GB2083242A - A multi-layered silver halide color photographic material - Google Patents

Abstract

In order to overcome problems associated with providing a sharp image without causing desensitization, a multi-layered silver halide color photographic material wherein blue-, green- and red-photosensitive silver halide emulsion layers are provided on one side of a support has a coupler in the photosensitive layer furthest from the support which, upon colour development, yields a dye having a larger molecular extinction coefficient than those of the dyes formed by the couplers in the underlying layers. Preferably the material is a 'false colour' material and may contain magenta or cyan couplers in an outermost blue- photosensitive silver halide emulsion layer.

Description

SPECIFICATION A multi-layered silver halide color photographic material The present invention relates to a multi-layered silver halide color photosensitive material, particularly to a novel multi-layered silver halide color photosensitive material for taking photographs utilizing a negative-positive printing process wherein the sharpness thereof is improved (hereinafter referred to as the multi-layered color photosensitive material).

In recent years, the miniaturization of photographic camera body is being still more accelerated. To miniaturize cameras in size, there are the ways that cameras are miniaturized without changing any size of multi-layered color photosensitive material to be used and any picture size thereof, and that multi-layered color photosensitive material to be used is miniaturized or a picture size is miniaturized and then cameras are miniaturized. The former way is irrelevant to the photographic performance of a multi-layered color photosensitive material because miniaturization of cameras can be accomplished by miniaturizing camera parts, however, there is a limination of its own accord to miniaturize such cameras.

On the other hand, the latter way is a more efficient one to enable cameras to be immensely miniaturized.

However, the smaller a picture size of a multi-layered color photosensitive material is, the larger the magnification of a photographic enlargement to make a print in the same size becomes, so that the print image quality will be worsen in sharpness. Therefore, to miniaturize a picture size of a multi-layered color photosensitive material and to miniaturize a camera, it is necessary to get multi-layered color photosensitive materials having a high image quality and an excellent sharpness in a photographic performance.

Developments of the multi-layered color photosensitive materials having photographic performance of high quality image as described above is desired.

By the several important and commonly known reasons, multi-layered color photosensitive materials of substractive color processing type contain at least three different layers having been coated onto a support such as cellulose ester or polyester. Generally, the layer coated nearest the support contains silver halide and cyan couplers out of which the former is spectrally sensitized in a red color gamut of visible spectrum.

And, generally, on said layer, there is a silver halide layer which is spectrally sensitized in a green color gamut of visible spectrum and contains magenta couplers. As the third layer on said green-sensitive layer, there is a silver halide layer which is substantially sensitive only to the blue color gamut of the visible spectrum and contains yellow couplers.

The processes to improve sharpness of multi-layered color photosensitive materials have so far been variously developed.

The technology relating to the improvements of an image sharpness are roughly classified into the process utilizing development effects and the process utilizing optical effects.

As for the technology for improving a sharpness by utilizing development effects that is a technology wherein a concentration gradient of an inhibitory substance in development process, there are given the examples of concrete processes such as the process wherein a development solution is diluted with water, the process wherein stirring is done slowly in developing process and the process making the compound which reacts to oxide of a developing agent and releases developing inhibitors contain into a photosensitive material, and the last of which is particularly distinguished in the improvement effects among them. As for the compounds of the above type, there are the well-known compounds, for example, the ones as described in the U.S.Patents No. 3,148,062 and No.3,227,554, wherein dyes are produced by coupling to oxides of a developing agent and developing inhibitors are released therefrom (hereinafter referred to as DIR coupler), or, the ones as described in the U.S. Patent No. 3,632,345, wherein developing inhibitors are released therefrom by coupling to oxides of a color developing agent but no dye is produced (hereinafter referred to as DIR substance). (Hereinafter collectively referred to as DIR compound for the abovementioned DIR coupler and DIR substance). Especially, said DIR compound has the excellent characteristics in the effects in sharpness improvements made by utilizing a development effects.

On the other hand, as for the technology for improving sharpness by utilizing the aforesaid optical effects, there are given the technology such as the one utilizing a prevention method against light scattering caused in a multi-layered color photosensitive material, through silver halide grains therein, the ones utilizing a prevention method against halation caused from a support or the like, or the ones utilizing a device of layer constitution.

For example, there are given the methods such as the ones reducing the amount of silver halide as described in the Japanese Patent Publication Open to Public Inspection Nos. 117032/1976 and 115219/1977; the ones wherein a portion of blue-photosensitive layer is positioned underneath a green-photosensitive layer or red-photosensitive layer and the effective sensitivity of the blue- photosensitive layer is left as it is maintained and then the influence of light scattering upon the green-photosensitive layer is lessen; the ones wherein a portion of green-photosensitive layer described in the Japanese Patent Examined Publication No.

37018/1978 is positioned as the uppermost layer; and the irradiation or halation prevention method wherein acid dyes are mordantly processed with minute coacervate grains of cationic nitrogen activator. However, even if any method utilizing either development effects or optical effects which has so far been known is wisely used, it has still been unable to obtain a desired performance. It has been found in the method utilizing the optical effects inter alia a sharp desensitization or a worsen color pureness.

