JPS62180358A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide high sensitivity and to improve the graininess by using a compound releasing a fogging agent, a development accelerator or a precursor thereof in accordance with the amount of silve developed. CONSTITUTION:A silver halide color photographic sensitive material is produced by forming photographic constituent layers including at least one photosensitive silver halide emulsion layer on a support. At this time, the silver halide emulsion layer contains silver halide having a crystal face defined by Miller indices (110) on the outer surface. The silver halide is practically silver bromide and/or silver iodobromide. At least one of the photographic constituent layers contains a compound (FR compound) releasing a fogging agent, a development accelerator or a precursor thereof in accordance with the amount of silver developed when the silver halide is developed with an aromatic primary amine developing agent. A compound represented by the formula (where R1 is H, <=15C optionally substituted alkyl, <=20C optionally substituted aryl or a heterocyclic group) is preferably used as a substance accelerating the growth of (110) crystal face (crystal controlling compound).

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, a silver halide color photographic light-sensitive material having high sensitivity and improved graininess. It is related to.

In general, silver halide color photographic light-sensitive materials have three types of photographic silver halide emulsion layers selectively sensitized to have sensitivity to blue light, green light, and red light, coated on a support. For example, in silver halide photographic light-sensitive materials for color negatives, 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. 1 Usually, a bleachable yellow filter layer is placed between the blue-sensitive silver halide emulsion layer and the green-sensitive silver halide emulsion layer in order to absorb the blue light that passes through the blue-sensitive silver halide emulsion layer. is provided. Furthermore, 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 a different arrangement from the above, and each silver halide emulsion layer is provided in 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 providing sensitivity. In these silver halide color photographic materials, exposed silver halide grains are developed using, for example, an aromatic primary amine color developing agent as a single color developing agent, and the resulting color developing agent is oxidized. A dye image is formed by reaction of the product with the dye-forming coupler. In this method, 1. typically is used to form cyan, magenta and yellow dye images. Phenol- or naphthol-based cyan couplers, 5-pyrazolone-based, pyrazolinobenzimidazole-based, pyrazolotriazole-based, indacylon-based or cyanoacetyl-based magenta couplers, and acylacetamide-based yellow couplers are used, respectively. These dye-forming couplers are contained in a light-sensitive silver halide emulsion layer or a developing solution.The present invention is a silver halide color in which the couplers are previously non-diffuse and are contained in a silver halide emulsion layer. It is suitable as a photographic material.

[Background of the Invention] In recent years, silver halide color photographic light-sensitive materials have been developed to have high sensitivity, and to ensure that the color of the image forming group is smooth and not rough, that is, that graininess is good. Photographic properties or requested. In recent years, with the increasing sensitivity of color photosensitive materials and the miniaturization of cameras, such demands have become increasingly strong.

As a technique for increasing sensitivity, when developing silver halide using an aromatic primary amine developing agent, a compound that releases a fuming agent, a development accelerator, or a precursor thereof in accordance with the amount of developed silver is used. A technique for incorporating it into the photographic structure I& layer is known, and examples of this technique disclosing this technique include JP-A No. 60-221751, but this technique has the drawback of worsening graininess. there were.

A known technique for improving graininess is to provide an intermediate layer between a high-speed emulsion layer and a low-speed emulsion layer. Japanese Patent Publication No. 49-15495 discloses that an intermediate layer containing gelatin or a medium-sensitivity silver halide emulsion layer with low color density is provided as an intermediate layer, and Japanese Patent Publication No. 53-7230 discloses that an oxidized form of a color developing agent is provided as an intermediate layer. JP-A-57-155539 discloses the provision of a medium-sensitivity halogenated tR layer containing a DIR compound that reacts with the emulsion layer to release a development-inhibiting substance. Techniques have been described, such as providing a non-light-sensitive interlayer containing a coupler with a slower coupling rate than the sensitive emulsion layer.

However, these techniques for providing an intermediate layer have many drawbacks, such as not only insufficient improvement in graininess, but also the provision of an intermediate layer increases the film thickness and deteriorates the image quality.

[Object of the Invention] Therefore, the technical object of the present invention is to achieve high sensitivity and improve graininess.

[Means for Solving the Problems] The silver halide color photographic light-sensitive material of the present invention which solves the above-mentioned technical problems comprises a photographic constituent layer including at least one light-sensitive silver halide emulsion layer on a support. In the silver halide color photographic light-sensitive material having at least 1)3
The photosensitive silver halide emulsion layer has a crystal plane defined by a Miller index (110) on its outer surface, contains silver halide consisting essentially of silver bromide and/or silver iodobromide, and contains at least When the 15 photographic constituent layers are developed with silver halide using an aromatic primary amine developing agent, a compound (hereinafter referred to as FR compound).

In this specification, the term "photographic constituent layer" refers to all the wood-philic colloid layers involved in image formation, such as a silver halide emulsion layer, a lower layer, an intermediate layer (mere intermediate layer, filter layer, etc.).
(ultraviolet absorption layer, anti-halation layer, etc.), protective layer, etc.

The progress that led to the completion of the present invention is as follows.

The present inventor attempted to solve the above technical problem by incorporating a fogging agent or a development accelerator (hereinafter referred to as an FA compound) into a silver halide color photographic light-sensitive material, and as a result of extensive research, It has been learned that the silver halide grains used in the photosensitive emulsion layer are closely related to the above technical problem. In particular, in the case of silver halide grains having crystal faces defined by the Miller index (110), (l
1l) The surprising fact has been found that unlike silver halide grains having crystal faces and/or (100) crystals, high sensitivity and graininess are improved.

The silver halide grains having the crystal plane defined by the mirror finger a(+10) used in the present invention are disclosed in Japanese Patent Application Laid-open No. 60-222.
No. 84, but it was completely unknown that combinations with FA compounds also exert effects on high sensitivity and graininess, which was truly surprising.

The present invention will be explained in more detail below.

The silver halide grains according to the present invention have a Miller index (+1
0) on its outer surface and consists essentially of silver bromide and/or silver iodobromide.

In addition to the (110) crystal plane, the surface of the particle has (100)
There may be crystal planes, (Ill) crystal planes, etc., but if the ratio of (110) crystal planes to the total surface area is 20
% or more, and particularly preferably 80% or more.

Furthermore, the presence of (110) crystal planes and their ratio can be determined by a method using an electron microscope or a dye adsorption method.

The silver halide emulsion of the present invention preferably contains silver halide grains having (110) crystal faces in an amount of 10 wt % or more, more preferably 50 wt % or more.

In the silver halide composition of the silver halide grains according to the present invention, "consisting essentially of silver bromide or silver iodobromide" means that halides other than silver bromide and silver iodobromide are contained within a range that does not impair the effects of the present invention. Silver 1 means that it may contain, for example, silver chloride, specifically.

In the case of silver chloride, the ratio is preferably 5 mol% or less, more preferably 1 mol% or less.

The proportion of silver iodide in the silver halide grains according to the present invention is preferably 0 to 40 mol%, more preferably 0 to 20 mol%, and particularly preferably 0 to 15 mol%.

