JPH0621922B2 - Silver halide color photographic light-sensitive material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a silver halide color photographic light-sensitive material, and more specifically to a silver halide color photographic light-sensitive material having high sensitivity and improved graininess. It is about.

Generally, a silver halide color photographic light-sensitive material has three types of photographic silver halide emulsion layers which are spectrally sensitized selectively so as to have a sensitizer for blue light, green light and red light 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 light-sensitive silver halide emulsion layers is provided in an arrangement different from that described above. Further, as each silver halide emulsion layer, light-sensitivity to each color light in substantially the same wavelength range is obtained. It is also known to use a photosensitive silver halide emulsion layer having two or more layers having different properties and different sensitivities. In these silver halide color photographic light-sensitive materials, the 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 cyan, magenta and yellow dye image, a phenol or naphthol cyan coupler, 5-pyrazolone, pyrazolinobenzimidazole, pyrazolotriazole, indazolone or cyano, 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 Recently, photographic characteristics such as high sensitivity in a silver halide color photographic light-sensitive material, that the density of a pixel group forming an image is smooth and not rough, that is, good graininess. Is 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 increasing the sensitivity, a compound that releases a fog agent or a development accelerator or a precursor thereof when developing a silver halide using an aromatic primary amine developing agent is used. A technique for incorporating the photographic component into the photographic constituent layer is known, and as a disclosure of the technique, there is JP-A-60-221751, and the like. However, this technique has a drawback that graininess is deteriorated. It was

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. In JP-A-53-7230, an oxidation product of a color developing agent is used as an intermediate layer. To provide a medium-speed silver halide layer containing a DIR compound which releases a development-inhibiting substance by reacting with, and in JP-A-57-155539, an intermediate layer is formed with the same hue as that of the high-speed emulsion layer and has a high color. Techniques such as providing a non-photosensitive intermediate layer containing a coupler having a slower coupling rate than the sensitivity emulsion layer are described.

However, the techniques for providing these intermediate layers have many drawbacks such that not only the improvement of the graininess is insufficient, but also the film thickness is increased by providing the intermediate layer and the image is deteriorated.

[Object of the Invention] Therefore, the present invention has a technical object to improve the graininess with high sensitivity.

[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 light-sensitive silver halide emulsion layer contains silver halide grains having a crystal plane having a ridge in the center of the (110) plane, and at least one layer When the photographic constituent layer is subjected to silver halide development using an aromatic primary amine developing agent, a compound (hereinafter, referred to as FR compound) which releases a fogging agent or a development accelerator or a precursor thereof in accordance with the amount of developed silver. Is included).

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 attempted to solve the above technical problems by the technique of incorporating a fogging agent or a development accelerator (hereinafter referred to as FA 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. In particular, a silver halide grain having a crystal plane having a ridge in the center of the (110) plane, that is, a crystal plane defined by a Miller index (nn1) (n ≧ 2, n is a natural number) (hereinafter simply referred to as a (nn1) crystal plane). In the case of a silver halide grain having ()), unlike a silver halide grain having a (111) crystal plane and / or a (100) crystal,
We have found the surprising fact that the sensitivity and graininess are improved.

The silver halide grains having a (nn1) crystal plane used in the present invention are completely novel as far as the inventors of the present invention know, and when combined with an FA compound, they are also effective in high sensitivity and graininess. What to do was truly amazing.

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

The present invention relates to a silver halide grain having a crystal plane having a ridge in the center of the (110) plane, that is, a Miller index (n
n1) (n ≧ 2, n is a natural number) relating to a silver halide grain having a crystal plane as an outer surface.

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

FIG. 1 is a view showing the morphology of the whole silver halide microcrystal when the outer surface is composed of only the (nn1) crystal plane. Further, FIG. 2 is a side view seen from the direction of the straight line b ₁ b ₂ .
The equivalent crystal plane represented as the (nn1) crystal plane is 24
Exist individually. For this reason, all the crystals whose outer surfaces are composed of (nn1) crystal planes are in the shape of a tetrahedron, and each plane which constitutes the outer surface is an obtuse triangle. There are two types of vertices, that is, 6 vertices equivalent to a _{1 in} FIG. ₁ and 8 vertices equivalent to b ₁ . Vertex a ₁ 8 plane and is bounded, 3 plan Vertex b ₁ is bounded. There are also two types of edges. That is, there are 24 sides equivalent to the side a ₁ b ₁ in FIG. ₁ and 12 sides equivalent to the side a ₁ a ₂ .

Almost perfect 2 whose outer surface is composed of (nn1) crystal planes
An electron micrograph of tetrahedral silver halide grains is shown in FIG.

