JPH03233443A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To make improvement in sensitivity and preservable property by setting the position where the maximal value of the latent image distribution of the silver halide emulsion particles contained in emulsion layers exist at <0.03mum depth from the particle surfaces and further incorporating specific compds. into the photosensitive material. CONSTITUTION:The position where the maximal value of the latent image distribution of the silver halide emulsion particles contained in the emulsion layers exists is set at <0.03mum depth from the particle surfaces and further, at least >=1 kind of the compds. among the compds. expressed by formula I, etc., are incorporated into the photosensitive material. In the formula I, R1 denotes an unsubstd. or substd. alkylene group; X denotes a hydrogen atom, halogen atom, etc.; R2 denotes a hydrogen atom, -OM, etc.; R3, R4 respectively denote a hydrogen atom, halogen atom, etc.; R5, R6 respectively denote a hydrogen atom, lower alkyl group, etc.; R7 denotes a lower alkyl group, aryl group, etc.; M denotes a hydrogen atom, alkaline metal atom, the atom group necessary for forming monovalent cation; (m) denotes 1 to 6 integer; (n) denotes 0 or 1 to (6-m) integer. The improvement in the sensitivity and preservable property is made in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a silver halide photographic light-sensitive material (hereinafter abbreviated as light-sensitive material), and particularly to a hydrophilic colloid preservative used as a binder for the light-sensitive material.

(Prior Art) In general, photosensitive materials are prepared by coating at least one photosensitive emulsion layer on a support, and optionally forming photographic constituent layers such as a subbing layer, an intermediate layer, an antihalation layer, and a protective layer. It will be painted.

Hydrophilic colloids used as binders for these photographic constituent layers include gelatin, colloidal albumin, agar, gum arabic, alginic acid, cellulose derivatives such as hydrolyzed cellulose acetite, carboxymethyl cellulose, hydroxyethyl cellulose, and methyl cellulose. , synthetic binders such as polyvinyl alcohol, partially saponified polyvinyl acetate, polyacrylamide, polyN,N-dimethylacrylamide, polyN-vinylpyrrolidone, U.S. Pat. No. 3,341,332,
Water-soluble polymers such as those described in U.S. Pat. No. 3,615.424, U.S. Patent No. 3,860,428,
Gelatin derivatives such as phenylcarbamylated gelatin, acylated gelatin, and phthalated gelatin as described in U.S. Pat. No. 14.928 and U.S. Pat. No. 2,525,753; Examples include gelatin graft copolymerized with polymerizable ethylene group-containing monomers such as acrylic acid (ester), methacrylic acid (ester), and acrylonitrile, as described in No. 767. These binders can be used as a compatible mixture of two or more, if desired.

It is known that hydrophilic colloids used as binders for photosensitive materials are easily affected by microorganisms such as bacteria, yeast, and mold. In particular, when a photographic hydrophilic colloid is coated on a support, the influence of microorganisms becomes significant because the coating is carried out at a temperature suitable for the growth of microorganisms. For example, when hydrophilic colloids rot or decompose due to microorganisms, the viscosity of the coating solution decreases, the strength of the applied film decreases, and bacteria, etc. aggregate and form small clumps, resulting in comet-shaped defects. In some cases, a uniform coating film may not be obtained, and metabolites of microorganisms may cause adverse photographic effects.

Furthermore, if a photosensitive material is left under high temperature and high humidity conditions, mold and the like will grow, which may significantly impair the quality of the photosensitive material.

In order to prevent such defects caused by bacteria, yeast, mold, etc. in hydrophilic colloids used in photosensitive materials, it is known to add a bactericidal agent or a fungicidal agent to the photosensitive materials.

Generally, preservatives or fungicides for this purpose include, for example, compounds having a carbonyl group such as formaldehyde, paraformaldehyde, chloroacetaldehyde, geltaraldehyde, chloracetamide, methylolchloroacetamide, or benzoic acid, Carboxylic acids or their esters such as monobromoacetate, sorbic acid, or amines such as hexamethylenetetramine, alkylguanidine, nitromethylbenzylethylenediamine, disulfides such as tetramethylthiuram disulfide, 2-mercaptobenzthiazole, 2-( 4-thiazolyl)-
Nitrogen-containing polycyclic compounds such as benzimidazole, 2-methoxycarbonylaminobenzimidazole, or organic mercury compounds such as phenymercuric acetate, phenylpropionate, mercuric phenyloleate, or neomycin, kanamycin, polymycin, streptomycin, Antibiotics such as flamycin are known, and some of these are also known for use in photography.

However, these substances may be harmful to living organisms, effective only against specific bacteria, harmful to photography, or have no bactericidal effect due to interactions with other photographic additives. In many cases it is sufficient. For example, aldehydes such as formalin are effective against bacteria, but are ineffective against mold and are harmful to living organisms.

Antibiotics such as neomycin and kanamycin are effective against bacteria, but not against mold and yeast.

Furthermore, many of these preservatives react with latent images formed on the surfaces of silver halide grains by exposure, or promote the phenomenon of increased fog during storage.

This is an important obstacle when used in silver halide photographic materials, and a solution has been desired.

(Problems to be Solved by the Invention) The first object of the present invention is to provide a hydrophilic colloid composition that is used for coating a photographic constituent layer of a photosensitive material containing a hydrophilic colloid during production, storage, or after coating. The objective is to provide a new method of preserving food.

The second object is to provide a silver halide photographic material with excellent photographic performance (sensitivity) and storage stability.

(Means for Solving the Problem) As a result of various studies, the present inventors have found that the object of the present invention is to provide a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support. The position of the maximum value of the latent image distribution of the silver halide emulsion grains contained in the emulsion layer is located at a depth of less than 0.03 μm from the grain surface, and the light-sensitive material has general formulas [1] to [rV It has been found that this can be achieved by a silver halide photographic material containing at least one compound among the compounds represented by the following.

In the formula, R5 represents an unsubstituted or substituted alkylene group,
X represents a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, a cyano group, a lower alkyl group, a lower alkoxy group, an aryl group, an alkenyl group, a through Sol M, and R1 represents a hydrogen atom, -〇M, a lower alkyl group, Aryl group, aralkyl group, lower alkoxy group, aryloxy group, aralkyl group Rs, R- each represent a hydrogen atom, lower alkyl group, aryl group, aralkyl group, -cORt, -5otR, and are the same as each other. may also be different, Rs and Rs each represent a hydrogen atom, a lower alkyl group, an aryl group, an aralkyl group,
They may be the same or different, and R1 represents a lower alkyl group, aryl group, or aralkyl group, and M represents a hydrogen atom, an alkali metal atom, or an atomic group necessary to form a monovalent cation. Further, m represents an integer from 1 to 6, and n represents an integer from 0 or 1 to (6-m). m,
When n is 2 or more, the above groups may be the same or a plurality of them may be combined.

General formula [1] In the formula, Rs is a hydrogen atom, an alkyl group, an aralkyl group, an aralkyl group, an aryl group, a heterocyclic group, each R is a hydrogen atom, an alkyl group, an aryl group, a cyano group, a heterocyclic group, an alkylthio group , an alkylsulfoxy group, or an alkylsulfonyl group, and R1 and R1° may be bonded to each other to form an aromatic ring.

R11 and R11 each represent a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group.

General formula CI[[] ■ NOl During the ceremony, , is a hydrogen atom, alkyl group, hydroki represents a dimethyl group, represents a group.

General formula [■] is a hydrogen atom, In the alkyl formula, Y is a halogen atom, nitro group, hydroxy group, cyano group, lower alkyl group, lower alkoxy group, aryl group, alkenyl group, sulfonyl group, -3o, M'' , Ro is a hydrogen atom, -0M "lower alkyl group, aryl group, aralkyl group, lower alkoxy group, aryloxy group, aralkyl R+ s, R17 is a hydrogen atom, lower alkyl group, aryl group, aralkyl group, - COR1°,=SO*R,. and may be the same or different from each other, R4 and Ro each represent a hydrogen atom, a lower alkyl group, an aryl group, or an aralkyl group, and may be the same or different from each other, and R2゜Represents a lower alkyl group, aryl group, aralkyl group, M', M'' represents a hydrogen atom, an alkali metal atom, and an atomic group necessary to form a monovalent cation, p represents an integer from 1 to 5,
When p is 2 to 5, Y may be the same group or a combination of two or more of the above groups.

Furthermore, the compound of the present invention will be explained in detail.

In the general formula [I], R2 represents an unsubstituted or substituted lower alkylene group (e.g., ethylene group, propylene group, methylethylene group, etc., and substituents include a halogen atom, nitro group, hydroxy group, cyano group, lower alkyl group, lower alkokene group, aryl group, alkenyl group, sulfonyl group, aralkyl group, etc.), and particularly preferably an alkylene group having 1 to 6 carbon atoms.

X is a hydrogen atom, a halogen atom (e.g. chlorine atom, bromine atom, fluorine atom), nitro group, hydroxy group, cyano group, lower alkyl group (e.g. methyl, ethyl, is○-propyl, tert-butyl), lower alkoxy group (e.g. methoxy, n-butoxy, 2-methoxyethoxy),
Aryl groups (e.g. phenyl, naphthyl, 2-methoxyphenyl, 3-acetamidophenyl), alkenyl groups (e.g. allyl, l-butenyl), sulfonyl groups (e.g. methylsulfonyl, benzenesulfonyl), aralkyl groups (e.g. benzyl, p-1so -propylbenzyl, 0-methylbenzyl) Rt is a hydrogen atom, -0M, a lower alkyl group (e.g. methyl, n-butyl,), an aryl group (e.g. phenyl, 4-chlorophenyl, 3-nitrophenyl), an aralkyl group (e.g. benzyl, p-1s
o-propylbenzyl, 0-methylbenzyl) lower alkoxy groups (e.g. methoxy, n-butoxy, 2-methoxyethquine), aralkyl groups (e.g. fenoquine, naphthoxy, 4-nitrophenoxy), aralkyloxy groups (e.g. benzyloxy, p-chlorobenzyloxy)
, R,, R, each represent a hydrogen atom, a lower alkyl group (e.g. methyl, ethyl, 2-ethylhexyl), an aryl group (e.g. phenyl, naphthyl, 2-methoxyphenyl,
3-acetamidophenyl), aralkyl group (e.g. benzyl, 0-chlorobenzyl), -CORt,
5O2R1, which may be the same or different, R,,R.

are hydrogen atoms, lower alkyl groups (e.g. methyl, 1s
o-propyl, 2-cyanoethyl), aryl groups (e.g. phenyl, 4-ethoxycarbonylphenyl, 3-nitrophenyl), aralkyl groups (e.g. benzyl, p-
chlorobenzyl), which may be the same or different, and R7 represents a lower alkyl group (e.g. ethyl, 2
-methoxyethyl, 2-hydrodiethyl), aryl groups (e.g. phenyl, naphthyl, 4-sulfophenyl,
4-carboxyphenyl), M represents a hydrogen atom, an alkali metal atom (e.g. sodium, potassium) and 1
It represents an atomic group necessary to form a valent cation (eg, ammonium cation, phosphonium cation), m represents 0 or l, and n represents 0 or an integer from 1 to 5.

