JPS62229144A - Quick processing method for silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enable a quick developing process and to prevent the contamination of an unexposed part by using a specific color developing agent and using a specific bleaching accelerator. CONSTITUTION:The color developing soln. contains at least one kind of a p- phenylene diamine color developing agent having at least one alkyl sulfon amide alkyl group on a benzene ring and/or amino group. A solvent is incorporated into the color developing soln. in the volumetric ratio range expressed by [volume of (the solvent having <0.4 logP)]/[volume of (water) + (solvent having <0.4 logP except water)] <= 0.003. A soln. prepd. by using the ferric complex salt of an org. acid and thiosulfate as essential components is used for a bleach fixer and an org. acid such as aminopolycarboxylic acid or oxalic acid, citric acid, etc., coordinated with ion ions is used for a bleaching agent.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for processing silver halide color photographic light-sensitive materials, and more specifically, the present invention relates to a method for processing silver halide color photographic light-sensitive materials, and more specifically, silver halide which enables rapid processing and prevents contamination of unexposed areas. This invention relates to a method for processing color photographic materials.

[Background of the Invention] In recent years, there has been a desire in the art for a method for processing silver halide color photographic materials that does not cause pollution problems and can be processed quickly.

In other words, silver halide color photographic light-sensitive materials are subjected to running processing in automatic processing machines installed in each laboratory, but as part of an effort to improve service to users, processing is carried out on the same day that processing is received. There is a need to process the item and return it to the user, and in recent years, there has been a demand for the item to be returned even within a few hours of receiving it, and there is an urgent need to develop technology that can process the item more quickly.

Furthermore, as symbolized by the so-called mini-lab boom, development of silver halide photographic materials has become popular, and there is a strong demand for non-polluting materials.

In silver halide color photographic materials, after color development,
Is there a step for bleaching (oxidizing) and fixing the produced silver image?In recent years, from the viewpoint of speeding up the processing, a bleach-fixing process in which bleaching and fixing are carried out in the same bath has been advantageously used. became.

and red blood salt, as an oxidizing agent for bleaching image silver,
Several serious drawbacks have been noted in the widespread use of inorganic oxidizing agents such as dichromates, or in the bleaching solutions containing these inorganic oxidizing agents. For example, red blood salt and dichromate are relatively good at bleaching silver images, but there is a risk that they will decompose when exposed to light and produce cyanide ions and hexavalent chromium ions that are harmful to the human body. ,
It has unfavorable properties in terms of pollution prevention. Therefore, bleach-fix solutions with oxidizing agents such as metal complex salts of organic acids, such as aminopolycarboxylic acid metal complex salts, have come to be used as solutions that have fewer pollution problems and meet the demand for faster processing. .

On the other hand, due to the demand for rapid processing, there is a technology that uses a color development accelerator when developing exposed silver halide color photographic light-sensitive materials using an aromatic primary amine color developing agent. As such color development accelerators, U.S. Pat. Nos. 2,950,970 and 2,515,14
No. 7, No. 2,496,903, No. 4,03L075, No. 4,119,462, British Patent No. 1,430,99
No. 8, 1,455.4], No. 3, JP-A-158-1973
No. 31, No. 55-62450, No. 55-62451, No. 55-62452, No. 55-62453, No. 5
No. 1-12422, No. 55-62453, Special Publication No. 1973
-12422, No. 55-49728, etc. Regarding the so-called paper sensitive materials in these T4ff and silver halide color photographic light-sensitive materials, benzyl alcohol is most frequently used because it exhibits an excellent effect in accelerating the reaction between the color developing agent and the image-forming coupler. However, poor solubility in organic solvents (with a P of 0.4 and benzyl alcohol as a typical example)
The following drawbacks can be seen in the above solvents.

That is, when a color developer is used for a long period of time, tar is likely to be generated, especially during running processing using a low replenishment method, and the generation of such tar adheres to the vapor-sensitive material to be processed, thereby significantly impairing its commercial value. It may even lead to serious malfunction.

In addition, since poorly soluble organic solvents have poor solubility in water, the preparation of the color developing solution itself is troublesome, such as requiring a stirring device.

Furthermore, poorly soluble organic solvents also have the above-mentioned pollution problem. That is, the pollution load value such as biochemical oxygen demand (BOD) is large, and it is impossible to dispose of it in sewers or rivers, and treatment of the waste liquid requires a great deal of labor and cost.

In response to recent demands for rapid processing, color development processing has become increasingly high temperature (33°C or higher), and low replenishment of color development solutions has been required to facilitate the disposal of waste solutions. Disadvantages or disadvantages are becoming more and more noticeable.

Therefore, the wood inventors attempted to remove the above-mentioned problems without using a poorly soluble organic solvent such as benzyl alcohol.

That is, an attempt was made to rapidly process silver halide color photographic light-sensitive materials using a color developing solution that does not use a poorly soluble organic solvent and a bleach-fix solution that uses a ferric complex salt of a Ja-containing acid as an oxidizing agent. .

However, it has been found that such processing causes dye staining in unexposed areas when the processed silver halide color photographic light-sensitive material is a so-called paper light-sensitive material.

The reason for this is not necessarily clear, but one reason is that color-forming stains of light-sensitive dyes, dyes, or couplers remain in the developed silver halide color photographic light-sensitive material due to the removal of poorly soluble organic solvents. This is thought to be the cause of contamination of the unexposed area. Separately, the color developing agent that adheres to the silver halide color photographic light-sensitive material and is carried into the bleach-fix solution is oxidized, and in the case of a fatigue solution, a large amount of thiosulfate, which has reducing power, coexists, and its reduction It is thought that the developability of the silver halide occurs due to the force, resulting in contamination of the unexposed areas.

Bleach-fix baths contain bleaching agents, which are oxidizing agents, and fixing agents, such as thiosulfates, which have reducing power, and preservatives, such as sulfites, in the same bath. Acid ferric complexes, such as iron ethylenediaminetetrabutyrate (Il[
I) When an iron (m) complex salt of an aminopolycarboxylic acid such as a complex salt is used and rapid processing is performed, especially when bleach-fixing is performed within 80 seconds, the problem of contamination of the unexposed area will occur significantly. It turns out.

In addition, in recent years, environmental conservation and water resource issues have become important in photofinishers that automatically and continuously develop photosensitive materials, and they are used in the washing process following fixing or bleach-fixing. It is desired to reduce or eliminate the large amount of washing water required. For this reason, a technique has been proposed in which a stabilization treatment is performed directly after fixing or bleach-fixing without washing with water. For example, special I38 Sho 57-8
No. 524, No. 57-13214E1, No. 57-148
No. 34 and No. 57-14834 each disclose a technique of processing with a water washing substitute stabilizing solution containing an inthiazoline derivative, a pentwinthiazoline derivative, a polycarboxylic acid, a soluble iron complex salt, and an organic phosphonic acid. It has been found that the above-mentioned contamination is also increased when the technique known in these publications, in which the water washing step following bleach-fixing is treated with a water washing substitute stabilizing solution, is used.

Furthermore, it has been found that it is preferable to increase the pH of the color developing solution in order to improve developability and speed.
It was found that the contamination increased.

[Object of the Invention] Therefore, an object of the present invention is to provide a method for processing a silver halide color photographic light-sensitive material, which enables rapid development and prevents contamination of unexposed areas.

[Structure and operation of the invention] The method for processing a silver halide color photographic light-sensitive material of the present invention which achieves the above object is a method for processing a silver halide color photographic light-sensitive material of the present invention. In a method for processing a silver halide color photographic light-sensitive material, which processes the silver halide color photographic light-sensitive material through at least a color development step and a bleach-fixing step after imagewise exposure, (1) the color developer used in the color development step contains a benzene ring; (1) Contains at least one p-phenylenediamine color developing agent having at least one alkylsulfonamide alkyl group in the top and/or amino group; The bleach-fixing solution used in the bleach-fixing process contains a solvent in a volume ratio range, and has the formula [A] as a main component.

(2) The bleach-fix solution is characterized in that it contains at least one compound represented by the general formulas [11 to (2)] described below.

That is, the present inventors have developed a silver halide color photographic light-sensitive material containing a silver chlorobromide emulsion using a color developing solution from which a poorly soluble organic solvent has been removed and a bleach-fixing solution using an organic acid ferric complex salt as an oxidizing agent. The inventors discovered the surprising fact that the above object can be achieved by using a specific color developing agent and a specific bleaching accelerator in the development process, leading to the present invention.

In a preferred embodiment of the present invention, (1) the color developer is p
H is 1000 or more, ■ The volume ratio of the formula [A] is 0 to 0.001, ■ The bleach-fix solution has p
H is in the range of 5 to 9; (2) the silver halide photographic material is subjected to a stabilization treatment as an alternative to water washing after being processed in a color development step and a bleach-fixing step;

The present invention will be explained in detail below.

