JPH0719038B2 - Silver halide color photographic light-sensitive material - Google Patents

Description

The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, the inter-image effect (interlayer effect; hereinafter referred to as IIE) is further emphasized. , A silver halide color photographic light-sensitive material having improved color reproducibility, sharpness and graininess.

In general, a silver halide color photographic light-sensitive material has three kinds of photographic silver halide emulsion layers, which are selectively spectrally sensitized to have sensitivity to blue light, green light and red light, coated on a support. ing. For example, in a silver halide photographic light-sensitive material for a color negative, a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer are generally coated in this order from the exposed side, A bleachable yellow filter layer is provided between the blue-sensitive silver halide emulsion layer and the green-sensitive silver halide emulsion layer to absorb blue light transmitted through the blue-sensitive silver halide emulsion layer. . Further, each emulsion layer is provided with another intermediate layer for various special purposes and a protective layer as the outermost layer. It is also known that each of these photosensitive silver halide emulsion layers is provided in an arrangement different from that described above, and further, as each silver halide emulsion layer, it has substantially the same wavelength range for each color light. It is also known to use a photosensitive silver halide emulsion layer consisting of two or more layers having photosensitivity and different sensitivities. In these silver halide color photographic light-sensitive materials, exposed silver halide grains are developed by using, for example, an aromatic primary amine type color developing agent as a color developing agent, and the generated color developing agent is oxidized. The reaction of the product with the dye-forming coupler forms a dye image. In this method, usually, in order to form a dye image of cyan, magenta and yellow, a phenol or naphthol type cyan coupler, a 5-pyrazolone type, a pyrazolinobenzimidazole type, a virazolotriazole type, an indazolone type or a cyano type, respectively. Acetyl magenta couplers and acylacetamide yellow couplers are used. These dye-forming couplers are contained in the light-sensitive silver halide emulsion layer or in the developing solution. INDUSTRIAL APPLICABILITY The present invention is suitable as a silver halide color photographic light-sensitive material in which a coupler is pre-diffused and contained in a silver halide emulsion layer.

BACKGROUND OF THE INVENTION Generally, in a silver halide color photographic light-sensitive material, the density of pixels forming an image is smooth and not rough, that is, the graininess is good, or the contour of the image is sharp and delicate. The image is rendered without blurring,
That is, photographic characteristics such as good sharpness are required. In recent years, as the sensitivity of color light-sensitive materials has been increased and the size of cameras has been reduced, the demand thereof has become stronger and stronger.

As a technique for improving graininess, it is known to provide an intermediate layer between the high sensitivity emulsion layer and the low sensitivity emulsion layer. In JP-B-49-15495, a gelatin layer or a medium-sensitivity silver halide emulsion layer having a low color density is provided as an intermediate layer, and in JP-A-53-7230, as an intermediate layer,
Providing a medium-sensitivity silver halide layer containing a DIR compound that reacts with an oxidant of a color developing agent to release a development-inhibiting substance, and JP-A-57-155539 discloses the same as a high-sensitivity emulsion layer as an intermediate layer. Techniques such as providing a non-photosensitive intermediate layer containing a coupler that develops a hue and has a slower coupling rate than the high-sensitivity emulsion layer are described.

However, the technique of providing these intermediate layers has many drawbacks such that not only the improvement of the graininess is insufficient, but also the film thickness becomes thicker by providing the intermediate layer and the sharpness deteriorates. .

It is also known that a technique for improving sharpness can be improved by utilizing an adjacency effect of a certain diffusing substance released during development. This effect is due to the change in the diffusive inhibitor released during development,
Specifically, there are a method of diluting a developing solution with water, a method of stirring strongly during development, a method of incorporating a compound which reacts with an oxide of a developing agent and releases a diffusible development inhibitor into a light-sensitive material. Are known. Among these, as a compound that reacts with the oxide of the developing agent to release the diffusible development inhibitor, for example, a dye by coupling with an oxidant of a color developing agent as described in U.S. Pat.Nos. 3,148,062 and 3,227,544. There are known compounds which generate a development inhibitor and release a development inhibitor, or compounds which release a development inhibitor by coupling with an oxidant of a color developing agent as described in US Pat. No. 3,632,345 and do not form a dye. In addition, JP-A-54-
No. 145135 discloses a DIR substance which indirectly releases an inhibitor by a secondary reaction induced by a reaction with an oxidized product of a color developing agent.

Adjacent effects of these diffusible development inhibitor substances released during development are disclosed in many patent publications and others in addition to the above technical disclosure. However, it is known that the sharpness is improved by the adjacent effect of these DIR compounds,
The level is not yet satisfactory, and the improvement in graininess is the same.

On the other hand, the color reproducibility is not yet sufficient like the image quality such as graininess and sharpness. In particular, there are many points that are not sufficient to reproduce the color saturation (chroma). This is because the spectral characteristics of the coloring dye obtained from the coupler used (there is no sufficient absorption in a specific wavelength range, or unnecessary in other wavelength ranges such as a phenolic cyan coupler having a ureido group at the 2-position). In addition to the color mixture due to the movement of the spectral sensitizing dye, the color mixture due to the oxidant of the color developing agent is considered.

One of the characteristics required for a color photographic light-sensitive material is that when one color-sensitive layer forms a dye image, the color phenomenon is generated by the oxidant of the color-developing agent and the other color-sensitive layer is colored. It is not cloudy, that is, it has high color purity.

Conventionally, an isolation layer (IL), which is also called an intermediate layer, is provided between different color-sensitive layers, and a scavenger of an oxidant of a color developing agent or a colorless coupler is added to the isolation layer (IL), or an isolation layer. It is known to add a diffusion inhibitor such as a sensitizing dye to (IL), for example, fine grain silver halide grains, cationic hydrophilic synthetic polymer, polymer latex and the like. However, even these methods have not yet reached the performance of exhibiting satisfactory color reproducibility.

As another method for improving color mixing, an automatic masking technique using a colored coupler is known, and it is commonly used in negative silver halide color photographic light-sensitive materials, but the level of color reproducibility is satisfactory. Absent.

There are techniques for improving color reproducibility by using a DIR coupler and emphasizing IIE, but various DIR compounds are used. For example, at the time of development, a so-called DIR coupler which reacts with an oxidized product of a color developing agent to form a color dye and releases a development inhibitor, and when developed, reacts with an oxidized product of a color developing agent to release a development inhibitor. A so-called DIR substance that does not form a coloring dye, a substance that directly releases a development inhibitor by reacting with an oxidant of a color developing agent, and a release agent that indirectly releases a development inhibitor,
For example, JP-A-54-145135, JP-A-57-154234 and JP-A-58-16.
No. 2949, No. 58-205150, No. 59-195643, No. 59-2068
No. 34, No. 59-206836, No. 59-210440, No. 60-7429, etc. (hereinafter referred to as a timing DIR compound). In the present specification, those exhibiting the DIR effect are generically referred to as DIR compounds.

JP-B-55-47379 and JP-A-57-93344 disclose a technique of using a so-called diffusible DIR compound to emphasize IIE from a certain color-sensitive layer to a different touch-sensitive layer.
No. 57-56837, No. 59-131937, etc., but the present situation is that even with these technologies, insufficient color reproducibility can be expected as described above.

[Object of the Invention] Therefore, the first technical object of the present invention is to improve the color reproducibility because the IIE between different color-sensitive layers is large.

On the other hand, as described in the above-mentioned patent publications and specifications, it is known that when a so-called diffusible DIR compound is used to generate IIE, the sharpness of an image is improved. This is due to the edge effect between layers as well as the edge effect IIE
This is due to the improvement in color contrast and so on.

Therefore, the second technical object of the present invention is to improve the sharpness of an image by emphasizing IIE using a DIR compound.

Furthermore, the present invention has a third technical object to improve graininess.

