US3756821A - Process for the formation of color photographic images - Google Patents

Abstract

A PROCESS FOR THE FORMATION OF COLOR PHOTOGRAPHIC IMAGES ON A MULTI-LAYER TYPE COLOR PHOTOGRAPHIC LIGHTSENSITIVE MATERIAL HAVING AT LEAST TWO SILVER HALIDE EMULSION LAYERS ON A SUPPORT, WHICH COMPRISES DEVELOPING SAID LIGHT-SENSITIVE MATERIAL WITH A COMPOUND OF THE FORMULA:

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

WHEREIN Q REPRESENTS AN ATOMIC GROUP NECCESSARY TO COMPLETE A HETEROCYCLIC RING, WHICH MAY FURTHER BE SUBSTITUTED AND R IS AN ALKYL GROUP HAVING 1-6 CARBON ATOMS, WHICH MAY FURTHER BE SUBSTITUTED 1-6 CARBON ATOMS, WHICH MAY FURTHER BE SUBSTITUTED OR A PHENYL GROUP, WHICH MAY BE SUBSTITUTED.

Description

United States Patent 3,756,821 PROCESS FOR THE FORMATION OF COLOR PHOTOGRAPHIC IMAGES Jun Hayashi, Reiichi Ohi, and Tadao Shishido, Kanagawa, Japan, assignors to Fuji Photo Film Co., Ltd.,

Kanagawa, Japan No Drawing. Filed Sept. 29, 1971, Ser. No. 184,951 Claims priority, application Japan, Sept. 29, 1970,

5/85,463 US. C]. 96-55 13 Claims ABSTRACT OF THE DISCLOSURE wherein Q represents an atomic group necessary to complete a heterocyclic ring, which may further be substituted and R is an alkyl group having 16 carbon atoms, which may further be substituted or a phenyl group, which may be substituted.

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

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 capability 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 these dyes reduces the color contrast. Hence, the color obtained tends to become dark and 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 interimage effect. 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 color contrast can be defined as follows. A silver halide emulsion layer 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 "Ice samples and one sample (Sample I) 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 eifect as that due to red light exposure. Thus, the lowermost redsensitive 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 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, 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 & C.A. Horton, in Journal of the Optical Society of America, 42, 663-669 (1952) and A. Thiels, in Zeitschritf fur Wissenschaftliche Photographic, 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 a 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 difiicult.

SUMMMARY OF THE INVENTION 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.

As the result of various studies, the inventors of this application 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 elfect occurs markedly if the light sensitive material is developed in the presence of a compound represented by Formula I:

heterocyclic ring and a substituted heterocyclic ring and R is a member selected from the group consisting of an alkyl group having 1-6 carbon atoms, a substituted alkyl group having 1-6 carbon atoms, a phenyl group, and a substituted phenyl group.

DETAILED DESCRIPTION OF THE INVENTION As the ring containing the atomic group necessary for forming a heterocyclic ring, which may be substituted and illustrated by Q in the Formula I, there are illustrated, for example, an imidazole ring, an imidazoline ring, a thiazole ring, a thiazoline ring, a thiadiazole ring, a benzothiazole ring, a benzoimidazole ring, a benzoxazole ring, a beuzoselenazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a triazole ring, a triazine ring, a tetrazole ring, a tetraazaiudene ring, and the like.

When R in Formula I is a hydrogen atom (and not alkyl) which is different from the case of this invention, the compound represented by Formula I becomes a compound having a mercapto group. Such a compound having the mercapto group tends to frequently inhibit strongly the development of silver halide this causing the reduction in sensitivity of a photographic light-sensitive material in development. On the other hand, in the case of the compound of this invention represented by Formula I in which R and Q are as defined above, a high interimage effect is obtained without greatly reducing sensitivity.