In the Wood specification, "substantially a silver chlorobromide emulsion" means that it may contain a trace amount of silver iodide in addition to silver chlorobromide,
For example, this means that silver iodide may be contained in an amount of 0.3 mol % or less, more preferably 0.1 mol or less. However, silver chlorobromide emulsions containing no silver iodide are most preferred in the present invention.

It is sufficient that at least one of the light-sensitive emulsion layers of the silver halide color photographic light-sensitive material processed according to the present invention consists essentially of a silver chlorobromide emulsion; Preferably, it consists of a silver emulsion.

In particular, it is preferable that the silver halide contained in the red-sensitive silver halide emulsion layer of the present invention is substantially silver chlorobromide. In the present invention, the silver bromide content is preferably 5 to 95 mol%, and from the viewpoint of the desired effect of the present invention, 10 to 85 mol%.
, especially preferably 20 to 60 mol %, particularly preferably 30 to 55 mol %.

The red-sensitive silver halide emulsion layer in the present invention may consist of two or more layers. In the present invention, the silver bromide content refers to the total silver bromide content of each layer in the total silver halide contained in the red-sensitive silver halide emulsion layers. When the silver bromide content exceeds 95 mol %, processing stability deteriorates, cyan fog occurs, and image quality deteriorates.

On the other hand, if the silver bromide content is less than 5 mol %, processing stability will be significantly degraded.

The composition of the silver halide contained in the blue-sensitive and green-sensitive silver halide emulsion layers may be silver bromide, silver chlorobromide, silver chloroiodobromide, or a mixture thereof, but is preferably is that the silver bromide content consists essentially of silver chlorobromide with a silver bromide content of 30 to 95 mol%. Furthermore, the blue-sensitive and green-sensitive silver halide emulsion layers in the present invention may consist of two or more layers.

The color developing agent used in the color developing solution of the present invention is a p-phelenediamine type color developing agent having at least one alkylsulfonamide alkyl group on the benzene ring and/or on the amino group, and specifically includes the following:

[Specific Example] H2'' The p-ferencyamine color developing agent of the present invention is generally preferably used at a concentration of 1.5 x 10-2 mol or more per 1M of color developer, particularly at a concentration of 1.5 x
It is preferable to use 10-2 to 15XI-0-2 mol.

The P-phenylenediamine derivative of the present invention can be used as a salt of an organic acid or an inorganic acid, such as hydrochloride, sulfur salt, phosphate, p-toluenesulfonate, sulfite, oxalate, Penzel disulfonate and the like can be used.

The color developing solution of the present invention is preferably used at a pH of 10.3 or higher, more preferably 10.50 or higher, particularly 10.75 or higher. The second limit is related to the fogging property of the photographic emulsion, but it is preferably used at a pl+ of 13 or less, more preferably at a pH of 10.8 to 11.5.
used within the range of

Examples of alkaline agents used to adjust the pH of the color developing solution include sodium hydroxide, potassium hydroxide, sodium metaborate, borax, potassium carbonate, sodium carbonate, potassium phosphate, potassium hydrogen carbonate, and the like.

soup'):, la (1shiVnYuI) tffu4 (King 1;
b-Mashibe = Ail, sheets 1% - 1% j].

General formula CI) General formula (II) General formula (II)
I) General formula [') General formula (V) General formula (Vl) General formula (VN) [In the above general formula, Q is a heterocycle containing one or more Ni molecules (
A represents an atomic group necessary to form a χ'' ll or n1-valent heterocyclic residue (including those in which at least one unsaturated ring of 5 to 6 shells is fused to it), B
represents an alkylene group having 1 to 6 carbon atoms, M represents a divalent metal atom, and X and X II are =S, =O or =NR
''', and R# represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, a heterocyclic residue (having as few as 5 to 6 unsaturated rings (both have one Represents a fused atom, ammonium group, amino group, nitrogen-containing hetero or alkyl group, R1 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, a heterocyclic residue ( R2, R'', R4, R5, R and R' each represent a hydrogen atom, a carbon number of 1 ~6 alkyl group, hydroxy group, carboxy group, ami7 group, acyl group having 1 to 3 carbon atoms, aryl group, or alkenyl group, provided that R4 and R5 are -
B-3Z may also be represented, and R and R', R'' and Rco, and R4 and R5 may each be cyclized with each other to form a heterocyclic residue (
(including those in which at least one unsaturated ring of 5 to 6 shells is fused thereto) may be formed.

R"tR' represents each, R9 is an alkyl group or 1, -(CHz)n, S
O=-, where R8 is -(CH2)IIs S O
, -, dan represents O or 1. ) G- is an anion,
ml (1 to 1 and nl to nsl±1 to 6 respectively)
An integer of 1, l, (represents an integer of 0 to 6. R8 is a hydrogen atom, an alkali I). However, Q' has the same meaning as Q above. D
] represents a simple bond, an alkylene group or monovinylene group having 1 to 8 monoprimes, and q represents an integer of 1 to 10. A plurality of D's may be the same or different, and the ring formed with the sulfur atom may be further fused with 10 unsaturated rings of 5 to 6 shells. X' is -COOM', -OH, -303M'
, -CONH2, -3O2NH2, -NH2, -3
H, -CN, -CO, R1', -5o2RIa1-OR
", -NR declaration 6R' F, S
Rl 8 , -5O3R'', -NHCOR heavy 6,
-NH8O□ R11! , -〇〇〇R'〆; or -8O2R, Y' represents a hydrogen atom, m and n each represent an integer from 1 to 10, RII, R12, Rl 4. R+5.
R17 and ty R18 represent a hydrogen atom, a lower alkyl group, an acyl group, or an R group HC+-X'R+2, and R" represents a lower alkyl group. R" is N R
``'R2' s OR'' 2-pronged S R22 ヲTable L, R20 and R'' represent a hydrogen atom or a lower alkyl group, and R'' represents an atomic group necessary to form a ring by connecting with RII. R20 or R" and R1' may be linked 17 to form a ring. M' represents a hydrogen atom or a cation. The compounds represented by the above general formulas (I) to (V) may be enolized. ] / (No change in content) General formula (x vm) [''In the general formula 2, Ar. is an aromatic linking group, B1 and B
2 each represents a lower alkylene group. R23, R2
4, R25 and R26 each represent a hydroxy-substituted lower alkyl group. G' is an anion, X and y each represent an integer of 0 or 1, and 2 represents an integer of 0.1 or 2. The bleaching agent of the present invention is represented by the general formula (T).

Although it is indicated by [■], typical examples include, but are not limited to, the following.

[Exemplary compounds]

(I-1) (1-2) (T-3)
(I-4) (I-5)
(I-6)C112COO[l
C112C112CI+2[;UIJII(I
-7) N-8) (r-9)
(1-10) (I-11
) (1-12)(I −
13) (T -14)(
I-17) (1-18)C
)I2C112COOI+ (T -21) (r -22
) (1-23) (T −
24) (1-25) (I
-, 26) (I -27)
(T-28) (1-33)
(T-34) (1-35)
(T-36) (I I7)
(13B) (IT-1) (
ff-2) SS (U-3> (TI-4)
(TI-5> (II-6
) (If-7) (IT
-8)(T[-9) (
n-10) (Tr-11)
(TI-12) (ff-13)
(II-14) (H-15)
(IT-16) (II-17)
(H-18) (TI-19
) (IT-20) (TI-21) (II-22> (TI-23) (IT-24) (n-25) (ff-26) (II-27) (n-28) 11□N- C5NI Cabinet ICS-1112 (Ir-29
) (Tr-30> (n-:Ill) (II-32) (TI-33) (TI-34) 1(2t4 C5N11(CI+2)2NIIC30
112 (I[-35) 112NC5N11 (CI+2) 48IICS NI+
2 (It-36) +12N-CSNII (C1l□)5NIIC3NI+
2 (TT-37) (II-38) (r[-39) (JT-40) (II-41) (IT-42) (IF-43) (TI-44) (T[-45) (IT -46) (■ -47) (II-48) (II-49) (TI-50) (II-51) (IT -52) (If-53) S (TI-54) (n-55) ( II-56) (ff-57) (II-58) (If -59) (II-60) (TI-61) (ff-63) (II-64) (IF-65) (I-66) ( ■ -67) Na Na (II-68) (II-69) (II-70) (II-71) (II -72) (■ -73) S (TI-74) (■ -75) C113NIIC112CII□NlIC5CH2C1
I□CIl□C00I+ (H-76) (II-77) (H-78) (IT-79) (If-80) (II-81) ([-82) (IT-83) (IT-84) (IT-85) (IT-86) (II-87) (IT-88) (II-89) (IT-90) (TI-91) (n-92) S (IT-93) (TI-94 ) NI-95) (II-96) f (■ -97) (H-98) (I[-99) (II-100) (II-101) (TI-102) (1'[-104) ( Tl -105) ([-107) ([[-108) ][ (IT-109) (IT-110) (II -111) ([-112
) (U -113) (TI -
114) δ (If -1,15) (II
-116) ([-1,17) (
TI-118) (IT 119)
(H120) (If -121)
(TI-122)S (H-123) (ff
-124)(r[-125)
(II-126>(11-127)
(n -128) (IT -129)
(TI-130) (I
I-131) (II
-132) (IT -133)
([-134) rll (II -135) (I
f -136) (ff -137)
(TI-138) (II-139)
(ff -140) (If -
141) (II-142
) (IT -143) (I[-144) Nl+ (I[-145) (II -146) ([-147) 8+1 (H-148) ([-149) (II -150) ([-151) ([-152) (IT-153) (II-154) (U-155) (TI -156) Mouth (If-157) (■-158) (Aim-1) 112N-CIl□CI+2-5ll (III -2) (III -3) (I[-4) (DI-5) +100c -CH2CH2畢5ll (III-6) (I[[-'7) (III-8) (III-9
)1la (II[-10) (III-11) (Iff-12) /-1-ON-Cl1□C112-5ll \-1-(III-13) rll.