[Means for Solving the Problems] The silver halide color photographic light-sensitive material of the present invention for solving the above technical problems comprises a photographic constituent layer containing at least one light-sensitive silver halide emulsion layer on a support. In the silver halide color photographic light-sensitive material having, at least one of the light-sensitive silver halide emulsion layers has a Miller index (nn1) (n ≧
(2, n is a natural number) contains a silver halide having a crystal plane defined on the outer surface, and at least one photographic constituent layer reacts with an oxidant of a developing agent to develop a development inhibitor or a development inhibitor precursor. It is characterized by containing a compound (DIR compound) which releases

In the present specification, the photographic constituent layer refers to all hydrophilic colloid layers involved in image formation, for example, a silver halide emulsion layer, an undercoat layer, an intermediate layer (simple intermediate layer, filter layer,
UV absorbing layer, antihalation layer, etc.), protective layer, etc.

The process leading to the completion of the present invention is as follows.

The present inventors have attempted to solve the above-mentioned first to third technical problems by a technique of incorporating a DIR compound into a silver halide color photographic light-sensitive material, and as a result of earnest research,
It has been found that the silver halide grains used in the photosensitive emulsion layer have a deep relationship with the above technical problems. Particularly, in the case of a silver halide grain having a crystal plane defined by Miller index (nn1) (n ≧ 2, n is a natural number), (111) crystal plane or / and (100) crystal plane or / and (110) Compared to a silver halide grain having a crystal plane, it is more susceptible to the inhibitory action of a development inhibitor, and has a Miller index (nn1) (n ≧ 2,
When a DIR compound is added to a layer adjacent to a photosensitive emulsion layer containing silver halide grains having a crystal plane defined by (n is a natural number), a large IIE is exhibited and color reproducibility is extremely improved. For example, Miller index (nn1) (n ≧ 2,
We have found the surprising fact that the addition of a DIR compound to the photosensitive emulsion layer itself containing silver halide grains having a crystal plane defined by (n is a natural number) improves the sharpness and graininess.

The silver halide grains having a crystal plane defined by the Miller index (nn1) (n ≧ 2, n is a natural number) used in the present invention are completely new to the knowledge of the present inventors, and DIR
It was truly surprising that the combination of the above with IIE exerts the effect that it contributes to color reproducibility, and that it exerts an effect on sharpness and graininess.

Hereinafter, the present invention will be described in more detail.

The present invention relates to a silver halide grain having a crystal plane defined on the outer surface by a Miller index (nn1) (n ≧ 2, n is a natural number) on the outer surface.

Hereinafter, the (nn1) crystal plane will be described with reference to the drawings.

FIG. 1 is a diagram showing the morphology of the entire silver halide microcrystal when the outer surface is constituted only by (nn1) crystal faces. Further, FIG. 2 is a side view seen from the directions of the straight lines b ₁ and b ₂ . (Nn
1) There are 24 equivalent crystal faces expressed as crystal faces. For this reason, all outer surfaces are composed of (nn1) crystal faces, and crystals have the shape of a dodecahedron, and each plane forming the outer surface is an acute triangle. There are two types of vertices,
That is, there are 6 vertices equivalent to a ₁ and 8 vertices equivalent to b ₁ in FIG. Vertex a ₁ 8 plane and is bounded, 3 plan Vertex b ₁ is bounded. There are also two types of edges. That is, it is equivalent to the sides a ₁ and b ₁ in FIG.
24 edges and 12 edges equivalent to a ₁ a ₂ .

FIG. 12 shows an electron micrograph of nearly perfect hexahedral silver halide grains whose outer surface is composed of (nn1) crystal faces.

Next, using the cross-sectional view, (nn1) crystal face, (111) crystal face,
The relationship of the (110) crystal plane will be described. A solid line 1 in FIG. 3 shows a cross-sectional view in a plane perpendicular to the triangles a ₁ a ₂ b ₁ and the triangle a ₁ a ₂ b ₂ including the tetrahedral line b ₁ b ₂ in FIG. That is, in FIG. 3, the solid line 1 represents the (nn1) crystal plane.
On the other hand, the broken line 2 represents the (110) crystal face and the dash-dotted line 3 represents the (111) crystal face, and the normal vector of each of the (nn1) crystal face, the (111) crystal face, and the (110) crystal face. ,
Indicated by.

= (110), = (111), = (111 / n) (n ≧ 2,
n can be expressed as a natural number. θ is an angle formed by two (nn1) crystal faces adjacent to each other with a ₁ a ₂ as a boundary, and n ≧ 2,
n is 110 ° C. <θ <180 ° C. due to the limitation of a natural number.

From the above, it is apparent that the (nn1) crystal plane according to the present invention is a crystal plane which is completely different from the (111) crystal plane and the (110) crystal plane which are conventionally known in silver halide microcrystals. Also, it does not require any particular explanation that it is different from the (100) crystal plane.

On the other hand, Japanese Patent Application No. 59-206765 discloses "a crystal plane having a ridge at the center of the (110) crystal plane". In the specification, this crystal plane is named as a quasi (110) plane, and it is described that "the angle between two roof-shaped quasi (110) planes sharing an ridgeline is an obtuse angle than 110 ° C". That is, the quasi (110) plane is synonymous with the (nn1) crystal plane (n ≧ 2, n is a natural number) according to the present invention.

The silver halide grains according to the present invention need not have all outer surfaces composed of (nn1) crystal faces. That is, (111)
A crystal face, a (100) crystal face, or a (110) crystal face may exist. Examples of these are shown in FIGS.
30 due to the mixture of (111) and (100) crystal faces
Face piece (Figs. 4, 5, 6), 38 face piece (Figs. 7, 8, 9),
It takes the form of a 32-sided body (Figs. 10 and 11).

In order to identify the crystal planes of silver halide grains, powder method X-ray diffraction [Brenting of the Society of Scientific Photography of Japan (Bulletion of the of the Society of Scientific potograph
y of Japan), Vol. 13, p. 5] can be used.

However, regarding the (nn1) crystal plane according to the present invention, even if all the outer surfaces are dodecahedron grains composed of (nn1) crystal planes, the ratio of the area of one surface to the grain volume is 8 Remarkably small compared to the face piece and rhomboid dodecahedron. For this reason, it is difficult to align the (nn1) crystal plane on the substrate. In addition, the (nn1) crystal plane is of higher order, so its diffraction intensity is also small. For the above reasons, powder method X-ray diffraction cannot be used to identify the (nn1) crystal plane, and at present, electron microscope photographs show the ratio of the two side lengths, the angle between the two planes, etc. In order to identify the Miller index of the surface.

According to this, it was found that the (nn1) crystal plane according to the present invention exists in a wide range of the value of n, and the effect of the present invention is exhibited in all cases.

The silver halide grain according to the present invention is a crystal having a (nn1) crystal face on the outer surface and may be a normal crystal or a twin crystal (including multiple twin crystals). In the crystal form, the particles include those that correspond to at least one of the following items.

The ratio of the surface area of the (nn1) crystal plane to the total surface area is at least 30%. If the boundary between two crystal planes is unclear (for example, the boundary has a rounded shape) when obtaining this ratio, the intersection line between these two planes is obtained as the boundary.

See FIG. 12 below and the description in Japanese Patent Application No. 59-206765.
It belongs to the range of crystal morphology shown in the electron micrographs of FIGS. 10 to 13.

It belongs to the range of crystal morphology shown in FIGS. 1 to 11 described later.

The composition of the silver halide grains according to the present invention can take various modes, but the ratio of silver iodide is preferably 0 to 40 mol%.
And more preferably 0 to 20 mol% and 0 to 15 mol%
Is particularly preferred. The ratio of silver chloride is 0-98.
Used in mol%.

Further, even a silver halide grain having a single composition has a plurality of layers or phases having different silver halide compositions (2
It may be a silver halide grain consisting of three or three layers.
The silver halide composition in each layer may be uniform or continuously variable. One of the most preferable forms is one having a high iodine shell inside the grain. That is, it is a silver halide grain having a layer or phases (a plurality of layers may be present) having a large iodide content on the grain surface.

The grain size of the silver halide grains according to the present invention is not particularly limited, and the present invention is effective at least in the range of preferably 0.1 to 3.0 μm. In the present specification, the grain size of silver halide refers to the length of one side of the cube which is equal to the volume.

The silver halide grains according to the present invention are usually produced and used in a form dispersed in a dispersion medium such as gelatin, that is, a form called an emulsion. The particle size distribution of the group of particles at this time may be monodisperse, polydisperse, or a mixture of these, and can be appropriately selected depending on the application etc., but the coefficient of variation of the particle size distribution is The effect of the present invention is more remarkable in a monodisperse emulsion of 20% or less. This coefficient of variation is Is a measure of monodispersity.