Further, it may be a silver halide grain having a single composition or a silver halide grain having a plurality of layers or phases having different silver halide compositions (two layers, 3ffi). If not, the silver halide composition inside the grain may be silver chloride, silver chlorobromide, etc.Also, even if the halide composition in each layer is uniform, it changes continuously. One of the most preferred forms is one having a high iodine shell inside the grain. In other words, it is a silver halide grain that has a layer or phase (or phases) having a high normal content on the surface of each grain inside the grain.

The grain size of the silver halide grains according to the present invention is not particularly limited, and the present invention is at least effective within the range of preferably 0.1 to 3.0 gm. In the Mizuhiki M■ book, the grain size of silver halide refers to the length of one side of a cube equal to its size.

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, in a form called an emulsion. At this time, the particle size distribution of the group of particles may be monodisperse or polydisperse.

Further, a distribution obtained by mixing these may be used, and the distribution can be appropriately selected depending on the purpose and the like.

As in the present invention, the particle surface had a (110) crystal plane. By using a silver halide emulsion containing silver halide grains consisting essentially of silver bromide or silver iodobromide, a conventional silver bromide emulsion or silver iodobromide emulsion that does not have a (110) crystal face can be produced. For example, it has become possible to obtain various advantages as a photographic emulsion that could not be obtained otherwise.
(2) Fog can be suppressed compared to silver bromide emulsions or silver iodobromide emulsions having only (111) crystal planes and/or (100) crystal planes.

(2) High sensitivity can be obtained compared to silver bromide emulsions or silver iodobromide emulsions having only (111) crystal planes and/or (100) crystal planes.

(2) It has a completely different spectral sensitization ability from silver halide emulsions having (111) and/or (100) crystal faces. For example, the spectral sensitization spectrum upon spectral sensitization can be made rectangular. Therefore, color reproducibility and fading prevention can be significantly improved.

Since the 0-minute sensitized spectrum is rectangular, stable exposure can be achieved even when exposed using an LED (light emitting diode) whose wavelength shifts easily depending on the environmental temperature.

In order to produce the silver halide grains having the (110) crystal plane according to the present invention, the method disclosed in Japanese Patent Application Laid-Open No. 60-222842 or Japanese Patent Application No. 59-158111 can be used.

That is, in JP-A No. 60-222842, in a method for producing a silver halide photographic emulsion in which the surface of silver halide grains consists essentially of silver bromide or silver iodobromide, hydrophilic colloids and (110) crystal faces are used. in an aqueous medium coexisting with compounds that promote the development of

It has been shown that silver halide grains having (1,,10) crystal planes can be produced by a method for producing a silver halide photographic emulsion, which is characterized by carrying out silver halide grain growth. (110) Substances that promote the development of crystal planes (hereinafter referred to as
Although a clear chemical classification of crystal control compounds (referred to as crystal control compounds) is not possible at all, specifically mercaptoazoles are preferred, and mercaptotetrazoles and mercaptothiadiazoles are particularly preferred.

More specifically, compounds represented by the following general formulas (I) to (V) are preferred.

General formula (I) In the formula, R4 is a hydrogen atom, an optionally substituted alkyl group (
15 or less carbon atoms in total), an optionally substituted aryl group (20 or less carbon atoms in total), and a peterocyclic group.

General Formula (■) In the formula, R2 represents a hydrogen atom or an optionally substituted alkyl group (total carbon number 12 or less).

General Formula (III) In the formula, R represents an optionally substituted alkyl group (total carbon number not more than 10) or an optionally substituted amino group (total carbon number not more than 10).

General formula (flr) In the formula, R4 is an optionally substituted alkyl group (total carbon number IO or less) or an optionally substituted aryl group (
The total number of carbon atoms is 10 or less.

General formula (V) In the formula, R, , R6 is an optionally substituted alkyl group (
10 or less) or an optionally substituted amino group.

The crystal control compounds (I) to (V) may be added at any time before the formation of silver halide grains is completed (including before the completion of Ostwald ripening), which is the period of one grain formation. There is a period from when silver ions and halogen ions are added until substantially no new crystal nuclei are generated (nucleation period), and a subsequent period during which particles grow without substantially generating new crystal nuclei. There is a period of nuclear growth (period of nuclear growth).

Preferably, it is added during silver halide grain growth. In particular, it is preferable to add the crystal control compounds *(I) to (V) after the completion of vegetation r& (nucleation) and before the completion of particle growth, in order to limit the production of large amounts of fine particles.

Conversely, it is preferable to use the crystal control compounds (1) to (V) during or before nucleation, since silver halide grains consisting of fine grains can be prepared.

Crystal control compounds (I) to (V) may be present in the reaction vessel in advance, or may be added after the start of precipitation. At this time, they may be added directly, or water, A solution consisting of a solvent such as an organic solvent (for example, methanol, ethanol, etc.) may be added.

Crystal control compounds (I) to (V) may be added alone to the reaction vessel or may be added in a silver supply solution (e.g. silver nitrate aqueous solution).
It may also be added to the reaction vessel together with a halogen supply solution (eg, an aqueous halide solution).

When crystal control compounds (I) to (V) are added, they may be added continuously or intermittently, depending on the increase in surface roughness of silver halide grains. It is preferable to increase the amount of the crystal control compounds (I) to (V) (for example, by increasing the amount added to the solution or increasing the concentration) in order to effectively control the crystal plane.

Regarding the ratio of the (110) crystal plane of the silver halide grains having the (11G) crystal plane of the present invention, the crystal rt1
The ratio can be easily changed by changing the amount of compound (V) added.

For example, as the amount of addition of crystal control compounds (I) to (V) increases, the ratio of (110) crystal faces increases, and in the range of addition amounts described below, the ratio of (110) crystal faces becomes maximum.
Furthermore, when the amount of the crystal control compounds (I) to (V) added exceeds the range described below, the ratio of the (100) crystal plane to the (110) crystal plane increases.

The amount of the crystal control compounds (I) to (V) to be added varies depending on various conditions such as the type of compound used, emulsion preparation conditions, halogen composition, and particle size, but it ranges from 5xlO to 5x per mole of halogenated tIi. 1 G-” mole is preferred;
More preferably 1 x 10-' to 1 x 10-'' moles, particularly 3 x 10-' to 6 x 10 moles.

On the other hand, Japanese Patent Application No. 59-158111 describes a method for producing silver bromide or silver iodobromide grains having (110) crystal faces, in which a water-soluble silver salt solution and a water-soluble halide are mixed in the presence of a protective colloid. In the step of mixing solutions to form silver halide grains, at least 3
During the period when 0 mol% is produced, the pAg of the emulsion is 8.0 to 9.5.
and within this period, the following general formula (Vl), (■), ('[) or (IX) is used as a crystal control compound.
At least one compound selected from the compound represented by and the compound having a repeating unit represented by the following general formula (X)
A method is disclosed, characterized in that a compound of 8i is included in the emulsion.

General formula (Vl) General formula (■) General formula (■) General formula (IX) General formula (X
) "R6 Mocats C-) In the formula, R3, R8 and R1 may be the same or different, and each represents a hydrogen atom, a halogen atom, an amino group, a derivative of an amino group, an alkyl group, a derivative of an alkyl group, an aryl group , an aryl group derivative, a cycloalkyl group, a cycloalkyl group derivative, a mercapto group, a mercapto group derivative or -C0NH-R, (R 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), R2 represents a hydrogen atom or an alkyl group, and R1 and R2 are bonded to form a ring (e.g. It is also possible to form a 5- to 7-membered carbocyclic ring, a polychoric ring), and X has the general formula (V[), (
A monovalent group obtained by removing one hydrogen atom from a compound represented by (■), (■) or (IX) (for example, the above general formula (V[)
or IX), -R.

or one hydrogen atom removed from the OH moiety), and J represents a linking group of 21aI+.

