JPH03100541A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a photosensitive material capable of forming an image superior in sharpness and storage stability of an image by forming a specified hydrophilic colloidal layer and a specified emulsion layer. CONSTITUTION:The hydrophilic colloidal layer contains at least one of compounds dispersed in fine crystals, and selected from groups represented by formulae I and II and the like, and in these formulae, A is an acidic unit; each of X and Y is an electron attractive group; R is H or alkyl; each of R1 and R2 is alkyl or aryl, and each may combine with each other to form a 5- or 6-membered ring; each of R3 and R6 is H, OH, or the like; each of R4 and R5 is H or a nonmetalic atomic group necessary to form a 5- or 6-membered ring together with R1 and R4 or R2 and R5; and p is 0 or 1, 2 0 or 1, and when p is 0, R3 is OH or the like, and each of R4 and R5 is H, and the emulsion layer contains flat photosensitive silver halide grains having an aspect ratio of >=3, thus permitting the obtained photosensitive body to be enhanced in image sharpness and image storage stability.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a silver halide window optical material with improved image sharpness and storage stability.

(Prior art) Usually, in a photographic light-sensitive material consisting of a silver halide emulsion layer,
It is known that light scattering by silver halide grains tends to reduce the sharpness of the emulsion layer.

U.S. Patent No. 4,434,226, No. 4,439.52
No. 0 or No. 4,433,048 describes improvements in sharpness etc. by using a tabular silver halide emulsion and its application to photographic light-sensitive materials.

However, when a photosensitive material containing tabular silver halide grains is stored at high temperature or high temperature and high humidity,
This had the major drawback of causing performance changes such as increased fog during storage.

It is well known that in silver halide photographic materials, dyes are included in the constituent layers of the material in order to absorb light of a specific wavelength for the purpose of light absorption filters, antihalation, or sensitivity adjustment of photosensitive emulsions. Therefore, coloring of the hydrophilic colloid layer with the above-mentioned dyes has been conventionally practiced.

Colloidal silver has traditionally been used for yellow light absorption filters and antihalation purposes. However, there is a problem in that this colloidal silver increases fog in the photosensitive silver halide emulsion layer adjacent to the colloidal Wi layer.

This poses a particularly serious problem when attempting to use the above-mentioned tabular silver halide grains.

Therefore, dyes used for such purposes must (I) have appropriate spectral absorption according to the purpose of use;

(2) It should not be bleached during the photographic processing process or be eluted into the processing solution or washing water, leaving no harmful coloring on the photographic material after processing.

(3) Do not diffuse from the dyed layer to other layers.

(4) Excellent stability over time in solutions or photographic materials and no discoloration or fading.

In addition to this condition, it must be photochemically inert.

That is, it is particularly important that the performance of the silver halide photographic emulsion layer is not adversely affected in a chemical sense, such as a decrease in sensitivity, latent image regression, or fog.

Many efforts have been made to find dyes that meet these requirements.

U.S. Pat. No. 4,420,555 uses an open chain methylene hengelidene dye of the following -S formula in the yellow filter layer, but this dye diffuses to other layers and desensitizes the blue-sensitive emulsion layer. There is a drawback.

6 JP-A No. 62-222248 solves this problem of dye diffusion to other layers and provides a yellow dye layer with excellent filtering effect. Although this method achieves the goal of no diffusion to other layers, it has the disadvantage that there may be residual color after treatment.

In addition, as a method to satisfy the above conditions (3) and (4) required for dyes, a hydrophilic polymer having a charge opposite to that of the dissociated anionic dye is allowed to coexist in the layer as a mordant.
A method of causing a dye to exist in a specific layer through interaction with dye molecules is disclosed in U.S. Pat. No. 2,548,564;
No. 124,386, No. 3.625:694, etc.

In addition, a method of dyeing a specific layer using a water-insoluble dye solid is disclosed in JP-A-56-12639 and JP-A-55-1553.
No. 50, No. 55-155351, No. 63-27838
No. 63-197943, European Patent No. 15,601
No. 274,723, No. 276.566, No. 29
No. 9,435, World Patent (WO) No. 88104794, and the like.

In addition, a method of dyeing a specific layer using metal salt fine particles to which a dye has been adsorbed is disclosed in U.S. Pat.
, No. 496,841, No. 2,496.843, and Japanese Unexamined Patent Publication No. 45237/1983. however,
These methods also have the problem of increased fog when tabular silver halide grains are present in the vicinity of the dye, and none of them has been able to satisfy both image sharpness and storage stability.

(Problems to be Solved by the Invention) Therefore, an object of the present invention is to improve image sharpness,
Moreover, it is an object of the present invention to provide a silver halide photographic material in which images have improved storage stability.

(Means for solving the problem) The above purpose is as follows - Formulas (I), (II), (III),
(IV), at least one selected from the group consisting of (IV)
a hydrophilic colloid layer containing a microcrystalline dispersion of a seed compound;
This was achieved by a silver halide photographic light-sensitive material characterized by having an emulsion layer containing photosensitive silver halide grains having an aspect ratio of 3 or more.

General formula (I) General formula (El) R general formula (I[+) A''L+ (L! -Ls), A'
- General formula IV) A'' (L+ -L!) t-q -B- Formula (V) (wherein, A and A' may be the same or different, each represents an acidic acid, and B represents a basic R represents a nucleus, X and Y may be the same or different, and each represents an electron-withdrawing group;
represents a hydrogen atom or an alkyl group, R1 and R□ each represent an alkyl group, an aryl group, an acyl group, or a sulfonyl group, and R+ and R1 may be linked to form a 5- or 6-membered ring.

R3 and R6 each represent a hydrogen atom, a hydroxy group, a carboxyl group, an alkyl group, an alkoxy group, or a halogen atom, and R4 and Rs each represent a hydrogen atom, or R+ and R4 or R2 and R5 are linked to form a 5- or 6-membered ring. m t, +, L*, and RI, which represent nonmetallic atomic groups necessary for forming, each represent a methine group.

m represents 0 or 1, n and q each represent 0.1 or 2, P represents O or 1, when p is 0, R1 represents a hydroxy group or a carboxyl group, and R4 and Rs represent hydrogen The compound represented by the formula % () is a dissociative compound that has a pKa in the range of 4 to 11 in a mixed solution with a volume ratio of water and ethanol of 1:1 in one molecule. It has at least one group. ) First, - formula CI), (n), (I), (rt/), (
IV) f The compound shown will be explained in detail.

The acidic nucleus represented by A or A' is preferably 2-pyrazolin-5-one, rhodanine, hydantoin, thiohydantoin, 2,4-oxazolidinedione, isoxazolidinone, barbylic acid, thiobarbital acid, indanedione, pyrazolopyridine. Or represents hydroxypyridone.

The basic nucleus represented by B preferably represents pyridine, quinoline, indolenine, oxazole, benzoxazole, naphthoxazole or pyrrole.

A group having a dissociable proton with a pKa (eaM dissociation constant) in the range of 4 to 11 in a mixed solution of water and ethanol at a volume ratio of 1:1 makes the dye molecule substantially insoluble in water at pH 6 or below. There is no particular restriction on the type and substitution position on the dye molecule as long as it makes the dye molecule substantially water-soluble at pH 8 or above, but preferably a carboxyl group, a sulfamoyl group, a sulfonamide group, A more preferred hydroxy group is a carboxyl group. The dissociative group may be substituted not only directly on the dye molecule, but also via a divalent linking group (eg, alkylene group, phenylene group).

Examples via a divalent linking group include 4-carboxyphenyl, 2-methyl-3-carboxyphenyl, 2,4-
Dicarboxyphenyl, 3,5-dicarboxyphenyl, 3-carboxyphenyl, 2,5-dicarboxyphenyl, 3-ethylsulfamoylphenyl, 4-phenylsulfamoylphenyl, 2-carboxyphenyl,
2. 4゜6-Dolyhydroxyphenyl, 3-benzenesulfonamidophenyl, 4-(p-cyamibenzenesulfonamido)phenyl, 3-hydroxyphenyl, 2
-Hydroxyphenyl, 4-hydroxyphenyl, 2-
Hydroxy-4-carboxyphenyl, 3-methoxy-
4-carboxyphenyl, 2-methyl-4-phenylsulfamoylphenyl, 4-carboxybenzyl, 2-
Carboxybenzyl, 3-sulfamoylphenyl, 4
-sulfamoylphenyl, 2,5-disulfamoylphenyl, carboxymethyl, 2-carboxyethyl,
3-carboxypropyl, 4-carboxybutyl, 8-
Examples include carboxyoctyl.

The alkyl group represented by R, Rs or Rh has 1 to 1 carbon atoms.
10 alkyl groups are preferred, and examples include groups such as methyl, ethyl, n-propyl, isoamyl, n-octyl and the like.

The alkyl group represented by R+ and Rz is an alkyl group having 1 to 20 carbon atoms (for example, methyl, ethyl, n-propyl, n-
-butyl, n-octyl, n-octadecyl, isobutyl, isopropyl) are preferred; ), alkoxycarbonyl groups (e.g. methoxycarbonyl, i-propoxycarbonyl), aryloxy groups (e.g. phenoxy), phenyl groups, amide groups (e.g. acetylamino, methanesulfonamide), carbamoyl groups (e.g. methylcarbamoyl). ,
ethylcarbamoyl), sulfamoyl group (eg, methylsulfamoyl, phenylsulfamoyl)].

