JPH02170160A - Processing method for silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To stabilize photographic performance even if the volume of the replenishing liquid of a color developing soln. in reduced and to improve the quality of images by using the color photographic sensitive material which contains specific compds. and is reduced in the film thickness on the photosensitive layer side. CONSTITUTION:The photosensitive material which contains >=1 kinds of the compds. expressed by the formula I and is specified in the dry film thickness from the surface on the photosensitive layer side up to the photosensitive layer nearest the base to <=18.0mum is subjected to imagewise exposing then to the processing including a color developing stage (A). The color development processing is executed by replenishing the replenishing liquid at <=700ml per 1m<2> photosensitive material in the stage A. In the formula, A denotes a group which cleaves -(L)n-... by reacting with the oxidant of the developing agent; L denotes a group which cleaves -X-... after cleavage from A; X denotes the groups of the formula II or III; Y denotes <=10C combination group; mere coupler; R denotes 1 to 6C aliphat. heterocycle; Z1, Z2 respectively denote prescribed nonmetallic atom groups; an * mark denotes the position combining with...L, an ** mark denotes the position combining with Y.... The compds. expressed by the formula IV is usable as the compd. expressed by the formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for processing a multilayer silver halide color photographic light-sensitive material. The present invention relates to the processing of multilayer silver halide color photographic materials that can provide high image quality during processing.

(Prior art) In recent years, with the spread of small-sized cameras (for example, 110 cameras), the image quality enlarged from a small-sized screen is equivalent to or higher than the image quality enlarged from a normal 35 mm size screen. This is becoming a requirement.

In order to satisfy these demands, it is necessary to develop a silver halide color photographic material that has enough graininess and sharpness that the print quality is not impaired even when the enlargement magnification is increased.

Conventionally, various methods for increasing the sharpness of images are known.

One of these is, for example, means for reducing the amount of light that is scattered by hitting silver halide grains that are randomly dispersed in the gelatin binder that is the medium of the sensitive material. This method involves adding a coloring material, such as a dye, as described in U.S. Pat. It is something that absorbs. however,
This method has the disadvantage that light that is originally absorbed by silver halide grains is also absorbed, reducing the sensitivity of the light-sensitive emulsion layer.

Furthermore, as a means to improve sharpness, it is possible to reduce the thickness of the photographic emulsion layer to suppress light scattering. In this case, it goes without saying that the thickness of the upper layer on the side away from the support has an effect on the sharpness of the lower layer closer to the support.

The thickness of each layer of the multilayer silver halide color photographic material is
It is mainly controlled by the amount of gelatin as a medium, the amount of coupler, and the amount of high boiling point a solvent for dispersing the organic material in gelatin, and by reducing these, it is possible to make the layer thinner. Among these, reducing the amount of coupler naturally has a limit because it results in a decrease in color density.

However, there is a method of reducing the coupler volume by using a low molecular weight coupler as described in JP-A No. 61-72243, but this reduces the diffusion resistance of the coupler and causes silver halide particles to form in the emulsion layer. This can cause adverse effects such as color mixing due to diffusion within the layer. Reducing the amount of high-boiling organic solvent used to disperse organic materials in gelatin generally reduces the color-forming performance of the coupler, impairs the stability of the dispersed coupler in the gelatin film, and prevents it from precipitating in the emulsion or coating film. It has disadvantages such as: Furthermore, depending on the coupler, the reduction in the amount of the high-boiling organic solvent may significantly reduce the stability of the image-forming dye formed after the development process. Reducing the amount of gelatin is the most effective way to make the layer thinner, but
Reducing gelatin, which is a binder, has the drawback of greatly changing the physical properties of the gelatin film and deteriorating the film quality.

On the other hand, in order to increase sharpness, U.S. Pat.
No. 227.554, No. 3.615,506, No. 3
, 617,291, 3,701.783, etc., or the DIR compound and DIR coupler described in Japanese Patent Publication No. 55-34933 to enhance the edge effect and improve sharpness. It is also known to cause

Further improved DIR compounds and DI described in JP-A-62-166334 and JP-A-63-37346
It is also known that the effect can be further enhanced by using an R coupler. However, even when using the above-mentioned DIR couplers, if it is necessary to produce a strong edge effect, a large amount of DIR couplers must be used, which inevitably greatly suppresses the development of the resulting image. Therefore, there is a natural limit to the amount of DIR coupler that can be used, and there is also a limit to the edge effect produced by the DIR coupler. . Increasing the coating amount of silver halide to solve this drawback not only results in an increase in product cost, but also increases light scattering due to silver halide, resulting in a decrease in the MTF curve in the high spatial frequency region and DIR. This has the effect of deteriorating the sharpness of not only the coupler-added layer but also the underlying layer (for more information on the MTF curve, see James, "Th
e Theory of Photography
Process.

4th Edition, published by Macmillan).

JP-A-59-131934 improves these drawbacks and develops a DIR compound that can particularly enhance the edge effect while keeping the maximum density of the image constant, and uses this compound to improve low frequency The present invention provides a photosensitive material capable of enhancing sharpness in a certain area, but this invention contains a development inhibitor-releasing compound that can react with an oxidation product of a developing agent and release a development inhibitor during color development. The invention relates to a silver halide color photographic material characterized by the following.

JP-A-61-173248 relates to image quality improvement related to the above invention, and states that when a DIR coupler is used, the MTF value in the low frequency region generally increases, resulting in an increase in psychological sharpness. Note that the image sharpness and multilayer effect are not sufficient, and attempts are made to further improve the MTF value in the low frequency region. 2
27.554, No. 3,701,783, No. 3.7
No. 03,375, No. 4,052,213, No. 4,
It is known to use DIR compounds via a timing group in sensitive materials as described in Japanese Patent No. 138.258, Japanese Patent No. 4,146.396, and Japanese Patent No. 4,421.845. Furthermore, for the purpose of improving the above-mentioned photographic performance, the use of compounds described in JP-A-60-185950 and JP-A-57-56837 has been proposed. However, the improvement effect of these compounds alone was still insufficient. In particular, the DIR compound described in JP-A No. 6,337,346 has a plurality of timing groups to increase the diffusion distance of the released development inhibitor precursor and improve the edge effect and multilayer effect. It has been found that when processing with a low replenishment amount of liquid is carried out, there is a serious problem in that the detached development inhibitor accumulates in the developer, causing fluctuations in photographic performance.

JP-A No. 62-148951 discloses a combination of a DIR coupler having a group that decomposes in a developer and a low replenishment process in a color development process in order to stably maintain photographic performance, and improves sharpness and graininess. Although improvements in image quality have been made, further general improvements are needed, and
The DIR couplers described in '346 require even faster resolution times.

On the other hand, in view of the desire to simplify the processing method, there is a strong desire for a method that requires less replenishment of the processing solution in the development processing step using a replenishment method.

In continuous development processing, the amount of developer replenishment varies somewhat depending on the type of photosensitive material to be processed, but is usually about 1300 to 1100 - per Irrl in the case of silver halide color photographic photosensitive materials.

Although it is desired to reduce the amount of replenishment from the above-mentioned point of view, it is generally very difficult to reduce the amount of replenishment because photographic characteristics deteriorate as a result of reducing the amount of replenishment.

On the other hand, in order to meet demands for environmental conservation, various color developer regeneration methods have been attempted in the color development process.

For example, the Journal of Applied Photographic Engineering (J, Appl, PhotoEn
g, ) + 5.208 (I979); Monthly Lab, Yu, 113 (I979) isMPTE Journal (
SMPTE.

J), 88.165 (I979); J, Ap
pl, Photo.

Eng-+ 5.32 (I974); SMP
TE, J, 88.16B (I979);
-143018; 52-146236; 53-
No. 149331; No. 54-9629; J, Appl
, Photo, Eng.

], 216 (I979) and the like.

Additionally, in general, when the amount of replenishment is reduced, the amount of eluates from the silver halide photographic light-sensitive material becomes relatively large (for example,
halogen ions produced by decomposition of silver halide),
There is a problem that sensitivity decreases.

To address this problem of decreased sensitivity, attempts have been made to raise the processing temperature to prevent the decrease in sensitivity and to reduce the amount of replenishment.

For example, Hunt's Color Paper Processing Agent CP-LR Processing Agent (specifically, Hunt's Color Paper Processing Agent CP-LR Processing Agent, published by Hunt, Photograph Inc. Bulletin 49)
No. 6 of phic Bulletjn NIL 49)
Page Color Print Chemistry
[Print Chemistry]], the method described in the Proceedings of the Photographic Society of Japan A-7 "Low Replenishment in Color Paper Processing" (I980), and the like.

In addition, for the former processing agent, the replenishment amount of the color developer is A to 2/
This will reduce the number to 3.

However, since these are processing agents for color paper, they cannot be immediately adopted for color photographic materials for photographing due to problems with photographic properties such as sensitivity, gradation, and color reproduction.

In the processing of color negative film, the above-mentioned Hunt Co. processing agent (published by Hunt Co., listed in Photographic Ink Bulletin No. 55) is used at a rate of 754 -
However, it is still not sufficient in terms of processing stability.

This is a problem specific to color photographic light-sensitive materials.
It is speculated that this is because the development inhibitor released from the R (development inhibitor releasing type) coupler flows out and accumulates in the developer after the coupling reaction.

Although it is stated that the use of the improved DIR compound described in JP-A-63-24237, JP-A-63-254453 and US Pat. No. 4,782,012 further improves the sharpness, the color developer There is no description of the above-mentioned image quality improvement effect, photographic performance, etc. in the low replenishment amount processing, nor can it be inferred.

Furthermore, JP-A-62-166334 and JP-A No. 631259
No. 37 and No. 63-210927 have improved DI
This method attempts to improve sharpness, color reproducibility, and graininess by reducing the dry film thickness of the emulsion layer using R compounds, but this method also reduces the amount of replenisher for the color developer. There is no mention of photographic performance, image quality improvement effects, etc. when such processing is carried out, and there is nothing that can be inferred.

(Problems to be Solved by the Invention) Therefore, an object of the present invention is to prepare a multilayer silver halide color photographic light-sensitive material containing an improved DIR compound and having a thinner dry film thickness of a photosensitive layer by replenishing a color developing solution. It is an object of the present invention to provide a processing method that provides excellent images with stable photographic performance and high image quality when color development processing is performed with a reduced amount of liquid.

(Means for Solving the Problem) As a result of various studies, the inventor was able to achieve the above object by the method described below.