Among the compounds of this invention represented by Formula I, the compounds represented by the following General Formulae Ia, Ib, and lo give much better results with particularly less desensitization:

in the General Formulae Ia, Ib and Ic, R has the same meaning as indicated in regard to Formula I, U and V each represent a hydrogen atom, an unsubstituted or substituted alkyl group, an aryl group, an alkoxycarbonyl group, a hydroxyl group, or an atomic group necessary for forming by bonding with each other a saturated or unsaturated ring (which may be substituted) having from to 6 carbon atoms; W represents a hydrogen atom or an alkyl group; X represents S, Se, 0, N--R (where R is a hydrogen atom, an unsubstituted alkyl group having 1-6 carbon atoms, an alkyl group having 1-6 carbon atoms substituted by an aryl group, etc., or a phenyl group), CR =CR (where R; and R each is a hydrogen atom or an atomic group necessary for forming by the bonding each other, a ring), or CR =N (where R is a hydrogen atom, an alkyl group or an S-substituted alkyl group); and Y and Z each represents a nitrogen atom or ill C-Rs (where R is a hydrogen atom, an alkyl group or an S- substituted alkyl group); at least one of Y and Z being a nitrogen atom.

The typical examples of the compounds used in this invention represented by the above general formulae include the following compounds:

Compound 1 Compound 2 Compound 3 Compound 4 Compound 6 Compound 9 Compound 10 Compound 11 Compound 12 Compound 13 Compound 14 Compound 15 Compound 16 SO H (n) N Compound 17 Compound 18 S CH: N

Compound 19 Compound 22 (Elm.

Compound 23 Compound 24 N Ems! Iq-scm,

S C 2H5 Compound 25 QIIITSCHa Compound 26 SCH H N NAN) Compound 27 Compound 28 Compound 29 Compound 30 Compound 31 H, S H,

I SCH; H

Compound 32 Compound 33 mo 4N\ son. U H

These compounds may be prepared by known methods. That is, each of them is prepared by alkylating the corresponding mercapto compound with an alkyl halide. A detailed description may be found, for example, in Berichte der Deutchen Chemischen Gesellschaf vol.. 18, page 2198; ibid.; vol. 21, page 45; ibi vol. 22, page 573; page 1153, and page 1357; ibid.; vol. 23, page 105 and page 968; ibid.; vol. 25, page 2360; ibid.; vol. 28, page 790; Journal of the Chemical Society; 1762 (1935); ibid."; 143 and 470 (1939); and Annalen der Chemie; vol. 236, page 12.

By incorporating the compound of this invention represented by 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 layer 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 multi-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 rnulti-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 5 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 atfect 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 solution, 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, l-phenyl-B-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 as the 1-phenyl-3-pyrazolidone, suitable ones are 1-phenyl-3-pyrazolidone, 1- phenyl-4,4-dimethyl-3-pyrazolidone, and the like.

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-3-methyl N methyl-N-(beta methylsulfoneamidoethyDaniline, 4 amino-3-methyl-N-ethyl-N-(betahydroxyethyl)aniline, and the like.

In increasing the interimage effect by the present invention, the multi-layer type color photographic lightsensitive material can be processed at ordinary processing temperatures, i.e., at from 20 to 30 C., but can be processed at higher temperatures, i.e., at 30 to C. or at an even higher temperature, if desired.

The compound of this invention can be used in any of the processes capable of forming color photographic images. That is to say, in processes for developing multilayer 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 light-sensitive 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 halide 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 dilfusible coupler to be coupled in each different 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 emulsions 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 feature that a developer solution, a coupler, or a dye is diffused from a light-sensitive layer to a reception layer in contact with the light-sensitive layer in proportion to the images in the light-sensitive ayer.

Still further, the compound of this invention can be used in the silver dye bleaching color photographic process, as described in the specification of US. 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 iodobrornide, 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 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 atom, such as sodium thiosulfate, allylthiocarbazide; a gold compound such as a gold (1) 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-S,5-diphenyl-9-ethyl-3,3-di(2-su1foethyl)-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-5-pentadecyl-hydroquinone or 2-methyl-5(l-phenyl-S-tetrazolylthio)-hydroquinone; a stabilizer, such as 4-hydroxy-6- methyl-1,3,3a, 7-tetraazaindene, benzimidazole, or l-phenyl-S-mercaptotetrazole; a hardening agent, such as formaldehyde or mucobromic acid; and a wetting agent, such as saponin or sodium alkylbenzene-sulfonate.

The invention now will be explained in greater detail by reference to the following examples which are considered to be merely illustrative and not limitative of the present invention. In the following examples, two types of color photographic processes are used. That is to say, the so-called coupler in developer type color system, wherein couplers are supplied from color developer solutions, and the so-called coupler-in-emulsion layer type system wherein couplers are incorporated into the photographic emulsion layers of a color photographic lightsensitive material.

