JPH01166039A - Silver halide color reversal sensitive material - Google Patents

Abstract

PURPOSE:To improve graininess of a silver halide color reversal sensitive material and to increase its sensitivity by providing a photosensitive silver halide photographic layer contg. a specified amt. of AgI on a base body, wherein at least one emulsion layer of the photographic layers is constituted of >=two kinds of emulsion consisting of particles having a mean particle size within a specified range. CONSTITUTION:The title material is constituted of a photosensitive silver halide photographic layer comprising photosensitive silver halide emulsion having <7.0mol.% mean AgI content on a base body, wherein at least one emulsion layer of the photographic layers consists of >=two kinds of emulsion having different particle sizes within a range of 0.05-3.0mu. There are >=two maxima in a particle size distribution curve of the silver halide particles, wherein difference between the particle size at the smallest maximum of the particle size and that at the next smallest maximum of the particle size is >=0.1mu, among each maximum. At least one kind of coupler, development accelerator, or a solvent for silver halide or a compd. liberating its precursor, is contained in the emulsion layer and/or in its adjacent intermediate layer, depending on the amt. of silver to be developed generated by an oxidation-reduction reaction or reactions succeeding thereto with a reaction product, with a developing agent. Thus, the title material having highly increased sensitivity and graininess is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide color reversal photosensitive material that is highly sensitive and has excellent graininess.

(Prior art) In recent years, silver halide color reversal photosensitive materials are required to have increasingly high image quality. It is necessary to improve the

Among these, improving graininess has become extremely important as photosensitive materials such as films are becoming smaller in format.
Many studies have been carried out to improve this graininess.

For example, in JP-A-57-178235, two or more types of monodispersed emulsions are used so that the particle size distribution curve has two or more maxima (mountains) in one layer, and A highly sensitive silver halide photographic material with excellent graininess is disclosed in which the distance between the largest moat and the next largest moat is 0.3 l or more. However, according to the research conducted by the present inventors, this method was not sufficiently satisfactory for achieving high sensitivity at the same time as improving graininess.

In addition, regarding high contrast and high sensitivity, JP-A-60-10
No. 7029 discloses a technique in which at least one layer contains a compound that releases a fogging agent under alkaline conditions through a redox reaction with an oxidized developer during development. However, although this technology is very effective in increasing sensitivity,
Graininess tends to deteriorate slightly.

Regarding the improvement of graininess, Japanese Patent Application Laid-Open No. 158435/1983 describes that at least 20% of the total projected area of all the silver halide grains in at least one layer have an average value of projected area equivalent diameter of 0.
Contains silver halide grains with a diameter of 5μ or less, at least 20% of the total projected area contains silver halide grains with an average projected area equivalent diameter of 0.71L or more, and the amount of developed silver during development. It is disclosed that graininess can be improved without increasing fog by containing a compound that releases a fogging agent, a development accelerator, or a precursor thereof.

(Problems to be Solved by the Invention) However, when the technique described in JP-A-60-158435 is applied to a halogenated color reversal photosensitive material that provides a color reversal image, it is necessary to increase the sensitivity and improve the graininess. The problem was that it could not be achieved.

Accordingly, the first object of the present invention is to provide a silver halide color reversal photosensitive material that forms color reversal images with improved graininess.

A second object of the present invention is to provide a silver halide color reversal photosensitive material that is highly sensitive without impairing the graininess of a color reversal image.

(Means for Solving the Problems) An object of the present invention is to provide a photosensitive silver halide photographic layer on a support in which the average silver iodide content of the photosensitive silver halide emulsion is less than 7.0 mol%. and at least one emulsion layer of the photographic layer has an average grain size of 0.05 to 3, o#1. The grain size distribution curve of the silver halide grains is composed of two or more types of emulsions with different grain sizes within the range of The difference in particle size between the smallest particle size and the maximum particle size is 0.1 μ or more, and the emulsion layer and/or its adjacent intermediate layer contains a redox reaction with a developer oxidation product or a subsequent reaction of the reaction. This was achieved by a silver halide color reversal light-sensitive material characterized by containing at least one compound that releases a fogging agent, a development accelerator, a silver halide solvent, or a precursor thereof in accordance with the amount of developed silver. .

In the present invention, the average silver iodide content of the light-sensitive silver halide photographic layer provided on the support is usually less than 7.0 mol%,
Preferably 1.0 to 6.5 mol%, more preferably 1.
It is in the range of 5 to 6.0 mol%. Here, the term "photographic layer" refers to a plurality of coated layers consisting of light-sensitive silver halide emulsion layers with different spectral sensitivities, which contribute to the formation of a color photographic image and are mutually permeable to a developing solution, and a protective layer. , including the middle layer or not including the back layer.

The development process for color reversal photosensitive materials is black and white development → reversal (or optical fogging) → color development → adjustment → bleaching → fixing → washing →
It consists of a stabilization process. In the above black and white development, the developer is
In general, a large amount of silver halide solvent is contained, and color reversal light-sensitive materials are developed while the silver halide is dissolved.However, if the silver iodide content of the silver halide in the emulsion exceeds 7 mol%, the above-mentioned black-and-white development occurs. Since it becomes difficult to dissolve in the film, development progresses slowly and the desired increase in sensitivity and improvement in graininess cannot be achieved.

In the present invention, at least one of the light-sensitive silver halide photographic layers has a particle size distribution curve having two or more maxima, and the internal liquid of each of the maxima also includes a maximum with a small particle size and a maximum with a next small particle size. The difference in particle size between It consists of photosensitive silver halide emulsion grains of IIL or higher, which may be composed of two or more types of polydisperse emulsions with different grain sizes, but preferably contain at least one type of monodisperse emulsion, and the average It is more preferable that the silver halide emulsion having the smallest grain size is a monodisperse emulsion. Most preferably, the emulsion is composed of monodisperse emulsions having different average particle sizes.

The average grain size here means the diameter in the case of spherical silver halide grains, or the diameter when the projected image is converted into a circular image of the same area in the case of grains with shapes other than cubic or spherical. In the case of a tabular emulsion, it is the average value of the diameter when the volume is converted to a sphere equivalent, and the individual grain size is ri and the number is ni. When,
The average particle diameter f is defined by the following formula.

Σn1ri Σni In the present invention, the average grain size of at least one silver halide emulsion layer in the photosensitive silver halide emulsion layer is 0.05 to 3.
It is 0 river. When the average particle size is smaller than 0.05,
The particles tend to dissolve during the development process, and no improvement in graininess is observed, and when it exceeds 3.0 liters, the graininess deteriorates. The average grain size of the silver halide emulsion in the present invention is preferably in the range of 0.1 to 2.5 l, more preferably in the range of 0.15 to 2.0 l. Among the two or more local maxima of the particle size distribution curve of the present invention, the local maximum having the smallest particle size,
The difference in particle size from the next smallest particle size is 0.15 to 1
．． It is preferable that it be in the range of 0 liters.

Furthermore, a monodisperse emulsion is one in which the value obtained by dividing the standard deviation S defined by the following formula by the above average grain size 7 is 0.20 or less.

Σni　　　　　　r Hereinafter, -x 100 will be referred to as the coefficient of variation (%).

During the development used in the present invention, a fogging agent or a development accelerator (hereinafter referred to as rFAJ
A redox compound (hereinafter referred to as an FR compound) that releases a compound (hereinafter referred to as an FR compound) or a precursor thereof is represented by the general formula (I).

General formula (I) RED-(TIME)-FA In the formula, RED represents a compound residue capable of redox reaction with an oxidized form of a developer.

-(TIME)-FA is bound to a device composed of RED by a redox reaction with an oxidized developer or a subsequent reaction thereof.

TIME represents a timing group that further releases FA after being detached from RED by a coupling reaction.

n represents 0 or 1, and when n is 0, FA is a group that can be separated from RED by a coupling reaction, and n
When it is 1, it is a group that can be released from TIME.

Here, FA represents a so-called fogging agent or development accelerator that acts on silver halide grains during development to produce fog nuclei capable of initiating development. Examples of FA include groups that act reductively on silver halide grains during development to produce fog nuclei, or act on silver halide grains to produce silver sulfide nuclei which are fog nuclei capable of initiating development. be able to.

A preferable group as FA is a group containing a group having adsorption properties to silver halide grains, and can preferably be represented as follows.

-AD-(L) -X AD represents a group having adsorption property to silver halide, L represents a divalent group, and m represents 0 or 1. X
represents a reducing group or a group capable of producing silver sulfide by acting on silver halide. However, if X is the latter, it may also have the function of AD, so AD-(L)- is not necessarily required in this case.

In general formula (1), the group represented by RED has a skeleton of hydroquinone, catechol, O-aminophenol or P-aminophenol, undergoes a redox reaction with the oxidized form of the developer, and subsequently undergoes alkaline hydrolysis. Te=(
TIME)-FA group (next, general formula (IIa) to (■a)
represents a group that releases rFRJ).

Specific examples thereof are shown in general formulas (IIa) to (■a).

Tl In the above formula, R6□ is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a cyano group,
Alkoxycarbonyl group, carbamoyl group, sulfamoyl group, carboxyl group, sulfo group, sulfonyl group, acyl group, carbonamide group, sulfonamide group, hydroxy group, acyloxy group, or heterocyclic group,
r represents an integer of 1 to 3, and p represents an integer of 1 to 4. When p and r are two or more, R61 may be the same or different, and the two at the vic-position are bonded to form a benzene ring or a 5- to 7-membered heterocycle. You can. R6□ represents an alkyl group, an aryl group, an acyl group, a carbamoyl group, a sulfonyl group or a sulfamoyl group. T1 represents a hydrogen atom or a group capable of being hydrolyzed and separated under alkaline conditions. 2 T1 in the molecule
If there are more than one, they may be different from each other.

Typical examples of T1 include a hydrogen atom, an acyl group, a sulfonyl group, an alkoxycarbonyl group, a carbamoyl group,
Examples include oxalyl group.

Preferred specific examples of general formulas (IIa) to (IIa) are shown below. Note that (*) in each structural formula indicates the position where FR is bonded.