Next, the relationship among the (nn1) crystal face, the (111) crystal face, and the (110) crystal face will be described with reference to cross-sectional views. 24 of FIG.
A cross-sectional view in a plane perpendicular to the triangle a ₁ a ₂ b ₁ and the triangle a ₁ a ₂ b ₂ including the straight line b ₁ b ₂ of the face piece is shown by a solid line 1 in FIG. That is, in FIG. 3, the solid line 1 is (nn
1) Represents a crystal plane. On the other hand, the broken line 2 represents the (110) crystal face, and the dashed-dotted line 3 represents the (111) crystal face, and the (nn1) crystal face, the (111) crystal face, and the (11) crystal face.
0) The normal vector of each crystal plane is shown by.

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

From the above, it is clear 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. Further, 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 describes "(1
10) A crystal plane having a ridge in the center of the crystal plane "is disclosed. In these specifications, this crystal plane is quasi (110)
They are named "faces" and have two roof-shaped quasi (1
10) The angle formed by the surface is obtuse than 110 °. It is described. 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 (nn1) crystal faces on the outer surface. That is, (1
11) Crystal plane, (100) crystal plane or (110) crystal plane may exist. Examples of these are shown in FIGS. A mixture of (111) crystal planes and (100) crystal planes results in the formation of a trihedron (Figs. 4, 5, 6),
Hedrons (Figs. 7, 8, 9), 32 faces (Figs. 10, 11)
Such a form.

In order to identify the crystal planes of silver halide grains, powder method X-ray diffraction [Brentin of the Society of Scientific Photography of Japan (Bulleti of the Society of
on of the Society of Scientific potography of Japa
n) Volume 13, page 5] can be used.

However, regarding the (nn1) crystal face according to the present invention, even if all the outer surfaces are dodecahedron grains composed of the (nn1) crystal face, the ratio of the area of one surface to the grain volume is 8 Remarkably smaller than a face piece, a rhombohedral dodecahedron, and the like. For this reason, it is difficult to align the (nn1) crystal plane on the substrate. Further, since the (nn1) crystal plane is of higher order, 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, from electron micrographs, the ratio of the two types of sides, 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 as an outer surface, and may be a normal crystal or a twin crystal (including a multiple twin crystal). 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%. To obtain this ratio, 2
When the boundary between two crystal planes is unclear (for example, because the boundary has a rounded shape), the line of intersection between these two planes is determined as the boundary.

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

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 used is 0 to 98 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.

The silver halide grains according to the present invention have (nn1) on the outer surface.
A plane other than the crystal plane, for example, a (111) crystal plane, (100)
As described above, the crystal plane may be included.
The ratio of the area of the (nn1) crystal plane to the total surface area is at least 30% or more, preferably 50%, as described above.
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 (110) crystal face or / and a (110) crystal face, Can be kept low and the sensitivity can be increased.

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

Among conventional emulsions, emulsions having a (110) crystal plane are known to be excellent in the fog-sensitivity relationship, but this has a drawback that storage stability at high temperatures is poor. 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.

In the production method described below, a tetrazaindene compound is used as a compound (hereinafter, referred to as a crystal control compound) that promotes the development of the (nn1) crystal plane, so that silver iodobromide grains having a desired silver iodide content can be obtained. It is relatively easy to obtain.

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 and each is a hydrogen atom, a halogen atom, an amino group, an amino group derivative, an alkyl group, an alkyl group derivative, an aryl group or an aryl group derivative. , A cycloalkyl group, a cycloalkyl group derivative, a mercapto group, a mercapto group derivative or -CONH-R ₄ (R ₄ is a hydrogen atom, an alkyl group, an amino group, an alkyl group derivative, an amino group derivative, a halogen atom, A cycloalkyl group, a derivative of a cycloalkyl group, an aryl group or a derivative of an aryl group), R ₅ represents a hydrogen atom or an alkyl group, and R ₁ and R ₂ are bonded to form a ring (for example, 5 to 5). 7-membered carbocycle, heterocycle) may be formed, and X is represented by the general formula (I),
A monovalent group obtained by removing one hydrogen atom from a compound represented by (II), (III) or (IV) (for example, the above general formula (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 produced 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. PA of silver halide outside this period
g is preferably in the range of 4 to 11.5, and preferably 6 to 11
The pH is suitably in the range of 2 to 12, and 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.