As described above, the silver halide grains according to the present invention may include a plane other than the (nn1) crystal plane, such as a (111) crystal plane or a (100) crystal plane, on the outer surface. The ratio of the area of the (nn1) crystal plane to the total surface area is as described above.
It is at least 30% or more, preferably 50% or more, more preferably 70% or more.

By using a silver halide emulsion containing a silver halide grain having a (nn1) crystal plane on the grain surface as in the present invention, a conventional silver halide emulsion having no (nn1) crystal plane can be obtained. It has become possible to obtain various advantages as photographic emulsions which were not available. For example, compared with an emulsion containing silver halide grains (hereinafter referred to as a conventional emulsion) whose outer surface is composed of a (111) crystal face or / and a (100) crystal face or / and a (110) crystal face,
Fogging can be suppressed low and sensitivity can be increased.

Accordingly, it is possible to provide a photographic light-sensitive material having more excellent graininess than conventional emulsions.

Among the conventional emulsions, emulsions having a (110) crystal plane are known to be excellent in the fog-sensitivity relationship, but this has the drawback of poor storage stability at high temperatures. On the other hand, an emulsion having a (nn1) crystal plane is excellent in the fog-sensitivity relationship and also excellent in storage stability at high temperature.

Since a tetrazaindene compound is used as a compound (hereinafter, referred to as a crystal control compound) that promotes the development of (nn1) crystal planes in the production method described below, silver iodobromide grains having a desired silver iodide content can be obtained. Can be done relatively easily.

This production method can produce an emulsion having particularly high monodispersity. In this respect, it is superior to an emulsion having a (110) crystal plane produced by using mercaptoazoles as a crystal control compound.

Accordingly, a photographic light-sensitive material having excellent sharpness can be provided.

Next, a method for producing a silver halide emulsion containing silver halide grains having a (nn1) crystal plane according to the present invention will be described.

That is, in the step of forming a silver halide grain by mixing a water-soluble silver salt solution and a water-soluble halide solution in the presence of a protective colloid, the pAg of the emulsion is adjusted to a period during which at least 30 mol% of all silver halide is produced. Controlled in the range of 7.0 to 9.8, and during this period, the following general formulas (I), (II), (III)
Or a compound represented by (IV) and the following general formula (V)
At least one compound selected from the compounds having the repeating unit represented by

Further, after the completion of the silver halide grain forming step, the period pAg before entering the desalting step is controlled within the range of 7.0 to 9.5.

In the formula, R ₁ , R ₂ and R ₃ may be the same or different,
Hydrogen atom, halogen atom, amino group, amino group derivative, alkyl group, alkyl group derivative, aryl group,
Aryl group derivative, cycloalkyl group, cycloalkyl group derivative, mercapto group, mercapto group derivative or -CONH-R ₄ (R ₄ is a hydrogen atom, alkyl group, amino group, alkyl group derivative, amino group derivative , Halogen atom, cycloalkyl group, derivative of cycloalkyl group,
It represents an aryl group or a derivative of an aryl group. ), R ₅ represents a hydrogen atom or an alkyl group, R ₁ and R ₂ may be bonded to form a ring (for example, a 5- to 7-membered carbocycle or heterocycle), and X is a general formula. 1 obtained by removing one hydrogen atom from the compound represented by (I), (II), (III) or (IV)
A valent group (for example, in the above general formulas (I) to (IV))
R _{1 to} R ₃ or an OH moiety excluding one hydrogen atom), and J represents a divalent linking group.

In the method for producing silver halide grains according to the present invention, seed grains may be used, and silver halide may be generated on the surface thereof to grow the grains. When the seed grains are used, the silver halide composition may be within the range capable of forming the silver halide grains according to the present invention.

The period for controlling the pAg is arbitrary as long as it is within the period during which silver halide is produced, and may be at the beginning, midway or end of the silver halide producing step. Further, this period is preferably a continuous period, but may be intermittent as long as the effect of the present invention is not impaired. PA in this period
g is preferably 7.3 to 9.5, more preferably 7.6 to 9.
Is 2. During this period, the pH of the emulsion is preferably kept in the range of 7-10. PAg of silver halide outside this period
Is suitably in the range of 4 to 11.5, preferably in the range of 6 to 11, and the pH is suitably in the range of 2 to 12, preferably in the range of 5 to 11.

In the method for producing silver halide grains of the present invention, any method such as an acidic method, a neutral method or an ammonia method can be used in the step of forming silver halide to form silver halide grains. As the method of reacting the soluble silver salt and the soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method and a combination thereof may be used. A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one form of the simultaneous mixing method, a method of keeping pAg constant in a liquid phase where silver halide is produced, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained. Further, it is preferable to use a silver halide solvent because the grain formation time can be shortened. For example, a commonly known silver halide solvent such as ammonia or thioether can be used.

In addition, in order to make the particle size uniform, British Patent 1,535,01
No. 6, JP-B-48-36890 and JP-B No. 52-16364, a method of changing the addition rate of an aqueous solution of silver nitrate or an alkali halide according to the grain growth rate, and US Pat.
As described in JP-A No. 4,242,445 and JP-A No. 55-158124, it is preferable to grow rapidly within a range not exceeding the critical saturation by using a method of changing the concentration of the aqueous solution.
These methods are preferably used also when forming grains having a plurality of layers having different halogen compositions, since nuclear silver halide grains are uniformly coated without re-nucleation.

When providing layers having different halogen compositions, a halogen substitution method can be used.

The halogen substitution method can be performed, for example, by adding an aqueous solution mainly containing an iodo compound (preferably potassium iodo), preferably an aqueous solution having a concentration of 10% or less. For details, refer to US Pat.
It can be carried out by the method described in 4,075,020 and JP-A-55-127549. At this time, in order to reduce the difference in iodine distribution between the grains of the high iodine shell, it is desirable to adjust the concentration of the aqueous iodine compound solution to 1 × 10 ⁻² mol% or less and to add it for 10 minutes or more.

When shells having different halogen compositions are provided, a desalting step may be carried out in accordance with a conventional method, if necessary, or shells may be continuously formed without carrying out the desalting step.

In the method for producing silver halide grains of the present invention, one of the most preferable forms is a method of adding an aqueous ammoniacal silver nitrate solution and an aqueous halide solution by a controlled double jet method in the presence of ammonia.

Next, the crystal control compound will be described.

In the general formulas (I) to (V), examples of the alkyl group represented by R _{1 to} R ₄ include a methyl group, an ethyl group, a propyl group, a pentyl group, a hexyl group, an octyl group, an isopropyl group, sec- Examples thereof include a butyl group, a t-butyl group and a 2-norbornyl group, and examples of the derivative of the alkyl group are substituted with an aromatic residue (a divalent linking group such as-
Alkyl group (may be through NHCO-, etc.) (eg, benzyl group, phenethyl group, benzhydryl group, 1-naphthylmethyl group, 3-phenylbutyl group, benzoylaminoethyl group, etc.), alkyl group substituted with an alkoxy group (For example, methoxymethyl group, 2-methoxyethyl group, 3
-Ethoxypropyl group, 4-methoxybutyl group, etc.), halogen atom, hydroxy group, carboxy group, methylcapto group, alkoxycarbonyl group or alkyl group substituted with a substituted or unsubstituted amino group (for example, monochloromethyl group, hydroxymethyl group). Group, hydroxyethyl group, 3-hydroxybutyl group, carboxymethyl group, 2
-Carboxyethyl group, 2- (methoxycarbonyl) ethyl group, aminomethyl group, diethylaminomethyl group, etc.), alkyl group substituted with cycloalkyl group (eg, cyclopentylmethyl group, etc.), the above general formula (I) to
Examples thereof include an alkyl group substituted with a monovalent group obtained by removing one hydrogen atom from the compound represented by (IV).