H nTJ H p H H H (JH R H H OI' H H H /'ITJ H H J as the timing group represented by U.S. Patent Section 4, No. 248,962, JP-A No. 57-56837, etc., which separates FA from RED by coupling reaction or redox reaction and then removes FA by intramolecular substitution reaction, British Patent Section 2,072,363A No., JP-A No. 57-154234, No. 57-188035, No. 56-114946, No. 57-56837, No. 58
-209736, 58-209737, 58-
No. 209738, No. 58-209740, No. 58-9
As in No. 8728, FA is separated by electron transfer via a conjugated system, and as in JP-A-57-111536, FA is released by a coupling reaction with an oxidized form of an aromatic primary amine developer. : Examples include those that are coupling components that can be separated. These reactions may occur in one step or in multiple steps.

When FA is a group containing AD-(L)-X, AD may be directly bonded to the carbon atom of RED, or X
However, they may be bonded to the carbon of RED as long as they can be released by a substitution reaction following a redox reaction. Moreover, what is known as a so-called 2-equivalent leaving group of a coupler may be present between the carbon of RED and AD. These two-equivalent leaving groups include alkoxy groups (e.g. methoxy groups), aryloxy groups (e.g. phenoxy groups), alkylthio groups (e.g. ethylthio groups), arylthio groups (e.g. phenylthio groups),
peterocyclic oxy group (e.g., tetrazolyloxy group),
There are heterocyclic thio groups (eg, pyridylthio group), heterocyclic groups (eg, hydantoinyl group, lazolyl group, triazolyl group, benzotriazolyl group, etc.). In addition, those described in British Patent Publication No. 2,011,391 can be used as the FA.

Groups adsorbable to silver halide represented by AD include nitrogen-containing heterocycles having a dissociable hydrogen atom (for example, virol, imidazole, pyrazole, triazole, tetrazole, benzimidazole, benzopyrazole, benzopyrazole, triazole, uracil, tetraazaindene, imidazotetrazole, pyrazolotriazole, pentaazaindene), petrochemicals having at least one nitrogen atom and another heteroatom in the ring (e.g., oxygen, sulfur, selenium) rings (e.g., oxazole, thiazole, thiazoline, thiazolidine, thiadiazole, benzothiazole, benzoxazole, benzoselenazole), petero rings with mercapto groups (e.g., 2-mercaptobenzothiazole, 2-mercaptopyrimidine, 2-mercaptobenzoxazole) , 1-
phenyl-5-mercaptotetrazole), quaternary salts (e.g., tertiary amines, pyridine, quinoline, benzthiazole, benzimidazole, benzoxazole, etc.)
thiophenols, alkylthiols (eg cysteine), aurea, dithiocarbamates, thioamides, rhodanine, thiazolidinethione, thiohydantoin, thiobarbital acid), and the like.

The divalent linking group represented by L in FA includes alkylene, alkenylene, phenylene, naphthylene, -o-,
-5-1-8O-1S O2-1-N=N-, carbonyl, amino, imino, amide, thioamide, sulfonamide, ureido, thioureido, petero ring, etc., or a composite thereof.

If a group that can be cleaved by the action of components in the developer (e.g., hydroxide ion, hydroxylamine, sulfite ion) is appropriately selected as one of the divalent linking groups constituting L, the fogging effect can be adjusted. It is also possible to deactivate it.

The group represented by X is a reducing compound (for example, hydrazine, hydrazide, hydrazone, hydroquinone,
Catechol, p-aminophenol, P-phenylenediamine, 1-phenyl-3-pyrazolidinone, enamine, aldehyde, polyamine, acetylene, aminoborane, tetrazolium salt, ethylene bispyridinium salt (carbazic acid) or silver sulfide during development. (e.g., thiourea, thioamide, dithiocarbamate, rhodanine, thiohydantoy). Among the groups represented by X, some of the groups that can form silver sulfide during development are themselves halogenated It has adsorptive properties to silver particles and can also serve as an adsorptive group AD.

Further, among FAs, particularly preferable ones have the following general formula (Vl
lra) and (IXa).

General formula (VI[[a) General formula (IXa) In the formula, R7□ represents an acyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group or sulfamoyl group, and R7□ Represents a hydrogen atom, an acyl group, an alkoxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, or an aryloxycarbonyl group, and R73 is a halogen atom, an alkoxy group, an alkyl group,
represents an alkenyl group, an aryl group, an aryloxy group, an alkylthio group, an arylthio group, a carbonamide group or a sulfonamide group, m represents an integer of 0 to 4, and 1
When m is 2 or more, R73 may be the same or different, or two or more may combine to form a condensed ring. L has the same meaning as described above, ie, represents a divalent linking group, and n represents 0 or 1. Zl represents a nonmetallic atomic group necessary to form a monocyclic or condensed heterocyclic ring, and Z2 represents a nonmetallic atomic group necessary to form a monocyclic or condensed heterocyclic ring with N. represent.

Examples of substituents are described in more detail below. R7□ is an acyl group (e.g., formyl, acetyl, propionyl, trifluoroacetyl, bilboyl), a carbamoyl group (e.g., dimethylcarbamoyl), an alkylsulfonyl group (e.g., methanesulfonyl), an arylsulfonyl group (e.g., benzenesulfonyl). ), an alkoxycarbonyl group (e.g. methoxycarbonyl), an aryloxycarbonyl group (e.g. phenoxycarbonyl group) or a sulfamoyl group (e.g. methylsulfamoyl), and R7□ is a hydrogen atom, an acyl group (
trifluoroacetyl), alkoxycarbonyl groups (e.g. methoxycarbonyl) or aryloxycarbonyl groups (e.g. phenoxycarbonyl),
an alkylsulfonyl group (e.g. methanesulfonyl),
Arylsulfonyl group (e.g. benzenesulfonyl)
, R73 is a halogen atom (e.g., fluorine atom, chlorine atom), an alkoxy group (e.g., methoxy, methoxyethoxy), an alkyl group (e.g., methyl, hydroxymethyl), an alkenyl group (e.g., allyl), an aryl group ( Even more preferably General formula (Xa) is mentioned as an example of AD.

General formula (Xa) K' (wherein, 2 represents a nonmetallic atom group necessary to form a 5- to 6-membered heterocycle, and Z may be substituted with a substituent. R is an aliphatic group and R2 is a hydrogen atom, an aliphatic group, or an aromatic group, and may be bonded with Z to form a ring.R and R2 may be substituted with a substituent.Aliphatic group of R and R2 The group is an unsubstituted alkyl group having 1 to 18 carbon atoms and an alkyl group in which the alkyl moiety has 1 to 18 carbon atoms. Examples of the substituent include those described below as a substituent for Z. In R2 The aromatic group represented has 6 carbon atoms.
~20 groups, such as phenyl group, naphthyl group, etc. Examples of the substituent include those described as the substituent for Z. At least one of the groups represented by al, R2 and Z contains an alkynyl group, an acyl group, a hydrazine group or a hydrazone group, or R1 and R2 form a 6-membered ring, and dihydropyridinium Forms the skeleton. Y is a counterion for charge balance. n' represents 0 or l. ) However, in the general formula Xa, the bond may be present at any position.

To explain the general formula (Xa) in detail below, the heterocycle completed by Z is, for example, quinolinium, benzothiazolium, benzimidazolium, pyridinium, thiazolinium, thiazolium, naphtho'thiazolium, selenazolium, benzoselenazolium, Mention may be made of imidazolium, tetrazolium, indolenium, pyrrolinium, acridinium, phenanthridinium, isoquinolinium, oxacillium, naphthoxacillium and benzoxacillium nuclei. As a substituent for Z,
Alkyl group, alkenyl group, aralkyl group, aryl group, alkynyl group, hydroxy group, alkoxy group, aryloxy group, halogen atom, amino group, alkylthio group, arylthio group, acyloxy group, acylamino group,
Sulfonyl group, sulfonyloxy group, sulfonylamino group, carboxyl group, acyl group, carbamoyl group, sulfamoyl group, sulfo group, cyano group, ureido group, urethane group, carbonate group, hydrazine group, hydrazone group, or imino group, etc. Can be mentioned. As the substituent for Z, for example, at least one substituent is selected from the above substituents, but in the case of two or more substituents, they may be the same or different. Moreover, the above-mentioned substituents may be further substituted with these substituents.

Further, as the substituent 2, a heterocyclic quaternary ammonium group completed with Z via a linking group may be included. In this case, it takes a so-called dimer structure.

The heterocycle completed by Z preferably includes quinolinium, benzothiazolium, benzimidazolium, pyridinium, acridinium, phenanthridinium, and isoquinolinium nuclei. More preferred are quinolinium, benzothiazolium, and benzimidazolium, and even more preferred are quinolinium and benzothiazolium. Most preferred is quinolinium.

At least one of the groups represented by R1, R2 and Z has an alkynyl group, an acyl group, a hydrazine group, or a hydrazone group, or R1 and R2 form a 6-membered ring, and a dihydropyridinium core is formed. However, these may be substituted with the groups mentioned above as substituents for the group represented by Z.

The hydrazine group preferably has an acyl group or a sulfonyl group as a substituent.

The hydrazone group preferably has an aliphatic group or an aromatic group as a substituent.

As the acyl group, for example, a formyl group and an aliphatic or aromatic ketone are preferred.

Some of the alkynyl groups possessed by either R1, R2 or Z have already been described, but to explain in more detail, those having 2 to 18 carbon atoms are preferable, such as ethynyl group, propargyl group, etc. group, 2-butynyl group, 1-methylpropargyl group, 1. These include agemethylpropargyl group, 3-butynyl group, and 4-pentynyl group.

Furthermore, these may be substituted with the groups mentioned as substituents for Z. Examples include 3-phenylpropargyl group, 3-methoxycarbonylpropargyl group, 4-methoxy-2-butynyl group, and the like.

It is preferable that at least one of the groups or substituents on the ring represented by R1, R2 and Z is an alkynyl group or an acyl group, or that R1 and R2 are linked to form a dihydropyridinium core, and R1, R
It is most preferable that at least one alkynyl group is included as a substituent to the group or ring represented by 2 and Z.

In particular, it is most preferred that R1 is a propargyl group.