It is an object of the present invention to eliminate the defects of the aforesaid technology which have so far been known, and particularly to provide a multi-layered color photosensitive material giving a dye image of excellent sharpness without causing any desensitization.

Other objects of the invention will become apparent from the following description of the invention.

The inventors of the invention have devoted themselves to study to accomplish the above described objects and consequently found that the objects of the invention can be accomplished by making use of the following multi-layered color photosensitive material.

That is to say, a multi-layered color photosensitive material of the invention comprises a bluephotosensitive silver halide emulsion layer, a green-photosensitive silver halide emulsion layer and a red-photosensitive silver halide emulsion layer on the same side of the transparent support thereof, and among the three kinds of the said emulsion layers, the blue-photosensitive silver halide emulsion layer contains any one out of the three kinds of nondiffusion couplers, that is, a yellow coupler, a magenta coupler and a cyan coupler which react with oxide in aromatic primary amine color developing agent and can produce dyes; the green-photosensitive silver halide emulsion layer comprised either one of the two kinds of couplers which are not comprised in said blue-photosensitive layers, out of the said three kinds of the couplers; and the red-photosensitive silver emulsion layer comprises the one kind of the coupler which is not comprised in anyone of the said blue-photosensitive silver halide emulsion layer and said green-photosensitive silver halide emulsion layer; and also a photosensitive silver halide emulsion layer positioning at the farthest place from said support comprises a nondiffusion coupler producing dye having the larger molecular extinction coefficient than that of a dye being produced by a nondiffusion coupler in the silver halide emulsion layer positioning at the place between said photosensitive silver halide emulsion layer positioning at the farthest place and said support; and the multi-layered color photosensitive materials of the invention are characterized in the above.

In the present invention, the combination of the three kinds of anti-diffusive couplers to be respectively contained in the three kinds of silver halide emulsion layers having the different color-sensitivity from each other is arbitrarily selectable from the publicly known nondiffusion couplers within the scope that a value of molecular extinction coefficient of a dye to be produced with said couplers and oxides of a color developing agent will satisfy the conditions of the invention.

With respect to the values of a molecular photoabsorption coefficient of a dye (hereinafter referred to as a color dye) which is to be produced with the anti-diffus# ~jscouplers of the invention and oxides of a color developing agent and to the measurement methods thereof, there have been the descriptions thereof in the Theory of the Photographic Process, 4th edition, p. 353 - 361; Journal of American Chemical Society, July 1949 issue, p. 2287 - 2290; ditto, March 1971 issue, p.919 - 926; ditto, June 1957 issue, p. 2919 - 2927; Photo Science and Engineering, vol.5, Num. 4. 1961 edition, p. 195 - 197; and so on.

In the embodiments of the invention, it is preferable when the molecular extinction coefficient of the color dyes in the coupler contained in a photosensitive silver halide emulsion layer positioning at the farthest place from the support side is larger by 5 x 103 ##or more than that of the color dyes by the couplers contained respectively in the other two kinds of photosensitive silver halide emulsion layers having different photosensitivity from each other, and is more preferable when the former is larger by 1 x 104 or more than the latter coefficient.

In the invention, a photosensitive silver halide emulsion layer positioning at the farthest place from a transparent support is desirably to be the one of blue-photosensitiveness from the viewpoint of color reproductivity.

The more preferable case is that red-photosensitive silver halide emulsion layer, green-photosensitive silver halide emulsion layer and blue-photosensitive silver halide emulsion layer are arranged in the order from the support side. And, as for the couplers to be contained in a photosensitive silver halide emulsion layer positioning at the farthest place from the support, anti-diffusive magenta or cyan couplers are preferable, among which the former is particularly preferable.

The most preferable embodiment of the invention is that the photosensitive silver halide emulsion layer positioning at the farthest place from the support is of blue-photosensitive, and that anti-diffusive magenta couplers contain therein.

As for the preferable anti-diffusive magenta couplers among the ones described above, they are given as 5-pyrazolone couplers which have so far been known, among which 1-phenyl-5-pyrazolone coupler is preferable, and on the other hand, as for the preferable anti-diffusive cyan couplers, they are given as naphthol couplers which have so far been known as well.

In the multi-layered color photosensitive material of the invention, it can be used therein pyrazolone compounds, indazolone compounds and cyanoacetyl compounds as to anti-diffusive magenta couplers; phenol compounds and naphthol compounds as to anti-diffusive cyan couplers; and a-acylacetanilide as to anti-diffusive yellow couplers, etc.

As for anti-diffusive magenta couplers, they can be given the ones described in U.S. Patent Nos. 2,600,788; 3,558,319; 3,468,666; 3,419,391; 3,311,476 and 3,253,924; British Patent No.1,293,640; and U.S. Patent Nos.

2,434,272; 3,476,564 and 3,476,560, as the examples thereof.

As for anti-diffusive cyan couplers, they can be given the ones described in U.S. Patent Nos. 2,369,929; 2,474,293; 3,591,383; 2,895,826; 3,458,315; 3,311,476; 3,419,390; 3,476,563 and 3,253,924; British Patent No.