(Iff -14) C112CIl□-511 (III -15) (rl[
-16) (I-17) (I
r[-18)(III-19)
(]'l[-20) (I[[-21)
(Iff-22) CH2C1125ll (III-23) (Ill
-24) (Ilf -25)
(III-26) (III-27) (l[-29) (m-30
) (III-31) (IT
[-32) (III-33) (I[r-34> (Iff -35) (If[-:36) (II[-37) (II/-1) CH3 (■-2> CIT yo (IV -3) (IV-4) (IV-5) CI!3 CI!3 (V-1) (V-2) (V-3
) (V-4) (V-5)
(V-6) (V-7)
(V-8) (V-9)
(V-10)■ (V-11) (V-1
2) (V -13) (V -1
4) (V -15) (V -1
6) (V-17) (V-18) (V -19) (V -20)
(V-21) (V-22) (
V-23) (V-24) (V
-'25) (V-26)
(V-27) (V-28)
(V-29) (V-30) (
V-31) (V-32) (V
-33) (V -34)(
V-35) (v-36)
(V-37) (V-38) (
V-39) (V-40) (V-41) (V-42) (V-43) (V-44) (
V-45) (V-46) (V
-47) (V-48) (V
-49) (V-50)(
V-51>(V-52>(
V-53) (V-54)C
I! 3 (V-55) (V-56)
(V-57) (V-58>
(V-59) (V-60)
(V-61) (V-62)(
V-63) (V-64)(
V-65) (V-66)(
V-67) (V-68)(
V -69) (V -70>(
V-71) (V-72) (V-
73) (V-74) (V-
75> (V -76)(
V-77) (V-78)(
V-79) (V-80)(
V-81) (V-82)
(V-83) (V-84
) (V-85> (V-86)
(V-87) (V-88>(
V-89) (V-90)(
V-91) (V-92) +121; 112N112
([1+2)3Nl12(V -93)
(V-94) (V-95)
(V-96) (V-97)
(V-98) (V-99)
(V-100) (V-101)
(V-102) (V-10
3) (V-104) (V-1
05) (V -106)(
V -107) (V -108) (y -109) (V -110) (V -111) (V -112) (V -113) (V -114) (V -115) (V -116) ( V -117) (V -118) (V -119) SH5ll (V -120) (V-121) (V -122) (V-123) (V -124
) (V-125) (V-126
) (V −127) (V −
128) (V -129) (
V-130) (V-131)
(V -132>(V -133)
(V-134) (V-135)
(V-136)03Na (V-137) (V-13
8) (V -139) (V
-140) (V -141)
(V-142) (V-143)
(V-144) (V-145)
(V-146) (V-147)
(V-148) (V-149)
(V-150) (V-151)
(V-152) (V-153)
(V-154) (V-155
) (V −156>qI+ (V −157) (V −158
) (V-159) (y 160
)(V-161) (V-1
62) (V-163) (V -
164) (V-165) (V
-166) (V-167> (
V-168) (V-169)
(V-170) (V-171)
(V-172) Sl! (V -173) K (V -174) (V -175
)(V-176) 1l (V-177) (V-17
8) (V-179) 5+1 (V-180) (V-18
1) (V -182) (V
-183)(V-184) H (VI-1) (V[-2)(
■-3) (W-4) (Vl
-5) (V[-6) (W-7)
(W-8) (T/T-9)
(W-10) (Vr-11) (W-1
2) (W-13) (■-14)
(W-15) (Vl-16) (V[-17
) (Vl-18) (VT-1
9) (Vr-20) (Vl-21)
(Vr-22) (VI-23) (V
l -24) (Vl-25) (Vr-26
) (Vl -27) (Vr
-28) (W-29) (■-30)
(Vr-31) (VI-32) (
Vr-33) (Vl-34) (W-35
) (VT-36) Below margin (■-3) +SCH, CIhNICIhCH2
CII□5O311hCI+.

(■-17) ll5CII2CII□NlI
C112CI+□011(■-18) HSC
1+2C'I□NCII, CI+2011C, l+.

(■-19) 1lsc112c112Hc1
1□C1l□)l(C1l:+)zCH.

(■-20) ll5C1[zc[l zNc
[IzcIl zOcII ZCI+ 20CIl s
COC■.

/ (no change in content) [■-2) N (CH□CH201() 3 [■-4] [■-5] (llOcH2cH2cH2) 2NCH2CH2N
(fl:112CH2CH2O11) 2 [■-6] The above compound is, for example, British Patent No. 1,138,842,
JP 52-20832, JP 53-28428, JP 53-95630, JP 53-104232, JP 53
-141832, 55-17123, 80-9
5540, U.S. Pat. No. 3,232.9313, U.S. Patent No. 3,
No. 722,020, No. 3,779,757, No. 3.8
It can be easily synthesized by the known technique described in No. 93,858 and the like.

The bleaching additive of the present invention only needs to be present when bleaching a silver image obtained by development, and is preferably added to a bleach-fixing bath, and added to a bath (pretreatment liquid) prior to the bleach-fixing bath. However, it is also preferable to introduce the silver halide color photosensitive material into the bleach-fixing bath. In this case, a method may be used in which the silver halide color photographic material is preliminarily contained in the silver halide color photographic light-sensitive material at the time of production, and then allowed to exist during processing in a bleach-fixing bath.

These bleaching additives of the present invention may be used alone or in combination.
More than one bleaching additive may be used in combination, and the amount of the bleaching additive added to the bleach-fixing solution is generally about 0.01% per solution.
Good results are obtained in the range of ~100g. In particular, treatment liquid 1
The amount per target is preferably 0.05 to 50 g', and more preferably 0.05 to 15 g per treatment liquid IJJ.

When adding the bleach additive of the present invention to a bleach-fixing bath,
Although it may be added and dissolved as is, it is common to add it by dissolving it in water, alkali, organic acid, etc. beforehand, and if necessary, dissolve it using an organic solution such as methanol, ethanol, acetone, etc. before adding it. You may.

In the following margin, the standing ogP according to the present invention is a value determined from the n-octatool/water-soluble partition coefficient P. The P value is determined by the following formula.

The logarithm of the P value obtained in this way is the logP value, and this value has been widely used as a measure of fat solubility.
Mical Review), Vol. 71, No. 6, 1971, pp. 555-813. Furthermore, although it can be determined by the calculation method described in Ecochemistry Vol. 6, pages 3 to 11, it is preferable to use actual measured values, and in the present invention, values measured using an n-octa tool are used. .

fLogPo, 4 or more solvents each have 5 to 2 carbon atoms.
0 aliphatic alcohol, aliphatic glycol ether, alicyclic alcohol, or aromatic alcohol.

As a specific example, benzyl alcohol DanogP 1.100
-Hydroxynebenzyl alcohol ogP 0473 cyclohexanol ogP 1.232
-Benzyloxyethanol 9. ogP O,4
1 Anisyl alcohol BunogP O,70
1-Pentanol Standing logP O, 4 or more Phenylethyl alcohol logP 1.38
P-tolylcarbinol ligP 1.31
3n-butanol BunogP O,4
Above phenol sentence ogP O,
4-LP-hydroxybenzyl alcohol uogP0
．． Benzylamine 4 or more ogP O
, 4 or more diethylene glycol monobutyl ether
Examples include gP O,41 and the like.

In addition, as a solvent with a standing ogP of less than 0.4, the number of carbon atoms is θ
-4 aliphatic alcohols, organic alcohols, etc., or compounds having 5 or more carbon atoms and having highly polar functional groups. Specific examples include the following solvents.

Acetic acid, ethanol, acetone, propionic acid, propatool, ethylene glycol, diethylene glycol, triethylene glycol, triethanolamine, jetanolamine.

Sulfites used in the color developer used in the present invention include sodium sulfite, potassium sulfite, sulfite,
Lithium sulfite, ammonium sulfite, preferably sodium sulfite and potassium sulfite.

The amount of these sulfites added is 2
10-3 mol or more, preferably 4 x 10
-3 to 100X 10-3 mol, particularly preferably 6X
10-3 to 80X 10-3 mol.