The counterion Y for charge balance is any anion that can cancel the positive charge generated by the quaternary ammonium salt in the heterocycle, such as bromide ion, chloride ion,
These include iodine ion, P-)luenesulfonate ion, ethylsulfonate ion, perchlorate ion, trifluoromethanesulfonate ion, and thiocyanate ion. In this case, n' is 1. When containing an anionic substituent such as a heterocyclic quaternary ammonium salt or a sulfoalkyl substituent, the salt can be in the form of a betaine, in which case no counterion is required and n' is 0. . When the heterocyclic quaternary ammonium salt has two anionic substituents, e.g. two sulfoalkyl groups, Y is a cationic counterion, e.g. an alkali metal ion (sodium ion, potassium ion, etc.) and ammonium salts (triethylammonium, etc.).

An example of the FR compound used in the present invention is JP-A-57-15
No. 0845, No. 59-50439, No. 59-1576
No. 38, No. 59-170840, No. 60-37556
No. 60-147029, No. 60-128446, etc.

An example of AD is shown below. The free bond bonds to -(L)-X and -(T I ME)-.

Iln H3 Nbe ■ H3 H3 ■ NHC3- -CH2CH2+ 10CH2- -OCH2CH2-.

5CH2- COO- An example of X is shown below.・ -NHNHCHO -NHNHCOCH3 -NHNH5O2CH3.

-NHNHCOCF3.

-N-NHCHO C00C2H5 -CONHNHC) (3 -CONHNH2 -CmiC-HCHO .Cio4- Furthermore, preferred specific examples of FA in general formula (I) are shown below.

CH2CH2CHO H3 Specific examples of the FR compound used in the present invention are as follows.

H H H H 0■ H CH2C=CH (1-i4) H ('IT-T H H 0■ OT-T H H H H (L-28) CH2CyoCH CH2C=CH AT-T CH2CmiCH H The compound used in the present invention is, for example, JP-A-57-15
It can be synthesized by a method similar to that described in JP-A No. 0845, JP-A-59-157638, and JP-A-60-107029.

FR compounds are, for example, research disclosure
(Research Disclosure) Magazine No.
No. 22534 (issued January 1983, pages 50-54), and methods described in US Pat. No. 4,471,044 and similar methods thereof.

The amount of the FR compound used in the present invention is 10 to 10 moles, preferably 10-5 to 10-1, per mole of silver halide contained in the layer containing the FR compound or the layer adjacent thereto. 1 mol, particularly preferably 10 to 1
It is 0-2 mol.

In the present invention, the FR compound can be introduced into the silver halide emulsion layer using known methods, such as U.S. Pat.
The method described in No. 27 is used. For example, phthalic acid alkyl esters (e.g., dibutyl phthalate, dioctyl phthalate), phosphoric acid esters (e.g., diphenyl phosphate, triphenyl) phosphate, tricresiflephosphate, dioctyl butyl phosphate, tributyl citrate), benzoic acid esters ( For example, octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, diethyl azelate),
Trimesic acid esters (for example, tributyl trimesate), etc., or organic solvents with a boiling point of 30°C to 150°C, such as lower alkyl acetates such as ethyl acetate, butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl After dissolving in ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, methanol, ethanol, propatool, fluorinated alcohol, etc., it is dispersed into a hydrophilic colloid. The above-mentioned high-boiling point organic solvent and low-boiling point organic solvent may be used in combination.

Also, Japanese Patent Publication No. 51-39853, Japanese Patent Publication No. 51-599
The polymer dispersion method described in No. 43 can also be used.

When the FR compound has an acid group such as carboxylic acid or sulfonic acid, it is introduced into the hydrophilic colloid as an alkaline aqueous solution.

The present invention also includes the following general formulas (n), (m), (IV)
, (V)g and (VI) can be preferably used. These compounds have the effect of controlling unfavorable photographic performance such as an increase in sensitivity and an increase in fog over time of the film when the compound represented by the general formula (I) is used.

General Formula (II) In the formula, Ml represents a hydrogen atom, a cation or a protecting group for a mercapto group that is cleaved with an alkali, and Z represents an atomic group required to form a 5- to 6-membered heterocycle.

In the formula, M1 is more specifically a hydrogen atom, a cation (e.g., sodium ion, potassium ion, ammonium ion, etc.), or a protecting group for a mercapto group that is cleavable with an alkali (e.g., -COR', -COOR', -CH2CH
2COR' etc. However, R' is a hydrogen atom, an alkyl group,
represents an aralkyl group, an aryl group, etc.

Z represents an atomic group necessary to form a 5- to 6-membered heterocycle. This heterocycle contains a sulfur atom, selenium atom, nitrogen atom, oxygen atom, etc. as a heteroatom, and may be fused, or may have a substituent on the heterocycle or the fused ring. good.

Examples of Z include tetrazole, triazole, imidazole, oxazole, thiadiazole, pyridine, torimishin, triazine, azabenzimidazole, purine, tetraazaindene, triazaindene, pentaazaindene, benztriazole, benzimidazole, benzoxazole, These include benzthiazole, benzselenazole, and naphthoimitazole. Substituents for these rings include alkyl groups (e.g., methyl, ethyl, n-hexyl, hydroxyethyl, carboxyethyl), alkenyl groups (e.g., allyl), aralkyl groups (e.g., benzyl, phenethyl), and aryl groups. (For example, phenyl, naphthyl, p-acetamidophenyl, p-carboxyphenyl, m-hydroxyphenyl, p-sulfamoylphenyl, p-acetylphenyl, 0-methoxyphenyl, 2,4-diethylaminophenyl, 2.4- dichlorophenyl), alkylthio groups (e.g. methylthio, ethylthio, n-butylthio), arylthio groups (e.g. phenylthio, naphthylthio), aralkylthio groups (e.g. benzylthio),
It may be substituted with a mercapto group or the like. Furthermore, in addition to the above-mentioned substituents, a nitro group, an amino group, a halogen atom, a carboxyl group, a sulfo group, etc. may be substituted particularly on the condensed ring.

Preferred specific examples of the compounds represented by the general formula (n) are shown below, but the invention is not limited thereto.

(I[-1) (I-2) (I[-3) (][-4) (I-5) (I-6) (l-7) (l-8) (L-9) (I -10) (I[-11) (I-13) (I-14) (II-17) (I[-18) (I[-19) R (I[-21) 51'i (If-22 ) bl'I (1[-24) H (l[-25) and H3 (I[-26) (I-28) (I[-29) (n-30) (I-31) CI[-34 ) (I[-35) (I-36) (I-37) (T38), 1 (II-39) (I-40) H (L-42) T-T INnurishi5n11 (II-43 ) q■ (II-44) H (I-45) R (I[-46) ST( (I-48) (if-49) (I-50) S)( LS-ctt2c″l-1, CUOH (I-51> (I[-52) (I-53) (I-54) General formula (II[) In the formula, R5 is a hydrogen atom, an unsubstituted or substituted alkyl group, an aralkyl group, an alkenyl group, Represents an aryl group or a heterocyclic residue, and V is O, S, Se, or NR6 (R6
represents an alkyl group, an aralkyl group, an alkenyl group, an aryl group, or a heterocyclic residue (which may be the same as or different from R5). Ql represents an atomic group necessary to form a 5- to 6-membered heterocycle, and may be fused.

In the formula, the alkyl group represented by Rs and Ra preferably has 1 to 20 carbon atoms and includes substituted ones.

Examples of substituents include halogen atoms (e.g. chlorine atoms)
, cyano group, carboxy group, hydroxy group, carbon number 2~
6 acyloxy groups (e.g. acetoxy), 2 carbon atoms
-22 alkoxycarbonyl groups (eg, ethoxycarbonyl, butoxycarbonyl), carbamoyl groups, sulfamoyl groups, sulfo groups, amino groups, substituted amino groups, and the like. Examples of preferred alkyl groups are: methyl, ethyl, propyl (n- or 1so-), butyl (n-1iso- or 1-), amyl (which may be branched; the same applies hereinafter), Hexyl, octyl, dodecyl, pentadecyl, heptadecyl, chloromethyl, 2-chloroethyl, 2-cyanoethyl, carboxymethyl, 2-carboxyethyl, 2-hydroxyethyl, 2-acetoN-diethyl, acetoxymethyl, ethoxycarbonylmethyl, butoxycarbonylmethyl , 2-methoxycarbonylethyl, benzyl, 0-nitrobenzyl, p-sulfobenzyl.

The aralkyl group represented by R5 and R6 preferably has 7 to 20 carbon atoms, and is, for example, a benzyl group or a phenethyl group.

The alkenyl group represented by R5 and R6 preferably has 2 to 18 carbon atoms, and is, for example, an allyl group.

The aryl group represented by R5 and R6 preferably has 6 to 10 carbon atoms, is monocyclic or bicyclic, preferably monocyclic, and includes substituted aryl groups. Examples of substituents include alkyl groups having 1 to 20 carbon atoms (e.g., methyl,
ethyl, nonyl), alkoxy groups having 1 to 20 carbon atoms (e.g., methoxy, ethoxy), hydroxy groups, halogen atoms (e.g., chlorine atoms, bromine atoms), carboxy groups,
There are sulfo groups, etc. Specific examples of the aryl group are phenyl group, P-tolyl group, p-methoxyphenyl group, P-hydroxyphenyl group, P-chlorophenyl group, 2,5-dichlorophenyl group, P-carboxyphenyl group, 0-carboxyphenyl group, 4-sulfophenyl group, 2,4-disulfophenyl group, 2.5-disulfophenyl group, 3-
These include sulfophenyl group and 3,5-disulfophenyl group.

Ql is an atomic group necessary to form a 5- to 6-membered heterocycle, preferably selected from C, S, N, and 0; thiazoline ring, thiazolidine ring, selenazoline ring, oxazoline ring, oxazolidine ring, Imidacillin ring, imidazolidine ring, 1°3.4-thiadiazolin ring, 1,3.4
-oxadiazoline ring, 1,3.4-triazoline ring,
These include tetrazoline rings and pyrimidine rings. Of course, these heterocycles include those in which a 5- to 7-membered carbon ring or petero ring is fused thereto. That is, benzothiazoline nucleus, naphthothiazoline nucleus, dihydronaphthothiazoline nucleus, tetrahydrobenzothiazoline nucleus, benzoselenazoline nucleus, benzoxazoline nucleus, naphthoxazoline nucleus, benzimidacilline nucleus, dihydroimidazolopyrimidine nucleus, dihydrotriazolopyridine nucleus , dihydrotriazolopyrimidine nucleus, and the like.