Further, in order to make the particle size uniform, British Patent 1,53
No. 5,016, Japanese Examined Patent Publication No. 48-36890, No. 52-16.
As described in U.S. Pat. No. 3,642,364, a method of changing the addition rate of silver nitrate or an alkali halide aqueous solution according to the grain growth rate, and U.S. Pat. No. 4,242,445 and JP-A-55-158124 are described. As described above, it is preferable to grow early in 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 because each silver halide grain is 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 carried out, for example, by adding an aqueous solution mainly containing an iodine compound (preferably potassium iodo), preferably an aqueous solution having a concentration of 10% or less. For details, see US Pat. No. 2,592,2.
50, 4,075,020, JP-A-55-127
It can be carried out by the method described in No. 549 or the like. At this time, in order to reduce the difference in iodine distribution between particles in the high iodine shell, the concentration of the aqueous iodine compound solution was set to 1 × 10.
^-It is desirable to make the content below ² mol% and to add it over 10 minutes.

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,
Examples thereof include a propyl group, a pentyl group, a hexyl group, an octyl group, an isopropyl group, a sec-butyl group, a t-butyl group, a 2-norbornyl group, and the like.
For example, an alkyl group (eg, a benzyl group, a phenethyl group, a benzhydryl group, or 1-substituted by an aromatic residue (which may be via a divalent linking group such as —NHCO—)).
Naphthylmethyl group, 3-phenylbutyl group, benzoylaminoethyl group, etc.), alkyl group substituted with an alkoxy group (eg, methoxymethyl group, 2-methoxyethyl group, 3-ethoxypropyl group, 4-methoxybutyl group, etc.) , A halogen atom, a hydroxy group, a carboxy group, a mercapto group, an alkoxycarbonyl group or an alkyl group substituted with a substituted or unsubstituted amino group (for example, a monochloromethyl group, a hydroxymethyl group, a hydroxyethyl group, a 3-hydroxybutyl group, A carboxymethyl group, a 2-carboxyethyl group, a 2- (methoxycarbonyl) ethyl group, an aminomethyl group, a diethylaminomethyl group, etc.), an alkyl group substituted with a cycloalkyl group (eg, a cyclopentylmethyl group), the above general formula ( I) ~
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. , Mesityl group, 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) phenyl group, 4-carboxy-1-naphthyl group, etc. Is mentioned.

Examples of the cycloalkyl group represented by R _{1 to} R ₄ include a cycloheptyl group, a cyclopentyl group, a cyclohexyl group and the like, and examples of the derivative of the cycloalkyl group include a methylcyclohexyl group and the like. R
Examples of the halogen atom represented by _{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. Is mentioned. 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 1) 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 between the alkylene groups. For example, methylene group, ethylene group, propylene _group, -CH 2 OCH _{2
-, - CH 2 CONHCH 2 -} , - CH 2 CH 2 COO
_{CH 2 -, - CH 2 CH} 2 OCOCH 2 -, - CH 2 N
HCOCH 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 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 -, - C
_{ONHCH 2 OCOCH 2 -, - CONHCH} 2 CH 2
_{CH 2 OCOCH 2 -, - COOCH} 2 -, - COOC
_{H 2 CH 2 -, - COOCH} 2 CH 2 OCOCH 2 -,
_{-COOCH 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.

(1) (2) (3) (4) (5) (6) (7) (8) (9) (10) (11) (12) (13) (14) (15) (16) (17) (18) (19) (20) (21) (22) (23) (24) (25) (26) (27) (28) (29) (30) (31) (32) (33) (34) (35) (36) The addition amount of the tetrazaindene compound used in the production of the silver halide grains of the present invention varies depending on the production conditions such as the desired final grain size of silver halide, the temperature of emulsion, pH, pAg, and silver iodide content. The range of 1 × 10 ⁻⁵ to 2 × 10 ⁻¹ mol is preferable per 1 mol of all silver halide produced.

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 generated during the preparation of silver halide grains, salts by-produced or no longer needed, salts such as ammonia, and compounds are a dispersion medium of the grains. Should be removed (desalting step). 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.

After obtaining the desired silver halide grains in the silver halide grain forming step, until the desalting step is performed,
The pAg of the mother liquor should be controlled in the range 7.0-9.5. 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 the (nn1) crystal plane according to the present invention are cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or its complex salt, rhodium salt or the same in the process of silver halide grain formation or physical ripening. 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. The 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, Hie Frieser edited by Die G
rundlagen der Photographiechen Prozesse mit Silber
halogeniden (Akademische Verlagsgesellschaft, 1968) 6
See the description on pages 75-734.

Preferred examples of the FR compound contained in the photographic constituent layer of the silver halide color photographic light-sensitive material of the present invention can be represented by the following general formulas [VI] and / or [VII].

The FR compounds that can be used in the present invention include the following.

