JPH0621944B2 - Silver halide photographic light-sensitive material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide multilayer color photographic light-sensitive material. More specifically, after image exposure, development is carried out using an aromatic primary amine color developing agent in the presence of a coupler which reacts with an oxidized product of a developing agent to form a dye, and a layer in which a photosensitive silver halide is present is developed. The present invention relates to a silver halide multilayer color light-sensitive material of the type in which a silver image and a dye image are formed, and thereafter only the silver image is removed to utilize only the dye image.

(Prior Art) In a multilayer color photographic light-sensitive material, various characteristics are required for the image. One of them is that the outline of the image is clear and a fine image is drawn without blurring, that is, the sharpness is good. Another characteristic is that, when one color-sensitive layer forms a dye image, the other color-sensitive layer does not develop color due to the oxidation product of the color-developing agent generated therein, that is, the color purity is high. Is.

Still another is that the formed dye image has good stability over time.

In order to meet these demands, various ideas have been conventionally applied to silver halide photographic light-sensitive materials, particularly silver halide multilayer color photographic light-sensitive materials.

Regarding the sharpness described above, it is mainly studied from the viewpoint of preventing optical scattering in the light-sensitive material and improving the adjacency effect during development,
To prevent or reduce optical scattering, select silver halide grains with less light scattering, reduce the number and amount of silver halide grains as a light scattering source, or thin photosensitive and non-photosensitive photographic functional layers. The method has been adopted.

Although the above-mentioned optical method also produced some results, the method alone may conflict with the photographic performance or the production of the light-sensitive material. .

On the other hand, regarding the adjacent effect at the time of development, the problem of color purity as well as the sharpness is taken into consideration. Firstly, from the viewpoint of the concentration gradient of the development-inhibiting substance such as iodide ion released during development, the developer dilution, Alternatively, measures such as weak agitation during development were attempted from the viewpoint of development operation, but due to complication of development operation, uncertainty of condition setting, etc., performance was apt to be varied and a satisfactory result could not be obtained. It was

Secondly, a method of positively increasing the adjacency effect by adding a compound which reacts with an oxidized product of a color developing agent to release a development inhibitor in the light-sensitive material has been studied, and a broad search for the compound has been conducted. It was conducted.

Examples of the compound that releases a development inhibitor by reacting with an oxidized product of a color developing agent include those described in U.S. Pat. Nos. 3,148,062 and 3,227,554. A compound that is coupled with an oxidant of a color developing agent to form a dye and releases a development inhibitor (hereinafter referred to as DI
R coupler) or US Pat. No. 3,632,3
As described in Japanese Patent No. 45, a compound (hereinafter referred to as a DIR substance) that releases a development inhibitor by coupling with an oxidized product of a color developing agent and does not form a dye is known (hereinafter referred to as DIR coupler and DIR substances are collectively referred to as DIR compound).

The characteristic of these DIR compounds is that they react with the oxidant of the color developing agent to release the development inhibitor directly from the coupling position.

Further, JP-A-54-145135 discloses a DIR compound which reacts with an oxidant of a color developing agent to release a development inhibitor by an intramolecular nucleophilic substitution reaction, and JP-A-56-114946. Describes a DIR compound that indirectly releases a development inhibitor by electron transfer along a conjugated chain. These compounds are characterized in that the reaction with the oxidant of the color developing agent indirectly releases the development inhibitor by a secondary reaction induced by the reaction (hereinafter, a DIR compound having this characteristic is referred to as T
-Collectively referred to as DIR compound).

These compounds form dyes that are alkali-insoluble products by reaction with the oxidant of the color developing agent and remain in the photographic element, such as in photographic sensitizers utilizing conventional non-diffusible dye images. The material has a serious defect that it causes color turbidity when used in a coupler-containing layer having a different hue, which is not preferable in color reproduction. It also has a drawback that it cannot be applied to a photographic system in which a dye image produced by a reaction with an oxidant of a color developing agent is transferred.

On the other hand, as a component of a photographic coupler, a compound which gives a colorless reaction product by a reaction with an oxidant of a color developing agent is advantageous because there is no problem of color turbidity in the light-sensitive material as described above. It has poor reactivity with an oxidized product of a color developing agent and has poor storage stability of the compound, and is not practical.

By using the DIR compound, the graininess and the exposure tolerance can be improved to some extent, but the improvement of the color purity is not so effective. Further, when the T-DIR compound is used, the effect of the inhibitor can be exerted at a position separated from the developed silver halide grain by a specific distance, so that the color purity is improved to some extent based on the so-called interlayer effect. . Although the sharpness is improved to some extent based on the adjacency effect, the effect of improving color purity and graininess is small. Therefore, improvement in sharpness, graininess, color purity and broadening latitude by using these DIR compounds and / or T-DIR compounds are still not sufficient.

It should be noted that the measurement of the adjacency effect at the time of development is said to have a correlation with the psychological image sharpness evaluation in the human visual system.
Although it is performed by the low frequency band of the spatial frequency of the mode transfer function (Modulation Transfer Functiou), there is still a point that the immediateness is unsatisfactory.

The time-dependent stability of the formed dye image, which is the third property required for the multilayer silver halide color photographic light-sensitive material, is an essential property for image recording and storage.
It is said that stability over time is significantly impaired by various kinds and a large amount of additives, which are added in response to the demands of the photographic material from other photographic properties or productivity, especially various compounds remaining after development. It has been considered and various improvements have been attempted, but no satisfactory results have been achieved yet.

(Object of the invention) In connection with the above-mentioned problems, the first object of the present invention is to provide a sharpness and derivatively good color purity, especially a low frequency band (0 to 20 lines / mm) of the spatial frequency of MTF. ) Is to provide a silver halide multilayer color photographic light-sensitive material having improved sharpness.

A second object is to provide a silver halide multilayer color photographic light-sensitive material in which the stability of a dye image formed by color development is improved with time.