The preferred carbon number of the lower alkyl group and lower alkoxy group described in the above general formula [I] is in the range of 1 to 8. Next, typical examples of the compound represented by the general formula [■] (hereinafter referred to as compound I) will be shown, but the compound represented by the general formula [■] of the present invention is not limited to these.

(Exemplary compound) I-7 -8! -9 -11 ■ 3 -10 -12 -14 -15 ■-17 -19 -16 ■-18 ■-20 Most of these exemplified compounds are commercially available as reagents and can be easily obtained. It can also be easily synthesized using existing synthetic methods. For example, J, A
rrr, Chem, Soc, Volume 41, Page 669 (L
Some of the compounds where n=1 can be easily synthesized by the method described in 919).

In general formula (I[), R8 is a hydrogen atom, a linear or branched substituted or unsubstituted alkyl group (e.g. methyl, ethyl, tert-butyl, n-octadecyl, 2
-hydroxyethyl, 2-carboxyethyl, 2-cyanoethyl, sulfobutyl, N,N-dimethylaminoethyl), substituted or unsubstituted cyclic alkyl groups (e.g. cyclohexyl, 3-methylcyclohexyl, 2-oxocyclopentyl), substituted or unsubstituted Substituted alkenyl groups (e.g. allyl, methylallyl), substituted or unsubstituted aralkyl groups (e.g. benzyl, p-methoxybenzyl, 0
-Chlorobenzyl, p-is.

-propylbenzyl), substituted or unsubstituted aryl groups (e.g. phenyl, naphthyl, O-methylphenyl, m
-nitrophenyl, 3. 4-')'10 Lophenyl)
, heterocyclic group (2-imidazolyl, 2-furyl, 2-thiazolyl, 2-pyridyl), R is each a hydrogen atom, a substituted or unsubstituted alkyl group (e.g. methyl, ethyl, chloromethyl, 2-hydroxyethyl, tert-butyl,
n-octyl), substituted or unsubstituted cyclic alkyl groups (
For example, cyclohexyl, 2-oxocyclopentyl),
Substituted or unsubstituted aryl groups (e.g. phenyl, 2-
methylphenyl, 3,4-dichlorophenyl, naphthyl, 4-nitrophenyl, 4-aminophenyl, 3-acetamidophenyl), cyano group, heterocyclic group (e.g. 2
-imidazolyl, 2-thiazolyl, 2-pyridyl), substituted or unsubstituted alkylthio groups (e.g. methylthio,
2-cyanoethylthio, 2-ethoxycarbonylthio)
Substituted or unsubstituted arylthio groups (e.g. phenylthio, 2-carboxyphenylthio, p-methquinphenylthio), substituted or unsubstituted alkylsulfoxy groups (
(e.g. methylsulfoxy, 2-hydroxyethylsulfoxy), substituted or unsubstituted alkylsulfonyl groups (e.g. methylsulfonyl, 2-bromoethylsulfonyl)
and R1 and R6 may be bonded to each other to form an aromatic ring (for example, a benzene ring or a naphthalene ring).

R, , R, each represents a hydrogen atom, a substituted or unsubstituted alkyl group (eg, methyl, ethyl, is.

propyl, 2-cyanoethyl, 2-n-butoxycarbonylethyl, 2-cyanoethyl), substituted or unsubstituted aryl groups (e.g. phenyl, naphthyl, 2-methoxyphenyl, m-nitrophenyl, 3,5-dichlorophenyl, 3- acetamidophenyl), substituted or unsubstituted aralkyl groups (e.g. benzyl, phenethyl, p-1
so-propylbenzyl, O-chlorobenzyl, m-methoxybenzyl).

Next, typical specific examples of the compound represented by the general formula [■] (hereinafter referred to as compound ■) are shown below.
are not limited to these (exemplary compounds) ■ -3 I-5 I-7 -2 I-4 ■ ■ -9 U ■-10 l-11 ■ 2 -13 -14 F-15 -17 ■ -16 ■-18 -19 -21 ■-22 ■-24 ■-20 ■-23 ■-25 ■-27 ■-29 f-31 ■-26 ■-28 ■-30 ■ 32 ■-37 ■-42 ■ 8 ■-43 Some of the above compounds are commercially available and can be easily obtained.
It can be synthesized according to the synthesis method described in No. 6.

Next, the compound of general formula (I[I) will be described.

R1 represents a hydrogen atom, a lower alkyl group (e.g. methyl, ethyl, is○-propyl), or a hydroxymethyl group; R1 represents a hydrogen atom, a lower alkyl group (e.g. methyl,
n-butyl, 1so-amyl). The lower alkyl group preferably has 1 to 5 carbon atoms, particularly one having 1 carbon atom.

Typical specific examples of the compound represented by the general formula (I[I] (hereinafter referred to as compound ①) are shown below, but the compound ② of the present invention is not limited to these.

(Exemplary compound) II[-1 r H○・CH, -C-CH20H OI ■ r H○・CH.

-C-CH-OH NO3 CH.

I[I-3 r HOCH.

CHs NO8 -4 r I[[-5 NO7 CH.

111-6 Br C.I. -C-CH.

H NO3 1[I-7 Ot Some of these compounds are commercially available from San-Ai Sekiyu ■. Further, the synthesis can be performed with reference to the following literature.

(1) Henry Recueil des tr
avaux chiniques des Rays-B
as upper 6'-251 (21Mass, Chemis
chess Zentralblatt 189917
9 (31E, Schmidt, Berichte de
rDeutchen Chemischen Ge5e
llschaft, 5297 (4) E, Schmidt, 1bid 55
317f51) 1enry Chemiches
Zentralblatt, 1897■ 3
38 In this case, the synthesis of 111-1 is based on the literature (1), (2) or 3), the synthesis of m-2 is based on the literature (2), the synthesis of I[[-3 is based on the literature (5), and the synthesis of m-4 is based on the literature (5). The synthesis should preferably follow the literature (2).

Next, the compound of general formula [IV] will be described.

In the general formula [IV], Y is a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom, a nitro group,
hydroxy group, cyano group, lower alkyl group (e.g. methyl, ethyl, 1so-propyl, tert-butyl),
Lower alkoxy groups (e.g. methoxy, n-butoxy, 2
-methoxyethoxy)aryl groups (e.g. phenyl, naphthyl, 2-methoxyphenyl, 3-acetamidophenyl), alkenyl groups (e.g. allyl, 1-butenyl)
, sulfonyl groups (e.g. methylsulfonyl, benzenesulfonyl), aralkyl groups (e.g. benzyl, p-1s
o-propylbenzyl, 0-methylbenzyl)) R11 is a hydrogen atom, -0M1, a lower alkyl group (e.g. methyl, n-butyl), an aryl group (e.g. phenyl,
4-chlorophenyl, 3-nitrophenyl), aralkyl groups (e.g. benzyl, p-1so-propylbenzyl, 0-methylbenzyl), lower alkoxy groups (e.g. methoxy, n-butoxy, 2-methoxyethoxy), aryloxy groups (e.g. phenoxy, naphthoxy, 4-nitrophenoxy)5. Aralkyloxy group (e.g. benzyloxy, p-chlorobenzyloxy), R4, Rl
+ represents a hydrogen atom, a lower alkyl group (e.g. methyl,
ethyl, 2-ethylhexyl), aryl groups (e.g. phenyl, naphthyl, 2-methoxyphenyl, 3-acetamidophenyl), aralkyl groups (e.g. benzyl, 0
-chlorobenzyl), -0ORI. , -8OtRt. , which may be the same or different < , R1
1, R+s each represents a hydrogen atom, a lower alkyl group (e.g. methyl, 1so-propyl, 2-cyanoethyl), an aryl group (e.g. phenyl, 4-ethoxycarbonylphenyl, 3-nitrophenyl), an aralkyl group (e.g. benzyl, p- chlorobenzyl), which may be the same or different, and R8 represents a lower alkyl group (e.g. ethyl, 2-methoxyethyl, 2-hydroxyethyl), an aryl group (e.g. phenyl, naphthyl, 4 -sulfophenyl, 4-carboxyphenyl), M'
, M' represents a hydrogen atom, an alkali metal atom (e.g. sodium, potassium), and an atomic group necessary to form a monovalent cation (e.g. ammonium cation, phosphonium cation), p represents an integer from 1 to 5, p is 2
In the case of 5 to 5, Y may be the same group or a combination of two or more of the above groups.

Next, typical specific examples of the compound represented by the general formula [■] (hereinafter referred to as compound ■) will be shown.
) compounds are not limited to these.

(Exemplary compound) 3r V-9 V-11 ■ 3 ■-10 ■-12 ■-14 ■ 5 ■ 8 ■-19 In the present invention, the hydrophilic colloid for photosensitive materials refers to the hydrophilic colloid for photosensitive materials. Binders contained in coating solutions used for coating various photographic constituent layers, namely natural hydrophilic polymers such as agar, colloidal albumin, including seratin, which was mentioned at the beginning of the description of the prior art. and solutions or dispersions of various water-soluble, sparingly soluble, or insoluble compounds used in preparing sols of synthetic hydrophilic polymers such as derivative gelatin, derivative cellulose, and polyvinyl alcohol, gel-like hydrocolloid liquids, and coating solutions. Refers to compositions such as those in the liquid preparation process, storage or formulation process, or finishing coating liquids, such as silver halide emulsions, couplers, dispersions of matting agents, surfactant liquids, dye solutions, and various additives. It is.

Bacteria, bacteria, which commonly grow in hydrophilic colloids,
Usually, not only one type of mold but a mixture of several types of mold reproduce.

For this reason, the use of only one type of bactericide or fungicide does not have a complete antiseptic effect, and often fails to achieve its purpose.

Therefore, it is preferable to use a combination of at least two or more selected from among the compounds represented by the general formulas [1'l to (IV]), and when three or more are used in combination,
More preferred.

The compounds (1), (2), (2), and (2) of the present invention are used in each layer constituting a photosensitive material containing a hydrophilic colloid, such as a silver emulsion layer, a subbing layer, an intermediate layer, a filter layer, an antihalation layer, a protective layer, etc. It may be applied to any of the following.

Further, in the manufacturing process, when each layer is prepared by mixing two or more liquids, it can be added to each layer.

Compounds CI), [■], (II[], [■], and [I
The amount of V'l added is not particularly limited, but the amount of compound [■] is 1000 to 100°0.00 p to the hydrophilic colloid.
pm, Compound (II) is 50 to 110,000 ppm, Compound (I [[ ] is] 1 to 1,000 ppm (IV) is 1
0-10. A range of OOOppm is suitable.

The compounds [I], [■], and CI[I] of the present invention are dissolved in water or organic solvents such as methanol, isopropanol, acetone, and ethylene glycol that do not adversely affect photographic performance, and are hydrophilic as a solution. It may be added to a sex colloid, coated on a protective layer, or immersed in a disinfectant solution. Alternatively, after dissolving in a high boiling point solvent, a low boiling point solvent, or a mixed solvent of both, emulsifying and dispersing in the presence of a surfactant, and then adding it to a liquid containing a hydrophilic colloid or coating it on a protective layer. It may depend on the method.

