JPH03194539A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a sensitive material having high sensitivity and satisfactory graininess and hardly causing fog by subjecting the emulsion in an emulsion layer to reduction sensitization with ascorbic acid or a deriv. thereof in the presence of a specified compd. and incorporating a compd. releasing a development accelerator or a fogging agent into the emulsion layer. CONSTITUTION:The emulsion in an emulsion layer is subjected to reduction sensitization with ascorbic acid or a deriv. thereof in the presence of a compd. represented by general formula I, II or III and a compd. releasing a development accelerator or a fogging agent by a reaction with the oxidized body of a color developing agent is incorporated into the emulsion layer. In the formula I-III, each of R, R<1> and R<2> is an aliphatic, arom. or heterocyclic group, M is a cation, L is a divalent combining group and m is 0 or 1. A sensitive material having high sensitivity and satisfactory graininess and hardly causing fog is obtd. A polymer contg. divalent groups derived from a structure represented by the formula I, II or III as repeating units may be used in place of the compd. represented by the formula I, II or III.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a silver halide photographic material.
This invention relates to a silver halide color photographic light-sensitive material that has high sensitivity, little fog, and improved graininess.

[Prior Art] In recent years, due to advances in the technology of photographic photosensitive materials, highly sensitive photosensitive materials have been released one after another. Expanding the range of photography by increasing the sensitivity of photosensitive materials, such as shooting without a strobe in a dark room, shooting with a high-speed shutter using a telephoto lens for sports photography, and shooting that requires long exposures such as astronomical photography. is an eternal theme for this industry.

Many efforts have been made to increase the sensitivity of photosensitive materials. Numerous studies have been conducted on formation methods such as the shape and composition of silver halide grains, chemical sensitization, spectral sensitization, additives, coupler structures, etc., and several useful inventions have been made. However, the demands for highly sensitive photosensitive materials are greater than the advances in technology, and unfortunately these methods alone have not been sufficient. Therefore, it has become common practice in the industry to increase the size of silver halide emulsion grains in combination with other techniques to produce high-sensitivity light-sensitive materials in order to increase sensitivity.

Increasing the size of the silver halide emulsion grains increases the sensitivity to a certain extent, but as long as the silver halide content is kept constant, the number of silver halide emulsion grains inevitably decreases, and therefore the development starting point increases. The major disadvantage is that the number is reduced and the graininess is greatly impaired. This problem is especially serious when the average particle size is 1.0 microns or more.

To compensate for this shortcoming, British Patent No. 923,045,
A photographic material having two or more emulsion layers having the same color sensitivity and different sensitivities, that is, different silver halide grain sizes, as described in Japanese Patent Publication No. 49-15495, Japanese Patent Publication No. 55-62454 A method using fast-reactive couplers as described in publications, etc., U.S. Patent No. 3,22
7,554, U.S. Patent No. 3,632,435, etc., methods using DIR compounds, yielding mobile dyes as described in British Patent No. 2,083,640. A method using such a coupler and a method using a silver halide having a high average silver iodide content as described in JP-A-60-128443 are known. Although each of these methods is an excellent invention with great effects, they are not sufficient technologies to meet the great demand for high sensitivity and high image quality. Therefore, in order to increase the grain size of silver halide emulsion grains and at the same time increase the number of development initiation points even slightly, high-sensitivity color negative light-sensitive materials are required to have various performances such as desilvering properties during bleach-fixing processing. Designs have been made in which the content of silver halide emulsion grains is increased within a range.

Another method for achieving high sensitivity is to incorporate a compound (hereinafter referred to as an FR compound) that can release a development accelerator or fogging agent upon reaction with an oxidized color developing agent into a light-sensitive material. U.S. Pat. No. 4,390.618, U.S. Pat. No. 4,518,6
No. 82, No. 4゜526.863, No. 4,482,62
No. 9, JP-A-59-157638, JP-A No. 59-1708
No. 40, No. 60-185950, No. 60-10702
It is written in No. 9 etc.

However, when an FR compound is used, it is often accompanied by increased fog and deterioration of graininess, and it has been impossible to use it without any adverse effects, especially when used in combination with large-sized particles.

On the other hand, it has been known to change the positions of the layers of a multilayer color negative photosensitive material in order to achieve high sensitivity or to achieve both high sensitivity and high image quality. For example, U.S. Patent No. 4,184.876
No. 4,129°446, No. 4,186,016, British Patent No. 1.560.965, U.S. Patent No. 4,1
86゜01), No. 4,267.264, No. 4,17
No. 3.479, No. 4,157,917, No. 4゜165
．． No. 236, British Patent No. 2. 138. No. 962, JP-A-59-177.552, British Patent No. 2.137,
No. 372, JP-A-59-180゜555, JP-A-59
-180.556, 59204.038, etc.

As described in JP-A-59-177.552, the emulsion layer closer to the support is affected by the emulsion layer farther away, resulting in a loss in exposure and a delay in development. It is known that this can result in low sensitivity and soft tone, so it is best to support the most sensitive emulsion layer of each of the red-sensitive emulsion layer and/or green-sensitive emulsion layer, which are located closer to the support than usual. The aim is to achieve high sensitivity by locating it far from the body. However, even with this color photosensitive material,
The number of interlayers that separate emulsion layers with different color sensitivities increases, and scavengers for oxidized developing agents are frequently used to prevent interlayer color mixing, resulting in problems such as higher silver content and thicker films. Even with this configuration, l5O100O
It was necessary to improve the graininess of the color photographic materials mentioned above.

On the other hand, the basic properties required of silver halide emulsions for photography are high sensitivity, low fog, and fine grains, but in order to increase the sensitivity of emulsions, (1) photons absorbed by a single grain (2) It is necessary to increase the efficiency of converting photoelectrons generated by light absorption into silver clusters (latent image), and (3) it is necessary to increase development activity in order to effectively utilize the formed latent image. There is. Increasing the size increases the number of photons absorbed by one particle, but reduces image quality. Increasing the development activity is also an effective means for increasing the sensitivity, but in the case of parallel development such as color development, graininess generally deteriorates. In order to increase sensitivity without causing deterioration of graininess, it is most preferable to increase the efficiency of converting photoelectrons into latent images, that is, to increase quantum sensitivity.

To increase quantum sensitivity, it is necessary to eliminate inefficient processes such as recombination and latent image dispersion as much as possible. It is known that reduction sensitization, which creates small silver nuclei with no development activity inside or on the surface of silver halide, is effective in preventing recombination.

Attempts at reduction sensitization have been considered for a long time.

Carroll, U.S. Patent No. 2. 487
．． In No. 850, the tin compound was manufactured by Lowe
disclosed that polyamine compounds were useful as reduction sensitizers in British Patent No. 2,512,925, and thiourea dioxide-based compounds were disclosed in British Patent No. 789,823. . Furthermore, Co1)ier (Korea) is a Photographer.
cScience and Engineering
Vol. 23, page 1) 3 (1979) compares the properties of silver nuclei produced by various reduction sensitization methods. She dimethylamine borane, stannous chloride, hydrazine,
A method of high pH ripening and low pAg ripening was adopted.

The method of reduction sensitization is further described in U.S. Pat. No. 2,518°698.
No. 3,201,254, No. 3゜41). 91
No. 7, No. 3,779,777, No. 3,930,8
It is also disclosed in No. 67.

Japanese Patent Publication Nos. 57-33572 and 58-1410 discuss not only the selection of reduction sensitizers but also the improvement of reduction sensitization methods.

Among these, conventionally known reduction sensitizers are listed, and ascorbic acid is mentioned among them. However, compounds such as thiourea dioxide are preferred, and those shown in the Examples are thiourea dioxide, silver ripening, and hydrazine. Therefore, favorable properties of ascorbic acid compounds as reduction sensitizers have not been found.

Further improvements are disclosed in Japanese Patent Application Laid-Open No. 179835/1983.

However, in order to put reduction sensitization into practical use, it is necessary to overcome the problem of the shelf life of light-sensitive materials. Regarding the technology for improving the storage stability of reduction-sensitized emulsions, Japanese Patent Application Laid-Open No. 57-8283
No. 1 and No. 60-178445, but it has not reached a sufficient level of improvement. Despite many studies as described above, the increase in sensitivity has not been sufficient compared to hydrogen sensitization in which photosensitive materials are treated with hydrogen gas under vacuum. This is reported in the Journal of Imagin
G 5science, Vol. 29, p. 233 (1985), Molsar et al.

At the same time, improvements in the storage stability of photographic materials containing reduction-sensitized emulsions have been awaited.

(Problems to be Solved by the Invention) An object of the present invention is to provide a color photographic material that has high sensitivity, low fog (and improved graininess).

(Means for solving problems) The object of the present invention was achieved by the following configuration.

fl) In a silver halide color photographic light-sensitive material having at least one blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layer, at least one emulsion in the emulsion layer has the general formula [1), [II ] or [I[[] is reduction sensitized with at least one ascorbic acid or its derivative in the presence of at least one compound represented by [], and contains an oxidized color developing agent in the emulsion layer. A silver halide color photographic light-sensitive material containing a compound capable of releasing a development accelerator or a fogging agent upon reaction.

(1) R-8o, S-M [II] R-So, S-R [1) 1) R-8O2S-Lm-8SO, -R"In the formula, R, R'SR" may be the same or different. may represent an aliphatic group, an aromatic group, or a heterocyclic group, and M represents a cation. L represents a divalent linking group, and m is 0 or 1.

The compound of general formula [l] or II[) may be a polymer containing a divalent group derived from the structure represented by [I] or I[[) as a repeating unit.

(2) In a silver halide color photographic light-sensitive material having at least one blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layer, at least one emulsion in the emulsion layer is a compound according to claim (1). reduction sensitized with at least one kind of ascorbic acid or its derivative in the presence of at least one compound represented by the general formula [ID, [■]] or CI [[], and halogen in the emulsion layer. A silver halide color photographic material characterized in that the average grain size of silver halide grains is 1.0 micron or more.

(3) It has blue-sensitive, green-sensitive, and red-sensitive silver halide emulsion layers, at least one of which is composed of two or more layers with mutually different sensitivities, and these two or more layers are on the side of the support. A color light-sensitive material in which at least one silver halide emulsion layer having different color sensitivity is arranged in order from a low-sensitivity layer to a high-sensitivity layer when viewed from above, and between the low-sensitivity layer and the high-sensitivity layer. At least one emulsion in the emulsion layer is defined in claim (1).
A halogenated compound characterized by reduction sensitization with ascorbic acid or at least one derivative thereof in the presence of at least one compound represented by the general formula (1), (ID or [■]) Silver color photographic material.