(I) A coupler which releases an FA compound by coupling with an oxidation product of an aromatic primary amine developing agent. (II) A coupler which couples with an oxidation product of an aromatic primary amine developing agent to form a diffusible compound. A coupler that forms a colored or non-colored dye, and the diffusible dye acts as an FA compound. (III) An oxidation-reduction reaction occurs with the oxidation product of the developing agent, and a decomposition reaction subsequent to the oxidation reaction causes Redox compounds that release FA compounds.

The above compounds (I), (II) and (III) are represented by the following general formulas [VI], [VII] and [VIII], respectively.

[VI] Cp-FB [VII] FB-Cp-BALL [VIII] RED-FB In the above formula, the FB group is-(TIME) _m- (L) _n- F.
Represents A. Here, the FA group represents a group having an ability to fog silver halide or a group having a development promoting ability, L represents a divalent linking group, and TIME represents a timing group. It is particularly preferable when the FB group has a group capable of adsorbing silver halide. m and n each represent 0 or 1. Further, Cp represents a coupler residue capable of undergoing a coupling reaction with an oxidation product of an aromatic primary amine developing agent, BALL represents a diffusion resistant group, and RED represents an aromatic primary amine.
It represents a compound residue capable of cross-oxidizing with an oxidized product of a primary amine developing agent.

Each of the general formulas [VI], [VII] and [VIII] will be described below.

In the general formula [VI], the FB group is a group bonded to the coupling position of the coupler and released during the coupling reaction with the oxidation product of the aromatic primary amine developing agent.

Typical examples of the yellow coupler among the couplers are US Pat. Nos. 2,875,057 and 2,407,2.
No. 10, No. 3,265,506, No. 2,298,44
No. 3, No. 3,048, 194, No. 3, 447, 928
No. etc. Among these yellow couplers, acylacetamide derivatives such as benzoylacetanilide and pivaloylacetanilide are preferable.

Therefore, as the yellow coupler residue (Cp), those represented by the following general formulas [IX] and [X] are preferable.

In addition, * represents a bonding position of the FB group (hereinafter, represented by the general formula [XV
II) until the same).

Here, R ₁ represents diffusion resistance with a total carbon number of 8 to 32, and R _1
2 is a hydrogen atom, one or more halogen atoms, a lower alkyl group, a lower alkoxy group or a total carbon number of 8 to 32
Represents a nondiffusible group. When R ₂ is 2 or more, they may be the same or different.

A typical example of a magenta coupler is US Pat.
0,788, 2,369,489, 2,34
No. 3,703, No. 2,311,082, No. 3,15
2,896, 3,519,429, 3,06
2, 653, 2,908, 573 and the like. Among these magenta couplers, pyrazolone or pyrazoloazoles (pyrazolopyrazole, pyrazoloimidazole, pyrazolotriazole, pyrazolotetrazole and the like) are preferable.

Therefore, as the magenta coupler residue (Cp), those represented by the following general formulas [XI], [XII] and [XIII] are preferable.

Here, R ₁ represents a diffusion resistant group having 8 to 32 carbon atoms, and R _1
2 represents one or more halogen atoms, a lower alkyl group, a lower alkoxy group, a phenyl group, or a substituted phenyl group. Z represents a group of non-metal atoms necessary to form a 5-membered azole ring containing 2 to 4 nitrogen atoms, and the azole ring may have a substituent (including a condensed ring).

A typical example of a cyan coupler is US Pat.
No. 162, No. 2,895,826, No. 3,002,8
No. 36, No. 3,034,892, No. 2,474,29
No. 3, No. 2,423,730, No. 2,367,531
No. 3,041,236 and the like. Of those cyan couplers, phenols or naphthols are preferable.

Therefore, as the cyan coupler residue (Cp), those represented by the following general formulas [XIV], [XV], [XVI] and [XVII] are preferable.

Here, R ₁ represents a diffusion resistant group having a total carbon number of 8 to 32,
R ₂ represents one or more halogen atoms, a lower alkyl group or a lower alkoxy group, and when R ₂ is 2 or more, they may be the same or different.

The FA group is the most basic functional group that expresses the function of the FR compound. Examples of this group include reducing compounds (hydrazine, hydrazide, hydrazone, hydroquinone, catechol, p-aminophenol, p-phenylenediamine, 1-phenyl-3-pyrazolone, enamine, aldehyde, polyamine, acetylene, aminoborane, tetrazolium salt. , Quaternary salts typified by ethylene bispyridinium salt, carbazic acid, etc.), or compounds capable of forming silver sulfide during development (such as thiourea, thioamide, dithiocarbamate, rhodanine, thiohydatoin, and thiazolidinethione, And those having a partial structure)).

TIME represents a timing group, which utilizes an intramolecular substitution reaction as described in US Pat. No. 4,248,962, JP-A-57-56837, British Patent 2,072, 363A, JP-A-57-154234.
JP-A-57-188035 and JP-A-58-987.
As described in No. 28, etc., those utilizing electron transfer via a conjugated system in the molecule can be cited.