In the present invention, the color developing solution has an oxidation-reduction potential of
It is preferable that the voltage be made up only of compositions that are more base than 00 mV. That is, it is preferable that the color developing solution is made up only of a compound whose potential as a single substance is more base than -300 ffIV with respect to a silver-silver chloride electrode in a solution having a pH of 10.

Note that the measurement was performed by the method shown below.

10 g/l of the compound to be measured was dissolved in pure water, the pH was adjusted to 10 with potassium hydroxide and sulfuric acid, and while bubbling nitrogen, the potential of the platinum electrode was measured using a silver-silver chloride electrode as a reference electrode. The measurement was performed by measuring the change in potential over time, and the value at which the potential became constant over time was measured. The measurement took about 1 hour.

The compounds whose redox potential is more base than 1300 mV used in the present invention include halides (sodium chloride, sodium bromide, potassium bromide, potassium chloride, potassium iodide, sodium iodide, etc.) that are usually used in color developing solutions.
, organic solvents such as methanol, dimethylformamide and dimethyl sulfoxide, amine polycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, ■-
Organic phosphonic acids such as hydroxyethylidene-1,1-diphosphonic acid, aminopolyphosphonic acids such as aminotri(methylenephosphonic acid) or ethylenediaminetetramethylenephosphonic acid, oxycarboxylic acids such as citric acid or gluconic acid, 2-phosphonobutane-1 , phosphonocarboxylic acids such as 2,4-tricarboxylic acid, polyphosphoric acids such as tripolyphosphoric acid or hexametaphosphoric acid, and polyhydroxy compounds.

On the other hand, -300 mV which is preferably excluded from the present invention
Examples of compounds with higher potential include the following.

These include hydroxylamine, ascorbic acid, hydrazine, hydroxylated poron hydride, and stannous chloride. These may be used in the form of salts such as hydrochloride, sulfate, phosphate, P-)toluene sulfate. The presence of these compounds reduces the effects of the present invention.

The hydrophilic binder used to coat silver halide in color photographic light-sensitive materials is usually gelatin, but high-molecular polymers may also be used, and the film swelling rate T%
should be less than 20 seconds, and the film swelling rate 734 of the binder can be measured according to any technique known in the art, eg, A. Green and G. 1. P.

Lettensan J, Photo, Sci, V
ol, 20. It can be measured by using a swellometer (swelling film) of the type described in P2O5-210, and one station measures 90% of the maximum swollen film thickness reached when processed with color development at 30°C for 13 minutes and 30 seconds. The saturated film thickness is defined as the time required to reach the film thickness at this point (see Figure 1).

The binder of the photographic constituent layer used in the silver halide color photographic light-sensitive material of the present invention has a swelling rate '12 of 20 seconds or less, and from the viewpoint of the LI effect of the present invention, the smaller the better, but the lower limit is that if it is too small, it will become hard. The time is preferably 2 seconds or more because failures such as scratches are likely to occur without forming a film. Particularly preferably, the time is 15 seconds or less, most preferably 10 seconds or less. If it is longer than 20 seconds, the storage stability of the dye image tends to be low, and a sufficiently rapid development time cannot be obtained, making it impossible to obtain sufficient dye formation in a short period of time. Membrane swelling rate 73
4 can be adjusted depending on the amount of hardener used.

In the present invention, the average grain size of the silver halide used in the red-sensitive silver halide emulsion is preferably 0.2 to 0.8 μm, more preferably 0.3 to 0.6 μm.

In the present invention, the average grain size r means, in the case of cubic silver halide grains, the length of its side, or, in the case of grains having a shape other than a cube, the length of one side when converted to a cube having the same volume. In this sense, when the individual particle size is ri, r is defined by the following formula.

Σn1-ri Σni In the present invention, if the average grain size of silver halide in the red-sensitive layer is less than 0.2Ji, m, the sensitivity is insufficient;
If it is higher than 1 Lar, the developing speed will be insufficient, and from the viewpoint of fully exhibiting the desired effect of the present invention, the range is 0.2 to 1 Lar.
A range of 0.81 Lm is preferably used, especially when the average grain size of silver halide pores in the red-sensitive layer is 0.3 to 0-811 Lm.
．． Particularly favorable effects are obtained when the value is within the range of m.

Although the silver halide pores used in the light-sensitive material of the present invention may be a polydisperse emulsion in which the average grain size is distributed over a wide range, a monodisperse emulsion is preferred.

The above-mentioned monodisperse emulsion is one in which most of the silver halide grains appear to have the same shape and uniform grain size when the emulsion is observed using an electron microscope, and the coefficient of variation of the grain size distribution is 15% or less. means.

The particle size here has the same meaning as the particle size described above regarding the average particle size.

The average grain size of the silver halide contained in the green-sensitive silver halide emulsion layer and the blue-sensitive silver halide emulsion layer is not particularly limited, but is 0.1 to 2 Bm, more preferably 0.2 to 1k.
m, particularly preferably from 0.25 to 0.8 m.

In the silver halide color photographic light-sensitive material of the present invention, the amount of silver (silver deposition amount) in the silver halide emulsion layer is 0.3 to 1 g/rr in the entire photosensitive silver halide emulsion layer? It is preferable that That is, in order to obtain excellent image quality, the amount of silver must be
/m'' or less, and on the other hand, in order to obtain a high maximum density and high sensitivity, it is preferably 0.3 g/d or more. In the present invention, it is particularly preferable that the silver amount is 0.
．． 4 to 0-8 g/m'.

When a triazylstilbene-based optical brightener is used in the color developing solution of the present invention, the effects of the present invention are better exhibited, and another effect is also achieved in that the tar properties of the solution during storage are also improved. Therefore, it is more preferably used in the present invention.

The triazylstilbene fluorescent brightener used in the present invention is preferably one represented by the following general formula [IX].

General formula [ ] , p-sulfophenoxy, etc.), alkyl groups (e.g. methyl, ethyl, etc.), aryl groups (e.g. phenyl 1, methoxyphenyl, etc.), amide 7 groups, alkylamino 7 groups (e.g. methylamino, ethylamino, propylamine, dimethylamino) , cyclohexylamino, β-hydroxyethylamino, di(β-hydroxyethyl)amine, β-sulfoethylamino, N-(β-sulfoethyl)-N'-methylamino, N-(β-hydroxyethyl-N'- methylamino, etc.), arylamino groups (e.g. acolino, 0-1
m-1p-sulfoanilino, 0-1m-1p-chloroanilino, o-, m-1p-)luidino, 0-1m-1P
-carboxyanilino, 0-1m-1p-hydroxyanilino, sulfonaphthylamino, 0-1m-1p-aminoanilino, 0-1m-1p-anilino, etc.). M
represents a hydrogen atom, sodium, potassium, ammonium or lithium.

Specifically, the following compounds may be mentioned, but the invention is not limited thereto.

The following margins [Exemplary compounds] (A-1) (A-2) (A-3) (A-4) (A=S) (A-6) (A-7) (A-s) S Comb V ( )
Z The triazylstilbene-based brightener of the present invention can be synthesized, for example, by the usual method described in "Fluorescent Brightener" by the Japan Chemical Industry Association (published in August 1976), page 8.

These triazylstilbene type brighteners are preferably used in an amount of 0.2 to 6 g, particularly preferably 0.4 to 3 g, per color developer of the present invention.

In addition, the bromide ion in the color developing solution of the present invention is 0.7X.
When containing 10-2 to 3.5X 10-2 mol/ml, the objective effects of the present invention described above can be better achieved, and another effect that fogging is less likely to occur during high-activity development can also be achieved. It is more preferably used in the invention.

As the bromide ion, potassium bromide, sodium bromide, lithium bromide, etc. are usually used as a supply source.

In the processing method of the photographic light-sensitive material of the present invention, it is possible to use the color developing solution according to the present invention. In addition, various other methods including bath processing, such as a spray method in which the processing liquid is atomized, a web method in which contact is made with a carrier impregnated with the processing liquid, or a developing method using a viscous processing liquid, etc. Processing schemes can be used.

In addition to the above, various processing methods can be applied to the photographic material of the present invention. For example, a typical method is a method in which, after color development, bleach-fixing treatment is performed, and if necessary, further water washing and/or stabilization treatment is performed.

As the bleaching agent used in the bleach-fix solution of the present invention, one in which iron ions are coordinated with an aminopolycarboxylic acid or an organic acid such as oxalic acid or citric acid is used. Representative examples of the above aminopolycarboxylic acids include the following.

Ethylenediaminetetraacetic aciddiethylenetriaminepentaacetic acidpropylene diaminetetraacetic acidnitrilotriacetic acidiminodiacetic acid glycol ether diaminetetraacetic acidethylenediaminetetrabrobionic acidethylenediaminetetraacetic acid disodium saltdiethylenetriaminepentaacetic acidpentasodium saltnitrilotriacetic acid sodium saltThe bleach-fix solution of the present invention comprises the above-mentioned The bleach-fix solution contains a silver halide fixer in addition to a bleaching agent, and the bleach-fix solution may further contain a halogen compound such as potassium bromide. As with the bleach solution mentioned above, various other additives such as pH buffers, optical brighteners, antifoaming agents, surfactants, preservatives, chelating agents, stabilizers, organic solvents, etc. are added. It may be added or contained.