The conditions that hydrophilic colloids for photosensitive materials must meet as a sterilizing and antifungal agent are (1) that they do not interact with photographic additives;

[2] A small amount has a large bactericidal and antifungal effect.

[3] No effect on photographic performance such as desensitization, fogging, graininess, sharpness, etc.

[4] Processing performance such as developability, desilvering property, recoloring property, etc. shall not be affected.

[5] There should be no impact on the environmental ecosystem.

[6] There should be no adverse effects on the human body.

etc. is desired.

Compounds 1, ■, ■, and ■ meet these requirements [1
3, [2] and [4] to [6] can be satisfied. However, the compounds (1) to (2), especially the compounds (1) and (2), react with the latent image formed on the surface of the silver halide grain by exposure, and may sensitize the recovery that lowers the sensitivity during storage.

Therefore, in order to improve the storage stability, it is necessary that the maximum value of the latent image distribution of the silver halide emulsion grains is not located on the surface, but is located inside. If the maximum value of the latent image distribution exists at a deep position of 0.03 μm or more from the surface, even if a practical developer is used for black-and-white, color negative, or color reversal photosensitive materials, the development will be insufficient, and sensitivity is impaired.

Here, the latent image distribution is defined as the depth of the latent image from the particle surface (
Sμm), and the number of latent images (y) is plotted on the vertical axis. Here, X is 8g.

S: Silver halide emulsion average grain size (μm) Ag+:
Amount of silver remaining after performing the following treatment on an unexposed emulsion coated sample Ago: the amount of coated silver before treatment, and y is the amount of silver remaining after performing white exposure for 1/100 second;
It is the reciprocal of the exposure amount that gives a density of overlap +0.2 when the following processing is performed. The processing conditions for obtaining the above latent image distribution are: N-methyl-p-aminophenol sulfate 2.5g L-7 sodium scorbate, 10g sodium metaborate 35g potassium bromide
Add 1g water
0 to 10 g/l of sodium thiosulfate is added to a treatment solution called IA (pH 9.6), and the treatment is carried out at 25° C. for 5 minutes. Here, the amount of sodium thiosulfate is 0 to 10g/l.
By changing the number up to , the depth from the surface of the latent image in the silver halogenide grains developed during processing changes, and it is possible to know the change in the number of latent images in the depth direction.

The above-mentioned practical developer is a developer in which the silver halide solvent is intentionally removed so as to develop only the surface latent image,
It is not a developer containing a large amount of silver halide solvent intended to develop the internal latent image.

The former developer cannot optimally develop the sensitivity of the internal latent image type emulsion of the present invention, and in the latter case, the silver halide may dissolve too much during processing or the graininess may deteriorate due to contagious development. . Specifically, it is preferable that the developing solution contains 100 g/l or less of potassium iodide or 100 g/l or less of sodium sulfite or potassium sulfite as a silver halide solvent. In addition, potassium thiocyanate or the like can be used as a silver halide solvent in the developer.

In the present invention, the maximum value of the latent image distribution is 0°03μ from the surface.
The depth is preferably less than 0.02 μm and 0.003 μm or more, and even more preferably less than 0.01 μm and 0.005 μm or more.

A method for preparing internal latent image emulsions is described in U.S. Pat. No. 39792.
No. 13, No. 3966476, No. 3206313, No. 3917485, Special Publication No. 43-29405, Special Publication No. 43
5-13259 etc. can be used, but in any method, in order to obtain an emulsion having the latent image distribution of the present invention, chemical sensitization method or precipitation after chemical sensitization can be used. The amount of silver halide and precipitation conditions must be adjusted.

The method described in Japanese Patent Application No. 1-150728 can be used as the method for preparing the emulsion most preferably used in the present invention. This method consists of core particle formation,
It consists of core chemical sensitization and shell formation process.

Silver potential in the process of forming a shell on the core particle (
SCE) is preferably +80 mV or less and −30 mV or more. If the voltage is higher than +80 mV, the chemical sensitizer that was not used during chemical sensitization during the shell formation process will easily react with the shell portion, making the surface sensitivity much higher than the internal sensitivity.

Furthermore, if the shell is formed on the core particle at less than -30 mV, the chemically sensitized surface of the core particle undergoes an oxidation reaction due to excess halogen, resulting in a decrease in sensitivity. A more preferable silver potential in the core particle growth step is -10 mV or more,
+60mV or less.

In the present invention, the temperature in the step of forming a shell on the core particles is preferably +70°C or lower and +45°C or higher. When the temperature is higher than +70'C, the remaining chemical sensitizer tends to react with the shell portion as described above, so that the surface sensitivity cannot be made lower than the internal sensitivity. Also +
If the core grain is grown at a temperature below 35°C, new nuclei are likely to be generated during the crystal growth process (new silver halide is not sufficiently precipitated on the chemical sensitization site of the core grain. In other words, new nuclei are generated during the shell formation process). This is not preferable because it tends to occur.More preferable temperature in the shell forming step is 45
℃ or higher and 60℃ or lower.

In the present invention, it is preferable that the water-soluble silver salt solution and the water-soluble halide solution in the step of growing grains from core grains be in the range of 30 to 100% of the critical crystal growth rate.

The crystal critical speed is defined as the upper limit at which new nuclei are not substantially generated during the grain growth process. Further, "substantially no generation" means that the weight of newly generated crystal nuclei is preferably 10% or less of the total weight of silver halide.

In the present invention, the chemical sensitization of the core particles is described in The Theory of James (T. H. James).
Photographic Process, 4th edition, Macmillan Publishing, 1977, (T. H. James.

The Theory of the Photographer
aphic Process, 4thed, M
Acmillan, 1977), pp. 67-76, or with activated gelatin, as described in Research Disclosure, Vol. 120, 1.
April 974, 12008. Research Disclosure, Volume 34, June 1975, 13452, U.S. Patent Nos. 2,642,361, 3,297,446, 3,772,031, 3,857,711, 3
．． 901.714, 4,266.018 and 3°904.415, and British Patent No. 1,315
As described in No. 755, sulfur, selenium, chirulu,
This can be done using gold, platinum, palladium, iridium or a combination of these sensitizers.

However, in the most preferred embodiment, in the presence of a gold compound and a thiocyanate compound, and in U.S. Pat.
No. 7,711, 4. 266, 018 and 4
In the presence of a sulfur-containing compound or a sulfur-containing compound such as hypo, thiourea-based compound, or rhodanine-based compound described in No. 054,457, the silver potential (S CE) ± Om
It is preferable to carry out at a voltage of V or more and +120 mV or less, more preferably +30 mV or more and +120 mV or less, even more preferably +60 mV or more and +120 mV or less. Increasing the silver potential, that is, lowering pAg, not only allows the chemical sensitization reaction to proceed effectively, thereby obtaining good sensitivity, but also reduces the amount of residual chemical sensitizer remaining during shell formation. It is preferable.

The silver halide photographic emulsion used in the present invention may contain any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride.

The preferred silver halide is silver iodobromide or silver iodochlorobromide containing up to about 30 mole percent silver iodide.

Particularly preferred is silver iodobromide containing from about 0.5 mole percent to about 15 mole percent silver iodide.

The emulsion grains of the present invention preferably have a maximum value of silver iodide distribution within the grains.

The maximum value of silver iodide distribution within the grain may be one or more. Further, the silver iodide content at the maximum value is preferably twice or more, more preferably four times or more, the average silver iodide content of the entire grain, and most preferably silver iodide itself. The position of the maximum value may be anywhere as long as it is under the internal chemical sensitization reaction. It is preferable that the change gradient of the silver iodide composition to reach the maximum value is as large as possible, and in extreme cases, an epitaxial junction may be provided.

The crystal structure other than the region forming the maximum value of silver iodide distribution is -
It may be of a different type, or it may be of a different halogen composition, or it may have a layered structure.

These emulsion grains are described in British Patent No. 1. 027. 14
No. 6, U.S. Patent No. 3,505,068, 4°444
．． No. 877 and Japanese Patent Application No. 58-248469.

Further, the grains of the present invention may themselves be joined to silver halide having a different composition by epitaxial joining, or may be joined to a compound other than silver halide, such as silver rhodan or lead oxide.

These emulsion grains are described in US Pat. 094. 68
No. 4, No. 4,142,900, No. 4,459°353
No. 2,038,792, U.S. Patent No. 4.
No. 349,622, No. 4,395゜478, No. 4,4
No. 33,501, No. 4,463.087, No. 3,65
No. 6.962, No. 3゜852.067, Patent Application No. 1983-
It is disclosed in No. 162540 and the like.

The light-sensitive material of the present invention only needs to have at least one silver halide emulsion layer of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer on the support. There are no particular restrictions on the number or order of the layers and non-photosensitive layers.A typical example is to deposit a plurality of silver halides with substantially the same color sensitivity but different photosensitivity on the support. A silver halide photographic light-sensitive material having at least one light-sensitive layer formed from an emulsion layer, and the light-sensitive layer is a unit light-sensitive layer sensitive to any one of blue light, green light, and red light. In a multilayer silver halide color photographic light-sensitive material, the unit photosensitive layers are generally arranged in this order from the support side: a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer. However, depending on the purpose, the above-mentioned installation order may be reversed, or the installation order may be such that different photosensitive layers are sandwiched between the same color-sensitive layer.

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. 13438, No. 59-113440, No. 61-20
Coupler, DIR compound, etc. as described in No. 037 and No. 61-20038 may be included,
It may also contain a gamma color inhibitor as commonly used.

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 German Patent No. 1,121,470 or British Patent No. 923.045. A two-layer configuration can be preferably used.

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.
No. 112751, No. 62200350, No. 62-20
As described in No. 6541, 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, starting from the side farthest from the support, low sensitivity blue sensitivity IN (BL) / high sensitivity blue sensitivity ji! (BH)
/ High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (
GL)/high-sensitivity red-sensitive layer (RH)/low-sensitivity red-sensitive layer (IIL), or BH/BL/GL/GH/R
11/RL order, or Bl(/BL/GH/GL/R
They can be installed in the order of L/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. Furthermore, as described in JP-A Nos. 56-25738 and 62-63936, the blue-sensitive layer/GL/RL/Gll/R1 (blue-sensitive layer/GL/RL/Gll/R1) may be arranged in this order from the farthest side from the support. can.

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-sensitivity 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.

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

Silver halides other than those of the present invention contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention will be explained. Preferred silver halides are silver iodobromide, silver iodochloride, or silver iodochlorobromide, containing up to about 30 mole percent silver iodide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mole percent to about 10 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 silver halide is approximately 0.2. The emulsion may be a fine grain of less than one micrometer or a large grain having a projected area diameter of 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) NIL17643
(December 1978), pp. 22-23, '■, Emulsion preparation an
d types)'', and rotation magnet 18716 (197
November 9), p. 648, same patient 307105 (1
(November 989), pp. 863-865, and “Physics and Chemistry of Photography” by Grafkide, published by Paul Montell (P.
GIafkides, Chemie et Ph1s
ique Photographique, Paul
Montel, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G, F, Duffi
n.