That is, at least one red-sensitive layer on the support,
A dry film having a green-sensitive layer and a blue-sensitive layer, containing at least one compound represented by the following general 2 (I'l), and extending from the surface of the side having the photosensitive layer to the photosensitive layer closest to the support. In a method in which a silver halide color photographic light-sensitive material having a thickness of 18.0 μm or less is imagewise exposed and then processed including a color development step, the color development step per 1rr+ of the light-sensitive material;
This could be achieved by replenishing the color developer with a replenisher of 700 liters or less and carrying out color development processing.

- Killing (I) ] % Formula % In the formula, A represents a group that reacts with the oxidized developing agent to cleave a group represented by (L)Il-X-Y-COOR, and L represents Il after cleavage from A. Represents a group that cleaves the group represented by X-Y-COR,
, Y represents a divalent linking group having 10 or less carbon atoms or a simple bond, and R represents an aliphatic group or a heterocyclic group having 1 to 6 carbon atoms. Here, 21 represents a group of nonmetallic atoms necessary to form a heterocycle together with a carbon atom and a nitrogen atom, Z2 represents a group of nonmetallic atoms necessary to form a heterocycle together with a nitrogen atom, and the * mark indicates A- (L),
, and **marks represent the respective bonding positions with Y-COOR.

Next, the compound represented by the general formula (T) will be explained in detail.

In general formula (I), A specifically represents a coupler residue or a redox group.

Examples of the coupler residue represented by coupler residues (e.g. zoloimidazole type), cyan coupler residues (e.g. phenol type, naphthol type or European Published Patent Application No. 249)
, 453) and colorless coupler residues (for example, indanone-type or acetophenone-type coupler residues). Also, U.S. Patent Nos. 4,315,070 and 4,18
No. 3,752, No. 4,174゜969, No. 3,961
, No. 959, No. 4,171.223, JP-A-63-2
No. 61262, No. 52-82423 or No. 51-1
It may also be a heterocyclic coupler residue described in No. 04825.

When A represents a redox group, the redox group is a group that can be cross-oxidized by an oxidized developing agent, such as hydroquinones, catechols, pyrogallols, 1,
Examples include 4-naphthohydroquinones, 1,2-naphthohydroquinones, sulfonamidophenols, hydrazides, and sulfonamidonaphthols. Specifically, these groups include, for example, JP-A Nos. 62-230135, 62-251746, 61-278,852, U.S. Pat. No. 3,364,022, and 3,379.5
No. 29, No. 3,639.417, No. 46 B 4. '
No. 604 or J, Org, Cheml, 29,58
8 (I964).

-Jllu The group represented by L in formula (I) preferably includes the following.

(I) A group that utilizes the hemisecure cleavage reaction, such as U.S. Pat. No. 4,146.396, JP-A-60-2491
It is a group described in No. 48 and No. 60-249149, and is represented by the following -Sakatsu. Here, the * mark indicates the general formula (I
) represents the bonding position with A of the compound represented by *
The * mark represents the position where XY-C00R is bonded.

-Satsutsu (T-1) In the formula, W represents an oxygen atom, a sulfur atom, or a -NI3 group, R11 and R1□ represent a hydrogen atom or a substituent, RI3 represents a substituent, and t is 1 or 2
represents. When t is 2, two R1+WC- represent the same thing or different things. R1
When + and RI2 represent a substituent, representative examples of R13 are RIS group, R+, CO- group, R16S, respectively.
Examples include an O□- group, an R,5NCO- group, or an Ib R,5NSO2- group. Here, RI5 is fat I
6 represents an aliphatic group, aromatic group or heterocyclic group, and RI6 represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group.

A case where each of R11, R, □ and R13 represents a divalent group and is linked to form a cyclic structure is also included. −Slaughter (
Specific examples of the group represented by T-1) include the following groups.

CH, CH3 (2) A group that causes a cleavage reaction using an intramolecular nucleophilic substitution reaction Examples include timing groups described in US Pat. No. 4,248,962. The following can be expressed as - slaying.

General formula (T-2) *-Nu-Link-E-** In the formula, Nu represents a nucleophilic group, an oxygen atom or a sulfur atom is an example of a nucleophilic species, E represents an electrophilic group, and Nu It is a group that can cleave the bond with the mark ** upon receiving a nucleophilic attack, and Link represents a linking group that sterically relates Nu and E so that they can undergo an intramolecular nucleophilic substitution reaction. −
Specific examples of the group represented by Funatsuri (T-2>) include the following.

It may also be a component of a ring or a heterocycle.

Examples include the following groups.

Specific (3) A group that causes a cleavage reaction using an electron transfer reaction along a conjugated system.

For example, US Patent No. 4409323, US Patent No. 442184
No. 5, JP-A-57-188035, JP-A No. 58-9872
No. 8, No. 58-209736, No. 58-209737
No. 5B-209738, etc., and is a group represented by the following -Sakatsu (T-3).

General formula (Y-3) In the formula, * mark, ** mark, W, RI+, R1□ and t are (
It has the same meaning as explained for T-1). However, R11 and R11 are bonded to form benzene CH2 Cl2-** (4) A group that utilizes a cleavage reaction due to ester hydrolysis.

For example, the linking groups described in West German Published Patent Application No. 2,626,315 include the following groups.

In the formula, * and ** have the same meaning as explained for general formula (T-1).

General formula (T-4) - Killing (T-5) (5)
A group that utilizes the cleavage reaction of iminoketal.

For example, it is a linking group described in US Pat. No. 4,546.073, and is a group represented by the following general formula.

General formula (T-6) When X in the general formula (r) represents a group represented by the following -Sakatsu (D-1), General formula (D-1) In the formula, *, **, and W are It has the same meaning as explained in general formula (T-1), and RI4 represents the same meaning as R13. - Specific examples of the group represented by T-6 include the following groups.

Zl preferably represents, together with -C-N-, a group of nonmetallic atoms necessary to form a 5- to 7-membered heterocycle, which may be substituted or fused. Examples of such heterocycles include pyrazole, triazole, tetrazole,
imidazole, pyrrole, oxazole, thiazole,
Mention may be made of oxadiazole, thiadiazole, benzimidazole, pyridine, pyrimidine or indazole. Particularly preferred among these are tetrazole, 1,3,4-thiadiazole, 13.4-oxadiazole and 1.2.11) liazole.

In general formula (I), when X represents a group represented by the following formula (D-2), -Z2 (D-2) * -1'J -+-* )k゛°Z2 Z2 is preferably nitrogen It represents a 5- to 7-membered heterocycle which may be substituted together with atoms. Examples of such heterocycles are imidazole, 1,2.4. -) Riazole, 1,
2.3-) lyazole, pyrazole, pyrrole, imidacilline-2-thione, oxazoline-2-thione, 1,
2.4-) riazoline-3-thione, or l 3,
4-Thiadiazoline-2-thione is mentioned. Among these, particularly preferred are l,2,41-lyazole,
1.2.1-) lyazole and pyrazole.

When the heterocycle represented by general formulas (D-1) and (D-2) has a substituent at a substitutable position other than A-(L) and Y-COOR, examples thereof include aliphatic Group (
1 to 10 carbon atoms, e.g. methyl, ethyl), halogen atoms (e.g. chloro, fufu, brome), heterocyclic groups (
1 to 5 carbon atoms, a 3 to 6-membered ring selected from an oxygen atom, a sulfur atom, or a nitrogen atom as a petro atom, such as a furyl group, a thiophene group, an imidazolyl group), a nitro group,
Cyano group, aromatic group (having 6 to 10 carbon atoms, e.g. phenyl), amino group, alkylthio group (having 1 to 1 carbon atoms)
0, eg methylthio, ethylthio), or acylamino groups (having 2 to 10 carbon atoms, eg acetamide, henzamide).

- The divalent group represented by Y in saccharide (I) is preferably an ether bond, a 1,000-onythyl bond, -NHC
It represents an aliphatic group or aromatic divalent linking group or a simple bond which may contain a linking group containing a petero atom such as O-1so, ---co-1 or -NISO,-.

Particularly preferred Y here is an aliphatic group which may contain an ether bond or a thioether bond.

For example, methylene, ethylene, propylene, CH5GH
Mention may be made of the z 5CH CH3CH3 CHt OCHz S CHz CHz- or the CHz S G Hz- group.

- In Sakuhatsu (I), the group represented by R is preferably an aliphatic group having 1 to 6 carbon atoms, which may be substituted. Examples of substituents include those listed above as substituents that the heterocyclic group represented by (])-1) may have.

The compounds of the present invention can be used, for example, in JP-A-63-261262, JP-A-61-254453, and U.S. Pat. No. 4,782,012.
or No. 4477563.

(Compound example) NO□ N = N NO□ N02 H N = N 0υ H =33 CH3 CH2CO□C3H.

H CH3 α乃H CH2 H2 0e 0! fl NO□ H The compound represented by the general formula (I) of the present invention is preferably added to a light-sensitive silver halide emulsion layer or a layer adjacent thereto in a light-sensitive material, and the amount added is lXl0-
6 to 1×10 −″ mol/po, preferably 3×10
-'~5X10-'mol/M, more preferably IX
10-' to 2 x 10-' mol/1.

The compound represented by the general formula [I] of the present invention can be added in the same manner as for ordinary couplers, as described below.

Incidentally, the film thickness of the multilayer silver halide color photographic light-sensitive material in the present invention was measured by the following method.

First, we measured the total thickness of the sample that had been stored for 7 days at 25°C and 150% RH, and then, after removing the coating layer on the support, we measured the thickness again, and the difference was calculated as follows. This was defined as the thickness of the entire coating layer of the above-mentioned photosensitive material excluding the support. At this time, the thickness was measured using a film thickness measuring device using a contact type piezoelectric transducer (^nri tsuElectric C
o, Ltd., K-402B 5TAND, ). Further, the coating layer on the support was removed using an aqueous sodium hypochlorite solution.

Next, using a scanning electron microscope, take a cross-sectional photograph of the sensitive material (preferably a magnification of 3,000 or more), measure the total thickness of the coating layer on the support and the thickness of each layer, and measure the thickness of the coating layer on the support. The thickness of each layer was calculated by comparing the measured values with a thickness measuring device.

The thickness of the entire coating layer excluding the support is preferably 18 μm or less. More preferably, it is 12 to 17 μm.

Next, the processing of the present invention will be explained in detail.