In the following examples, in the coupler-in-developer type color system, a 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 mg./ 100 cm.*.

Second layer: Green-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./cm.

Third layer: Yellow filter layer A layer formed by coating a yellow colloidal silver dispersion containingv 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./

Also in the examples shown below rating to the coupler-in-developer type color system, the multi-layer type photographic light-sensitive material was processed using the following procedures:

(16) Water washing and drying The temperatures of the processing baths in the above process were 27 C. The compositions of the baths are as shown below:

Hardening bath:

Sodium hexametaphosphate g 2.0 Sodium bisulfite g 5.0 Sodium pyrophosphate (IOH 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 1,000 cc. Negative developer solution:

N-methyl-p-aminophenol sulfate g 5 .0 Sodium sulfite g 79.0 Hydroquinone g 2.0 Sodium hydroxide 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% G-nitrobenzoindazole nitrate cc 5.0 Water added to make the total volume to 1,000 cc. Cyan color developer solution:

Potassium bromide g 2.9 1% 6-m'trobenzoimidazole 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-B-methyl-N-ethyl-N (beta hydroxyethyl)-aniline sulfate g 2.5 Sodium hydroxide g 3.4 l-hydroxy-N-(2 propionamidophenethyl) 2- naphthamide g 1.5 2,4-dichloro-l-naphthol g 0.2 2-methyl-2,4-pentanediol ....cc.. 10.0 Polyoxyethylene-methylphenyl ether g 0.5 'Monobenzyl-p-aminophenol hydrochloride g-.. 0.4 p-Aminophenol hydrochloride g 0.1

Water added to make the total volume to 1,000 cc.

Water added to make the total volume to 1,000 cc. Magenta color developer solution:

Cone. 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 methylsulfonamideethyl)-aniline sulfate g 2.0 Ethylene diamine cc 6.0 Sodium hydroxide cc 0.3 1-(2,4,6-trichlorophenyl)-3-(4-nitroanilino) 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 1,000 g. Bleaching solution:

Potassium ferricyanide g 100.0

Potassium bromide g 30.0

Water added to make the total volume to 1,000 cc. Fixing solution:

Sodium thiosulfate g 125.0

Sodium sulfite g 9.0

Water added to make the total volume to 1,000 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 cmP.

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

Third layer: Red-sensitive silver halide emulsion/layer A layer formed by coating a high speed gelatino silver iodobromide 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-Z-naphthamide in tricresyl phosphate and dispersing the solution in gelatin) so that the amount of silver is mg./100 cm.

Fourth layer: Intermediate layer A layer formed by coating gelatin in an amount of 13.4 mg./100 cmfl.

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

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

Seventh layer: Blue-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-benzoyl-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 a 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:

Process: Time (min.) Hardening bath 1 Water washing 1 First development 3 Water washing 0.5 Reversal exposure Second development 4 Water washing 1 Bleaching 1 Water washing 0.5 Fixing 1 Water washing 1 The temperatures of the above-described processing baths in the procedure were 30 C. The compositions of the processing baths were as shown below:

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 1,000 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 5.0 Potassium thiocyanate g 1.0

Water added to make the total volume to 1,000 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 volume to 1,000 cc.

13 Bleaching solution:

Ferricyanide g 100 Sodium acetate g.. 40 Glacial acetic acid g 20 Potassium bromide g 30 Water added to make the total volume to 1,000 cc.

Fixing solution:

Sodium thiosulfate g 150 Sodium acetate g 70 Sodium sulfite g 10 Potassium alum g 20 Water added to make the total volume to 1,000

EXAMPLE According to the above-described technique, two types of multi-layer 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-i-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 m/7 wherein 7 represents the gamma value of the cyan dye image when the sample is exposed to red light, while 7 represents the gamma value of the cyan dye image when the sample is exposed to white light). Also, the interimage effect 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 E=-0.6 of the cyan dye image when exposed to red light)]. In other words, if the interimage efiect to the cyan dye image is larger, the ratio Y /7 is higher and also the A log E becomes larger.

The results obtained are shown in Table 1.

The results in Table 1 show clearly that by incorporating the Compounds 1, 8, 9, 21, 3 and 32, the values 'y /'y and A log E are increased and thus the interimage effect is increased.