1,201,110; and U.S. Patent Nos. 3,034,892; 3,386,301 and 2,434,272, as the examples thereof.

The amount to be used of anti-diffusive couplers of the invention is normally 2 x 103 ##mol to 5 x 10-1 mol, preferably 1 x 10-2 mol to 5 x 10-1 mol per mol of silver in photosensitive silver halide emulsion.

As for the diffusion processes of anti-diffusive couplers, a variety of the processes such as the so-cailed alkaline solution diffusion process, solid diffusion process, latex diffusion process and oil drop-in-water type emulsification diffusion process, can be taken and they are suitably selectable according to chemical structures of anti-diffusive couplers, etc.

For the invention, latex diffusion process and oil drop-in-water type emulsification diffusion process are particularly effective. These diffusion processes have so far been well known and among them latex diffusion process and the effectiveness thereof have been described in Japanese Patent Publication Open to Public Inspection Nos. 74538/1974,59943/1976 and and32552/1979, and Research Disclosure, vol. No. 14850, pp.

77 - 79, August, 1976.

The suitable latexes are, for example, homopolymers, copolymers and terpolymers of monomers such as styrene, ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, 2-aceto-acethoxyethyl methacrylate, 2- (methacryloyloxy) ethyltrimethyl ammonium methosulfate, 3-(methacryloyloxy) propane-1 -sodium sulfonate, N-iscpropylacrylamide, N- [ 2-(2-methyl-4-oxopentyl) ] acrylamide, and 2-acrylamide-2-methylpropane sulfonic acid. As for oil drop-in-water type diffusion processes, any process having so far been publicly known can be used, wherein hydrophobic additives such as couplers are made to diffuse.

As for silver halide to be used in silver halide emulsion layer of the multi-layered color photosensitive materials relating to the present invention, any arbitrary materials such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide and silver chloroiodobromide to be used in normal type of silver halide photographic emulsions, are included therein.

These silver halide grains may be either coarse grains or fine grains and the distribution of grain diameter may also be either narrow or wide. And, the crystals of these silver halide grains may be either normal cyrstals or twin and also the ratio of [100] surface to [ 111 ] surface can be applied arbitrarily. Further, the crystal structures of said silver halide grains may be either of uniformity from the inside to the outsjde thereof or of the layer structures of the inside and outside heterogeneous from each other. Also, said silver halide may be either of the types that a latent image is made to form mainly on a surface or of the types that a latent image is made to form inside the grains thereof. These silver halide grains can be prepared by taking a publicly known process that has been commonly used by the skilled in the art.

It liris desirable to remove soluble salts from silver halide emulsion to be used in the invention, but it is possible to use those without removing soluble salts. Also it is possible to mixedly use two or more kinds of silver halide emulsions which have been prepared separately from each other in advance.

As for the binders for silver halide emulsion layers of the multi-layered color photosensitive materials of the invention, the conventionally known binders are used for, and for example, gelatin derivatives such as gelatin, phenylcarbamyl gelatin, acylated gelatin and phthalic gelation are given. The each of these binders can be used in form of two or more compatible mixtures as occasion demands.

Silver halide photographic emulsions, wherein the aforesaid silver halide grains were dispersed in binder solution, can be sensitized by the use of a chemical sensitizer. The chemical sensitizers which can effectively be used along with such emulsions, are classified roughly into four kinds thereof, namely noble metal sensitizers, sulfur sensitizers, selenium sensitizers and reduction sensitizers.

As for noble metal sensitizers, gold compounds and compounds of ruthenium, rhodium, iridium, platinum, etc. can be used for.

And, when gold compounds are used, ammonium thiocyanate and sodium thiocyanate can jointly be used therewith.

As for sulfur sensitizers, active gelatins as well as sulfuric compounds can be used for.

As for selenium sensitizers, active or inactive selenium compounds can be used for.

As for reduction sensitizers, there are given as monovalent tin salts, polyamine, bisalkylaminosulfide, silane compounds, iminoaminomethane sulfinic acid, hydrazinium salts, hydrazine derivatives, etc.

In the multi-layered color photosensitive materials of the invention, a variety of additives effective for photosensitve materials such as stabilizers, development accelerators, emulsion layer hardeners, surface active agents, contamination inhibitors, lubricants, and ultra-violet ray absorbents, can be used, besides the aforegiven additives.

Silver halide multi-layered color photosensitive materials of the invention may suitably have auxiliary layers such as protective layers, inter-layers, filter layers, anti-halation layers and backing layers, besides silver halide emulsion layers.

As for supports, any support such as plastic film, plastic laminated paper baryta paper, and synthesized paper which have so far been known, can suitably be selected for each purpose of using photosensitive materials. These supports are normally subbing-layered so as to strengthen the adhesion to photographic emulsion layer.

in the multi-layered color photosensitive materials of the invention, an image can be obtained through a color development process having normally been taken after an exposure was made to light. In a fundamental process taken through the negative-positive process, color development, bleaching and fixing processes are included therein. There are the cases that each fundamental process is taken independently, while there are also the cases that, instead of taking two or more processes, only a single process is taken with a solution having the aforesaid functions.For example, a monobath color development process containing color developing agent, ferric salt bleaching constituent and thiosulfate fixing constituent, or monobath bleach-fix process containing iron (III) ethylenediamine tetraacetate complex salt bleaching constituent and thiosulfate fixing constituent.