(Structure of the Invention) The present inventors have further described the above-mentioned DIR and T-DIR compounds having the above-mentioned object, the silver halide grains as the above-mentioned optical factors and the adjacent effect during development. As a result of diligent research on the reaction efficiency between the silver halide grains, the color developing agent and the DIR or T-DIR compound and the proper amount ratio for causing the reaction, at least one photosensitive silver halide emulsion layer was formed on the support. In the silver halide photographic light-sensitive material having, in the light-sensitive silver halide emulsion layer, a development inhibitor is released by the reaction of substantially monodisperse silver halide grains and an oxidized color developing agent, In addition, in the reaction for forming a mobile reaction product, the DIR having a good reaction efficiency and a small amount is sufficient due to the synergistic effect with the monodisperse silver halide grains.
And / or T-DIR compound (excluding the following compounds) The silver halide photographic light-sensitive material of the present invention is constituted by containing and in a selected combination.

Due to the above-mentioned constitution, the adjacency effect, and hence the sharpness is remarkably improved and the color purity is secondarily improved, and it is formed surprisingly by the decrease of the addition amount of the DIR compound and the like and the outflow of the reaction product from the light-sensitive material layer. The temporal stability of the dye image was good.

Further, the adjoining effect in the light-sensitive silver halide emulsion layer described above can be effectively expressed in each layer of the multilayer light-sensitive material without any trouble, and the silver halide multilayer color photographic light-sensitive material aimed at by the present invention can be obtained.

Next, the DIR and T-DIR compounds which release a development inhibitor and produce a mobile reaction product by the reaction with the oxidized color developing agent used in the present invention will be explained.

General formula (I) A-Z General formula (II) A-TIME-Z Here, A is a group which is eliminated from the compound represented by the general formula (I) or (II) after the reaction with an oxidized color developing agent. Represents a group capable of forming a mobile reaction product,
Represents a timing group capable of being eliminated together with Z from the compound represented by the general formula (II) by the reaction of A with an oxidized product of a color developing agent, and then releasing Z.
Represents a group having a development inhibiting effect.

Hereinafter, the present invention will be described in detail.

The compound represented by the general formula (I) or (I
In I), A is a group capable of forming a mobile or alkali-soluble reaction product by leaving from the compound represented by the general formula (I) or (II) when it reacts with an oxidized product of a color developing agent. Specifically, it represents a photographic coupler residue.

Therefore, the above A in the present invention means a coupler residue or the like which forms an alkali-soluble reaction product when it is eliminated from the compound represented by the above general formula by reacting with an oxidized product of a color developing agent. .

Examples of the above-mentioned coupler residue used in the present invention include those having various coupler mother nuclei,
For example, in yellow couplers, open-chain ketomethylene compounds such as benzoylacetanilide compounds, pivaloylacetanilide compounds or pivaloylacetanilide compounds are useful, and in magenta couplers, pyrazolone compounds, indazolone compounds, pyrazolotriazole compounds. A compound or the like can be used, and in the case of a cyan coupler, a phenol compound, a naphthol compound and the like can be mentioned.

In the present invention, the reaction product formed when reacting with the oxidized product of the color developing agent must be soluble in alkali regardless of which coupler residue is used. In order to impart it to the above reaction product, at least one molecule of the coupler residue or the oxidized product of the color developing agent must have an alkali-soluble group.

Therefore, in the present invention, an alkali-soluble group may be introduced into the photographic coupler residue represented by the above A, or an alkali-soluble group may be introduced into an oxidized product of a color developing agent. A soluble group may be introduced. In the present invention, it is preferable to introduce an alkali-soluble group into the above coupler residue.

As described above, TIME represented by the general formula (II) is eliminated from the compound represented by the general formula (II) together with Z represented by the general formula (II) in the coupling reaction according to the above, and then Z is It represents a releasable timinder group.

As an example of such a timing group, for example, a group having the above-mentioned development inhibitory action by the intramolecular nucleophilic substitution reaction described in US Pat. No. 4,248,962 and JP-A-57-56837 can be used. What can be released and JP-A-56-1
14946, JP-A-57-154234, and the like, which release a group having a development-inhibiting action by an electron transfer reaction along a conjugated chain can be mentioned.

The TIME group useful in the present invention has the following general formula:
The present invention includes, but is not limited to, those shown in (a), (b) and (c).

General formula (a) Here, X represents an atomic group necessary for forming a benzene ring or a naphthalene ring, and Y represents -O-, -S-, And is bonded to the coupling position of the compound represented by the general formula (II), and R ₁ , R ₂ and R ₃ each represent a hydrogen atom, an alkyl group or an aryl group.

Also Is substituted at the ortho or para position with respect to Y, while the other is attached to the heteroatom of the group represented by Z.

General formula (b) Here, Y, R ₁ and R ₂ have the same meaning as in the general formula (a). R ₄ is a hydrogen atom, an alkyl group, an aryl group, an acyl group, a sulfone group, an alkoxycarbonyl group, or a heterocyclic group, and R ₅ is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aminoacylamide. Base,
It represents a sulfonamide group, a carboxy group, an alkoxycarbonyl group, a carbamoyl group or cyano. And
The mode of bonding of this timing group to A and Z represented by the general formula (II) is the same as in the case of the general formula (a).

General Formula (c) —Nu—X ₁ —E— Here, Nu is a nucleophilic group having an electron-rich oxygen, sulfur or nitrogen atom, and A in the above general formula (II)
Is coupled to the coupling position of. E is an electrophilic group having an electron-deficient carbonyl group, thiocarbonyl group, phosphinyl group, or thiophosphinyl group, and is bonded to the hetero atom of Z in the general formula (II).
X ₁ is sterically related to the Nu group and the E group, and is accompanied by formation of a 3-membered ring to a 7-membered ring after the Nu group is released from the compound represented by the general formula (II). It represents a linking group capable of undergoing an intramolecular nucleophilic substitution reaction and releasing Z in the general formula (II) by the reaction.