The oryl group represented by R3 or R2 is preferably a phenyl group or a naphthyl group, and the substituent [the substituent is the above R
, and the groups and alkyl groups (eg, methyl, ethyl) listed as substituents for the alkyl group represented by Rt. ].

The acyl group represented by R1 or R2 is preferably an acyl group having 2 to 10 carbon atoms, and includes, for example, acetyl, propionyl, n-octanoyl, n-decanoyl, isobutanoyl, benzoyl, and the like. R3 or R
Examples of the alkylsulfonyl group or arylsulfonyl group represented by 2 include methanesulfonyl, ethanesulfonyl, n-methanesulfonyl, n-octanesulfonyl, benzenesulfonyl, 1)-)luenesulfonyl,
Groups such as 0-carboxybenzenesulfonyl can be mentioned.

The alkoxy group represented by R1 or R6 has 1 to 1 carbon atoms.
Preferably, O is an alkoxy group, including groups such as methoxy, ethoxy, n-butoxy, n-octoxy, 2-ethylhexyloxy, isobutoxy, and impropoxy. Examples of the halogen atom represented by RS or Rh include chlorine, bromine, and fluorine.

Examples of the ring formed by linking R1 and R4 or R2 and RS include a julolidine ring.

Examples of the 5- or 6-membered ring formed by linking Rt and Rz include a piperidine ring, a morpholine ring, and a pyrrolidine ring.

The methine group represented by I, +, Lx or ri may have a substituent (for example, methyl, ethyl, cyano, phenyl, chlorine atom, hydroxypropyl).

The electron-withdrawing groups represented by X or Y may be the same or different. , hexadecanoyl, 1-oxo-7-chlorohebutyl), arylcarbonyl group (optionally substituted carbonyl group, such as benzoyl, 4-ethoxycarbonylbenzoyl, 3-chlorobenzoyl)
, alkoxycarbonyl group (an alkoxycarbonyl group that may be substituted, such as methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, t-amyloxycarbonyl, hexyloxycarbonyl, 2-ethylhexyloxycarbonyl, octyloxycarbonyl, decyloxy Carbonyl, dodecyloxycarbonyl, hexadecyloxycarbonyl, octadecyloxycarbonyl, 2-butoxyethoxycarbonyl, 2-
Methylsulfonylethoxycarbonyl, 2-cyanoethoxycarbonyl, 2-(2-chloroethoxy)ethoxycarbonyl, 2-(2-(2-chloroethoxy)ethoxy]ethoxycarbonyl), aryloxycarbonyl group (which may be substituted) -ruoxy carbonyl group, such as phenoxycarbonyl, 3-ethylphenoxycarbonyl, 4-ethylphenoxycarbonyl, 4-ethylphenoxycarbonyl,
-Fluorophenoxycarbonyl, 4-nitrophenoxycarbonyl, 4-methoxyphenoxycarbonyl, 2
．． 4-di(t-amyl)phenoxycarbonyl), carbamoyl group (carbamoyl group which may be substituted,
For example, carbamoyl groups ethylcarbamoyl, dodecylcarbamoyl, phenylcarbamoyl, 4-methoxyphenylcarbamoyl, 2-bromophenylcarbamoyl, 4-chlorophenylcarbamoyl, 4-ethoxycarbonylphenylcarbamoyl, 4-propylsulfonylphenylcarbamoyl, 4-cyanophenylcarbamoyl, 3-methylphenylcarbamoyl, 4-hexyloxyphenylcarbamoyl, 2,4-di(t-amyl)phenylcarbamoyl, 2-chloro-3-(dodecyloxycarbamoyl)phenylcarbamoyl, 3-(hexyloxycarbonyl)phenylcarbamoyl ), sulfonyl groups (e.g. methylsulfonyl, phenylsulfonyl), sulfamoyl! << is a sulfamoyl group which may be substituted, for example, sulfamoyl, methylsulfamoyl).

Next, specific examples of dyes used in the present invention will be given.

-4 1-9 ■-11 ! -5 -6- 7- ■-12 ■-13 ■-14 C) (3 ! -15 ■-17 ■-18 -19 ■-21 1-2 1-3 1-4 I'i co rl-5 ■-6 1[[-1 -2 11-7 -9 ff-3 -4 ■-5 ■ 1l-10 -il ff-12 ■-14 ■-16 ■-20 ■-21 ■-22 ■-17 ■-18 ■-19 ■-24 ■-25 Shuuub [1-29 ■ 3 ff-34 CH.

CH.

ShigH5 ■-30 ll-31 CH.

Hx To, HS CHs CzHs 1Hs Tt/-,15 CzHs ■-10 ■-12 CzHs z　Hs CzHs CH3 CH2 -4 V-5 -6- 7 CH.

The dye used in the present invention is covered by International Patent W08810479.
No. 4, European Patent EPO 274723A1, No. 2
No. 76,566, No. 299,435, JP-A-52-9
No. 2716, No. 55-155350, No. 55-155
No. 351, No. 61-205934, No. 48-6862
No. 3, U.S. Pat. No. 2,527,583, U.S. Pat. No. 3,486,897
No. 3746539, No. 3933798, No. 41
It can be easily synthesized by the method described in No. 30429, No. 4040841, and the like.

In the present invention, the dye is formed into a solid fine powder dispersion for inclusion in a layer, such as a hydrophilic colloid layer, coated on a photographic element. The fine powder dispersion can be prepared by precipitating the dye in the form of a dispersion and/or in the presence of a dispersing agent by known comminution means, such as ball milling (ball mill, vibratory ball mill, planetary ball mill, etc.), sand milling. , colloid milling, jet milling, roller milling, etc. In that case, a solvent (for example, water, alcohol, etc.) may be present. Alternatively, after dissolving the dye in a suitable solvent, a non-solvent for the dye may be added to precipitate a microcrystalline powder of the dye.
In that case, a dispersing surfactant may be used. Alternatively, by controlling the pH of the dye, the dye may be first dissolved and then crystallized by changing p).The dye particles in the dispersion have an average particle size of 10 μm or less, more preferably 2 μm or less. Yes, particularly preferably 0.5
μm or less, and in some cases (L1 μm or less) is more preferably a fine powder.

The amount of dye used in the present invention is 1~1000/
Used in the range d. Preferably 5■~80Qqr/
It is rd.

The dye dispersion of the present invention can be added to any layer, regardless of whether it is an emulsion layer or an intermediate layer.

However, the effects of the present invention are remarkable when a part or all of the colloidal silver, which is commonly used in the yellow filter layer and/or antihalation layer, is used as a substitute.

In the present invention, tabular silver halide grains (hereinafter referred to as "tabular grains") have two opposing parallel principal planes, and have a circular equivalent diameter of the supranuclear plane (a circle having the same projected area as the principal plane). Particles whose particle size (diameter) is twice or more larger than the distance between principal planes (i.e. particle thickness).

The average grain diameter/grain thickness ratio of the emulsion containing the tabular grains of the present invention is preferably from 3 to 12, particularly preferably from 5 to 10.

Here, the average grain diameter/grain thickness ratio is obtained by averaging the grain diameter/grain thickness ratio of all tabular grains, but a simple method is to calculate the average diameter of all tabular grains and the average of all tabular grains. It can also be determined as a ratio to the thickness.

The diameter (equivalent to a circle) of the tabular grains of the present invention is 0.3 to 10 μm
, preferably 0.5 to 5.0 μm1, more preferably 0
．． It is 5 to 2.0 μm.

The particle thickness is 0.5 μm or less, preferably 0.05 to 0.5 μm.
5 μm, more preferably 0.08 to 0.3 μm.

The particle diameter and particle thickness in the present invention can be determined from electron micrographs of the particles by the method described in US Pat. No. 4,434,226.

As the halogen composition of the tabular grains, specifically, silver chloroiodide, silver iodobromide, silver chloride, silver chlorobromide, and silver chlorobromide can be used. It may also contain thiocyanate, silver cyanate, and the like.

As methods for producing tabular grains, US Pat. No. 4,434,226, US Pat.
No. 6156, No. 4400463, No. 441430
This can be accomplished by appropriately combining the methods described in No. 6, No. 4435501, and the like.

For example, seed crystals containing tabular grains of 40% or more by weight are formed in an atmosphere with a relatively high p and Ag value of pBrl, 3 or less, and a silver and halogen solution is grown while maintaining the pBr value at the same level or higher. It can be obtained by adding and growing seed crystals.

1B! In the grain growth process due to the addition of and10r halogen, it is desirable to add a silver and halogen solution so that new crystal nuclei are not generated.

The size of the tabular grains can be adjusted by controlling temperature, selection of the type and amount of solvent, silver salt used during grain growth, rate of addition of halide, etc.

The internal sensitivity of the tabular grains of the present invention after surface chemical sensitization can be increased by chemically sensitizing the tabular grains at a stage before the completion of grain formation. Preferably, chemical aggravation is carried out before 80% of the total silver content of the grains is reached.