The silver halide fixing agent used in the bleach-fix solution of the present invention is a thiosulfate, and examples thereof include sodium thiosulfate and ammonium thiosulfate.

In addition, some compounds that react with silver halides to form water-soluble silver salts, such as potassium thiocyanate, sodium thiocyanate, thiourea, and thioether, which are used in normal fixing processing, should not be used in combination. do not have.

The pH value of the bleach-fix solution of the present invention is preferably 5 to 9.

Color development of the silver halide color photographic light-sensitive material of the present invention can be carried out at 30° C. or higher and within 120 seconds. Bleach-fixing may also be carried out at 25° C. or higher, preferably at 30° C. or higher and within 80 seconds. Furthermore, the processing temperature of various processing steps such as washing with water and stabilization, which are carried out as necessary, is preferably carried out at 30° C. or higher from the viewpoint of rapid processing.

The silver halide color photographic light-sensitive material of the present invention is disclosed in Japanese Unexamined Patent Publication No. 58
-14834, 58-105145, 58-1
No. 34634 and No. 58-18631 and patent application 1973
8-2709 and No. 59-89288, etc., when the water washing alternative stabilization treatment is performed, the sentence ogP is 0.
It is more preferably used in the present invention because it has the additional effect of improving poor image storage properties (particularly staining in unexposed areas) at high temperatures and high humidity caused by compounds with a size larger than 4.

In the present invention, "treatment with a stabilizing solution as an alternative to water washing" refers to a stabilizing treatment that is performed immediately after treatment with a processing solution that has a fixing ability and does not substantially require a washing treatment. The processing liquid used in the treatment is called a washing alternative stabilizing solution, and the treatment tank is a washing alternative stabilizing bath (tank) or a stabilizing bath (
It is called a tank).

In the present invention, the number of washing alternative stabilizing tanks may be one, but desirably 2 to 3, and preferably 9 or less at most. That is, if the replenishment amount is the same, the more tanks there are, the lower the contaminant concentration in the final washing alternative stabilizing bath will be.

As described above, the treatment with the water-washing substitute stabilizing liquid of the present invention is carried out after the treatment with the treatment liquid having fixing ability.

In the present invention, compounds preferably used in the water washing alternative stabilizer have a chelate stability constant of 8 for iron ions.
The above-mentioned chelating agents are mentioned, and these are preferably used to achieve the object of the present invention.

Here, the chelate stability constants are L, G, 5illen
・A.E. Marte11, “5tability”
Con5tants of Metal-ion Co
plexes'', The Chemical
5ociety, London (1984). S,C
Haberek * Written by A. E. Martell,”
Organic Sequestering Agent
s'', a constant commonly known by Wiley (1959) and others.

Examples of chelating agents having a chelate stability constant of 8 or more for iron ions that are preferably used in the water washing alternative stabilizer of the present invention include organic carboxylic acid chelating agents, organic phosphoric acid chelating agents, inorganic phosphoric acid chelating agents, polyhydroxy compounds, etc. can be mentioned. Note that the above-mentioned iron ion means ferric ion (Fe3.).

Specific examples of compounds of chelating agents having a chelate stability constant of 8 or more with ferric ions include, but are not limited to, the following compounds. Namely, ethylenediaminediorthohydroxyphenylacetic acid, diaminopropanetetraacetic acid, nitrilotriacetic acid, hydroxyethylenediaminetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid, ethylenediaminenibropionic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, diamino Brohanoltetraacetic acid, transcyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediaminetetrakismethylenephosphonic acid, nitrilotrimethylenephosphonic acid, l-hydroxyethylidene-1,1-diphosphonic acid, 1,1-diphosphonethane-2 -carboxylic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxy-1-phosphonopropane-1,2,3-tricarboxylic acid, catechol-3,5-diphosphonic acid, sodium birophosphate, tetra Examples include sodium polyphosphate and sodium hexametaphosphate, particularly preferably diethylenetriaminepentaacetic acid, nitrilotriacetic acid, nitrilotrimethylenephosphonic acid, 1-hydroxyethylidene-1,
1-diphosphonic acid and the like, among which 1-hydroxyethylidene-1,1-diphosphonic acid is most preferably used.

The amount of the above chelating agent used is 0 per water washing alternative stabilizer IJI.
．． 01-50g is preferable, more preferably 0.05-50g
It is in the range of 20g.

Furthermore, as a compound to be added to the water washing alternative stabilizing liquid of the present invention,
Ammonium compounds are particularly preferred.

These are supplied by ammonium salts of various inorganic compounds, including ammonium hydroxide, ammonium bromide, ammonium carbonate, ammonium chloride, ammonium hypophosphite, ammonium phosphate, ammonium phosphite, and fluoride. Ammonium, acidic ammonium fluoride, ammonium fluoroborate, ammonium arsenate, ammonium bicarbonate, ammonium hydrogen fluoride, ammonium sulfur butyrohydrogen, ammonium sulfate, ammonium iodide, ammonium nitrate, ammonium pentaborate, ammonium acetate, ammonium adipate, laurine Ammonium tricarboxylate, ammonium benzoate, ammonium carbamate, ammonium citrate, ammonium diethyldithiocarbamate, ammonium formate, ammonium hydrogen malate, ammonium hydrogen oxalate, ammonium phthalate, ammonium hydrogen tartrate, ammonium thiosulfate, ammonium sulfite, ethylenediaminetetra Ammonium acetate, ferric ammonium ethylenediaminetetraacetate, ammonium lactate, ammonium malate, ammonium maleate, ammonium oxalate, ammonium phthalate, ammonium picrate, ammonium pyrrolidine dithiocarbamate, ammonium salicylate, ammonium succinate, ammonium sulfanilate, These include ammonium tartrate, ammonium thioglycolate, 2,4.13-)linitrophenol ammonium, and the like. Among these ammonium compounds, ammonium thiosulfate is particularly preferred in achieving the effects of the present invention.

The amount of ammonium compound added is 1. OX is preferably 10-5 or higher, more preferably stabilizer 19. Hit 0.0o
f to 5.0 mol, more preferably 0.00 mol
It is in the range of 2 to 1.0 mol.

Further, it is desirable that the washing substitute stabilizing solution in the present invention contains sulfite within a range that does not contradict the purpose of the present invention, that is, within a range that does not cause the generation of bacteria.

In the present invention, the sulfite to be contained in the water washing alternative stabilizing solution may be any organic or inorganic substance as long as it releases sulfite ions, but is preferably an inorganic salt.
Preferred specific compounds include sodium sulfite, potassium sulfite, ammonium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, sodium metabisulfite, potassium ivy bisulfite, ammonium metabisulfite, and hydrosulfide, cartaraldehyde bisulfite. Examples include sodium bisulfite, sodium chloride aldehyde bisbisulfite, and the like.

The above sulfite is contained in the water washing alternative stabilizing solution at least 1, OX
It is preferable to add an amount of 10-5 mol/liter, more preferably 5 x 10-5 mol/liter~
1. The amount of OX to be added is 10-1 mol/U. Although it may be added directly to the washing substitute stabilizing solution, it is preferable to add it to the washing substitute stabilizing replenishing solution.

The water washing substitute stabilizing liquid used in the present invention is as follows.

It is desirable to contain an anti-pyre agent, which can further improve sulfurization prevention and image preservability.

Preferred anti-spill agents to be added to the stabilizer of the present invention include sorbic acid, benzoic acid compounds, phenol compounds, thiazole compounds, pyridine compounds, guanidine compounds,
Carbamate compounds, triazole compounds, morpholine compounds, quaternary phosphonium compounds, ammonium compounds, urea compounds, isoxazole compounds,
propatoolamine compounds, sulfamide compounds,
These are pyronone compounds and amino compounds.

The benzoic acid compounds include salicylic acid, hydroxybenzoic acid, and ester compounds of hydroxybenzoic acid such as methyl ester, ethyl ester, propyl ester, butyl ester, etc., but preferably n-butyl ester and isobutyl ester of hydroxybenzoic acid. ester, propyl ester, and salicylic acid, and more preferably a mixture of the three hydroxybenzoic acid esters.

The phenolic compound is a compound that may have a rhodane atom, a nitro group, a hydroxyl group, a carboxylic acid group, an amino group, an alkyl group (especially an alkyl group whose alkyl group is 01 to B), or a phenyl group as a substituent. Preferred are ortho-phenylphenol, ortho-cyclohexylphenol, nitrophenol, chlorophenol, cresol, quaiacol, aminephenol, phenol and the like.

The thiazole compound is a compound having a nitrogen atom and a sulfur atom in a five-membered ring, and preferably 1,2-benzinthiazolin 3-one, 2-methyl-4-isothiazolin 3-one, 2-octyl-4- Inthiazolin 3-one, 5-chloro-2-methyl-4-inthiacyly 3-one, and 2-(4-thiazolyl)benzimidazole.