The present invention will be explained in detail below.

The manufacturing process of silver halide emulsions is broadly divided into steps such as grain formation, desalting, chemical sensitization, and coating. Particle formation is nucleation
It is divided into maturity, growth, etc. These steps are not performed uniformly; the order of the steps may be reversed, or the steps may be repeated. The term "reduction sensitization" being carried out during the production process of the silver halide emulsion basically means that it can be carried out at any step. Reduction sensitization can be carried out during nucleation, which is the initial stage of grain formation, during physical ripening, or during growth (and may be carried out prior to sensitization by gold sensitization, sulfur or selenium sensitization, or a combination of these). It may be carried out after sensitization. When chemical sensitization is carried out in combination with gold sensitization, it is preferable to carry out reduction sensitization before chemical sensitization to avoid undesirable fogging. Most preferably, reduction sensitization is carried out before chemical sensitization. This is a method in which reduction sensitization is performed during the growth of silver halide grains. Here, growing means that the silver halide grains are growing due to physical ripening or addition of a water-soluble silver salt and a water-soluble alkali halide. This means that the method of performing reduction sensitization also includes the method of performing reduction sensitization while temporarily stopping growth during growth, and then further growing.

Specific examples of ascorbic acid and its derivatives (hereinafter referred to as "ascorbic acid compounds") include the following.

(A-1) L-ascorbic acid (A-2) Sodium L-ascorbate (A-3
) Potassium L-ascorbate (A-4) DL
-Ascorbic acid (A-5) D-Sodium ascorbate (A-6
) L-ascorbic acid-6-acetate (A-7) L-ascorbic acid-6-palmitate (A-8) L-ascorbic acid-6-benzoate (A-9) L-ascorbic acid-6-diacetate ( A-10) L-Ascorbic acid-5,6-0-isopropylidene In order to add the above-mentioned ascorbic acid compounds in the production process of the silver halide emulsion of the present invention, they may be directly dispersed in the emulsion. Alternatively, it may be added during the manufacturing process after being dissolved in a solvent such as water, methanol, or ethanol alone or in a mixed solvent.

It is desirable to use the ascorbic acid compound used in the present invention in a larger amount than the amount in which conventional reduction sensitizers are preferably used. For example, Japanese Patent Publication No. 57-33572 states that ``The amount of reducing agent is usually 0.75Xl per g of silver ions.''
O-" milliequivalent (8XlO-1 mol/Ag
molar) is often effective. ” (converted value is by the inventors). US-2,487,8
50, ``The amount of silver compound that can be used as a reduction sensitizer is 1X10-'' to 44X10-'mol.''
It states: Furthermore, in JP-A-57-179835, the amount of thiourea dioxide added is approximately 0.00000000000000 per mole silver halide. O1■ to about 2■, about 0.0 as stannous chloride. O1■～
It is stated that it is appropriate to use approximately 3 ■. The preferred amount of the ascorbic acid compound used in the present invention is determined by the emulsion grain size, halogen composition, emulsion preparation temperature, p.
Although it depends on factors such as H and pAg, it is desirable to have 5X10-'mol-1X10-' per mole of silver halide. More preferably, it is selected from the range of 5XlO-' mol - lXl0-'' mol. Particularly preferably selected from the range of lXlO-'' mol - lXl0-2 mol.

Although the ascorbic acid compound of the present invention may be added at any stage of the emulsion manufacturing process, it is particularly preferred to add it during grain growth. It may be added to the reaction vessel in advance, but it is preferable to add it at an appropriate time during particle formation. Alternatively, a reduction sensitizer may be added in advance to an aqueous solution of a water-soluble silver salt or a water-soluble alkali halide, and these aqueous solutions may be used to form particles. It is also a preferable method to add the solution of the reduction sensitizer in several portions or continuously over a long period of time as the particles are formed.

Although the reduction sensitization method using the ascorbic acid compound of the present invention is superior to conventional reduction sensitization methods in terms of sensitivity, fog, and stability over time, other reduction sensitization methods In some cases, it is more preferable to combine with However, it can only be used in combination as an auxiliary means for reduction sensitization, and it is better to use the ascorbic acid compound as the main means for reduction sensitization. The combination methods include a method of adding a known reducing agent to a silver halide emulsion, a method of growing or ripening in an atmosphere with a low pAg of pAg 1 to 7, which is called silver ripening, and a method of growing or ripening it in an atmosphere with a low pAg of pAg 1 to 7, which is called high pH ripening. You can choose either growing or aging in an atmosphere of

The method of adding a reduction sensitizer is a preferred method since the level of reduction sensitization can be finely adjusted.

Although stannous salts, amines and polyamines, hydrazine derivatives, formamidine sulfinic acid, silane compounds, and borane compounds are known as reduction sensitizers, ascorbic acid compounds are superior to these known reduction sensitizers. Give results.

The reduction sensitization of the present invention is carried out in the production process of silver halide emulsions by reduction with an ascorbic acid compound in the presence of at least one compound selected from the compounds represented by the general formulas (I), [II] and t. Characterized by sensitization.

[1] R-3O2S-M (n) R-So2S-R (III) R-3o2S-Lm-3SO2-R' In the formula, R, R', and R2 may be the same or different, and are an aliphatic group, It represents an aromatic group or a heterocyclic group, and M represents a cation. L represents a divalent linking group, and m is O or l.

To explain the compounds of general formulas [I], [II] and CI) in more detail, when R, R' and R2 are aliphatic groups,
Preferred are alkyl groups having 1 to 22 carbon atoms, alkenyl groups and alkynyl groups having 2 to 22 carbon atoms, and these may have a substituent. Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, 2-ethylhexyl, decyl,
Examples include dodecyl, hexadecyl, octadecyl, cyclohexyl, isopropyl, and t-butyl.

Examples of the alkenyl group include allyl and butenyl.

Examples of the alkynyl group include propargyl and butynyl.

The aromatic groups for R, R' and R2 preferably have 6 to 20 carbon atoms, such as phenyl and naphthyl. These may be substituted.

The heterocyclic group of R, R' and R2 includes nitrogen, oxygen,
A 3- to 15-membered ring containing at least one element selected from sulfur, selenium, and tellurium, such as pyrrolidine, piperidine, pyridine, tetrahydrofuran, thiophene, oxazole, thiazole, imidazole, benzothiazole, benzoxazole, benzimidazole, and selenazole. , benzoselenazole, tetrazole, triazole, benzotriazole, tetrazole,
Examples include oxadiazole and thiadeazole.

Examples of substituents for R, R' and R2 include alkyl groups (e.g. methyl, ethyl, hexyl), alkyne groups (
For example, methoxy, ethoxy, octyl), aryl groups (
For example, phenyl, naphthyl, tolyl), hydroxy group,
Halogen atoms (e.g. fluorine, chlorine, bromine, iodine), aryloxy groups (e.g. phenoxy), alkylthio groups (
methylthio, butylthio), arylthio groups (e.g. phenylthio), acyl groups (e.g. acetyl, propionyl, butyryl, valeryl), sulfonyl groups (e.g. methylsulfonyl, phenylsulfonyl), acylamino groups (e.g. acetylamino, benzamino), sulfonylamino groups (methanesulfonylamino, benzsulfonylamino), acyloxy group (eg, acetoxy, benzoxy), carboxyl group, cyano group, sulfo group, amino group, and the like.

L is preferably a divalent aliphatic group or a divalent aromatic group. Examples of the divalent aliphatic group of L include (CHt
). (n=1-12), -CH2-CH=CH-CH2 -CH! c=ccHt can be given. Examples of the divalent aromatic group for L include phenylene and naphthylene.

These substituents may be further substituted with the substituents described above.

M is preferably a metal ion or an organic cation. Examples of metal ions include lithium ions, sodium ions, and potassium ions. Organic cations include ammonium ions (e.g. ammonium, tetramethylammonium, tetrabutylammonium)
, phosphonium ion (tetraphenylphosphonium)
, guanidine group, etc.

Specific examples of the compounds represented by the general formula [I], [II] or [III) are listed in Table A, but the invention is not limited thereto.

The compound of general formula (I) can be easily synthesized by the method described in JP-A-54-1019 and British Patent No. 972,21).

The compound represented by general formula (1), CIII or (I[[) is 1O-7 to 1O-1 per mole of silver halide.
Preferably, it is added in moles. Further, the addition amount is preferably from 10-6 to 10-2, particularly from 10-' to 10-3 mol, 1 mol Ag.

The compounds represented by the general formulas [I] to (II[) can be added during the manufacturing process by a method commonly used when adding additives to photographic emulsions.

For example, for water-soluble compounds, make an aqueous solution of an appropriate concentration,
Compounds that are insoluble or sparingly soluble in water are dissolved in a suitable organic solvent that is miscible with water, such as alcohols, glycols, ketones, esters, amides, etc., and does not adversely affect photographic properties. However, it can be added as a solution.

The compound represented by formula (1), (III) or (III) may be added at any stage during grain formation of the silver halide emulsion, before or after chemical sensitization.Preferably, reduction is A method in which compounds are added before or during sensitization and these compounds coexist during reduction sensitization is particularly preferred. It is a way of feeling.

It may be added to the reaction vessel in advance, but it is preferable to add it at an appropriate time during particle formation. Alternatively, the compounds (1) to (III) may be added in advance to an aqueous solution of a water-soluble silver salt or a water-soluble alkali halide, and these aqueous solutions may be used to form particles. It is also a preferable method to add the solutions of compounds (1) to (I[1) in several portions or continuously for a long period of time as the particles are formed.

The most preferred general formula of compounds for the present invention are those of the general formula CI).

In silver halide emulsions prepared using conventional methods, the grain size is increased to obtain high sensitivity (even if the grain size is increased to 1.0 microns or more, the increase in fog cannot be ignored, and sufficient sensitivity and
No graininess was obtained.

On the other hand, the reduction sensitization of the present invention combines the effective use of latent images and the fog suppressing effect, making it possible to use large-sized silver halide grains of 1.0 microns or more at a low fog level, compared to conventional methods. Compared to the emulsion prepared by the above preparation method, we were able to create a color photographic material with lower fog and superior graininess at the same sensitivity, and with higher sensitivity at the same size.