Examples of the aryl group represented by R _{1 to} R ₄ include a phenyl group and a 1-naphthyl group, and examples of the derivative of the aryl group include a p-tolyl group, m-ethylphenyl group and m-cumenyl group. A mesityl group, a 2,3-xylyl group,
p-chlorophenyl group, o-bromophenyl group, p-hydroxyphenyl group, 1-hydroxy-2-naphthyl group, m-methoxyphenyl group, p-ethoxyphenyl group, p-carboxyphenyl group, o- (methoxycarbonyl) Examples thereof include a phenyl group and a 4-carboxy-1-naphthyl group.

Examples of the cycloalkyl group represented by R _{1 to} R ₄ include a cycloheptyl group, a cyclopentyl group and a cyclohexyl group, and examples of the derivative of the cycloalkyl group include a methylcyclohexyl group. Examples of the halogen atom represented by R _{1 to} R ₄ include fluorine, chlorine, bromine and iodine, and examples of the derivative of the amino group represented by R _{1 to} R ₄ include butylamino group, diethylamino group and anilino group. Etc. Examples of the mercapto group derivative represented by R _{1 to} R ₃ include a methylthio group, an ethylthio group, and a phenylthio group.

The alkyl group represented by R ₅ preferably has 1 to 6 carbon atoms, and examples thereof include a methyl group and an ethyl group.

R ₅ is particularly preferably a hydrogen atom or a methyl group.

J is a divalent linking group, and preferably has a total carbon number of 1 to 20. Among such linking groups, the following formula (J-
Those represented by I) or (J-II) are preferable.

In the formula, Y is -O- or (Here, R ₆ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Z is an alkylene group (preferably having up to 10 carbon atoms. An amide bond, an ester bond, or an ether bond may be interposed in the middle of the alkylene group. For example, a methylene group, an ethylene group, a propylene group-CH ₂ OCH. ₂ −, −CH ₂ CO
_{NHCH 2 -, - CH 2 CH} 2 COOCH 2 -, - CH 2 CH 2 OSOCH 2 -, - CH 2
NHCOCH ₂ — etc.) —O-alkylene group, —CONH-alkylene group, —COO-alkylene group, —OCO-alkylene group or —NHCO-alkylene group (these alkylene groups preferably have up to 10 carbon atoms) or It represents an arylene group (preferably having 6 to 12 carbon atoms, for example, p-phenylene group).

Particularly preferable divalent linking groups as J include the following.

−CONHCH ₂ −, −CONHCH ₂ CH ₂ −, −CONHCH ₂ OCOCH ₂ −, −
_{CONHCH 2 CH 2 CH 2 OCOCH 2} -, - COOCH 2 -, - COOCH 2 CH 2 -,
-COOCH ₂ CH ₂ OCOCH _2- , -COOH ₂ CH ₂ CH ₂ OCOCH _2- , The compound having the unit represented by the general formula (V) may be a homopolymer or a copolymer, and examples of the copolymer include acrylamide, methacrylamide, acrylic ester, methacrylic ester and the like.

Next, the general formula (I), (II), (III) or (I
Representative specific examples of the compound represented by V) or the compound having the repeating unit represented by the general formula (V) (hereinafter, referred to as tetrazaindene compound used in the present invention) are shown.

The addition amount of the tetrazaindene compound used in the production of the silver halide grains of the present invention varies depending on the desired final grain size of silver halide, the temperature of the emulsion, pH, pAg, and the production conditions of the silver iodide content, 1 per 1 mol of total silver halide produced
The range of × 10 ^{-5 to} 2 × 10 ^-1 mol is preferable.

When the tetrazaindene compound is a compound having a unit represented by the general formula (V), the number of moles of the tetrazaindene portion is the addition amount. The more preferable addition amount is as shown in Table A with respect to the particle size. The addition amount with respect to the particle size other than the particle size described in Table A can be obtained by the extrapolation method or the interpolation method by making the addition amount inversely proportional to the particle size.

Further, more preferable addition amount is as shown in Table B with respect to pAg and silver iodide content.

The tetrazaindene compound may be added in advance in a protective colloid solution, gradually added as the silver halide grains grow, or added together.

In a usual use form of the silver halide emulsion of the present invention, an excess halogen compound produced during the preparation of silver halide grains or salts and compounds such as acetate salts, ammonia and the like, which are by-produced or become unnecessary, are dispersed in the grains. It should be removed (desalting step) from the medium. The removal method is the Nudel water washing method, dialysis method or inorganic salt, anionic surfactant, anionic polymer (eg polystyrene sulfonic acid), or gelatin derivative (eg acylated gelatin, carbamoylated gelatin etc.) which is commonly used in general emulsions. It is possible to appropriately use a precipitation method utilizing coagulation, a coagulation precipitation method (flocculation), or the like.

The pAg of the mother liquor must be controlled in the range of 7.0 to 9.5 after the desired silver halide grains are obtained in the silver halide grain formation step and before the desalting step is performed. During this period, the pAg is preferably 7.4 to 9.2, more preferably 7.8 to 9.0. The pH is preferably 5-8, more preferably 5-7. The time from the end of the particle forming step to the start of the desalting step is preferably short, preferably within 30 minutes, more preferably within 20 minutes.

The feature of this production method is that a silver halide emulsion having excellent monodispersity can be supplied, as described in Japanese Patent Application No. 59-158111.

The silver halide grains having a (nn1) crystal plane according to the present invention are cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or a complex salt thereof, rhodium salt or a salt thereof in the process of silver halide grain formation or physical ripening. A complex salt, an iron salt, an iron complex salt, a gold salt, a gold complex salt, or the like may coexist. Further, the addition amount thereof may be a small amount or a large amount depending on the intended light-sensitive material.

In order to remove the soluble salts from the emulsion after the precipitation or after the physical ripening, the Nudel washing method in which gelatin is gelatinized may be used, and inorganic salts, anionic surfactants, anionic polymers (for example, polystyrene) may be used. Alternatively, a precipitation method (flocculation method) using a sulfonic acid) or a gelatin derivative (eg, acylated gelatin, carbamoylated gelatin, etc.) may be used.

The silver halide emulsion may or may not be chemically sensitized. For chemical sensitization, for example, H. Frieser edited by Die Grundlagen der Photographie-chen
Prozesse mit Silberhalogeniden (Akade-mische Ver
lagsgesellschaft, 1968) pp. 675-734.

Preferred examples of the DIR compound contained in the photographic constituent layers of the silver halide color photographic light-sensitive material of the present invention are represented by the following general formula [V
I] and / or [VII], of which the most preferred DIR compound is a compound represented by the following general formula [VII].

In the general formula [VI] A ₁ -Z ₁ , A ₁ is a coupling component (compound) capable of coupling with an oxidant of a color developing agent, for example, a closed ketomethylene compound such as acylacetanilide or acylacetate, or pyrazolone. And pyrazolotriazoles, pyrazolinobenzimidazoles, indazolones, phenols, naphthols, and other dye-forming couplers, and acetophenones, indanones, oxazolones, and other coupling components that do not substantially form dyes.

Further, Z ₁ in the above formula is a component (compound) which is released by the reaction with a color developing agent and suppresses the development of silver halide, and preferred compounds are benztriazole and 3-
There are heterocyclic compounds such as octylthio-1,2,4-triazole and heterocyclic mercapto compounds (the heterocyclic mercapto group includes i-phenyltetrazolylthio group).

Examples of the heterocyclic group include a tetrazolyl group, a thiadiazolyl group, an oxadiazolyl group, a thiazolyl group, an oxazolyl group, an imidazolyl group, and a triazolyl group. Specifically, 1-phenyltetrazolyl group, 1-ethyltetrazolyl group, 1- (4-hydroxyphenyl) tetrazolyl group, 1,3,4-thiazolyl group, 5
-Methyl-1,3,4-oxadiazolyl group, benzthiazolyl group, benzoxazolyl group, benzimidazolyl group, 4H-1,2,4-triazolyl group and the like.

In the general formula [IV], Z ₁ is bonded to the active site of A ₁ .

In the general formula [VII] A ₂ -TIME-Z ₂ Formula, Z ₂ is the same as Z ₁ as defined in the general formula [VII]. A ₂ also includes a coupling component that forms a completely diffusible dye, as defined in the general formula [VII]. TIME represents a timing group capable of releasing from the compound represented by the general formula [VII] together with Z _{2 when} A ₂ reacts with the oxidant of the color developing agent, and then releasing Z _2. General formulas [VIII], [IX],
It is represented by [X], [XI] and [VII], but is not limited thereto.