Specifically, the pyridine compounds include 2,8-dimethylpyridine, 2,4.8-)dimethylpyridine, and sodium pyridine.
Examples include 2-pyridinethiol-1-oxide, but radium-2-pyridinethiol-1-oxide is preferred.

Specifically, guanidine compounds include cyclohexidine,
Examples include polyhexamethylene biguanidine hydrochloride, dodecylguanidine hydrochloride, etc., and dodecylguanidine and its salts are preferred.

Specific examples of carbamate compounds include methyl 1-(butylcarbamoyl)-2-benzimidazole carbamate and methylimidazole carbamate.

Specific examples of morpholine compounds include 4-(3-nitrobutyl)morpholine and 4-(3-nitrobutyl)morpholine.

Quaternary phosphonium compounds include tetraalkylphosphonium salts, tetraalkoxyphosphonium salts, etc.
Preferred are tetraalkylphosphonium salts, and more specific preferred compounds are tri-n-butyl-tetradecylphosphonium chloride and triphenyl-nitrophenylphosphonium chloride.

Specific examples of quaternary ammonium compounds include benzalkonium salts, benzethonium salts, tetraalkylammonium salts, alkylpyridium salts, and more specifically dodecyldimethylbenzylammonium chloride, dodecyldimethylammonium chloride, and laurylpyridinium. There are chloride etc.

Specifically, urea-based compounds include N-(3,4-dichlorophenyl)-N'-(4-chlorophenyl)urea, N-(
Examples include 3-)lifluoromethyl)-N'-(4-chlorophenyl)urea.

Specific examples of isoxazole compounds include 3-hydroxy-5-methyl-isoxazole.

Propatur amino compounds include n-prop/-ols and isopropatol, specifically DL-2-benzylamino-1-propatol, 3-diethylamine-1-propatol, 2-dimethyl Amino-2-methyl-1-propatol, 3-amino-1-propatol,
Idopropaturamine, diisopropaturamine,
N,N-dimethyl-isopropanolamine and the like.

Specifically, sulfamide compounds include 0-nitrobenzenesulfamide, p-aminobenzenesulfamide, fluorinated sulfamide, 4-chloro-3,5-dinitrobenzenesulfamide, and α-amino-p-toluenesulfamide. famid, sulfanilamide, acetosulfaguanidine, sulfathiazole, sulfadiazine, sulfamethacine, sulfamethacine, sulfaine oxazole, homosulfamine, sulfamidine, sulfaguanidine, sulfamethizole, sulfapyrazine, phthalinsulfathiazole, succinylsulfate Fatiazole etc.

Specific examples of pyronone compounds include dehydroacetic acid and the like.

A specific example of the amino acid compound is N-lauryl-β-alanine.

Specific examples of triazole compounds include 2-aminotriazole, benzotriazole, and 5-methyl-benzotriazole.

Among the above-mentioned anti-spill agents, compounds preferably used in the present invention are thiazole compounds, sulfamide compounds, and pyronone compounds.

The amount of anti-piping agent added to the stabilizer is 1! 0 per L
It is preferable to use it in the range of −001 to 30 g,
More preferably, it is used in a range of 0.003 to 5 g.

The pH of the stabilizer used in the present invention is not particularly limited, but is preferably in the range of pH 0.5 to 12.0, more preferably in the range of pH 5.0 to 9.0, particularly preferably pHEl, It ranges from 0 to 8.0.

The amount of replenishment of the stabilizing solution of the present invention is 3.0 ml per rn' of photosensitive material.
000mJL or less is preferable, more preferably 500m
41 or less, particularly preferably 50 mJL to 500 m
This is within the JL range.

The stabilizing solution in the present invention preferably contains a metal salt in combination with a chelating agent.

Such metal salts include Ba, Ga, Ce, Go.
, In.

La, Mn, old, Bi, Pb, Sn, Zn,
It is a metal salt of Ti, Zr, Mg, An, or Sr, and can be supplied as an inorganic salt such as a halide, hydroxide, sulfate, carbonate, phosphate, or acetate, or as a water-soluble chelating agent. The usage amount is IX 10 per liter of stabilizer.
-4 to LX 10-1 mol, preferably 4
The range is from X 10-4 to 2X 10-2 mol.

The processing method of the present invention is a color development-bleach-fixing-stabilization process, and the total processing time is preferably within 6 minutes, more preferably within 5 minutes, and particularly preferably within 2 minutes. The range is 3 minutes and 30 seconds.

Further, in the present invention, other compounds that can be added to the water washing alternative stabilizer include organic acid salts (citric acid, acetic acid, succinic acid, oxalic acid, benzoic acid, etc.), TIH buffers (phosphoric acid,
borates, hydrochloric acid, sulfuric acid, etc.) or surfactants, but the amount of these compounds added is necessary to maintain the pH of the water washing alternative stabilizing solution according to the present invention and to maintain the stability of color photographic images during storage. Any compound may be used in any combination as long as it does not adversely affect the generation of precipitates.

The treatment temperature during stabilization treatment is 50℃ or less, especially 15℃.
℃~50℃ is preferable, more preferably 30℃~45℃
A range of is good. In addition, from the viewpoint of rapid processing, the shorter the treatment time, the better, but it is usually 20 seconds to 10 minutes, most preferably 1 minute to 5 minutes, and in the case of multiple tank stabilization treatment, the first stage tank should be used in a shorter time. It is preferable that the treatment time in the subsequent tank is long.

In particular, it is desirable to perform the treatment sequentially with a treatment time 20% to 50% longer than in the previous tank. After the stabilization treatment according to the present invention, no water washing treatment is required at all, but rinsing with a small amount of water in a very short time, surface cleaning, etc. can be optionally performed as necessary.

When the method for supplying the washing substitute stabilizing solution in the stabilization treatment step according to the present invention is a multi-tank countercurrent method, it is preferable to supply it to the rear bath and overflow from the front bath. Of course, it can also be treated in a single tank. In addition, the above compounds can be added as a concentrated liquid to the stabilization tank, or the above compounds and other additives may be added to the washing alternative stabilizing solution supplied to the stabilizing tank, and this can be added as a washing alternative stabilizing solution. There are various methods such as using it as a supply liquid for a liquid, and any method of addition may be used.

The photographic constituent layer of the silver halide color photographic light-sensitive material of the present invention may contain a water-soluble dye or a dye (AI dye) that can be decolorized with a color developing solution. Examples of the AI dye include oxonol dye, hemioxonol dye, Dyes, merocyanine dyes and azo dyes are included. Among them, oxonol dyes, hemioxonol dyes, merocyanine dyes, and the like are useful. Examples of AI dyes that can be used include British Patent No. 58
4, [No. 109, No. 1,277.429, Japanese Unexamined Patent Application Publication No. 1973
-85130, 49-99620, 49-11
No. 4420, No. 49-129537, No. 52-108
No. 115, No. 59-25845, No. 59-11164
No. 0, No. 59-111641, U.S. Patent No. 2,274,
No. 782, No. 2,533,472, No. 2,956,8
No. 79, No. 3,125,448, No. 3,148,18
No. 7, No. 3,177.078, No. 3,247,127
No. 3,260. fio No. 1, 3.540,887
No. 3,575,704, No. 3,653,905
No. 3,718,472, No. 4,071,312, and No. 4,070.352.

These AI dyes are generally used at a concentration of 2 per mole silver in the emulsion layer.
It is preferable to use 1 x 10-3 to 5 x 10-'' moles, more preferably 1 x 10-2 to 1 x 1
0-'' mole is used.

The crystals of the silver halide grains may be normal crystals, twin crystals, or other crystals, and any ratio of [1,'0.01 planes to [1,1,11 planes] can be used. Further, the crystal structure of these silver halide grains may be uniform from the inside to the outside, or may have a layered structure (core-shell type) in which the inside and outside are different. In addition, these silver halides are of the type that mainly forms latent images on the surface.
It may also be of a type formed inside the particles. Furthermore, tabular silver halide grains (see JP-A-58-113934 and Japanese Patent Application No. 59-170070) can also be used.

Silver halide grains particularly preferably used in the present invention are:
As mentioned above, there is a material that is substantially monodisperse, and this may be obtained by any preparation method such as an acid method, a neutral method, or an ammonia method.

Alternatively, for example, seed particles may be prepared using an acid method, and then grown using an ammonia method, which has a high growth rate, to grow to a predetermined size. When growing silver halide grains, the pH, pAg, etc. in the reaction vessel are controlled, and the amount of silver ions commensurate with the growth rate of silver halide grains is controlled, for example, as described in JP-A-54-48521. It is preferable to implant and mix the and halide ions sequentially and simultaneously.

Preferably, the silver halide grains according to the present invention are prepared as described above. A composition containing the silver halide grains is referred to as a silver halide emulsion in the specification.