This chemical sensitization was developed by James (T.
), The Theory of Photographic Process, 4th edition, Macmillan Publishing, 1977, (T.
H. James, The Theory of the
PhotographicProcess, 4t
h ad, Macmillan+ 1977)
It can be carried out using activated gelatin as described on pages 67-76, or as described in Research Disclosure, Vol. 120, April 1974, 12008;
Disclosure, 34%, June 1975, 134
52, U.S. Patent No. 2,642.361, U.S. Patent No. 3,297
, No. 445, No. 3772.031, No. 3,857,
No. 711, No. 3.901.714, No. 4,266.0
18 and 3,904,415, and pAg5 as described in British Patent No. 1,315,755.
~101 pH 5-8 and temperature 30-80°C using sulfur, selenium, chiru, gold, platinum, palladium, iridium, rhodium or combinations of these sensitizers. Chemical sensitization is optimally carried out in the presence of a gold compound and a thiocyanate compound and as described in US Pat.
857.711, 4,266.018 and 4
Chemical aggravation can also be carried out in the presence of a chemical aggravation aid, such as in the presence of a sulfur-containing compound or a sulfur-containing compound such as hypo, thiourea-based compounds, rhodanine-based compounds, etc., as described in No. 054.457. The chemical sensitizing aid used is a compound known to suppress fog and increase sensitivity during the process of chemical sensitization, such as azaindene, azapyridazine, and azapyrimidine. Examples of chemical sensitizer modifiers include U.S. Pat. No. 2,131,038.
No. 3,411,914, No. 3,554,757, Japanese Unexamined Patent Publication No. 126526/1983, and the aforementioned "
"Photographic Emulsion Chemistry", pp. 138-143.

In addition to or in place of chemical sensitization, U.S. Pat.
Reduction sensitization can be performed, for example, using hydrogen, as described in U.S. Pat. Nos. 91,446 and 3,984,249;
3°182 and 2,743,183 using stannous chloride, thiourea dioxide, polyamines and such reducing agents, or with low pAg (e.g. less than 5) and/or high pH. (e.g. greater than 8)
Reduction sensitization can be achieved by treatment. Chemical sensitization methods described in US Pat. No. 3,917,485 and US Pat. No. 3,966,476 can also be applied.

Also, patent application No. 59-122981 and No. 59-122984.
Sensitization using an oxidizing agent as described in can also be applied.

Another method for increasing the internal sensitivity is to introduce a gap in the halogen composition at a stage before the completion of grain formation. This is also preferably introduced at a stage before 80% of the total silver content of the grains.

The larger the gap in halogen composition, the higher the internal sensitivity. For example, in the case of silver iodobromide, it is preferable that there is a difference in silver iodide content of 5 mol% or more, and more preferably 10 mol% or more. Preferably, there is a difference in content.

In the present invention, the following monodisperse hexagonal tabular grains can be used.

The emulsion is a silver halide emulsion consisting of a dispersion medium and silver halide grains, in which 70% or more of the total projected area of the silver halide grains has a maximum area of 70% or more relative to the length of the side having the minimum length. It is a hexagonal shape in which the ratio of the lengths of its sides is 2 or less, and is occupied by tabular silver halide having two parallel surfaces as outer surfaces, and further, the hexagonal tabular halogen Coefficient of variation of grain size distribution of silver oxide grains [value obtained by dividing the variation (standard deviation) of grain size expressed by the circular diameter of its projected area by the average grain size]
has a monodispersity of 20% or less, an aspect ratio of 2.5 or more, and a particle size of 0.2 μm or more.

The composition of the hexagonal tabular grains includes silver bromide, silver iodobromide,
When containing iodide ions, which may be either silver chlorobromide or silver chlorioodobromide, the content is 0 to 30 mol%,
The crystal structure may be --like, the inside and outside may have different halogen compositions, or may have a layered structure, and it is preferable that the grains contain reduction-sensitized silver nuclei.

The silver halide grains can be produced through nucleation-Ostwald ripening and grain growth,
The details are as described in Japanese Patent Application No. 61-299155.

When producing the tabular grains of the present invention, it is preferable to increase the addition rate, amount, and concentration of a silver salt solution (for example, AgN0j aqueous solution) and a halide solution (for example, KBr aqueous solution), which are added to accelerate grain growth. used.

These methods are described, for example, in British Patent No. 1°335.
No. 925, U.S. Patent No. 3,672,900, U.S. Patent No. 3,
650.757, 4,242.445, JP-A-55-142329, JP-A-55-158124, etc. can be referred to.

Silver halide solvents are useful for promoting ripening. For example, it is known to have an excess of halide ions present in the reactor to promote ripening. It is therefore clear that ripening can be accelerated simply by introducing a halide salt solution into the reactor. Other ripening agents can be used, and these ripening agents can be incorporated in their entirety into the dispersion medium in the reactor before the silver and halide salts are added, and one or more ripening agents can be used. The ripening agent can also be introduced into the reactor together with the addition of the halide salt, silver salt or peptizer; another variant is to introduce the ripening agent separately at the halide salt and silver salt addition steps. You can also do it.

As ripening agents other than halogen ions, ammonia or amine compounds, thiocyanate salts 2, such as alkali metal thiocyanate salts, especially sodium and potassium thiocyanate salts, and ammonium thiocyanate salts can be used. The use of thiocyanate ripening agents is described in U.S. Pat. Nos. 2,222,264 and 2,4.
48,534 and 3,320,069. Also, U.S. Patent No. 3,271,157;
．． Conventional thioether ripening agents such as those described in No. 574,628 and No. 3,737.313 can also be used. Or JP-A No. 53-82408,
Thione compounds such as those disclosed in No. 53-144319 can also be used.

The properties of silver halide grains can be controlled by allowing various compounds to be present during the silver halide precipitation formation process. Such compounds may be initially present in the reactor or may be added along with one or more salts in accordance with conventional methods. Between US patents 2.
448. No. 060, No. 2,628.167, No. 3
, No. 737゜313, No. 3,772,031, and Research Disclosure, Vol. 134, 1975.
Halogenated compounds such as copper, iridium, lead, bismuth, cadmium, zinc, (chalcogenic compounds such as sulfur, selenium and tellurium), gold and compounds of Group II noble metals as described in June 2013, 13452. The properties of silver halide can be controlled by making it present in the silver precipitation process. Special Publication No. 58-1410, Moisar et al., Journal of Photographic Science, Vol. 25, 1977.19-27
As described on page 1, silver halide emulsions can undergo reduction sensitization of the interior of the grains during the precipitation formation process.

In the tabular grains used in the present invention, silver halides of different compositions may be bonded by epitaxial bonding, or may be bonded with compounds other than silver halide, such as silver rhodan or lead oxide. These emulsion grains are described in U.S. Pat. No. 4,094,684;
No. 142,900, No. 4,459,353, British Patent No. 2. No. 038.792, U.S. Pat. No. 4,349.6
No. 22, No. 4,395.478, No. 4. 433.
No. 501, No. 4,463,087, No. 3,656゜9
No. 62, No. 3,852,067, JP-A-59-162
No. 540, etc.

The surface of the tabular grains of the present invention must be chemically sensitized. This is because the internal sensitivity is high, and sufficient sensitivity cannot be obtained using a normal surface developing solution.

Chemical sensitization is by James ('l'', H, James).
Author, The Theory of Photographic Process, 4th edition, Macmillan Publishing, 1977, (T, H
, James, The Theory of the
PhotographicProcess +4th
ad, Macmillan, 1977) 67
- can be carried out using activated gelatin as described on page 76 and also in Research Disclosure 1.
Volume 20, April 1974, 12008; Research Disclosure, Volume 34, June 1975, 13452
, Yoneka Patent No. 2,642.361, Patent No. 3,297,4
No. 46, No. 3゜772.031, No. 3,857,71
No. 1, No. 3.901,714, No. 4,266.018
and pAg5-1 as described in British Patent No. 3,904,415 and British Patent No. 1,315.755.
Chemical sensitization can be carried out using sulfur, selenium, tellurium, gold, platinum, palladium, iridium or multiple combinations of these sensitizers at 0, pl (5 to 8 and temperatures of 30 to 80 °C. in the presence of a gold compound and a thiocyanate compound, and in U.S. Patent No. 3,857,71
No. 1, No. 4.266.018 and No. 4,054.4
Chemical sensitization can also be carried out in the presence of a chemical sensitization aid in the presence of a sulfur-containing compound described in No. 57 or a sulfur-containing compound such as hypo, a thiourea compound, or a rhodanine compound. Chemical sensitization aids used include compounds known to suppress capri and increase sensitivity during the chemical sensitization process, such as azaindene, azapyridazine, and azapyrimidine. Examples of chemical sensitization aid modifiers are U.S. Pat. No. 2,131,038;
No. 11.914, No. 3,554,757, Japanese Unexamined Patent Publication No. 1983
-126526 and the aforementioned "Photographic Emulsion Chemistry" by Duffin, pp. 138-143. In addition to or in place of chemical sensitization, U.S. Patent No. 3.891.446
No. 3,984.249,
For example, reduction sensitization can be performed using hydrogen, or stannous chloride, as described in U.S. Pat. Reduction sensitization can be performed using thiourea dioxide, polyamines, and such reducing agents, or by low pAg (eg, less than 5) and/or high pH (eg, greater than 8) treatments. Also, U.S. Patent No. 3.917,
Color sensitization can also be improved by the chemical sensitization method described in No. 485 and No. 3,966.476.

Also, patent application No. 59-122981 and No. 59-122984.
Sensitization using an oxidizing agent as described in can also be applied.