Various substituents can be present on the nucleus of these heterofused ring nuclei. In addition to those listed above as substituents for the aryl group represented by R5 and R6, alkylthio groups (e.g., ethylthio), unsubstituted or substituted amino groups (e.g., methylamino, diethylamino, benzylamino, anilino), acylamino groups (e.g. acetylamino, benzoylamino), sulfonamide groups (e.g. methanesulfonamide, p-)luenesulfonamide), thioamide groups (e.g. propionylthioamide), alkenyl groups having 2 to 20 carbon atoms (e.g. allyl )
, an aralkyl group having 1 to 4 carbon atoms in the alkyl moiety (e.g., benzyl group), a cyano group, a carbamoyl group (including substituted ones, such as methylcarbamoyl), an alkoxycarbonyl group having 2 to 22 carbon atoms (e.g. , butoxycarbonyl), an alkylcarbonyl group having 2 to 22 carbon atoms (eg, caproyl), and the like.

The alkyl group may be further substituted with a carboxy group, a sulfo group, an alkoxycarbonyl group, an acyloxy group, an aryl group, or the like.

The above compound is published in Japanese Patent Publication No. 48-34169, Pharmaceutical Journal 7.
No. 4, pages 1365 to 1369 (1954), Special Publication No. 49-23368, Be1lsteinX1! -39
It can be synthesized by the method described in Japanese Patent Publication No. 47-18008, page 4, TV-121, Japanese Patent Publication No. 47-18008.

Preferred specific examples of the compounds represented by the general formula (III) are listed below, but the invention is not limited thereto.

(III-1) (Ii[-2) (I-3) (]Il-4) (l[-5) ♀H3 (II-6) (l[-7) (I-8) (III-9 ) (Il[-10) 2H5 (IM-12) (N-1,3) Fuki (III-14) (II-15) Explosion H3 (I-17) (ll[(8) (II-19) ( If-20) H3 The compound having a repeating unit represented by the general formula (IT) will be explained in detail.

General formula (IV) I, R and R' are each a hydrogen atom, carbon number 1
~12 alkyl group, hydroxyalkyl group, sulfoalkyl (or salt thereof) group, carboxyalkyl (or salt thereof) group, aralkyl group, or sulfo (or salt thereof)-, carboxyl (or salt thereof)-1 carbon number 1
~4 alkyl-1 C6-12 aryl group with or without a C1-4 alkoxy or halogen substituent, or cycloalkyl group 11'
ln or R and R' may both form an alkylene ring or an alkylene ring containing 10-, and R2, R3, R4 and R5 are each a hydrogen atom or a carbon atom having 1 to 4 carbon atoms. Represents an alkyl group, Y, , Y2. Y3 and Y4 each have 2 to 2 carbon atoms.
12 polymethylene groups, C2-C12 polymethylene groups substituted with C1-C4 alkyl groups or sulfo (or salts thereof)-, carboxyl (or salts thereof)-
1 Represents an arylene group with or without an alkyl or halogen substituent having 1 to 4 carbon atoms, or a cycloalkylene group, where z): -o-1-802- or -cH2- I, Sen and m represent 0 or 1.

S represents 2 to 100.

The compound having a repeating unit represented by the general formula (Il/) of the present invention is known, and Japanese Patent Publication No. 46-154
It can be easily synthesized by the method described in Japanese Patent No. 71.

Next, typical compounds having a repeating unit of the general formula (IV) used in the present invention are shown, but the compounds used in the present invention are not limited to these.

(IV-5) (IV-6) 1(lr+ 10・i (IV-12) (IV-13) (IV-14) (IV-15) (IV(6) (TV-17) (■-21 ) (IV-27) (■-28) (■-30) Next, the compound represented by general formula (V) will be explained in detail.

General formula (V) In the formula, R1□ to R14 are an alkyl group, an aryl group, or an aralkyl group (however, the total number of carbon atoms in R1□ to R14 is 6 or more)
represents. Further, R1□, R12, and R13 may form a petero ring containing quaternary nitrogen. X represents an anion, and n represents 0 when the compound forms an inner salt, and 1 otherwise.

In the formula, R1□ to R14 are more specifically alkyl groups having up to 30 carbon atoms (for example, methyl, ethyl,
n-butyl, n-hexyl, n-dodecyl), aryl groups with up to 30 carbon atoms (e.g. phenyl,
(naphthyl, tolyl, p-ethylphenyl), and examples of the aralkyl group include those having up to 30 carbon atoms (eg, benzyl, phenethyl). R1□ to R14 are selected such that their total number of carbon atoms is 6 or more.

A compound represented by the following general formula (ma) or a dimer thereof is preferred.

General formula (Va) Q is a petero ring containing quaternary nitrogen, and examples thereof include a pyridinium ring, a thiazolium ring, a benzthiazolium ring, and a benzimidazolium ring.

These rings may further include alkyl groups (e.g., methyl, ethyl, n-hexyl, hydroxydiyl, carboxyethyl), alkenyl groups (e.g., allyl), aralkyl groups (e.g., benzyl, phenethyl), aryl groups (e.g., phenyl, naphthyl), etc. , p-acetamyl-phenyl, p-calphokidiphenyl, m-hydroxyphenyl,
p-sulfamoylphenyl, p-acetylphenyl,
〇-methoxyphenyl, 2,4-diethylaminophenyl, 2,4-dichlorophenyl), alkylthio groups (e.g. methylthio, ethylthio, n-methylthio), arylthio groups (e.g. buenyldio, naphthylthio)
, an aralkylthio group (eg, benzylthio), or the like. In addition to the above substituents, particularly on the condensed ring, nitro groups, amino groups, halogen atoms,
A carboxyl group, a sulfo group, etc. may be substituted.

R4, X, and n have the same meanings as previously defined.

The dimer of the general formula (V) (including the general formula (Va)) is a divalent group such as an alkylene group or an arylene group of the general formula (
V) are linked together.

All of the compounds represented by the general formula (V) of the present invention are known and can be easily obtained or synthesized.

Among the compounds represented by the general formula (V), preferred specific examples are shown below, but the invention is not limited to these.

(V() (V-2) (V-3) (V-4) k12 kl=n2 (V-5) n C3H7 (V-6) (V-7) (V-8) 1G ( V-9) Next, the compound represented by the general formula <Vl) will be explained in detail.

General formula (Vl) In the formula, Y and Z each independently represent methine, substituted methine, or an elementary atom, and Q2 is an atomic group necessary to form a 5- to 6-membered heterocycle. and these rings may be further fused. M2 is
Represents a hydrogen atom or a cation such as an alkali metal cation or ammonium ion.

In the formula, the ring formed by Q2 includes 1-lyazole, tetrazole, imidazole, oxazole, thiadiazole, pyridine, torimishin, triazine, azabenzimidazole, purine, tetraazaindene,
triazaindene, pentaazaindene, benztriazole, penzimitazole, benzoxazole, benzthiazole, benzselenazole, indazole,
These include naphthoimidazole.

These rings may further include alkyl groups (e.g., methyl, ethyl, n-hexyl, hydroxyethyl, carboxyethyl), alkenyl groups (e.g., allyl), aralkyl groups (e.g., benzyl, phenethyl), aryl groups (e.g., phenyl, naphthyl, p-acetamidophenyl,
p-carboxyphenyl, m-hydroxyphenyl, p
-sulfamoylphenyl, p-acetylphenyl, 〇-methoxyphenyl, 2,4-diethylaminophenyl, 2,4-dichlorophenyl), alkylthio groups (e.g. methylthio, ethylthio, n-butylthio), arylthio groups (e.g. phenylthio , naphthylthio),
It may also be substituted, such as aralkylthio (eg, pencylthio). Furthermore, in addition to the above-mentioned substituents, a nitro group, an amino group, a halogen atom, a carboxyl group, a sulfo group, etc. may be substituted on the condensed ring.

The compounds represented by the general formula (VI) of the present invention are all known and can be easily obtained or synthesized.

Among the compounds represented by the general formula (VI), preferred specific examples are shown below, but the invention is not limited thereto.

(VI-1) (W-2) (VI-3) (Vl-4) (W-5) (VI”6) Roofing (W-7) (■-8) (VI-9) (V[- 11) (VI-12) (Vl-13) (■-14) (Vl-15) (W-16) In general formula (II), (III), (IV), (V)- or (VI) The compound of the present invention varies depending on the nature, purpose, and development method of the silver halide photographic material to which it is applied, but generally it is 10-1 to 2-1 of silver halide present in the same layer or an adjacent layer. ~10-6
mol, preferably 5 x 10 to 3 x 10'''5 mol.

In order to introduce the compound represented by general formula (II), (m), (IV), (V) or (Vl) of the present invention into a light-sensitive material, water, methanol, ethanol, propatool,
Alternatively, it is dissolved in a solvent commonly used in photographic materials such as fluorinated alcohol, and then added to the hydrophilic colloid. When contained in the silver halide emulsion layer, it may be contained at the time of grain formation of the silver halide emulsion, at the time of physical ripening, immediately before chemical sensitization, during chemical sensitization, after chemical sensitization, or at the time of preparing the coating solution. Selected according to purpose.

The photosensitive material to which the present invention is applied may be, for example, any color reversal photographic material such as a color reversal film (inner mold and outer mold) or a color reversal vapor.

In the photographic emulsion layer of the photographic light-sensitive material used in the present invention, any of silver halides including silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used in combination. The preferred silver halide is silver iodobromide or silver iodochlorobromide containing up to about 10 mole percent silver iodide. Particularly preferred is about 0.5
Silver iodobromide containing from mol % to about 8 mol % silver iodide. These silver halide grains may be so-called regular grains having regular crystal structures such as cubes, octahedrons, and dodecahedrons, or may have irregular crystal shapes such as tabular or spherical shapes. , one with crystal defects such as twin planes, or a composite form thereof. Also, a mixture of particles of various crystal forms may be used.

The grain size may be fine particles of about 0.1 g or less or large particles with a projected area diameter of up to about 10 g, and may be a monodisperse emulsion with a narrow distribution or a polydisperse emulsion with a wide distribution.

The silver halide photographic emulsion that can be used in the present invention can be produced by a known method, such as Research Disclosure,
Volume 176, No. 17643 (December 1978),
pp. 22-23, '1. Emulsion production (Emulsion P
187, No. 18716 (November 1979), p. 648.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Grafkide, published by Paul Montell (P.