These silver halide emulsions contain: active gelatin; sulfur sensitizers such as allylthiocarbamide, thiourea, cystine; selenium sensitizers; Urea, polyamines, etc.; noble metal sensitizers such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-aurothio 3-
Sensitizers such as methylbenzothiazolium chloride or water-soluble salts such as ruthenium, palladium, platinum, rhodium, iridium, etc., specifically ammonium chlorovaladate, potassium chloroaurate and 1-lium chlorovaladate. (These kinds of substances act as sensitizers or fog suppressants depending on the amount.) Either alone or in combination as appropriate (for example, a combination of gold sensitizer and sulfur sensitizer, gold sensitizer It may also be chemically sensitized (e.g., in combination with a selenium sensitizer).

The silver halide emulsion according to the present invention is chemically ripened by adding a sulfur-containing compound, and before, during, or after this chemical ripening, a nitrogen-containing emulsion having at least one hydroxytetrazaindene and mercapto group is produced. It may also contain at least one type of terocyclic compound.

The silver halide used in the present invention contains a sensitizing dye other than the present invention in an amount of 5 x 10 -8 to 3
Optical sensitization may be achieved by adding 0 to 3 moles. Various sensitizing dyes other than those of the present invention can be used, and each sensitizing dye can be used alone or in combination of two or more.

The red-sensitive silver halide emulsion layer, the blue-sensitive silver halide emulsion layer and the green-sensitive silver halide emulsion layer according to the present invention each contain a coupler, that is, a compound capable of reacting with an oxidized form of a color developing agent to form a dye. can be contained.

Yellow couplers that can be used in the present invention include open-chain ketomethylene compounds, active point -0-aryl substituted couplers, so-called 2-equivalent type couplers, and active point -0-acyl substituted couplers.

Active point hydantoin compound substituted couplers, active point urazole compound substituted couplers, active point substituted couplers with succinimide compounds, active point fluorine substituted couplers, active point chlorine or bromine substituted couplers, active point -〇-sulfonyl substituted couplers, etc. are effective yellow. It can be used as a coupler. Specific examples of yellow couplers that can be used include U.S. Pat. Nos. 2,875,057 and 3,265
, No. 506, No. 3.408, 194, No. 3,551
, No. 155, No. 3,582,322, No. 3,725
, No. 072, Ibid., No. 891,445, West German Patent 1.
547,868, West German Application No. 2,219,917, West German Application No. 2,261,361, West German Application No. 2,414,006,
British Patent No. 1,425.020, Special Publication No. 1978-1078
No. 3, JP-A-47-26133, JP-A No. 4B-73147
No. 51-102636, No. 5.0-6341,
No. 50-123342, No. 50-130442, No. 51-21827, No. 50-87650, No. 52-
No. 82424, No. 52-115219, No. 58-95
Examples include those described in No. 346 and the like.

Examples of magenta couplers that can be used in the present invention include pyrazolone-based, pyrazolotriazole-based, pyrazolinobenzimidazole-based, and indasilone-based compounds. These magenta couplers may be not only 4-equivalent type couplers but also 2-equivalent type couplers like the yellow couplers. Specific examples of magenta couplers that can be used in combination include U.S. Pat. same:
l, No. 419,391, No. 3,519.429, No. 419,391, No. 3,519.429, No.
3,558. : No. 119, No. 3,582,322, No. 3,615,506, No. 3,834,908,
No. 3,891,445, West German Patent No. 1,810,46
No. 4, West German Patent Application (OLS) No. 2.408,665,
No. 2,417,945, No. 2,418,959, No. 2,424,467, Japanese Patent Publication No. 40-6031, Japanese Patent Publication No. 20826-1982, No. 52-58922, No. 49
-129538, 49-74027, 50-1
No. 59336, No. 52-42121, No. 49-740
Examples include those described in No. 28, No. 50-60233, No. 51-26541, No. 53-55122, and No. 55-110943.

Further, cyan couplers that can be used in the present invention include, for example, phenol couplers, naphthol couplers, and the like. And these cyan couplers are not only 4-equivalent couplers like yellow couplers, but also 2-equivalent couplers.
It may also be an equivalent type coupler. Specific examples of cyan couplers that can be used in combination include U.S. Patent No. 2,369,929;
No. 2,434,272, No. 2,474,293, No. 2,521,908, No. 2,895.826, No. 3
, No. 034,892, No. 3,311,476, No. 3.
458,31.5, 3,476.563, 3
, No. 583,971, No. 3,591,383, No. 3,
No. 767.411, No. 3,772,002, No. 3,9
No. 33,494, No. 4,004,929, West German Patent Application (OLS) No. 2,414,830, No. 2,4
No. 54,329, JP-A-48-59838, JP-A No. 51-
No. 26034, No. 4B-5055, No. 51-1468
Examples include those described in Japanese Patent Publication No. 27, No. 52-69624, No. 52-90932, No. 5B-95346, and Japanese Patent Publication No. 49-11572.

Couplers such as non-diffusible DIR compounds, colored magenta or cyan couplers, polymer couplers, and diffusible DIR compounds may be used in combination in the silver halide emulsion layer of the present invention and other photographic constituent layers. Non-diffusible DIR compounds, colored magenta or cyan couplers are described in Japanese Patent Application No. 193611 of the present applicant, and polymer couplers are described in Japanese Patent Application No. 59-1 of the present applicant.
72151 can be referred to.

The amount of the above-mentioned coupler that can be used in the present invention is not limited, but is preferably from 1 x 10-3 to 5 mol, more preferably from 1 x 10-2 to 5 x 10 per mol of silver.
−'Mole.

In order to incorporate the above-mentioned couplers into the silver halide emulsion according to the present invention, if the couplers are alkali-soluble, they may be added as an alkaline solution; if they are oil-soluble, they may be added as an alkaline solution; No. 2,322,02
No. 7, No. 2,801,170, No. 2,801,1
No. 71, No. 2,272,191 and No. 2.30
It is preferable to dissolve the coupler in a high boiling point solvent, optionally in combination with a low clearing point solvent, according to the method described in each specification of No. 4,940, disperse it in the form of fine particles, and add it to the silver halide emulsion. At this time, if necessary, other hydroquinone derivatives, ultraviolet absorbers, anti-fading agents, etc. may be used in combination.

It is also possible to use a mixture of two or more couplers.

In addition, the above couplers and the like may be dispersed using a latex dispersion method. The latex dispersion method and its effects are described in JP-A Nos. 49-74538, 51-59943, and 5
4-32552 and Research Disclosure, August 1976, No. 14850, pages 77-79.

The silver halide color photographic light-sensitive material of the present invention may contain various other photographic additives, such as antifoggants, stabilizers, ultraviolet absorbers, etc. described in Research Disclosure No. 17643, A color stain inhibitor, a fluorescent whitening agent, a color image fading inhibitor, an antistatic agent, a hardening agent, a surfactant, a plasticizer, a wetting agent, etc. can be used.

In the silver halide color photographic light-sensitive material of the present invention, the woody colloids used to prepare the emulsion include gelatin, derivative gelatin, graft polymers of gelatin and other polymers, proteins such as albumin and casein, Any of cellulose derivatives such as hydroxyethyl cellulose derivatives and carboxymethyl cellulose, starch derivatives, single or copolymer synthetic hydrophilic polymers such as polyvinyl alcohol, polyvinylimidazole, and polyacrylamide are included.

Examples of the support for the silver halide color photographic light-sensitive material of the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, a transparent support provided with a reflective layer or a reflective material, such as a glass plate, and cellulose acetate. , polyester films such as cellulose nitrate or polyethylene terephthalate, polyamide films, polycarbonate films, polystyrene films, etc., and other usual transparent supports may be used.

These supports are appropriately selected depending on the intended use of the photosensitive material.

Various coating methods such as dipping coating, air doctor coating, curtain coating, and hopper coating can be used to coat the silver halide emulsion layer and other photographic constituent layers used in the present invention. Also, U.S. Patent No. 2,751
, No. 791 and No. 2,941,898 can also be used to simultaneously coat two or more layers.

' In the present invention, the coating position of each emulsion layer can be determined arbitrarily. For example, in the case of a full-color photosensitive material for photographic paper, it is preferable to sequentially arrange a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer from the support side. Each of these photosensitive silver halide emulsion layers may consist of two or more layers. The effects of the present invention are most effective when all of these photosensitive emulsion layers are substantially composed of silver chlorobromide emulsion.

In the photosensitive material of the present invention, it is optional to provide an intermediate layer with an appropriate thickness depending on the purpose, and a filter layer,
Various layers such as an anti-curl layer, a protective layer, and an antihalation layer can be used in appropriate combinations as constituent layers.

Hydrophilic colloids that can be used in the emulsion layers as described above can be used as binders in these constituent layers, and various types of colloids that can be contained in the emulsion layers as described above can be used in these layers. Photographic additives may be included.

[Effects of the Invention] According to the present invention, rapid development processing is possible, and even if the developing solution generated is exhausted due to the processing of many photographic materials, it is possible to prevent contamination of unexposed areas.

[Examples] Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

Example 1 On a paper support laminated with polyethylene, the following layers were sequentially coated from the support side to prepare a silver halide color photographic light-sensitive material sample.