There is no particular restriction to the processes of multi-layered color photosensitive materials of the invention, and any process can be applied thereto. For example, the typical processes are given as follows; the process in which, after color development was made, bleaching and fixing processes are taken and, if necessary, washing and stabilizing processes are further taken; the process in which, after color development was made, bleaching and fixing are made separately and if occasion demands washing and stabilizing processes are further taken; or, the process in which prehardening, neutralizing, color developing, stopping-fixing, washing, bleaching, fixing, washing, after hardening and washing are made in order; the process in which color developing, washing, supplementary color developing, stopping, bleaching, fixing, washing, and stabilizing are made in order; the development process in which, after halogenation-bleached developed silver produced by color development, the amount of produced color dyes is increased by another color development; and the process in which a less silver contained photosensitive material is processed by making use of amplifier such as peroxide and cobalt complex salts; and any process among which can be used to process.

As for aromatic primary amine color developing agents, any one of p-phenylenediamine series and any one of p-aminophenol series can be given and the former is the typical among them.

Also, it can be used by adding color developing agent into a multi-layered color photosensitive material.

As for the precursors of color developing agents to be used in the invention, Schiff's base types of color developers described in U.S. Patents No.2,507,114, No.2,695,234 and No.3,342,599, and Research Disclosure, vol. 151, No. 15159, Nov., 1979 and those described in Research Disclosure, vol. 129, No. 12924, Oct., 1976, ibid., vol. 121, No. 12146, Jun., 1974, ibid., vol. 139, No. 13924, Nov., 1975, etc., can be applied to.

And, if occasion demands, a variety of additives can be added into color developing solution.

It is possible to form a natural color image on a photosensitive material for print use by making use of the multi-layered color photosensitive materials of the invention, and here follows the combinations of multi-layered color photosensitive material and photosensitive material for print use to be used in the said occasion and the combinations of photosensitive silver halide emulsion layer and anti-diffusive coupler in the respective occasions thereof: (1) Combination of multi-!ayered color photosensitive material A and photosensitive material for print use B: Multi-layered color photosensitive material:: A multi-layered color photosensitive material having red-photosensitive silver halide emulstion layer containing anti-diffusive cyan couplers, green-photosensitive silver halide emulsion layer containing anti-diffusive yellow couplers and blue-photosensitive silver halide emulsion layer containing anti-diffusive magenta couplers, on the support thereof.

Photosensitive material for print use A: Photcsensitive material for print use having red-photosensitive silver halide emulsion layer containing anti-diffusive cyan couplers, green-photosensitive silver halide emulsion layer containing anti-diffusive yellow couplers and blue-photosensitive silver halide emulsion layer containing anti-diffusive magenta couplers, on the support thereof.

(2) Combination of multi-layered color photosensitive material B and photosensitive material for print use B: Multi-layered color photosensitive material B: Multi-layered color photosensitive material having red-photosensitive silver halide emulsion layer containing anti-diffusive magenta couplers, green-photosensitive silver halide emulsion layer containing anti-diffusive yellow couplers and blue-photosensitive emulsion layer containing anti-diffusive cyan couplers, on the support thereof.

Photosensitive material for print use B: Photosensitive material having red-photosensitive silver halide emulsion layer containing anti-diffusive yellow couplers, green-photosensitive silver halide emulsion layer containing anti-diffusive cyan couplers and blue-photosensitive silver halide emulsion layer containing anti-diffusive magenta couplers, on the support thereof.

As for the basic materials and additives to be used in photosensitive materials to be used in this case, any conventional type of photosensitive materials which have so far been known, can be used.

Thanks to the present invention, it has become possible to remarkably improve the sharpness of color dye images to be obtained in a multi-layered color photosensitive material, particularly those to be obtained in an emulsion layer coated on the furthest position from the support out of the emulsion layers having the different color photosensitivity from that of the emulsion layer coated on the furthest position from the support side.Especially, it is preferable when the emulsion layer positioning in the middle among the three different color sensitive emulsion layers from each other, is green-photosensitive one, because of the following reason: That is, the sharpness of color dye images to be formed on the green-photosensitive silver halide emulsion layer of a multi-layered color photosensitive material has a great influence upon the quality of photosensitive materials for print use which are the final photographic products.

The present invention is illustrated by the following examples, however, it is to be understood that the invention is not limited thereto.