Glafkides, Chimie et Phys
ique PhotographiquePaul M
ontel, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Cal Press (G, F, Duffj.
n.

Photographic Emulsion Che
Mistry (Focal Press.

1966), “Production and Coating of Photographic Emulsions” by Zelikman et al., published by Focal Press (V, L, Zelik
Manet al, Making and
Coating PhotographicEmul
sion, Focal Press, 1964)
It can be prepared using the method described in et al.

That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method, a combination thereof, etc. Good too.

It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method). PAg in the liquid phase in which silver halide is produced as a form of simultaneous mixing method
The method of keeping constant the
A double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

The silver halide emulsion consisting of the regular grains described above can be obtained by controlling PAg and pH during grain formation. For more information, please see Photographic Science
and engineering (Photography
c 5science and Engineer
ing), Vol. 6, pp. 159-165 (1962)
, Journal of Photographic Science
5science), vol. 12, pp. 242-251 (19
64), US Pat. No. 3,655,394 and British Patent No. 1,413,748.

A method for making such an emulsion is described in U.S. Pat. No. 3,574.6.
No. 28, No. 3,655,394 and British Patent No. 1
, No. 413,748. Also, JP-A-48
-8600, 51-39027, 51-830
No. 97, No. 53-137133, No. 54-48521
Monodisperse emulsions such as those described in Japanese Patent Application No. 54-99419, Japanese Patent No. 58-37635, and Japanese Patent No. 58-49938 can also be preferably used in the present invention.

The crystal structure may be --like, the inside and outside may have different halogen compositions, or it may have a layered structure. These emulsion grains are described in British Patent No. 1,027,
No. 146, U.S. Patent No. 3.505.068, U.S. Patent No. 4,4
No. 44,877 and Japanese Patent Application No. 58-248469. Furthermore, silver halides having different compositions may be bonded by epitaxial bonding, or compounds other than silver halide such as silver rhodan or lead oxide may be bonded. These emulsion grains are disclosed in U.S. Patent No. 4,094,684, U.S. Pat.
No. 92, U.S. Patent No. 4,349,622, U.S. Patent No. 4,39
No. 5,478, No. 4,433,501, No. 4,463
, No. 087, No. 3,656,962, No. 3,852.
No. 067, JP-A-59-162540, etc.

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present.

These various emulsions may be either a surface latent image type in which a latent image is mainly formed on the surface, or an internal latent image type in which a latent image is formed inside the grains.

In order to remove soluble silver salts from the emulsion before and after physical ripening, noodle washing, flocculation sedimentation method, ultrafiltration method, etc. are used.

The emulsion used in the present invention is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization. Additives used in such processes are listed in the aforementioned Research Disclosure No. 17643 (December 1978) and Research Disclosure No. 17643 (December 1978).
o, 18716 (November 1979), and the relevant sections are summarized in the table below.

Known photographic additives that can be used in the present invention are also listed in the two Research Disclosures mentioned above, and their locations are shown in the table below.

Additive type RD 17643 RD 1871
61 Chemical sensitizers Page 23 Page 648 Right column 2
Sensitivity enhancer Same as above 3 Spectral sensitizers, pages 23-24 Page 648 right column - Super sensitizers
Page 649, right column 4 Brightener
Page 24 5 Antifouling agent Pages 24-25 Page 649 Right column ~
and Stabilizer 6 Light absorber, pages 25-26, page 649, right column ~
Filter dyes Page 650 left column Ultraviolet absorber 7 Stain inhibitors Page 25 right column Page 650 left to right columns 8 Dye image stabilizers Page 25 9 Hardeners Page 26 Page 651 left column 10
Binder, page 26 Same as above 11 Plasticizer, lubricant Page 27 Page 650 right column 12 Coating aid, pages 26-27 Same as above Surface active agent 13 Static prevention Page 27 Same as above Stop agent Can various color couplers be used in the present invention? A specific example of this is the aforementioned Research Disclosure N.
o, 17643, ■-〇～G. As the dye-forming coupler, it is important to use a coupler that can produce the three primary colors (i.e., yellow, magenta, and cyan) in subtractive color development, and specific examples of diffusion-resistant, hydrophobic, 4-equivalent or 2-equivalent couplers are mentioned above. Research Disclosure No. 17643, ■-C
In addition to the couplers described in the patents described in Section D and D, the following can be preferably used in the present invention.

Typical examples of yellow couplers that can be used in the present invention include hydrophobic acylacetamide couplers having a ballast group. Specific examples include U.S. Patent Section 2,
No. 407,210, No. 2,875,057, and No. 3,265,506. The use of two-equivalent yellow couplers is preferred for the present invention, and U.S. Pat.
:31, 3,933,501 and 4,022.6
20, etc., or Japanese Patent Publication No. 58-10739, U.S. Patent Section 4
, No. 401,752, No. 4,326,024, RD
18053 (April 1979), British Patent Section 1,425
, 020, West German Application No. 2,219,917, West German Application No. 2,261,361, West German Application No. 2,329,587 and West German Application No. 2,433,812, Patent Application No. 1983-: L87
A typical example thereof is the nitrogen atom separation type yellow coupler described in No. 995 and the like. α-pivaloylacetanilide couplers have excellent color fastness, especially light fastness, while α-benzoylacetanilide couplers provide high color density.

Magenta couplers that can be used in the present invention include hydrophobic indacylon or cyanoacetyl couplers, preferably 5-pyrazolone and pyrazoloazole couplers, which have a ballast group. Is the 3-position 1 in 5-pyrazolone couplers? (2) Couplers substituted with an arylamino group or an acylamino group are preferred from the viewpoint of the hue and color density of the coloring dye, and representative examples thereof include U.S. Pat.
No. 2,343,703, No. 2,600,788, No. 2,908,573, No. 3,062,653
No. 3,152.896 and No. 3,936.0
It is written in No. 15 etc. As a leaving group for a two-equivalent 5-pyrazolone coupler, U.S. Patent Section 4,310.6
No. 19 or U.S. Patent Section 4
, 351,897 is particularly preferred. Further, the 5-pyrazolone coupler having a ballast group described in European Patent No. 73.636 provides high color density.

As pyrazoloazole couplers, U.S. Patent Section 3,
061,432, preferably pyrazolo[5,1-c][1,2,4]) lyazoles as described in U.S. Pat. , 242
20 (June 1984) and JP-A-60-33552
Pyrazolotetrazoles and Research Disclosure No. 24230 (June 1984)
and pyrazolopyrazoles described in JP-A-60-43659. Imidazo[1,2-b]pyrazoles described in U.S. Pat. No. 4.500.630 are preferred from the viewpoint of low yellow side absorption and light fastness of coloring dyes, and those described in European Patent No. 119.860A. Pyrazolo [
1,5-bl[1,2,4] triazoles are particularly preferred.

Cyan couplers that can be used in the present invention include hydrophobic, diffusion-resistant naphthol and phenolic couplers, such as the naphthol couplers described in U.S. Pat. No. 2,474,293, preferably U.S. Pat. 052,2
No. 12, No. 4,146; No. 396, No. 4,228
Typical examples include two-equivalent naphthol couplers of the oxygen atom dissociation type described in No. 233 and No. 4,296,200. Further, specific examples of phenolic couplers are given in U.S. Patent Nos. 2,369,929 and 2,80.
No. 1,171, No. 2,772,162, No. 2,8
No. 95,826, Japanese Patent Application Laid-Open No. 60-55340, etc.

Cyan couplers that are stable against humidity and temperature are preferably used in the present invention, and a typical example thereof is as described in U.S. Pat. Phenolic cyan couplers having U.S. Patent Nos. 2,772,162, 3,758.308, and 4,126,396,
2゜5-diacylamino substituted phenolics described in German Patent Publication No. 4,334,011, No. 4,327,173, West German Patent Publication No. 3,329,729, European Patent No. 121,365, etc. Coupler and U.S. Pat. No. 3,44
No. 6,622, No. 4,333.999, No. 4.4
No. 51,559 and No. 4,427,767, etc., which have a phenylureido group at the 2-position and have a 5-
These include phenolic couplers having an acylamino group in the position.

The dye-forming coupler for J3 and the above-mentioned special couplers may form a dimer or higher polymer. A typical example of a polymerized dye-forming coupler is U.S. Pat. No. 3,451,820.
No. 4,080,211. Specific examples of polymerized magenta couplers are described in British Patent No. 2,
No. 102,173 and U.S. Pat. No. 4,367.282.

Couplers that release photographically useful residues upon coupling may also be preferably used in the present invention. As the DIR coupler that releases a development inhibitor, the patented coupler described in the aforementioned Research Disclosure, No. 17643, Section 1-F is useful.゛Preferable in combination with the present invention is JP-A-57-15
Developer deactivated type represented by No. 1944; U.S. Patent No. 4,
248,962 and JP-A-57-154234; a reaction-type as typified by JP-A-59-39653; particularly preferred are JP-A-57-151944 and JP-A-57-15423; Developer-deactivated DIR described in Japanese Patent Application No. 1987-217932, Japanese Patent Application No. 59-75474, Japanese Patent Application No. 59-82214, and Japanese Patent Application No. 59-90438, etc.
This is a reactive DIR coupler described in Japanese Patent Application No. 59-39653.

The coupler used in the present invention can be introduced into the photosensitive material by various known dispersion methods, such as a solid dispersion method, an alkali dispersion method, preferably a latex dispersion method, and more preferably an oil droplet dispersion method in ice. be able to. In the oil-in-water dispersion method, after dissolving in a high boiling point organic solvent with a temperature of 175°C or higher and a low-temperature so-called auxiliary solvent, either alone or in a mixture of both, water or water is dissolved in the presence of a surfactant. Finely dispersed in an aqueous medium such as an aqueous gelatin solution. Examples of high boiling point organic solvents are U.S. Pat.
It is described in No. 027, etc. Dispersion may be accompanied by phase inversion, and if necessary, an auxiliary solution may be removed or reduced by distillation, noodle washing, ultrafiltration, or the like before use for coating.

Specific examples of latex dispersion processes, effects, and latex for impregnation are described in U.S. Pat. No. 4,199,363, OLS No. 2,541.
No. 541,230, etc.

The light-sensitive materials produced using the present invention contain hydroquinone derivatives, aminophenol derivatives, amines, gallic acid derivatives, catechol derivatives, ascorbic acid derivatives, colorless couplers, and sulfonamides as color cast prevention agents or color mixing prevention agents. It may also contain phenol derivatives and the like.