As the divalent linking group represented by L, an alkylene group, an alkenylene group, a phenylene group, a naphthylene group, -0-,
_{-S -, - SO -, -} SO 2 -, - N = N-, carbonamido group, thioamide group, a sulfonamido group, a ureido group, a thioureido group, a group selected from the group consisting of heterocyclic group, or the use To be done.

The above FB group consisting of FA group, TIME, and L is
It is particularly preferable to have a group capable of adsorbing to silver halide (this group may be in any part of FA, TIME, or L). The group capable of adsorbing to silver halide has a nitrogen-containing heterocyclic group having a dissociable hydrogen atom, a heterocyclic group having at least one nitrogen atom and another hetero atom in the ring, and a mercapto group. Heterocyclic group, quaternary salt, thiols, And a group derived from a compound having a partial structure of.

In the general formula [VII], the FB group is bonded to the uncoupling position of the coupler. The BALL group is a group that is bonded to the coupling position of the coupler and is released during the coupling reaction with the oxidation product of the aromatic primary amine developing agent. Here, Cp and FB have the same meanings as described in the general formula [VI].

The non-diffusible group represented by BALL may have a size and shape that give the coupler non-diffusion property, and may be a polymer having a plurality of leaving groups linked to each other. It may have an alkyl group and / or an aryl group. In the latter case an alkyl group and /
Alternatively, the total carbon number of the aryl group is preferably about 8 to 32. BALL has a group for binding to the coupling position of Cp, and its typical one is-
O-, -S-, -N = N-, And -N <which constitutes a heterocycle.

In the general formula [VIII], RED is hydroquinone,
It has a skeleton of catechol and O-aminophenol (both of which include condensed rings), cross-oxidizes with an oxidant of an aromatic primary amino developing agent, and undergoes alkaline hydrolysis to release an FB group. Represents the group FB is a general formula [V
I] has the same meaning as described above, but when FB is directly connected to the benzene ring of RED, -O-, -S-, -N
= N-, And RED is bonded to any one of the groups of -N <constituting a heterocycle, and RED has an o-aminophenol or p-aminophenol skeleton (both include condensed rings), and FB Are not directly linked to their benzene rings, FB is Via (i.e., forming a sulfonamide group).

Next, specific examples of the FR compounds represented by the general formulas [VI], [VII], and [VIII] are shown, but the FR compounds are not limited thereto.

[Exemplified compound]

(1) (2) (3) (4) (5) (6) (7) (8) (9) (10) (11) (12) (13) (14) (15) (16) (17) (18) (19) (20) (21) (22) (23) (24) (25) (26) (27) (28) (29) These FR compounds of the present invention are based on generally known compounds and are disclosed in JP-A Nos. 57-150845 and 57-1386.
36, No. 59-50439, No. 59-170840.
No. 60-37556, No. 60-107029,
US Pat. Nos. 3,214,377 and 3,253,924
Can be synthesized by the method described in No.

The FR compound of the present invention is contained in a photographic constituent layer of a silver halide color photographic light-sensitive material, but particularly preferably in a silver halide emulsion layer or a layer adjacent thereto, and further contained in a silver halide emulsion layer. Is preferred.

Further, the addition amount of the FR compound of the present invention is 1 × 10 ⁻⁹ to 1 × 10 ⁻¹ mol, and preferably 1 × 10 ⁻⁹ to 1 × 10 ⁻¹ mol, per 1 mol of silver halide contained in the layer containing the FR compound or the adjacent layer. It is from 1 × 10 ⁻⁸ to 1 × 10 ⁻² mol.

In particular, the FR compound of the present invention is a light-sensitive silver halide emulsion containing a silver halide grain having a crystal plane having a ridge in the center of the (110) plane, that is, a silver halide grain having a (nn1) crystal plane of the present invention. It is preferably added to the layer and / or its adjacent layers (including an intermediate layer).

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

For example, in the case of a full-color film, a red-sensitive emulsion layer containing silver halide grains having a (nn1) crystal face, a silver halide grain having a (nn1) crystal face, or another halogenated substance are sequentially formed on a support. A green-sensitive emulsion layer containing silver and a blue-sensitive emulsion layer containing silver halide grains having a (nn1) crystal plane are provided, and the green-sensitive emulsion layer contains the FR compound of the present invention, or That is, the green-sensitive emulsion layer contains the FR compound of the present invention.