In the above general formula (I) or (II), Z represents a group having a development inhibitory action as described above, but in a photographic element, it is a group that can be used as an imagewise pattern. Typical examples of the compound having a group having such a development inhibitory action include US Pat. Nos. 3,227,554, 3,384,657, 3,615,506, and US Pat. No. 3,617,291, No. 3,733,201 and British Patent No. 1,450,479, each of which describes mercaptotetrazole, selenotetrazole, mercaptobenzothiazole, selenobenzothiazole, mercaptobenzoxazole. , Selenobenzoxazole, mercaptobenzimidazole, selenobenzimidazole, benzotriazole, benzodiazole and iodide.

As is clear from the above detailed description, the compound represented by the general formula (I) or (II) according to the present invention is not only enhanced in reactivity with the oxidant of the color developing agent, but also The reaction product as a result of the reaction is endowed with alkali-solubility and can be flowed out of the photographic element, thus offering a wider range of utilization compared to prior art compounds,
It is an extremely advantageous compound in the design of photosensitive materials.

Specific representative examples of the compounds according to the present invention are shown below,
The present invention is not limited to these.

(Compound example) T-1 T-2 T-3 T-4 T-5 T-6 T-7 T-8 T-9 T-10 T-11 T-12 T-13 T-14 T-15 T-16 T-17 T-18 T-19 T-20 T-21 T-22 T-23 T-24 T-25 T-26 T-27 T-28 T-29 T-30 T-31 T-32 T-33 T-34 T-35 T-36 T-37 T-38 T-39 T-40 T-41 T-42 T-43 T-44 T-45 T-46 T-47 T-48 T-49 T-50 T-51 T-52 T-53 T-54 T-55 T-56 D-1 D-2 D-3 D-4 D-5 D-6 D-7 D-8 D-9 D-10 D-11 D-12 D-13 D-14 D-15 D-16 D-17 D-18 D-19 D-20 D-21 D-22 D-23 D-24 D-25 D-26 D-27 D-28 D-29 D-30 D-31 D-32 D-33 D-34 D-35 D-36 D-37 D-38 D-39 D-40 D-41 D-42 D-43 D-44 D-45 D-46 D-47 D-48 D-49 D-50 D-51 D-52 D-53 D-54 D-55 D-56 In the present invention, the DIR compound and / or the T-DIR compound may be contained in at least one of the silver halide emulsion layers containing substantially monodisperse silver halide grains. For example, when it is applied to an ordinary multilayer color photographic light-sensitive material having a blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer, it may be contained in one layer or two or more layers, but at least green. It is preferably contained in the sensitive emulsion layer. Further, when the emulsion layer having a certain color sensitivity is composed of a plurality of layers having different sensitivities, one or two of them are used.
It may be contained in more than one layer, but it is preferably contained in at least the low-sensitivity emulsion layer.

In the color photographic light-sensitive material according to the present invention, the total amount of DIR compound and / or T-DIR compound is preferably in the range of 0.0005 to 0.05 mol with respect to 1 mol of silver halide in the emulsion. Particularly preferably, it is in the range of 0.001 to 0.01 mol.

As the color developing agent used in the present invention, any color developing agent used for developing a silver halide color photographic light-sensitive material can be applied, for example, an aromatic primary agent such as p-phenylenediamine and p-aminophenol. A primary amine color developing agent can be applied.

The coupler used in the color photographic light-sensitive material of the present invention, that is, the compound that reacts with the oxide of the developer to form a dye is preferably a non-diffusible one having a hydrophobic group called a ballast group in the molecule. The coupler may be either 4-equivalent or 2-equivalent with respect to silver ion.

The coupler may have a low molecular weight or a so-called polymeric coupler.

As the yellow coupler, a known open chain ketomethylene type coupler can be used. Among these, benzoylacetanilide compounds and pivaloylacetanilide compounds are useful.

A pyrazolone compound, an indazolone compound, a cyanoacetyl compound can be used as the magenta coupler, and a phenol compound, a naphthol compound, etc. can be used as the cyan coupler.

These couplers generally contain 2 moles per mole of silver in the emulsion layer.
× 10 ^-3 mol to 5 × 10 ^-1 mol, preferably 1 × 10 ^-1 mol 5
× 10 ^-1 mol is added.

In the present invention, which coupler is added to which silver halide emulsion layer in the multilayer color photographic light-sensitive material is not necessarily limited, but a blue-sensitive silver halide emulsion layer is provided with a yellow coupler and a green-sensitive silver halide light-sensitive layer. A magenta coupler for the red-sensitive silver halide emulsion layer and a cyan coupler for the red-sensitive silver halide emulsion layer, or a magenta coupler for the blue-sensitive silver halide emulsion layer, and a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer. It is preferred to use a yellow coupler on one side and a cyan coupler on the other side.

There are various methods for incorporating the DIR compound or / and the T-DIR compound or the coupler according to the present invention into the light-sensitive material, and the latex dispersion method and the oil-in-water emulsion dispersion method are particularly effective. These dispersion methods are conventionally well known, and the latex dispersion method and its effects are described in JP-A-49-745.
No. 38, No. 51-59943, No. 54-32552 Publications and research
Research Disclosure, August 1976, No. 14,850, pp. 77-79.

Suitable latices are, for example, styrene, ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, 2-acetoacetoxyethyl methacrylate, 2
-(Methacryloyloxy) ethyltrimethylammonium sulfate, 3- (methacryloyloxy) propane-1-sulfonic acid sodium salt, N-isopropylacrylamide, N- [2- (2-methyl-4-oxopentyl)] acrylamide, 2- Acrylamide-2
-Homopolymers, copolymers and terpolymers of monomers such as methylpropane sulfonic acid and the like. As the oil-in-water emulsion dispersion method, a conventionally known method of dispersing a hydrophobic additive such as a coupler can be applied. The DIR compound and / or T-DIR compound used in the present invention may be dispersed simultaneously with other couplers, or may be separately dispersed and added independently.