Various anti-fading agents can be used in the light-sensitive material of the present invention. Organic anti-fading agents include hydroquinones,
6-hydroxycoumaras, 5-hydroxycoumarans,
Spirochromans, p-alkoxyphenols, hindered phenols centered on bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and the phenolic hydroxyl groups of these compounds are silylated and alkyl Typical examples include ether or ester derivatives. Further, metal complexes such as (bissalicylaldoximado)nickel complex and (bis-N,N-dialkyldithiocarbamado)nickel complex can also be used.

The invention is also applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support. Multilayer natural color photographic materials usually have at least one each of a red-sensitive emulsion layer, a green-sensitive emulsion layer and a blue-sensitive emulsion layer on a support. The arrangement of these layers can be arbitrarily selected as required. The preferred order of layer arrangement is red sensitivity, green sensitivity, and blue sensitivity from the support side, or blue sensitivity, red sensitivity, and green sensitivity from the support side. Further, each of the above-mentioned emulsion layers may be composed of two or more emulsion layers having different sensitivities, or a non-photosensitive layer may be present between two or more emulsion layers having the same sensitivity. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case.

The light-sensitive material according to the present invention includes, in addition to the silver halide emulsion layer,
Protective layer, intermediate layer, filter layer, antihalation layer,
It is preferable to appropriately provide an auxiliary layer such as a back layer.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are coated on a flexible support such as plastic film, paper, or cloth, or a rigid support such as glass, ceramic, or metal, which is commonly used in photographic light-sensitive materials. be done. Useful flexible supports include films made of cellulose derivatives (cellulose nitrate, cellulose acetate, cellulose acetate, etc.), synthetic polymers (polystyrene, polyvinyl chloride, polyethylene phthalate, polycarbonate, etc.), baryta layers or α-olefin polymers (e.g. polyethylene, polypropylene, ethylene/butene copolymers)
It is paper coated or laminated with etc. The support may be colored using dyes or pigments. It may be made black for the purpose of blocking light. The surface of these supports is generally treated with an undercoat to improve adhesion to photographic emulsion layers and the like.

The surface of the support may be subjected to glow discharge, corona discharge, ultraviolet irradiation, flame treatment, etc. before or after the undercoating treatment.

Various known coating methods such as dip coating, roller coating, curtain coating, and extrusion coating can be used to coat the photographic emulsion layer and other wood-philic colloid layers. U.S. Pat. No. 2.681,2 as appropriate.
No. 94, No. 2761.791, No. 3,526,
Multiple layers may be applied simultaneously using coating methods such as those described in US Pat.

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. As the color developing agent, aminophenol compounds are also useful, or p-phenylenediamine compounds are preferably used, representative examples of which are 3-methyl-4-amino-N, N-diethylaniline, 3- Methyl-4-amino-N-ethyl-N
-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N
-β-methoxyethylaniline and their sulfates, hydrochlorides or P-)-luenesulfonates. Two or more of these compounds can be used in combination depending on the purpose.

The color developer may contain pH buffering agents such as alkali metal carbonates, borates or phosphates, bromide salts, iodide salts,
It generally contains a development inhibitor or antifoggant such as benzimidazoles, benzothiazoles or mercapto compounds. In addition, if necessary, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenylsemicarbalads, triethanolamine, catechol sulfonic acids, triethylenediamine (1,4-diazabiscif'C2[2°2.2
] Octane), organic solvents such as ethylene glycol and diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, and amines, dye-forming couplers,
competition coupler.

Fogging agents such as sodium boron hydride, 1
- an auxiliary developing agent such as phenyl-3-pyrazolidone,
Viscosifying agents, various chelating agents such as aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids, such as ethylenediaminetetraacetic acid.

Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N, Representative examples include N',N'-tetramethylenephosphonic acid, ethylene glycol (0-hydroxyphenylacetic acid), and salts thereof.

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

The pH of these color developing solutions and black and white developing solutions is generally 9 to 12. The amount of replenishment of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 39 mm or less per rn" of light-sensitive material, and by reducing the bromide ion concentration in the replenisher,
It can also be less than i. When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the area of contact with the air in the processing tank. Furthermore, the amount of replenishment can be reduced by using means for suppressing the volume of bromide ions in the developer.

After color development, the photographic emulsion layer is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed separately. Furthermore, in order to speed up the processing, a processing method may be used in which a bleaching treatment is followed by a bleach-fixing treatment.

Furthermore, treatment with two consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment can be carried out as desired depending on the purpose. Examples of bleaching agents include compounds of polyvalent metals such as iron (m), cobalt (■), chromium (■), and copper (TI), peracids,
Quinones, nitro compounds, etc. are used. Typical bleaching agents include ferricyanide: dichromate: organic complex salts of iron (m) or cobalt (m), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, and 1,3-diaminoacetic acid. Aminopolycarboxylic acids such as propanetetraacetic acid, glycol ether diaminetetraacetic acid, or citric acid,
Complex salts such as tartaric acid and malic acid; persulfates: bromates; permanganates; nitrobenzenes and the like can be used. Among these, aminopolycarboxylic acid iron(III) complex salts and persulfates, including iron(m) complex salt of ethylenediaminetetraacetate, are preferable from the viewpoint of rapid processing and prevention of environmental pollution. Furthermore, aminopolycarboxylic acid iron(III) complexes are particularly useful in both bleach and bleach-fix solutions. P and H of bleaching solutions or bleach-fixing solutions using these aminopolycarboxylic acid iron (III) complex salts are usually 5.5 to 8.
However, to speed up the process, it is also possible to process at an even lower pH.

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

Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893,858, German Pat.
, No. 290,812, JP-A-53-95630, Research Disclosure No. 17129 (197
Compounds having a mercapto group or disulfide bond described in JP-A No. 50-140129 (July 1983), etc.: Thiazolidine derivatives described in JP-A-50-140129: U.S. Patent No. 3,706,5
Thiourea derivatives described in No. 61: JP-A-58-1623
Iodide salt described in No. 5; West German Patent No. 2,748.430
Polyoxyethylene compounds described in No. 1973-
Polyamine compounds described in No. 8836: bromide ions, etc. can be used. Among them, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large promoting effect.
Especially U.S. Patent No. 3. ．． No. 893,858, West German Patent No. 1
, 290.812 and JP-A-53-95630 are preferred. Additionally, U.S. Patent No. 4,552.
Compounds described in No. 834 are also preferred. These bleach accelerators may be added to the photosensitive material. These bleach accelerators are particularly effective when bleaching and fixing optical materials to obtain color impressions for photography.

Examples of fixing agents include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used, with ammonium thiosulfate being the most widely used. Can be used for As the preservative for the bleach-fix solution, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred.

After desilvering, the silver halide color photographic light-sensitive material of the present invention undergoes a washing and/or stabilization process in one boat. 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 (the 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
Urnal of the 5ociety of M
tion Picture and Televisi
on Engineers Vol. 64, p. 248-25
3 (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. The problem arises. In the processing of the color photosensitive material of the present invention, as a solution to such problems,
The method described in Japanese Patent Application No. 61-131632 for reducing both calcium ions and magnesium ions to 3 ppm or less can be found and used very effectively. Also,
Chlorinated disinfectants such as isothiazolone compounds and cyabendazoles, chlorinated sodium isocyanurate, and other benzotriazoles described in JP-A-57-8542, "Chemistry of antibacterial and antifungal agents" by Hiroshi Horiguchi, Hygiene It is also possible to use the fungicides described in the complete technical book ``Sterilization, sterilization, and anti-mold technology of microorganisms'' and ``Encyclopedia of anti-bacterial and anti-mold agents'' edited by the Nikki Antibacterial and Prevention Society.

The pH of the washing water in the processing of the photosensitive material of the present invention is 4 to 9.
and preferably 5 to 8. The washing water temperature and washing time can be set variously depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds to 10 minutes at 15 to 45°C, preferably 25 to 45°C.
A range of 30 seconds to 5 minutes at ~40°C is selected. Furthermore, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of washing with water. In such stabilization treatment, known methods such as multistage countercurrent stabilization treatment, low replenishment thereof, and ion exchange treatment described in JP-A-5'7-8543, JP-A-58-14834, and JP-A-60-220345 are available. All methods can be used.

Further, the water washing treatment may be followed by a further stabilization treatment, and an example thereof is a stabilization bath containing formalin and a surfactant, which is used as a final bath for color photosensitive materials for photography. Various chelating agents and antifungal agents can also be added to this stabilizing bath.

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

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 it, it is preferable to use various precancers of color developing agents. For example, U.S. Patent No. 3,342,59
Indoaniline compound described in No. 7, No. 3,342,
No. 599, Schiff base-type compounds described in Research Disclosure No. 14850 and Research Disclosure No. 15159, Research Disclosure No. 13
Aldol compounds described in '924, U.S. Patent No. 3.71
Metal salt complex described in No. 9,492, JP-A-53-1356
Examples include the urethane compounds described in No. 28.

The silver halide color light-sensitive material of the present invention may optionally contain various 1-phenyl-3
- Pyrazolidones may be incorporated. Typical compounds are described in JP-A-56-64339, JP-A-57-144547 and JP-A-58-1.15438.

The various processing solutions in the present invention are used at 10°C to 50°C. Normally, the standard temperature is 33°C to 38°C, but higher temperatures can be used to accelerate processing and shorten processing time, or lower temperatures can be used to improve image quality and stability of the processing solution. I can do something. Further, in order to save silver on the photosensitive material, a treatment using cobalt intensification or hydrogen peroxide intensification as described in German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be carried out.

(Effects of the Invention) The silver halide color reversal photosensitive material of the present invention has an excellent effect in that a color reversal image with improved graininess can be formed. In particular, the silver halide color reversal light-sensitive material of the present invention achieves high sensitivity and improved graininess at the same time and provides images of high quality.

(Example) Next, the present invention will be explained in more detail based on examples.

Example 1 On a subbed cellulose triacetate film support,
A multilayer color photosensitive material consisting of each layer having the following composition was prepared and designated as Sample 101.