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

In order to incorporate these FR compounds in the silver halide emulsion according to the present invention or in the coating solution for other photographic constituent layers, when the FR compounds are alkali-soluble, they may be added as an alkaline solution, If it is oil-soluble,
For example, U.S. Patent Nos. 2,322,027, 2,801,170, and
No. 2,801,171, No. 2,272,191 and No. 2,304,940 according to the method described in each of the FR compounds in the high boiling point solvent, if necessary by using a low boiling point solvent in combination, and dispersed in fine particles to halogenate It is preferably added to the silver emulsion. At this time, two or more kinds of FR compounds may be mixed and used if necessary. Further, in detail, a preferable addition method of the FR compound in the present invention is to use one or more kinds of the FR compound as organic acid amides, carbamates, esters, ketones, urea derivatives, ethers, hydrocarbons. And the like, especially di-n-butyl phthalate, tricresyl phosphate, triphenyl phosphate, di-isooctyl azelate, di-n-butyl sebacate, tri-n-hexyl phosphate, N, N-di-ethyl-caprylamide Butyl, N, N-diethyllaurylamide, n-pentadecyl phenyl ether, di-octyl phthalate, n-nonylphenol, 3-pentadecyl phenyl ethyl ether, 2,5-di-sec-amyl phenyl butyl ether, monophenyl-di -o-Chlorophenyl phosphate or high boiling point solvent such as fluoroparaffin, and / or acetic acid Chill, ethyl acetate, propyl acetate, butyl acetate, butyl propionate, cyclohexanol,
Diethylene glycol monoacetate, nitromethane,
Soluble in a low boiling point solvent such as carbon tetrachloride, chloroform, cyclohexanetetrahydrofuran, methyl alcohol, acetonitrile, dimethylformamide, dioxane and methyl ethyl ketone, and an anionic surfactant such as alkylbenzenesulfonic acid and alkylnaphthalenesulfonic acid and / or sorbitan sesquiolein. Acid ester and a nonionic surfactant such as sorbitan monolauryl ester and / or an aqueous solution containing a hydrophilic binder such as gelatin are mixed, and a high-speed rotary mixer,
It is emulsified and dispersed by a colloid mill or an ultrasonic disperser and added to the silver halide emulsion.

In addition, the FR compound may be dispersed by using a latex dispersion method. The latex dispersion method and its effects are described in JP-A-49-74538, JP-A-51-59943, and JP-A-51-59943.
4-32552 and Research Disclosure, August 1976, No. 14850, pp. 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,
Homopolymers, copolymers and terpolymers of monomers such as N- [2- (2-methyl-4-oxopentyl)] acrylamide, 2-acrylamido-2-methylpropanesulfonic acid and the like.

Each of the silver halide emulsion layers according to the present invention may contain a coupler other than the present invention, 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-aryl-substituted coupler, active point-o-acyl substituted coupler, active point hydantoin compound substituted coupler, active point urazole compound substituted coupler and active point succinimide compound substituted coupler, active Fluorine-substituted couplers, chlorine- or bromine-substituted couplers, and active-o-sulfonyl-substituted couplers 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
No., 3,551,155, 3,582,322, 3,725,072,
No. 3,891,445, West German patent 1,547,868, West German application publication 2,
219,917, 2,261,361, 2,414,006, UK patent
1,425,020, JP-B-51-10783, JP-A-47
No. 26133, No. 48-73147, No. 51-10.
No. 2636, No. 50-6341, No. 50-12334
2, No. 50-130442, No. 51-21827
No. 50-87650, No. 52-82424, No. 52-115219, No. 58-95346 and the like.

Particularly preferred couplers are:

(Y-1) (Y-2) (Y-3) (Y-4) (Y-5) (Y-6) (Y-7) (Y-8) (Y-9) (Y-10) (Y-11) (Y-12) (Y-13) (Y-14) (Y-15) [Y-16] [Y-17] [Y-18] [Y-19] [Y-20] [Y-21] [Y-22] [Y-23] [Y-24] [Y-25] [Y-26] [Y-27] [Y-28] [Y-29] 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, 2,417,945, 2,418,959, 2,424,467,
JP-B-40-6031, JP-A-51-20826,
52-58922, 49-129538, 4
9-74027, 50-159336, 52-
42121, 49-74028, 50-602.
No. 33, No. 51-26541, No. 53-55122
And Japanese Patent Application No. 55-110943.

Particularly preferred couplers are:

(M-1) (M-2) (M-3) (M-4) (M-5) (M-6) (M-7) (M-8) (M-9) (M-10) (M-11) (M-12) (M-13) (M-14) (M-15) (M-16) (M-17) (M-18) (M-19) 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, 3,767,41
No. 1, 3,772,002, 3,933,494, 4,004,929,
West German patent application (OLS) 2,414,830, 2,454,329,
JP-A-48-59838, 51-26034, 48-5055, 51-146827, 52-
69624, 52-90932, 58-953.
No. 46, Japanese Patent Publication No. 49-11572 and the like can be mentioned.