General formula [VIII] In the formula, X represents an atomic group necessary for completing a benzene ring or a naphthalene ring. Y is -0-, -S-, (Wherein R ₃ represents a hydrogen atom, an alkyl group or an aryl group) and is bonded to the coupling position. Also
R ₁ and R ₂ each represent a group having the same meaning as R ₃ above, Is substituted in the ortho or rose position with respect to Y and is bonded to the heteroatom contained in the inhibitor Z ₂ .

General formula [IX] In the formula, W is a group having the same meaning as Y in the general formula [VIII], and R ₄ and R ₅ are also groups having the same meaning as R ₁ and R ₂ in the general formula [VIII].

R ₆ is a hydrogen atom, an alkyl group, an aryl group, an acyl group, a sulfo group, an alkoxycarbonyl group, a heterocyclic residue,
R ₇ is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic residue,
It represents an alkoxy group, an amino group, an acylamido group, a sulfonamide group, a carboxy group, an alkoxycarbonyl group, a carbamoyl group, and a cyan group. And this timing group is attached to the coupling position of A ₂ by W, Binds to the heteroatom of inhibitor Z ₂ .

Next, an example of a timing group that releases the inhibitor Z ₂ by an intramolecular nucleophilic substitution reaction is shown by the general formula [X].

General formula [X] In the formula, Nu is a nucleophilic group having an electron-rich oxygen, sulfur, or nitrogen atom and is bonded to the coupling position of A ₂ . E is an electrophilic group having an electron-deficient carbonyl group, thiocarbonyl group, phosphinyl group, or thiophosphinyl group, and is bonded to the heteroatom of the inhibitor Z ₂ .

V sterically relates Nu and E, and after Nu is released from A _2, undergoes an intramolecular nucleophilic substitution reaction involving the formation of a 3-membered ring or a 7-membered ring, and thereby an inhibitor It is a linking group capable of releasing Z ₂ .

General formula (XI) In the formula, R ₈ represents a hydrogen atom, an alkyl group or an aryl group,
The oxygen atom is bonded to the coupling position of A ₂ and the carbon atom is bonded to the nitrogen atom of the inhibitor Z ₂ .

General formula (XII) In the formula, Y'is a group having the same meaning as Y in the general formula [VIII], R ₉ is an alkyl group, an aralkyl group, an aryl group,
It represents a heterocyclic group, which is bonded to the coupling position of A ₂ with Y ′ and to the hetero atom of the inhibitor Z ₂ with a carbon atom.

As described above, as a typical example of the DIR compound of the present invention, a group capable of forming a compound having a development inhibiting action when released from the active site is introduced into the active site of the coupler.
There are DIR couplers, these are for example British Patent 935,454.
U.S. Pat.Nos. 3,227,554, 4,095,984, 4,149,88
No. 6, JP-A-57-151944. DIR above
The coupler has a property that, when the coupler reacts with the oxidation product of the color developing agent, the mother nucleus of the coupler forms a dye, while releasing the development inhibitor. Further, in the present invention, when a coupling reaction with an oxidant of a color developing agent is carried out, a development inhibitor is released, but a compound which does not form a dye is also included.These are U.S. Pat.Nos. 3,652,345, 3,928,041, and 3,958,993.
No. 3,961,959, No. 4,052,213, JP-A-53-110529.
No. 54-13333, No. 55-161237, etc. Furthermore, upon reaction with the oxidant of the color developing agent, the mother nucleus forms a dye or a colorless compound, while
Also included in the present invention are so-called timing DIR compounds, in which the released timing group is a compound that releases a development inhibitor by an intramolecular nucleophilic substitution reaction or an elimination reaction, and these are also included in the present invention, and these are disclosed in JP-A Nos. 52-90932 and 54-145135. No. 56-114946, No. 5
7-154234, 58-205150 and 60-7429. It also includes a timing DIR compound having a timing group as described above bonded to a coupler mother nucleus which forms a dye that is completely diffusible when it reacts with an oxidized product of a color developing agent. Sho 58-160954,
No. 58-162949, etc.

In addition to those described in the above-mentioned patent publications or publications, DIR compounds of the present invention include JP-A-60-182438 and 60-
-184248, 60-185950, 60-213944, 60-
No. 214358, No. 60-218644, No. 60-221750, No. 60-
225156, 60-225844, 60-229030, 60-23
No. 0139, No. 60-232549, No. 60-233648, No. 60-2336
No. 49, No. 60-233650, No. 60-237446, No. 60-237447
No. 60-249148, No. 60-249149 and the like.

Hereinafter, typical specific examples of the DIR compound according to the present invention will be described, but the present invention is not limited thereto.

[Exemplified compound] The DIR compound of the present invention can be added to a light-sensitive silver halide emulsion layer and / or a non-light-sensitive photographic constituent layer, but it can be added to a light-sensitive silver halide grain having (nn1) crystal faces of the present invention. It is preferably added to the silver halide emulsion layer and / or its adjacent layers (including an intermediate layer).

The preferred use of the DIR compound of the present invention is as follows.

That is, when the DIR compound of the present invention is contained in the photosensitive emulsion layer itself containing silver halide grains having a (nn1) crystal plane, the sharpness and graininess improving effects are mainly remarkable. The DIR compound of the invention is used as a layer adjacent to a light-sensitive emulsion layer containing silver halide grains having (nn1) crystal faces (for example, silver halide grains having (nn1) crystal faces in the present invention, or other halogenated silver halide grains). A photosensitive emulsion layer containing silver,
Or in a non-photosensitive intermediate layer), IIE is exhibited from the adjacent layer to the photosensitive emulsion layer containing the silver halide grains having the (nn1) crystal plane of the present invention, and color reproducibility is extremely good. Becomes

For example, in the case of a full-color film, a red-sensitive emulsion layer containing silver halide grains having a (nn1) crystal face on a support, a silver halide grain having a (nn1) crystal face in the present invention, or otherwise. And a blue-sensitive emulsion layer containing silver halide grains having a (nn1) crystal plane, and the green-sensitive emulsion layer contains the DIR compound of the present invention. IIE from the green-sensitive emulsion layer to the red-sensitive emulsion layer and / or the blue-sensitive emulsion layer is exerted, resulting in extremely good color reproducibility, and the green-sensitive emulsion layer having the (nn1) crystal plane of the present invention. If particles are included, their sharpness and graininess are significantly improved.

In order to expect the effect of improving the sharpness and graininess in the above-mentioned full-color film, for example, in the red-sensitive emulsion layer, the DIR compound of the present invention may be contained in the red-sensitive emulsion layer.

Two or more kinds of the DIR compound of the present invention may be contained in the same layer.
Also, the same DIR compound may be contained in two or more different layers.

Generally, these DIR compounds are preferably 2 × 10 ^{−5 to} 5 × 10 ⁻¹ , and more preferably 1 × 10 5 per mol of silver in the emulsion layer.
^-4 to 1 x 10 ^-1 mol is used.