1st layer: antihalation layer black colloid 0.25g/rn' UV absorber U-10,04g/rn' UV absorber U-20
,1g/rn' Ultraviolet absorber U-30,1g/rn2 High boiling point organic solvent 0-1 0,1 r,c/rn
'Compound A 0.5mg/rn'
Gelatin layer containing (dry film thickness 2IL) 2nd layer: Intermediate layer compound H-10.05g/rn' 1.52 High boiling point organic solvent 0-20, '05cc/m'
Gelatin layer (dry film thickness Iμ) 3rd layer: 1st red-sensitive emulsion layer sensitizing dye S-1 (0,93fi1g/rn') and S
Monodisperse silver iodobromide emulsion spectrally sensitized with -2 (0.04 mg/G) Silver amount...0.33 g/m'' (Iodine content 4 mol%, average grain size 0.3 mm, grain size Coefficient of variation (hereinafter simply referred to as coefficient of variation) 8%) Compound B 0.75 mg/l If Coupler C-10, 13 g/rn' Coupler C-20, o 33 g/m'' High-boiling organic solvent 0-2 0, 08 cc /rn' gelatin layer (dry film thickness 0.7IL) 4th layer: 2nd red-sensitive emulsion layer sensitizing dye S-1 (1,1 mg/m') and S-2<
o, o 4tng/rr? ) Monodisperse silver iodobromide emulsion spectrally sensitized Silver amount...0.53 g/rn'
(Iodine content 3 mol%, average particle size 0.5%, coefficient of variation 16%) Coupler C-10.40g/Coupler C-20.07g/Contains high boiling point organic solvent 0-2 0.22cc/rn' Gelatin layer (dry film thickness i, 'y=) 5th layer: 3rd red-sensitive emulsion layer sensitizing dyes S-1 (1, 1 mg/rn') and S-2 (
Monodisperse silver iodobromide emulsion spectrally sensitized with silver content -0.0, 53 g/rn' (iodine content 2
gelatin layer containing 0.24 cc/m'' of high-boiling organic solvents (Dry film thickness 1.8IL) 6th layer: Intermediate layer compound H-10, 1g1rd High boiling point organic solvent 0.1cc/gelatin layer containing black (Dry film thickness IIL) 7th layer: 1st green-sensitive emulsion layer increase Sensitive dye S-3 (2,2 mg/ln') and 5-4 (
Monodisperse silver iodobromide emulsion spectrally sensitized at 1.0 mg/m') Silver amount...0.5 g/m' (iodine content 4
mol%, average particle size 0.3 hi, coefficient of variation 8%) Gelatin layer containing coupler C-60, 27 g/go high boiling point organic solvent 0-2 0.17 cc/rn' (dry film thickness o, 'y# L,) 8th layer: 2nd
Green-sensitive emulsion layer sensitizing dye 3-3 (0.9 mg/m'') and S-4 (0
, 3 mg/m'') Monodisperse silver iodobromide emulsion spectrally sensitized Silver amount...0.5 g/rn' (Iodine content 2
．． 5 mol%, average particle size 0.5 #L, coefficient of variation 18
%) Gelatin layer containing compound C0.80mg/Gokabura C-60.2g/Gokabura point organic solvent 0.13cc/ln' (dry film thickness t,'yp) 9th layer: 3rd green-sensitive emulsion layer increase Sensitive dyes S-3 (0,9-g/G) and S-4 (0,3-g/G)
Monodisperse silver bromide emulsion spectrally sensitized at
Silver amount...-0.5g/rn' (Iodine content 2 mol%, average particle size 0.6μ, coefficient of variation 17%) Compound (:, 0.80mg/m''
Gelatin layer containing coupler C-40, 2g/high boiling point organic solvent 0-2 0.03cc/rr1'' (dry film thickness 1.7p) 10th layer: Intermediate layer compound H-10,.05g/high boiling point Gelatin layer containing organic solvent o-2 0.1 g/rn' (dry film thickness 1 l) 11th layer: Yellow filter layer Yellow colloidal silver 0.1 g/rn' Compound H-10.02 g/rn' Compound H- 20,03, g/rn' Gelatin layer containing high boiling point organic solvent 0-2 0.04 cc/m'' (dry film thickness l) 12th layer: 1st blue-sensitive emulsion layer Sensitizing dye S-5 (1 , 0Iag/g occupies 50x of the projected area of the particle.Average thickness of particles 0.101L) Coupler C-50.5g/m'' Gelatin layer containing high boiling point organic solvent 0-2 0.1cc/ln' (dry film thickness 1.5IL) $13 layer: 2nd blue-sensitive emulsion layer Tabular silver iodobromide emulsion spectrally sensitized with sensitizing dye S-6 (2,0+*g/rn') Silver amount...-1,1 g/m'' (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. Average particle thickness 0.151 L) Coupler c-s 1.2 g/go height Gelatin layer containing boiling point organic solvent 0-2 0.23cc/rn' (dry film thickness 3μ) 14th layer: 1st protective layer UV absorber U-10,02g/Go UV absorber U-20,03g/rn 'Ultraviolet absorber U
-30,03g/rn' UV absorber U-40,29g
/rn' High Buddha point organic solvent 0 1 0.28cc/r
Gelatin M containing n' (dry film thickness 2p) 15th layer: Fine grain silver iodobromide emulsion covered with the second protective layer Silver amount...0.1 g/rn' (Iodine content 1 mol%.

Average particle size: 0.06 mm) Yellow colloidal silver amount for yellow filter layer: 0.01 g/m' Gelatin layer containing polymethyl methacrylate particles (average particle size: 1.5 JJ) (dry film thickness: 0.8 (l) In addition to the above composition, gelatin hardener H-3 and a surfactant were added to each layer.

In addition, Compound A was added to each emulsion layer at 4x10-
3 moles were added.

The compounds used to prepare the samples are shown below.

C-ni C-hiroh3 C-, t [J-/ -C4Hg GO U-co-c4h9 U-g H-/ 1 to 2 H-2 1 (-J 3/ 1 to 3 S-yu 0 S- Hiroshi 16.1 -g Compound A Compound B Compound C Preparation of Sample 102 Sample 102 was prepared in exactly the same manner as Sample 101 except that the silver iodide content of the photosensitive silver halide emulsion of Sample 101 was all set to 6.5 mol%. was created.

Preparation of Sample 103 Sample 103 was prepared in exactly the same manner as Sample 101 except that the silver iodide content of the photosensitive silver halide emulsion of Sample 101 was all set to 7.1 mol %.

Preparation of Sample 104 The monodisperse silver iodobromide emulsions of the third, fourth, fifth, seventh, eighth, and ninth layers of Sample 101 were prepared with the same average grain size and iodine content as Sample 101. Sample 104 was prepared in exactly the same manner as Sample 101, except that the emulsion in each layer was replaced with the same polydispersity (variation coefficient 25%) emulsion.

Preparation of Sample 105 The emulsions of the third and seventh layers of Sample 101 were made into an emulsion with an iodine content of 4 mol%, an average grain size of 0.3%, and a coefficient of variation of 19%. IIi,,
Sample 1 was prepared in exactly the same manner as Sample 101, except that a mixed emulsion was used in which an emulsion with a variation coefficient of 6% was mixed with a silver content ratio of 3=1.
05 was produced.

The grain size distribution curve of the mixed emulsion used in the 3rd N and 7th layers had two peaks, and the difference in grain size between the peaks was 0.20 hi.

Preparation of Sample 106 An emulsion with an iodine content of 6.5 mol%, an average grain size of 0.1 l, and a coefficient of variation of 6% was added to the emulsion of the third and seventh layers of Sample 102. 3:1 so that the total amount of silver in the third and seventh layers is the same as that of sample 102.
Sample 106 was prepared in exactly the same manner as Sample 102 except that the mixed emulsion mixed in step 1 was used.

The grain size distribution curve of the mixed emulsion used in the third and seventh layers had two peaks, and the difference in grain size between the peaks was 0.1871.

Preparation of Sample 107 The emulsions of the 3rd to 5th layers, the 7th to 9th layers, and the 12th to 13th layers were prepared using emulsion A as shown in Table 1 below, in which the iodine content and coated silver amount of each layer were the same as those of sample 101. Sample 107 was prepared in exactly the same manner as Sample 101 except that B was used as the mixed emulsion.

Preparation of sample 108 The third layer of sample 103 as an emulsion for the third and seventh layers,
The seventh layer emulsion had an iodine content of 7.1 mol% and an average grain size of 0.1/7. , sample 103 except that a mixed emulsion with a coefficient of variation of 8% was mixed at a ratio of 3:1 so that the total silver amount in each of the third and seventh layers was the same as sample 103.
Sample 108 was prepared in exactly the same manner. This third layer,
The grain size distribution curve of the mixed emulsion used in the seventh layer had two peaks, and the difference in grain size between the peaks was 0.18 #L.

Preparation of sample 109 The third layer of sample 104 as an emulsion for the third and seventh layers,
The emulsion in the first layer has an iodine content of 4 mol% and an average grain size of 0.
．． Sample 109 was prepared in exactly the same manner as Sample 104, except that a mixed emulsion containing an emulsion with a coefficient of variation of 6% and a silver content ratio of 1:1 was used. When the emulsions were mixed in the third and seventh layers, there were two peaks in the particle size distribution curve, and the difference in particle size between the peaks was 0.191L.

Preparation of sample 110 Instead of the emulsion with an average grain size of 0.1o and a coefficient of variation of 6% mixed into the third and seventh layers of sample 105, an emulsion with an average grain size of 0.211L and a coefficient of variation of 6% was used. Sample 110 was prepared in exactly the same manner as sample 105 except that the sample 110 was used.

In the third and seventh layers, there were two peaks in the grain size distribution curve when the emulsions were mixed, and the difference in grain size between the peaks was 0.08.

Preparation of samples 111-119 Samples 101-104, 108.110, 105.106
．． Samples 101-104, 108, 110, and 105.1 were used, except that 1 x 10 mol of compound Ni 11 was added to the third and seventh layers of No. 109 per mol of silver in the emulsion of each layer.
Samples 111 to 119 were prepared in exactly the same manner as No. 06.109.

Preparation of Samples 120 to 127 Compounds l-13, I-1, I-4, I-8,
Sample 10 except that I-9, l-12, ■-18, and l-29 were added in lXl0-4 mol per mol of silver in the emulsion of each layer.
Samples 120 to 127 were prepared in exactly the same manner as in Example 7.