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

The above 1) Ag control period is arbitrary as long as it is within the period in which silver halide is produced, and may be at the beginning, middle, or end of the silver halide production process. Further, although this period is preferably a continuous period, it may be intermittent as long as the effect of the present invention is not impaired. l)Ag in this period is preferably 7.3 to 9°5, more preferably 7.6 to 9.2. During this period, it is preferable to maintain the pH of the emulsion in the range of 7 to 1O. The 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 2.
A range of 12 to 12 is appropriate, preferably a range of 5 to 11.

In the method for producing silver halide grains of the present invention, any method such as an acid method, a neutral method, an ammonia method, etc. can be used in the step of generating silver halide to form silver halide grains. Further, as a method of reacting the soluble silver salt and the soluble halogen salt, any one of a one-sided mixing method, a simultaneous mixing method, a combination thereof, etc. may be used. A method in which particles are formed in an excess of silver ions (so-called back-mixing method) can be used. I)A in the liquid phase in which silver halide is produced as a form of simultaneous mixing method
It is also possible to use a method of keeping g constant, ie, the so-called Chondral double jet method. According to this method, a silver halide emulsion having a regular crystal shape and a nearly 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, commonly known silver halide solvents such as ammonia and thioether can be used.

Also, to make the particle size uniform, British patent 1.53
No. 5,016, Special Publication No. 48-36890, No. 52-16
As described in No. 364, there is a method of changing the addition rate of silver nitrate or aqueous alkali halide solution depending on the grain growth rate, and as described in U.S. Pat. It is preferable to use a method of varying the concentration of the aqueous solution as described above to grow quickly within a range that does not exceed the critical saturation level. These methods do not cause re-nucleation and each silver halide grain is coated uniformly, so they are preferably used even when forming grains having a plurality of layers having different halogen compositions.

In the case of providing regions with 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 consisting of an iodo compound (preferably potassium iodo), preferably at a concentration of 10% or less. For more information, see U.S. Patent 2,592,2
No. 50, No. 4,075,020, Japanese Unexamined Patent Publication No. 55-127
This can be carried out by the method described in No. 549 and the like. At this time, in order to reduce the difference in iodine distribution between particles in the high iodine shell, the iodine compound aqueous solution should be adjusted to 6 degrees LX 10
- It is preferable to add it over 10 minutes or less at mol % or less. ' If shells with different halogen compositions are provided, a desalting step may be carried out according to a conventional method if necessary during the desalting process. Shell formation may be carried out continuously without the salting step.

In the method for producing silver halide grains of the present invention, one of the most preferred methods is a method in which an ammoniacal silver nitrate aqueous solution and a halide aqueous solution are added in the presence of ammonia by the Chondrold double jet method.

Next, the crystal control compound will be explained.

In the general formulas (V[) to (X), the alkyl group represented by R1-R4 includes, for example, a methyl group, an ethyl group, a propyl group, a pentyl group, a hexyl group, an octyl group,
Isopropyl group, 8eC-butyl group, -butyl group, 2
Examples of derivatives of alkyl groups include, for example, those substituted with aromatic residues (divalent linking groups,
Substituted with an alkyl group (e.g., benzyl group, phenethyl group, benzhydryl group, 1-naphthylmethyl group, 3-phenylbutyl group, benzoylaminoethyl group, etc.), an alkoxy group, which may be substituted with -NHCO-, etc.) Alkyl groups (e.g. methoxymethyl group, 2-methoxyethyl group, 3-ethoxypropyl group, 4-methoxybutyl group, etc.), halogen atoms, hydroxy groups, carboxy groups,
A mercapto group, an alkoxycarbonyl group or an alkyl group substituted with a substituted or unsubstituted amino group (e.g. monochloromethyl group, hydroxymethyl group, hydroxyethyl group, 3-hydroquinbutyl group, carboxymethyl group, 2-carboxy ethyl group, 2-(methquincarbonyl)ethyl group, aminomethyl group, diethylaminomethyl group, etc.), an alkyl group substituted with a cycloalkyl group (e.g. cyclopentylmethyl group, etc.), the above general formula (VI)
Examples include alkyl groups substituted with monovalent groups obtained by removing one hydrogen atom from the compounds represented by -(IX).

Examples of the aryl group represented by R4-R4 include phenyl group, 1-naphthyl group, etc., and examples of derivatives of the aryl group include p-tolyl group, m-ethylphenyl group, m-phenyl group, mesityl group, etc. group, 2.3-xylyl group, p-chlorophenyl group, 0-bromophenyl group, p
-Hydroxyphenyl group, 1-hydroxy-2-naphthyl group, 1-methoxyphenyl group, p-ethoxyphenyl group, p-carboxyphenyl group, 0-(methoxycarbonyl)phenyl group, 4-carboxy-1-naphthyl group, etc. can be mentioned.

Examples of the cycloalkyl group represented by R, -R include a cycloheptyl group, cyclopentyl group, and cyclohexyl group, and examples of derivatives of the cycloalkyl group include a methylcyclohexyl group. R,
Examples of the halogen atom represented by -R include fluorine,
Examples of amino group derivatives in which chlorine, bromine, and iodine are represented by R1-R4 include butylamino group, diethylamino group, anilino group, and the like. Examples of the mercapto group derivatives represented by R1-R1 include methylthio group, ethylthio group, and phenylthio group.

The alkyl group represented by R5 preferably has 1 to 6 carbon atoms.
Examples thereof include a methyl group and an ethyl group.

Particularly preferred as R6 are a hydrogen atom and a methyl group.

Although J is a divalent linking group, it is preferable that the total number of carbon atoms is 1 to 20. Among such linking groups, the following formula (J
-1') or (J-It) is preferred.

(J-1) (J-II) R6 In the formula, Y is -0- or -N- (where R6 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Z is an alkylene group (preferably up to 10 carbon atoms).

In the middle of the alkylene group, there is an amide bond, an ester bond,
Alternatively, an ether bond may be present. For example, ethylene group, ethylene group, propylene group, -CHtOCH
2-1-〇HtCONHCH! -, CHt CHt
COOCHt -, -CHfCHIOCOCH, -,
-C)[2NHCOCH,-etc.)-〇-Alkylene!
, -CONH-alkylene group, -COO-alkylene group, -0CO-alkylene group or -NHCO-alkylene group (these alkylene groups preferably have 10 carbon atoms)
) or arylene group (preferably carbon number 6)
~12 things. For example, p-phenylene group, etc.).

Particularly preferable divalent linking groups as J include the following.

-CON HCH! -1-CONHCH,CH! -1-
CONHCH,0COCH,-1-CONHCHtCH
*CHtOCOC) [t-1COOCHt-1-COo
CHtCH,-1-COOCH,CH,0COCHt-
1-cOOCHtCHtCHtOCOCHt It may be a homopolymer or a copolymer (eg, copolymers include acrylamide, methacrylamide, acrylic ester, methacryl ester, etc.).