Photographic Emulsion Che
mistry (Focal Press1966))
, Zelikman et al., “Production and Coating of Photographic Emulsions J,” published by Focal Press (V, L, Zelivaneta 1
1 gate making and coating Photo
graphic E+5ul-sion, 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 3 or greater can also be used in the present invention. Tabular grains are described in Cutoff, 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. 2.112.157.

The crystal structure may be --like, the inside and outside may have different halogen compositions, it may be a layered structure, or silver halides with different compositions may be joined by epitaxial bonding. It may also be bonded with compounds other than silver halide, such as silver rhodan or lead oxide, or compounds of particles of various crystal forms may be used.

The above-mentioned emulsions may be of the surface latent image type in which the latent image is mainly formed on the surface, the internal latent image type in which the latent image is formed inside the grains, or the type in which latent images are formed both on the surface and inside the grains, but negative-tone emulsions It is necessary that Among the internal latent image type emulsions, a core/shell type internal latent image type emulsion described in JP-A-63-264740 may be used. This core/shell type internal i
The method for preparing the ll imitative emulsion is described in Japanese Patent Application Laid-Open No. 59-133542.
listed in the number.

The shell thickness of this emulsion varies depending on the development process, etc., but is preferably from 3 to 40 ns+, particularly preferably from 5 to 20 n-.

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, same N [L 18716 and turning magnet 30710
5, and the relevant sections are summarized in the table below.

The photosensitive material of the present invention includes grain size, grain size distribution, halogen composition, grain shape,
Two or more types of emulsions differing in at least one characteristic of sensitivity can be mixed and used in the same layer.

Silver halide grains coated with grain surfaces as described in U.S. Pat. No. 4,082,553, U.S. Pat. No. 4,626,4
Silver halide grains and colloidal silver with covered grain interiors described in No. 98 and JP-A No. 59-214852 are preferably used in a photosensitive silver halide emulsion layer and/or a substantially non-photosensitive hydrophilic colloid layer. Can be used.

Silver halide grains that have their interiors or surfaces covered are defined as - (
A method for preparing silver halide grains in which the interior or surface of silver halide grains can be developed (in a non-imagewise manner) is described in U.S. Pat. No. 4,626,498 and JP-A-59 -214852.

The silver halide forming the inner core of the core/shell type silver halide grains may have the same or different halogen composition. As the silver halide, any of silver chloride, silver chlorobromide, silver iodobromide, and silver chloroiodobromide can be used. Although there is no particular limitation on the grain size of these fogged silver halide grains,
The average particle size is preferably 0.01 to 0.75 pm, particularly 0.05 to 0.6 μm, and the particle shape is not particularly limited, and regular particles may be used.
It may be a polydisperse emulsion, but it may be a monodisperse emulsion (at least 95% of the weight or number of silver halide grains is ±4 of the average grain size).
0% or less) is preferable.

In the present invention, it is preferable to use non-photosensitive fine grain silver halide. It is preferable that these are fine silver halide grains that are not substantially developed, and that they are not couplered in advance.

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 preferably has an average grain size (average of circle equivalent diameter of projected area (if) of 0.01 to 0.5 μ-
0.02 to 0.2μ steel 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, before adding this to the coating solution, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or mercapto-based compound or a zinc compound. Colloidal silver can preferably be contained in the layer containing fine silver halide grains.

The coating silver amount of the photosensitive material of the present invention is preferably 6.0 g/rrf or less, and 4.5 g/rr? The following are most preferred.

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

In addition, in order to prevent deterioration of photographic performance due to formaldehyde gas, U.S. Patent No. 4,411.987 and U.S. Pat.
It is preferable to add to the photosensitive material a compound that can be immobilized by reacting with formaldehyde, as described in No. 435,503.

The photosensitive material of the present invention includes U.S. Pat. No. 4,740.454, U.S. Pat.
It is preferable to contain a mercapto compound described in JP-A-1-283551.

A compound that releases a fogging agent, a development accelerator, a silver halide solvent, or a precursor thereof irrespective of the amount of developed silver produced during the development process, which is described in JP-A-1-106052, is added to the light-sensitive material of the present invention. It is preferable to contain.

The dye material dispersed in the photosensitive material of the present invention by the method described in International Publication No. WO 88104794 and Japanese Patent Application Publication No. 1-502912 is disclosed in EP 317,308A and US Pat.
, 420,555 and JP-A-1-259358.

Various color couplers can be used in the present invention, and specific examples thereof include the above-mentioned Research R Isclosure.
k 17643, ■-C-C1 and turning magnet 307105
, ■-C-G.

As a yellow coupler, for example, U.S. Patent No. 3.93
No. 3,501, No. 4,022,620, No. 4.3
No. 26,024, No. 4,401.752, No. 4.
248,961, Japanese Patent Publication No. 58-10739, British Patent No. 1425.020, British Patent No. 1,476.760,
U.S. Patent No. 3,973,968, U.S. Patent No. 4.314,0
No. 23, No. 4,511,649, European Patent No. 249
, No. 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. 3725,067, Research Disclosure Nα24220 (June 1984), JP-A-60-3
No. 3552, Research Disclosure Nil 2
4230 (June 1984), JP-A-60-4365
No. 9, No. 61-72238, No. 60-35730,
No. 55-118034, No. 60-185951, U.S. Patent No. 4.500,630, No. 4.540.65
No. 4, No. 4,556,630, International Publication WO381
Particularly preferred are those described in No. 04795 and the like.

Cyan couplers include phenolic and naphthol couplers, and are described 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
4.011, 4.327,173, West German Patent Publication No. 3゜329,729, European Patent No. 121,365
No. 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.
No. 254212, No. 4.296.199, Japanese Unexamined Patent Publication No. 6
1-42658 and the like are preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat. Nos. 3,451,820; 4,080,211; 4,367.282;
No. 4,576°910, British Patent No. 2.102.
No. 137, European Patent No. 341°188A, etc.

Couplers whose coloring 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 Seed 17643.
-G term, -G term of Ni1307105, U.S. Patent No. 4,163,670, Japanese Patent Publication No. 57-39413, U.S. Patent No. 4.004.929, No. 4.138.25
No. 8, UK Patent No. 1,146.368 is preferred, and the fluorescent dye released upon coupling as described in U.S. Pat. No. 4,774,181 compensates for unwanted absorption of the chromogenic dye. Coupler, U.S. Patent Nos. 4 and 7
It is also preferable to use a coupler having as a leaving group a dye precursor group capable of forming a dye by reacting with a developing agent as described in No. 77,120.

Compounds that release photographically useful residues upon coupling can also be preferably used in the present invention.

DIR couplers that release development inhibitors include the Ro
17643, ■-F term and rotation 307105, ■-F
Patents described in Sections, JP-A No. 57-151944, JP-A No. 57-154234, JP-A No. 60-184248, JP-A No. 6
No. 3-37346, No. 63-37350, U.S. Patent 4
, 248,962 and 4,782,012 are preferred.

Couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent No. 2,097,140;
No. 2,131,188, JP 59-157638
No. 59-170840 is preferred.
Also, JP-A-60-107029, JP-A No. 60-2523
Compounds that release fogging agents, development accelerators, silver halide solvents, etc. through redox reactions with oxidized developing agents described in No. 40, JP-A-1-44940, and JP-A-1-45687 are also preferred.

Other compounds that can be used in the light-sensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4,130,427, U.S. Pat. , the multi-weight coupler described in JP-A-60-185950, etc.
DIR redox compound releasing couplers, DIR coupler releasing couplers, DI described in JP-A-6224252 etc.
R coupler releasing redox compound or DIR redonx releasing redox compound, European Patent No. 173°302
No. A, a coupler that releases a dye that recovers color after separation as described in No. 313,308A, R, D, Na 11449,
No. 24241, bleach accelerator releasing coupler described in JP-A-61-201247, etc., U.S. Patent No. 4,555,47
Ligand releasing coupler described in No. 7 etc., JP-A-63-7
Couplers that emit leuco dyes as described in US Pat. No. 5,747, and couplers that emit fluorescent dyes as described in US Pat.

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.

The boiling point at normal pressure used in the oil-in-water dispersion method is 175°C.
Specific examples of the above-mentioned high boiling point organic solvents include phthalic acid ester If (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis(2,4-di-t-amylphenyl) phthalate, bis(2,4-di-t-amyl phenyl) isophthalate, bis(1,1-diethylpropyl) phthalate, etc.), esters of phosphoric acid or phosphonic acid (triphenyl phosphate, tricresyl phosphate,
2-ethylhexynoldiphenyl phosphate, tricyclohexynorphosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tryptoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenyl phosphonate, etc.)
, benzoic acid esters (2, ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl-ρ-
hydroxybenzoate, etc.), amides (N,N-diethyldodecanamide, 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-diptyl 2-)toxy-5-tert-octylaniline), hydrocarbons M (paraffin, dodecylbenzene,
diisopropylnaphthalene, etc.).

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.

The steps and effects of latex dispersion methods and specific examples of latex for impregnation are described in U.S. Pat. has been done.

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 box 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 Nα17643, 647 of circular 18716
It is described from the right column of pages to the left column of page 648, and on page 879 of Nα307105.

In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28μ or less, more preferably 23μ or less, even more preferably 18μ or less, and 16μ or less. is particularly preferred, and the membrane swelling rate TI/Z is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness was measured at 25°C and 55% relative humidity (2
The membrane swelling rate TI/□ means the membrane thickness measured in days).
It can be measured according to techniques known in the art. For example, nee green (11,[;ree
Photogr, Sci, Eng
), 194', No. 2, pp. 5124-129, it can be measured by using a swellometer (swelling membrane), and TI/□ is measured when treated with a color developer for 13 minutes and 15 seconds at 30°C. The saturated film thickness is defined as 90% of the maximum swollen film thickness reached, and is defined as the time until the saturated Ill thickness of 172 is reached.

The membrane swelling rate TI/□ 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 photosensitive material of the present invention has a hydrophilic colloid layer (with a total dry thickness of 2 μm to 20 μm) on the side opposite to the side having the emulsion layer.
It is preferable to provide a back layer (referred to as a back layer), which includes the aforementioned light absorbers, filter dyes, ultraviolet absorbers, static inhibitors, hardeners, binders, plasticizers,
It is preferable to contain a lubricant, a coating aid, a surface active agent, etc., and the swelling ratio of this bank layer is preferably 150 to 500%.

The color photographic material according to the present invention can be produced by the conventional method described in the aforementioned RD, pages 28-29 of 17643, 651 left column to right column of 1B716, and pages 880-881 of Mafu 307105. It can be developed by

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-fuynylenediamine compounds are preferably used, representative examples of which include 3-methyl-4-amino-N, N-diethylaniline, 3- Methyl-4-amino-N-ethyl-N-β
-Hydroxyethylaniline, 3-methyl-4-agono-N-ethyl-Nβ-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-β-methoxyethylaniline and their sulfates, hydrochloric acid Examples include salts and p-toluenesulfonates. Among these, especially 3-methyl-4-amino-N-ethyl-N
β-hydroxyethylaniline sulfate is preferred. Two or more of these compounds can be used in combination depending on the purpose.