14 EXAMPLE 2 According to the above-described 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, were 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 the ratio y /w 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, after which 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 /7 and the sensitivity value 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):

N SH N 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. 1 to No. 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 Amount S (relative (mg/mole sensitivity of blueof blue- Experlment sensitive sensitive Number Compound AgX) ynl'yw layer) 0 1. 18 100 6 1. 20 103 60 1. 31 101 600 1. 45 101 1, 500 1.58 200 1. 35 400 1. 51 97 200 1. 29 95 o 400 1.44 95 Compound 11...... 200 1. 25 98 do 400 1.41 93 TABLE 2Continued Amount S (relative (mg/mole sensitivity of blue of blue- Experiment sensitive sensitive Number Compound AgX) ya/1w l y r) 2 Control 1.12 100 Compound l2. 200 1. 30 99 -..-.do 400 1.45 06 Compound 13. 200 1. 31 98 .do 400 1.58 200 1. 26 400 1. 40 200 1. 26 400 1. 53 200 1. 37 400 1.51

3 Control 0 1.16 Compound 18 200 1.33 ..-..do- 400 1.47 Compound 200 1. 31 o 400 1.58 Compound 20 200 1. 36 ....-do 400 1.48 Compound 23 200 1. 32 -..do 400 1.48 90 Compound 24 200 1. 36 99 ..do. 400 1.44 93 4 Control 0 1. 13 100 Compound 26.. 200 1. 28 98 .do 400 1.48 96 Compound 27. 200 1. 30 97 ..do 400 1.45 91 200 1. 99 400 1. 40 90 200 1. 20 55 o 400 1.29 32 Compound Y..-. 200 1. 25 49 do 400 1.30

From the results shown in Table 2, it can be seen that by incorporating compounds 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 R is a hydrogen atom (i.e., Compound X or Y which can assume a mercapto form on enolation) the value of 7 /7 becomes larger, but the sensitivity is greatly reduced.

As shown above the compounds of this invention have the advantages of increasing the interimage elfect 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 1ight+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 the 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 'y /y 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. From the table it can be seen that by incorporating the compounds of this invention in the negative developer 16 solution, the interimage eifect was increased in the yellow dye layer, magenta dye layer and cyan dye layer.

TABLE 3 Amount (mg/liter) of negative Co p op YR/1w 'vo/vw YB/7W Control 0 1.13 1.05 1.00 d 5 5 1.16 1.07 1.01 50 1.30 1.15 1.01 200 1.38 1.21 1.03 500 1.50 1.28 1.04 50 1.25 1.18 1.02 200 1.35 1.23 1.03 50 1.28 1.20 1.01 200 1.37 1.25 1. 05 50 1.33 1.22 1.01 200 1.41 1.27 1.04 50 1.31 1.21 1.03 200 1.44 1.29 1.03 50 1.29 1.18 1.02 200 1.45 1.30 1.05

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 Compounds 4, 5, 31 and 33 were 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 and YB/7w were obtained by measuring the densities in the same manner as in Example 3.

The results are shown in Table 4.

TABLE 4 Com- Layer pound Amount YR/7W 'rol'rw YB/"(W COIllJl'Ol 0 1.29 1.16 1.08 Protective layer 4 l 6 1.31 1.18 1.09 DO 4 60 1.48 1.22 1.11 4 600 1.60 1.30 1.15 4 1,500 1.71 1.34 1.18 5 2 200 1.41 1.20 1.13 5 400 1.60 1.31 1.16 31 a 200 1.35 1.18 1.11 31 400 1.55 1.28 1.14 33 3 200 1.38 1.19 1.11 33 3 400 1.59 1.30 1.15

1 6 Mg./ gr. gelatin. 2 Mg./mole AgX. B Mg./100 gr. gelatin.

When other compounds represented by the general Formula 1, other than the compounds described in Examples 1, 2, 3 and 4 were used, similar better results were obtained. Also, when other developing procedures other than those described in the above examples were employed, similar excellent results were obtained.

Although the present invention has been adequately described in the foregoing specification and examples included therein, it is readily apparent that various changes and modifications can be made without departing from the spirit and scope thereof.