By interposing one or more scavenger layers at appropriate positions in the constituent layers of the light-sensitive material, the layer or unit layer affected by the development inhibitor can be controlled.

The silver halide used in the color photographic light-sensitive material according to the present invention preferably consists essentially of silver iodobromide having an iodide of less than 12 mol%. It shows that even if the silver iodide formed in the process contains some silver iodobromide grains exceeding 12 mol%, the average is less than 12 mol%. In the present invention, the more preferable mol% of iodine is 2 to 9 mol%. The silver iodobromide emulsion may be large grains or small grains, but is substantially a monodisperse emulsion.

The monodisperse emulsion layer in the present invention means one having a standard deviation S defined by the following equation, which is 0.20 or less when divided by the average grain size.

The average grain size referred to here is the average value of the diameter of spherical silver halide grains, and the diameter of the projected image converted to a circular image of the same area in the case of grains having a shape other than spherical. Therefore, when each particle size is ri and the number is ni, is defined by the following formula.

The emulsion can be a negative emulsion or a direct positive emulsion. They are mainly surface latent image type emulsions that form a latent image on the surface of silver halide grains, internal latent image type emulsions that form a latent image inside silver halide grains, or surface latent image type emulsions and internal latent image type emulsions. A mixture with can be used.

The silver halide grain used in the silver halide color photographic light-sensitive material according to the present invention may be a so-called twin crystal having an irregular shape such as a spherical shape or a plate shape, and may have a cubic shape, an octahedral shape or a tetradecahedral shape. It may have a regular shape, but the latter is more preferable. Further, regular ones, irregular ones and the like can be mixed and used.

The silver halide grains used in the silver halide color photographic light-sensitive material of the present invention may be obtained by any of the acidic method, the neutral method and the ammonia method. Alternatively, for example, a method in which seed particles are formed by an acidic method and further grown by an ammonia method having a high growth rate to grow to a predetermined size may be used. When growing silver halide grains, p in the reaction kettle
By controlling H, PAg, etc., for example, as described in JP-A-54-48521, silver ions and halide ions are successively injected and mixed in an amount matching the growth rate of silver halide grains. Is desirable.

These silver halides include active gelatin; sulfur sensitizers such as allylthiocarbamide, thiourea, and cystine; selenium sensitizers; reduction sensitizers such as stannous salt, thiourea dioxide, and polyamines. Etc .; noble metal sensitizers such as gold sensitizers, specifically potassium aurithiocyanate,
Potassium chloroaurate, 2-aurosulfobenzothiazioniochloride, etc. or a sensitizer of a water-soluble salt such as ruthenium, palladium, platinum, rhodium, iridium, specifically ammonium chloroparadate, potassium chlorobrathiate and Sodium chloroparadate, etc. (some of these act as a sensitizer or an antifoggant depending on the amount); and the like, alone or in combination (for example, metal sensitizer and sulfur sensitizer). It may be chemically sensitized by the combined use, the metal sensitization and the selenium sensitizer.

Further, this silver halide can be optically sensitized to a desired wavelength region, and for example, it can be used alone or with an optical sensitizer such as a cyanine dye such as a zeromethine dye, a monomethine dye, a dimethine dye and a trimethine dye or a merocyanine dye. In combination (for example, supersensitization), they can be optically sensitized.

Other specific constitutions of the silver halide color photographic light-sensitive material according to the present invention are Research Disclosure No. 1
The contents described in 8431 can be applied.

The silver halide color photographic light-sensitive material according to the present invention is usually provided with a red light-sensitive silver halide emulsion layer, a green light-sensitive silver halide emulsion layer and a blue light-sensitive silver halide emulsion layer in this order on a support. ing.

In the present invention, each light-sensitive silver halide emulsion layer may have a plurality of silver halide emulsion layers having substantially the same color sensitivity but different photosensitivities. In this case, the combination of the present invention, that is, the combination of the monodisperse silver halide emulsion and the T-DIR compound and / or DIR according to the present invention, has a plurality of color sensitivities which are substantially the same but different sensitivities. The present invention may be applied to all the silver halide emulsion layers of, but at least to a silver halide emulsion layer having lower photosensitivity.

The binder of the silver halide emulsion according to the present invention,
Various hydrophilic colloids such as gelatin are used. In that case, gelatin includes not only gelatin but also derivative gelatin. Derivative gelatin includes a reaction product of gelatin and an acid anhydride, a reaction product of gelatin and an isocyanate, or a compound having gelatin and an active halogen atom. The reaction product and the like are included.

In addition to the above-mentioned usual photographic gelatin and derivative gelatin, if necessary, colloidal albumin, agar, gum arabic, dextran, alginic acid, for example, a cellulose derivative such as cellulose acetate hydrolyzed to an acetyl content of 19 to 26%. , Polyacrylamide,
Imidized polyacrylamide, casein, vinyl alcohol polymers containing urethane carboxylic acid groups or cyanoacetyl groups such as vinyl alcohol-vinyl cyanoacetate copolymers, polyvinyl alcohol-polyvinylpyrrolidone, hydrolyzed polyvinyl acetate,
A polymer obtained by polymerizing a protein or a saturated acylated protein with a monomer having a vinyl group, polyvinyl pyridine, polyvinyl amine, polyaminoethyl methacrylate, polyethylene imine and the like can also be used.