The tabular grains used in the present invention can be used in combination with ordinary chemically sensitized silver halide grains (hereinafter referred to as non-tabular grains) in the same silver halide emulsion layer, especially in the case of color photographic light-sensitive materials. It is possible to use tabular grains and non-tabular grains in different emulsion layers and/or in the same emulsion layer. Examples of non-tabular grains include regular grains with regular crystal shapes such as cubes, octahedrons, and tetradecahedrons, and grains with irregular crystal shapes such as spherical and potato shapes. can. Further, as the silver halide of these grains, any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride may be used, and preferred silver halide is 3
Silver iodobromide or silver iodochlorobromide containing 0 mol% or less of silver iodide. Particularly preferred is 2 mol% to 25 mol%.
It is silver iodobromide containing silver iodide up to.

The grain size of the non-tabular grains used here may be fine grains of 0.1 micron or less, large grains with a projected area diameter of up to 10 microns, monodisperse emulsions with a narrow distribution, or multiple emulsions with a wide distribution. A dispersed emulsion may also be used.

The non-tabular grains used in the present invention are described in "Physics and Chemistry of Photography" by Glaf Kide, CP published by Paul Montell, Glaf
kids, Chimie et PhysiqueP
photographique Paul Mont
el + 1967), "Photographic Emulsion Chemistry" by Duffin
, published by Focal Press (G, F, Duffin
r PhotographicEa+ulsion C
hemistry (Focal Press 119
66) “Production and Coating of Photographic Emulsions” by Zelikman et al.
, Focalplane Publishing (V, L, Zelika+
an et alMaking and Coatin
g Photographic Emulsion.

Focal Press, 1964). 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. 9 It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method). As one type of simultaneous mixing method, it is also possible to use a method in which l) Ag in the liquid phase in which silver halide is produced is kept constant, that is, the so-called Chondrald double jet method. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Two or more types of silver halide emulsions formed separately may be mixed and used.

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.
5science and engineering
g) Volume 6, pages 159-165 (I962);
Journal of Photographic Science (J
Oural of Photographic 5
12, pp. 242-251 (I9
64), US Pat. No. 3,655,394 and British Patent No. 1,413,748.

Regarding monodispersed emulsions, JP-A No. 48-8600,
same! No. 51-39027, No. 51-83097, No. 5
No. 3-137133, No. 54-48521, No. 54-
No. 99419, No. 58-37635, No. 58-499
No. 38, Japanese Patent Publication No. 47-11386, U.S. Patent No. 3.6
55,394 and British Patent No. 1.413.748.

The crystal structure of these non-tabular grains may be --like, the inside and outside may have different halogen compositions, or they may have a layered structure. No. 027,146, U.S. Patent No. 3,505,
No. 068, No. 4,444.877, and patent application No. 1983-
It is disclosed in No. 248469 and the like.

In the present invention, 0.6μ or less, preferably 0.6μ or less is used. A non-photosensitive fine grain emulsion of 2 μm or less may be added to the silver halide emulsion layer, intermediate layer or protective layer for the purpose of accelerating development, improving storage stability, and effectively utilizing reflected light.

The tabular grains of the present invention are preferably used in color photographic photosensitive materials.

The tabular grains of the present invention may be able to simultaneously improve sharpness and granularity, especially when used in the same and/or different emulsion layers as non-tabular, monodisperse silver halogenide grains.

Here, monodisperse silver halide emulsion (non-tabular grain) is
It is defined that 95% or more of the total weight or total number of silver halide grains contained therein is within ±40% of the average grain size, more preferably within ±30%. The use of a monodisperse silver halide emulsion in a silver halide photographic light-sensitive material to improve the granularity is disclosed in the above-mentioned Japanese Patent Publication No. 47.
-11386, JP-A-55-142329, JP-A-57-1
7235, 59-72440, etc.

Also, the above-mentioned book by T. H. James, “The Theory of Photographic Process 0.580-585
As described on the page, monodisperse silver halide grains of 0.3μ to 0.8μ have a high light scattering property for light in a specific wavelength range, but have a high light scattering property for light in other wavelength ranges. It is also known that it has a property of relatively low light scattering.

Therefore, by appropriately arranging a tabular silver halide emulsion with a grain diameter/thickness ratio of 5 or more and a monodisperse silver halide emulsion, taking into consideration the optical properties and graininess of each silver halide emulsion, It may be possible to simultaneously improve the sharpness and granularity of the silver halide photographic material.

Some examples of such aspects will be listed.

Example 1) In a light-sensitive material in which a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are arranged in this order from the support side, the average grain size of the silver halide grains contained in the silver halide emulsion layer constituting the blue-sensitive layer is in the range of 0.3μ to 0°8μ,
Tabular silver halide grains are used in the emulsion layer, and if the average grain size is not within the above range, monodisperse silver halide is used to improve the sharpness of the green and red sensitive layers and improve the blue It is possible to improve the granularity of the sensitive layer.

Example 2) In a photosensitive material having the same layer arrangement as Example 1,
Regarding the silver halide emulsion layer constituting the green-sensitive layer, the average grain size of the silver halide grains contained therein is 0.4μ to 0.4μ.
If the average grain size is in the range of 8μ, tabular silver halide grains are used in the emulsion layer, and if the average grain size is not in the above range, a monodisperse emulsion is used to improve the sharpness of the red-sensitive layer. At the same time, it is possible to improve the granularity of the green-sensitive layer.

Example 3) In a light-sensitive material having the same layer arrangement as in Example 1 and consisting of two or more emulsion layers having the same color sensitivity and a plurality of layers having different sensitivities, the blue-sensitive layer 1 has the highest sensitivity.
．． If the light scattering in the blue-sensitive layer with lower sensitivity is large with monodisperse silver halide of 0 μ or more (especially double-structure grains are preferred), use tabular grains in the blue-sensitive layer with lower sensitivity, and use tabular grains in the green-sensitive layer. and the sharpness of the red-sensitive layer can be improved.

Example 4) When a light-sensitive material having the same Jii arrangement as in Example 3 has multiple green-sensitive layers that all have large light scattering, tabular grains are used in all of the green-sensitive layers to improve the sharpness of the red-sensitive layer while improving the sharpness of the red-sensitive layer. It is possible to improve the granularity of the green-sensitive layer.

Especially when the blue-sensitive layer, green-sensitive layer, and red-sensitive layer each consist of a plurality of emulsion layers, as in Examples 3 and 4, in order to improve sharpness and granularity, it is necessary to use an emulsion layer with high light scattering. Consideration should be given to using tabular silver halide grains and using monodisperse emulsions in emulsion layers with low light scattering. In addition, when tabular grains are further used in the red sensitive layer in Example 4,
Light scattering between emulsion layers increases, which may worsen the sharpness of the green-sensitive layer above the red-sensitive layer, and it may not be desirable to use tabular grains in the red-sensitive layer closest to the support. .

As mentioned above, the tabular grains and non-tabular grains used in the present invention are usually those that have been subjected to physical ripening, chemical ripening and spectral enhancement. Additives used in such processes are described in Research Disclosure Arashi 17643 and Research Disclosure 18716, 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 187
161 Chemical sensitizers 2 Sensitivity enhancers 3 Spectral sensitizers, supersensitizers 4 Brighteners 5 Antifoggants and stabilizers 6 Light absorbers, filter dyes UV absorbers 7 Anti-stain agents 8 Dye image stabilizers 9 Hardener 10 Binder 23 True 23-24 pages 648 right column Same as above page 648 right column ~ 649 right column 24 pages 24-25 649 right column 25-26 pages 649 right column ~ 650 left column 25 pages right @Page 650 Left to right column 25 Page 26 Page 26 Page 651 Left column Same as above 11 Plasticizer, lubricant Page 27 Page 650 Right column 1
2 Coating aid, pages 26-27 Page 650, right column Surfactant 13 Static, page 27 Same as above Patch agent In addition, in order to prevent deterioration of photographic performance due to formaldehyde gas, U.S. Pat. Fourth
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.

Various color couplers can be used in the present invention, specific examples of which can be found in the above-mentioned Research Disclosure (
RD) Nα17643, described in the patent described in ■-C-G.

As a yellow coupler, for example, U.S. Patent Tube 3.93
3.501, same No. 4,022,620, same No. 4,
326, No. 024, No. 4.40L, No. 752, No. 4,248,961, Japanese Patent Publication No. 10739/1983, British Patent No. 1,425,020, No. 1,476.76
No. 0, U.S. Patent Tube 3.9” 13.α68, U.S. Patent No. 4.3
Preferred are those described in European Patent No. 14.023, European Patent No. 4.5LL649, European Patent No. 249.473A, and the like.

As magenta couplers, 5-pyrazolone and pyrazoloazole compounds are preferred, and US Pat.
0,619, European Patent No. 4゜351,897, European Patent No. 73.636, US Patent No. 3,061,432, US Patent No. 3゜725.067, Research Disclosure Na24220 (June 1984) ), Japanese Patent Application Publication No. 1983-
No. 33552, Research Disclosure N (L
24230 (June I9B4), JP-A-60-436
No. 59, No. 61-72238, No. 60-35730, No. 55-118034, No. 60-185951,
U.S. Patent No. 4.500.630, U.S. Patent No. 4.540.6
No. 54, No. 4,556,630, International Publication 1881
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
No. 4.011, No. 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
, 254.

No. 212, No. 4,296,199, JP-A-61-4
Those described in No. 2658 and the like are preferred.