Further, the above effects become more noticeable when the average size of the emulsion grains is 1.4 microns or more, which is more preferable as an embodiment.

The average particle size in the present invention is expressed as a volume-weighted equivalent sphere diameter, and ranges from 1.0 microns to 5.0 microns.
A range of 0 microns is preferred. More preferably, 1.
It ranges from 4 microns to 3.0 microns.

(I-1) (I-2) (1-3) (I-4) (1-5) (I-6) (1-7) CH3(CHri3 CH,SO,5Na C,H,SO25Na C, H, SO, 5K C4He SO2SL i Cs H+550g 5Na C* H+ t SO! S N aCHCH*
SO25-NH4 C*Hs (I-8) (1-9) C1°H2 Sow, H,, SO.

Na Na (1-10) (I-1)) s H3s S O2 Na (I 12) t C4Hs Sow
5Na(1-13) CH=OCH,CH,SO
,S'Na(I-15)CH,=CHCHzSOzS
Na (I-17) (f-18) (I-19) (I-25) (1-26) (I-27) CI-28) (1-20) (I-21) (D-22) (I-23) (r-24) (I-29) KSSCh (CHz)zsOzsK (I-30) Na S S 0X (CHz)4s ChS Na
(I-31) Na 5SOt (CHz) 4S (CHz), SO, S
Na(I-32) (I-33) (It -1) czHssozs-cHa (TL-2> C* H+ t S Ot S CH* CHxl-3
) (TI -4) (II -5') (, H5SO!5CHICHICN (I[-6> Ca H9SO* S CHCH! CN(II-1
2) (u-13) (TL-14) (1-15) (1-8) (u-9) (IL-10) (II-1)) (1)-16) (It-17) (It-18) C! H1S OtS CHICHtCHxCHzOH(
If--19) (n-20) (u-21) CH3S S 0x(CHl)4S OzS CHs(
In-1) (n-22) CH,SSO□(CHz)zs O! S CHz(II
-23) (ILL -2) CJsSOzSCHzCHzS(hcHtcHzssO
□C! H3(III-3) (u-24) (m-4) x:y-2/1 (molar ratio) CHzCHzOH (IL-25) (m-5) (m-6) (Tll-7) (I -8) C, HsS OzS SS 0zCzHs(n)
Cs H? SO! S S S Oz C3Ht
(n) In the present invention, a compound (hereinafter referred to as rFAFA compound) capable of releasing a development accelerator, a fogging agent, or a precursor thereof (hereinafter referred to as rFAFA compound) in accordance with the amount of developed silver during development.
Hereinafter referred to as "rFR compound". ) may be added to any of the photographic layers.

Further, it is preferable to use the present invention in combination with a reduction-sensitized silver halide emulsion having an average grain size of 1.0 microns or more.

FR compounds useful in the present invention include the following.

(i) Coupling with the oxidation product of an aromatic primary amine developing agent to release the FA compound; (ii) Coupling with the oxidation product of the aromatic primary amine developing agent to release a diffusible FA compound. a coupler (i) which undergoes a redox reaction with an oxidation product of a developing agent to form a colored or colorless dye, such that the diffusible dye acts as an FA compound;
A redox compound that releases an FA compound through a decomposition reaction that occurs following an oxidation reaction.

The above compounds (i), (ii) and (ii) are represented by the following general formulas [1], [2] and [3], respectively.

(1) Cp-FB (2) FB-Cp-BALL [3] RED-FB In the above formula, the FB group is -(TIME) knee (L),
- represents FA. Here, the FA group represents a group having the ability to couple silver halide or a group having the ability to promote development, L represents a divalent linking group, and TIME represents a timing group. It is particularly preferred if the FA group has a group capable of adsorbing silver halide. m and n each represent 0 or l. In addition, Cp is an aromatic primary
BALL represents a diffusion-resistant group,
RED represents a compound residue that is cross-oxidized with an oxidized product of an aromatic primary amine developing agent.

Each of the general formulas [1], [2] and [3] will be explained below.

In the general formula [1], 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, typical examples of yellow couplers among couplers are U.S. 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 general formulas (Cp-1) and (Cp-I[) are preferred.

General formula [Cp-1) R9 t * General formula (Cp-II) I? * Note that * represents the bonding position of the FB group (hereinafter general formula [
Same as Cp-■].

Here, R5 represents the diffusion resistance of a total carbon number of 8 to 32,
R2 represents a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkoxy group having a total of 1 to 9 atoms, or a diffusion-resistant group having a total of 8 to 32 carbon atoms. When R7 is 2 to 9, 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, 31), No. 082, No. 3,152, 8
No. 96, No. 3,519,429, No. 3,062,65
No. 3, same 2. 908. It is described in No. 573, etc. Among these magenta couplers, pyrazolones or pyrazoloazoles (pyrazolopyrazole, pyrazoloimidazole, pyrazolotriazole, pyrazolonetetrazole, etc.) are preferred.

Therefore, the magenta coupler residue (Cp) is
Those represented by the following general formulas (Cp-n[), (Cp-I'V) and (Cp-V) are preferred.

General formula (Cp-II[) R1 General formula (Cp-IV) General formula (Cp-V) , , , , 2-・ Here, R5 represents a diffusion-resistant group having a total number of carbon atoms of 8 to 32. In the formula, R1 represents a halogen atom, a lower alkyl group, a lower alkoxy group, a phenyl group, or a substituted phenyl group. Z represents a group of nonmetallic 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 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. 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, etc. Among these cyan couplers, phenols or naphthols are preferred.

Therefore, as the cyan coupler residue (Cp), those represented by the following general formulas CCp-VI) and [Cp-■] are suitable.

General formula (Cp-VI) * General formula (Cp-■) * In the formula, R5 represents an alkyl group, an aryl group, a heterocyclic group, or an amino group, and these groups may be further substituted. Substitution Representative examples of the amino group include an arylamino group and a nitrogen-containing heterocyclic group.

R6 represents a halogen atom, an alkyl group, an alkoxy group, an acylamino group, or an alkoxycarbonyl group, and these groups may be further substituted. When 2 to 3 R6's are present, they may be the same or different, or two R6's may be linked to each other to form a 5- to 6-membered saturated or unsaturated carbocycle or heterocycle. These rings may be further substituted. Examples of the heteroatoms forming the heterocycle include nitrogen, oxygen, and sulfur. Specific examples of the ring fused with the above-mentioned heterocycles include 3,4-dihydrocarbostyryl.

R1 represents an alkyl group or an aryl group, and these groups may be further substituted.

R1 has the same meaning as R6, and two R, are connected to each other to form 5
- When forming a 6-membered saturated or unsaturated carbon ring or heterocycle, the groups listed for R6 above can be used as the groups that can be further substituted on these rings, and furthermore, sulfonamide groups and the like can be used.

In order to impart diffusion resistance to FR compounds having coupler residues represented by general formulas (Cp-VI) and (Cp-■),
The total number of carbon atoms in R6 and R8 or R7 and R8 is 8 to 80
It is preferable that

The FA group is the most basic functional group that expresses the functions of FR compounds. This group includes reducing compounds (hydrazine, hydrazide, hydrazone, hydroquinone, catechol, p-aminophenol, p-phenylenediamine, ■-phenyl-3-pyrazolone, enamine, aldehyde, polyamine, acetylene, aminoborane, tetrazolium salt, Quaternary salts such as ethylene bispyridinium salts, carbazic acid, etc.), or compounds that form silver sulfide during development (thiourea, thioamide, dithiocarbamate, rhodanine, thiohydantoy, etc.) The tautomeric structure of -C=N- allows the sulfur atom to form a TI
May bind to ME, Cp or RED.

Preferred as the FA group are hydrazide, hydrazine or hydrazone among the above, among which the following general formula [
A hydrazide represented by Cp-■] is most preferred.

General formula [Cp-■] * In the general formula (Cp-■), * represents the bonding position with the above (L), and R9 is an acyl group having 1 to 10 carbon atoms (e.g. formyl, acetyl, propanoyl, benzoyl, trifluoroacetyl, octanoyl), alkoxycarbonyl groups having 2 to 10 carbon atoms (e.g. methoxycarbonyl, butoxycarbonyl), 1 carbon atom
~1O represents an alkyl or arylsulfonyl group (e.g. methylsulfonyl, benzylsulfonyl, phenylsulfonyl) or an alkoxysulfonyl group having 1 to 10 carbon atoms (e.g. methoxysulfonyl, ethoxysulfonyl), and R1° is a halogen atom (fluorine atom,
chlorine atom, bromine atom, iodine atom), number of carbon atoms 1-10
an alkyl group (e.g. methyl, ethyl, t-butyl, trifluoromethyl) or an alkoxy group having 1 to 10 carbon atoms (e.g. methoxy, ethoxy, benzyloxy,
methoxyethoxy), and l represents an integer of 0 to 4. However, when l is plural, the plural RIMs may be the same or different. In the general formula (Cp-■), R1 is preferably an acyl group (particularly a formyl group or an acetyl group), and l is preferably 0.

TIME represents a timing group, which includes those using intramolecular substitution reactions as described in US Pat. No., Japanese Patent Publication No. 57-154234
No., JP-A-57-188035, JP-A-54-987
Examples include those that utilize electron transfer via a conjugated system within a molecule, as described in No. 28.

The divalent linking group represented by is an alkylene group,
alkenylene group, phenylene group, naphthylene group, -o-
-s--5o--so.

A group selected from the group consisting of -N=N-, carbonamide group, thioamide group, sulfonamide group, ureido group, thioureido group, heterocyclic group, etc. is used.

F consisting of the above FA group, TIME, and/or
It is particularly preferred when the B group has a group capable of adsorbing silver halide (this adsorbable group may be present on any part of FA, TIME, or L). Groups that can be adsorbed to silver halide include nitrogen-containing heterocyclic groups having a dissociable hydrogen atom, heterocyclic groups having at least one nitrogen atom and another heteroatom in the ring, and mercapto groups. Examples include heterocyclic groups with , quaternary salts, thiols, and groups with .

In general formula [2], the FB group is bonded to the non-coupling position of the coupler. The BALL 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, Cp and FB have the same meaning as described in the general formula (1) above.

