 1. 25 l. 13 D0 400 mg./mol Ag 1. 80 1. 39 1. 18 Yellow filter layer. 200 mg./ g. gelatin.. 1. 41 1. 2O 1. 12 o 400 mg./100 g. gelatin 1. 75 1. 36 1. 14 Intermediate layer 200 mg./10D g. gelatin 1. 38 1. 21 1. 13 Do 400 mg./100 g. gelatin.. 1. 45 1. 28 l. 15

From the results shown above it can be seen that by incorporating Compound 21, the values of /y 'y /y and 'y /'yw were markedly increased, that is to say, the interimage effect was increased.

EXAMPLE 9 According to the above-described procedures, 11 types of the multi-layer type color photographic light-sensitive materials for the coupler-in-emulsion layer type color system were prepared. One of them was prepared as a control sample and the remaining ten have the same composition as that of the control sample except that each of the compounds shown in Table 9 was incorporated in the blue-sensitive silver halide photographic emulsion layer (the above-described eighth layer).

The multi-layer type color photographic light-sensitive materials thus prepared were exposed in the same manner as in Example 1 and developed in the same manner as in Example 4. Then, the densities were measured as in Example 4 to provide 'y /y The results are shown in Table 9.

TABLE 9 Compound Amount 1 'ynl'yw Control 0 1. 27 Compound 25. 200 1. 38 Do 400 1.45

1 Mg./mo1 of silver halide.

:From the results shown in Table 9, it can be seen that the incorporation of Compounds 25, 26, 31, 3S and 36 increased the value of 'y /y markedly, that is to say, the interimage effect was increased.

wherein Q represents an atomic group necessary to complete a heterocyclic ring selected from the group consisting of the thiazolidine-2-thion ring series, the imidazolidine-2-thion ring series, the selenazolidine-Z-thion ring series, the 1,3,4-thiadiazline-2-thion ring series, the 1,3,4- selenadiazoline-Z-thion ring series, the 4-thiazoline-2-thion ring series, the 4-selenazoline-2-thion ring series, the 1,2- dihydropyridine-2-thion ring series, the benzthiazoline-Z- thion ring series, the benzoxazoline-Z-thion ring series, the benzimidazoline-Z-thion ring series, the benzselenazoline-2-thion ring series and the 1,2-dihydroquinoline-2- thion ring series, wherein R is an alkyl group having 1 to 6 carbon atoms, a hydroxy or an aryl substituted alkyl group, said alkyl group having from 2 to 6 carbon atoms, an aryl group, an alkyl, an alkoxy, or a halogen substituted aryl group, or a Z-pyridyl group.

2. The process as claimed in claim 1, wherein the compound of the general Formula I is selected from the group consisting of compounds having the general Formulae Ia, Ib and Ic:

l /o=s B it (Ib) and s "T J wherein X is selected from the group consisting of a sulfur atom, an oxygen atom, a selenium atom, a N- group and a CH=CH-- group; wherein A and B each is selected from the group consisting of a hydrogen atom, an alkyl group, a hydroxyl or a halogen substituted alkyl group, said alkyl group having from 1 to 6 carbon atoms, an aryl group, an alkyl, a hydroxyl or a halogen substituted aryl group, an alkoxycarbonyl group,.by the combination of the A and B a trimethylene group and a tetramethylene group, and an atomic group necessary to complete, by the combination of said A and B, a benzene ring and a benzene ring substituted with a member selected from the group consisting of an alkyl group, an aryl group, an alkoxyl group, and a halogen atom; wherein Y is selected from the group consisting of an alkyl group, an alkoxyl group, and an alkylthio group; and wherein R and R" are selected from the group consisting of an alkyl group having from 1 to 6 carbon atoms, a hydroxyl or an aryl substituted alkyl group, said alkyl group having from 2 to 6 carbon atoms, an aryl group, an alkyl, an alkoxy or a halogen substituted aryl group, and a 2-pyridyl group.

3. The process as claimed in claim 2, wherein each of A and B is selected from the group consisting of a hydrogen atom, an alkyl group, a hydroxyl or a halogen substituted alkyl group, said alkyl group having from 1 to 6 carbon atoms, an aryl group, an alkyl, a hydroxyl or a halogen substituted aryl group, an alkoxycarbonyl group, by the combination of A and B a trimethylene group and a tetramethylene group, and an atomic group necessary to complete, by the combination of A and B, a benzene ring and a benzene ring substituted with a member selected from the group consisting of an alkyl group, an aryl group, an alkoxyl group, and a halogen atom; wherein Y is selected from the group consisting of a methyl group, an ethyl group, an n-butyl group, an n-hexyl group, a methoxy group, an ethoxy group, a methylthio group, an ethylthio group and a 2-(4-phenyl- S-thio- 1 ,3,4-thiadiazoline-2-yl -mercaptoethylthio group.

4. The process as claimed in claim 1, wherein the compound of the general Formula I is incorportaed in at least one of the layers selected from the group consisting of the silver halide emulsion layers of the multi-layer type color photographic light-sensitive material and the layers adjacent to the silver halide emulsion layers of the multilayer type color photographic light-sensitive material.

5. The process as claimed in claim 1, wherein the compound of the general Formula I is incorporated in a developer solution.

6. The process as claimed in claim 1, wherein at least one of the silver halide emulsion layers contains a member selected from the group consisting of silver chloroiodide, silver iodobromide and silver chloroiodo-bromide, said layer having an iodine content of from 1 to 10 molar percent.

7. The process as claimed in claim 1, wherein said processing of the multi-layer type color photographic light-sensitive material is using a reversal color system.

8. The process as claimed in claim 7, wherein a dye image is formed by successively developing the light-sensitive material using color developer solutions each containing a ditfusible coupler to be coupled in each different color layer.

9. The process as claimed in claim 7, wherein a dye image is obtained by incorporating each diffusion resisting coupler capable of being coupled in each ditferent color layer in each silver halide emulsion layer of the light-sensitive material and processing the light-sensitive material using color developer solutions containing no couplers.

10. The process as claimed in claim 1, wherein the compound of the general Formula I has the formula (i in.

11. The process as claimed in claim 1, wherein the compound of the general Formula I has the formula CaHl 29 30 12. The process as claimed in claim 1, wherein the 16. The process as claimed in claim 1, wherein the compound of the general Formula I has the formula compound of the general Formula I has the formula c=s s H: N

E III AIHI CH: 1 17. The process as claimed in claim 1, wherein the The process as claimed in claim 1, wherein the compound of the general Formula I has the formula compound of the general Formula I has the formula S HzCS SE=S 1, 15

14. The process as claimed in claim 1, wherein the R Ct 11 compound of the general Formula I has the formula eferences l e UNITED STATES PATENTS 2,742,832 4/1956 Salminen 96-74 0:3 2,353,754 7/1944 Peterson 96-56 2,652,328 9/1953 Sprung 96-74 N 3,026,201 3/1962 Rauch et a1. 96109 5 3,152,905 10/1964 Gaspar 9674 3,161,520 12/1964 Rauch et a1. 96109 15. The process as claimed in claim 1, wherein the 3,252,799 5/1966 compound of the general Formula I has the formula Gotze et 96-109 OH, OTHER REFERENCES I I\ Abbott: Defensive Publication T882,019, J an. 26, 1971.

0:5 I. TRAVIS BROWN, Primary Examiner US. Cl. X.R.