Next, the general formula (V[), (■), (■) or (I
Representative examples of the compound represented by X) or the compound having a flip-back unit represented by the general formula (X) (hereinafter referred to as the tetrazaindene compound used in the present invention) are shown below.

(3)・(4)(10)
(Eye) (+4) I 01 Y R OI+ (2B) (29) Copolymer with H υH Y: 5 to 50 mol % Addition amount of the tetrazaindene compound used in the production of the silver halide grains of the present invention varies depending on production conditions such as desired final grain size of silver halide, emulsion temperature, PHS ($) Ag, silver iodide content, etc., but is 1 x 10"S to 2 x per mole of total silver halide produced. A range of 1 (I'' mole) is preferred.

In addition, when the tetrazaindene compound is a compound having a unit represented by the general formula (X), the amount added is determined by the number of moles of the tetrazaindene moiety. More preferable addition m is as shown in Table 1 with respect to particle size. The addition m for particle sizes other than those listed in Table 1 can be determined by extrapolation or interpolation by making the addition amount inversely proportional to the particle size.

Table 1 Preferable addition m for desired grain size Further, more preferable addition amounts are shown in Table 2 for PAg and silver iodide contents.

Table 2 More preferable addition amount (mol/Agx1 mol) at each pAg and Agl content rate (desired final particle size 0
．． 8 .mu.m) The tetrazaindene compound may be added in advance into the colloidal solution, gradually added as the silver halide grains grow, or a combination of these methods may be used.

In the normal use form of the silver halide emulsion of the present invention, excess halogen compounds generated during the preparation of 11 halide grains, salts and compounds such as by-products or unnecessary nitrates and ammonia are used as a dispersion medium for the grains. removed from (
desalination step). Removal methods include the Tardel water washing method, which is commonly used in general emulsions, or inorganic salts, anionic surfactants, anionic polymers (e.g., polystyrene sulfonic acid), or gelatin derivatives (e.g., acylated gelatin, carbamoylated gelatin, etc.). ), a coagulation precipitation method (flocculation method), etc. can be used as appropriate.

After obtaining desired silver halide grains in the silver halide grain forming step and before the desalting step is performed,
The pAg of the mother liquor must be controlled between 7.0 and 9.5. During this period, the preferred pAg is 7.4 to 9.2.
and more preferably 7°8 to 9.0. pH
is preferably 5-8, more preferably 5-7.

The shorter the time from the end of the particle formation step to the start of the desalting step, the better, preferably within 30 minutes, more preferably within 2 minutes.
Within 0 minutes.

Book! ! The characteristics of the IJ manufacturing method are as follows:
As stated in the specification of the present invention, it is possible to supply a silver halide emulsion with excellent monodispersity.

The outline of the method for producing silver halide grains having a (+10) crystal face according to the present invention has been described above.

For details, see JP-A No. 60-222842, patent application No. 59-15.
You can find out about it in Meiji No. 8111.

In the process of silver halide grain formation or physical ripening, the silver halide grains having the (1lfl) crystal plane according to the present invention are prepared using cadmium salt, zinc salt, lead 1i4, thallium salt, iridium salt, or a complex salt thereof.

Rhodium 11! Or its complex salt, iron salt or iron complex salt, gold salt or gold salt! '9 may also coexist.

The amount of these additions may be small or large depending on the intended photosensitive material.

Soluble from the emulsion after precipitation or physical ripening 34!
In order to remove gelatin, the Tardel water washing method performed by gelatinization may be used, and inorganic salts, anionic surfactants, anionic bombers (e.g. polystyrene sulfonic acid), or gelatin derivatives (e.g. acylated A sedimentation method (flocculation method) using gelatin, carbamoylated gelatin, etc.) may also be used.

The silver halide emulsion may or may not be chemically sensitized, e.g.

11.Die Grundlagen edited by Frlescr
der Photographie-chen P
rozesse wit Silverbalog
eniden (Akade-sische Ver.
lagsgesellschaf L, 1968)
See the description on pages 675-734.

A preferred example of the FR compound to be contained in the photographic constituent layer of the silver halide color photographic light-sensitive material of the present invention is the following general formula (
It can be expressed as X[) and/or (Xll).

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

(1) A coupler (I [) that couples with the oxidation product of an aromatic primary amine developing agent to release an FA compound. A coupler (I[) that couples with the oxidation product of an aromatic primary amine developing agent to release a diffusible FA compound. A coupler (III) that forms a colored or colorless dye, and the diffusible dye acts as an FA compound. A decomposition reaction that causes a redox reaction with the oxidation product of a developing agent and that occurs subsequent to the oxidation reaction. Redox compounds such as those that release FA compounds.

The above compounds (1), (I[) and (I[[) have the following general formulas [X[), [■] and (XIII
).

[Kari] CP-F'B [Kari] FB-Cp-BALL (XI[) RED-FB In the above formula, the FB group is -(T I M E ) m -(
L) represents n-FA. Here, FAW is a group having the ability to fog silver halide or development acceleration 1+1
represents a group having i force, L represents a divalent linking group, TI
ME represents a timing group. It is particularly preferred if the FB group has a group capable of adsorbing silver halide. m and n each represent O or 1.

Furthermore, cp represents a coupler residue capable of coupling reaction with an oxidized form of an aromatic primary amine developing agent, BALL represents a diffusion-resistant group, and RED represents a coupling reaction with an oxidized form of an aromatic primary amine developing agent. Represents a compound residue that can be cross-oxidized.

Each of the general formulas (Xl), [■] and (XI[I] will be explained below.

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

Here, among couplers, a typical example of a yellow coupler is U.S. Pat. No. 2,875,057, US Pat.
No. 10, No. 3,265.506, No. 2゜298.44
No. 3, No. 3,048,194, No. 3 447.928
It is stated in the number etc. Among these yellow couplers, acylacetamide derivatives such as benzoylacetanilide and pivaloylacetanilide are preferred.

Therefore, as the yellow coupler residue (Cp), those represented by the following general formulas (X*) and (XV) are suitable.

Note that * represents the bonding position of the FB group (hereinafter general formula (X
Same up to X[)).

Here, Rt represents diffusion resistance with a total carbon number of 8 to 32, and R
1 is a hydrogen atom, one or more halogen atoms, a lower alkyl group, a lower alkoxy group, or a total number of carbon atoms of 8 to 32
represents a diffusion-resistant group. Rlh (If there are two or more, they may be the same or different.

A typical example of a magenta coupler is U.S. Patent No. 2.600.
．． No. 788, No. 2,369.489, No. 2゜343.
No. 703, No. 2,311,082, No. 3゜152.8
No. 96, No. 3,519,429, No. 3゜062.65
No. 3, No. 2,908,573, etc. Among these magenta couplers, pyrazolones or pyrazoloazoles (pyrazolopyrazole, pyrazoloimidazole, pyrazolotriazole, pyrazolotetrazole, etc.) are preferred.

Therefore, the remaining magenta coupler W (Cp) is:
Those represented by the following general formulas (XVI:l, [X■] and [X■] are preferred.