EXAMPLE 1 Sample 1: Sample 1 has been prepared by coating with each layer in order of the following steps, onto triacetate base having been coated with an antihalation layer: 1 sot layer: 1 -hydroxy-N- [ 4-(2,4-di-t-amylphenoxy)butylj-2-naphthoamide, that is an antidiffusive cyan coupler, of 10.6 g were heatedly dissolved in 10.6 ml of tricresyl phosphate and 20 ml of ethyl acetate. The solution thus obtained was mixed with 20 ml of 10% solution of sodium alkyl naphthalene sulfonate and 200 mi of 5% solution of gelatin, and the mixture thereof was emulsified and dispersed by a colloidal mill, and the dispersive solution C-l thus obtained was added into 1 kg of red-photosensitive silver iodobromide emulsion (containing 4 mol% of silver iodide), and the material thus obtained was coated to prepare the layer.

2nd layer: The interlayer containing 0.5 g/m2 of gelatin and 0.1 g/m2 of 2,5-di-t-octyl hydroquinone was coated to serve as the layer.

3rd layer: 1-(2,4,6-trichlorophenyl)-3- [ 3-a(2,4-di-t-amylphenoxy acetoamide)benzamide]-5-pyrazolone, that is anti-diffusive magenta coupler, of 15 g were heatedly dissolved in the mixture of 30 ml of ethylacetate and 15 ml of tricresyl phosphate. The solution thus obtained was mixed with 20 ml of 10% sodium alkylnaphthalene sulfonate solution and 200 ml of 5% gelatin solution, and the mixture thereof was emulsified and dispersed by a colloidal mill, and the dispersive solution M-1 thus obtained was added into 1 kg of green photosensitive silver iodobromide emulsion (containing 4 mol% of silver iodide), and the material thus obtained was coated to prepare the layer.

4th layer: The yellow filter layer containing 0.12 g/m2 of yellow colloidal silver, 0.07 g/m2 of 2,5-di-t-octyl hydroquinone and 0.9 g/m2 of gelatin was coated to serve as the layer.

5th layer: #pivaIoyI-a(1 -benzyl-1 ,3-imidazole-2,4-dion-3-yl)-2-chloro-5- [ y-(2,4-di-t- amylphenoxy)butaneamide ] acetanilide, that is antidiffusive yellow coupler, of 17 g were heatedly dissolved in 30 ml of ethylacetate and 15 ml of dibutyl phthalate. The solution thus obtained was mixed with 20 ml of 10% sodium alkylnaphthalene sulfonate solution and 200 ml of 5% gelatin solution, and the mixture thereof was emulsified and dispersed by a colloidal mill, and the dispersive solution Y-1 thus obtained was added into 1 kg of blue-photosensitive silver iodobromide (containing 4 mol% of silver iodide), and the material thus obtained was coated to prepare the layer.

6th layer: The protective layer containing 1.3 g/m2 of gelatin and 1 ,2-bisvinylsulfonyl ethane was coated to serve as the layer.

Sample 2: Sample 2 was prepared in the similar process to that of sample 1, except that 3rd and 5th layers of sample 1 were replaced by the undermentioned 3rd and 5th layers.

3rd layer: a-pivaloyl-a(1 -benzyl-1,3-i midazole-2,4-dion-3-yl)-2-chloro-5 [ y-(2,4-di4- amylphenoxy)butaneamide]acetanilide, that is antidiffusive yellow coupler, of 17 g were heatedly dispersed in 30 ml of ethyl acetate and 15 ml of dibutyl phthalate. The solution thus obtained was mixed with 20 ml of 10% sodium alkylnaphthalene sulfonate solution and 200 ml of 5% gelatin solution, and the mixture thereof was emulsified and dispersed by a colloidal mill. The dispersive solution thus obtained was added into 1 kg of green-photosensitive silver iodobromide (containing 4 mol% of silver iodide), and the material thus obtained was coated to prepare the layer.

5th layer: 1 -(2,4,6-trichlorophenyl)-3- [ 3-(2,4-di-t-amylphenoxyacetamide)benzamide ] -5-pyrazolone, that is antidiffusive magenta coupler, of 15 g were heatedly dissolved in 30 ml of ethyl acetate and 15 ml of tricresyl phosphate. The solution thus obtained was mixed with 20 ml of 10% sodium alkylnaphthalene sulfonate solution and 200 ml of 5% gelatin solution, and the mixture thereof was emulsified and dispersed by a colloidal mill. The dispersive solution thus obtained was added into 1 kg of blue-photosensitive silver iodobromide emulsion (containing 4 mol% of silver iodide), and the material thus obtained was coated to prepare the layer.

Sample 3: Sample 3 was prepared in the similar process to that of sample 2, except that antidiffusive magenta coupler used in 5th layer of sample 2 was replaced by 1-(2,4,6-trichloro)phenyl-3- [ 5-octadecenyl succinimide)-2-chloro]anilino-5-pyrazolone.

Sample 4: Sample 4 was prepared in the similar process to that of sample 2, except that 1st and 5th layers of sample 2 were replaced by the undermentioned 1 st and 5th layers; 1 sot layer: The dispersed solution M-1 used in sample 1 was added into 1 kg of red-photosensitive silver iodobromide emulsion (containing 4 mol% of silver iodide), and the material thus obtained was coated to prepare the layer.

5th layer: The dispersive solution C-1 used in sample 1 was added into 1 kg of blue-photosensitive silver iodobromide emulsion (containing 4 mol% of silver iodide), and the material thus obtained was coated to prepare the layer.