The silver halide emulsion according to the present invention can contain various additives usually used depending on the purpose. Examples of these additives include azaindenes, triazoles, tetrazoles, imidazolium salts, tetrazolium salts, stabilizers and antifoggants such as polyhydroxy compounds; aldehyde-based, aziridine-based, inoxazole-based, vinyl sulfone-based, Hardening agents such as acryloyl-based, arpodiimide-based, maleimide-based, methanesulfonate-based, triazine-based, etc .; development accelerators such as benzyl alcohol, polyoxyethylene-based compounds, etc .; chroman-based, coumaran-based, bisphenol-based, phosphite ester System image stabilizers; waxes, glycerides of higher fatty acids, and lubricants such as higher alcohol esters of higher fatty acids. Further, a coating aid as a surfactant, an agent for improving the permeability to a treatment liquid, a defoaming agent or a material for controlling various physical properties of a sensitive material, an anionic type,
Various types of cation type, nonionic type or amphoteric type can be used. As the antistatic agent, diacetyl cellulose, a styrene perfluoroalkyl sodium sulphate maleate copolymer, an alkali salt of a reaction product of a styrene-maleic anhydride copolymer and p-aminobenzenesulfonic acid, and the like are effective. Examples of the matting agent include polymethylmethacrylate, polystyrene and alkali-soluble polymers. It is also possible to use colloidal silicon oxide. Examples of the latex added to improve the physical properties of the film include copolymers of acrylic acid ester, vinyl ester and the like with other monomers having an ethylene group. Examples of the gelatin plasticizer include glycerin and glycol compounds, and examples of the thickener include styrene-sodium maleate copolymer and alkyl vinyl ether-maleic acid copolymer.

Examples of the support according to the present invention include baryta paper,
Polyethylene coated paper, polypropylene synthetic paper, glass,
There are cellulose acetate, cellulose nitrate, polyvinyl acetal, polypropylene, polyester films such as polyethylene terephthalate, polystyrene, etc., and these supports are appropriately selected according to the intended use.

These supports are subjected to a subbing process, if necessary.

As the coating method used in the present invention, a dip coating method, an air knife coating method, a curtain coating method, or US Patent No. 2,
Various coating methods including an extrusion coating method using a hopper of the type described in No. 681,294 can be mentioned. If desired, two or more layers can be co-applied by the methods described in US Pat. No. 2,761,791 and British Patent No. 837,095.

The silver halide color photographic light-sensitive material according to the present invention includes all kinds of silver halide color photographic light-sensitive materials such as a color negative film, a color positive film, a color reversal film and a color paper.

The color developing agent used in the present invention is an aromatic primary amine compound, particularly preferably a p-phenylenediamine type developing agent such as 4-amino-N, N-diethylaniline, 3-methyl-4-amino. -N, N-diethylaniline, 4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-
4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline, 3-β-methanesulfonamidoethyl-4-amino -N, N-diethylaniline, 3-methoxy-4-amino-N-ethyl-N-
β-hydroxyethylaniline, 3-methoxy-4-amino-N-ethyl-N-β-methoxyethylaniline,
3-acetamido-4-amino-N, N-diethylaniline, 4-amino-N, N-dimethylaniline, N-ethyl-N-β- [β- (β-methoxyethoxy) ethoxy]
Ethyl-3-methyl-4-aminoaniline, N-ethyl-N-β (β-methoxyethoxy) ethyl-3-methyl-4-aminoaniline and salts thereof such as sulfates, hydrochlorides, sulfites, p- For example, toluene sulfonic acid.

The photographic additives used in these color developers include alkali agents (eg, alkali metal or ammonium hydroxides, carbonates, phosphates), pH adjusters or buffers (eg, acetic acid, boric acid). Weak acids and weak bases and their salts), development accelerators (eg pyridinium compounds, cationic compounds, potassium nitrate and sodium nitrate, polyethylene glycol condensates and their derivatives, nonionic compounds such as polythioethers, sulfite) Polymer compounds having ester, other pyridine, ethanolamines, organic amines, benzyl alcohol, hydrazines, etc., antifoggants (for example, alkali bromide, alkali iodide and nitrobenzimidazole,
5-methylbenzotriazole, 1-phenyl-5-mercaptotetrazole, compounds for rapid processing liquid, nitrobenzoic acid, benzothiazolium derivative, phenazine-N
-Oxides, stain or sludge inhibitors, layering accelerators, preservatives (e.g. sulfites, acid sulfites,
Hydroxyamine hydrochloride, form sulfite, alkanolamine sulfite adduct, etc.).

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed at the same time as the fixing process, or may be performed individually. As a bleaching agent, iron (III), cobalt (I
Compounds of polyvalent metals such as V), chromium (IV) and copper (II), peracids, quinones, nitrone compounds and the like are used. For example, ferricyanide compounds, dichromates, organic complex salts of iron (III) or cobalt (III), aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,5-diamino-2-propanoltetraacetic acid, or quinic acid. Acids, tartaric acid, complex salts of organic acids such as malic acid, persulfates, permanganates, and nitrosophenol can be used. Of these, potassium ferricyanide,
Sodium iron (III) diaminetetraacetate and iron (III) ammonium ethylenediaminetetraacetate are particularly useful. The ethylenediaminetetraacetic acid iron (III) complex salt is useful both in the independent bleaching solution and in the one-bath bleach-fixing solution.

For bleaching or bleach-fixing solutions, U.S. Pat.No. 3,042,520,
In addition to the bleaching accelerators described in JP-B No. 3,241,966, JP-B-45-8506 and JP-B-45-8836, and the thiol compounds described in JP-A-53-65732, various kinds of additives can be added.

(Examples) The present invention will be specifically described below with reference to examples, but the embodiments of the present invention are not limited thereto.

The effect of improving the sharpness was detected by finding the MTF and comparing the sizes of the MTFs when the spatial frequency was 10 lines / mm.

Next, the method for preparing the emulsion used in the examples will be described below.

[Preparation of polydisperse emulsion]

Ammoniacal silver nitrate and alkali halide aqueous solution, gelatin aqueous solution and excess halide were added in advance, and the temperature was adjusted to 60 ° C.
Then, let it fall naturally into the reaction kettle kept at 0 ° C, and then add Kao Atlas's Demol N aqueous solution and magnesium sulfate aqueous solution to perform precipitation and desalting. Add gelatin, pAg7.8, pH
An emulsion of 6.0 was obtained. Further, sodium thiosulfate, chloroauric acid and ammonium rhodanate were added, and the mixture was chemically aged at 52 ° C for 70 minutes to give 4-hydroxy-6-methyl-1,3,3a, 7-
Tetrazaindene and 6-nitrobenzimidazole were added, and gelatin was further added to obtain a polydisperse silver iodobromide emulsion. Here, by changing the alkali halide composition, the silver iodide mol% and by changing the addition time of the ammoniacal silver nitrate and the alkali halide aqueous solution, the average grain size,
The particle size distribution was changed.