・2 Here, R1 represents a diffusion-resistant group having 8 to 32 carbon atoms,
R8 is! or more halogen atoms, lower alkyl groups, lower alkoxy groups, phenyl groups, or substituted phenyl groups. Z represents a group of nonmetallic atoms necessary to form a 5-membered azole ring containing 2 to 4 nitrogen atoms,
The azole ring may have a substituent (including a fused ring).

A typical example of a cyan coupler is disclosed in U.S. Pat. No. 2,772.
No. 162, No. 2,895,826, No. 1; l.

No. 002.836, No. 3,034.892, No. 2゜4
No. 74.293, No. 2,423,730, No. 2゜36
No. 7.531, No. 3,041,236, etc. Among these cyan couplers, phenols or naphthols are preferred.

Therefore, as cyan coupler residues (Cp), the following general formulas (XIX), (XX), [XXI] Oyohi [X
(2) is preferable.

O1!岑Here, R3 represents a diffusion-resistant group having a total carbon number of 8 to 32,
R2 represents a halogen atom, a lower alkyl group, or a lower alkoxy group of ■ or more, and when R is two or more, they may be the same or different.

The FA group is the most basic functional group that expresses the functions of PR compounds. This group includes reducing compounds (hydrazine, hydrazide, hydrazone, hydroquinone, catechol, p-aminophenol, p-)unilenediamine, 1-phenyl-3-pyrazolone, enamine, aldehyde, polyamine, acetylene, aminoborane, tetrazolium salts, quaternary salts represented by ethylene bispyridinium salts, carbazic acid, etc.), or compounds that can form silver sulfide during development (such as thiourea, thioamide, dithiocarbamate, rhodanine, thiohydatoin, thiazolidinethione, - Examples include those having a partial structure of C--N-).

TIME represents a timing group, which includes those using intramolecular substitution reactions as described in U.S. Pat. No. 363A, JP-A-57-154234
No., JP-A-57-188035, JP-A-58-987
Examples include those that utilize electron transfer via a conjugated system within a molecule, as described in No. 28.

Examples of divalent linking groups represented by include alkylene group, alkenylene group, phenylene group, naphthylene group, -0-1
A group selected from the group consisting of -S-1-SO-1-9O, -1-N=N-, carbonamide group, thioamide group, sulfonamide group, ureido group, thioureido group, heterocyclic group, etc. is used. be done.

The FB group consisting of the above FA group, TIME, and L is
Particularly preferred is the case where it has a group capable of adsorbing silver halide (this group may be present in any part of FA, TIME, or L).

Groups that can be adsorbed to silver halide 1a include a nitrogen-containing heterocyclic group having six dissociable hydrogen atoms, a heterocyclic group having at least one nitrogen atom and a pond heteroatom in the ring,
Heterocyclic groups with mercapto groups, tetradisperse salts, thiols,
Examples include groups derived from compounds having an N-C- partial structure.

In the general formula [■], FBM is bonded to the non-coupling 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 oxidized product of the aromatic primary amine developing agent. Here, Cp and FB represent the same meanings as described in the general formula (XI).

The diffusion-resistant group represented by BALL has a size and shape that imparts non-diffusivity to the coupler, and may be in the form of a polymer in which a number of breakaway groups are linked. It may have an alkyl group and/or an aryl group. In the latter case, the alkyl group and/or
Alternatively, the total number of carbon atoms in the aryl group is preferably about 8 to 32. BALL has a group for bonding to the coupling position of Cp, and representative examples include:
-0-1-S-1-N=N-1-O-C-1-O-S-
1 and 1N constituting a heterocycle.

In the general formula (Xm), RED is hydroquinone,
It has a catechol or 0-aminophenol skeleton (all of the above, including fused rings), and cross-oxidizes with the oxidized product of an aromatic primary amine developing agent, and undergoes alkaline hydrolysis to release an FB group. FB, which represents a group that
N-1 is bonded to RED through any of the -N groups, RED has an 0-aminophenol or p-aminophenol skeleton (including the case of fused rings), and FB is bonded to them. When FB is not directly bonded to the benzene ring of , it is bonded to these amino groups via -8- (ie, forming a sulfonamide group).

Next, specific examples of PR compounds represented by the general formulas CXI), [■], and (XII[) will be shown, but the invention is not limited thereto.

[Exemplary compounds]

n CO N11゜CO CsH+++LSCO CO (lO) Cθ rθ 11+1 n++ Song ≧ 0 Kaisho 57-150845, Kaisho 57-138
636, No. 59-50439, No. 59-170840
No. 60-37556, No. io-107029, U.S. Pat. No. 3,214,377, U.S. Pat.
It can be synthesized by the method described in No. 4, etc.

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

Further, the amount of the Fr compound of the present invention added is txt o-@~lxt per mole of silver of silver halide contained in the layer containing the Fll compound or the layer adjacent thereto.
o-' moles, preferably from 1 x 10-6! ×10-1
It is a mole.

In particular, the FR compound of the present invention has a Miller index of 1 (11
It is preferable to add it to a photosensitive silver halide emulsion layer containing silver halide grains having a crystal plane defined by 0) and/or its adjacent layer (including an intermediate layer).

Preferred uses of the FR compound of the present invention are as follows.

For example, in the case of a full color film, on the support +
11' primary, a red-sensitive emulsion layer containing silver halide grains having crystal planes defined by Miller index (110); silver halide grains having crystal planes defined by Miller index (+10) in the present invention; or a green-sensitive emulsion layer containing silver halide other than that, and an h-sensitive emulsion layer containing silver halide grains having a crystal plane defined by the Miller index (110), and the green-sensitive emulsion layer is The FR compound of the present invention is contained, or the FR compound of the present invention is contained in the red-green sensitive emulsion layer.

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

In order to incorporate these FR compounds into the silver halide emulsion or other photographic constituent layer coating solution according to the present invention, if the FR compound is alkali-soluble, it may be added as an alkaline solution. If it is oil soluble,
For example, U.S. Patent Nos. 2,322,027 and 2,80
No. 1,170, No. 2,801,171, No. 2,2
No. 72,191 and No. 2,304,940 each Mei 4
+1 It is preferable to dissolve the FR compound in a high-temperature solvent and, if necessary, in combination with a low-temperature solvent, and to disperse the compound in the form of fine particles and add it to the silver halide emulsion, according to the method of Furukawa Ki. At this time, two or more types of FR compounds may be mixed and used if necessary. Further, to explain in detail the preferred method of adding FR compounds in the present invention, one or more of the FR compounds, such as α-acid amides, carbamates, esters, ketones, urea derivatives, ethers, carbonized Hydrogens, etc., especially di-n-butyl phthalate, triresyl phosphate, triphenyl phosphate, di-isooctyl azelate, di-n-phthyl sehacate, tri-hexyl phosphate, N,N-di-ethyl-caprylamitophate. Chyl, N, N-diethyl laurylamide, n-pentadecyl phenyl ether, she-octyl phthalate, n-nonylphenol, 3-pentadecyl phenylethyl ether, 2.5-cy 5e
High-density solvents such as c-amyl phenyl butyl ether, monophenyl-di-chlorophenyl phosphate or fluoroparaffin, and/or methyl acetate, ethyl acetate, propyl acetate, butyl acetate, butyl propionate, cyclohexanol, diethylene glycol monoacetate, Nitromethane, carbon tetrachloride.