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 multiple leaving groups are linked, or an alkyl group that imparts non-diffusivity. It may have a group and/or an aryl group. In the latter case, the total number of carbon atoms in the alkyl group and/or aryl group is preferably about 8 to 32. BALL has a group for bonding to the coupling position of Cp, and one representative example thereof is -0--3--N=N--0-C-.

In general formula [3], RED is a skeleton of hydroquinone, catechol, 0-aminophenol, or p-aminophenol (including cases in which all of the above are fused rings)
represents a group that has the following formula and cross-oxidizes with an oxidized product of an aromatic primary amine developing agent, and undergoes alkaline hydrolysis to release an FB group. RED may have a protecting group (for example, an acyl group) that is removed in a developer. FB is a general formula [!
], but if FB is directly connected to the benzene ring of RED, -0-0.

1) 1 -3- -N=N--0-C--0-S1 and RED is bonded to O-aminophenol or p - has an aminophenol skeleton (including the case of fused rings), and when FB is not directly connected to those benzene rings, FB has an amino group and -
1 (i.e., forming a sulfonamide group) through S-.

Next, specific examples of FR compounds represented by general formulas (1), [2], and [3] will be shown, but the invention is not limited thereto.

Examples of compounds represented by general formula [1] (1-1) (1-3) (1-4) Hs Us PII7 l (1 6) (1-9) (1 10) (1-8) (2-1) (2-2) (3-2) (3-3) 0OH NHNHHCCH.

1 (2-5) general formula Examples of compounds represented by (3 1) (3-6) (3-7) (3-8) NHNH3O,C! H.

These compounds of the present invention are based on generally known compounds and are disclosed in JP-A-57-150845 and JP-A-57-1386.
36, U.S. Patent 3. 214. No. 377, 3,25
No. 3,924, JP-A-59-50439, JP-A-60
-37556, JP-A-60-107029, and the like.

Among the FR compounds used in the present invention, a preferable one is a group in FB that adsorbs to silver halide (JP-A-59-1
It has the same meaning as the adsorption group defined in No. 58552).

Two or more FR compounds may be used in combination. The amount of the FR compound added is 0.00% per mole of silver in the same layer or adjacent layer. 2
It is less than or equal to 0.02 mole and more than 10-' mole, preferably less than 0.02 mole and more than 10-' mole.

When the FR compound according to the present invention is used in an emulsion layer consisting of silver halide grains prepared by a conventional preparation method, although an increase in sensitivity can be obtained, the increase in fog is significant and the graininess is severely deteriorated, which is difficult to use in practice. The contribution to sensitivity improvement was not sufficient. On the other hand, when the FR compound according to the present invention was used in the emulsion layer containing the reduction-sensitized emulsion according to the present invention, the increase in fog was unexpectedly small and the sensitivity could be improved.

There are no particular restrictions on where the silver halide grains of the present invention can be used, but they are preferably used in silver halide emulsion layers with high sensitivity. Particularly preferred is use in the layer with the highest sensitivity among blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layers. When each color-sensitive silver halide emulsion layer has an emulsion layer having an intermediate sensitivity, it is also preferable to use the emulsion layer for the intermediate sensitivity layer. Although there is no particular restriction on the location where the FR compound of the present invention is used, it is preferable to use a silver halide emulsion layer with high sensitivity. It is particularly preferable to use the silver halide grains of the present invention in a layer using an FR compound. It is also preferable to use the silver halide grains of the present invention in a silver halide emulsion layer adjacent to a layer using an FR compound.

By using the reduction-sensitized emulsion according to the present invention in an emulsion layer having the following layer arrangement, a color photographic material with high sensitivity and excellent graininess can be obtained.

That is, the red-sensitive emulsion layer, the green-sensitive emulsion layer, and the blue-sensitive emulsion layer are each composed of two or more emulsion layers having different sensitivities, and the red-sensitive emulsion layer has the highest sensitivity, the green-sensitive emulsion layer has the highest sensitivity,
At least one emulsion layer having color sensitivity different from that of the highest sensitivity layer closest to the support is located between the blue-sensitive emulsion layer having the highest sensitivity and the layer closest to the support.

The reduction-sensitized emulsion according to the present invention is contained in at least one of the emulsion layers having the above structure. Preferably, at least each
Contained in the most sensitive emulsion layer.

Furthermore, it is preferable to contain a small amount of the above-mentioned FR compound together with the reduction-sensitized emulsion according to the present invention in each emulsion layer having the highest sensitivity, in order to obtain an ultra-high-sensitivity light-sensitive material with high image quality.

Furthermore, it is also preferable to combine it with a silver halide emulsion having an average grain size of 1.0 microns or more.

Further, in order to further improve graininess, it is more preferable that each color-sensitive layer be composed of three layers. This technique is described in Japanese Patent Publication No. 49-15.495.

A non-light sensitive layer may be present between each light sensitive emulsion layer. This non-light sensitive layer may be present between two or more emulsion layers having the same color sensitivity. Furthermore, when photosensitive emulsion layers having different color sensitivities are adjacent to each other, it is preferable to provide a non-photosensitive layer between them. A scavenger substance may also be contained in such a non-photosensitive intermediate layer. Also, JP-A-59-
It is also preferred to provide a non-light-sensitive reflective layer under the light-sensitive emulsion layer to improve sensitivity, as described in No. 160.135. Further, the color negative light-sensitive material of the present invention usually contains a yellow filter layer, although it is not necessarily necessary.

Specific examples of the arrangement order of the light-sensitive emulsion layers in the color negative light-sensitive material of the present invention are listed below, but the order is not limited thereto. Although the non-photosensitive layer is omitted here, it may be present at the position described above.

(1) Support, low sensitivity red sensitive emulsion layer (hereinafter referred to as RL), low sensitivity green sensitive emulsion layer (hereinafter referred to as GL), low sensitivity blue sensitive emulsion layer (hereinafter referred to as BL), high sensitivity red sensitive emulsion layer (RH) high sensitivity Green-sensitive emulsion layer (GH), high-sensitivity blue-sensitive emulsion layer (BH).

(2) Support, RL, GLXBL, GH, RH, BH
(3) Support, RL, GL, BL, RH, medium-opening green-sensitive emulsion layer (GM), GH, BH (4) Support, RL
, GL, GM, BL, RH.

GH, BH (5) Support, RL, medium-opening red-sensitive emulsion layer (hereinafter referred to as RM)
, GL, GM, BL, medium-opening blue-sensitive emulsion layer (hereinafter referred to as BM
), RH, GH, BH (6) Support, RL, GL, BL, RM,, RH.

GM, GH, BM, BH (7) Support, RL, GL, RH, GH, BL, Bl (
(8) Support, GL, RL, RH, GH, BL, BH (
9) Supports, RL, GL, RH, GM, GH.

BL, BH (10) Support, RL, GL, GH, RH, BL, BH The light-sensitive material of the present invention has halogens in the blue-sensitive layer, green-sensitive layer, and red-sensitive layer on the support. It is sufficient that at least one silver halide emulsion layer is provided, and there are no particular restrictions on the number or layer order of the silver halide emulsion layer and the non-photosensitive layer. A silver halide photographic light-sensitive material having at least one light-sensitive layer consisting of a plurality of silver halide emulsion layers having the same color sensitivity but different light sensitivities, and the light-sensitive layer has blue light, green light, It is a unit photosensitive layer that is sensitive to either light or red light, and in a multilayer silver halide color negative photosensitive material, the unit photosensitive layers are arranged in -g in order from the support side to the red sensitive layer. layer, a green-sensitive layer, and a blue-sensitive layer are installed in this order. However, depending on the purpose, the order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers.

Non-photosensitive layers such as various intermediate layers may be provided between the above-mentioned silver halide photosensitive layers and between the uppermost layer and the lowermost layer.

The intermediate layer includes JP-A Nos. 61-43748 and 59-1.
) No. 3438, No. 59-1) No. 3440, No. 61-20
Coupler, DIR compound, etc. as described in No. 037 and No. 61-20038 may be included,
It may also contain a commonly used color mixing inhibitor.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are composed of a high-speed emulsion layer and a low-speed emulsion layer, as described in West German Patent No. 1,121,470 or British Patent No. 923,045. Two-layer structure can be preferably used 8
Usually, it is preferable to arrange the layers so that the photosensitivity decreases toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer.
1) No. 2751, No. 62-200350, No. 62-2
As described in No. 0654.1, No. 62-206543, etc., a low-sensitivity emulsion layer may be provided on the side far from the support, and a high-sensitivity emulsion layer may be provided on the side close to the support.

As a specific example, from the side farthest from the support: low sensitivity blue sensitive layer (BL) / high sensitivity blue sensitive IJ (BH) / high sensitivity green sensitive layer (GH) / low sensitivity green sensitive layer (GL) /
High-sensitivity red-sensitive layer (RH) / low-sensitivity red-sensitive layer (RL)
) or BH/BL/GL/G)I/RH/RL
or in the order of BH/BL/GH/GL/RL/RH.

Further, as described in Japanese Patent Publication No. 55-34932, from the side farthest from the support, the blue-sensitive layer/GH/R
They can also be arranged in the order of H/GL/RL. Alternatively, as described in JP-A-56-25738 and JP-A-62-63936, the blue-sensitive layer/GL/RL/GH/RH can be arranged in this order from the farthest side from the support. .

In addition, as described in Japanese Patent Publication No. 49-15495, the upper layer is a silver halide emulsion layer with the highest sensitivity, the middle layer is a silver halide emulsion layer with lower sensitivity, and the lower layer is more sensitive than the middle layer. An example is an arrangement consisting of three layers with different photosensitivity, in which a silver halide emulsion layer with a low density is disposed and the photosensitivity gradually decreases toward the support. Even when it is composed of three layers with different photosensitivity, as described in JP-A No. 59-202464,
In the same color-sensitive layer, medium-sensitivity emulsion layer/high-sensitivity emulsion layer/low-sensitivity emulsion layer may be arranged in this order from the side remote from the support.

In addition, high-sensitivity emulsion layer / low-temperature emulsion layer / medium-sensitivity emulsion layer,
Alternatively, they may be arranged in the order of low-speed emulsion layer/medium-speed emulsion layer/high-speed emulsion layer, etc.

Furthermore, even in the case of four or more layers, the arrangement may be changed as described above.