[Preparation of monodisperse emulsion]

To the reaction kettle in which potassium iodide and gelatin aqueous solution have been added in advance, add ammoniacal silver nitrate aqueous solution and potassium bromide aqueous solution in proportion to the surface area increase during grain growth while keeping the pAg in the reaction kettle constant. did. Next, Kao Atlas's Demol N aqueous solution and magnesium sulfate aqueous solution were added, precipitation and desalting were performed, gelatin was added, and pA
An emulsion having g7.8 and pH 6.0 was obtained. Further, sodium thiosulfate, chloroauric acid and ammonium rhodanate are added, chemical ripening is performed, and 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene and 6-nitrobenzimidazole are added,
Further, gelatin was added to obtain a monodisperse silver iodobromide emulsion. Here, the mol% of silver iodide should be changed by changing the ratio of potassium iodide to potassium bromide to keep it constant in the reaction vessel.
The crystal habit was changed by changing the pAg value. The particle size was changed by changing the addition amounts of ammoniacal silver nitrate and potassium halide.

Example 1. 50 g of 1- (2,4,6-trichlorophenyl) -3- [3- (2,4-di-t-amylphenoxyacetamide] -5-pyrazolone as a magenta coupler and DIR according to the present invention shown in Table 1. The compound and the following comparative DIR compound were dissolved in 200 m of ethyl acetate and 100 m of tricresyl phosphate, and this was added to an aqueous gelatin solution containing alkanol B (alkylnaphthalene sulfonate, manufactured by DuPont) and emulsified and dispersed by a colloid mill. Then, this dispersion was added to a green-sensitive silver iodobromobromide emulsion as shown in Table 1 and coated and dried on a triacetate base having an antihalation layer so that the amount of silver was 2.0 g / m ^2. did.

Each of the samples 1 to 13 thus obtained was separately subjected to contact exposure with a transparent rectangular wave chart or wedge and line image exposure with a soft X-ray to a width of 4 mm and a width of 10 μm. Processing gave a sample with a dye image.

Comparative DIR compound (1) Comparative DIR compound (2) The composition of the processing solution used in each processing step is as follows.

[Color developer]

[Bleaching solution] [Fixer] [Stabilizing liquid] The soft X-ray exposure was performed by scanning with a microdensitometer using green light to measure the density. Assuming that the density of the line image of 10 μm is D ₁ ^G and the density of the line image of 3 mm is D ₂ ^G , (D ₁ ^G −D ₂ ^G ) / D ₁ ^G is the edge effect of the sample when observed with green light. Indicates the size. That is, D ₁ ^G -D ₂ ^G / D ₁ ^G
It can be said that the larger the value of, the greater the edge effect when observed with green light. Table 1 shows the responsibility D ₁ ^G −D ₂ ^G ) / D ₁ ^G value of each sample. This is described in "Developer Release (DIR) Coupler for Color Photography" (Photographic Science and Engineering, pp. 78-79, Vol. 1).
A detailed explanation can be found in March, No. 2 March-April (1969).

The description of the apparatus used for producing an X-ray image is "Apparatus for Making S
harp Photographic Images with X-Rays) The Review of Scientific Instruments Vol.
38, No. 11, 1619-1622, Nov. 1967.

Moreover, the light resistance, heat resistance, and humidity resistance of the dye image were examined using the sample obtained by wedge exposure.

The results obtained are shown in Table 1. In the table, the light resistance is
The residual density after each image obtained was exposed for 300 hours using a xenon fade meter, and the density before exposure was expressed as 100.
The humidity resistance was expressed as the residual concentration after storage for 3 weeks under the conditions of 60 ° C. and 70% relative humidity, where the concentration before the test was 100. Further, the heat resistance was represented by the residual concentration after storage for 3 weeks under the condition of 77 ° C., with the concentration before the test being 100. (However, the initial concentration
1.0) As is clear from Table 1, when the results of Samples 1 to 6 are examined, the adjacency effect at the time of development when the DIR compound of the present invention is used in the polydisperse emulsion system is slightly different from that of the comparative DIR compound. Although the effect is noticeable, the storage stability of the dye image is not improved at all. Also, in the case of the monodisperse emulsion systems of Samples 7 to 8, both the adjacency effect and the storage stability of the dye image are the same as those of Samples 1 to 6. However,
Surprisingly, in Samples 7 to 13, the adjacency effect during development and the storage stability of the dye image were significantly improved, and the superiority of the present invention is apparent in this respect.

Example 2. Multilayer color negative light-sensitive materials (Samples 14 to 24) were prepared by sequentially coating the following layers 1 to 13 on a transparent cellulose triacetate film.

First layer: antihalation layer An aqueous gelatin solution containing black colloidal silver was applied so as to have a silver content of 0.3 g / m ² .

Second layer: intermediate layer An aqueous gelatin solution was applied to give a dry film thickness of 1.0 μm.