Anionic surfactants such as alkylbenzenesulfonic acids and alkylnaphthalenesulfonic acids and/or sorbitan sesquioleate It is mixed with an aqueous solution containing a nonionic surfactant such as sorbitan monolaurate and/or a gelatin chamber containing hydrophilic paint, and emulsified and dispersed using a high-speed rotary mixer, colloid mill, ultrasonic dispersion type, etc. to form a silver halide emulsion. added to.

In addition, the above-mentioned FR compound may be dispersed 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-5
4-32552 and Research Disclosure, August 1976, No. 14850, pages 77-79.

Suitable latexes include, for example, styrene, acrylate,
n-phthyl acrylate, n-phthyl acrylate, 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-acrylamide-2-
Seven-dimensional homopolymers, copolymers and terpolymers such as 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 above-mentioned couplers that can be used 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 couplers or 4-equivalent type couplers, and it is also possible to use a diffusible dye-releasing type coupler or the like in combination with these couplers.

The yellow coupler is a closed ketomethylene compound (especially preferably a benzoylacetanilide compound or a pivaloylacetanilide compound), and furthermore, a so-called 2
Active point -〇-aryl substituted coupler, active point -〇-acyl substituted coupler, active point hydantoin compound substituted coupler, active point urazole compound substituted coupler and active point succinimide compound substituted coupler, active point called this 1 coupler. A fluorine-substituted coupler, a 1N or bromine-substituted coupler at the active site, a 0-sulfonyl-substituted coupler at the active site, and the like can be used as effective yellow couplers. Specific examples of yellow couplers that can be used include U.S. Pat.
No. 6, No. 3,408,194, No. 3,551,155
No. 3,582,322, No. 3,725.072, No. 891,445, West German Patent No. 1,547,8
No. 68, West German Application No. 2,219,917, No. 2,2
No. 51,361, No. 2,414.006, British Patent 1
, 425,020, JP 51-10783, JP 47-26133, JP 48-73147, JP 51
-102636, 50-6341, 50-12
No. 3342, No. 50-130442, No. 51-218
27, No. 50-87650, No. 52-82424, No. 52-115219, No. 58-95346, and the like.

Margin below Particularly preferred couplers are listed below.

Coo(HCOO(3, □H25 (E2) (゛“-now) (γ-bu) Product(Y-72 (Y-/I> (E//nC(-/λ) (y-7in I O, H5 (Y -16) t H3 [Y-2 da] C1 (y-zh) t (Y-z6] t (Y-, i'7) (Y-Zf?) [Y-2'I ] t Below margin Also, as magenta couplers used in the present invention, pyrazolone-based, pyrazolotriazole-based, pyrazolinobenzimidazole-based, and indasilone-based compounds can be mentioned.These 7-zenta couplers are similar to yellow couplers. Specific examples of magenta couplers that may include not only 4-equivalent couplers but also 2-equivalent couplers include U.S. Pat. Nos. 2,600.7H, 2,983,
5el1, same), 062,653, same, 127,
No. 269, Ko, Ko 11.476, No. 3,419,3
No. 91, No. 3,519,429, No. 3.558,31
No. 9, No. 3,582.32/j, No. 3,615,50
No. 6.

834.9011, 3,891,445, West German patent t, alo, 464, West German patent application (OL
S) No. 2,408.665, No. 2,417,9
No. 45, No. 2,418,959, No. 2,424.46
No. 7, Special Publication No. 40-6031, Japanese Patent Publication No. 51-2082
No. 6, No. 52-58922, No. 49-129538, No. 49-74027, No. 50-159336, No. 52-42121, No. 49-74028, No. 50-
No. 60233, No. 51-26541, No. 53-551
22, Japanese Patent Application No. 55-110943, and the like.

Particularly preferred couplers are as follows.

(M-ri.6 (M-z) (I114-6) CM-7). 2 (M-r) 2H5 (t4- f) 0 figure-rt) (M-+, z) <t-q-rs) (H-1~) (M-+Q (t'l-17) More books Cyan couplers useful in the invention include, for example, phenolic couplers, naphthol couplers, etc.These cyan couplers are not only 4-equivalent type couplers, but also 2-equivalent type couplers, like the yellow couplers. Specific examples of cyan couplers include U.S. Pat. Nos. 2,369,929 and 2
, No. 434, 272.

2,474,293, 2,521,908, 2,895,826, 3,0:14,892, 3,311,476, 3,458.315, same, 476.55:1, same, 58, 971, same, 591,383, same: l, 767.411, same 1
, No. 772,002.

1.9:13,494, 4,004,929,
West German Patent Application (OLS) No. 2,414,830, No. 2,454. : No. 129, JP-A-48-59838
No. 51-26034.

4B-5055, 51-146827, 52
-69624, 52-90932.

No. 5B-95346, Special Publication No. 1973-. Examples include those described in No. 11572 and the like.

Preferred couplers for I# are listed below.

Cc-r) 04H8 02H.

C5Htt(t) C,)I,L(t) (C-1?) (C-18) (C-tS) OCH2CHzSCHCσ17)-1 C11Hco5(Silver halide emulsion layer of the present invention, other photographs A polymer coupler or the like may be used in combination in the constituent layers, and the polymer coupler is described in Japanese Patent Application No. 59-1721 filed by the present applicant.
You can refer to the description in No. 51.

In the following margins, a conventional colored magenta coupler can be used in the green-sensitive emulsion of the present invention. As a colored magenta coupler, U.S. Pat.
, No. 519.429, Japanese Patent Publication No. 48-27930, etc. may be used.

Colored magenta couplers that are preferably used are as follows.

CcM-3) Oh.

α Further, a common colored cyan coupler can be used in the red-sensitive emulsion layer of the present invention. , power, as a lard cyan turnip, Special Publication No. 55-32461, British I! i
Those described in Patent No. 084,480 and the like can be used.

A particularly preferred force is 2-docyancap-poor.

The following may be mentioned.

CCC-I:) (cc-3') OH CCC-Lh'') OH The method for adding the above coupler that can be used in the present invention into the photographic constituent layer of the present invention is the same as before, and the amount of the above coupler added is as follows. Without limitation, l x 1 per mole of silver
Preferably 0-2 to 5 mol, more preferably t x t
o-" to s x to"'.

The silver halide color photographic light-sensitive material of the present invention may also contain various other photographic additives. A color stain inhibitor, a fluorescent whitening agent, a color image fading inhibitor, an antistatic agent, a hardening agent, a surfactant, a plasticizer, a wetting agent, etc. can be used.

In the silver halide color photographic light-sensitive material of the present invention, the woody colloids used to prepare the emulsion include gelatin, derivative gelatin, graft polymers of gelatin and other polymers, proteins such as albumin and casein, Any of cellulose derivatives such as hydroxyethyl cellulose conductor, carboxymethyl cellulose, Wi powder derivatives, single or copolymer synthetic hydrophilic polymers such as polyvinyl alcohol, polyvinylimidazole and polyacrylamide are included.

Examples of the support for the silver halide color photographic light-sensitive material of the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, a transparent support provided with one reflective layer or a reflective material, a glass plate, and cellulose. Polyester films such as acetate, cellulose nitrate or polyethylene terephthalate, polyamide films,
Transparent supports such as polycarbonate films and polystyrene films are used, and these supports are appropriately selected depending on the intended use of the photosensitive material.