TABLE 1-1 Blue-photosensitive Layer Green-photosensitive Layer Sample Amount coated, Thickness Amount coated, No mole2 of emulsion mole/m2 Coupler AgX ctd. Coupler AgX Other than 1 the invention 1.86x10-5 1.86x10-4 8.8 1.39x10-5 1.39x10-4 2 The invention 1.39x10-5 1.39x10-4 6.8 2.20x10-5 1.39x10-4 3 ,, 1.26x10-5 1.26x10-4 5.7 Other than 4 the invention 1.70x10-5 1.70x10-5 8.3 And, the molecular photoabsorption coefficient of coloring matter of each coupler used was measured in the manner that said coloring matter was dissolved in the solution of ethyl acetate and n-butanol of which mixing ratio is 1::1 to prepare the solution of 5 x 10~5 M, and the solution thus obtained was measured by making use of a General Electric Automatic Recording Spectrophotometerer through a 1 cm cell. The results thereof are shown in Table 1-3.

TABLE 1-3 Molecular Antidiffusive photoabsorption Coupler coefficient 1 -hydroxy-N- [ 4-(2,4-di-t-amyl- 1 phenoxy)butyl ] -2-naphthoamide 2.4 x 104 1 -(2,4,6-trichlorophenyl)-3- [ 3 2 a(2,4-di-t-amylphenoxyacetamide) 4.6 x 104 benzamide]-5-pyrazolone a-pivaloyl-a-(1 -benzyl-1,3 3 imidazole-2,4-dion-3-yl)-2- 1.3 x 104 chloro-5- [ y-(2,4-di-t-amyl phenoxy)butanamidelacetanilide 1-(2,4,6-trichloro)-phenyl-3- [ 5- 4 octadecenyl succinimide)-2- 5.7 x 104 chlorojanilino-5-pyrazolone Samples 1 - 4 were processed respectively in accordance with the following steps:: Step Processing Time Color development 3' 15" Bleach 6' 30" Wash 3' 15" Fix 6' 30" Wash 3' 15" Stabilizing 1'30" Composition of the processing liquids used in each step are as follows; Composition of Color Developer: 4-amino-Nethyl-N(p-methanesulfonamide ethyl)-m-toluidine sulfate 4.8 g Sodium sulfite anhydrous 0.14 g Hydroxyamine 1/2 sulfate 1.98 g Sulfuric acid 0.74 g Potassium carbonate anhydrous 28.85 g Potassium hydrogencarbonate anhydrous 3.46 g Potassium sulfite anhydrous 5.10 g Potassium bromide 1.16 g Sodium chloride 0.14 g Nitrilotriacetic acid .3 sodium salt (monohydrate) 1.20 g Potassium hydroxide 1.48 g Add water to make 1 Itr.

Composition of Bleaching solution: Iron ethylenediamine tetraacetate ammonium salt 100.0 g Ethylenediamine tetraacetate 2 ammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 ml Add water to make 1 Itr.

Adjust pH at 6.0 by making use of aqueous ammonia Composition of Fixing Solution: Ammonium thiosulfate 175.0 g Sodium sulfite anhydrous 8.6 g Sodium metasulfite 2.3 g Add waterto make 1 Itr.

Adjust pH at 6.0 by making use of acetic acid Composition of Stabilizer: Formalin (37% solution) 1.5 ml Koni-Dux (mfd. by Konishiroku Photo Ind. Co., Ltd.) 7.5 ml Add water to make 1 Itr.

Next, on each color image formed on the green-photosensitive layer of the respective sample, wach sharpness thereof was evaluated. The results thereof are shown in Table 1-2.

Wherein, the evaluation of said image sharpness was performed by obtaining MTF values (Modulation Transfer Function) and by comparing the values of MTF with each other at the space frequency of 30 lines/mm.

TABLE 1-2 Blue Green photosensitive Photosensitive Layer Layer Sample No. Max. Color Max. Color Density Density MTF Other than 1 the invention 1.63 1.58 30 The 2 invention 1.62 1.59 48 3 " 1.63 1.59 65 Other than 4 the invention 1.62 1.59 33 From Table 1-2, it can be found the facts that no desensitization is caused on sample 2 and 3 of the invention, and the values of MTF were remarkably high, and that the sharpness of the image formed on green-photosensitive layer was greatly improved.

EXAMPLE 2 Sample 5: Sample 5 was prepared in the similar process to that of sample 1, except that 1st layer of sample 1 was replaced by the undermentioned 1st layer.

1 st layer: Red-photosensitive emulsion layer 1 -hydroxy-4- [ ss-methoxyethylamino carbonylmethoxyl-N- [ 4 (2,4-di-t-amylphenoxy)butyll-2-naphthoamide, that is antidiffusive cyan coupler, of 13.5 g were heatedly dissolved in 13.5 ml of tricresyl phosphate and 30 ml of ethyl acetate. The solution thus obtained was mixed with 20 ml of 10% sodium alkyinaphthalene sulfonate solution and 200 ml of 5% gelatin solution, and the mixture thereof was emulsified and dispersed by a colloidal mill, and the dispersive solution C-2 thus obtained was added in 1 kg of red-photosensitive silver iodobromide emulsion (containing 4 mol% of silver iodide), and the material thus obtained was coated to prepare the layer.