To improve color reproduction, U.S. Patent No. 4,663゜2
No. 71, No. 4.705.744, No. 4,707.
No. 436, JP-A-62-160448, JP-A No. 63-89
The multilayer effect donor layer (C
L) is preferably arranged adjacent to or close to the main photosensitive layer.

As mentioned above, various layer structures and arrangements can be selected depending on the purpose of each photosensitive material.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide, containing about 30 mol% or less of silver iodide. . Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mole percent to about 25 mole percent silver iodide.

Silver halide grains in photographic emulsions include those with regular crystals such as cubes, octahedrons, and tetradecahedrons, those with irregular crystal shapes such as spherical and plate shapes, and those with twin planes. may have crystal defects, or a composite form thereof.

The grain size of the silver halide may be fine grains of about 0.2 microns or less, or large grains with a projected area diameter of up to about 10 microns, and may be a polydisperse emulsion or a monodisperse emulsion.

Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure (RD) N1) 17643
(December 1978), pp. 22-23, "■, Emulsion preparation and
d types)'', and same number 18716 (197
January 9th), 64B pages, Graphic "Physics and Chemistry of Photography", Published by Paul Montell (P, GIafkid
es, Ches+ie et Phtsiqu
e Photograph-ique+ Paul
Montel+ 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G, F, Duffin
+Photographic Emulsion
Chemistry (Focal Press.

1966)), "Manufacture and coating of photographic emulsions" by Zelikman et al., published by Focal Press (V, L, Zelikm)
anet al, + Making and Coat
ing Photographic Emulsion
, Focal Press+ 1964).

U.S. Patent No. 3,574.628, U.S. Patent No. 3,655,39
Monodisperse emulsions such as those described in No. 4 and British Patent No. 1.413.748 are also preferred.

Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described by Gutoff, Photographic Science and Engineering.
ence and Engineering), Vol. 14, pp. 248-257 (1970); U.S. Patent No. 4
, 434,226, 4,414.310, 4,
433,048, 4,439.520, and British Patent No. 2.1) 2.157.

The crystal structure may be --like, the inside and outside may have different halogen compositions, it may be a layered structure, or silver halides of different compositions may be joined by epitaxial mounting. Also, for example, a
The particles may be bonded with a compound other than silver halide, such as silver dune or lead oxide, or a mixture of particles of various crystal forms may be used.

The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization. Additives used in such processes are subject to Research Disclosure Nα1
7643 and Ncc 18716, and the relevant parts are summarized in the table below.

In the present invention, it is preferable to use a non-light-sensitive fine-grain silver halide.
It is preferable that these are fine silver halide grains that are not substantially developed in the development process, and that no roughening coupler is present.

The fine-grain silver halide has a silver bromide content of 0 to 100 mol%, and may contain silver chloride and/or silver iodide as necessary, preferably silver iodide in a content of 0.5 to 100 mol%. It contains 10 mol%.

The fine grain silver halide has an average grain size (average diameter equivalent to a circle of projected area) of 0. O1 to 0.5 μm is preferable, and 0.
02 to 0.2 μm is more preferable.

Fine-grain silver halide can be prepared in the same manner as ordinary photosensitive silver halide. In this case, the surface of the silver halide grains does not need to be optically sensitized, nor is spectral sensitization necessary. However, prior to adding this to the coating solution, it is preferable to add in advance a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or mercapto-based compound, or a zinc compound.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant descriptions are shown in the table below.

Pot plate plate I plate ■[Dokugetsu L7m 1 Chemical sensitizer page 23 Page 648 right column 2 Sensitivity enhancer Same as above 3 Spectral sensitizer,
Pages 23-24 Page 648 Right column ~ Super sensitizer
Page 649 right column 4 Brightener Page 24 5 Antifoggant Page 24-25 Page 649 right column ~ and stabilizer 6 Light absorber, page 25-26 Page 649 right column ~ Filter dye, page 650 left column Ultraviolet absorber 7 Anti-stain agent Page 25 right column i Page 650 left to right column 8 Dye image stabilizer Page 25 9 Hardener page 26 ・Page 651 left column 10
Binder Page 26 Same as above 1) Plasticizer, lubricant Page 27 Page 650 Right column 12 Coating aid, Pages 26-27 Page 650 Right column Surface active agent 13 Static Page 27 Same as above Patch Also, photographic performance with formaldehyde gas In order to prevent the deterioration of
．． It is preferred that a compound capable of reacting with and immobilizing formaldehyde as described in No. 435.503 is added to the photonic material.

Various color couplers can be used in the present invention, specific examples of which can be found in the above-mentioned Research Disclosure (
RD) NIL 17643, described in the patent described in ■-C-C.

As a yellow coupler, for example, U.S. Patent No. 3.93
3.501, same No. 4,022,620, same No. 4,3
No. 26,024, No. 4,401,752, No. 4.
248,961, Japanese Patent Publication No. 5B-10739, British Patent No. 1,425,020, British Patent No. 1,476.760, U.S. Patent No. 3,973.968, British Patent No. 4.314,
023, 4,51), 649, European Patent No. 24
9.473A, etc. are preferred.

As the magenta coupler, 5-pyrazolone and pyrazoloazole compounds are preferred, and U.S. Pat.
No. 0,619, No. 4.351,897, European Patent No. 73,636, US Patent No. 3.061.432, US Patent No. 3.725.067, Research Disclosure No. 124220 (June 1984) ), Japanese Patent Application Publication No. 1986
-33552, Research Disclosure Nil
24230 (June 1984), JP-A-60-43
No. 659, No. 61-72238, No. 60-35730
No. 55-1) 8034, No. 60-185951, U.S. Pat.
No. 654, No. 4.556,630, International Publication-08
Particularly preferred are those described in No. 8104795 and the like.

Cyan couplers include phenolic and naphthol couplers, and are disclosed in U.S. Patent No. 4.052.212.
No. 4.146.396, No. 4.228.23
No. 3, No. 4,296.200, No. 2.369.9
No. 29, No. 2.801.171, No. 2.772.
No. 162, No. 2.895.826, No. 3,772
．． No. 002, No. 3.758.308, No. 4,33
No. 4.01), No. 4,327.173, West German Patent Publication No. 3゜329.729, European Patent No. 121.365
A, No. 249°453A, U.S. Patent No. 3.446
．． No. 622, No. 4.333.999, No. 4,77
No. 5,616, No. 4,451,559, No. 4,4
No. 27.767, No. 4,690,889, No. 4.
Preferred are those described in No. 254.212, No. 4,296.199, and Japanese Patent Application Laid-Open No. 61-42658.

Typical examples of polymerized dye-forming couplers are U.S. Pat.
No. 4.576°910, British Patent No. 2.102.
No. 137, European Patent No. 341°188A, etc.

Couplers whose colored dyes have appropriate diffusivity include U.S. Patent No. 4,366.237 and British Patent No. 2.125.
．． 570, European Patent No. 96,570 and German Patent Publication No. 3.234.533 are preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes are described in Research Disclosure No. 17643.
- Section G, U.S. Patent No. 4.163.670, Special Publication No. 1983
-39413, U.S. Patent No. 4,004,929, U.S. Patent No. 4.138.258, British Patent No. 1.146,36
No. 8 is preferred, and also US Patent No. 4.7
74,181, which corrects unnecessary absorption of coloring dyes by the fluorescent dye released during coupling; and U.S. Patent No. 4,777,120, which can react with a developing agent to form a dye. It is also preferred to use couplers having a dye precursor group as a leaving group.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors include the aforementioned RD 17643.
, Patents described in sections ■ to F, Japanese Patent Application Laid-Open No. 57-15194
No. 4, No. 57-154234, No. 60-184248
Preferred are those described in U.S. Pat. No. 63-37346, U.S. Pat.

As a coupler that releases a nucleating agent or a development accelerator imagewise during development, British Patent No. 2.097.140;
No. 2.131.188, JP 59-157638
No. 59-170840 is preferred.

Other compounds that can be used in the photosensitive material of the present invention include the competitive couplers described in U.S. Pat. , the multi-equivalent coupler described in JP-A-60-185950, etc.
DIR redox compound releasing coupler, DIR coupler releasing coupler, D as described in JP-A-62-24252 etc.
IR coupler releasing redox compound or DIR redox releasing redox compound, European Patent No. 173゜30
R, D, Na 1) 449, a coupler which releases a dye that after separation is described in No. 2A, No. 313,308A.
, No. 24241, JP-A No. 61-201247, etc., bleaching accelerator releasing couplers, U.S. Pat. No. 4,555,4
Gantt release coupler described in No. 77 etc., JP-A-63-
75747, a leuco dye-releasing coupler;
Examples include couplers that emit fluorescent dyes as described in U.S. Pat. No. 4,774,181.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027 and the like.

Specific examples of high-boiling organic solvents with a boiling point of 175°C or higher at normal pressure used in the oil-in-water dispersion method include phthalic acid esters II (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis(2,4-di-t-amyl phenyl) phthalate, bis(2,4-di-t-7 milphenyl) isophthalate, bis(1,1-diethylpropyl) phthalate, etc.), phosphoric acid or Phosphonic acid esters (
triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexyl phenyl phosphate, etc.) , benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p
-hydroxybenzoate, etc.), amides (N, N-
diethyldodecaneamide, N,N-diethyllaurylamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2
．． 4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (bis(2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N, N-dibutyl 2-butoxy-5-tert-octylaniline, etc.), hydrocarbons [(paraffin, dodecylbenzene, diisopropylnaphthalene, etc.), and the like.

Further, as the auxiliary solvent, an organic solvent having a boiling point of about 30°C or higher, preferably 50°C or higher and about 160°C or lower, can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, and cyclohexanone. , 2-ethoxyethyl acetate, dimethylformamide, and the like.

Specific examples of latex dispersion processes, effects, and latex for impregnation include U.S. Pat. It is described in.

The color photosensitive material of the present invention contains phenethyl alcohol and JP-A-63-257747, JP-A-62-272248
1,2-benzisothiazolin-3-one, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5 described in JP-A-1-80941
-dimethylphenol, 2-phenoxyethanol, 2
- It is preferable to add various preservatives or antifungal agents such as (4-thiazolyl)benzimidazole.

The present invention can be applied to various color photosensitive materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color paper, color positive film, and color reversal paper.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, page 28 of N(1) 7643, and Nα187 of the same
16, from the right column on page 647 to the left column on page 648.