Color photosensitive materials for photography, such as color negative films, are usually replenished with about 1200 mf of color developer replenisher per 1% of the film during color development processing. In fact, with such a replenishment amount, even when processing a considerably small amount and under conditions where the processing amount fluctuates, problematic fluctuations in processing performance are unlikely to occur. However, the replenishment amount is 7
When reduced to 00 mβ or less, the above problem increases significantly.

These changes in performance are caused by higher gradations and higher fog density due to evaporative concentration of the developer, softer gradations and lower fog density due to oxidation of the color developing agent, and fluctuations in throughput. Increasing or decreasing the bromine ion concentration, increasing or decreasing the gradation, increasing or decreasing the fog density, and even DIR.
Changes in performance such as sensitivity and gradation due to the accumulation of the development inhibitor released from the compound in the developer are mutually related, and the situation is extremely complex. However, no solution to this problem has been found.

The present inventor has proposed that D represented by the above general formula [I] be used as a photosensitive material.
Using an IR compound, a light-sensitive material with a dry film thickness of 18 μm or less of the constituent layers excluding the support can be processed continuously with a color developer replenisher amount of 100 ml or less per IM of the light-sensitive material, and the sharpness can be significantly improved. It has been found that the photographic performance can be improved and stable photographic performance can be obtained.

In the present invention, the replenishment amount of color developer is 70 per 11
0mj! The preferred range where the effect is more pronounced is 100 mj! It is not less than 6 tlO-, and the more preferable range is not less than 200 m# and not more than 500 ml.

The color developing agent used in the color developer and color developer replenisher is an aromatic primary amine compound, and includes known compounds that are widely used in various color photographic processes. However, in the present invention, the preferred color developing agent is fl+4-(N-ethyl-N-β-
hydroxyethylamino)-2-methylaniline sulfate (214-(N-ethyl-N-β-methanesulfonamidoethylamino)-2-methylaniline sulfate f3) 4-(N-ethyl-N-β-methoxy ethylamino)-2-methylaniline-p-toluenesulfonate f4.1 4-(N, N-diethylamino)-2-
Methylaniline sulfate (514-(N-ethyl-N-dodecylamino) = 2-
N,N-dialkyl-p-phenylenediamine color developing agents such as methylaniline sulfate (61N, N-diethyl-p-phenylenediamine hydrochloride).
．． 005-0.05 mol/β, preferably 0.01-0.04 mol/A, particularly preferably 0.015-0.03 mol/l. In addition, in the color development replenisher, it is preferable to add it to a higher concentration than the above concentration. Specifically, how high the concentration should be depends on the setting of the replenishment amount, but generally it is 1.05-2.0 times the color developer (mother solution), more often 1.2-1. It is added in an 8-fold range.

The above color developing agents may be used alone or in combination depending on the purpose. Examples of preferable combinations include (I) and (2), and (I) and (2) among the above color developing agents.
3), (2) and (3).

In the present invention, the bromide ion concentration of the color developer is 0.0.
05-0.02 mol/11 (alco in the D range is preferred, but for this purpose the bromide content of the replenisher should be reduced to 0.00
It is preferable to keep it at 5 mol/e or less. In general, the more the replenishment amount is reduced, the lower the bromide content in the replenisher should be set. In particular, in the present invention, the replenisher should not contain bromide in order to significantly reduce the replenishment amount. preferable.

Note that examples of the bromide include potassium bromide, sodium bromide, lithium bromide, hydrobromic acid, and the like.

The color developing solution and the color developing replenisher include hydroxylamine, diethylhydroxylamine, triethanolamine, the compound described in West German Patent (OLS) No. 2622950, the compound described in Japanese Patent Application No. 61265149, sulfites, Preservatives such as bisulfite are used.

In addition, various chelating agents are also added for the purpose of water softening and metal hiding, but in the present invention, in particular, the following general formula (B
), (C), and (D).

General formula (B) CH2C00M General formula (C) 2ChP O3MZ H General formula (D) In the formula, n represents 1 or 2, R represents a lower alkyl group, M may be the same or different, and a hydrogen atom , an alkali metal atom, or ammonium.

)M )M R is particularly preferably a methyl group or an ethyl group, and M is preferably a hydrogen atom or a sodium atom. The above compounds have the effect of suppressing changes in gradation and fog density, especially in low replenishment processing of color light-sensitive materials.

Therefore, the present invention provides a color developer and a color developer replenisher,
At least one compound of general formula (B), (C), (D)
This can be carried out more effectively by including seeds.

In particular, it is more preferable to use one or more of the compounds represented by (B) and (C) or (B) and (D) in combination.

Specific examples of compounds represented by general formulas (B), (C'), and (D) are shown below.

(B-1) CH2C○OH CHZCOOH CH.

H203P C-PO3H2 H 2H5 z03P C-P 03H2 CH The compound of general formula (B) is added to the color developer and its replenisher in an amount of 0.0005-0.02 mol/7! (It is added in the D range, preferably 0.001-0.01 mol/l. Also, the compounds of -killing (C) and (D) are added in the same manner as 0.001-0.01 mol/l.
01-0.1mo) L, /It, preferably 0.005-
It is added in a range of 0.05 mol/A.

When the compounds of general formulas (B) and (C) or (B) and (D) are used together, the compound of (B) is 2 to 20 times the molar ratio of the compound of (C) or (D), The amount is preferably set to 3-15 times, more preferably 3-10 times.

Among the above specific examples, especially (B-1), (C1), (B
It is preferable to use -1) and (D-1) together.

In addition to the above-mentioned compounds, the color developing solution used in the present invention includes PI (buffers; iodides, benzimidazoles, etc.) such as alkali metal carbonates, borates or phosphates.
Development inhibitors or antifoggants such as benzothiazoles, mercapto compounds; organic solvents such as diethylene glycol; development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammoniums, amines, thiocyanates; sodium porohydride. Nucleating agents such as; auxiliary developing agents such as 1-phenyl-3-virapritone; viscosity-imparting agents;
In addition to the compound represented by (D), various chelating agents such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, and the organic phosphonic acid described in Research Disclosure 18170 (May 1979), They can be used alone or in combination.

In the present invention, the pH value of the color developer and its replenisher is usually 9 or more, preferably 9.512, particularly preferably 9.5-11.0.

In the above range, the replenisher for the color developer is
It is preferable to set the value to about 0.05-0.3 higher.

In addition, the temperature in the color development process is 30-45°C, but in order to achieve a wider low replenishment process, a high temperature is preferable, and in the present invention, the temperature is 35-45°C.
1. It is particularly preferable to carry out the reaction at 3B-42°C.

Although the present invention can be carried out using either an automatic processor or manual processing, it is preferable to carry out the process using an automatic processor. In the process of an automatic processor, a single color developer tank or multiple color developer tanks may be used, but replenishment can be further reduced by using multiple tanks and using a multi-stage forward replenishment system in which the first tank is refilled and the color developer is sequentially flowed into the rear tanks. be able to. In addition, it is preferable that the contact area between the developer and the air in the tank be as small as possible.Specifically, the contact area between the developer and the air in the tank should be as small as possible.
Using a shielding means such as a tank structure with a narrowed opening as described in No. 283 further enhances the effects of the present invention.

Further, as a means for enhancing the effects of the present invention, it is preferable to replenish water in accordance with the amount of evaporation in order to correct evaporation concentration of the developer. The water to be replenished is preferably deionized water that has undergone ion exchange treatment, or deionized water that has been treated with reverse osmosis, distillation, or the like.

The color developer and color developer replenisher are prepared by sequentially adding and dissolving the above-mentioned chemicals in a certain amount of water, and it is preferable to use the above-mentioned deionized water as the water for preparation.

In the present invention, the silver halide color photographic material is imagewise exposed, then subjected to color development treatment as described above, and then treated with a processing solution having bleaching ability.

Here, the processing solution having bleaching ability refers to soluble silver salts such as silver thiosulfate complex salts or insoluble root salts such as silver bromide, by oxidizing metallic silver produced by the development reaction and colloidal silver contained in the sensitive material. It refers to a processing liquid that has the ability to change the color of a liquid, such as a bleaching liquid, a bleach-fixing liquid, etc. In the present invention, it is preferable to immediately process with a processing solution having bleach-fixing ability after the color development process.

Bleaching agents used in the treatment solution having bleaching ability of the present invention include ferric complex salts such as ferricyanide iron complex salts and ferric citrate complex salts, peroxides such as persulfates and hydrogen peroxide,
Among them, ferric aminopolycarboxylic acid complex salts are preferred, which are complexes of ferric ions and aminopolycarboxylic acids or salts thereof.

Representative examples of these aminopolycarboxylic acids and their salts include: ■ Diethylenetriaminepentaacetic acid ■ Diethylenetriaminepentaacetic acid pentasodium salt ■ Ethylenediamine-N-(β-oxyethyl)N,
N', N'-1-lyacetic acid■ Ethylenediamine-N-(β-oxyethyl)N,
N',N'-)triacetic acid trisodium salt■ Ethylenediamine-N-(β-oxyethyl)-N
, N', N'-) triammonium acetate ■ 1,2-diaminopropane tetraacetic acid ■ 1,2-
Diaminopropanetetraacetic acid disodium salt ■ Nitrilotriacetic acid ■ Nitrilotriacetic acid sodium salt [Phase] Cyclohexanediaminetetraacetic acid ■ Cyclohexanediaminetetraacetic acid disodium salt ON-methyl-iminodiacetic acid 0 Iminodiacetic acid ■ Dihydroxyethylglycine [Phase] Ethyl ether diamine tetraacetic acid Acetic acid [phase] Glycol ether diamine tetraacetic acid O ethylenediaminetetrapropionic acid [phase] 1.3 diamine propane tetraacetic acid [phase] Ethylenediaminetetraacetic acid and the like can be mentioned, but of course the compounds are not limited to these exemplified compounds.

Among these compounds, ■, ■, ■, ■, [phase], ■
, @, [phase], and [phase] are particularly preferred.

Aminopolycarboxylic acid ferric complex salts may be used in the form of complex salts, or may be used in the form of ferric salts, such as ferric sulfate, ferric chloride,
A ferric ion complex salt may be formed in a solution using ferric sulfate, ferric ammonium sulfate, ferric phosphate, etc., and aminopolycarboxylic acid. When used in the form of complex salts,
One type of complex salt may be used, or two or more types of complex salts may be used. On the other hand, when forming a complex salt in a solution using a ferric salt and an aminopolycarboxylic acid, one or more types of ferric salts may be used. Furthermore, one type or two or more types of aminopolycarboxylic acids may be used. Also,
In either case, the aminopolycarboxylic acid may be used in excess of the amount required to form the ferric ion complex.