Sample 6: Sample 6 has been preapared in such a manner that each layer thereof was coated onto triacetate base on which an antihalation layer had been coated, in the order in accordance with the following steps: 1 st layer: The dispersive solution Y-1 of sample 1 was added in 1 kg of red-photosensitive silver iodobromide emulsion (containing 4 mol% of silver iodide), and the material thus obtained was coated to prepare the layer.

2nd layer: Interlayer The same type of 2nd layer in sample 1 was coated to prepare the layer.

3rd layer: Green-photosensitive emulsion layer Dispersive solution C-2 of sample 1 was added in 1 kg of green-photosensitive silver iodobromide emulsion (containing 4 mol% of silver iodide), and the material thus obtained was coated to prepare the layer.

4th layer: Yellow filter layer Yellow filter layer that is the same type of 4th layer of sample 1 was coated to prepare the layer.

5th layer: Blue-photosensitive emulsion layer Dispersive solution M-1 used in sample 1 was added in 1 kg of blue-photosensitive silver iodobromide emulsion (containing 4 mol% of silver iodide), and the material thus obtained was coated to prepare the layer.

6th layer: Protective layer that is the same type of 6th layer of sample 1 was coated to prepare the layer.

TABLE 2-1 Blue Photosensitive Layer Green Photosensitive Layer Amount Coated, Thickness Amount Coated, mole/m2 of mole/m2 Sample Emulsion No. Coupler AgX Coated Coupler AgX (F) Other than 5 the invention 1.90x10-5 1.86x10-4 8.8 1.39x10-5 1.39x10-4 6 The invention 1.39x10-5 1.39x10#5 6.5 1.20x10-5 1.39x10-4 Molecular Photo-absorption Antidiffusive Cyan Coupler Coefficient 1 -hydroxy-4- [ P-methoxyethylamino carbonylmethoxy)-N-[4-(2,4-di-t amylphenoxy)butyl ] -2-naphthoamide 2.4x104 Each sample was processed in the similar manner to that for Example 1, and then the evaluation of the sharpness thereof was performed.

The results thereof are shown in Table 2-2.

TABLE 2-2 Blue Photosensitive Green Photosensitive Layer Layer Sample Max. Color Max. Color No. Density Density MTF Other than 5 the invention 1.63 1.58 30 The 6 invention 1.60 1.59 65 From Table 2-2, it can be found the facts that, in using sample 5 of the invention, no desensitization is caused, and the sharpness of the image formed on green-photosensitive layer has been greatly improved.

EXAMPLE 3 Sample 7: Sample 7 was-prepared by coating each layer onto triacetate base on which an antihalation layer had been coated, in the order according to the following steps: 1st layer: Red-photosensitive emulsion layer 2-(p-nitrophenyl carbamoyl)-1-naphthol, that is anti-diffusive cyan coupler, of 9.5 g were heatedly dissolved in 9.5 ml of tricresyl phosphate and 19 ml of ethyl acetate. The solution thus obtained was mixed with 20 ml of 10% sodium alkylnaphthalene sulfonate solution and 200 ml of 5% gelatin solution, and the mixture thereof was emulsified and dispersed by a colloidal mill, and the dispersive solution C-3 thus obtained was added into 1 kg of red-photosensitive silver iodobromide emulsion (containing 4 mol% of silver iodide), and the material thus obtained was coated to prepare the layer.

2nd layer: Interlayer The interlayer containing 0.5 g/m2 of gelatin and 0.1 g/m2 of 2,5-di-t-octyl hydroquinone was coated to prepare the layer.

3rd layer: Green-photosensitive emulsion layer 1 -phenyl-3-n-pentadecyl-5-pyrazolone, that is antidiffusive magenta coupler, of 13 g were heatedly dissolved in 13 g of tricresyl phosphate and 26 ml of ethyl acetate. The solution thus obtained was mixed with 20 ml of 10% sodium alkylnaphthalene sulfonate solution and 200 ml of 5% gelatin solution, and the material thus obtained was emulsified and dispersed by a colloidal mill, and the dispersive solution M-2 thus obtained was added in 1 kg of green-photosensitive silver iodobromide emulsion (containing 4 mol% of silver iodide), and the material thus obtained was coated to prepare the layer.

4th layer: Yellowfilterlayer The yellow filter layer containing 0.12 g of yellowish colloidal silver, 0.07 g of 2,5-di-t-octyl hydroquinone and 0.9 g/m2 of gelatin, was coated to prepare the layer.

5th layer: Blue-photosensitive emulsion layer Dispersive solution Y-1 was added in 1 kg of blue-photosensitive silver iodobromide emulsion (containing 4 mol% of silver iodide), and the material thus obtained was coated. to prepare the layer.

6th layer: Protective layer The protective layer containing 1.3 g/m2 of gelatin and 1 ,2-bisvinylsulfonyl ethane, was coated to prepare the layer.