In the photosensitive material of the present invention, the total thickness of all hydrophilic colloids on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, even more preferably 18 μm or less, and 16 μm or less. It is particularly preferable that the membrane swelling rate T is 30 seconds or less, more preferably 20 seconds or less.
(day), and the membrane swelling rate T1/l is:
0, which can be measured according to techniques known in the art, e.g.
Photogr, Sc1.Eng.
It can be measured by using a swellometer (swelling membrane) of the type described in Vol. 19, No. 2, pp. 124-129, and T17! The saturated film thickness is 90% of the maximum swelling film thickness reached when treated with a color developer for 13 minutes and 15 seconds at 30°C.
It is defined as the time required to reach the saturated film thickness of 172 mm.

The film swelling rate T178 can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. Further, the swelling rate is preferably 150 to 400%. The swelling rate can be calculated from the maximum swollen film thickness under the above-mentioned conditions according to the formula: (maximum swollen film thickness - film thickness)/film thickness.

The color photographic light-sensitive material according to the present invention is described in the aforementioned RD, Ishi 17643, pages 28-29, and Sou 18716, 6.
51. Development processing can be carried out by the usual methods described in the left column to right column.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but p-phenylenediamine compounds are preferably used, representative examples of which are 3-methyl-4-amino-N, N-diethylaniline, 3-methyl -4-amino-N-ethyl-N-
β-hydroxyethylaniline, 3-methyl-4-aminoethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-β-methoxyethylaniline and their sulfates, hydrochloric acid Examples include salts and p-toluenesulfonates. Among these, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline sulfate is particularly preferred, and two or more of these compounds may be used in combination depending on the purpose.

The color developer may contain p)I buffers such as alkali metal carbonates, borates or phosphates, chloride salts, bromide salts, iodide salts, benzimidazoles, benzothiazoles or mercapto compounds. It generally contains a development inhibitor or an antifoggant. In addition, if necessary, hydroxylamine, diethylhydroxylamine, sulfites, hydrazines such as N,N-biscarboxymethylhydrazine, phenylsemicarbazides,
Various preservatives such as triethanolamine, catechol sulfonic acids, organic solvents such as ethylene glycol, diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, competitive couplers. , auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting agents, various chelating agents such as aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids, such as ethylenediamine. Tetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid,
Cyclohedondiaminetetraacetic acid, hydroxyethyliminodiacetic acid, l-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N,N,N-)rimethylenephosphonic acid, ethylenediamine-N,N,N,N- Typical examples include tetramethylenephosphonic acid, ethylene glycol (0-hydroxyphenylacetic acid), and salts thereof.

Further, when performing reversal processing, black and white development is usually performed and then color development is performed. This black and white developer contains known black and white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol. Alternatively, they can be used in combination.

The pH of these color developing solutions and black and white developing solutions is generally 9 to 12. The amount of replenishment of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 32 or less per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher, 500
It can also be less than i. When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the area of contact with the air in the processing tank.

The contact area between the photographic processing solution and air in the processing tank can be expressed by the aperture ratio defined below.

That is, it is preferably 0.001 to 0.05. As a method for reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the surface of the photographic processing solution in the processing tank, methods using a movable lid described in JP-A No. 1-82033, The slit development processing method described in No. 63-216050 can be mentioned. Reducing the aperture ratio is preferably applied not only to both color development and black and white development steps, but also to all subsequent steps, such as bleaching, bleach-fixing, fixing, washing, and stabilization. Furthermore, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

The time for color development processing is usually set between 2 and 5 minutes, but the processing time can be further shortened by using a high temperature, high p)I, and a high concentration of color developing agent. .

After color development, the photographic emulsion layer is usually bleached.

The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately.In order to further speed up the process, the above aperture ratio is set to 0 after bleaching process and bleach-fixing process.
．． A processing method may be used in which it is preferable that the number is 1 or less.
Furthermore, treatment with two consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment can be carried out as desired depending on the purpose. Examples of bleaching agents that can be used include compounds of polyvalent metals such as iron (1[[), peracids, quinones, and nitro compounds.
Typical bleaching agents include organic complex salts of iron ([[), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid,
Cyclohexanediaminetetraacetic acid, methyliminodiacetic acid,
Aminopolycarboxylic acids such as 1.3-diaminopa pantetraacetic acid and glycol ether diamine tetraacetic acid, or complex salts such as citric acid, tartaric acid, and malic acid can be used. Among these, aminopolycarboxylic acid iron (Ul) complex salts, including ethylenediaminetetraacetate iron (I[[) complex salt and 1,3-diaminopropanetetraacetic acid iron (I[l) complex salt], are suitable for rapid processing and prevention of environmental pollution. Aminopolycarboxylic acid iron [III] complex salts, which are preferred from the viewpoint of the above, are particularly useful in both bleaching solutions and bleach-fixing solutions. The pH of the bleach solution or bleach-fix solution using these aminopolycarboxylic acid iron [III] complex salts is usually 4.0 to 8, but it may be processed at an even lower pH value to speed up the processing. can.

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary.

Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893,858, German Pat.
．． No. 290,812, No. 2,059,988, JP-A No. 53-32736, No. 53-57831, No. 53-
No. 37418, No. 53-72623, No. 53-956
No. 30, No. 53-95631, No. 53-104232
Compounds having a mercapto group or a disulfide group described in JP-A-53-124424, JP-A-53-141623, JP-A-53-28426, Research Disclosure No. k17129 (July 1978), etc.; JP-A-50-140129 Thiazolidine derivatives described in Japanese Patent Publication Nos. 45-8506, 52-20832, 53-32735, and U.S. Pat. No. 3,706,561; West German Patent No. 1.127 ,71
No. 5, iodide salts described in JP-A-58-16,235;
Polyoxyethylene compounds described in West German Patent No. 966.410 and West German Patent No. 2,748,430;
Polyamine compounds described in No. 836; other JP-A-49-
No. 40.943, No. 49-59,644, No. 53-9
No. 4.927, No. 54-35.727, No. 55-26
, No. 506, the compound described in No. 58-163.940;
Bromide ion etc. can be used. Among these, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large promoting effect, and are particularly preferred, such as U.S. Pat.
The compounds described in U.S. Pat. No. 4,552,834 are preferred, and the compounds described in U.S. Pat. These bleach accelerators are particularly effective when bleach-fixing materials.

In addition to the above-mentioned compounds, the bleaching solution and bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach staining. Particularly preferred organic acids have an acid dissociation constant (pKa) of 2.
-5, specifically acetic acid, propionic acid, etc. are preferred.

Examples of fixing agents used in fixing solutions and bleach-fixing solutions include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used. Among them, ammonium thiosulfate is the most widely used. It is also preferable to use a combination of thiosulfate, thiocyanate, thioether compounds, thiourea, etc. As a preservative for fixing solutions and bleach-fixing solutions, sulfites, bisulfites, carbonyl bisulfite adducts, or European patented The sulfinic acid compounds described in No. 294769A are preferred. Furthermore, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution and bleach-fixing solution for the purpose of stabilizing the solution.

The total time for the desilvering process is preferably as short as possible without causing desilvering defects.The preferred time is 1 minute to 3 minutes, more preferably 1 minute to 2 minutes. In addition, the processing temperature is 25°C to 5°C.
0°C1 is preferably 35°C to 45°C. In a preferred temperature range, the desilvering rate is improved and the occurrence of staining after processing is effectively prevented.

In the 1i silver process, it is preferable that stirring be as strong as possible.Specific methods for strengthening stirring include:
A method of impinging a jet of processing liquid on the emulsion surface of a photosensitive material described in JP-A-62-183460, and JP-A-62-18
A method of increasing the stirring effect using the rotating means of No. 3461,
Furthermore, there is a method to improve the stirring effect by moving the photosensitive material while bringing the emulsion surface into contact with a wiper blade provided in the liquid to create turbulence on the emulsion surface, and a method to increase the circulation flow rate of the entire processing liquid. can be mentioned. Such means for improving agitation is effective for all bleaching solutions, bleach-fixing solutions, and fixing solutions. It is believed that the improvement in fl stirring speeds up the supply of bleaching agent and fixing agent into the emulsion film, and as a result increases the desilvering rate. Further, the agitation improving means described above is more effective when a bleach accelerator is used, and can significantly increase the accelerating effect and eliminate the fixing inhibiting effect caused by the bleach accelerator.

The automatic developing machine used for the photosensitive material of the present invention is
No. 0-191257, No. 60-191258, No. 60
It is preferable to have a photosensitive material conveying means as described in Japanese Patent Laid-open No. 191259-1912. This effect is particularly effective in shortening the processing time in each step and reducing the amount of processing solution replenishment.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to water washing and/or stabilization steps after desilvering treatment.

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is
urn-al of the 5ociety of
Motion Picture and Te1e-v
ision Engineers No. 64S, P, 2
48-253 (May 1955 issue),
You can ask for it.

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. In the processing of the color photosensitive material of the present invention, such problems can be solved by:
The method for reducing calcium ions and magnesium ions described in JP-A No. 62-288,838 can be used very effectively. Also, JP-A-57-8,542
Chlorine-based disinfectants such as inchiazolone compounds, cyabendazoles, chlorinated sodium isocyanurate, and other benzotriazoles described in the issue, Hiroshi Horiguchi, "Chemistry of antibacterial and fungicidal agents J (1986), Sankyo Publishing, Hygiene Technical extras: “Sterilization, sterilization, and anti-mildew technology for microorganisms,” (1982)
Industrial Technology Center, Japan Antibacterial and Antifungal Research Institute, “Encyclopedia of Antibacterial and Antifungal Agents” (
It is also possible to use the fungicides described in (1986).

The pi of the washing water in the processing of the photosensitive material of the present invention is 4 to 4.
9, preferably 5-8. The washing water temperature and washing time can also be set variously depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds to 10 minutes at 15 to 45°C, preferably 20 minutes.
A range of 30 seconds to 5 minutes at 5 to 40°C is selected. Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water.

In such stabilization treatment, Japanese Patent Application Laid-Open No. 57-1) 1
No. 543, No. 58-14834, No. 60-22034
All known methods described in No. 5 can be used.

Further, following the water washing treatment, a further stabilization treatment may be performed. An example of this is a stabilization bath containing a dye stabilizer and a surfactant, which is used as a final bath for color photographic materials. Examples of dye stabilizers that can be used include aldehydes such as formalin and glutaraldehyde [
, an N-methylol compound, hexamethylenetetramine, or an aldehyde sulfite adduct.