The color developer may contain phi buffers such as alkali metal carbonates, borates or phosphates, chloride salts, bromide salts,
It is common to include development inhibitors or antifoggants such as iodide salts, benzimidazoles, henzothiazurs or mercapto compounds. In addition, if necessary, various preservatives such as hydroxylamine, diethylhydroxylamine, sulfites, hydrazines such as N,N-biscarboxymethylhydrazine, phenyl semicarbazides, triethanolamine, catechol sulfonic acids, ethylene glycol, etc. , organic solvents such as 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 agent, aminopolycarboxylic acid, aminopolyphosphonic acid,
Various chelating agents such as alkylphosphonic acids and phosphonocarboxylic acids, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxoethyliminodiacetic acid, l-hydroxyethylidene-11- diphosphonic acid, nitrilo-N,N,N-)rimethylenephosphonic acid,
Typical examples include ethylenediamine-)1, N, N, N-tetramethylenephosphonic acid, ethylenediaminedi(O-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 dihydroxyhairzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol. It can be used alone or in combination.

The pi of these color developing solutions and black and white developing solutions is 9 to 12.
It is common that Although the amount of replenishment of these developing solutions depends on the color photographic light-sensitive material being processed, it is generally less than 31 per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher,
It can also be set to 0- or less. 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, the above aperture ratio is preferably 0.1 or less, more 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 liquid in the processing tank,
Method using a movable lid described in No. 033, JP-A-63
The slit development processing method described in Japanese Patent No. 216050 can be mentioned. Reducing the aperture ratio is important not only for both color development and black and white development processes, but also for subsequent processes,
For example, it is preferable to apply it to all steps such as bleaching, bleach-fixing, fixing, washing with water, 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 setting the pH to a high value and using a color developing agent at a high concentration.

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

The bleaching process may be carried out simultaneously with the fixing process (a white fixing process), or may be carried out separately. Furthermore, in order to speed up the processing, it is possible to use a processing method in which bleaching is followed by bleach-fixing, furthermore, processing in two consecutive bleach-fixing baths, fixing before bleach-fixing, or bleach-fixing. A post-bleaching treatment can also be optionally carried out depending on the purpose. As the bleaching agent, compounds of polyvalent metals such as iron (I), peracids, quinones, nitro compounds, etc. are used. Typical bleaching agents include organic complex salts of iron (l[l), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, chlorohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, etc. Aminopolycarboxylic acids or complex salts of citric acid, tetratalic acid, malic acid, etc. can be used. Among these, aminopolycarboxylic acid iron(I[) complex salts, including ethylenediaminetetraacetic acid iron(l[[) complex salt and 1,3-noaminopropanetetraacetic acid iron(III) complex salt], are suitable for rapid processing and prevention of environmental pollution. preferred from the viewpoint of In addition, iron aminopolycarboxylate (if
f) Complex salts are particularly useful in both bleach and bleach-fix solutions. These aminopolycarboxylic acid iron (I[
[) The pH of bleach or bleach-fix solutions using complex salts is usually 4.
．． 0-8, but lower p for faster processing
It can also be treated with H.

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their pre-bath, 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-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 as described in JP-A No. 53-124424, No. 53-141623, No. 53-28426, Research Disclosure No. 117129 (July 1978), etc.; JP-A-50-140129 Thiazuridine derivatives described in Japanese Patent Publication No. 45-8506, JP-A-52-20832, JP-A-53-32735, U.S. Patent No. 3,706,56
Thiourea derivatives described in No. 1; West German Patent No. 1,127.
No. 715, iodide salt described in JP-A-58-16.235; West German Patent No. 966.410, JP-A No. 2,748,43
Polyoxyethylene compounds described in No. 0; Japanese Patent Publication No. 1973
-Polyamine compound described in No. 8836; Other JP-A No. 4
No. 9-40,943, No. 49-59.644, No. 53
-94,927, 54-35.727, 55-
Compounds described in No. 26,506 and No. 58-163.940: bromide ions, etc. can be used. Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and are particularly preferred as described in U.S. Pat. No. 3,893,85
No. 8, West German Patent No. 1.290.812, Japanese Unexamined Patent Publication No. 1983-
The compounds described in No. 95,630 are preferred. Furthermore, the compounds described in US Pat. No. 4,552,834 are also preferred; these bleach accelerators may be added to the sensitive material. These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for photography.

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. In particular, 1m thioammonium can be used most widely. Further, a combination of thiosulfate, thiocyanate, thioether compound, thiourea, etc. is also preferred. As the preservative for the fixer and bleach-fixer, sulfites, bisulfites, carbonyl bisulfite adducts, or sulfinic acid compounds described in European Patent No. 294,769A are preferred. Furthermore, it is preferable to add various aminopolycarboxylic acids and organic phosphonic acids to the fixing solution and bleach-fixing solution for the purpose of stabilizing the solution.

In the present invention, the fixer or bleach-fixer contains a compound having a ρKa of 6.0 to 9.0 for pH adjustment, preferably imidazole, 1-methylimidazole, 1-ethyl-yodazole, 2-methyl-imidazole, and 2-methylimidazole. It is preferable to add 0.1 to 10 mol/l of imidazole such as dazole.

The total time of 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 ~
50°C, 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 desilvering process, it is preferable to strengthen the stirring as much as possible.A specific method for strengthening the stirring is to impinge a jet of processing liquid on the emulsion surface of a photosensitive material as described in JP-A-62-183460. Method and JP-A-62-183
No. 461 is a method of increasing the stirring effect using a rotating means, and furthermore, the stirring effect is further improved by moving the photosensitive material while bringing the emulsion surface into contact with a wiper blade provided in the layer to create turbulence on the emulsion surface. Examples include a method of increasing the circulation flow rate of the entire treatment liquid. Such means for improving agitation is effective for all bleaching solutions, bleach-fixing solutions, and fixing solutions. It is believed that improved 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 the photosensitive material conveying means described in Japanese Patent Application No. 191259. As described in the above-mentioned Japanese Patent Application Laid-Open No. 60-191257, such a conveying means can significantly reduce the carry-over of the processing liquid from the front bath to the rear bath, and is highly effective in preventing deterioration of the performance of the processing liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid 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 Volume 64, P, 24
8-253 (May 1955 issue).

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, as a solution to this problem,
The method for reducing carunium 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 Full volume of technology “Microbial sterilization, sterilization, and anti-mildew technology J (1982)
Society of Industrial Engineers, Japan Society of Antibacterial and Antifungal Agents [r Dictionary of Antibacterial and Antifungal Agents]
It is also possible to use the fungicides described in (1986).

The pH 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 in various ways depending on the characteristics of the photosensitive material, its use, etc., but generally it is in the range of 20 seconds to io minutes at 15 to 45°C, preferably 30 seconds to 5 minutes at 25 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. 57-854
All known methods described in No. 3, No. 58-14834, and No. 60-220345 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 the dye stabilizer that can be used include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts.

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

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

When each of the above-mentioned processing liquids undergoes 'a shrinkage' due to evaporation during processing using an automatic processor or the like, it is preferable to add water to correct the i4 shrinkage.

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 processing. In order to incorporate a color developing agent, it is preferable to use various precursors of the color developing agent. U.S. Patent No. 3,342.59
Indoaniline compounds described in No. 7, No. 3,342.
No. 599, Research Disclosure Sou 14, 85
0 and Nα15.159, aldolized metal compounds described in U.S. Pat. No. 13,924, metal salt complexes described in U.S. Pat.
Examples include urethane compounds described in No.-135628.

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

Typical compounds are JP-A-56-64339 and JP-A No. 57-
No. 144547 and No. 58-115438.

The various processing solutions used in the present invention are used at a temperature of 10°C to 50°C. Normally, the temperature is 33°C to 38°C, but higher temperatures may be used to accelerate the processing and shorten the processing time. Conversely, it is possible to improve the image quality and the stability of the processing solution by lowering the temperature.

Furthermore, the silver halide photosensitive material of the present invention is disclosed in US Pat.
, 500, No. 626, JP-A-60-133449,
It can also be applied to the heat-developable photosensitive materials described in Patent No. 59-218443, 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.

Example 1 (1) Preparation of emulsion (emulsion 1) 1,560 cc of gelatin aqueous solution (3
, 7%) and KBrSK with 900 cc of 15% silver nitrate aqueous solution while maintaining the pH at 6.4 silver potential (SCE) + 80 mV.
I is 0. 85. 0. Add an aqueous solution containing 031 mol/A over 50 minutes using a double jet.
was prepared. Next, compound A-2 as a sulfur sensitizer, sodium chloroaurate as a gold sensitizer, and compounds A-17 and 18 were added to this core emulsion at 4.7μ, 2.9μ, and 4.2μ, respectively, to this core emulsion.
Add ゜3■, 0.1■, pH 6.4, 5 at +80mV
Chemical sensitization was performed for 5 minutes. Here, A-16 and A-19 are each 0. 14g, 0. After adding 8g, lower the temperature to 50℃
and then add 100cc of 15% silver nitrate aqueous solution and KBr again.
(0,85moA/jri, KI (0,031mo
The aqueous solution containing f/j was adjusted to pH 6.4 + lO over 5 minutes.
The shell was characterized by mV addition to give a final size of 0.22 μm and an average silver iodide content of 3.5 mole %. The soluble silver salt was removed from this by ordinary flocculation to obtain emulsion 1.

(Emulsions 2 and 3) In Emulsion 1, the amount of silver nitrate aqueous solution used for core emulsion formation was reduced from 900 cc to 250 cc or 500 cc, and the amount of silver nitrate aqueous solution used for shell precipitation was reduced to 100 cc.
Emulsions 2 and 3 were obtained by changing the cc to 750cc or 500cc. At this time, the amounts of the sulfur sensitizer and sodium chloroaurate were 1.5 times and 1.3 times, respectively.

(Emulsion 4) Emulsion 4 was obtained by chemically ripening Emulsion 1 after removing the soluble silver salt and adjusting the pH to 6.4 without adding a chemical sensitizer before forming the shell. Ta.

(Emulsion 5, 6) Emulsion 1. Emulsion 5.6 was obtained by increasing the final size to 0.45 μm by adding NH, OH to the aqueous solution of Seratin in Step 4. At this time, the potential during formation of the core emulsion of Emulsion 5 and chemical sensitization of the core emulsion was lowered from +80 mV to +30 mV.