Particularly preferred couplers are:

(C-1) (C-2) (C-3) (C-4) (C-5) (C-6) (C-7) (C-8) (C-9) (C-10) (C-11) (C-12) (C-13) (C-14) (C-15) (C-16) (C-17) (C-18) (C-19) A polymer coupler and the like may be used in combination in the silver halide emulsion layer and the other photographic constituent layers of the present invention. The polymer coupler is disclosed in Japanese Patent Application No. 59-1721 by the present applicant.
See the description of No. 51.

A usual colored magenta coupler can be used in combination in the green-sensitive emulsion layer of the present invention. As the colored magenta couplers, those described in U.S. Pat. Nos. 2,801,171, 3,519,429 and JP-B-48-27930 can be used.

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

(CM-1) (CM-2) (CM-3) (CM-4) (CM-5) Further, a usual color cyan dye coupler can be used in the red-sensitive emulsion layer of the present invention. As a color cyan dye coupler, Japanese Patent Publication No. 55-32461, British Patent 1,08
Those described in No. 4,480 can be used.

Particularly preferred color cyan couplers include the following.

(CC-1) (CC-2) (CC-3) (CC-4) The method of adding the above-mentioned coupler usable in the present invention to the photographic constituent layer of the present invention is the same as before, and the addition amount of the above-mentioned coupler is not limited, but it is 1 × 10 1 per mol of silver.
^{-3 to} 5 mol is preferable, and 1 x 10 ^-2 is more preferable.
˜5 × 10 ⁻¹ .

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 film hardening agent, 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 preparing emulsions 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 color developing solution, a method of performing a bleach-fixing treatment and further washing with water and / or a stabilizing treatment if necessary, 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 of the alkaline aqueous solution. The aromatic primary amine developing agent as the color developing agent is a primary developing agent on the aromatic ring.
It is a compound having a primary amino group and capable of developing exposed silver halide, and if necessary, a precursor for forming such a compound may be added.

Typical examples of the color developing agent are p-phenylenediamine type compounds, 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-hydroxyethylalinine, 3-methyl-4-amino-N- Ethyl-N
-β-methoxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methoxy-4-amino-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 and 50-1.
Nos. 31526, 51-95849 and Bent et al., Journal of the American Chemical Society, Volume 73, pages 3100 to 3125 (1951), are also representative.

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 0.0002 mol / to 0.7 mol /. 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- A combination of N-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 added to the color developing solution include potassium bromide, bromide such as ammonium bromide, alkali iodide, nitrobenzimidazole, mercaptobenzimidazole, 5-methyl-benzotriazole, 1-phenyl. -5-Mercaptotetrazole and other compounds for rapid processing liquids, as well as stain inhibitors, anti-sludge agents, preservatives, layer effect accelerators, chelating agents, etc.

As the bleaching solution used in the bleaching solution or the bleach-fixing solution in the bleaching step, those in which metal ions such as iron, cobalt and copper are coordinated with an organic acid such as aminopolycarboxylic acid or oxalic acid and 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 Ethyldiaminediaminetetraacetic acid Ethylenediaminetetrapropionacetic 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. And, as in the case of the above bleaching solution, various other additives,
For example, a pH buffer, a defoaming agent, a surfactant, a preservative, a chelating agent, a stabilizer, an organic solvent, etc. may be added and contained.

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 The processing temperature of various processing steps such as color development, bleach-fixing (or bleaching / fixing) of the silver halide color photographic light-sensitive material of the present invention, and optionally washing with water, stabilization, drying, etc. is from the viewpoint of rapid processing. It is preferably carried out at 30 ° C. or higher.

The silver halide color photographic light-sensitive material of the present invention is described in JP-A-58 / 58.
No. 14834, No. 58-105145, No. 58-1
34634 and 58-18631 and Japanese Patent Application No. 5
You may perform water washing alternative stabilization treatment as shown by 8-2709 and 59-89288 etc.

[Effects of the Invention] The silver halide color photographic light-sensitive material of the present invention can simultaneously satisfy the contradictory requirements of improving high sensitivity and graininess.