Third layer: Red-sensitive low-sensitivity silver halide emulsion layer Silver iodobromide emulsion (average grain size 0.6 μ, silver iodide 4 mol%
Was mixed with a silver iodobromide emulsion having a mean grain size of 0.3 μm and a silver iodobromide emulsion containing 4 mol% of silver iodide in a ratio of 2: 1) by chemical sensitization with gold and sulfur sensitizers. Further, as a red-sensitive sensitizing dye, anhydrous 9-ethyl-3.3'-di- (3-sulfopropyl) -4,5,4 ', 5'-dibenzothiacarbocyanine hydroxide; anhydrous 5,5'-dichloro -9-Ethyl-3.3'-di- (3-sulfobutyl) thiacarbocyanine hydroxide; and anhydrous 2- [2-{(5-chloro-3-ethyl-2 (3H) -benzothiazolidene) methyl} -1-Butenyl-5-chloro-3- (4-sulfobutyl) benzoxazolium was added, and then 4-hydroxy-6-methyl-1,3.3a, 7 tetrazaindene 1.0 g,
20.0 mg of 1-phenyl-5-mercaptotetrazole was added to prepare a red-sensitive low-sensitivity emulsion. Further, 1 mol of silver halide is used as a cyan coupler per mol of silver halide.
[4- (2,4-di-t-amylphenoxy) butyl] 59
g, and 0.5 g of dodecyl gallate were added, and a mixture of 65 g of tricresyl phosphate and 136 m of ethyl acetate was dissolved by heating, added to 550 m of 7.5% gelatin aqueous solution containing 5 g of sodium triisopropylnaphthalenesulfonate, and then added with a colloid mill. A red-sensitive low-sensitivity emulsion was prepared by adding the emulsion-dispersed dispersion, and coating was performed so that the coated silver amount was 2.0 g / m ² . (Contains 160 g of gelatin per mol of silver halide.) Fourth layer: red-sensitive high-sensitivity silver halide emulsion layer Silver iodobromide emulsion (average grain size 1.2 μm, silver iodide 7 mol%)
Is chemically sensitized with gold and sulfur sensitizers, and anhydrous 9-ethyl-3.3'-di- (3-
Sulfopropyl) -4,5,4 ', 5'-dibenzothiacarbocyanine hydroxide, anhydrous 5,5'-dichloro-9-ethyl-3.3'-di- (3-sulfobutyl) thiacarbocyanine hydroxide; and Add anhydrous 2- [2-{(5-chloro-3-ethyl-2 (3H) -benzothiazolidene) methyl} -1-butenyl-5-chloro-3- (4-sulfobutyl) benzoxazolium. After that 4-hydroxy-6-methyl-1,3.3a, 7 tetrazaindene 1.0g and 1-phenyl-5-mercaptotetrazole 10.0mg
Was added to prepare a red-sensitive high-sensitivity emulsion. Further, 1 mole of silver halide is used as a cyan coupler per mole of silver halide.
17 g of N- [4- (2,4) -di-t-amylphenoxy) butyl] -2-naphthamide, 0.5 g of dodecyl gallate
Was added, and a mixture of 20 g of tricresyl phosphate and 60 m of ethyl acetate was heated and dissolved, and the mixture was added to 30 m of a 7.5% gelatin aqueous solution containing 1.5 g of sodium triisopropylnaphthalenesulfonate and emulsified and dispersed by a colloid mill. In addition, a red-sensitive high-sensitivity emulsion was prepared with a silver coating amount of 2.0.
It was applied so as to be g / m ² . (Contains 160 g of gelatin per mol of silver halide.) Fifth layer: intermediate layer Same as second layer Sixth layer: green-sensitive low-sensitivity silver halide emulsion layer Silver iodobromide emulsion as shown in Table 2 Are chemically sensitized with gold and sulfur sensitizers, respectively, and anhydrous as a green sensitizing dye.
5,5'-dichloro-9-ethyl-3.3'-di- (3-sulfobutyl) oxacarbocyanine hydroxide; anhydrous 5,
5'-diphenyl-9-ethyl-3.3'-di- (3-sulfobutyl) oxacarbocyanine hydroxide and anhydrous 9-ethyl 3.3'-di- (3-sulfopropyl) -5,
Add 6,5 ', 6'-dibenzooxacarbocyanine hydroxide and then 4-hydroxy-6-methyl-1,3.3a, 7
Tetrazaindene (1.0 g) and 1-phenyl-5-mercaptotetrazole (20.0 mg) were added to prepare a conventional method. The two kinds of silver halide emulsions thus obtained were mixed at a ratio of 1: 1 to prepare a green-sensitive low-sensitivity silver halide emulsion.

Further, 1 mol as a magenta coupler per mol of silver halide
-(2,4,6-Trichlorophenyl) -3- {3- (2,4-
100 g of di-t-amylphenoxy) acetamide} -5-pyrazolone, 1 as a colored magenta coupler
2.5 g of-(2,4,6-trichlorophenyl) -4- (1-naphthylazo) -3- (2-chloro-5-octadecenylsuccinimidoanilino) -5-pyrazolone, 0.5 g of dodecyl gallate, As a DIR compound, as shown in Table 2, a mixture of 120 g of tricresyl phosphate and 240 m of ethyl acetate was dissolved by heating, added to a gelatin aqueous solution containing sodium triisopropylnaphthalenesulfonate, and emulsified and dispersed by a colloid mill. The dispersion was added to prepare a green-sensitive low-sensitivity emulsion, which was coated so that the coated silver amount was 1.5 g / m ² . (Contains 160 g of gelatin per mol of silver halide.) Seventh layer: green sensitive high-sensitivity silver halide emulsion layer Silver iodobromide emulsion (average grain size 1.2 μ, silver iodide 7 mol%)
Are chemically sensitized with gold and sulfur sensitizers, and anhydrous 5,5'-dichloro-9-ethyl-3.3'-di- (3-sulfobutyl) oxacarbocyanine hydroxy is used as a green sensitizing dye. Anhydrous; 5,5'-diphenyl-9-ethyl-3.3'-di (3-sulfobutyl) oxacarbocyanine hydroxide and anhydrous-9-ethyl-3.3'-
Di- (3-sulfopropyl) -5,6,5 ', 6'-dibenzooxacarbocyanine hydroxide was added followed by 4-hydroxy-6-methyl-1,3.3a, 7-tetrazaindene 1.
0 g and 1-phenyl-5-mercaptotetrazole 1
0.0 mg was added to prepare a green-sensitive high-sensitivity silver halide emulsion. Further, 1- (2,4,6-trichlorophenyl) -3- {3-as a magenta coupler per mol of silver halide.
(2,4-di-t-amylphenoxy) acetamide}-
80 g of 5-pyrazolone, 1- (2,4,6-trichlorophenyl) -4- (1-naphthylazo) -3- (2-chloro-5-octadecenylsuccinimidoanilino) -5 as a colored magenta coupler -Pyrazolone 2.5g, 2,5
-Di-t-octylhydroquinone (1.5 g) was added as a DIR compound as shown in Table 2, and a mixture of 120 g of tricresyl phosphate and 240 m of ethyl acetate was dissolved by heating to contain sodium triisopropylnaphthalenesulfonate. A green-sensitive high-sensitivity emulsion was prepared by adding a dispersion obtained by emulsifying and dispersing in a gelatin aqueous solution with a colloid mill, and coating so that the coated silver amount was 1.8 g / m ² . (Contains 160 g of gelatin per mol of silver halide) Eighth layer: Intermediate layer Same as second layer Ninth layer: Yellow filter layer Yellow colloidal silver dispersed in gelatin aqueous solution 2,5
3 g of di-t-octylhydroquinone and 1.5 g of di-2-ethylhexyl phthalate were dissolved in 10 m of ethyl acetate, and sodium triisopropylnaphthalene sulfonate 0.3 g was dissolved.
A dispersion liquid dispersed in a gelatin aqueous solution containing g was added, and this was coated so that gelatin was 0.9 g / m ² and 2,5-di-t-octylhydroquinone was 0.10 g / m ² .