In addition, aminopolycarboxylic acid Fe(I) excluding the above [phase]
II) At least one complex salt and an ethylenediamine tetracomplex acid Fe(III) complex salt may be used in combination.

Further, the treatment liquid having bleaching ability and containing the above-mentioned ferric complex salt may contain complex salts of metal ions such as cobalt, nickel, and copper other than iron ions.

The amount of bleaching agent per 1 p of the processing solution having bleaching ability of the present invention is 0.1 mol to 1 mol, preferably 0.2 mol to 0.
．． It is 5 moles. In addition, the pH of the bleaching solution is 4,0 to 8,0.
It is preferable that it is, and it is especially preferable that it is 5.0-7.5.

In addition to bleaching agents and the above-mentioned compounds, the treatment bath having bleaching ability constituting the present invention may contain bromides, such as potassium bromide, sodium bromide, ammonium bromide, or chlorides, such as potassium chloride, sodium chloride, ammonium chloride. can include rehalogenating agents such as. In addition, the pH buffering capacity of nitrates such as sodium nitrate and ammonium nitrate, boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, and tartaric acid. Additives commonly known for use in bleach-fixing solutions can be added, such as one or more inorganic acids, organic acids, and salts thereof having the following.

In the present invention, thiosulfates such as sodium thiosulfate, ammonium thiosulfate, sodium ammonium thiosulfate, and potassium thiosulfate, ammonium thiocyanate, and potassium thiocyanate are added to the fixing bath following the bleaching bath or the processing bath having bleach-fixing ability. thiocyanate,
Known compounds as fixing agents such as thiourea and thioether can be included. The amount of these fixing agents added is 1 jl of a processing solution having fixing ability or a processing solution having bleach-fixing ability! It is preferably 3 mol or less, particularly preferably 2 mol or less.
Less than a mole.

The processing solution having bleach-fixing ability of the present invention includes so-called sulfite ion-releasing compounds, such as sulfites and bisulfites such as sodium sulfite and ammonium sulfite, or aldehyde and bisulfite adducts such as carbonyl bisulfide. can be contained.

Furthermore, aminopolycarboxylic acid salts, nyletine diamine tetrakis methylene phosphonic acid, diethylene triamine pentakis methylene phosphonic acid, 1.3 diaminopropane tetrakis methylene phosphonic acid, nitrilo-N
, N,N-t') methylenephosphonic acid, 1-hydroxyethylidene-11'-diphosphonic acid, and other organic phosphonic acid compounds can be included.

In the present invention, the treatment solution having bleaching ability may contain at least one bleach accelerator selected from compounds having a mercapto group or disulfide bond, isothiourea derivatives, and thiazolidine derivatives. . The amount of these compounds per 11 having bleach-fixing ability is preferably from 1X10-5 to 1×10 H mol, particularly preferably from 1X10-' to 5X10-'' mol.

In the present invention, the bleach accelerator contained in the treatment having bleaching ability is a compound having a mercapto group or a disulfide bond selected from thiazolidine derivatives, thiourea derivatives and isothio derivatives,
Any material may be used as long as it has a bleaching accelerating effect. Preferably, compounds and specific examples of general formulas (a) to (g) described on pages 63 to 77 of Japanese Patent Application No. 61-313598 can be mentioned.

In order to add these compounds to a treatment solution, it is common to dissolve them in aqueous alkaline organic acid organic solvents, etc. However, it has no effect on its bleaching promotion effect.

Furthermore, in the present invention, the bleaching accelerator can also be incorporated into the light-sensitive material. In this case, the bleaching accelerator is used in any of the blue, green, and red emulsion layers, the top layer, the middle layer,
It can be contained in a gelatin layer such as the bottom layer.

The processing bath having bleach-fixing ability of the present invention may be a process consisting of one tank, but it may be a process consisting of two or more tanks, and the replenisher may be supplied in a multi-stage countercurrent system in the tank group. , and the replenisher may be supplied to one bath of the tank group by alternately circulating the process liquid in the tank group to provide a generally -like process liquid.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to a water washing and/or stabilization step after desilvering treatment such as fixing or bleach-fixing.

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 flushing tanks and the amount of water in the multistage countercurrent method is described in the Journal on the Society on Motion Picture and Television Engineers (J
our own of the 5ociety of
Motion Picture and Te1evis
ion Engineers) Volume 64, P, 248-
253 (I, May 955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be greatly reduced, but the increased residence time of water in the tank causes bacteria to propagate and the generated suspended matter to adhere to the photosensitive material. Problems such as this arise. In the processing of the color light-sensitive material of the present invention, as a solution to such problems, the method for reducing calcium and magnesium described in Japanese Patent Application No. 131632/1988 can be used very effectively. In addition, chlorine-based disinfectants such as isothiazolone compounds, thiahendazole neck, chlorinated sodium isocyanurate, etc. described in JP-A No. 57-8542, and other chlorinated disinfectants such as hensitriazoles, "Chemistry of germicidal and fungicidal agents" by Hiroshi Horiguchi, It is also possible to use the disinfectants described in the sanitary technology complete volume "Microbial sterilization, sterilization, and anti-mold technology" and the "Encyclopedia of anti-bacterial and anti-mold agents" published by the Japanese Society of Anti-bacterial and Anti-mold.

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

Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water. In such stabilization treatment, Japanese Patent Application Laid-Open Nos. 57-8543 and 58-1483
No. 4, 59-184.34.3, 60-220345
No. 60-238832, No. 60-239784, 6
0-239' 74.9, 61-4054, 61-
All known methods described in No. 118749 and the like can be used. Especially 1-hydroxyethylidene-1,1
A stabilizing bath containing -diphosphonic acid, 5-chloro-2-methyl-4-isothiazolin-3-one, a bismuth compound, an ammonium compound, etc. is preferably used.

Further, following the water washing treatment, a further stabilization treatment may be carried out, such as a stabilizing bath containing formalin and a surfactant, which is used as a final bath for color photosensitive materials for photography. .

The photosensitive material of the present invention preferably has a membrane swelling rate T, /2 of 30 seconds or less.

The membrane swelling rate TI/□ can be measured according to techniques known in the art. For example, photographic
Science and Engineering (Photog
r, Sci, Eng, )+ Volume 19, No. 2, 124~
It can be measured by using a swellometer (swelling membrane) of the type described on page 129, and T, 7□ can be measured by using a color developing solution.
The saturated film thickness is defined as 90% of the maximum swollen film thickness reached when treated at 0°C for 13 minutes and 15 seconds, and is defined as the time required to reach the film thickness of T172. The membrane swelling rate TI/2 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 ratio can be calculated from the maximum swollen film thickness under the conditions described above according to the formula: (maximum swollen film thickness - film thickness)/film thickness.

1, etc.), aniline derivatives (N,N-dibutyl-2butyl-xy-5-1ert-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.), and the like. In addition, as an auxiliary solvent, the boiling point is about 30'C or higher, preferably 50°C.
Organic solvents with a temperature above about 1.60°C or below can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl chloride, cyclohexanone, 2-
Examples include 1-xyethyl acetate, dimethylborumamide, and the like.

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

The present invention can be applied to various color photosensitive materials. It is particularly preferable to apply the present invention to color negative films for general use or movies.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, No. 17643, page 28, and the same No.
18716, from the right column on page 647 to the left column on page 648.

esters of phosphoric or phosphonic acids (triphenylbosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, (-dicyclohexyl) phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate), l-rib-1-xyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexyl phenyl phosphonate, etc.), benzoic acid esters (2-ethylhexyl phenyl phosphonate, etc.),
-Ethylhenzoate, dodecylhenzoate 1
-12-ethylhexyl-Kano hydroxyhenzoate, etc.), amides (N,N-diethyldodecanamide, N
, N-diethyl laurylamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (bis(2-ethylhexyl), ) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrecabra, DIR coupler releasing coupler, DIR coupler releasing redox compound or DIR redox releasing redox compound, after withdrawal as described in EP 173 302A. Couplers that release coloring dyes, R, D, No. 11449, No. 24241, bleaching accelerator releasing couplers described in JP-A-61-201247, etc., U.S. Pat. No. 4,553,477
Ligand-releasing coupler described in JP-A-63-75
Examples include couplers that release leuco dyes as described in US Pat. No. 747, couplers that release fluorescent dyes as described in US Pat. No. 4,774,181, and the like.

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 high boiling point organic solvents of C or higher include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis(2,4-di-L-amylphenyl) phthalate, screws (2,4-G t91.0, British patent 2
．． 102.173 etc.

Couplers that release photographically useful residues upon camping are also preferably used in the present invention. In addition to those represented by the general formula (I) of the present invention, the DIR couplers that release a development inhibitor include the above-mentioned RD 17643,
The patent described in Section F, JP-A-57-151944,
Preferably, those described in No. 57-154234, No. 60-184248, No. 63-37346, and US Pat. No. 4,248,962.

Couplers that imagewise release a nucleating agent or a development accelerator upon development include British Patent Section 2.097.140;
No. 2,131,188, JP 59-157638
No. 59-170840 is preferred.

Other couplers that can be used in the light-sensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4,130,427, U.S. Pat. , IIR redox compound release No. 212 described in JP-A-60-185950, JP-A-6224252, etc., JP-A No. 4,296,199, Preferred are those described in JP-A-61-42658 and the like.

Colored couplers for correcting unnecessary absorption of coloring dyes are described in Research Disclosure No.
No. 7-39413, U.S. Patent No. 4,004,929,
No. 4.138.258, British patent tube 1,146,3
The one described in No. 68 is preferred. Also, U.S. patent cylinder 4,
No. 774,181, a coupler that corrects unnecessary absorption of a coloring dye by a fluorescent dye released during coupling, and a coupler that can react with a developing agent to form a dye, as described in U.S. Pat. No. 4,777,120. It is also preferred to use couplers having a dye precursor group as a leaving group.