Coating of the silver halide emulsion layer and other photographic constituent layers used in the present invention includes dip coating, air doctor coating, and curtain coating.

Various coating methods can be used, such as hopper coating.

Also, U.S. Patent Nos. 2,761,791 and 2,941,8
A simultaneous coating method of two or more coatings according to the method described in No. 98 can also be used.

In the present invention, the coating position of each emulsion layer can be determined arbitrarily. For example, in the case of a full-color photographic film, a red-sensitive silver halide emulsion layer and a green-sensitive silver halide emulsion layer are sequentially applied from the support side.

The arrangement of blue-sensitive silver halide emulsion layers is preferred, and each of these light-sensitive silver halide emulsion layers may consist of two or more layers.

The effects of the present invention are most effective when all of these photosensitive emulsion layers are substantially composed of silver bromide or silver iodobromide emulsions.

In the photosensitive material of the present invention, it is optional to provide an intermediate layer with an appropriate thickness depending on the purpose, and a filter layer,
Various layers such as an anti-curl layer, a protective layer, and an antihalation layer can be used in appropriate combinations as constituent layers.

In these structures tF3, hydrophilic colloids that can be used in the emulsion layers as described above can be used as binders, and various types of colloids that can be contained in the emulsion layers as described above can be used as binders. Photographic additives may be included.

There are no particular restrictions on the method of processing the photographic material according to the present invention, and any processing method can be used, for example,
Typical methods include bleach-fixing after color development, followed by further washing and/or stabilization treatment if necessary. 1 After color development, bleaching and fixing are carried out separately, and further washing and/or stabilization are carried out if necessary. Or how to do stable processing:
Or a method of performing prehardening, neutralization, color development, stop-fixing, washing with water, bleaching, fixing, washing with water, post-hardening, and washing with water,
Color development, washing, supplementary color development, stop, W! white, fixed,
Washing with water and stabilization in that order Method 1: After halogenation bleaching of the developed silver produced by color development, color development is performed again to increase the amount of dye produced. good.

The color developing solution used in the processing of the silver halide color photographic light-sensitive material of the present invention is not limited to, but contains a color developing agent of 911 or more, preferably 8 or more.

More preferably, it is an alkaline aqueous solution in which 911 is 9 to 12. The aromatic primary amine developing agent used as the color developing agent is a compound having a primary amino group on an aromatic ring and has the ability to develop silver halide exposed to light. Precursors that form such compounds may also be added.

The color developing agents mentioned above are typically p-phenylenediamine type ones, and preferred examples include primary ones.

4-Amino-N, N-diethylaniline, 3-methyl-
4-amino-N, N-diethylaniline, 4-amino-
N-ethyl-N-β-hydroxyethylaniline, tomethyl-4-amino-N-β-hydroxyethylaniline, 3-methyl-4-aminoethylroot β-methoxyethylaniline, 3-methyl-4-aminoethylaniline −
N-β-methanesulfonamidoethylaniline, 3-methoxy-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methoxy-4-aminoethyl-N-β-methoxyethylaniline, two-acetamide -4-amino-N,N-dimethylaniline, toethyroot β-(β-(β-methoxyethoxy)ethoxy)ethyl-3-methyl-4-aminoaniline, N-ethyroot β-(β-methoxyethoxy)ethyl- 3-methyl-4
-aminoaniline and their salts such as sulfates, hydrochlorides, sulfites, p-toluenesulfonates, etc.

Further 1, for example, JP-A No. 48-64932, JP-A No. 50-1
No. 31526, No. 51-95849, and Bent et al., Journal of the American Chemical Society, Vol. 73, pp. 1100-125 (1951).
The one described in 2010) is also cited as a representative example.

The amount of these aromatic primary amino compounds used depends on where the activity of the developer is set, but in order to increase the activity, it is preferable to increase the amount used, and the amount used is 0. It is used in a range from 0,002 mol/i to 0.7 mol/l. In addition, two or more compounds may be used in appropriate combination depending on the purpose. For example, tomethyl-4-amino-N,N-diethylaniline and 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamide. Ethylaniline, 3-methyl-4-amino-N-
Combinations such as ethyl-N-β-methanesulfonamidoethylaniline and 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline may be used freely depending on the purpose.

The color developer used in the present invention further contains various commonly added components, such as alkaline agents such as sodium hydroxide and sodium carbonate, alkali metal sulfites,
Alkali metal bisulfite, alkali total thiocyanate, alkali metal halide, benzyl alcohol,
Water softener.

A thickening agent, a development accelerator, etc. can also be optionally included.

Examples of additives other than the above added to the color developing solution include bromides such as potassium bromide and ammonium bromide;
In addition to compounds for quick processing solutions such as alkali iodide, nitrobenzimidazole, mercaptobenzimidazole, 5-methyl-benzotriazole, 1-phenyl-5-mercaptotetrazole, anti-stain agents, anti-sludge agents, preservatives, There are multilayer effect promoters, chelating agents, etc.

Bleaching agents used in bleaching solutions or bleach-fixing solutions in the bleaching process are generally known to be those in which diagonal ions such as iron, cobalt, and copper are coordinated with aminopolycarboxylic acids, B acids, and organic acids such as citric acid. It is being Representative examples of the above aminopolycarboxylic acids include the following.

Ethylenediaminetetraacetic aciddiethylenetriaminepentaacetic acidpropylenediaminetetraacetic acidnitrilotriacetic acidiminodiacetic acid ethyl ether diaminetetraacetic acidethylenediaminetetrabrobion fused ethylenediaminetetraacetic acid disodium saltdiethylenetriaminepentaacetic acid pentasodium saltnitrilotriacetic acid sodium saltBleaching solutions can be used with various bleaching agents as mentioned above. It may contain additives, and when a bleach-fixing solution is used in the bleaching step, a solution containing a silver halide fixing agent in addition to the bleaching agent is used. The bleach-fix solution may further contain a halogen compound such as potassium bromide, and as in the case of the bleach solution described above, various other additives such as pH buffers, antifoaming agents, surfactants, etc. An activator, preservative, chelating agent, stabilizer, organic solvent, etc. may be added or contained.

The silver halide fixing agent is 1, for example, sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, sodium thiocyanate, or thiourea, thioether, etc., which react with silver halide and become water-soluble. Compounds that form silver salts can be mentioned.

Color development of the silver halide color photographic light-sensitive material of the present invention,
The processing temperature of bleach-fixing (or bleaching, fixing), and various processing steps such as water washing, stabilization, and drying, which are performed as necessary, is preferably 30° C. or higher from the viewpoint of rapid processing.

The silver halide color photographic light-sensitive material of the present invention is disclosed in Japanese Unexamined Patent Publication No. 58
-14834, 5B-105145, 58-1
No. 34634 and No. 58-18631 and patent application 1973
A stabilizing treatment as an alternative to washing may be performed as shown in Japanese Patent No. 8-2709 and Japanese Patent No. 59-89288.

[Effects of the Invention] According to the silver halide color photographic light-sensitive material of the present invention, the contradictory demands of high sensitivity and improvement in graininess can be simultaneously satisfied.