Colored couplers to correct unnecessary absorption of coloring dyes are listed in Research Disclosure 17643.
- Section G, U.S. Patent No. 4.163.670, Special Publication No. 1983
-39413, U.S. Patent No. 4.004.929, U.S. Patent No. 4.138.258, British Patent No. 1,146,36
Preferably, those described in U.S. Pat. No. 4,7
74,181, which corrects unnecessary absorption of coloring dyes by the fluorescent dye released during coupling; and U.S. Patent No. 4,777,120, which can react with a developing agent to form a dye. It is also preferred to use couplers having a dye precursor group as a leaving group.

Couplers in which color 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.

Typical examples of polymerized dye-forming couplers are U.S. Pat.
No. 20, No. 4.576゜910, British Patent No. 2.10
2.173 etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors include the aforementioned R[l 1764
Patent described in 3.1-1, JP-A-57-1519
No. 44, No. 57-154234, No. 60-18424
No. 8, No. 63-37346, No. 63-37350,
U.S. Patent No. 4,248.962, U.S. Patent No. 4,782.012
Preferably, those listed in No.

Couplers that imagewise release a nucleating agent or a development promoting side during development include British Patent No. 2,097,140;
No. 2.131.188, JP 59-157638
No. 59-170840 is preferred.

In addition, examples of couplers that can be used in the photosensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4,130,427, U.S. Pat. , long equivalent couplers described in JP-A-60-185950, JP-A-62-24252, etc., DIR coupler-releasing couplers,
DIR coupler releasing redox compound or DIR redox releasing redox compound, European Patent No. 173゜3
02A, 313.308A, [1,D, bi11449]
, No. 24241, JP-A No. 61-201247, etc., a bleach accelerator releasing coupler, U.S. Patent No. 4.553.4
Ligand releasing coupler described in No. 77 etc., JP-A-63-
75747, a leuco dye-releasing coupler;
Examples include couplers that emit fluorescent dyes as described in US Pat. No. 4,774,181.

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

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

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

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

Specific examples of latex dispersion process, effects, and latex for impregnation can be found in U.S. Pat. etc. are listed.

The color photosensitive material of the present invention includes JP-A-63-2577
No. 47, No. 62-272248, and JP-A-1-8
1,2-benzisothiazoline-3 described in No. 0941
-one, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol,
2-phenoxyethanol, 2-(4-thiazolyl)
It is preferable to add various preservatives or fungicides such as benzimidazole.

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

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, page 28 of Ni117643, and 1871
6, from the right column on page 647 to the left column on page 648.

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 28 μm or less, more preferably 23 μm or less, even more preferably 20 μm or less, and the film swelling rate is TI/! is preferably 30 seconds or less, more preferably 20 seconds or less.

The film thickness means the film thickness measured at 25°C and 55% relative humidity (2 days), and the film swelling rate T'+zt can be measured according to methods known in the art. , Photographic Science and Engineering (Photogr, Sci, Eng,) + 1 by A. Green et al.
It can be measured by using a swellometer (swelling membrane) of the type described in Vol. 9, No. 2, pp. 124-129, and T,
/2 is defined as the time required to reach the saturated film thickness of 172, with 90% of the maximum swollen film thickness reached when treated with a color developing solution at 30° C. for 3 minutes and 15 seconds as the saturated film thickness.

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 color photographic material according to the present invention includes the above-mentioned RD, N
α17643 pages 28-29, and Nα18716
615, left column to right column.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. As this color developing agent, although aminophenol compounds are also used, p-phinidine diamine compounds are preferably used, and a representative example thereof is 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-β-
Examples include methoxyethylaniline and their sulfates, hydrochlorides, p-toluenesulfonates, and the like. Among these, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline sulfate is particularly preferred, and two or more of these compounds may be used in combination depending on the purpose.

The color developer may contain pH buffering agents 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, benzothiazoles or mercapto compounds. If necessary, various preservatives such as hydroxylamine, diethylhydroxylamine, sulfites, hydrazines such as N,N-biscarboxymethylhydrazine, phenyl semicarbazides, triethanolamine, and catechol sulfonic acids, ethylene glycol, Organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, auxiliary developing agents such as 1-ferro-3-pyrazolidone. , viscosity imparting agent, aminopolycarboxylic acid, aminopolyphosphonic acid,
Various acidifying agents such as alkylphosphonic acids and phosphonocarboxylic acids, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenedolyaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene -1,1-diphosphonic acid, nitrilo-N,N,N-)limethylenephosphonic acid, ethylenediamine-N,N,N,N-tetramethylenephosphonic acid, ethylenediamine-di(0-hydroxyphenylacetic acid) and their Salt can be cited as a representative example.

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 dihydroxybenzene 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 being processed, but in general it is 31 or less per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher, it can be increased to 500 or less.
−Can also be less than or equal to: 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, and stabilization.Also, the amount of replenishment can be reduced by using means to suppress the accumulation of bromide ions in the developer. .

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

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

The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately (bleach-fixing process), or in order to speed up the process, it may be carried out in two ways: bleach-fixing process after bleaching process. Depending on the purpose, treatment may be carried out in consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment. Examples of bleaching agents that can be used include compounds of polyvalent metals such as iron (II), peracids, quinones, and nitro compounds. Typical bleaching agents include organic complex salts of iron (II), such as ethylenediamine. Tetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropane tetra! Aminopolycarboxylic acids such as ¥ acid, glycol ether diamine tetraacetic acid, etc., or complex salts such as citric acid, tartaric acid, malic acid, etc. can be used. Among these, aminopolycarboxylic acid iron(III) complex salts, including ethylenediaminetetraacetic acid iron(II) complex salt and 1,3-diaminopropanetetraacetic acid iron(I) complex salt, are used from the viewpoint of rapid processing and environmental pollution prevention. Further preferred are aminopolycarboxylic acid iron (I
I[) complex salts are particularly useful in both bleach and bleach-fix solutions. These aminopolycarboxylic acid iron (I
II) The pH of the bleach or bleach-fix solution using complex salts is usually 4.0 to 8, but it is also possible to process at an even lower pH for speeding up the process.

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

Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893.858, German Pat.
, No. 290,812, No. 2,059,988, JP-A-53-32736, No. 53-57831, No. 53-
No. 37418, No. 53-72623, No. 53-956
No. 30, No. 53-95631, No. 53-104232
No. 53-124424, No. 53441623,
Compounds having a mercapto group or disulfide group described in JP-A No. 53-28426, Research Disclosure No. 81117129 (July 1978), etc.; Thiazolidine derivatives described in JP-A-50-140129;
Japanese Patent Publication No. 45-8506, Japanese Patent Publication No. 52-20832,
No. 53-32735, U.S. Patent No. 3,706,561
Thiourea derivatives described in West German Patent No. 1,127,7
No. 15, iodide salts described in JP-A-58-16,235; West German Patent No. 966.410, West German Patent No. 2.748,430
Polyoxyethylene compounds described in No. 1973-
Polyamine compounds described in No. 8836; other JP-A-49
-42.434, 49-59,644, 53-
No. 94.927, No. 54-35.727, No. 55-2
Compounds described in No. 6,506 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. 3,893,858.
No., West German Patent No. 1.290,812, Japanese Unexamined Patent Publication No. 1983-9
Preferred are the compounds described in US Pat. No. 5.630, and also preferred are the compounds described in US Pat. No. 4,552,834.
These bleach accelerators may be added to the negative phase, and 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. Among them, ammonium thiosulfate is the most widely used. It is also preferable to use a combination of thiosulfate, thiocyanate, thioether compounds, thiourea, etc. As a preservative for fixing solutions and bleach-fixing solutions, sulfites, bisulfites, carbonyl bisulfite adducts, or European patented The sulfinic acid compounds described in No. 294769A are preferred. Furthermore, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution and bleach-fixing solution for the purpose of stabilizing the solution.

The total time for the desilvering process is preferably as short as possible without causing desilvering defects.The preferred time is 1 minute to 3 minutes, more preferably 1 minute to 2 minutes. In addition, the processing temperature is 25°C ~
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 that the stirring be as strong as possible.A specific method for strengthening the stirring is the treatment on the emulsion surface of the photosensitive material described in JP-A-62-183460 and JP-A-62-183461. A method of colliding liquid jets, a method of increasing the stirring effect using a rotating means as described in JP-A No. 62-183461, and a method of moving the photosensitive material while bringing the emulsion surface into contact with a wiper blade provided in the liquid. , a method of improving the stirring effect by creating turbulence on the surface of the emulsion, and a method of increasing the circulation flow rate of the entire processing liquid. Such agitation enhancement means include bleaching solutions,
It is effective in both bleach-fixing solutions and fixing solutions.

It is believed that improved stirring speeds up the supply of bleach and fixing agent into the emulsion film, and as a result increases the desilvering rate. Further, the agitation improving means described above is more effective when a bleach accelerator is used, and can significantly increase the accelerating effect and eliminate the fixing inhibiting effect caused by the bleach accelerator.