Couplers whose coloring dyes have appropriate diffusivity include U.S. Patent No. 4.366, 237 and British Patent No. 2,125.
, No. 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. 4,576, No. 73.636, U.S. Patent No. 3,
No. 061,432, No. 3725, 064, Research Disclosure No. 24220 (June 1984), JP-A-60-33552, Research Disclosure No. 24230 (June 1984)
, JP-A-60-43659, JP-A-61-72238,
No. 60-35730, No. 55-1.18034, No. 60-185951, U.S. Patent No. 4500.630, No. 4,540,654, No. 4,556,630
Particularly preferred are those described in WO (PCT) No. 88104795 and the like.

Cyan couplers include phenolic and naphthol couplers, and are disclosed in U.S. Patent No. 4.052.212.
No. 4,146,396, No. 4.228,23
No. 3, No. 4,296,200, No. 2.369,9
No. 29, No. 2,801.171, No. 2.772.
No. 162, No. 2,895.826, No. 3.772
．． No. 002, No. 3.758.308, No. 4,33
No. 4.011, No. 4,327,173, West German Patent Publication No. 3329.729, European Patent No. 121,365A
No. 249453A, U.S. Patent No. 3,446,6
No. 22, No. 4,333,999, No. 4,753,
No. 871, No. 4,451,559, No. 4,427
, No. 767, No. 4,690,889, No. 4,25
In addition, in order to prevent deterioration of photographic performance due to formaldehyde gas, U.S. Pat. No. 4.41L987 and U.S. Pat.
It is preferable to add to the photosensitive material a compound that can be immobilized by reacting with formaldehyde as described in No. 435,503.

Various color couplers can be used in the present invention, specific examples of which can be found in the above-mentioned Research Disclosure + -
(RD) No. 17643, described in the patent described in ■-C-G.

As a yellow coupler, for example, U.S. Patent Tube 3.93
No. 3,501, No. 4,022,620, No. 4,3
No. 26,024, No. 4.401.752, No. 4,
No. 248,961, Japanese Patent Publication No. 5B-10739, British Patent No. 1.425.020, No. 1,476.760, US Patent No. 3.973.968, No. 4.314,
No. 023, No. 4,511,649, European Patent No. 24
No. 9,473A, etc. are preferred.

As magenta couplers, 5-pyrazolone and pyrazoloazole compounds are preferred, and US Pat.
No. 0.619, European Patent No. 4.3SL897, and the relevant descriptions are shown in the table below.

1 additional layer 1? D17643 RD18716
1 Chemical sensitizers Page 23 Page 648 Right column 2 Sensitivity enhancers ・ Same as above 3 Spectral sensitizers,
Pages 23-24 Page 648 Right column ~ Super sensitizer
Page 649 right column 4 Brightener Page 24 5 Anti-fog agent Page 24-25 Page 649 right column ~ and stabilizer 6 Light absorber, page 25-26 Page 649 right column ~ Filter dye, page 650 left column Ultraviolet absorption Agent 7 Anti-stain agent Page 25, right column Page 650, left to right column 8
Dye image stabilizer page 25 9 Hardener page 26 page 651 left column 10
Binder page 26 Same as above 11 Plasticizer, lubricant page 27 Page 650 right column 12 Coating aid, pages 26-27 Page 650 right column Surfactant 13 Statinc Page 27 Same as above (I9
1970); U.S. Patent No. 4,434,226, 4,4
No. 14,310, same! , No. 433.048, 4. ，
No. 139.520 and British patent cylinder 2.11.2.15
It can be easily prepared by the method described in No. 7, etc.

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

Also, mixtures of particles of various crystal forms may be used.

The silver halide emulsion used is usually one that has been subjected to physical Y1 formation, chemical ripening and spectral sensitization. Additives used in such processes are subject to Research Disclosure No.
, 17643 and No. 18716, and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the two Research Disclosures mentioned above (Emulsi
on preparation and types)
”, and same No. 18716 (I979 1
January), 648 pages, ``Physics and Chemistry of Photography'' by Grafkide, published by Beaumontel (P, GIafkicles)
, Chemic et Ph1sique Photo
ographique, Paul Montel,
196'l), Duffin, "Photographic Emulsion Chemistry" 5, published by Focal Press (G, F, DuffinPhotogr.
aphic Emulsion Chemistry
(Focal Press 1966)), “Production and Coating of Photographic Emulsions” by Zelikman et al. J11 Focal Press (V, L, Zelikmanet a+,
Making and Coating Pho
Mugraphic Emulsion, Foca
1 Press+ 1964).

U.S. Patent Nos. 3,574,628 and 3,655,39
Monodisperse emulsions such as those described in No. 4 and British Patent Box L 413,748 are also preferred.

Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described by Gutoff, Photographic Science and Engineering.
ence and Engineering), Vol. 14, 248-257 As mentioned above, various layer structures and arrangements can be selected depending on the purpose of each photosensitive material.

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

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

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

Examples of silver halide photographic emulsions that can be used in the present invention include Research Disclosure (RD) N.

17643 (I, December 97B), pp. 22-23,
"l, emulsion can be produced.

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

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

Compounds etc. may be included, and a color mixing inhibitor may be included as commonly used.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are disclosed in West German Patent No. LI22,470 or British Patent No. 9
As described in No. 23,045, a two-layer structure consisting of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer can be preferably used. Usually, it is preferable to arrange the layers so that the photosensitivity decreases toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Also, JP-A-57-1
No. 12751, No. 62-200350, No. 62-20
As described in No. 6541, No. 62-206543, etc., a low-sensitivity emulsion layer may be provided on the side far from the support, and a high-sensitivity emulsion layer may be provided on the side close to the support.

As a specific example, from the side farthest from the support, low-sensitivity blue-sensitive layer (BL) / high-sensitivity blue-sensitive jliF (BH)
/High sensitivity green photosensitive layer (GH) /Low sensitivity green photosensitive layer (G
L)/high-sensitivity red-sensitive layer (R11)/low-sensitivity red-sensitive layer (RL), or BH/BL/GL/IJ/RH
/RL order, or 3) 1/BL/GH/GL/RL/
R) In the photographic material of the present invention, each of the silver halide emulsion layers of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer is provided on the support in the following order: There are no particular restrictions on the number of layers and the layer order of the silver halide emulsion layer and the non-photosensitive layer. As a typical example, a blue-sensitive, green-sensitive, and red-sensitive light-sensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different light sensitivities is formed on a support. This is a silver halide photographic light-sensitive material having -a, in which unit photosensitive layers are arranged in order from the support side: a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer.

However, depending on the purpose, the above-mentioned installation order may be reversed, or the installation order may be such that different photosensitive layers are sandwiched between the same color-sensitive layer.

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

The intermediate layer includes JP-A Nos. 61-43748 and 59-1.
No. 13438, No. 59-113440, No. 61-20
Coupler and DIR as described in No. 037 and No. 61-20038 (Example) The present invention will be explained in more detail by Examples below.
The present invention is not limited to these.

(Example 1) The following layers were placed in order from the support on a support made of subbed cellulose triacetate film.
I created 08 from 1.

In the following examples, silver halide emulsions and colloidal silver are expressed in terms of silver (g/rr?) l. The materials used were also expressed in terms of coating amount (g/rrf). However, the sensitizing dye is expressed in moles per mole of silver.

(Creation of sample 01) 1st layer (antihalation layer) Black colloidal silver 0.2 gelatin
2.0 UV absorber UV-1
0,2 High boiling point organic solvent 01L-10,02 Film thickness 1,7 μm 2nd layer (intermediate layer) Gelatin 1. Compound Cpd-
AQ.

High boiling point organic solvent 01L - 20° Film thickness 1° Third layer (first red-sensitive emulsion layer) Monodispersed silver iodobromide emulsion (silver iodide 5 mol%, diameter 0.3 μ) 1
゜Gelatin 3゜Sensitizing dye A
1. Ox sensitizing dye B
2. OX sensitizing color dye 1. Ox coupler (, -20゜Coupler C-33゜Coupler C-40゜Coupler C-59゜High boiling point organic solvent 01 L-10゜OI >2 0゜Film thickness 3゜Average grain 5μm 4th layer (second red Sensitive emulsion layer) Monodispersed silver iodobromide emulsion (silver iodide 4 mol%, average grain size 0.7
μ) Gelatin sensitizing dye A Sensitizing dye B Sensitizing dye C Coupler C-1 Coupler (, -3 Coupler C-6 Coupler C-5 High boiling point organic solvent OIL ■, 2 2.5 3X10-'2X10-' lXl0 -' 0, 02 0, 03 0, 05 0, 02 0.1 Film thickness 2.4μm 5th layer (intermediate layer) Gelatin compound Cpd-A High boiling point organic solvent 0 ■ 1゜0゜L-20゜Film thickness 1゜6th layer (first green-sensitive emulsion layer) Monodispersed silver iodobromide emulsion (silver iodide 3 mol%, average grain size 0.3
μ) 0.5 Monodisperse silver iodobromide emulsion (silver iodide 6 mol%, average grain size 0.5
μ) Gelatin sensitizing dye Sensitizing dye E Sensitizing dye F Coupler C-7 Coupler C-8 Coupler C-9 Coupler C-10 High boiling point organic solvent OIL 1.0 3.0 3X10-'2X10-' lXl0- '0, 4 0.1 0,02 0,01 0,05 Film thickness 3.1μm 7th layer (second green-sensitive layer) Monodispersed silver iodobromide emulsion diameter 0.8μ) Gelatin sensitizing dye sensitization Dye E Sensitizing Dye F Coupler C-9 Coupler (, -7 (4 mol% silver iodide, ■).

2゜2 x 1 1.5 Solvent 01L-1 Film thickness 9th layer (yellow filter layer) Yellow colloidal silver 0° gelatin
1゜Compound cpd-A
O.

High boiling point organic solvent 011. -1 0゜Film thickness 1゜10th layer (first blue-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (silver iodide 7 mol%, average grain size 0.3
μ) 0.4 monodispersed silver iodobromide emulsion (silver iodide 6 mol%, average grain size 0.6 μ) Gelatin sensitizing dye E Coupler C-11 Coupler C-5 High boiling point organic solvent O 0,4 2, 0 2 .5μ)0
゜Gelatin 1・Sensitizing dye E
1×1 coupler C-110° coupler (, -50° high boiling point organic solvent 01 >3 0° film thickness 1° average grain 0″4 6 μm 12th layer (first protective layer) Fine grain silver bromide emulsion (iodide Silver 4 mol%, average particle size 0.07
μ) 0.3 Gelatin 1.0 Ultraviolet absorber UV-20,1 Ultraviolet absorber UV-30,2 High boiling point organic solvent 01L-30,01 Film thickness 1.2μm Sensitizing dye A 13th layer (second protection layer) Gelatin 1.0 Polymethyl methacrylate particles (diameter 1.5μ) 0.1 Formaldehyde scavenger S-1 film thickness 1.1μ
m In addition, a surfactant W-1 and a hardening agent H-1 were added.