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

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

1st N red-sensitive emulsion layer Silver iodobromide emulsion EM-A or EM-B shown in Table 1 Silver coating amount...3.4 g/rrr Silver iodobromide emulsion (EM-A or EM-B shown in Table 1) ) Sensitizing dye I-6 x 10-' moles per mole of sensitizing dye I-fi 2 x 10-' moles per mole of silver Coupler dissolved in tricresyl phosphate 0.5 mi/rn'' A・-jl0.06 mol per 1 mol FR compound￥'IIC Table 1)-[o, oo per 1 mol
Gelatin with 1.3 g/m" and 2.4 with 0.05 g/m"
- Protective layer coupler A containing dichloro-6-hydroxy-S-triazine sodium Silver iodobromide grains (silver iodide content 4
An emulsion containing 0.29 mol (mol%) was dispersed in distilled water for 100 hours (containing 30 mJl of 25% ammonia), then 95 sJl of methanol was added and the emulsion was heated to 0 at 50°C.
．． 1000sjL of a 47 mol/l silver nitrate aqueous solution and a necessary and sufficient mixed aqueous solution of potassium bromide and potassium iodide (containing 4 mol% potassium iodide) were added in 40 minutes using a controlled double jet method to control 9 kg to 1000. It was manufactured by

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

As a result of electron microscopy, EM-A (l l 1
) It contained an almost perfect regular octahedron consisting of crystal planes.

Production method of EM-H Silver iodobromide grains with an average grain size of 0.40 ru (silver iodide content 4
mol %) Emulsion containing 0.29 mol of distilled water 10010
0O (containing 25% ammonia 30IIi) and then 1-phenyl-5-mercaptotetrazole 0
．． Add 95% of 1% methanol solution.

0.47 mol/cross silver nitrate aqueous solution 11 at 506C
000a and a necessary and sufficient amount of potassium bromide and potassium iodide mixed aqueous solution (containing 4 mol % potassium iodide) was added in 40 minutes using a controlled double jet method while controlling the pAg to 1000.

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

As a result of electron microscopic observation, EM-B contained an almost perfect rhombic dodecahedron consisting of (110) crystal planes.

Compound used to make the sample.

Sensitizing dye I: anhydride-5,5'-dichloro-3,3'-di(γ
-Sulfopropyl)-9-ethyl-thiacarbocyanine hydroxide pyridium salt sensitizing dye ■: Anhydride-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.

A dye image was obtained by processing with the following processing steps.

Processing steps (38°C) Color development 2 minutes 40 seconds bleaching 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. It is as follows.

[Color developer] 4-amino-3-methyltoethyl (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 (l hydrate) 2.5g potassium hydroxide 1-0g Add water to make up.

[Bleach solution] Ethylenediaminetetraacetic acid iron ammonium salt 100. g Ethylenediaminetetraacetic acid 2 ammonium salt 10.0 g ammonium bromide lso, 0 g glacial acetic acid 10.0 ml water was added to bring the solution to 141, and the pH was adjusted to 6.0 using aqueous ammonia.

[Fixer] Ammonium thiosulfate 175.0g Anhydrous sodium sulfite 8.5g Sodium metasulfite 2.3g Add water and lIL
1) Adjust A to lI = 6.0 using acetic acid.

[Stabilizing solution] Formalin (37% aqueous solution) 1. smM
Conidax (manufactured by Konishiroku Photo Industry Co., Ltd.) 7.5 @ Add the water to make one sentence.

The obtained characteristic values are shown in Table 1.

As is clear from Table 1, sample No. 4°N according to the present invention
Samples o, 5, ribs, and 8 had higher sensitivity than the comparative samples, and the combination of the emulsion of the present invention and the FR compound of the present invention improved graininess, demonstrating the effectiveness of the present invention. .

Example 2 Each layer having the composition shown below was sequentially provided on a cellulose triacetate film support to prepare a multilayer color photosensitive material sample. That is, as shown in Table 2, sample No.
Samples No. 9 to No. 16 were prepared.

1st layer Antihalation layer Black gelatin layer containing colloidal silver 2nd layer Intermediate gelatin layer 3rd layer Red-sensitive emulsion layer Silver iodobromide emulsion EM-A or EM-B shown in Table 2 Silver coating amount - 3.4 g /rrf Sensitizing dye I・-21 mole: Ca
Molar coupler A: 0.06 mol per mol of silver Coupler C: 0.00:3 mol per mol of tricresyl phosphate Coating amount: 0,5-cross/G 4th layer
Intermediate gelatin layer 5th layer Green-sensitive emulsion layer Silver iodobromide emulsion EM-A or EM-B shown in Table 2 Silver coating amount - 2.4 g/rn' Sensitizing dye ■... per 1 mole of silver 3 X 10-' mol Sensitizing dye ■... l X 10-' per 1 mol of silver
1 mol coupler B... 0.08 mol coupler M for 1 mol of silver - o, oooa for 4 t mol Rephosphate coating Q-2.81 / Go 6th layer
Yellow filter Single layer Gelatin layer 7th layer formed by coating a yellow colloidal silver in an aqueous gelatin solution Blue-sensitive emulsion layer Silver iodobromide emulsion EM-A or EM-B shown in Table 2 Silver coating amount -1, 1 g/m' Coupler Y - at mole Q, 125 mole tricresyl phosphate coating amount -0,5 m Jl/m'' 8th P
3. Protective layer A gelatin layer formed by coating gelatin containing polymethyl methacrylate particles (diameter 1.5 IL-).

The couplers in each layer are prepared by adding the couplers to a solution of tricresyl phosphate and ethyl acetate, adding sodium p-dodecylbenzenesulfonate as an emulsifier and dissolving them by heating.
The mixture was mixed with a heated 10% gelatin solution and emulsified using a colloid mill.

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

Coupler B Coupler C Coupler M Sensitizing dye ■: Anhydride-9-ethyl-5,5'-dichloro-3,3
′-di(γ-sulfopropyl)-oxacarbocyanine hydroxyto sodium salt sensitizing dye β-(β-
(γ-Sulfopropoxy)ethoxy))ethylimidazolocarbocyanine hydroxide sodium salt Blue light, green light, red light, and white light are applied to each of the above samples No. 9 to Sample No. 16 through a wedge. The same treatment as in Example 1 was performed to obtain a one-dye image. As in Example 1, the results are shown in Table 2.

As is clear from Table 2, it can be seen that Kokumei samples No. 12, No. 14 to No. 16, have high sensitivity.

Samples Nos. 009 to 16 were used separately from the above exposure.

When a landscape was actually photographed and compared with an image printed on color vapor, it was observed that the sample of the present invention had very bright colors and good graininess.

Claims (1)

[Claims] In a silver halide color photographic light-sensitive material having a photographic constituent layer including at least one light-sensitive silver halide emulsion layer on a support, the at least one light-sensitive silver halide emulsion layer has a Miller index of (110). It has defined crystal planes on its outer surface, contains silver halide consisting essentially of silver bromide and/or silver iodobromide, and at least one photographic constituent layer is an aromatic primary amine developing agent. 1. A silver halide color photographic light-sensitive material, which contains a compound that releases a fogging agent, a development accelerator, or a precursor thereof in accordance with the amount of developed silver when silver halide is developed using a silver halide color photographic material.