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

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

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. can be set over a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is
urn-al of the 5ociety of
Motion Picture and Te1e-v
ision Engineers 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, such problems can be solved by:
The method for reducing calcium ions and magnesium ions described in JP-A No. 62-288.838 can be used very effectively. Also, JP-A-57-8.542
Chlorine slaughter of isothiazolone compounds, thiabendazole, chlorinated sodium isocyanurate, etc. described in the issue.
Jing, other benzotriazoles, etc., Hiroshi Horiguchi, Chemistry of Antibacterial and Antifungal Agents J (I986), Sankyo Publishing, Hygiene Technology Metals, Sterilization, Disinfection, and Antifungal Technology of Microorganisms J (I982)
Industrial Technology Society, Japan Society of Antibacterial and Mildew Akebono “Encyclopedia of Antibacterial and Antifungal Agents” (
It is also possible to use the fungicides described in I986).

The pI (pI) of the washing water in the processing of the photosensitive material of the present invention is 4
-9, preferably 5-8. The washing water temperature and washing time can be set in various ways depending on the characteristics of the photosensitive material, its use, etc.
- Finally, a range of 20 seconds to 10 minutes at 15-45°C, preferably 30 seconds to 5 minutes at 25-40°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.

Various chelating agents and antifungal agents can also be added to this stabilizing bath.

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

When the above-mentioned processing solutions are concentrated by evaporation during processing using an automatic processor or the like, it is preferable to add water to correct the 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, it is preferable to use various precursors of color developing agents. For example, U.S. Pat. No. 3,342.59
Indoaniline compound described in No. 7, No. 3,342,
No. 599, Research Disclosure 14,850
Schiff base-type compounds described in No. 15,159 and aldol compounds described in No. 13.924, U.S. Patent No. 3
, 719.492, JP-A-53-1
Examples include urethane compounds described in No. 35628.

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

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

The various processing solutions used in the present invention are used at a temperature of 10°C to 50°C.9 Usually, the standard temperature is 33°C to 38°C, but higher temperatures may be used to accelerate the processing and shorten the processing time. Conversely, by lowering the temperature, it is possible to improve the image quality and the stability of the processing solution.

In addition, West German Patent No. 2.226,7 was developed to save silver on photosensitive materials.
70 or U.S. Pat. No. 3,674.499 using cobalt or hydrogen peroxide intensification.

Further, the silver halide photosensitive material of the present invention is disclosed in US Patent No. 4.
No. 500,626, JP-A-60-133449, No. 5
It can also be applied to the heat-developable photosensitive materials described in No. 9-218443, No. 61-238056, European Patent No. 210.66OA2, and the like.

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

Example 1 (I) Manufacturing method of fine powder dye dispersion A dye (CpdJ) was dispersed in a vibrating ball mill by the following method.

Water (21,71d) and 5% aqueous solution of P-octylphenoxyethoxyethoxyethoxyethanesulfonic acid sodium 3d,5
% aqueous solution of P-octylphenoxy poly(degree of polymerization 10)
Add 0.5 g of oxyethylene ether to 700 d/ton, add 1.00 g of dye and 500 d of zirconium oxide beads (diameter 1 m + 1) to reduce the contents to 2.
Spread out time. The vibratory ball mill used was a BO type manufactured by Chuo Kakoki.

The contents were taken out and added to 8 g of a 12.5% aqueous gelatin solution, and the beads were filtered to obtain a dye gelatin dispersion.

(2) Preparation of emulsion Emulsion A: 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 2 itl for 1 minute at 55"C, pBrl.

(This addition (I) added 2°40 of the total silver amount.
% consumed), gelatin aqueous solution (I7%, 300″)
After stirring at 55°C, sodium 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). Subsequently, the pH was adjusted to 5.5, and a 20% silver nitrate aqueous solution was added at a constant flow rate until the pBr reached 1.40 (
This addition (II) consumed 5,0% of the amount of gold and silver), 20% potassium bromide solution with potassium iodide and 33%
of silver nitrate aqueous solution was added over 80 minutes using a double jet method. (With this addition (III), the amount of gold and silver increased to 92.
6% was consumed. ) During this time, the temperature was increased to 55'C5pBr to 1
．． It was held at 50. The amount of silver nitrate used in this emulsion was 425 g.

Next, after desalting using the usual flocculation method, gold/sulfur sensitization was optimally performed (particle surface chemical sensitization). In this preparation procedure, by changing the amounts of chloroauric acid and sodium thiosulfate used for internal chemical sensitization, the average particle diameter/particle thickness ratio 6 with various surface sensitivity/internal sensitivity ratios listed in Table 1 is obtained. .5, legal equivalent diameter 0. 8
Emulsion A was prepared using tabular AgBr I (Ag I = 2.0 mol %) having a diameter of .mu.m. These emulsion grains were monodisperse hexagonal tabular emulsions with a variation coefficient of grain size distribution of 15% or less.

Emulsion BSC For comparison with Emulsion A, silver iodobromide (SR2 iodide) was prepared by the double jet method in the presence of ammonia.

(0 mol %) granular particles were prepared. The average size of the emulsion grains obtained was 0.8 μm. A chemical sensitizing dye was applied to this using a combination of gold and sulfur.

The emulsion thus obtained will be referred to as emulsion B hereinafter.

Furthermore, without the presence of ammonia in emulsion B,
1 double jet! Cubic particles having an iodide content of 212.0 mol % and an average particle size of 0.8 μm were prepared by carrying out the process while maintaining the potential (SCE) at +80 mV. This was chemically sensitized using a combination of gold and sulfur. (Emulsion C) (3) Preparation of coating sample A multilayer color light-sensitive material consisting of each layer with the following composition was prepared on an undercoated cellulose triacetate film support with a thickness of 127 μm. Samples were prepared by sequentially adding silver. The numbers represent the amount added per M; the effects of the added compounds are not limited to the described uses.

1st layer: antihalation layer black colloidal silver 0.25g 1.9g 1 0.04g 2 0.1g 3 0.1g6
0.1g 1l-10.1g Gelatin UV absorber U UV absorber U- UV absorber U- UV absorber U- High boiling point organic solvent 0 2nd N: Intermediate layer gelatin compound Cpd-D 0.40g 10■ High boiling point Organic solvent 0il-340■ 3rd layer: Fine grain silver iodobromide emulsion covered with intermediate layer (average grain size 0.06 μm, Ag I content 1 mol%) Weight 0.05g Gelatin 0.4g 4th layer:
Low-speed red-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-1 and S-2 (average grain size 0.25 gm, Ag T content 3°4 mol%, monodisperse cubic and average grain size) 0.2μ, 4:6 mixture of monodisperse cubes with Agl content 4.5 mol%)
Silver amount 0.4g gelatin
0.8g Coupler C-10, 20g Coupler C-90, 20g High boiling point organic solvent Of! -10.1g 5th layer: medium-sensitivity red-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-1 and S-2 (average grain size 0.5 μm, Agr content 4 mol% monodisperse) cube) 1l amount 0.48 gelatin
0.8g Coupler C-10.2g Coupler C-20.05g Coupler C-3' 0.2g High-boiling organic solvent 04l-10.1g No. 6N: High sensitivity red-sensitive emulsion layer sensitizing dyes S-1 and S- Silver iodobromide emulsion spectrally sensitized with 2 (monodispersed twin grains with average grain size 0.7 μm and Agl content 2 mol%) Silver amount 0.4 g gelatin
1.1g Coupler C-30.7g Coupler C-10.3g 7th N: Intermediate layer gelatin 036g Dye D
-10.02g 8th layer: Silver iodobromide emulsion covered with intermediate layer (average grain size 0.06μm, Ag
T content 0.3 mol%) Gelatin 0.1 g Color mixing inhibitor Cpd-A 0.2 g No. 9 N;
Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-3 and S-4 (average grain size 0.15 μm, Agl content 4.5 mol%, monodispersed cubic and average grains) Diameter 0.2 μm, Ag [content 4,5
1ri mixture of monodisperse cubes in mol%)
Silver film 0.5g gelatin
0.5g Coupler C-40, 10g Coupler C-70, 10g Coupler C-80, 10g Compound Cpd-80, 03g Compound Cpd-E 0.1g Compound Cpd-F 0.1g Compound C
pd-G O, 1g compound Cpd
-H0.1g 10th layer: Medium-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-3 and S-4 (average grain size 0.3 gm, Ag T containing N2°4 mol/ Gelatin coupler C-4 Coupler (, -7 Coupler C-8 Compound Cpd-B Compound Cpd-E Compound cp d-F Compound Cpd-G Compound Cpd-H High-boiling organic solvent Oi1-1 11th layer: High-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-3 and S-4 (Monodisperse twinned particles with an average particle size of 0.8 μm and SAg1 content of 1°3 mol%) 5g gelatin
1.0g coupler C-40,
4g Coupler C-70,2g Coupler C-80,2g Compound Cpd-80,08g Silver color 0.4g 0.6g 0.1g 0.1g 0.1g O,03g 0.1g 0,1g 0.05g 0 .05g 0.01g Compound Cpd-E O, 1g Compound Cpd-F O, 1g Compound C
pd-G O, 1g compound Cpd
-H0.1g 12th layer: Intermediate layer gelatin 0.6g Dye D
-2 0.05g 13th layer: Yellow filter material Yellow filter material (listed in Table 1) Gelatin 1.1g Color mixture prevention agent c
pd-A, 0.01g 14th layer: Intermediate layer gelatin 0.6g 15th layer: Low-sensitivity blue-irradiation emulsion layer Silver iodobromide emulsion sensitized with sensitizing dyes S-5 and S-6 (
A 1:l mixture of monodisperse cubes with an average particle size of 0.4 μm and an Agl content of 3 mol % and monodisperse cubes with an average particle size of 0.2 μm and an Agl content of 3 mol %) 1 barb 1 0.
6g Gelatin 0.8g Coupler C-50, 6g 16th layer: Medium-sensitivity blue-irregular emulsion layer Silver iodobromide emulsion sensitized with sensitizing dyes S-5 and S-6 (
Average particle size: 0.5 μm, Agl content: 2 mol% (listed in Table 3) Silver content: 0.4 g gelatin
0.9g Coupler C-50, 3g Coupler C-60, 3g 17th layer: High-sensitivity pre-malignant emulsion layer Silver iodobromide emulsion sensitized with sensitizing dyes S-5 and S-6 (
Listed in Table 3 Silver 1 0.4g Gelatin 1.2g Coupler C-6
0.7g 18th layer: 1st protective layer gelatin UV absorber U-1 UV absorber U-3 UV absorber U-4 UV absorber U-5 UV absorber U-6 0.7g 0.04g 0. 03g 0.03g 0.05g 0.05g Formalin scavenger Cpd-CO, 8g Dye D-30, 05g 19th layer: Fine grain silver iodobromide emulsion covered with second protective layer (average grain size 0°06μ)
m, Agl content 1 mol%) Silver amount 0.1 g Gelatin 0.4 g 20th layer: 3rd protective layer Gelatin 0.4 g Polymethyl methacrylate (average particle size 1.5 μ) 0.1 g Methyl methacrylate and acrylic acid 4 : Copolymer of 6 (average particle size 1.5 μm) 0.1g silicone oil 0.03g surfactant W-13
,0■ In addition to the above composition, a gelatin hardener 11-1 and a surfactant for coating and emulsification were added to each layer.