A sample prepared with the above layer configuration is referred to as sample 01.

The coating layer located farthest from the support of sample 01 (first
The dry film thickness of the constituent layers from the third layer) to the color-sensitive layer (third layer) coated at the position closest to the support was 22.0 μm.

The structural formulas of the materials used in the examples are shown below.

(C)12) 3SO3Na (C) It) as (h.

(CHHz) 3sO3Na 2H5 (CHHz) aSO3゜ Sensitizing dye E Coupler C (CH2) 3S03゜ (CH2) 3sO3Na Coupler C (CHz) zS(h.

(CHz)3SOJa Sensitizing dye G Coupler C H 86~ Coupler C 0CR2CH2CON)ICH2CH20CH3 Coupler C Coupler C C7! Coupler C ■ Coupler C Cβ Coupler C Coupler C ■ H -CsHz Coupler C ■ Surfactant W Dispersion oil 01L-3 Hardener H-1 CH,=CH3O□CHz CH2S Oz CH=
CHZ formalin scavenger-8 Dispersion oil OIL Ultraviolet absorber UV-1 Same as above Ul-2 CH Same as above UV-3 Same as above 1L-2 2H5 Compound CpdA CH CH Next, in place of sample 01, the following samples were prepared.

(Preparation of Samples 02 to 04) The amount of gelatin used in each layer from the 3rd layer to the 13th layer of Sample O1 was 77% for Sample 01, and 77% for Sample O3.
was reduced to 74%, and sample O4 was reduced to 70% to prepare samples 02 to 04. At this time, the dry film thickness of the constituent layers defined above for each sample was 18.5 μm for sample 02 and 1 μm for sample 03.
It was 8.0 μm, and 17.5 μm for sample 04.

(Preparation of sample 05) The amount of gelatin in the third layer of sample 01 was 3.0 g/n (1.5 g/n)
g/po, 1.2g of gelatin amount of 4th layer 2.5g/M
/rrr, the amount of gelatin in the 5th layer is 1.5 g / 0.7
Sample 05 was prepared by reducing the weight to 5 g/rr+, using the same amount of gelatin in other layers as Sample 04, and using the same materials as Sample 01. At this time, the dry film thickness of the constituent layers defined above was 16°4 μm @ (Preparation of sample 06) The amount of gelatin in the 8th and 9th layers of sample 01 was 1°5 g/r
rr to 0.90 g/m, gelatin amount in the 12th layer 1.0
g1rd to 0.60 g/r+(, the amount of gelatin in the 13th layer was reduced from 1.0 g/m to 0.50 g/m, the amount of gelatin used in other layers was the same as sample 05, and the materials used in each layer were Sample 06 was prepared in exactly the same manner as sample 01. The dry film thickness of the constituent layers defined above at this time was 15.9 μm.

The materials used in Samples 01 to 06 other than gelatin and their amounts used are exactly the same as Sample 01, but the amount of hardener H-1 was changed depending on the amount of gelatin used, and the weight of hardener/gelatin was changed. The ratio was added to be constant.

(Preparation of Samples 07.09.11.13.15.17) The DIR compound and coupler c-4 used in the third and fourth layers in the previous samples 01 to 06 were replaced with the instant CI of the present invention) The compound (21) represented by is replaced in an equimolar amount, the coupler C-5 of the third layer is replaced with the compound (6) of the present invention in an equimolar amount, and then the coupler C used in the sixth and seventh layers -10 was replaced with the compound 0 of the present invention in an equimolar amount, and the coupler (, -5) used in the 10th and 11th layers was replaced with the compound (3) of the present invention in an equimolar amount, respectively. Sample 07.09.11.13.15
．． No. 17 was produced. In addition, sample 07 is sample o1, o9 is 02.11 is 03.13 is 04.15 is 05.17 is 0
6 corresponds to the amount of gelatin used.

(Preparation of Samples 08.10.12.14.16 and I8) The amount of the compound represented by Ikkatsu CI of the present invention of Sample 07.09.11.13.15.17 was changed from equimolar substitution to 2. Each sample was prepared by substituting .5 times the molar amount. Therefore, in Sample 07.08, a sensitive material was prepared with the amount of gelatin used corresponding to that of Sample 01, and in Sample 08, the amount of the compound represented by Ikkatsuretsu CI) of the present invention used in Sample 07 was 2.5 times the molar amount. It is. The following samples were prepared using gelatin amounts corresponding to sample 09.1o, sample 02, sample 11.12, sample 03, sample 13.14, sample 04, sample 15.16, sample 05, and sample 17.18 to sample 06. did.

(Preparation of Sample 19.20) Couplers C4 and C-5 used in the third layer of Sample 06
And the coupler C4 used in the fourth layer was added to the compound (9) of the present invention in an equimolar amount (sample 19) and a 2.5 times molar amount (sample 19).
Sample 20) W was replaced with an equimolar amount (
Sample 19) and 2.5 times the molar amount (sample 20) were substituted, and the coupler C-5 used in the 10th and 11th layers was replaced with the compound (6) of the present invention in an equimolar amount (sample 19) and 2.5
Samples 19 and 20 were prepared by substituting twice the molar amount.

(Preparation of Sample 21.22) Compound 0υ of Samples 19 and 20 of the compound (9) of the present invention
Sample 21.22 was prepared by replacing compound (22) of the present invention with compound (20) and replacing compound (6) of the present invention with compound (2).

(Preparation of Samples 23 to 28) Coupler C-5 (3rd layer, 10.11th layer) and Coupler C-10 (6.7th layer) used in Samples 01 to 06 were replaced with the compounds shown below (comparative compound Samples 23 to 28 were prepared by replacing the same molar amount with ).

Sample 23 is attached to sample 01, sample 24 is attached to sample 02, sample 25
is sample 03, sample 26 is sample 04, sample 27 is sample 05
Sample 28 corresponds to sample 06 and was prepared using the same amount of gelatin.

Comparative compound (Compound example (2) described in JP-A-62-148951) CH3C1(3 (Preparation of sample 29) The amount of the comparative compound used in sample 28 was increased by 2.5 times the equimolar amount of sample 01. Sample 29 in terms of molar amount
was created. The amount of gelatin applied is the same as Sample 06.

(Preparation of Sample 30.31) Third layer couplers C4 and C in Samples 05 and 06
-5, 4th layer coupler C-4, 6th layer and 7th layer C
Samples 30 and 31 were prepared in exactly the same manner as Samples 05 and 06, except that the amount of each of C-5 used in the -10, 10th and 11th layers was increased by 2.5 times.

Samples 01 to 31 produced as described above were cut and processed into a width of 35H, and used as test samples in the experiment shown below.

First of all, these samples O1 to O31 were subjected to cloth exposure (
The color temperature of the light source was 4800°K), and each sample was processed using an automatic processor in the steps described below.

Process Processing time Processing temperature Replenishment amount Color development 3 minutes 15 seconds 38.0℃
White 6 minutes 30 seconds 38.0°C300 fixation 3 minutes 15 seconds 38.0°C 800ml Tank capacity 0j2 20β 10! Table-1 Water washing (2) 1 minute 40 seconds 35.0℃ 80 (ld
47! Stable 1 minute 20 seconds 38.0℃ 800
m14j2 Drying 1 minute 30 seconds 55.0°C In the above table, the replenishment amount is per 1nf of photosensitive material.

Next, the 35 mm cut sample 01 was placed in a camera, exposed to light, and then subjected to processing steps 1 to 4 listed in Table 1.
While replenishing the color developer so that the amount of replenisher was 51 per day, processing was continued using an automatic developing machine until the cumulative amount of replenisher reached 20β (twice the capacity of the color developer tank).

The composition of the treatment liquid used is described below.

(Color developer) Mother solution (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.01-Hydroxyethyrythene-1,1-diphosphonic acid 3.0 3.2 Sodium sulfite 4.0 4.9 Potassium carbonate
30.0 30.0 Potassium Bromide
1.4 (listed in Table 1) Potassium iodide
1.5■Hydroxylamine sulfate 4-(N-ethyl-N β-hydroxyethylamino)-2 Add methylaniline sulfate water p) ((Bleach solution) Sodium ferric ethylenediaminetetraacetate trihydrate Ethylenediaminetetraacetate Disodium acetate Ammonium bromide Ammonium nitrate Aqueous ammonia (27%) Add water 2.4 3.6 4.5 (listed in Table-1) 1.0β I, ON 10.05 10.10 Mother liquor (g) 100.0 10.0 140.0 30.0 6.5m1 1.0 j2 Replenisher (g) 140.0 11.0 1B0.0 40.0 2.5m1 1.01 H 6,05,5 (Fixing Solution) Mother liquor (g) Replenisher solution (g) Ethylenediaminetetraacetic acid disodium salt Sodium sulfite Sodium bisulfite Ammonium thiosulfate aqueous solution (70%) Add water to H (Washing solution) Mother liquor and replenisher Common tap water to H-type strong acid Water was passed through a mixed bed column filled with a cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and an OH type anion exchange resin (Amberlite IR-400) to reduce the concentration of calcium and magnesium ions to 3 mg. /7! or less, and then 20 μ/β of sodium isocyanurate dichloride and sodium sulfate were added.

0.5 170, Omf 240.0m1 1, OIl 1.0/ 6.7 6.6 1.0 12.0 9.5 The pal of this solution was in the range of 6.5-7.5.

(Fixer) Mother solution (g) Replenisher (g) Formalin (37%) 2,0 mR3, O
mR polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10%) 0.3 0.45 Ethylenediaminetetraacetic acid disodium salt 0.05 0.08 Add water 1.0j! 1.0IlpH
5,0-8,05,0-8,0 The cumulative replenishment amount of color developer replenisher is 20j! When the temperature was reached, the process was carried out by applying wafer exposure under the same conditions as above. The density of the obtained color images was measured to obtain respective characteristic curves.

The above experiments were conducted for samples 02 to 31, respectively,
Characteristic curves were obtained in the same way.

The sensitivity and gradation of these samples 01 to 31 were examined as processing variations in photographic properties between before and after the continuous processing in processing units 1 to 4.

Sensitivity is the exposure value (
The difference (ΔS) between before and after the continuous treatment of I0gE) was calculated.