Sample 8: Sample 8 was prepared in the similar process to that for preparing sample 7, except that 1 sot, 3rd and 5th layers of sample 7 were replaced by the following Ist, 3rd and 5th layers: 1st layer: Red-photosensitive emulsion layer Dispersive solution M-2 was added in 1 kg of red-photosensitive silver iodobromide emulsion (containing 4 mol% of silver iodide), and the material thus obtained was coated to prepare the layer.

3rd layer: Green-photosensitive emulsion layer Dispersive solution Y-1 was added in 1 kg of green-photosensitive silver iodobromide emulsion (containing 4 mol% of silver iodide), and the material thus obtained was coated to prepare the layer.

5th layer: Blue-photosensitive emulsion layer Dispersive solution C-3 was added in 1 kg of blue-photosensitive silver iodobromide emulsion (containing 4 mol% of silver iodide), and the material thus obtained was coated to prepare the layer.

Samples 7 and 8 were processed in the similar manner to that for Example 1 and the evaluation of the sharpness was then performed, and the results therefrom have proved that, with respect to sample 7 of the invention containing antidiffusive cyan couplers in the upper most emulsion layer thereof to form the coloring matter of which molecular photoabsorption co-efficient is the highest, there has caused no desensitization and greatly improved the sharpness of the image formed on the green-photosensitive layer, similar to the results from Examples 1 and 2.

Claims (11)

1. A multi-layered silver halide color photographic material which comprises a blue-photosensitive silver halide emulsion layer, a green-photosensitive silver halide emulsion layer and a red-photosensitive silver halide emulsion layer provided on one side of a support; said blue-photosensitive silver halide emulsion layer comprising a non-diffusion coupler selected from (a) yellow couplers, (b) magenta couplers and (c) cyan couplers, which is capable of reacting with an oxidation product of an aromatic primary amine color developing agent to produce a color dye; said green-photosensitive silver halide emulsion layer comprising a non-diffusion coupler selected from whichever of types )a), (b) and (c) of coupler is not employed in said blue-photosensitive silver halide emulsion layer; said red-photosensitive silver halide emulsion layer comprising a non-diffusion coupler selected from whichever of types (a), (b) and (c) of coupler is not employed in said blue-photosensitive or said green-photosensitive silver halide emulsion layers; and the photosensitive silver halide emulsion layer located farthest from said support comprising a non-diffusion coupler which produces dye having a molecular extinction coefficient larger than that of any dye produced by a non-diffusion coupler in the silver halide emulsion layers located between said farthest photosensitive silver halide emulsion layer and said support.

2. A multi-layered silver halide color photographic material according to claim 1, wherein the blue-photosensitive silver halide emulsion layer comprises a non-diffusion cyan coupler.

3. A multi-layered silver halide color photographic material according to claim 2, wherein the blue-photosensitive silver halide emulsion layer comprises a non-diffusion cyan coupler, the greenphotosensitive silver halide emulsion layer comprises a non-diffusion yellow coupler, and the redphotosensitive silver halide emulsion layer comprises a non-diffusion magenta coupler.

4. A multi-layered silver halide color photographic material according to claim 1, wherein the blue-photosensitive silver halide emulsion layer comprises a non-diffusion magenta coupler.

5. A multi-layered silver halide color photographic material according to claim 4, wherein the blue-photosensitive silver halide emulsion layer comprises a non-diffusion magenta coupler, the greenphotosensitive silver halide emulsion layer comprises a non-diffusion yellow coupler, and the redphotosensitive silver halide emulsion layer comprises a non-diffusion cyan coupler.

6. A multi-layered silver halide color photographic material according to claim 4, wherein the blue-photosensitive silver halide emulsion layer comprises a non-diffusion magenta coupler, the greenphotosensitive silver halide emulsion layer comprises a non-diffusion cyan coupler, and the redphotosensitive silver halide emulsion layer comprises a non-diffusion yellow coupler.

7. A multi-layered silver halide color photographic material according to any one of the preceding claims wherein the photosensitive silver halide emulsion layer farthest from the support is a blue-photosensitive silver halide emulsion layer.

8. A multi-layered silver halide color photographic material according to any one of the preceding claims wherein the support is provided with, in order, the red-photosensitive silver halide emulsion layer, the green-photosensitive silver halide emulsion layer and the blue-photosensitive silver halide emulsion layer.

9. A multi-layered silver halide color photographic material according to any one of the preceding claims wherein the molecular extinction coefficient of the dye produced by the non-diffusion coupler comprising the photosensitive silver halide emulsion layer farthest from the support is at least 5 x 1103 more than that of dye produced by the non-diffusion couplers comprising the silver halide emulsion layers between said farthest photosensitive silver halide emulsion layer and the support.

10. A multi-layered silver halide color photographic material according to claim 9, wherein the molecular extinction coefficient of the dye produced by the non-diffusion coupler comprising the photosensitive silver halide emulsion layer farthest from the support is at least 1 x 104 larger.

11. A multi-layered silver halide color photographic material substantially as hereinbefore described with reference to any one of Samples 2,3,6 and 7.