In addition, in the emulsion used here, monodisperse means that the coefficient of variation is 20% or less.

Each of the above samples was exposed to white light and subjected to the following development treatment.
The results are shown in Table 1 along with the sharpness determined as the F value.

Step - Developing 6 minutes* 38°C First washing
45 seconds 38〃Reversal 4
5〃38〃Color development 6 minutes
38〃Bleaching 2 I
38 〃Bleach fixing 4〃
38〃Second water washing (]) 1138〃Second washing (2) 1〃 38〃Stable
1〃25〃*In the evaluation of suitability for sensitization development, processing for 8 minutes was also performed.

The composition of each treatment liquid was as follows.

Nitrilo-N,N,N-)rimethylenephosphonic acid pentasodium salt 2.0g Sodium sulfite 30g Hydroquinone potassium monosulfonate 20'g Potassium carbonate 33g 1-phenyl-4-methyl-4-hydroxymethyl-3 Pyrazolidone 2 .0g potassium bromide 2.5g potassium ocyanate 1.2g potassium iodide
2.0 ■ Add water
1000dpH9.60 pH was prepared with hydrochloric acid or potassium hydroxide.

First washing liquid Mother liquor Ethylenediamine tetramethylene Renphosphonic acid Disodium phosphate add water 2゜Og 5.0g 1000sN pH 7,00 pH was adjusted with hydrochloric acid or sodium hydroxide.

No pH adjustment Nitrilo-N, N, N-) Methylenephosphonic acid 5Na thorium salt Tin chloride dihydrate p-aminophenol Sodium hydroxide glacial acetic acid add water pH pH is determined by hydrochloric acid or potassium hydroxide. 3.Og 1.0g 0.18 g 5d 1000d! 6.00 Adjusted with ram.

Nitrilo-N, N, N-1 Li Methylenephosphonic acid 5Na thorium salt sodium sulfite Trisodium phosphate potassium bromide 12 hydrate salt 2.0g 7.0g 6g 1.0g potassium iodide 0mg Sodium hydroxide 3.0g Citrazic acid 1.5g N-ethyl-N-(β-meta (sulfonamide ethyl) 3-methyl-4-amino Aniline sulfate 3.6-cythiaoctane-1° 8-diol add water pH The pH is 1.0g 000d 11.80 Adjusted with hydrochloric acid or potassium hydroxide.

1g Ethylenediaminetetraacetic acid, sodium salt, dihydrate ethylenediaminetetraacetic acid, (III), symmonium, ammonium bromide, ammonium nitrate bleach accelerator 10.0g Fe dihydrate 120g 00g 0g 0.005 mol Add water 1000dp H6,
30 pH was adjusted with hydrochloric acid or aqueous ammonia.

Ethylenediaminetetraacetic acid, Fe U) ・Ammonium, dihydrate 50g Ethylenediaminetetraacetic acid, 2sodium, dihydrate 5.0g Sodium thiosulfate 80g Sodium sulfite 12.0g Add water
1000〆pH6゜60 The pH was adjusted with dihydrochloric acid or aqueous ammonia.

The water from the Seishin Water Tap was placed in a hotbed column packed with a strongly acidic cation exchange resin (1) type (Amberlite IR-120B manufactured by Rohm and Haas) and an OH type anion exchange resin (Amberlite JR-400). Water was passed through the solution to reduce the concentration of calcium and magnesium ions to 3111 g/f or less, and then 20 g/l of sodium dichloride isocyanurate and 1.5 g/l of sodium sulfate were added.The pH of this solution was 6.
．． It is in the range of 5 to 7°5.

Formalin (37%) Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) Add water to pH 5, M 0.5d tooO#Ii! Example 2 without adjustment Example 1 Samples 201 to 210 were prepared by replacing the high-sensitivity red-sensitive layer emulsion and the black colloidal silver of the antihalation layer in Sample 102 as shown in Table 2, and the same study as in Example 1 was carried out. I did it.

The results are shown in Table 2.

-1 C -3 -6- 7 H COOCJ7(iso) -4 Coupler C H 11 il ■ Dibutyl phthalate i1 Tricresyl phosphate pd A H pd-8 pd] - CP d -H pd-D H pd- 1 (Compound of U.S. Pat. No. 4,420,555) Samples 301 to 3 were coated with an emulsion layer having the following composition.
08 was produced. For silver halides and colloidal silver, the amount is expressed in g/rd of silver; for couplers, additives, and gelatin, the amount is expressed in g/rtr; for sensitizing dyes, the amount of halogen in the same layer is It is expressed as the number of moles per mole of silveride.