It is also possible to add various botanical agents and antifungal agents to this stabilizing bath.

The overflow liquid from water washing and/or replenishment of the stabilizing liquid can be reused in other processes such as the desilvering process.

When each of the above-mentioned processing liquids is concentrated by evaporation in processing using an automatic processor or the like, it is preferable to correct the concentration by adding water.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing.In order to incorporate a color developing agent, it is preferable to use various precursors of the color developing agent. For example, U.S. Patent No. 3,342,59
Indoaniline compounds described in No. 7, No. 3,342.
No. 599, Research Disclosure 14,850
Schiff base-type compounds described in No. 15.159 and aldol compounds described in No. 13.924, U.S. Patent No. 3
, 719.492, JP-A-53-1
Examples include urethane compounds described in No. 35628.

The silver halide color light-sensitive material of the present invention may optionally contain various 1=phenyl-3
- Pyrazolidones may be incorporated.

Typical compounds are JP-A-56-64339 and JP-A No. 57-
No. 144547, and No. 58-1) No. 5438.

The various processing solutions used in the present invention are used at lo'c to 50°C, usually at a temperature of 33" to 38°C, but it is possible to use higher temperatures to accelerate the processing and shorten the processing time. Or, conversely, by lowering the temperature, it is possible to improve the image quality and the stability of the processing solution.

Further, the silver halide photosensitive material of the present invention is disclosed in U.S. Patent No. 4,
No. 500.626, JP-A No. 60-133449, No. 5
It can also be applied to heat-developable photothermographic materials described in No. 9-218443, No. 61-238056, European Patent No. 210.66OA2, and the like.

(Examples) The present invention will be explained in more detail below with reference to Examples, but the present invention is not limited thereto.

An emulsion according to the present invention and a conventional emulsion as a comparative example were prepared as follows.

Using silver iodobromide seed crystals having a silver iodide content of 6 mol %, emulsions having different grain sizes as described below were prepared. The seed crystal had a legal equivalent diameter of 0.4 μm, and the coefficient of variation indicating the size distribution was 25%. After adding the seed crystals to the reaction tank,
Silver iodobromide having a silver iodide content of 30 mol % was grown to form a first coating layer by a flow rate accelerated controlled double jet method. Next, silver iodobromide having a silver iodide content of 4 mol % was grown to form a second coating layer. The silver ratio of the first and second coating layers is 1:2.
It has been confirmed from X-ray diffraction measurements that these particles have a clear layered structure. By changing the total silver amount of the first and second coating layers and the silver amount ratio of the seed crystal, the size can be adjusted to 0. All of the emulsions whose diameter was changed from 9 to 2.1 μm have almost similar structures.

The average silver iodide content of the final grains was about 12 mol %, the coefficient of variation indicating size distribution was about 23%, and the average aspect ratio of all the grains was about 4.5.

After grain formation, the emulsion was subjected to a normal desalting water washing step and redispersed at 40° C. under the conditions of pAg 8.9 and pH 6.3. The emulsions thus made were Em-a, Em-b, Em-c,
Let it be Em-d.

On the other hand, 3X10-' mol of thiosulfonic acid compound I-2 shown in Table A was added per 1 mol of Ag one minute before the formation of the second coating layer was started, and 1 minute after the formation of the second coating layer was started, the reduction increased. Sensitizer L-ascorbic acid 2X per mole of Ag
The emulsion Em according to the present invention is
-e, Em-f, Em-g, and Em-h were formed. These are summarized in Table 1.

Table 1 Emulsions Em-a-Em-h were then optimally sensitized with gold and sulfur using each emulsion using sparingly soluble thiosulfuric acid and chloroauric acid. These were designated as Em-A-Em-H, corresponding to Em-a to Em-h.

Example 1 On a subbed cellulose triacetate film support,
Sample 101, which is a multilayer color light-sensitive material consisting of each layer having the composition shown below, was prepared.

(Composition of photosensitive layer) The coating amount is g for silver halide and colloidal silver.
The amount of silver expressed in /rd, and for coupler additives and gelatin in g/rrr, and for sensitizing dyes the amount of silver halide in the same layer.
Expressed in moles per mole.

1st layer: antihalation layer black colloidal silver Silver coating amount 0.2 gelatin
2.2UV-10,1 UV-20,2 Cpd-10,04 Cpd-20,02 Solv-10,30 Solv-20,01 2nd layer: Intermediate layer fine grain silver iodobromide (Ag1). 0 mol% Equivalent sphere diameter 0.0
7μm) Silver coating amount 0.15 Gelatin 1. 0ExC-
40,03 Cpd-30,2 Third layer: First red-sensitive emulsion layer (first RL) Silver iodobromide emulsion (AgI5.0 mol%, surface high Agl type,
Equivalent sphere diameter 0.9 μm, coefficient of variation of equivalent sphere diameter 21%, tabular grain, diameter/thickness ratio 7.5) Silver coating amount
0.42 Silver iodobromide emulsion (Ag 14.0 mol%, internal high AgI type, equivalent sphere diameter 0.4 μm, coefficient of variation of equivalent sphere diameter 18%, dodecahedral grains) Silver coating amount 0.40 Gelatin 1 .0ExS-1
4,5XIO-'mol ExS-21,5xto-'mol ExS-30,4xlO-'mol ExC-10,50 ExC-20,1) ExC-30,009 ExC-40,023 Solv-10,24 Layer: Second red-sensitive emulsion layer (second RL) Silver iodobromide emulsion (Ag1 8.5 mol%, internal high AgI type, equivalent sphere diameter 1.0 μm, coefficient of variation of equivalent sphere diameter 25%, plate-like grains, Diameter/thickness ratio 3.0) Silver coating amount 0.
85 Gelatin 0.7ExS-1
3xlO'mol ExS-21xlO-'mol ExS-30,3xlO-'mol ExC-10,10 ExC-20,05 ExC-40,025 Solv-10,10 5th layer: 3rd red-sensitive emulsion layer (3rd RL ) Silver iodobromide emulsion (Em-C) Silver coating amount 1,50 0,6 2XIO-'mol 0.6X10-'mol 0.2X10-'mol 0,08 0,01 Gelatin xS-I xS-2 xS -3 ExC-2 ExC-4 ExC-50,06 Solv-10,12 Solv-20,12 6th layer: Intermediate layer gelatin 1. 0Cpd-
40,1 Solv-10,1 7th layer: First green-sensitive emulsion layer (first GL) Silver iodobromide emulsion (Ag15.0 mol%, surface high Agl type,
Equivalent sphere diameter 0.9 μm, coefficient of variation of equivalent sphere diameter 21%, tabular grain, diameter/thickness ratio 7.0) Silver coating amount
0.28 silver iodobromide emulsion (Ag 14.0 mol%, internal high Agl type, equivalent sphere diameter 0.4 μm, coefficient of variation of equivalent sphere diameter 18%, dodecahedral grains) Silver coating amount 0.16 Gelatin 1 ．． 2ExS-5
5xlO-'mol ExS-62X10'-'mol ExS-71XIO-'mol ExM-10,50 ExM-20,10 ExM-50,03 Solv-10,2 Solv-30,03 8th layer: Second green feeling Emulsion layer (2nd GL) Silver iodobromide emulsion (AgI 8.5 mol%, internal high iodine type, equivalent sphere diameter 1.0 μm, coefficient of variation of equivalent sphere diameter 25%,
Plate-shaped particles, diameter/thickness ratio 3゜0) Silver coating amount
0.57 gelatin
0.35ExS-53,5X10-'molExS-61,4X10-'molExS-70,7XIO""molExM-10,12 ExM-20,01 ExM-30,03 Solv-10,15 Solv-30, 03 9th layer: Intermediate layer gelatin 0. 5Solv
-10,02 1st O layer: 3rd green-sensitive emulsion layer (3rd GL) silver iodobromide emulsion (
Em-C) Silver coating amount 1. 3 Gelatin 0. 8ExS-
52XIO-'mol ExS-60,8X10-'mol ExS-70,8XlO-'mol ExM-40,04 ExC-40,005 ExM-60,01 Cpd-50,01 Solv-10,2 1st) layer: Yellow filter layer (YF) Cpd-60
,05 Gelatin 0.5Solv-
10,1 12th layer: Intermediate layer gelatin 0.5Cpd-3
0,1 13th layer: 1st blue-sensitive emulsion layer (1st BL) silver iodobromide emulsion (
Ag1 2 mol%, uniform iodine type, equivalent sphere diameter 0.55
μm, coefficient of variation of equivalent sphere diameter 25%, tabular grain, diameter/
Thickness ratio 7゜0) Silver coating amount 0. 2
Gelatin 1.0ExS-8
3X10-4 mol ExY-10,6 ExY-20,02 Solv-10,15 14th layer: 2nd blue-sensitive emulsion layer (2nd BL) silver iodobromide emulsion (
Agl 19.0 mol%, internal high Agl type, equivalent sphere diameter 1.
0 μm, coefficient of variation of equivalent sphere diameter 16%, octahedral particles) Silver coating amount 0.19 Gelatin 0.3ExS-8
2X10-'mol ExY-10,22 Solv-10,07 15th layer: Intermediate layer fine grain silver iodobromide (Ag1 2 mol%).

Silver coating amount Gelatin 16th layer: 3rd blue-sensitive emulsion layer (3rd BL) Silver iodobromide emulsion (
Em-D) Silver coating amount 1,55 0.5 5X10-'mol 0.2 0,07 Gelatin xS-9 xY-1 olv-1 17th layer: 1st protective layer Gelatin V-1 V-2 olv- 1 olv-2 18th layer: 2nd protective layer fine grain silver chloride (equivalent sphere diameter 0°l).

07 μm) Uniform Yaw 0°0, 36 Silver Coating Amount 0.36 Gelatin 0.7 Polymethylmethacrylate Particles (1.5 μm in Diameter) 0. 2W-1
0,02 H-10,4 Cpd-71,0 In addition to the above, each layer contains B-1 (total 0.20 g/n?),
1.2-penzithysoazolin-3-one (average 200 ppm based on gelatin), n-butyl, p-hydroxybenzoate (approximately 1 ml).

000 ppm) and 2-phenoxyethanol (between about 10.000 ppm).

I: C00CH.