To incorporate these DIR compounds into the silver halide emulsion according to the present invention or other photographic constituent layer coating solution,
If the DIR compound is alkali-soluble, it may be added as an alkaline solution, and if it is oil-soluble,
For example, U.S. Patent Nos. 2,322,027, 2,801,170, and
No. 2,801,171, No. 2,272,195 and No. 2,304,940, the DIR compound is dissolved in a high-boiling solvent according to the method described in each specification, if necessary in combination with a low-boiling solvent, and dispersed in fine particles to be halogenated. It is preferably added to the silver emulsion. At this time, two or more kinds of DIR compounds may be mixed and used if necessary. Furthermore, in detail, the preferred method of adding a DIR compound in the present invention is to use one or more DIR compounds as organic acid amides, carbamates, esters, ketones, urea derivatives, ethers, hydrocarbons. Etc., especially di-n-butyl phthalate,
Tricresyl phosphate, triphenyl phosphate, di-isooctyl azelate, di-n-butyl sebacate, tri-n-hexyl phosphate, N, N-di-
Ethyl-caprylamidobutyl, N, N-diethyllaurylamide, n-pentadecylphenyl ether, di-octylphthalate, n-nonylphenol, 3-pentadecylphenylethyl ether, 2,5-di-sec-amylphenylbutyl ether, A high boiling point solvent such as monophenyl-di-o-chlorophenyl phosphate or fluoroparaffin, and / or methyl acetate, ethyl acetate,
Propyl acetate, butyl acetate, butyl propionate, cyclohexanol, diethylene glycol monoacetate, nitromethane, carbon tetrachloride, chloroform, cyclohexane tetrahydrofuran, methyl alcohol, acetonitrile, dimethylformamide, dioxane, dissolved in a low boiling point solvent such as methyl ethyl ketone, Mixing with an aqueous solution containing an anionic surfactant such as alkylbenzene sulfonic acid and alkylnaphthalene sulfonic acid and / or a nonionic surfactant such as sorbitan sesquioleate and sorbitan monolauryl ester and / or a hydrophilic binder such as gelatin Then
It is emulsified and dispersed by a high-speed rotary mixer, colloid mill, ultrasonic dispersion device, etc. and added to the silver halide emulsion.

In addition, the DIR compound may be dispersed using a latex dispersion method. The latex dispersion method and its effect are described in JP-A-49-74538, JP-A-51-59943 and JP-A-54-32552, and Research Disclosure, August 1976, No. 148.
50, p. 77-79.

Suitable latices include, for example, styrene, acrylates,
n-butyl acrylate, n-butyl methacrylate,
2-acetoacetoxyethyl methacrylate, 2- (methacryloyloxy) ethyltrimethylammonium methosulfate, 3- (methacryloyloxy) propane-1-sulfonic acid sodium salt, N-isopropylacrylamide, N- [2- (2-methyl-4) -Oxopentyl)] acrylamide, 2-acrylamido-2-
Homopolymers, copolymers and terpolymers of monomers such as methyl propane sulfonic acid and the like.

The above-mentioned DIR compounds are described in U.S. Patents 3,227,554 and 3,615,50.
No. 6, No. 3,617,291, No. 3,632,345, No. 3,928,041,
3,933,500, 3,938,996, 3,958,993, 3,9
61,959, 4,046,574, 4,052,213, 4,063,95
0, 4,095,984, 4,149,886, 4,234,678,
British Patents 2,072,365, 2,070,266, Research Disclosure 21228 (1981), JP-A-50-81144
No. 50, No. 81-145145, No. 51-13239, No. 51-64927,
51-104825, 51-105819, 52-65433, 5
2-82423, 52-117627, 52-130327, 52-
No. 154631, No. 53-7232, No. 53-9116, No. 53-29717
No. 53-70821, No. 53-103472, No. 53-110529
No. 53-135333, No. 53-143223, No. 54-13333
No. 54, No. 54-13838, No. 54-114241, No. 57-35858,
54-145135, 55-161237, 56-114946,
57-154234, 57-56837 and Japanese Patent Application No. 57-44831,
No. 57-45809, and other methods described in the above-mentioned patent publications or publications can be used for synthesis.

The DIR compound of the present invention can be added to the light-sensitive silver halide emulsion layer and / or the non-light-sensitive photographic constituent layer as described above, but it is preferably contained in at least one of the silver halide emulsion layers. Is. For example, when it is applied to an ordinary multi-layer color photographic light-sensitive material having a blue-sensitive silver halide emulsion, a green-sensitive silver halide emulsion and a red-sensitive silver halide emulsion, it may be contained in one or more layers. Good.

Each silver halide emulsion layer according to the present invention may contain a coupler, that is, a compound capable of reacting with an oxidized product of a color developing agent to form a dye.

As the coupler usable in the present invention, various yellow couplers, magenta couplers and cyan couplers can be used without particular limitation. These couplers may be so-called 2-equivalent type or 4-equivalent type couplers, and it is also possible to use diffusible dye releasing type couplers in combination with these couplers.

As the yellow coupler, a closed ketomethylene compound (in particular, a benzoylacetanilide compound and a pivaloylacetanilide compound are preferable), and a so-called 2
Active point-o-anneal substitution coupler, active point-o-acyl substitution coupler, active point hydantoin compound substitution coupler, active point urazole compound substitution coupler and active point succinimide compound substitution coupler, active point called equivalent type coupler Fluorine-substituted couplers, active-point chlorine or bromine-substituted couplers, active-point-o-sulfonyl-substituted couplers and the like can be used as effective yellow couplers. Specific examples of yellow couplers that can be used include U.S. Patents 2,875,057, 3,265,506, 3,408,194,
3,511,155, 3,582,322, 3,725,072, 3,8
91,445, West German patent 1,547,868, West German application publication 2,219,9
No. 17, No. 2,261,361, No. 2,414,006, British Patent 1,425,
020, Japanese Patent Publication No. 51-10783, JP-A Nos. 47-26133 and 48.
-73147, 51-102636, 50-6341, 50-123
No. 342, No. 50-130442, No. 51-21827, No. 50-8765
0, No. 52-82424, No. 52-115219, No. 58-95346 and the like.

Particularly preferred couplers are:

Examples of the magenta coupler used in the present invention include pyrazolone-based, pyrazolotriazole-based, pyrazolinobenzimidazole-based and indazolone-based compounds. These magenta couplers may be not only 4-equivalent type couplers but also 2-equivalent type couplers like the yellow couplers. Specific examples of magenta couplers include U.S. Patents 2,600,788, 2,983,608 and 3,06.
2,653, 3,127,269, 3,311,476, 3,419,391
No. 3,519,429, 3,558,319, 3,582,322,
3,615,506, 3,834,908, 3,891,445, West German patent 1,810,464, West German patent application (OLS) 2,408,665,
No. 2,417,945, No. 2,418,959, No. 2,424,467, Japanese Patent Publication No. 40-6031, JP-A No. 51-20826, No. 52-58922,
49-129538, 49-74027, 50-159336, 52
-42121, 49-74028, 50-60233, 51-265
41, No. 53-55122, Japanese Patent Application No. 55-110943 and the like can be mentioned. Particularly preferred couplers are:

Further, useful cyan couplers used in the present invention include, for example, phenol type and naphthol type couplers. And these cyan couplers may be not only 4-equivalent type couplers but also 2-equivalent type couplers like the yellow couplers. Specific examples of cyan couplers include U.S. Patents 2,369,929 and 2,434,272.
No. 2, 2,474,293, 2,521,908, 2,895,826,
3,034,892, 3,311,476, 3,458,315, 3,4
76,563, 3,583,971, 3,591,383, 3,767,
No. 411, No. 3,772,002, No. 3,933,494, No. 4,004,929
Issue, West German patent application (OLS) 2,414,830, 2,454,329
No. 48-59838, No. 51-26034, No. 48-5055
No. 51, No. 51-146827, No. 52-69624, No. 52-90932,
Examples thereof include those described in JP-A-58-95346 and JP-B-49-11572.

Particularly preferred couplers are:

A polymer coupler and the like may be used in combination in the silver halide emulsion layer and other photographic constituent layers of the present invention. For the polymer coupler, the description in Japanese Patent Application No. 59-172151 by the present applicant can be referred to.

A usual colored magenta coupler can be used in combination in the green-sensitive emulsion layer of the present invention. As the colored magenta coupler, those described in U.S. Pat. Nos. 2,801,171, 3,519,429 and Japanese Patent Publication No. 48-27930 can be used.

Colored magenta couplers which are particularly preferably used are as follows.

Further, a usual color cyan dye coupler can be used in the red-sensitive emulsion layer of the present invention. As a color shear coupler, Japanese Patent Publication No. 55-32461, U.S. Pat.
Those described in No. etc. can be used.

Particularly preferred color cyan couplers include the following.

The method of adding the above-mentioned coupler which can be used in the present invention to the photographic constitutional layer of the present invention is the same as before, and the addition amount of the above-mentioned coupler is not limited, but 1 × 10 ^-3 to 1 mol of silver is added.
5 mol is preferable, and more preferably 1 × 10 ^{−3 to} 5 × 10 ^−1.
Is.