For gradation, read the density of the exposure value (ffiogE) that gives the density of (minimum density + 0.2), add 1.5 as the logarithm of the exposure amount, and from that value, read the density of the exposure value (ffiogE) that gives the density of (minimum density + 0.2). The value obtained by subtracting the value of 2) was obtained before and after the continuous processing was started, and the difference (ΔG) was calculated.

Table 2 shows the results of determining changes in these photographic characteristic values due to continuous processing for magenta images.

From the results in Table 2, it is clear that Samples 11 to 22, which use the compound represented by the general formula [■] of the present invention and have a dry film thickness of 18.0 μm or less, are clearly It can be seen that even when the sample of the present invention is processed with a low replenishment amount of color developing solution, stable processing can be performed with small fluctuations in both sensitivity and gradation. In particular, the general formula [I] of the present invention
It is surprising that the fluctuation is small even when the amount of the compound represented by This is thought to be because the compound undergoes decomposition before being transferred to a compound that not only has a development inhibiting effect but is also photographically inactive. On the other hand, the DIR coupler or DIR compound used in the comparative sample ultimately exhibits a development inhibiting effect.
Since the IR compound is difficult to decompose, it is thought to diffuse into other layers and even into the developer and remain, causing fluctuations in photographic performance.

It is also clear that stable processing with a low replenishment amount of the color developing solution can be achieved even in Samples 19 to 22 under the same conditions except that the compound represented by the general formula (I) of the present invention was changed.

Example 2 Using samples 01 to 31 prepared in Example 1, the following experiment was conducted.

First, we investigated the multilayer effect as a measure of color reproducibility.

For measurements of interlayer effects, see T. H. James, “T.
he theory of the photography
phic Process (4th Edition,
Macmillan Co.) Chapter 18, EP532-534, and the procedure described below.

First, each sample 01 to 31 was exposed to uniform green light, and the exposure amount of each sample was adjusted so that the G density was 1.5.
After applying wedge exposure to red light, the following development process is performed, and a characteristic curve f of a cyan color image as shown in Fig. 1 is obtained.
A magenta color image density curve (2) was obtained. Here, when the red-sensitive emulsion layer is developed from point A in the unexposed area to point B in the exposed area, the density curve of the green-sensitive emulsion layer given uniform exposure is the same as the development of the red-sensitive emulsion layer to RG. This indicates the degree of suppression (ΔDG) that the green-sensitive emulsion layer receives depending on the value. That is, in FIG. 1, curve 1 represents the characteristic curve of the cyan image of the red-sensitive emulsion layer, and curve 2 represents the density of the magenta image of the green-sensitive emulsion layer upon uniform exposure to green light.

Point A represents the minimum density portion of the cyan image, and point B represents the exposed portion that provides a cyan image density of 2.0.

Magenta density (D, = 1) at point A in the unexposed area.

5) and the magenta density (D,) at the same point B (
ΔD, expressed as ΔDG-D, -])b), can be evaluated as the degree of color turbidity, and the larger ΔD is, the better the purity of the color (cyan in this case) is, so it is a measure of color reproduction. It can be done.

The above method was carried out for samples 01-31.

The results obtained are shown in Table 3.

Subsequently, the MTF value was measured as a measure of sharpness.

The measurement was carried out in Chapter 21 of the above-mentioned document, C14, P609-64.
It was carried out according to the method described in 1.

The results are also shown in Table 3.

Processing method step Processing time Processing temperature Replenishment amount Tank capacity Color development 3 minutes 15 seconds 38℃ 450mf 2On
Bleach 6 minutes 30 seconds 38°C 30M 4Ql
! Washing with water 2 minutes 10 seconds 35℃ 300mf
20# fixation 4 minutes 20 seconds 38°C600m1
．． 3CN2 water washing (2) 1 minute 00 seconds 35'c
600+nj! 10j! Stable 1 minute 05 seconds 38℃ 300mR10j! Drying 4 minutes 20
Seconds 55℃ The amount of replenishment is determined using an automatic developing machine per photosensitive material IM.
-100 exposures were processed before the samples for this experiment were processed.

Next, the composition of the treatment liquid will be described.

(Color developer) Mother solution (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.11-Hydroxyethyrythene-1,1-diphosphonic acid Sodium sulfite Potassium carbonate Potassium bromide Potassium iodide Hydroxylamine sulfate 4- (N-Ethyl-N-β-hydroxyethylamino)-2 Add methylaniline sulfate to pH (bleaching solution) Sodium ferric ethylenediaminetetranolate 3.0 4.0 30.0 1.4 1.5 ■ 3.2 4.9 30.0 2.4 3.6 4.5 7.2 1, OR1,0j2 10.05 10.10 Mother liquor (g) Replenisher (g) Trihydrate 100.0 140. 0 Ethylenediaminetetraacetic acid disodium salt 10.0 11.0 Ammonium bromide 140.0 180.0 Ammonium nitrate 30.0 40.0 Ammonia water (27%> 6.5+++j 2.5m! Add water 1.0j2 1 .01pH6,
05.5 (Fixer) Mother liquor (g) Replenisher (g) Ethylenediamine tetranoic acid disodium salt 0.5 1.0 Sodium sulfite 7.0 12.0 Sodium bisulfite 5.0 9.5 Ammonium thiosulfate aqueous solution ( 70%), 170.0+d 240.
(Add ld water l, Qll, Oj
! pH 6,76,6 (Water solution) Mother liquor and replenisher Common tap water was mixed 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). ) to reduce the concentration of calcium and magnesium ions to below 3/I, and then add 20/l of sodium isocyanurate dichloride and 0.1/l of sodium sulfate. 5 g/l was added.

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

(Stabilizing solution) Mother solution (g) Replenishment solution (g) Formalin (37%) 2.0TR13,0t
sl polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) Add ethylenediaminetetranoic acid disodium salt solution to pH 0,3 0,45 0,050,08 1, (H! 1.Ol 5.0 -8.0 5.0-8.0 Table 3 Table 3 (continued) Process color development bleaching bleaching fixing processing time processing temperature 3 minutes 15 seconds 38.0℃ 1 minute 00 seconds 38.0℃ 3 minutes 15 seconds 38 .0℃ Replenishment amount listed in Table 4 80〇 - Tank capacity 107! Wash 11 with water (2) 1 minute 00 seconds 35.0℃ 800d
4 A stable 40 seconds 38.0℃ 530
+d 4j2 Drying 1 minute 15 seconds 55.0°C In the above table, the replenishment amount is per 1 d of photosensitive material.

Table-4 The composition of the treatment liquid used is described below.

From the results in the above table, when comparing samples with the same amount of gelatin applied, the sample using the compound represented by the general formula (J) of the present invention is superior to the comparative sample in both color reproducibility and sharpness. I can see that the comparison is poor. Furthermore, when considered together with the results of Example 1, the general formula of the present invention (
When the compound represented by I) is added in an increased amount, the photographic performance is not impaired by continuous processing with low replenishment of color developer, and the results of this example show that when the amount added is increased, both color reproducibility and sharpness are better. It is also clear that there is an improvement effect.

It is also clear from comparison with comparative samples that the use of the compound represented by the general formula [1] of the present invention has a greater effect of improving color reproducibility and sharpness as the dry film thickness becomes thinner.

Example 3 Using Samples 01 to 31 prepared in Example 1, experiments were conducted in the same manner as in Example 1, except that the treatment steps and treatment liquid composition were changed as shown below.

(Color developer) Diethylenetriamine pentachoic acid 1-hydroxyethylitine-1,1-diphosphonic acid Sodium sulfite Potassium carbonate Potassium bromide Potassium iodide Hydroxylamine sulfate 4-(N-ethyl-N β-hydroxyethylamino)- 2 Add methylaniline sulfate solution and H Mother liquor (g) Replenisher solution (g) 1.0 1.1 3.03°2 4.0 4.4 30.0 37.0 1.4 (listed in Table 4) 1.5 ■ 2.4 2.8 4.5 (listed in Table 4) 1.07! 1. Oj! 10.05 10.10 (Bleach solution) Common to mother liquor and replenisher solution (unit: g) Ethylenediaminetetraacetic acid ferric ammonium trihydrate 120.0 Ethylenediaminetetraacetic acid disodium salt 10.0 Ammonium bromide 100.0 Ammonium nitrate
10.0 Bleach accelerator 0
．． 005mol ammonia water (27%) 1
Add 5.0mff1 water 1
．． Oj! pH' 6.3 (
Bleach-fix solution) Mother solution and replenisher common (unit: g) Ethylenediaminetetraacetic acid ferric ammonium trihydrate 50.0 Ethylenediaminetetraacetic acid disodium salt 5.0 Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution (70%) 240.0
ml ammonia water (27%) 6.0m
Add water to 1.0l pH7,
2 (Water wash solution) Mother solution and replenisher Common tap water was filled with H-type strongly acidic cation exchange resin (Amberlite IR-120B, manufactured by Rohm and Haas) and OH-type anion exchange resin (Amberlite IR-400, manufactured by Rohm and Haas). Water was passed through a mixed bed column to reduce the concentration of calcium and magnesium ions to 3 .mu./l or less, and then 20 .mu./l of sodium isocyanurate dichloride and 1.5 g/l of sodium sulfate were added.

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

(Stabilizing solution) Common to mother solution and replenisher solution (Unit: g) Formalin (3
7%) 2. Qmβ polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 Ethylenediaminetetraacetic acid disodium salt 0.05 Add water 1.01 pH 5,0-8,0 Color developer per 1-sensitive material The amount of replenishment fluid is 1200.700
．． When continuous color development processing was carried out at 500 and 300 -, the processing variations in photographic performance, sensitivity and gradation in this experiment were exactly the same as the results obtained in Example 1, and satisfied the constituent requirements of the present invention. It was confirmed that the fluctuations in the photographic performance of Samples 11 to 22 were small, and that they exhibited excellent improvement effects.

It was also observed that by reducing the dry film thickness by the amount of gelatin, there was a tendency for the process to be more stable with less variation.

Example 4 Using Samples 01 to 31 prepared in Example 1, the stability of the photosensitive materials over time was evaluated by storing them under the following conditions.

(I) 45°C, 80% RH, 3 days +2150°C, no humidity control, 3 days (3) 5°C, refrigerated storage The exposure described in Example 1 was given, and the processing steps and processing liquid composition were described below. A color image was obtained by processing with a cumulatively replenished color developer in an amount twice the capacity of the color developer tank. These densities were measured and their photographic characteristic values, sensitivity and gradation were determined. These characteristic values were determined according to the method described in Example 1.