2: X/y 7/3 (ti male υ xC-4 xM 5 xM l 1 1 xY I 1 I Cpd-6 Solv-1 Solv-3 xS H H -1 ■ CH,=CH3O, CH2CONH-CH.

xS-3 xS-5 ExS ExS-8 Next, the FR compound (1-3) was added to the 16th layer of sample 101.
Sample 101 except that 3 x l O-'g/% was added.
A sample prepared in exactly the same manner as above was designated as sample 102. Furthermore, a sample was created in which the emulsion in the 16th layer of sample 101 was changed to Em-H, and a sample in which the emulsion in the 16th layer of sample 102 was changed to Em-H, and these samples were used as samples 103 and 1, respectively.
It was set as 04.

In addition, FR compound (1-3) of sample 104 was added to (1-6)
Alternatively, samples 105 and 10 were prepared in exactly the same manner as sample 104 except for changing (1-7).
It was set at 6.

The color photographic material thus obtained was wedge exposed and then developed according to the following development process.

The development used here was carried out at 38°C as described below.

■ Color development...3 minutes 15 seconds 2
White...6 minutes 30 seconds 3 Wash...
・・・・・・3 minutes 15 seconds 4 Fixed・・・・・・・・・
・6 minutes 30 seconds 5 Washing with water・・・・・・3 minutes 15
6 seconds Stable...3 minutes 15 seconds The composition of the processing liquid used in each step is as follows.

Color developer Sodium nitrilotriacetate 1.0g Sodium sulfite 4.0g Sodium carbonate
30.0g potassium bromide
1.4g hydroxylamine sulfate
Add 2.4g 4-(N-ethyl-N-β-hydroxyethylamino)-2 methylalline sulfate 4.5g water
1) Bleach solution Ammonium bromide 160.0g Aqueous ammonia (28%) 25.0cc Ethylenediamine-tetraacetic acid sodium iron salt 130.0g Glacial acetic acid
Add 14.0cc water
1) Fixer Sodium tetrapolyphosphate 2.0g Sodium sulfite 4.0g Ammonium thiosulfate (70X) 175. Add 0cc sodium bisulfite 4.6g water
1) Stabilizing liquid formalin 8.0 cc of water was added to each treated sample and the concentration was measured using a blue filter. The photographic performance results obtained are shown in Table 2.

Note that the relative sensitivity is the reciprocal of the exposure amount that gives a density of fog +0.2, and is a relative value when the result of sample 101 is set as 100.

Table 2 As is clear from Table 2, when an FR compound is used in combination with a normal emulsion (sample 102), the fog increases significantly and the sensitivity improves little, but in the case of the emulsion according to the present invention, Even when an FR compound is used, the increase in fog is extremely small and the sensitivity is significantly improved.

In addition, when we observed the grains of samples 102 and 104 using an optical microscope through a blue filter, we found that 104 was 102
It was found that the grain quality was improved even though the sensitivity was higher than that of the previous method.

Example 2 Sample 103 and All (Samples 107 to 1) 0 were prepared in the same manner as in Example 1, except that the emulsion of the first θ layer of sample 103 was changed as shown in Table 3.

Next, Sample 1)1 was prepared in the same manner except that 1.0XIO-''g/% of the FR compound (l-6) was added to the 10th layer of Sample 1)0.

These samples were exposed to wedge light and then processed using an automatic processor in the following manner.

Color developer Diethylenetriamine Pentaacetic acid l-Hydroxyethylidene 1,1-diphosphonic acid Sodium sulfite Potassium carbonate Potassium bromide Potassium iodide Hydroxyamine 4-(N-ethyl-N-β-hydroxyethylamino) 2-Methylaniline Sulfate water Add H bleaching solution> Ethylenediamine 4 ferric ammonium acetate salt Ethylene diamine 4 acetic acid disodium salt Aqueous ammonia 1, 0 4.5 1 10.00 Add ammonium nitrate ammonium bromide aqueous solution and add H. Fixing solution> Ethylene diamine 4 acetic acid 2 Sodium salt Sodium sulfite Sodium bisulfite Ammonium thiosulfate aqueous solution (70%) Add water and rinse with water > Tap water (contains calcium 21ml/L and 10mm/L) 10.0g 50g 1 6.0 1, 0g 4 .0g 4.6g 75d 1 6.6 Magnesilla 00g 10.0g Stable liquid> Formalin (37% w/v) Polyoxyethylene-p-7nononyl phenyl ether (average degree of polymerization 10) 0.3g Water 1) The density of each treated sample was measured using a green filter, and fogging and sensitivity were evaluated. As in Example 1, the sensitivity is expressed as relative sensitivity, with the result of sample 103 set as 100. Samples 103 and 109 were also exposed with a wedge for RMS grain size measurement and developed.
For 1)0.1)1, the RMS value of an aperture diameter of 48 μm at a magenta density of fog +0°2 was measured to evaluate graininess.

The results obtained are summarized in Table 3.

From Table 3, it is clear that sample 109.1)0 according to the present invention not only has lower fog than sample 103.107 made of a normal emulsion and can achieve high sensitivity, but also has a remarkable improvement in graininess. .

Further, Sample 1) 1 shows that it is possible to provide a photosensitive material with extremely high sensitivity with fog and graininess comparable to those of Sample 103.

Example 3 According to the method for preparing sample 103 of Example 1, samples 1) and 2, which were color photosensitive materials having the layer structure and composition shown in Table 4, were prepared. However, the composition of the ninth layer is
The composition of the fifth layer of 03 and the silver coating amount of the silver iodobromide emulsion are 0.9
It is the same except that it is 2 g/i (1.5 g/rr for sample 103).

The composition of the first) layer is the composition of the first θ layer of sample 103 and the silver coating amount of the silver iodobromide emulsion of 1.2 g/r+? (1.3 g/rrr for sample 103).

Next, the emulsion of the 9th layer and the 1st) layer of sample 1)2 was emulsified by Em.
Sample 1) 3 was a sample prepared in exactly the same manner as Sample 1) 2 except that -G was changed. Furthermore, the 9th layer of sample 1) 3,
The silver coating amount of the first layer was 0.78g/m and 0.98g, respectively.
Samples 1) and 4 were prepared in the same manner except that / was changed.

The comparison table sample 103, sample 1) 2, and sample 1) 3 having the fourth surface layer structure were each subjected to sensitometric exposure, and then processed using an automatic processor using the following steps and processing solution.

Processing method Process Processing time Color development 2 minutes 30 seconds Bleach fixing 3 minutes 00 seconds Washing with water (1) 20 seconds Wash with water (2120 seconds Stability 20 seconds Dry 50 seconds Next, the composition of the treatment liquid will be described.

(Color developer) Diethylenetriaminepentaacetic acid l-hydroxyethylidene 1, l-diphosphonic acid Sodium sulfite Potassium carbonate Potassium bromide Treatment temperature 40°C 40°C 35°C 35°C 35°C 65°C (Unit: g) 2 .0 Potassium iodide hydroxylamine sulfate 4-[N-ethyl-N-(β-hydroxyethyl)amino] = pH by adding 2-methylaniline sulfate (bleach-fix solution) Ferric ammonium ethylenediaminetetraacetate Water salt Ethylenediaminetetraacetic acid disodium salt Sodium sulfite ammonium thiosulfate aqueous solution (70%) Nitric acid (98%) Bleach accelerator 1, 5 ■ 2.4 4.5 1, OI! 10.05 (unit g) 50, 0 5.0 12, 0 260, O- 5, 〇- Add 0,01 mol water 1.01 pH 6,
0 (Washing liquid) Tap water was poured into a mixed bed column packed with an H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and an OH-type anion exchange resin (Amberlite IR-400 manufactured by Rohm and Haas). Water was passed through to reduce the concentration of calcium and magnesium ions to 3/l or less, and then sodium dichloride isocyanurate 20/l and sodium sulfate 1. 5 g/l was added.

The pH of this solution is in the range of 6.5-7.5.

(Stabilizing solution) (Unit: g) Formalin (37%) 2. 01rI polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 Ethylenediaminetetraacetic acid disodium salt 0.05 Add water 1,0R pH 5,0-8,
The concentration of the sample obtained by the 0 treatment was measured using a red filter,
The photographic performance obtained is shown in Table 5. The relative sensitivity is
As in Example 1, sample 103 was evaluated as 100.

I found out that

Furthermore, when the desilvering speed was compared between Sample 103 and Sample 1)4, it was confirmed that the desilvering speed was faster in Sample 1)4.

Claims (3)

[Claims] (1) In a silver halide color photographic material having at least one blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layer, at least one emulsion in the emulsion layer has the general formula [I], [ II] or [III], the emulsion layer is reduction sensitized with at least one ascorbic acid or its derivative, and the oxidized color developing agent is present in the emulsion layer. A silver halide color photographic light-sensitive material characterized by containing a compound capable of releasing a development accelerator or a fogging agent upon reaction with a silver halide color photographic material. [I] R-SO_2S-M [II] R-SO_2S-R^1 [III] R-SO_2S-Lm-SSO_2-R^2 In the formula, R, R^1, and R^2 may be the same or different. Often represents an aliphatic group, an aromatic group, or a heterocyclic group, and M represents a cation. L represents a divalent linking group, and m is 0 or 1. The compounds represented by formulas [I] to [III] may be polymers containing divalent groups derived from the structures represented by [I] to [III] as repeating units. (2) In a silver halide color photographic light-sensitive material having at least one blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layer, at least one emulsion in the emulsion layer is as defined in claim (1). reduction sensitized with ascorbic acid or at least one derivative thereof in the presence of at least one compound represented by the general formula [I], [II] or [III], and in the emulsion layer. A silver halide color photographic material characterized in that the average grain size of the silver halide grains is 1.0 micron or more. (3) It has blue-sensitive, green-sensitive, and red-sensitive silver halide emulsion layers, at least one of which is composed of two or more layers with mutually different sensitivities, and these two or more layers are on the side of the support. A color light-sensitive material in which at least one silver halide emulsion layer having different color sensitivity is arranged in order from a low-sensitivity layer to a high-sensitivity layer when viewed from above, and between the low-sensitivity layer and the high-sensitivity layer. At least one emulsion in the emulsion layer is defined in claim (1).
Ascorbic acid or in the presence of at least one compound represented by the general formula [I], [II] or [III]
A silver halide color photographic material characterized in that it has been reduction sensitized with at least one derivative thereof.