The silver halide color photographic light-sensitive material of the present invention may contain various other photographic additives, for example, antifoggants, stabilizers, and ultraviolet absorbers described in Research Disclosure Magazine 17643. A color stain preventing agent, a fluorescent whitening agent, a color image fading preventing agent, an antistatic agent, a hardener, a surfactant, a plasticizer, a wetting agent and the like can be used.

In the silver halide color photographic light-sensitive material of the present invention, hydrophilic colloids used for adjusting the emulsion include gelatin, derivative gelatin, graft polymers of gelatin and other polymers, proteins such as albumin and casein, and hydroxy. Any one of ethyl cellulose derivative, cellulose derivative such as carboxymethyl cellulose, starch derivative, single or copolymer synthetic hydrophilic polymer such as polyvinyl alcohol, polyvinyl imidazole, polyacrylamide and the like is included.

The support of the silver halide color photographic light-sensitive material of the present invention includes, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, a transparent support provided with a reflective layer, or in combination with a reflector, or a glass plate, cellulose acetate. Transparent supports such as polyester films such as cellulose nitrate or polyethylene terephthalate, polyamide films, polycarbonate films, polystyrene films, etc., and these supports are appropriately selected depending on the intended use of the light-sensitive material.

Various coating methods such as dipping coating, air doctor coating, curtain coating, and hopper coating can be used for coating the silver halide emulsion layer and other photographic constituent layers used in the present invention. U.S. Patent 2,761,791
It is also possible to use a simultaneous coating method of two or more layers by the method described in No. 2,941,898.

In the present invention, the coating position of each emulsion layer can be arbitrarily determined. For example, in the case of a full-color photographic film, it is preferable to sequentially arrange a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a blue-sensitive silver halide emulsion layer from the support side. Each of these light sensitive silver halide emulsion layers may consist of two or more layers. The effect of the present invention is great when all the photosensitive emulsion layers are substantially composed of silver bromide or silver iodobromide emulsion.

In the light-sensitive material of the present invention, it is optional to provide an intermediate layer having an appropriate thickness depending on the purpose, and further, a filter layer,
Various layers such as an anti-curl layer, a protective layer and an antihalation layer can be appropriately combined and used as constituent layers. A hydrophilic colloid which can be used in the emulsion layer as described above can be similarly used as a binder in these constituent layers, and various hydrophilic colloids can be contained in the emulsion layer as described above. The above photographic additives can be incorporated.

The processing method of the photographic light-sensitive material according to the present invention is not particularly limited, and any processing method can be applied. For example,
Typical examples thereof include a method of performing bleach-fixing treatment after color development and further washing and / or stabilizing treatment if necessary, and a method of performing bleaching and fixing separately after color development, and further washing with water and / or as necessary. Or a method of stabilizing treatment;
Alternatively, pre-hardening, neutralization, color development, stop-fixing, washing, bleaching, fixing, washing, post-hardening, washing in this order, color developing, washing, supplementary color developing, stopping, bleaching, fixing, washing, Any method may be used, such as a method in which the development is performed in the order of stability, a development method in which developed silver produced by color development is subjected to halogenation bleaching, and then color development is performed again to increase the amount of dye formed.

The color developing solution used for processing the silver halide color photographic light-sensitive material of the present invention is not limited, but preferably has a pH containing a color developing agent of 8 or more, more preferably 9 to 10.
12 alkaline aqueous solution. The aromatic primary amine developing agent as the color developing agent is a compound having a primary amino group on the aromatic ring and capable of developing exposed silver halide. A precursor forming such a compound may be added.

Typical examples of the color developing agent include those of p-phenylenediamine type, and the following are preferred examples.

4-amino-N, N-diethylaniline, 3-methyl-4
-Amino-N, N-diethylaniline, 4-amino-N-
Ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-β-hydroxyethylaniline,
3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3
-Methoxy-4amino-N-ethyl-N-β-hydroxyethylaniline, 3-methoxy-4-amino-N-ethyl-N-β-methoxyethylaniline, 3-acetamido-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 sulfate, hydrochloride, sulfite, p-toluenesulfonate and the like.

Further, for example, JP-A-48-64932, 50-131526,
No. 51-95849 and Bent's Journal of the American Chemical Society, Volume 73, 3100-
The one described on page 3125 (1951) is also mentioned as a typical example.

The amount of these aromatic primary amine compounds used depends on where the activity of the developer is set, but it is preferable to increase the amount of use in order to increase the activity. The amount used is in the range of 0.0002 mol / l to 0.7 mol l. Further, two or more compounds can be used in an appropriate combination depending on the purpose. For example, 3-methyl-4-amino-N, N-diethylaniline and 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl- N-
A combination of β-methanesulfonamidoethylaniline and 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline and the like can be freely combined and used according to the purpose.

In the color developer used in the present invention, various components that are usually added, for example, sodium hydroxide, an alkali agent such as sodium carbonate, an alkali metal sulfite,
Alkali metal bisulfite, alkali metal thiocyanate, alkali metal halide, benzyl alcohol,
A water softening agent, a thickening agent, a development accelerator and the like may be optionally contained.

Examples of additives other than the above that are added to the color developing solution include potassium bromide, bromide such as ammonium bromide, alkali iodide, nitrobenzimidazole, mercaptobenzimidazole, 5-methyl-benzotriazole, and 1-phenyl. Examples include compounds for rapid processing liquids such as -5-mercaptotetrazole, stain inhibitors, anti-sludge agents, preservatives, layering effect accelerators, chelating agents and the like.

As the bleaching agent used in the bleaching solution or the bleach-fixing solution in the bleaching step, those in which a metal ion such as iron, cobalt or copper is coordinated with an organic acid such as aminopolycarboxylic acid or oxalic acid or citric acid are generally known. There is. And the following can be mentioned as a typical example of said amino polycarboxylic acid.

Ethylenediaminetetraacetic acid diethylenetriaminepentaacetic acid propylenediaminetetraacetic acid nitrilotriacetic acid iminodiacetic acid ethyl etherdiaminetetraacetic acid ethylenediaminetetrapropionic acid ethylenediaminetetraacetic acid disodium salt diethylenetriaminepentaacetic acid pentasodium salt nitrilotriacetic acid sodium salt You may contain an agent. When a bleach-fixing solution is used in the bleaching step, a solution having a composition containing a silver halide fixing agent in addition to the bleaching agent is applied. Further, the bleach-fixing solution may further contain a halogen compound such as potassium bromide. Then, as in the case of the bleaching solution described above, various other additives such as a pH buffer, an antifoaming agent, a surfactant, a preservative, a chelating agent, a stabilizer, and an organic solvent are added and contained. Good.

The silver halide fixing agent is, for example, sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, sodium thiocyanate, or thiourea, thioether, etc. Compounds forming a silver salt of

Color development of the silver halide color photographic light-sensitive material of the present invention,
From the viewpoint of rapid processing, it is preferable that the processing temperature of bleach-fixing (or bleaching / fixing) and, if necessary, various processing steps such as washing with water, stabilization and drying is carried out at 30 ° C. or higher.

The silver halide color photographic light-sensitive material of the present invention is disclosed in JP-A-58-
14834, 58-105145, 58-134634 and 58-1
Stabilization treatment as a substitute for washing with water as shown in Japanese Patent Application No. 8631 and Japanese Patent Application Nos. 58-2709 and 59-89288 may be performed.

[Effects of the Invention] According to the silver halide color photographic light-sensitive material of the present invention, IIE can be increased between different color-sensitive layers, whereby color reproducibility is improved and image sharpness and graininess are improved. It is also possible to improve the sex.

[Examples] Specific examples of the present invention will be described below, but embodiments of the present invention are not limited thereto.

Example 1 Silver halide color photographic light-sensitive material samples No. 1 to No. 8 were prepared by sequentially providing each layer having the composition shown below on a cellulose triacetate film support.