Emulsion 7: Add 6 g of potassium bromide and 30 g of inert gelatin to 3.0 g of distilled water.
While thoroughly stirring an aqueous solution dissolved in 71, a 14% aqueous potassium bromide solution and 2
0% silver nitrate aqueous solution at a constant flow rate for 1 minute,
Added at 55°C, pBrl, 0 (this addition (1
) a gelatin aqueous solution (which consumed 2.40% of the gold and silver amount in )
After adding 17%, 300') and stirring at 55°C, sulfurium hydroxide was added to adjust the pH to 9.0. Here, chloroauric acid and sodium thiosulfate were added and left to stand for 20 minutes (particle internal chemical sensitization). Then the pH was adjusted to 5.5,
A 20% silver nitrate aqueous solution was added at a constant flow rate until pBr reached 1.40 (this addition (n) added 5.0% of the amount of gold and silver).
became poor). Further, a 20% potassium bromide solution containing potassium iodide and a 33% silver nitrate aqueous solution were added over 80 minutes by a double jet method so that 8.3 g of potassium iodide was added. (This addition (In) consumed 92.6% of the total silver amount.) During this time, the temperature was kept at 55°C.
, pBr was maintained at 1.50. The amount of silver nitrate used in this emulsion was 425 g. Next, desalting was carried out by a normal flocculation method to obtain a flat Ag plate with an average particle diameter/particle thickness ratio of 6.5 and an equivalent sphere diameter of 0.8 μm.
BrI (Agl=2.0 mol%), emulsion 7 was prepared. These emulsion grains have a coefficient of variation of grain size distribution of 15
It was a monodisperse hexagonal tabular emulsion of less than %.

Emulsion 8 Emulsion 7 was subjected to addition (1) and (2) and desalting without internal grain chemical sensitization, and then gold and sulfur sensitized at pH 6, 4, and 60°C (the amount of sensitizer added was the same as in Emulsion 7). Each of 1.
2x, 1. 4 times) for 60 minutes to obtain Emulsion 8.

In addition, in Emulsions 4 and 8, the grain size and KI content were adjusted to the desired value by changing the addition rate of the silver nitrate aqueous solution and the ratio of KBr to KI in the aqueous solution containing KBr and Kl.

Preparation of Emulsions 9 and 10 A cubic silver bromide emulsion with an average grain size of 0.15 μm was prepared by the Chondrald double jet method and fogged with hydrazine and a total complex salt under low pAg (referred to as Emulsion 9).

0.025% silver bromide was added to the surface of emulsion A prepared in this way.
The emulsion with a shell having a thickness of μm is called emulsion 1O.

(2) Preparation of coated sample Preparation of sample 101 A multilayer color photosensitive material consisting of each layer having the composition shown below was prepared on an undercoated cellulose triacetate film support with a thickness of 127 μm and designated as sample 101. .

1st layer: Antihalation layer Black colloidal silver 0.25g/rrr Ultraviolet absorber U-10,04g/rd Ultraviolet absorber U-20,1g/rd Ultraviolet absorber U-30,1g/d High boiling point organic solvent 0 -1 0. 1 cc/rr
Gelatin layer containing f (dry film thickness 2μ) 2nd layer: Intermediate layer A-142,5■/Compound resistant H-10,05g/Po emulsion 9 Silver amount 0.05g/rrr High boiling point organic solvent 0-2 0 ．． Gelatin layer containing 0.05 cc/rrr (dry film thickness lμ) 3rd layer: 1st red-sensitive emulsion layer sensitizing dyes S-1 (0.47 μ/d) and S-2 (0.0
Monodisperse silver iodobromide emulsion spectrally sensitized with 2■/e)
Silver content: 0.15 g/rrr (Iodine content: 4 mol%, average particle size: 0°20 μm, coefficient of variation regarding particle size (hereinafter simply referred to as variation coefficient): 12%) Sensitizing dye S-1 (0,51■/d) and S-2 (0,0
3■ Monodisperse internal latent image type silver iodobromide emulsion spectrally sensitized with #) Silver amount: 0.20 g/rrr (Iodine content: 4 mol%, average grain size: 0°40 μm,
Distance from latent image to grain surface: 0°01 μm, coefficient of variation: 14%) Emulsion lO Silver amount -・-・0. 05 g/rrlA-
10,60■/E Compound H-60,O1g/rrr Coupler C-10,13g/rrf Coupler C-20,033g/rd Coupler C-100゜l g/d High boiling point organic solvent 0-2 0.02cc/ - gelatin layer (dry film thickness 0.7 μm) 4th layer: 2nd red-sensitive emulsion layer sensitizing dyes S-1 (1,1 /d) and S-2 (0,04
Monodisperse silver iodobromide emulsion spectrally sensitized with
Silver amount...0.53g/rr? (Iodine content 3
Mol%, average particle size 0°55μm1 coefficient of variation 16%
) A-40,02■/d Coupler C-10,40g/Bocoupler C-20,07g/nr Coupler C-90,05g/% High boiling point organic solvent 0-2 0. 22cc/rrr
gelatin layer (dry thickness 1.7μ) 5th layer: 3rd red-sensitive emulsion layer containing sensitizing dyes S-1 (1,1 /d) and S-2 (0,04
Monodisperse silver iodobromide emulsion spectrally sensitized with
Silver content: 0.53 g/m (Iodine content: 2 mol%, average particle size: 0°07 μm, coefficient of variation: 17%) A-71,2■/d Coupler C-60,35 g/rrr Coupler C -80,20g/rrr High boiling point organic solvent O-20,06cc/rrr Seratin layer (dry film thickness 1.8μm) 6th layer: Intermediate layer A-1010■/d A-115■/d Compound H- 10.1glrd High boiling point organic solvent 0-2 0. 1 cc/rr
gelatin layer (dry film thickness 1 μm) containing 7th layer: 1st green emulsion layer sensitizing dye S-3 (2,2 /nf) and S-4 (1,0
■ Monodisperse silver iodobromide emulsion spectrally sensitized with /r/) l
Silver amount...0.5g/rrf (Iodine content 3.
5 mol%, average particle size 0.22 μm, coefficient of variation 19
%) Emulsion Silver amount...0.05g/r
rrA-50,12■/Compound H-60,O1g/rrr Compound H-50,005g/lrr Coupler C-30,27g/% High-boiling organic solvent 0-2 0. 05cc/rrr
Gelatin layer containing (dry film thickness 0.7 μm) 8th layer: 2nd layer
Green-sensitive emulsion layer sensitizing dyes S-3 (0.29 g/rr?) and S-4 (0.29 g/rr?)
, 3■/rd') monodisperse silver iodobromide emulsion spectrally sensitized, 5 Silver amount...0. 5 g/m (Iodine content 3.5 mol%, average particle size 0.45μ
m, coefficient of variation 18%) A-60,2■/Po compound H-60,01g/Bocoupler C-30,2g/Bo High boiling point organic solvent 0-2 0. Gelatin layer containing 13 cc/m (dry film thickness 1.7 μm) 9th layer: 3rd green emulsion layer containing sensitizing dyes S-3 (0.9 g/rr?) and S-4 (0.9 g/rr?).
Tabular silver iodobromide emulsion spectrally sensitized at 3/rrr)
7 Silver content...0.5g/n ((Iodine content 2
Particles with a mole percent diameter/thickness ratio of 6°5 or more account for 50% of the total particle projected area. Average thickness of particles 0.20
μm) A-21,5■/Pocoupler C-40,2g/PoHigh boiling point organic solvent 0-2 0. 03cc/rr?
Gelatin layer containing (dry film thickness 1.7 μm) 1st O layer: Intermediate layer compound H-40, 1glrd High boiling point organic solvent 0-2 0. 1 cc/rr
Gelatin layer containing r (dry film thickness 0.05 μm) 11th layer: Yellow filter layer Yellow colloidal silver Silver amount 0.12 g/rrl' Compound A-150, 22 g/rr? Compound H-10.02g/Compound resistance H-20.03g/i High boiling point organic solvent 0-2 0. 04cc/rr?
Gelatin layer containing (dry film thickness 1 μm) 12th layer, 1st blue-sensitive emulsion layer Tabular silver iodobromide emulsion spectrally sensitized with sensitizing dye S-5 (1.0 g 1rd) Amount of silver... ...0.6 g/rrr (Grains with an iodine content of 3 mol% and a diameter/thickness ratio of 7 or more occupy 50% of the projected area of all grains. Average grain thickness 0.10 μm) Emulsion A Silver amount 0 .1
g/rrfA-70.5mg/rr? Coupler C-50,5glrd High boiling point organic solvent 0-2 0. 1 cc/rr
? Gelatin layer containing (dry thickness 1.5 μm) 13th layer: 2nd blue-sensitive emulsion layer Tabular silver iodobromide emulsion spectrally sensitized with sensitizing dye S-5 (2, Og/rrr) Silver amount・・・・・・1. 1 g/r+? (Particles with an iodine content of 2.5 mol% and a diameter/thickness ratio of 7 or more occupy 50% of the projected area of all particles.The average thickness of the particles is 0.1
5μm) A-1210■/d Coupler C-71, 2g/rd Coupler C-80, 2g/bo Gelatin layer containing high boiling point organic solvent 0-2 0.07cc/rd (dry film thickness 3μm) 14th layer: 1st protective layer A-130,10■/d Ultraviolet absorber U-10,02g/rd Ultraviolet absorber
U-20.03g/rr? Ultraviolet absorber U-30,0
3g/rrr Ultraviolet absorber U-40, 29g/rrr
Koroten organic solvent 0-2 0. Gelatin layer containing 28 cc/% (dry film thickness 2 μm) 15th layer, fine grain silver iodobromide emulsion covered with the surface of the second protective layer Silver amount: 0. 1 g/i (Iodine content 1 mol%, average particle size 0°06 μm) Yellow colloidal silver Silver amount...0.01 g/r
rrA-810■/bopolymethyl methacrylate particles 0.1g/rr? (
Average particle 1. 5μ) A-30,2g/1ri A-91,0@/rd gelatin layer (dry film thickness 0.8μm) In addition to the above composition, each layer contains antifoggant A-16 and gelatin hardener H. -3, and a surfactant were added.

The compounds used to prepare the samples are shown below.

-3 CH.

-5 COOCs　Ht(iso) OOH U-4 t-C, H9 t-Ct H9 H -3 CH2 CH3O, CH2C0NHCH2 CH,=CH3O, CH2C0NHCH.

○H H H H -2 -4 S -1 -4 -9 2Hs C@F+tSO2NCH,C00K C,Hl -12 13 -15 0sNa H 9 H -N Preparation of samples 102 to 119 Emulsion l used for green-sensitive layer , 5.7 were replaced as shown in Table 1 to prepare samples 102 to 119.

In addition, the compounds shown in Table 1 were added to each layer of each sample.

The amount added is expressed as a weight ratio to gelatin in each layer.
The unit was ppm.

A portion of the emulsion for the first O layer used in preparing these samples was infected at the same concentration with bacteria decomposed from the spoiled gelatin solution.

To promote biological production, the infected test emulsions were kept at 37° C. and the viscosity was measured after 2 and 4 days. The results are shown in Table 1.

After the silver halide color photographic light-sensitive material prepared as described above was exposed, it was processed using an automatic processor according to the method described below until the cumulative amount of liquid replenishment reached three times the tank capacity.