The evaluation was based on the characteristic values obtained under the conditions (3) above, and the differences therebetween were calculated. The results are shown in Table 5 for cyan density, Table 6 for magenta density, and Table 7 for yellow density.

Processing method Step Processing time Processing temperature Color development 2 minutes 30 seconds 40℃ Bleach fixing 3 minutes OO seconds 40℃ Replenishment amount Tank capacity 350mj 8j2 60M 8# Water washing (2+ 20 seconds 35°C 300mj! 2
j2 stable 20 seconds 35℃ 300
mJ! 2ff drying 50 seconds 65
℃ The replenishment amount is determined by using an automatic developing machine per 1 d of photosensitive material, and using Fuji Film, Super HR, etc. until the cumulative replenishment amount of color developer reaches twice the tank capacity.
-100 exposed samples were processed before processing the samples for this experiment.

Next, the composition of the treatment liquid will be described.

(Color developing solution) Mother solution (g) Replenisher (g) Diethylenetriamine Pentanotic acid 1-Hydroxyethyrythene-1,1-diphosphonic acid Sodium sulfite Potassium carbonate Potassium bromide Potassium iodide Hydroxylamine sulfate 4-(N-ethyl -N β-hydroxyethylamino)-2 2,O 2,2 3,0 4,0 30,045,0 1,4 1,5 Akebono 5.5 3.2 2.4 3.0 Methyl 7 Niline Sulfate Salt 4.5 7.5
Add water l, Q7!1.0j2p
H10,0510,20 (Bleach-fix solution) Common to mother liquor and replenisher (unit: g) Ethylenediaminetetranodic acid ferrous ammonium trihydrate 90.0 Ethylenediaminetetraacetic acid disodium salt 5.0 Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution ( 70%) 260. Omf acetic acid (98%) 5.0 + d Bleach accelerator 0.01 mol Add H 1,0β 6.0 (Water solution) Mother liquor, replenisher Common tap water to H-type strongly acidic cation exchange resin (Rohm and Haas Water was passed through a mixed-bed column packed with Amberlite IR-120B) and an OH type anion exchange resin (Amberlite IR-400) to bring the concentration of calcium and magnesium ions to 311W/7! Processed below, followed by sodium dichloride isocyanurate 20■/7! and 0.15 g/Il of sodium sulfate were added.

The I)H of this liquid is in the range of 6.5-7.5.

(Stabilizing solution) Common to mother solution and replenisher solution (Unit: g) Formalin (3
7%) 2.0ml.

Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 Ethylenediaminetetraacetic acid disodium salt 0.05 Add water 1. OI! pH5,0-8,
0 From the results in Tables 5 to 7, it can be seen that the cyan, magenta, and yellow color images of the samples using the compound represented by the general formula (I) of the present invention have excellent stability over time in comparison with the comparative samples. It is clear from this. In addition, in Samples 11 to 22 that meet the constituent requirements of the present invention, it was found that reducing the amount of gelatin and making the film thinner improved the stability over time, and that It is surprising that the aging stability does not change even if the amount of the compound added is increased. This is probably due to the excellent stability of the compound of the present invention in the photosensitive film.

Next, using Samples 01 to 31, the following experiment was conducted to evaluate the storage stability of latent images of these samples after exposure.

First, the above sample was exposed to light as described in Example 1 and then stored under the following conditions.

(I140℃, 70% RH, 7 days + 2150℃, no humidity, 7 days + 3) 0"c, 7 days The stability of the photosensitive material over time was evaluated using the samples stored under the above conditions (I) to (3). The same treatments evaluated were carried out in the same manner.

The density of the obtained color image was measured, and the sensitivity was determined as a photographic characteristic value. Sensitivity evaluation was performed according to Example 1, latent image storage stability was evaluated based on the sensitivity of condition (3),
The difference (ΔS) was calculated. The results are shown in Table 8.

From the results in Table 8, it is clear that the samples using the compounds of the present invention exhibit excellent storage stability of latent images. Furthermore, in the sample using the compound of the present invention, when the dry film thickness was reduced, the stability was not impaired, but rather the stability was improved, and the dry film thickness was 18. Samples of 0 μm or less (Samples 11 to 22
) gives particularly good results. This result showed the same tendency as the stability of the above-mentioned photosensitive material when used, and the general formula (I) of the present invention
This is thought to be due to the excellent performance of the compound represented by.

Example 5 A resistance test against sweating phenomenon was conducted on samples O1 to O31. The sweating phenomenon refers to a phenomenon in which when a sensitive material is placed under high temperature and high humidity conditions, oil-soluble components in the film are not retained in the gelatin binder and gush out onto the film surface like water droplets.

The experimental method is shown below.

A sample with a sample area of 35 wm x 120 m was uniformly exposed to internal light and then subjected to the color treatment described above, and the treated sample thus obtained was allowed to stand under conditions of 80'C and 140% RH for 10 days. After testing under the above conditions, the film surface of the sample is observed using a looper, and the number of minute oil droplets gushing out on the surface is counted.

Evaluation was performed in the following two stages.

○: No minute oil droplets can be detected on the sample surface. ×: 10 minute oil droplets or less on the sample surface. The results are shown in Table 9.

Table 9 Table 9 (Continued) Table 9 (Continued) The results in the above table show that the samples using the compound of the present invention did not sweat even if the applied amount of gelatin was reduced (the ratio of material used + high boiling point organic solvent / gelatin became high). It can be seen that the phenomenon tends to be less likely to occur.

The film strength at this time is determined by pressing a thin needle (a needle with a 0.05 m diameter ball at the tip) against the sample film surface, applying a continuous load, and rubbing the needle against the film surface to scrape off the film. We conducted a "scratching strength" test to determine the load when As a result, samples 01 to 31 had a weight in the range of 160 to 200 g, and there was no significant difference.

Example 6 Using samples 01 to 31 prepared in Example 1, the same
The exposure described in Example 1 was applied, and the color development time was changed as shown in Table 10 in the processing column 7 of Example 3, Table 4, and processing was carried out. The treatment liquid composition is the same as in Example 3. The magenta density of the obtained color image was measured, and its sensitivity was determined according to the method described in Example 1. The color development time of 3 minutes and 15 seconds for each sample was taken as a reference, and the difference (ΔS) was calculated.

The results are shown in Table 10.

From the results in Table 10, in the samples (samples 11 to 22) that meet the constituent requirements of the present invention, development progresses quickly even if the development time is changed, and fluctuations in sensitivity are small. It is clear that even with a short development time of 2'30", the difference in sensitivity is smaller than that with a development time of 3" and 15".The reason for this is not clear, but the general formula (I
) The DIR compound, which is finally released in the coloring reaction process of the compound, has a development-inhibiting effect on silver halide, and the dye formation process due to the coupling reaction of the coupler with the oxidized developing agent, as well as the silver halide used. This result was surprising, although it can only be assumed that this was due to the delicate balance of development speed combined with the performance of the emulsion.

Next, samples 01 to 31 were evaluated for color reproducibility and sharpness in the same manner as in Example 2. The processing was carried out in this example (Example 3)
, color development time 2'30'' of treatment tlh7) listed in Table 4
and 3'15''.

The results are shown in Table 11.

From Table 11, it is observed that there is almost no difference in the MTF value measured as a sharpness evaluation scale for development times of 2'30" and 3'15" depending on the color development time, and as in Example 2, this value It is clear that samples meeting the requirements of the invention exhibit excellent sharpness improvement effects. Regarding ΔDG, which was measured as a scale for color reproducibility evaluation, 2, which has a short development time,
At '30', the value is slightly lower and the effect is slightly weaker, but
However, it can be seen that the use of the compound represented by the general formula CI) of the present invention has a clearly greater improvement effect than the comparative sample. Furthermore, when the results of development progress shown in Table 10 are taken into account, it becomes clearer that the use of the compound represented by the general formula (N) of the present invention exhibits an excellent improvement effect.

Therefore, by using the compound represented by the general formula (I) of the present invention, reducing the dry film thickness, which is a component of the present invention, and performing low replenishment treatment of the color developer,
It is clear that stable photographic performance and high quality images can be obtained, and furthermore, this example and Examples 2 and 3
From the above results, it is clear that the overall processing time of the process can be shortened, and furthermore, it is possible to perform a rapid, low-replenishment continuous process in which the amount of replenisher for the color developing solution is reduced. Moreover, the general formula (I) of the present invention
It can be seen that the use of the compound represented by the above is excellent in terms of the stability of the sensitive material over time and the storage stability of the latent image.

[Brief explanation of the drawing]

FIG. 1 represents the characteristic curve. The curve fil represents the characteristic curve of the cyan image of the red-sensitive layer, and the curve (2) represents the magenta image density of the green-sensitive layer with uniform green exposure. The dashed line (3) represents the theoretical straight line of the curve (2). Patent Applicant Fuji Photo Film Co., Ltd. Procedural Amendment Heisei/Year/@f Date

Claims (1)

[Scope of Claims] The support has at least one red-sensitive layer, one green-sensitive layer and one blue-sensitive layer, each containing at least one compound represented by the following general formula [I], and the photosensitive layer A method of processing a silver halide color photographic material having a dry film thickness of 18.0 μm or less from the surface thereof to the photosensitive layer closest to the support, including a color development step after imagewise exposure. The color development process is 700m per 1m^2 of the photosensitive material.
1. A method for processing a silver halide color photographic light-sensitive material, characterized in that color development processing is performed by replenishing a replenisher of a color developing solution of 1 or less. General formula (I) ▲There are numerical formulas, chemical formulas, tables, etc.▼ In the formula, A represents a group that reacts with the oxidized developing agent to cleave the group represented by -(L)_n-X-YCOOR, and L represents After cleavage from A, it represents a group that cleaves the group shown by ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, and X represents ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ , Y represents a divalent linking group having 10 or less carbon atoms or a simple bond, and R represents an aliphatic group or a heterocyclic group having 1 to 6 carbon atoms. Here, Z_1 represents a group of nonmetallic atoms necessary to form a heterocycle together with a carbon atom and a nitrogen atom, Z_2 represents a group of nonmetallic atoms necessary to form a heterocycle together with a nitrogen atom, and the * mark indicates A- (L
)_n and ** marks each represent the bonding position with Y-COOR.