[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 3 Silver coating amount: 3.4 g / m ² Sensitizing dye I: 6 × 10 ⁻⁵ mol increase per 1 mol of silver Dye II: Coupler A dissolved in 2 × 10 ⁻⁵ mol tricresyl phosphate 0.5 m / m ² per mol of silver Coupler A: 0.06 mol per mol of silver FR compound (shown in Table 3): Silver 1 protective layer coupler a containing 0.0005 mole of the second layer protective layer 1.3 g / m ² gelatin layer and 0.05 g / m ² 2,4-dichloro-6-hydroxy -S- triazine sodium moles 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 m of distilled water (containing 25% of ammonia 30 m), Methanol 95m
And 0.47 mol / silver nitrate aqueous solution at 50 ° C
It was produced by adding 1000 m and a necessary and sufficient mixed aqueous solution of potassium bromide and potassium iodide (containing 4 mol% potassium iodide) 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.

EM-B production method A solution containing a silver iodobromide seed emulsion having an average grain size of 0.15 μm (silver iodide content 4 mol%) was mixed with gelatin at 40 ° C. and pAg 8.6.
Generation of small particles by control double jet method in the presence of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene in aqueous ammoniacal silver nitrate solution, mixed aqueous solution of potassium bromide, potassium iodide and gelatin It was prepared by adding without a minimum time. 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, EM-B was a nearly complete rhombohedral dodecahedron grain composed of (nn1) crystal faces having a grain size of 0.45 μm and a silver iodide content of 4 mol%.

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 exposed to white light through a wedge and processed in the following processing steps 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 trisodium salt (monohydrate) 2.5g Potassium hydroxide 1.0g Add water to make 1.

[Bleach] Ethylenediaminetetraacetic acid iron ammonium salt 100.g Ethylenediaminetetraacetic acid diammonium salt 10.0g Ammonium bromide 150.0g Glacial acetic acid 10.0m Add water and adjust to pH = 6.0 using 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 m Conidax (Konishi Rokusha Kogyo Co., Ltd.) 7.5 m Add water to make 1.

The obtained characteristic values are shown in Table 3.

As is clear from Table 3, samples No. 4, No. 6 and N according to the present invention
O.8 has higher sensitivity than the comparative sample, and the graininess is also improved by the combination of the emulsion of the present invention and the FR compound of the present invention, 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 4, the emulsions of the third, fifth and seventh layers were changed, and the FR compound was added in an amount of 0.0003 mol to 1 mol of silver in each layer to prepare Sample No. 9 to Sample No. 1.
Created 6.

First layer Antihalation layer Gelatin layer containing black colloidal silver Second layer Intermediate layer Gelatin layer Third layer Red-sensitive emulsion layer Silver iodobromide emulsion EM-A or EM-B shown in Table 4 Silver coating amount ... 3.4 g / 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 mol per mol of silver Coupler C: 0.003 mol tricresyl phosphate coating amount per mol of silver 0.5 m / m ² 4th intermediate layer Gelatin layer 5th green-sensitive emulsion layer Silver iodobromide emulsion EM-A or EM-B shown in Table 4 Silver coating amount: 2.4 g / m ² Sensitizing dye III: 3 × 10 ⁻⁵ mol per mol of silver Sensitizing dye IV: 1 × 10 ⁻⁵ mol per mol of silver Coupler B: 1 mol of silver 0.008 mol tricresyl phosphate coating weight relative to 0.08 mole coupler M ... silver mole for ... 2.8 m / m ² layer 6 Ye Iodobromide emulsion EM-A or EM-B silver laydown shown gelatin layer 7 Soao sensitive emulsion layer Table 4 formed by applying those containing yellow colloidal silver in the over filter layer an aqueous gelatin solution ... 1.1 g / m ² Coupler Y ... 0.125 mol tricresyl phosphate coating amount per 1 mol silver ... 0.5 m / m ² 8th layer protective layer A gelatin layer formed by coating gelatin containing polymethylmethacrylate particles (diameter 1.5 μm).

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, then mixed with a heated 10% gelatin solution and emulsified with a colloid mill. I used one.

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

Coupler B Coupler C Coupler Y Coupler M 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'-telorachloro-1,1'-diethyl-3,3'-di- (β- [ β- (γ-sulfopropoxy) ethoxy]) ethyl imidazolocarbocyanine hydroxide sodium salt Each of the above sample No. 9 to sample No. 16 was exposed to blue light, green light, red light, and white light through a wedge. And subjected to the same treatment as in Example 1 to obtain a dye image. The results are shown in Table 4 as in Example 1.

As is clear from Table 4, Sample Nos. 12 and 14 of the present invention
It turns out that No. 16 has high sensitivity.

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 are very vivid and have graininess. Good results were observed.

[Brief description of drawings]

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.

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 comprises ( 110) containing silver halide grains having a crystal plane having a ridge in the center thereof, and at least one photographic constituent layer is silver halide developed with an aromatic primary amine developing agent. A silver halide color photographic light-sensitive material comprising a compound which releases a fogging agent or a development accelerator or a precursor thereof in an amount corresponding to the amount.