Treatment process Time Temperature Tank capacity Filling stage
Development 6 minutes 38°C12II 2200m
//m” 1st water wash 45 seconds 38/12〃2200
〃Reversal 451/38ノ/2 ノ' 1
100/1 color development 6 minutes 38/1121122
00/l bleaching 2〃 38//
4 l/860 〃Bleach fixing 41138
118〃1100/l Second washing (1) l〃38ノ/
21/----Second water washing (2) 1/138〃21111
00 Stable l25112/1l100/l
Drying l// 65" ----------Here, to replenish the second water wash, introduce the replenisher solution to the second water wash (2), and transfer the overflow liquid from the second water wash (2) to the second water wash (1). A so-called countercurrent replenishment method was adopted, which leads to

The composition of each treatment liquid was as follows.

Nitrilo-N, N, N4 Lime 2. Og 2.0g
Tyrenephosphonic acid pentasodium salt Sodium sulfite 30g 30g Hydroquinone monosulfone 20g 20g Potassium acid potassium carbonate 33g 33g1
-Phenyl-4-methyl-42.0g 2.0g Hydroxymethyl-3-pyrazolidone Potassium bromide 2.5g 1.4
g Potassium thiocyanate 1.2g 1.
2g potassium iodide 2.0■ -m-
Add 1000 d 100
0 pH 9,609,60 pH is ethylenediaminetetramethylene adjusted with hydrochloric acid or potassium hydroxide 2. Add 5.0g of Ogne phosphonic acid phosphate disodium
1000 dpH 7,00 The same pH of the mother liquor was adjusted with hydrochloric acid or sodium hydroxide.

Nitrilo-N, N, N-trime 3. Og tyrenephosphonic acid pentatrilam salt stannous chloride dihydrate 1. Ogp-aminophenol 0.1g Sodium hydroxide
Add 8g glacial acetic acid 15- 1000 +Jp H6,
00 pH was adjusted with hydrochloric acid or sodium hydroxide.

Same nitrilo-N,N,N-trimethylenephosphonic acid, 5-sodium salt, sodium sulfite, trisodium phosphate, decahydrate 2.0 g 2.0 g 7.0 g 6 g 7.0 g 6 g Potassium bromide 1.0 g Potassium iodide 90 ■ Sodium hydroxide
3.0g 3.0g Citrazic acid
1.5g 1.5gN-ethyl-N-(β-
Methane Ilg l1g sulfonamidoethyl)-
3 Monomethyl-4-aminoaniline sulfate 3.6-cythiaoctane-1. 1. Og 1.0
Add g8-diol and make 1000 ydloooo
dpH 11,8012,00 pH was adjusted with hydrochloric acid or potassium hydroxide.

Ethylenediaminetetraacetic acid, 2 10.0g Sodium salt, dihydrate Ethylenediaminetetraacetic acid, Fe 120g (II[)
- Ammonium dihydrate Ammonium bromide too g Same ammonium nitrate bleach accelerator in mother liquor 0 g O, 005 mol pH pH 6,30 The pH was adjusted with hydrochloric acid or aqueous ammonia.

Ethylenediaminetetraacetic acid・re 50g(〉・Ammonium・dihydrate ethylenediaminetetraacetic acid・2 5.0g sodium・
Add 80 g of ammonium thiosulfate dihydrate and 12.0 g of sodium sulfite.
1000 WTl pH 6,60 pH was adjusted with hydrochloric acid or aqueous ammonia.

Hoshi Nihon Ituma Use tap water for both mother liquid and replenisher liquid.
type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Andhaas Co., Ltd., which has the same mother liquor as the Rohm mother liquor),
OH type anion exchange resin (Amberlite IR-40)
Water was passed through a mixed bed column packed with 0) to reduce the concentration of calcium and magnesium ions to 3 μ/l or less, and then sodium dichloride isocyanurate 20 μ/1 and sodium sulfate 1.5 g/l were added. Added. The pH of this solution is 6
．． It is in the range of 5 to 7.5.

Formalin (37%) Polyoxyethylene-p-monononylphenyl nityl (average degree of polymerization 10) was added to pH 5, 〇-to the mother liquor the same 0.5-1000 m/addition of the present invention from Table 1 without adjustment. By introducing these substances, the viscosity of the emulsion does not decrease as the emulsion ages due to putrefaction. Furthermore, although the change in D max after storage becomes large, it can be seen that by introducing the emulsion of the present invention, the change in D wax can be reduced and the sensitivity can also be improved.

In Example 1, the results were shown only for the green-sensitive layer, but similar results were obtained for the red-sensitive layer and the blue-sensitive layer.

Example 2 On a subbed cellulose triacetate film support,
Sample 201, which is a multilayer color photosensitive material, was prepared by applying layers having the compositions shown below.

(Photosensitive layer composition) The numbers corresponding to each component indicate the coating amount expressed in g/g units, and for silver halide, the coating amount is expressed in terms of silver. However, for sensitizing dyes, the coating amount is expressed in moles per mole of silver halide in the same layer.

(Sample 201) 1st layer (antihalation layer) Black colloidal silver Silver 0° gelatin
1° Second layer (intermediate layer) 2.5-di-t-pentadecylhydroquinone 0°EX-10°EX-30°EX-120,0 U-IQ.

U-2Q.

U-30゜ HBS-10゜ HBS-20° Gelatin l.

No. 371 (first red-sensitive emulsion layer) Emulsion A Silver 0° emulsion B
Silver 0°sensitizing dye I
6. 9X18 0 5 5 -5 Sensitizing dye ■ Sensitizing dye ■ EX-2 EX-10 -1 -2 -3 B5-1 Gelatin 4th layer (second red-sensitive emulsion layer) Emulsion G Sensitizing dye ■ Sensitizing dye ■ Sensitizing dye ■ EX-2 EX-3 EX-10 -1 -2 -3 1,8X10-' 3, lX10-' 0, 335 0, 020 0, 07 0, 05 0, 07 0, 060 0, 87 Silver 1.0 5, lXl0-'1.4X10-'2.3X10-' 0, 400 o, o s.

O,015 0,07 0,05 0,07 gelatin 5th layer (3rd red-sensitive emulsion layer) Emulsion D Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ EX-3 EX-4 EX-2 B5-1 B5-2 gelatin 6th layer (middle layer) EX-5 B5-1 gelatin 7th eyebrow (1st green emulsion layer) Emulsion A Emulsion B Sensitizing dye V silver 1.60 5.4XlO-' 1.4XIQ-' 2.4X10-' 0,010 o, os.

O,097 0,22 0゜ 10 1,63 0,040 0,020 0,80 Silver O1 Silver 0゜3.0X10-' Sensitizing dye■ Sensitizing dye■ X-6 X-1 X-7 X- 8 B5-1 B5-3 Gelatin 8th layer (second green emulsion layer) Emulsion C Sensitizing dye V Sensitizing dye ■ Sensitizing dye ■ X-6 X-8 X-7 B5-1 B5-3 Gelatin i , oxto-' 3, 8X10-' 0, 260 0, 021 0, 030 0, 025 0, 100 0, 0 10 0, 63 Silver 0.45 2, lXl0-'7.0X10-'2.6X10-' 0,094 0.018 0,026 0,1 60 o, o o s Oo 50 9th layer (third green-sensitive emulsion layer) Emulsion E! 1° Sensitizing Dye V 3 5X1 Sensitizing Dye VI
8. OX1X1 sensitization ■
3. 0・11th layer (first blue-sensitive emulsion layer) Emulsion A Silver 0° emulsion B
Silver 0° emulsion F
Silver 0゜8 7 7 Sensitizing dye ■ X-9 X-8 B5-1 Gelatin 12th layer (second blue-sensitive emulsion layer) Emulsion G Sensitizing dye ■ X-9 X-10 B5-1 Gelatin 13th layer (Third blue-sensitive emulsion layer) Emulsion H Sensitizing dye ■ 0.45 2, lX10-' 0,1 54 0,007 0,05 0,78 Silver 0.77 2.2X10-' 0,20 0,07 0,69 Silver 0.20 U-40,11 U- 50,17 HBS-10,05 Gelatin 1.00 15th layer (second protective layer) Polymethyl acrylate particles (diameter approximately 1.5 μm) 0.548-1
0.20 gelatin
1.20 In addition to the above ingredients, each layer contains gelatin hardening agent H1, gelatin preservative/moldproofing agent 1, 2
-Benzisothiazolin-3-one, 2-phenoxyethanol, phenethyl alcohol and a surfactant were added.

In the above table, Emulsion A is different from Emulsion 4 in Example 1 (average A
gI content of 3.5 mol%, average particle size of 0.45 μm), the core particle formation stage is divided into two, and the first stage is KBr.
, the concentration of the Kl aqueous solution was 0, 766 mol/1.0.
115 mol/C The second stage concentration was 0. 872mol
/CO,009 mol/1 to obtain a double structure particle with core/shell=1/3.

The amounts of NH and OH added at this time were increased four times. Regarding other emulsions, the concentration of KBr, Kl aqueous solution, N
By adjusting the amounts of H and OH added, emulsions having the characteristic values shown in the table above were prepared.

Preparation of samples 202 to 212 Among the emulsions used in sample 201, emulsions B and G.

Emulsions J and K were obtained by chemical sensitization after adding 95% of the A g N Os aqueous solution used for grain formation in D, and then further forming a shell portion.

L was prepared. Samples 202 to 212 were prepared by using Emulsion J in place of B, G, and D, and adding the compounds of the present invention as shown in Table 2.

Changes in emulsion viscosity were measured for these samples in the same manner as in Example 1. The results are shown in Table 2.

The compounds used for sample preparation are shown below.

X-1 X-3 X 4 X X X CH.

CH3 X-11 CH.

X-12 C2H.

C,H.

C2Hf　03Os.

X 3 4 (t)C4He (t) C, Hs x:y=70:30 (wtX) V-5 B5-1 tricresyl phosphate B.S. Di-n-butyl phthalate B5-3 Sensitizing dye■ Sensitizing dye■ Sensitizing dye V Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ H-1 CH2=CH 8o2-CH2-CONH CH.

CH2=CH-8o, -CH2 0NH CH.

The photographic element was exposed to 25 CMS using a tungsten light source with a color temperature adjusted to 4800°K with a filter, and then processed at 38°C according to the processing steps described below.

Color development 3 minutes 15 seconds Bleach White 6 minutes 30 seconds Water Wash 2 minutes 10 seconds Fixed arrival time: 4 minutes 20 seconds Water wash 3 minutes 15 seconds Stable 1 minute 05 seconds The composition of the treatment liquid used in each step was as follows.

Color developer diethylenetriaminepentaacetic acid 1.0 g 1-hydroxyethylidene 1, I-diphosphonic acid 2.0 g Sodium sulfite 4.0, potassium carbonate
30.0g potassium bromide
1.4g potassium iodide
1.3■ Hydroxylamine sulfate 4-(N-ethyl-N~β-hydroxyethylamino)-2 Add methylaniline sulfate water and add 2° 4.5 g 1.01 pH 10° Bleach solution Ethylenediaminetetraacetic acid 2nd Iron ammonium salt 100゜Disodium ethylenediaminetetraacetate 10゜Ammonium bromide 150゜Ammonium nitrate
10° Add water 1° pH 6° Fixer ethylenediaminetetraacetic acid disodium salt sodium sulfite ammonium thiosulfate aqueous solution l.