What is claimed is:

1. 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 of the Formula I:

wherein Q represents an atomic group necessary to complete a heterocyclic ring which may be substituted with a member selected from the group consisting of a hydrogen atom, an alkyl group, a substituted alkyl group whose substituent is a hydroxy group, an aryl group, or an alkoxycarbonyl group, and wherein R is selected from the group consisting of an alkyl group and a substituted alkyl group having 1-6 carbon atoms whose substituents are selected from the group consisting of a hydroxy group and a phenyl group and an unsubstituted or substituted phenyl group whose substituent is a carboxy group, said compound serving to impart high saturation to the images thus obtained, unaccompanied by attendant reduction in sensitivity.

2. The process of claim 1, wherein the heterocyclic ring completed by Q is in the series selected from the group consisting of the imidazole ring series, the imidazoline ring series, the thiazole ring series, the thiazoline ring series, the thiadiazole ring series, the benzothiazole ring series, the benzoimidazole ring series, the benzoxazole ring series, the benzoselenazole ring series, the pyridine ring series, the pyrimidine ring series, the quinoline ring series, the triazole ring series, the triazine ring series, the tetrazole ring series, and the tetrazaindene ring series.

3. The process of claim 1, wherein the compound of the General Formula I is selected from the group consisting of compounds having the General Formulae Ia, lb and 1c.

wherein R is selected from the group consising of an alkyl group and a substituted alkyl group containing 1-6 carbon atoms whose substituents are selected from the group consisting of a hydroxy group and a phenyl group and an unsubstituted or substituted phenyl group whose substituent is a carboxy group; U and V each represent a member selected from the group consisting of a hydrogen atom, an unsubstitutedor substituted alkyl group whose substituent is a hydroxy group, aryl group, alkoxycarbonyl group, hydroxyl group and an atomic group necessary for forming a saturated or unsaturated ring, which may have been substituted with a member selected from the group consisting of a methyl group and a chlorine atom having from 5 to 6 carbon atoms; W represents a member selected from the group consisting of a hydrogen atom and an alkyl group; X represents a member selected from the group consisting of S, Se, 0, NR where R is a member selected from the group consisting of a hydrogen atom, an unsubstituted alkyl group having 1-6 carbon atoms, an alkyl group having 1-6 carbon atoms substituted by an aryl group, or a phenyl group,

-CR =CR where R and R are each a member selected from the group consisting of a hydrogen atom and an atomic group necessary for forming by bonding with each other a ring, and CR =R-, where R; is a member selected from the group consisting of a hydrogen atom, an alkyl group and an S-substituted alkyl group; and Y and Z each represent a member selected from the group consisting of a nitrogen atom and where R is a member selected from the group consisting of a hydrogen atom, an alkyl group and an S-substituted alkyl group; at least one of Y and Z being a nitrogen atom.

4. The process of claim 1, wherein the compound of Formula I is incorporated 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 multi-layer type color photographic light-sensitive material.

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

6. The process of 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 of claim 1, wherein said processing of the multilayer type color photographic light-sensitive material is employing a reversal color system.

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

9. The process of claim 7, wherein a dye image is obtained by incorporating each diffusion resisting coupler capable of being coupled in each different 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 of claim 1, wherein the compound of Formula I is incorporated into the silver halide emulsion layer in an amount of 0.006 to 1.5 g. per mole of silver halide.

11. The process of claim 1, wherein the compound of Formula I is incorporated into a layer adjacent said silver halide emulsion layer in an amount of 0.006 to 1.5 g. per 100 g. of gelatin.

12. The process of claim 1, wherein the compound of Formula I is incorporated in a developer solution in an amount of 0.1 mg. to 1.0 g. per liter of solution.

13. The process of claim 12, wherein said amount ranges from 5 mg. to 500 mg. per liter of solution.

References Cited UNITED STATES PATENTS 3,212,892. 10/ 1965 Konig et al 96--66 R 3,379,529 4/1968 Porter et al 9695 3,554,756 1/1971 Terashima et al 96-55 3,623,872 11/ 1971 Berthold et al. 96-95 2,553,498 5/1951 Duerr 96-59 3,420,664 1/ 1969 Dersch et al. 96--95 3,591,609 7/1971 Silverman 96-66 R NORMAN G. TORCHIN, Primary Examiner R. L. SCHILLING, Assistant Examiner U.S. Cl. X.R. 96-59, 66,