Layer 10: Blue-sensitive low-sensitivity silver halide emulsion layer Silver iodobromide emulsion (average grain size 0.6 μ, silver iodide 6 mol%
Are chemically sensitized with gold and sulfur sensitizers, and anhydrous 5,5'-dimethoxy-3.3'-di-
(3-Sulfopropyl) thiacyanine hydroxide was added, then 4-hydroxy-6-methyl-1,3.3a, 7 tetrazaindene 1.0 g and 1-phenyl-5-mercaptotetrazole 20.0 mg were added in the usual manner. A blue-sensitive low-sensitivity silver halide emulsion was prepared. Further, α-pivaloyl-α-as a yellow coupler per mol of silver halide.
(1-benzyl-2-phenyl-3.5-dioxo-1,2,4
-Triazolidin-4-yl) -2'-chloro-5'-
[Α- (dodecyloxycarbonyl) ethoxycarbonyl] acetanilide 120 g, α- {3- [α- (2,4-di-t-amylphenoxy) butyramide)} benzoyl-2′-methoxyacetanilide 50 g were added, and dibutyl was added. A mixture of 120 g of phthalate and 300 m of ethyl acetate was heated and dissolved, and the mixture was added to an aqueous gelatin solution containing sodium triisopropylnaphthalenesulfonate and emulsified and dispersed by a colloid mill to prepare a blue-sensitive low-sensitivity silver halide emulsion. The coating amount of silver was 0.7 g / m ² .
(Contains 160 g of gelatin per mol of silver halide) 11th layer: Blue-sensitive high-sensitivity silver halide emulsion layer Silver iodobromide emulsion (average grain size 1.2 μ, silver iodide 7 mol%)
Are chemically sensitized with gold and sulfur sensitizers, and anhydrous 5,5'-dimethoxy-3.3'-di-
(3-Sulfopropyl) thiacyanine hydroxide was added, and then 1.0 g of 4-hydroxy-6-methyl-1,3.3a, 7 tetrazaindene and 10.0 mg of 1-phenyl-5-mercaptotetrazole were added, followed by the usual method. To prepare a blue-sensitive high-sensitivity silver halide emulsion. Further, α-pivaloyl-α- (1-benzyl-2-phenyl-3.5-dioxo-1,2,4-triazolidin-4-yl) -2'-chloro-5'-as a yellow coupler per mol of silver halide. [Α- (Dodecyloxycarbonyl) ethoxycarbonyl] acetanilide 80g was added and a mixture of 80g dibutyl phthalate and 240m ethyl acetate was dissolved by heating and added to a gelatin aqueous solution containing sodium triisopropylnaphthalene sulfonate and emulsified and dispersed by a colloid mill. The dispersion was added to prepare a blue-sensitive high-sensitivity silver halide emulsion, which was coated so that the coating silver amount was 0.9 g / m ² . (Containing 240 g of gelatin per mol of silver halide) 12th layer: intermediate layer 2 g of di-2-ethylhexyl phthalate, 2- [3-cyano-3- (n-dodecylaminocarbonyl) arylidene] -1-ethylpyrrolidine 2g and ethyl acetate 2m are mixed, and triisopropyl naphthalene sulfonate sodium
A dispersion liquid dispersed in a gelatin aqueous solution containing 0.6 g was added, and this was coated so as to have a gelatin content of 1.0 g / m ² .

13th layer: Protective layer 1.3 g / m ^{2 of} gelatin aqueous solution containing 4 g of gelatin and 0.2 g of 1,2-bisvinylsulfonylethane per 100 m of gelatin.
Was applied. Sample 14 obtained in this way
24 was exposed and developed in the same manner as in Example 1. Further, the obtained dye image was evaluated in the same manner as in Example 1. The results obtained are shown in Table 2.

As is clear from Table 2, also in the multilayer sample, the combination of the monodisperse emulsion of the present invention and the DIR compound significantly improves the adjacency effect at the time of development and the temporal stability of the dye image, as in Example 1. You can see that it is done.

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, wherein the light-sensitive silver halide emulsion layer is a substantially monodisperse halogen. A silver halide photograph containing a silver halide grain and a development inhibitor releasing compound which releases a development inhibitor by a reaction with an oxidized product of a color developing agent and produces a mobile reaction product. Photosensitive material. However, the following compounds are excluded.