1st layer Red-sensitive emulsion layer Silver iodobromide emulsion EM-A or EM-B shown in Table 1 Silver coating amount: 3,4 g / m ₂ Sensitizing dye I: 6 × 10 ⁻ per mol of silver ⁵ mol Sensitizing dye II: Coupler A dissolved in 0.5 ml / m ² of 2 × 10 ^-5 mol tricresyl phosphate for 1 mol of silver A: 0.06 mol for 1 mol of silver DIR coupler (see Table 1) Shown) ... 0.000 for 1 mol of silver
5 mol Second layer Protective layer Protective layer containing 1.3 g / m ² of gelatin and 0.05 / m ² of sodium 2,4-dichloro-6-hydroxy-S-triazine. Method for producing EM-A An emulsion containing 0.29 mol of silver iodobromide grains having an average grain size of 0.40 μm (silver iodide content: 4 mol%) was dispersed in 1000 ml of distilled water (containing 30 ml of 25% ammonia). Add 96 ml of methanol and 1000 ml of 0.47 mol / l silver nitrate aqueous solution at 50 ° C
And a necessary and sufficient mixed aqueous solution of potassium bromide and potassium iodide (containing 4 mol% potassium iodide) were added for 40 minutes while controlling pAg to 10.0 by the control double jet method.

Then, after desalting by a conventional method, gelatin was added and redissolved.

As a result of electron microscope observation, EM-A contained a nearly perfect octahedron composed of (111) crystal faces.

Method for producing EM-B A solution containing a silver iodobromide seed emulsion having an average grain size of 0.15 μm (silver iodide content 4 mol%) was added with gelatin and 4-hydroxy-6-methyl- In the presence of 1,3,3a, 7-tetrazaindene, a mixed aqueous solution of ammoniacal silver nitrate solution, potassium bromide, potassium iodide and gelatin was controlled by the double jet method, requiring a minimum time without generation of small particles. It was manufactured by adding. At this time, the molar ratio of potassium iodide to added silver nitrate was 4%.

Then, after desalting by a conventional method, gelatin was added and redissolved.

As a result of electron microscopic observation, it was found that EM-B was a nearly perfect rhombus composed of (nn1) crystal faces with a grain size of 0.45 μm and a silver iodide content of 4 mol%.
It was a tetrahedral grain.

The compound used to make the sample.

Sensitizing dye I: Anhydro-5,5'-dichloro-3,3'-di- (γ-sulfopropyl) -9-ethyl-thiacarbocyanine hydroxide / pyridinium salt Sensitizing dye II: Anhydro-9-ethyl -3,3'-Di- (γ-sulfopropyl) -4,5,4 ', 5'-dibenzothiacarbocyanine hydroxide triethylamine salt Each sample was given white light through a wedge and treated as follows. Processed to obtain a dye image.

Processing process (38 ℃) Color development 2 minutes 40 seconds Bleach 6 minutes 30 seconds Washing 3 minutes 15 seconds Fixing 6 minutes 30 seconds Washing 3 minutes 15 seconds Stabilization 3 minutes 15 seconds Drying The composition of the processing solution used in each processing step is as follows. Is the street.

[Color developer] 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) -aniline ・ sulfate 4.75g anhydrous sodium sulfite 4.25g hydroxylamine ・ 1/2 sulfate 2.0g anhydrous potassium carbonate 37.5g Sodium bromide 1.3g Nitrilotriacetic acid.3 sodium salt (monohydrate) 2.5g Potassium hydroxide 1.0g Add water to make 1.

[Bleach] Ethylenediaminetetraacetic acid ammonium salt 100.g Ethylenediaminetetraacetic acid diammonium salt 10.0g Ammonium bromide 150.0g Glacial acetic acid 10.0ml Add water to make pH 1 and adjust to pH = 6.0 with ammonia water.

[Fixing solution] Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Add water to make 1 and adjust the pH to 6.0 with acetic acid.

[Stabilizer] Formalin (37% aqueous solution) 1.5 ml Conidax (Konishi Rokusha Kogyo Co., Ltd.) 7.5 ml Add 1 to add water.

The obtained characteristic values are shown in Table 1.

As is clear from Table 1, Sample Nos. 4 and 6 according to the present invention,
It can be seen that No. 8 has a smaller gamma and a higher MTF and can reproduce an image with high sharpness compared to the comparative sample. Also,
Regarding the graininess, the combination of the emulsion of the present invention and the DIR compound showed an improving effect, showing the effectiveness of the present invention.

Example 2 A multilayer color light-sensitive material sample was prepared by sequentially providing each layer having the composition shown below on a cellulose triacetate film support. That is, as shown in Table 2, the emulsions of the third layer, the fifth layer and the seventh layer were changed, and 0.0005 mol of DIR coupler was added to 1 mol of silver of each layer to prepare Sample No. 9 to Sample N.
Created o.16.

1st layer Antihalation layer Gelatin layer containing black colloidal silver 2nd layer Intermediate layer Gelatin layer 3rd layer Red-sensitive emulsion layer Silver iodobromide emulsion EN-A or EM-B shown in Table 2 Silver coating amount: 3.4g / m ² Sensitizing dye I: 6 × 10 ^-5 mol per mol of silver Sensitizing dye II: 2 × 10 ^-5 mol per mol of silver Coupler A: 0.06 per mol of silver Molar coupler C: 0.003 mol of tricresyl phosphate coating per mol of silver: 0.5 ml / m ² 4th layer Intermediate layer Gelatin layer 5th layer Green-sensitive emulsion layer Silver iodobromide emulsion EM shown in Table 2 -A or EM-B Silver coating amount: 2.4 g / m ² Sensitizing dye III: 3 × 10 ⁻⁵ mol per 1 mol of silver Sensitizing dye IV: 1 × 10 ⁻ per 1 mol of silver ⁵ mole coupler B ...... 0.008 mol tricresyl phosphate coating weight relative to 0.08 mole coupler M ...... silver mole per silver mole ...... 2.8ml / m ² layer 6 yellow Fi Ter layer Gelatin layer formed by coating yellow colloidal silver in an aqueous gelatin solution 7th layer Blue-sensitive emulsion layer Silver iodobromide emulsion EM-A or EM-B Silver coating amount: 1.1g / m ² coupler Y: 0.125 mol of tricresyl phosphate per 1 mol of silver Coating amount: 0.5 ml / m ² 8th layer Protective layer Gelatin formed by coating gelatin containing polymethylmethacrylate particles (diameter 1.5 μm) layer.

For the coupler of each layer, the coupler was added to a solution of tricresyl phosphate and ethyl acetate, sodium p-dodecylbenzenesulfonate was added as an emulsifier, and the mixture was heated and dissolved.
It was mixed with a heated 10% gelatin solution and emulsified with a colloid mill.

A gelatin hardening agent and a surfactant were added to each layer in addition to the above composition.

Sensitizing dye III: Anhydro-9-ethyl-5,5'-dichloro-3,3'-di- (γ-sulfopropyl) -oxacarbocyanine hydroxide sodium salt Sensitizing dye IV: Anhydro-5,6 , 5 ', 6'-Tetrachloro-1,1'-diethyl-3,3'-di- (β- [β- (γ-sulfopropoxy) ethoxy]) ethylimidazolocarbocyanine hydroxide sodium salt Each of Sample No. 9 to Sample No. 16 was provided with blue light, green light, red light, and white light via a wedge, and the same treatment as in Example 1 was performed to obtain a dye image. The results are shown in Table 2 as in Example 1.

As is clear from Table 2, Sample Nos. 12 and 14 of the present invention
It can be seen from No. 16 that the IIE between the color-sensitive layers is large and the color reproducibility is good.

Aside from the above exposure, samples No. 9 to No. 16 were used to actually photograph the landscape, and when compared with images printed on color paper, the samples of the present invention were very vivid and MT
A sharper image than expected with the F value was obtained. It seems to be a synergistic effect of color vividness and sharpness.

BRIEF DESCRIPTION OF THE DRAWINGS FIGS. 1 to 11 are views showing the crystal morphology of silver halide grains according to the present invention, and FIG. 12 is an electron micrograph thereof.

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Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material having a photographic constituent layer containing at least one light-sensitive silver halide emulsion layer on a support, wherein at least one light-sensitive silver halide emulsion layer is a mirror. Index (nn1) (n ≧ 2,
n is a natural number) contains silver halide having a crystal plane defined on the outer surface, and at least one photographic constituent layer reacts with an oxidized product of a developing agent to release a development inhibitor or a development inhibitor precursor. A silver halide color photographic light-sensitive material containing a compound (DIR compound).