1st layer (antihalation layer) Black colloidal silver ・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・0,2 gelatin ・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・1.3 Colored coupler C-7・・・・・・・・・・・・・・・・・・0.
16 Ultraviolet absorber U-6・・・・・・・・・・・・・
・・・・・・・・・・・・0.1 Same as above U-7・・・・・・
・・・・・・・・・・・・・・・・・・O12 dispersion oil Oi! -1・・・・・・・・・・・・・・・・・・
...0,01 Same as above 0i1-2 ...
・・・・・・・・・・・・・・・・・・0.01 2nd layer (
Intermediate layer) Fine grain silver bromide (average grain size 0.07 μm)
・・・・・・0.15 Gelatin ・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
...1.0 colored coupler C-8/old...
・・・・・・・・・・・・0.02 dispersion oil 04l-2
・・・River・Old・・・・・・・・・・・・・・・0.1 3rd
Layer (first red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 2 mol%, average grain size 0.3 μm)...old...root 0
．． 4 Gelatin ・・・・・・・・・・・・・・・・・・
・・・・・・・・・・l1・・・・・・・・・0゜6 Sensitizing dye S-7・・・・・・・・・・・・・・・・・・・・・
・1.0X10-' aggravation dye S-8...
・・・・・・・・・・・・3.0X10-' Sensitizing dye S
-9・・・・・・・・・・・・・・・・・・・・・・・・
・lXl0-';h 7" Ra-C-9...
・・・Old・Song・・Old・・・・・・・・・0.06 Kabler〇-10・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・0.06 color 7 color C-11・・・・
...Old...l1...0.04 coupler C-8......
・・・・・・・・・・・・0.03 Dispersion oil Oi! -2
......Song...Old...0.03 Same as above
0i1-4...Old...l1...0.012 Fourth layer (second red-glare emulsion N) Silver iodobromide emulsion (silver addition 5 mol%, average diameter 1.1 μm)...・・・・・・・・・・・・
・l1・・0.7ft [dye s-7・old・・・・・・
l1... Old... 1X10-' Sensitizing dye S-8/ Old...
・・・・・・・・・・・・・・・・・・3X10-' Sensitizing dye S-9・・・・・・・・・・・・・・・・・・
...lXl0-' coupler C-9...
・・・・・・・・・・・・・・・・・・・・・・・・0.
24 Coupler C-10・・・・・・・・・・・・・・・
・・・・・・・・・・・・0.24 Coupler C-11・
・・・・・・・・・・・・・・・・・・・・・・・・
・0.04 coupler C-8・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・ 0.04 Dispersion oil 0il-2・・・・・・・・・・・・・・・・・・
・・・0.15 Same as above 0i1-4・・・・・・・・・・・・
・・・・・・・・・0.02 Fifth layer (third red-glare emulsion layer) Silver iodobromide emulsion (silver iodide 5 mol%, average diameter 1°7 μm)
m) ・・・・・・・・・・・・・・・・・・・・・
...1 stick 1.0 gelatin ・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・1. 0 sensitizing dye S-7・
・・・・・・・・・・・・・・・・・・・・・・・・・・・I
X 10-' Exacerbating dye S-8・・・・・・・・・・・・
......3X10-' sensitizing dye S-9
・・・・・・・・・・・・・・・・・・・・・・・・・l
Xl0-'Coupler C-12・・・・・・・・・・・・
・・・・・・・・・・・・・・・0.05 Coupler C-
13・・・・・・・・・・・・・・・・・・・・・・
......0.1 dispersion oil 04l-2...
・・・・・・・・・・・・・・・・・・0.01 Same as above 0i1
-1・・・・・・・・・・・・・・・・・・・・・04
05 6th layer (middle layer) Gelatin ・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・1.0
Compound Cpd-F・・・・・・・・・・・・・・・
......0.03 dispersion oil 0f1-2
・・・・・・・・・・・・・・・・・・・・・0.0
5 Seventh layer (first green-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 4 mol%, average grain size 0.3 μm) i! i
! 0.30 Sensitizing dye 5-10 ・・・・・・・・・
・・・・・・・・・・・・・・・5 X 10-' Sensitizing dye 5-12 ・・・・・・・・・・・・・・・0.
3XlO-'sensitizing dye 5-11...
・・・・・・・・・・・・2X10-'gelatin ・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・1.0 coupler C-15
・・・・・・・・・・・・・・・Self・・・・・・・・・・・・
...0.2 coupler C-11...
・・・・・・・・・・・・・・・・・・0.03 Coupler C
-7・・・・・・・・・・・・・・・ Old・・・・・・
...0.03 dispersion oil 011-2 ...
・・・・・・・・・・・・・・・・・・・・・0.5 8th layer (second green-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 5 mol%, average grain size 0 , 5μm
1 shape is listed in Table 3) ・・・・・・・・・・・・ Silver 0.4 Aggravating dye 5-
10 ・・・・・・・・・・・・・・・・・・・・・・・・5
X10-'sensitizing dye 5-12...
・・・・・・・・・2×IO-'sensitizing dye 5-11
・・・・・・・・・・・・・・・・・・0.3X10-
'Coupler C-15・・・・・・・・・・・・・・・
・・・・・・・・・・・・0.25 coupler C-7...
・・・・・・・・・・・・・・・・・・・・・・・・
・・0.03 coupler C-16・・・・・・・・・・・
・・・・・・・・・0.015 Coupler C-11
・・・・・・・・・・・・・・・・・・・・・・・・
・・0.01 dispersion oil 0il-2・・・・・・・・・
・・・・・・・・・・・・・・・0.2 9th layer (third green emulsion layer) Silver iodobromide emulsion (silver iodide 5 mol%, average diameter 17 μm, shape is shown in Table 3) ) ・・・・・・・・・・・・ i艮 0.85 Gelatin ・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・1.0 Sensitizing dye 5-13 ・・・・・・・・・・・・・・・・・・3
．． 5X10-' Exacerbating dye 5-14 ・・・・・・・・・
・・・・・・・・・1.4X10-'Coupler C-17
・・・・・・・・・・・・・・・・・・・・・・・・
・・0.01 coupler C-18・・・・・・・・・・・・
・・・・・・・・・1 Old・0.03 Coupler C-19・
・・・・・・・・・・・・・・・・・・・・・・・・
・0.20 coupler C-7・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・ 0.02 Coupler C-21・・・・・・・・・・・・・・・・・・・・・
・・・・・・0.02 Dispersion oil Oi+-2・・・・・・
・・・・・・・・・・・・・・・0.20 Same as above Oi!
-1・・・・・・・・・・・・・・・・・・0.
05 10th layer (yellow filter layer) Seratin ・・・・・・・・・・・・ Old old old...
...... Old...1.2 Yellow filter material (listed in Table 3) Compound cpd-c ...1 Old...
...Old...0.1 dispersion oil 0il-2...1
Old... Old... 0.3 11th layer (first blue-sensitive emulsion layer) Monodisperse silver iodobromide agent (silver iodide 4 mol%, average grain size 0.3 μm)
)・・・・・・・・・・・・・・・・・・・・・
・Old...Silver 0.4 Gelatin ・・・・・・・・・・・・
···················song·····
・・1.0 sensitizing dye 5-15 ・・Song・・・・・・・・
...Old...2 x 10-' coupler C-20...
・・・・・・・・・・・・・・・・・・・・・ Old...
0.9 coupler C-11・・・・・・・・・・・・・・・
・・・・・・・・・・・・0.07 Dispersion oil 0il
-2.1 Old...old...old...0.2 12th layer (second blue-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 5 mol%, average diameter 1, 7
μ m) ・・・・・・・・・・・・・・・・・・
...Old...il 0.5 gelatin...
・・・・・・・・・・・・・・・・・・・・・・・・
...Old...0.6 sensitizing dye 5-15...
...... Old... Bow Xl0-' Coupler C-20... Old...
...o, 251 oil 0il-2... river...
...Old...0.07 13th layer (1st protective layer) Gelatin ...Old...Old...
・・・・・・・・・・・・・・・・・・0.8 Ultraviolet absorber U-6・・・・1 Old・・・・・・・・・・・・
・0.1 interval U-7・・・・・・・・・・・・・・・
......0.2 dispersion oil 04l-2...
・・・・・・・・・Old・・・・・・o, oi min lit oil Oi I-1・・・・・・Old・・・・・・・・・
...0.01 14th layer (second protective layer) Fine grain silver bromide (average particle size 0.07 μm) River...Silver 0.5 Seratin ...... Old... Old・・・・・・
...old old old...0.45 polymethyl methacrylate particles (1.5 μm in diameter)...old...old...old...0.2 hard Membrane agent 11-1 ・・・・・・・・・
・・・・・・・・・・・・・・・・・・ Old・0.
4 Formaldehyde Schachenzier Cp d -H... River... Old...
・・・・・・・・・・・・・・・0.5 Formaldehyde Schachenzier Cpd-1・・・・・・Old・・・Old・・・・・・・・・
...Old...0.5 In addition to the above components, a surfactant was added to each layer as a coating aid.

Next, the chemical structural formulas or chemical names of the compounds used in the present invention are shown below.

6 C.R.

CHl -(C11゜ C←(I1□-C" 0th eye bis phthalate (2 ethylhexyl) 0 -12 L C(CHs)t H 14 -15 -18 9 H3 2 COOCnlI.

m=25 =25 s+ol.

wt.

Approximately 20°6 0 1 CH1 7 2 3 4 pd pd -10 pd pd ■ ■ ■ After exposing this photographic element to 250M5 using a tungsten light source and adjusting the color temperature to 4800'K with a filter, the following Development processing was performed at 38° C. according to the processing steps. Table 3 shows the results of the same study as in Example 1.

Color development 3 minutes 15 seconds bleaching 6 minutes 30 seconds washing with water 2 minutes 10 seconds fixing
Wash with water for 4 minutes 20 seconds 3 minutes 15 minutes
Stable for 1 minute 05 seconds The composition of the treatment liquid used in each step was as follows.

Color developer Diethylenetriaminepentaacetic acid 1.0g 1-Hydroxyethylidene 1,1-diphosphonic acid 2.0g Sodium sulfite 4.0g Potassium carbonate
30.0g potassium bromide
1.4g potassium iodide hydroxylamine sulfate 4-(N-ethyl-N-β-hydroxyethylamino) 2-methylaniline sulfate water added 1.31g 2.4g 4.5g 1.0! ! .

H 10,0 Bleach solution Ethylenediaminetetraacetic acid ferric ammonium salt 100.0g Ethylenediaminetetraacetic acid disodium 10.0g Ammonium bromide 1500g Ammonium nitrate 10.0g Add water
1.02 pH 6.0 Fixer Ethylenediaminetetraacetic acid disodium salt Sodium sulfite 1.0 g 4.0 g Ammonium thiosulfate aqueous solution (70%) Add sodium bisulfite water 175.0- 4.6 g 1.0! p) (6,6 Stable liquid formalin (40%) Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) Add water 2, Od 0.3g 1, On!

Claims (1)

[Claims] The following general formulas (I), (II), (III), (IV) and (V
) and an emulsion layer containing tabular photosensitive silver halide grains having an aspect ratio of 3 or more. Silver halide photographic material. General formula (I) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (II) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (III) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (IV) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula (V) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, A and A' may be the same or different, each represents an acidic nucleus, and B R represents a basic nucleus, X and Y may be the same or different, and each represents an electron-withdrawing group;
represents a hydrogen atom or an alkyl group, R_1 and R_2 each represent an alkyl group, an aryl group, an acyl group, or a sulfonyl group, and R_1 and R_2 may be linked to form a 5- or 6-membered ring. R_3 and R_6 each represent a hydrogen atom, a hydroxy group, a carboxyl group, an alkoxy group, or a halogen atom, and R_4 and R_5 each represent a hydrogen atom or R_
1 and R_4 or R_2 and R_5 are connected to make 5 or 6
Represents a group of nonmetallic atoms necessary to form a membered ring. L_1
, L_2 and L_3 each represent a methine group. m represents 0 or 1, n and q each represent 0, 1 or 2, p is 0
or 1, and when p is 0, R_3 represents a hydroxy group or a carboxyl group, and R_4 and R_5 represent a hydrogen atom. However, general formula (I), (II), (III), (IV) or (
The compound represented by V) has a pK_a of 4 to 1 in a mixed solution in which the volume ratio of water and ethanol is 1:1 in one molecule.
It has at least one dissociable group in the range of 1. )