4.0g 175.0i (70%) Add sodium bisulfite water to pH stabilized formalin (40%) Polyoxyethylene-p-7nononylphenyl ether (average degree of polymerization 10) Add water to make 1nl (Example 3) Preparation of Sample 301 A multilayer color light-sensitive material consisting of each layer having the composition shown below was prepared on an undercoated cellulose trihedral film support having a thickness of 127 μm, and designated as Sample 101. The numbers represent the amount added per d. Note that the effects of the added compound are not limited to the described uses.

1st layer: Antihalation layer Black colloidal silver 0.25g Gelatin 1.9g Ultraviolet absorber U-1
0,04g Ultraviolet absorber U-20,1g Ultraviolet absorber U-30,1g Ultraviolet absorber U-40,1g Ultraviolet absorber U-60,Ig High boiling point organic solvent 0i1-10.1g 2nd layer: Intermediate layer Gelatin 0.40g Dye D
-40,4■ Third layer: Fine-grain silver iodobromide emulsion covered with the surface and inside of the intermediate layer (average grain size 0.06 μm, coefficient of variation 18%, Agr content 1 mol%)
) Silver amount 0.05g Gelatin 0.4g 4th layer: Low sensitivity red-sensitive emulsion layer Emulsion A Silver amount 0.2g Emulsion B
Silver amount 0.3g gelatin
0.8g Coupler C-10.15g Coupler C-20.05g Coupler C-90.05g Compound Cpd-D 10 ■High boiling point organic solvent 0i1-20.1g 5th Mi: Medium-sensitivity red-sensitive emulsion layer Emulsion B Silver amount 0 .2g Emulsion C Silver amount 0.3g Gelatin 0.8g Coupler C
-10,2g Coupler C-20,05g Coupler C-30,2g High boiling point organic solvent ○1l -20.1g 6th layer: High sensitivity red-sensitive emulsion layer Emulsion D Silver amount 0.4g Ceratin
1.1g coupler C-30,7
g Coupler C-10.3g Additive P-10.1g 7th layer 2 middle layer Seratin 0.6g Additive M
-10.3g Color mixing prevention agent Cpd-K 2. 6 ■Ultraviolet absorber U-10.1g Ultraviolet absorber U-60.1g Dye D-10.02g 8th layer Silver iodobromide emulsion covered with the surface and inside of the intermediate layer (average grain size 0.
06 μm, coefficient of variation 16%, AgI content 0.3 mol%
) Silver amount 0.02g Seratin
L, 0g additive P-1 d Color inhibitor Cpd-J Color mixing inhibitor Cpd-A 9th layer: Low-sensitivity green-sensitive emulsion layer Emulsion E Emulsion F Emulsion G Gelatin coupler C-4 Coupler C-7 Coupler C-8 Compound Cpd-B Compound Cpd-E Compound Cpd-F Compound cpa-c; Compound Cpd-H Compound cpa-D High boiling point organic solvent 0i1-1 High boiling point organic solvent 011-2 10th layer: medium-sensitivity green-sensitive emulsion layer 0 .2 0.1 0.1 Amount of silver 0.3 g Amount of silver 0.1 g Amount of silver 0.1 g 0,5 g 0,2 g 0,1 g 0.1 g 0.03 g 0.02 g 0.02 g 0. 02g 0.02g 0mg o, 1 g oyt g Emulsion G Silver amount Emulsion H Silver amount Gelatin Coupler C-4 Coupler C-7 Coupler-C-8 Compound Cpd-B Compound Cpd-E Compound Cpd-F Compound Cpd-G Compound Cpd-H High-boiling organic solvent 0i1-2 11th layer: High-sensitivity green-sensitive emulsion layer Emulsion ■ Silver amount Ceratin Coupler C-8 Coupler C-4 Compound Cpd-B Compound Cpd-E Compound Cpd-F g g g g g g 3g 2g 2g 5g 5g 1g g g g g 8g 2g 2g Compound cpa-c Compound Cpd-H High boiling point organic solvent 0i1-1 High boiling point organic solvent 0i1-2 12th layer, middle layer gelatin dye D-2 Dye D -1 Dye D-3 13th layer: Yellow filter layer Yellow colloidal silver Silver amount Gelatin Color mixing inhibitor Cpd-A High boiling point organic solvent Oi1-1 14th layer: Intermediate layer Gelatin 15th layer: Low sensitivity blue-sensitive emulsion layer Emulsion J Silver amount emulsion K Silver amount emulsion L Silver amount 2g 2g 2g 2g g 5g g 7g g g 1g 1g Seratin coupler C-5 16th layer: Mid-sensitivity blue-sensitive emulsion layer Emulsion L Silver amount emulsion M Silver amount gelatin coupler C -5 Coupler C-6 17th layer: High sensitivity blue-sensitive emulsion layer Emulsion N Silver amount gelatin 0, 8 g 0.6 g Coupler C-6 18th layer: 1st protective layer gelatin UV absorber U-1 UV absorption Agent U-2 Ultraviolet absorber U-3 Ultraviolet absorber U-4 Ultraviolet absorber U-5 Ultraviolet absorber U-6 g 4g 1g 3g 3g 5g 5g High boiling point organic solvent Oi1-1 Formalin scavenger pd-c pd -I Dye D-30.05g 19th layer: 2nd protective layer colloidal silver Silver amount fine grain silver iodobromide emulsion (average grain size 0°AgI content 1 mol%) Silver amount gelatin 20th layer: 3rd protective layer gelatin O. Polymethyl methacrylate (average particle size l.

0゜4 copolymer of methyl methacrylate and acrylic acid (average particle size 1.5μ) 0゜Silicone oil O3 surfactant W
-13゜Surfactant W-20゜Ol 0゜2g g 5μ) g: 6g 3g O■ 3g 0゜0, 1 ■ 06μm1 0.1g 0.4g Also, all the emulsion layers contain the above composition. In addition, additive F-1
-F-7 was added. Furthermore, in addition to the above composition, a ceratin curing agent H-1 and coating and emulsifying surfactants W-3 and W-4 were added to each layer.

The silver iodobromide emulsion used in sample 301 is as follows.

Spectral sensitization of emulsion A-N S-6 Oo 6 Preparation of sample 302 after grain formation Sample 302 contains phenol as a preservative and anti-mold agent in each layer of sample 301. 2-benzisothiazolin-3-one, 2-phenoxyethanol, and phenethyl alcohol were added.

The above samples were treated in the same manner as in Example 1.

As a result, sample 302 was better than sample 301 in both the storage stability and sensitivity of the photosensitive material.

l -2 -5 -7 I s　nu -9 11-1 dibutyl phthalate i1 tricresyl phosphate H pd B pd pd CH2-CH.

H pd 2H5 pd-F pd pd-1 pd pd Hh H 5 2H5 C2H.

So, K SO, to So, K So, K So+Na ■ CH2 CH3O, CH2C0NHCH.

CH.

CH302CH, C0NHCH2 C,F,,So,NCH,C00K C,H.

CH,C00CH2CH(C2H5)C,H.

NaO+ 5 CHCOOCR2CH(C2Ha)C,H.

■ ■ PCH.

CI day C0NHC,H.

Go CH2 CH Chi C00C,H.

○H HN○.

Procedural amendment ( spontaneous) flat bottom 2 years cormorant 2nd day of the month 1゜ Display of incidents 1990 Patent No. 28945 2゜ name of invention Silver halide photographic material 3゜ person who makes corrections Relationship with the incident

Claims (1)

[Scope of Claims] In a silver halide photographic material having at least one light-sensitive silver halide emulsion layer on a support, a maximum value of the latent image distribution of silver halide emulsion grains contained in the emulsion layer is provided. A halogen located at a depth of less than 0.03 μm from the particle surface, and further characterized in that the photosensitive material contains at least one of the compounds represented by the general formulas [I] to [IV]. Silver chemical photographic material. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_1 represents an unsubstituted or substituted alkylene group, and X is a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, a cyano group, a lower alkyl group, Lower alkoxy groups, aryl groups, alkenyl groups, sulfonyl groups, aralkyl groups, -COR_2, ▲Mathematical formulas, chemical formulas, tables, etc.▼-
Represents SO_3M, R_2 is a hydrogen atom, -OM, lower alkyl group, aryl group, aralkyl group, lower alkoxy group, aryloxy group, aralkyloxy group, ▲ formula,
There are chemical formulas, tables, etc. Represents ▼. R_3 and R_4 are each a hydrogen atom, a lower alkyl group, an aryl group, an aralkyl group, -COR_7, -SO_2R_
Represents 7 and may be the same or different from each other,
R_5 and R_6 each represent a hydrogen atom, a lower alkyl group, an aryl group, or an aralkyl group, and may be the same or different from each other, R_7 represents a lower alkyl group, an aryl group, or an aralkyl group, and M is hydrogen Represents atoms, alkali metal atoms, and atomic groups necessary to form monovalent cations. Further, m represents an integer from 0 or 1 to (6-n), and n represents an integer from 1 to 6. If m and n are 2 or more,
Each of the above groups may be the same or a plurality of them may be combined. General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_8 is a hydrogen atom, an alkyl group, an alkenyl group,
Aralkyl group, aryl group, heterocyclic group, ▲Mathematical formulas, chemical formulas, tables, etc. are available▼, ▲Mathematical formulas, chemical formulas, tables, etc. are available▼, where R and R are hydrogen atoms, alkyl groups, aryl groups, and cyano groups, respectively. , heterocyclic group, alkylthio group, alkylsulfoxy group,
It represents an alkylsulfonyl group, and R_9 and R_1_0 may be bonded to each other to form an aromatic ring. R_1_1 and R_1_2 are each a hydrogen atom, an alkyl group,
Represents an aryl group or an aralkyl group. General formula [III] ▲There are numerical formulas, chemical formulas, tables, etc.▼ In the formula, R_1_3 represents a hydrogen atom, an alkyl group, or a hydroxymethyl group, and R_1_4 represents a hydrogen atom or an alkyl group. General formula [IV] ▲ Numerical formulas, chemical formulas, tables, etc. ▼ In the formula, Y is a halogen atom, nitro group, hydroxy group, cyano group, lower alkyl group, lower alkoxy group, aryl group, alkenyl group, sulfonyl group, aralkyl group group, -C
OR_1_5, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -
SO_3M'', R_1_5 is a hydrogen atom, -OM''
, lower alkyl group, aryl group, aralkyl group, lower alkoxy group, aryloxy group, aralkyloxy group,
▲There are mathematical formulas, chemical formulas, tables, etc.▼ Represents. R_1_6 and R_1_7 are each a hydrogen atom, a lower alkyl group, an aryl group, an aralkyl group, -COR_2_0, -
SO_2R_2_0, which may be the same or different from each other; R_1_8 and R_1_9 each represent a hydrogen atom, a lower alkyl group, an aryl group, or an aralkyl group, and may be the same or different from each other; R_2_
0 represents a lower alkyl group, aryl group, or aralkyl group, M' and M'' represent a hydrogen atom, an alkali metal atom, and an atomic group necessary to form a monovalent cation; p is an integer from 1 to 5; and when p is 2 to 5, Y may be the same group or a combination of two or more of the above groups.