Preparation of Sample 128 Compound Ni 23 was added to the second layer, sixth layer, io layer, 11N layer, and 14th layer of sample 107 at 2×10 −6 mol/m in each layer.
Sample 128 was prepared in exactly the same manner as Sample 107 except that the coating amount was 1.

These samples 101-128 were passed through a continuous wedge,
The film was exposed to white light from a 5400 mm light source, and the following development process was performed.

Processing process Time Temperature - Development 6 minutes 38℃ Water washing 2 minutes 38℃ Inversion 2 minutes 38℃ Color development 6 minutes 38℃ Adjustment 2 minutes 38℃ bleaching
6 minutes 38°C fixation 4 minutes
38°C water washing 4 minutes 38°C stability 1 minute 25°C The composition of each treatment solution was as follows.

Nitrilo-N,N,N- Trimethylenephosphonic acid, pentasodium 2.0g Sodium sulfite 30g Hydroquinone potassium monosulfonate 20g Potassium carbonate 33g 1-phenyl-4-methyl-4-hydroxymethyl-3- Pyrazolidone 2.0g Potassium bromide 2.5g Potassium thiocyanate 1.2g Potassium iodide
Add 2.0mg water 1
000ml10009,60 pH was adjusted with hydrochloric acid or potassium hydroxide.

Reverse strainer Nitrilo-N,N,N-trimethylenephosphonic acid pentasodium salt 3.0g stannous chloride dihydrate 1. Ogp-aminophenol
O, 1g sodium hydroxide
8g glacial acetic acid Add 15d water 1000100O6,0
0 PH was adjusted with hydrochloric acid or sodium hydroxide.

Moxibustion to Shihohen Nitrilo-N,N,N- trimethylenephosphonic acid, pentasodium salt 2.0g Sodium sulfite 7-0g Trisodium phosphate
12 hydrate salt 36g potassium bromide
1.0g potassium iodide 9
0mg Sodium hydroxide 3.0g Citrazic acid 1.5g N-ethyl-
N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 11g3.6-cythiaoctane-1.8-diol 1.0gAdd water
10007% pH 11.80 pH was adjusted with hydrochloric acid or potassium hydroxide.

trap! Smoked ethylenediamine tetraacetic acid, disodium salt, dihydrate salt 8. Og - Sodium sulfite 12g1-thioglycerin Add 0.4ml water
10001iii pH 6,20 pH was adjusted with hydrochloric acid or sodium hydroxide.

Ethylenediaminetetraacetic acid, disodium salt, dihydrate 2.0g Ethylenediaminetetraacetic acid, Fe(m), ammonium dihydrate 120g Potassium bromide 100g Ammonium nitrate
Add 10g water
1000100O5,70 pH was adjusted with hydrochloric acid or sodium hydroxide.

Fixed Fish Sodium Thiosulfate 80g Sodium Sulfite 5.0g Sodium Bisulfite
Add 5.0g water
1000100O6,60 pH was adjusted with hydrochloric acid or aqueous ammonia.

Landlord level formalin (37%) 5.0yn[i7
ri polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.5 mt of water was added for 1000 dThe cyan, magenta,
The yellow density was measured, and the maximum density, relative sensitivity at a density of 1.0, and graininess were measured. The result is the second
Shown in the table.

Note that the granularity is expressed as a value obtained by multiplying the RMS granularity by 1000.

From the results in Table 2, it can be seen that the present invention is superior to the comparative example in the following points.

■Higher sensitivity and better graininess than when mixed emulsion is not used (Samples 111 and 117).

(2) The sensitivity is extremely high compared to the case not containing the rFAJ-releasing compound (FR compound), and there is almost no deterioration in graininess (Samples 105 and 117).

(2) Compared to the case where the average silver iodide content of the photosensitive silver halide emulsion layer is 7 mol % or more, the sensitivity is extremely high and the deterioration of graininess is small (Samples 115 and 117 and 118).

■When the emulsion is mixed, the difference in grain size between the two peaks of the grain size distribution curve is O.
, tpL has higher sensitivity and better graininess than the case without vortex (
Samples 116 and 117).

Example 2 The same results as in Example 1 were obtained when Samples 101 to 128 of Example 1 were exposed in the same manner as in Example 1 and subjected to the following development treatment.

Processing process Time Temperature first development 6 minutes 38°C First water washing 45 seconds 38°C Inversion 45 seconds 38°C color development
6 minutes 38°C bleaching 2 minutes 38°C bleach-fixing
4 minutes 38°C Second water wash (1) 1 minute 38°C Second water wash (2) 1 minute 38°C Stable 1 minute 25°C The composition of each treatment solution was as follows.

First developer Nitrilo-N,N,N- trimethylenephosphonic acid, pentasodium salt 2.0g Sodium sulfite 30g Hydroquinone potassium monosulfonate 20g Potassium carbonate 33g 1-phenyl-4-
Methyl-4-hydroxymethyl-3-pyrazolidone 2.0g Potassium bromide 2.5g Potassium thiocyanate 1.2g Potassium iodide
Add 2.0mg water 10
00m [ipH 9,60 pH was adjusted with hydrochloric acid or potassium hydroxide.

First washing solution mother liquor Add ethylenediaminetetramethylenephosphonic acid 2.0g disodium phosphate 5.0g water
1ooovpH7.00 pH was adjusted with hydrochloric acid or sodium hydroxide.

Dilution solution Nitrilo-N,N,N-trimethylenephosphonic acid pentasodium salt 3.0g stannous chloride dihydrate 1. OgP-Aminophenol 0.1g Sodium hydroxide
8g glacial acetic acid 15
Add ml water to 1oooy pH6
,00 pH was adjusted with hydrochloric acid or sodium hydroxide.

Moxibustion acute nitrilo-N,N,N-trimethylenephosphonic acid pentasodium salt 2.0g Sodium sulfite 7.0g Trisodium phosphate dodecahydrate 36g Potassium bromide
1.0g potassium iodide
90+ag sodium hydroxide 3.0
g Citrazic acid 1.5 g N-ethyl-N-(β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 11 g 3.6-cythiaoctane-1.8-diol i, 0 g Add water
10001119pH 11.80 PH was adjusted with hydrochloric acid or potassium hydroxide.

Ethylenediaminetetraacetic acid, disodium salt, dihydrate 10.0g Ethylenediaminetetraacetic acid, Fe(m), ammonium, dihydrate 120g Ammonium bromide 100g Ammonium nitrate
10g bleach accelerator 0-
Add 005 mol water and make 1000 d
PH6.30 The pH was adjusted with hydrochloric acid or aqueous ammonia.

Nobutada Omura 1 Ethylenediaminetetraacetic acid, Fe() ・Ammonium, dihydrate 50g Ethylenediaminetetraacetic acid, disodium, dihydrate 5.0g Ammonium thiosulfate 80g Sodium sulfite
Add 12.0g water 1
000dpH6.60 pH was adjusted with hydrochloric acid or aqueous ammonia.

The second washing liquid tap water is passed through a mixed bed column packed with an H-type strongly acidic cation exchange resin (Amberlite IR-120B, manufactured by Rohm and Haas) and an OH-type anion exchange resin (Amberlite IR-400, manufactured by Rohm and Haas). The calcium and magnesium ion concentration was treated with water to a concentration of 3 tag/l or less, followed by sodium isocyanurate dichloride 20+*g/u.
and 1.5 g/liter of sodium sulfate were added. p of this liquid
H is in the range of 6.5 to 7.5.

Formalin (37%) 5.0m Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) Add 0.5d water 10007111ii Example 3 without pH adjustment Preparation of sample 301 Sample 3 of sample 101 Sample 301 was prepared in exactly the same manner as Sample 101 except that the emulsion in the seventh layer was a mixed emulsion as shown in Table 3 below.

Table 3: Preparation of Sample 302 Sample 302 was prepared in exactly the same manner as Sample 301, except that 1'X10-' mol of Compound I-11 was added to the third and seventh layers of Sample 301 per mol of silver in the emulsion of each layer. was created.

Sample 101.111.301.30 prepared in this way
Sample No. 2 was exposed and developed in the same manner as in Example 1, and the density, relative sensitivity and graininess were tested. The results are shown in Table 4.

]86 1R,q From the results in Table 4, it can be seen that the present invention has higher sensitivity and excellent graininess than the comparative example.

Example 4 Preparation of samples 401 to 410 Sample 120 except that the compound shown in the fifth layer was added to the 3rd layer 3.4.5.7.8.9.12.13 per 1 mole of silver, respectively lXl0' mole Similarly, samples 401-41
0 was created.

Samples 401 to 410 and sample 120 prepared as above
Divide it into two parts, leave one part at room temperature for 7 days, and leave the other part for 4 days.
It was left for 7 days under the condition of 5°050% RH. These samples were exposed using a sensitometric wedge, developed in the same manner as in Example 1, and measured for cyan, magenta, and yellow densities.

In addition, the difference in exposure amount Δ9-ogE required to develop a density of 1.0 between the sample stored at 45°C, 50% RH for 7 days and the sample stored at room temperature for 7 days, and the difference in maximum density were determined. .

The results are shown in Table 5.

Note that the larger the difference in ΔD wax, the greater the degree of sensitization during high-temperature storage, and the larger the value of ΔD wax, the greater the decrease in maximum density during high-temperature storage, both of which are unfavorable.

From the results in Table 5, it can be seen that the present invention exhibits less sensitization during high-temperature storage and less D'may sensitivity than the comparative example.

Claims (1)

[Claims] A light-sensitive silver halide photographic layer having a light-sensitive silver halide emulsion having an average silver iodide content of less than 7.0 mol % is provided on the support, and at least one emulsion layer of the photographic layer has an average grain size. is 0
．． The grain size distribution curve of silver halide grains is composed of two or more types of emulsions with different grain sizes in the range of 0.05 to 3.0μ, and the grain size distribution curve of the silver halide grains has two or more maximums, and among the maximums, the grain size is the most The difference in grain size between the smallest maximum and the next smallest maximum is 0.1μ.
above, and the emulsion layer and/or its adjacent intermediate layer undergoes a redox reaction with a developer oxidation product or
A silver halide color reversal photosensitive material containing at least one compound that releases a fogging agent, a development accelerator, a silver halide solvent, or a precursor thereof in accordance with the amount of developed silver by the subsequent reaction of the reaction. material.