Layer 1: 1.1g/gelatin, 0.30g/r
n' (in terms of silver, the same applies hereinafter) blue-sensitive silver chlorobromide gelatin emulsion (containing 90 mol% silver bromide, average grain size 0.611, I
! 1), 0.80 g/rn' yellow coupler (Y-1) dissolved in 0.45 g/g dioctyl phthalate
) containing a blue-sensitive silver halide emulsion layer.

Layer 2---0.68g/rrf gelatin, 10rn
g/rr? Anti-irradiation dye (AI-1)
, 5 mg/rn' of (AI-2).

F#3---1.26g/rn' gelatin, 0.
29g/rr? green-sensitive silver chlorobromide gelatin emulsion (containing 80 mol% silver bromide, average grain size 0.5 lm), 0
．． 0 dissolved in 30 g/m' of dioctyl phthalate,
Green-sensitive silver halide emulsion layer containing 60 g/rn' of magenta coupler (M-1).

Layer 4...IAg/m? middle layer consisting of gelatin.

Layer 5... 1.35g/m' gelatin, 0.26
g/rr? red-sensitive silver chlorobromide gelatin emulsion (80 mol%
Silver bromide content, average particle size is 0.4 JLm), 0.2
0,4 dissolved in 0 g/rn' dioctyl phthalate
Red-sensitive silver halide emulsion layer containing 4 g/rn' of cyan coupler (c-B).

Layer 6...0.40g/rr? A protective layer containing gelatin.

The silver halide used in each of the blue-sensitive silver halide emulsion layer, the green-sensitive silver halide emulsion layer, and the red-sensitive silver halide emulsion layer was color-sensitized with a general sensitizing dye.

(AI-1) (AI-2) (y-i) ρI (M-1) n/- (C-1) t In addition, as a hardening agent, 2,4-dichloro-6-hydroxy 5-) - Sodium riazine was added in layers 2.4 and 6 at a rate of 0.02 g/g of gelatin, respectively. After drying, the swelling rate T1/2 of the gelatin film was measured at 30° C. using the following color developer and found to be about 7 seconds. A Levenson-type swelling meter was used for the measurement.

After exposing the above light-sensitive material sample to light through an optical wedge, it was processed through the following steps.

Processing step (38°C) Color development Bleaching and fixing as shown in Table 1 Stabilization treatment as shown in Table 1 Drying for 60 seconds 60-80°C for 120 seconds The composition of each treatment solution is as follows.

[Color development tank liquid] Pure water 800ml benzyl alcohol (nogP 1.1.) Listed in Table 1 Potassium bromide 0.6g Potassium sulfite 4.25g Triethanolamine (nogP O, 27) 2.0g Color development Main drug (exemplified compound-1) Listed in Table 1 1-Hydroxyethylidene-1,1-diphos* :/ Buty (60% aqueous solution) 1.5u + JL Magnesium chloride 0.3g Potassium carbonate
Add 40g of pure water to make 1M and make 20%
Adjust to each pH shown in Table 1 using potassium hydride or 10% dilute sulfuric acid.

[Bleach-fixing tank solution] Pure water 550+N ethylenediaminetetraacetate iron(II) Ammonium salt 65g Ammonium thiosulfate (70% aqueous solution) 85g Sodium bisulfite 10g Sodium metabisulfite
2g Ethylenediaminetetraacetic acid-disodium 5g Bleach additive (general formula [I] ~ [■1) listed in Table 1 Add pure water to make one sentence, add aqueous ammonia or acetic acid to p.
Adjust to H7.0.

[Color developer replenisher] Pure water 800 m benzyl alcohol (JlogP 1.1) Potassium sulfite shown below 5.0g Triethanolamine (logP O, 27) 2.0g Color developing agent (Exemplary compound-1) 1 in Table 1 .25 times 1-hydroxyethylidene-1,1-diphosphonic acid (60% aqueous solution) 2. Omm basic magnesium chloride 0.4g potassium carbonate
40 g of pure water was added to make one sentence, and after adjusting the pFl to the value shown in Table 1 using potassium hydroxide or 10% dilute sulfuric acid, 5 g/l of potassium hydroxide was added.

[Bleach-fixing replenisher 1 Pure water 550mu Ethylenecyaminetetraacetate Iron(III) Ammonium salt 100g Ammonium thiosulfate (70% aqueous solution) 120g Sodium bisulfite 12g Metabisulfite 1
〜Rium 2.3g Ethylenediaminetetraacetic acid-disodium 5g Bleach additive (general formula [I]〜[
(J) Add the pure water listed in Table 1 to make a solution, and adjust the pH to 6.5 with aqueous ammonia or acetic acid.

[Stabilization treatment tank liquid and replenishment liquid] Pure water 800m 5-chloro-2-methyl-4-isothiazolin-3-one
0.1g ethylene glycol
2.0g 1-hydroxyethylidene-1,
1-Diphosphonic acid (60% aqueous solution) 31g Ammonia water (28% aqueous solution) Add 2.0g of pure water to make one sentence, and add ammonia water and dilute sulfuric acid to pH 8.
-2.

Table 1 shows the composition of the color developing tank liquid, and the amount of benzyl alcohol and color developing agent in the color developing replenisher was 1.25 times that of the color developing tank liquid. For the pH of the replenisher, potassium hydroxide and dilute sulfuric acid were used as appropriate so as to maintain the pH of the tank liquid shown in Table 1.

In the above, Exemplary Compound-1 represents its sulfate.

In addition, when the potential of each composition in the color developing solution was measured using a silver-silver chloride electrode as a reference electrode and a platinum electrode using the method described above, it was found that except for hydroxylamine sulfate, all others were -30.
It was meaner than On+V.

Fill an automatic developing machine with the above-mentioned color developing tank solution, bleach-fixing tank solution, and stabilization processing tank solution (alternative to water washing), and carry out color development as described in "2" every 3 minutes while processing the photoprint-exposed color paper. Continuous processing was performed while replenishing the replenisher, bleach-fixing replenisher, and stabilizing replenisher through a bellows pump. The replenishment amount is 170 mJL per color paper 1rrT' to the color developing tank.
Add 15% bleach-fix replenisher to the bleach-fix tank.
0nl, and the amount of replenishment to the stabilization tank was 200n+JL.

The stabilizing tanks of the automatic developing machine are the first tank to the third tank in the direction of the flow of the photosensitive material, and are replenished from the third tank.
A multi-stage countercurrent system was adopted in which the overflow from the third tank was flowed into the second tank, and then the overflow of the second tank was flowed into the first tank.

Continuous processing was carried out until the total replenishment amount of the color developer reached three times the capacity of the color developer tank.

As mentioned above, benzyl alcohol (logP
An example of a solvent having a logP of 0.4 or more, that is, the benzyl alcohol has a logP of 1.1) is varied as shown in Table 1,
After each of the above continuous treatments, the pH value of the color developing solution was adjusted to the value listed in Table 1 with KOH and F12SO, development was performed, and the yellow (440 nm) and magenta (540 nm) reflection densities of the unexposed areas were measured as a spectrum. 330 spectrophotometer (manufactured by Hitachi, Ltd.).

As is clear from Clothe 1, when a bleaching additive is used without benzyl alcohol (text og P is 1.1), yellow and magenta stains in the unexposed areas are small, and very favorable results are obtained.

In addition, in place of No. 9 bleaching additive (■ ~ 100), I
-31,I -37,Tl -2,II -8,II
-11,ll-20,II -26゜U-35,n
-60, II -80, IV-24, -34. V-
3, V-17゜V-27, V-40, V-58,
V -97, V -134, V -150゜■-1. ■
-4. ■-6. ■-12, ■-17. VW-2, V]1
When the same experiment was conducted for 1-5°■-7, similar results were obtained.

Example 2 The silver halide composition of the red-sensitive silver chlorobromide gelatin emulsion in the red-sensitive silver halide emulsion layer (layer 5) of the color vapor prepared in Example 1 was changed as shown in Table 2 below, A color vapor sample was prepared in the same manner as in Example 1 except for the above.

The color developer used in Example 1 (Experiment No. 6) was used. The contamination (yellow and magenta density) of the unexposed area of the sample after processing was measured.

Table 2 From Table 2 above, it was found that the effects of the present invention were seen only on silver halide color photographic materials having a photosensitive layer substantially containing silver chlorobromide.

Example 3 The color vapor used in Example 1 was developed using Experiment No. 6 developer. However, the pH value for bleach-fixing was changed as shown in Table 3.

Further, the color development processing temperature was 40°C, and the bleach-fixing temperature was 30°C. The yellow and magenta reflection densities of the unexposed areas after continuous processing were measured. The results are shown in Table 3.

Table 3 From Table 3 above, it was found that especially when the pH value of the bleach-fix solution was 5 to 9, the staining of the unexposed areas was small and good.

Example 4 The same experiment was conducted except that the temperature of the bleach-fix solution used in Experiments No. 6 and 6 of Example 1 was changed as shown in Table 4. The results are shown in Table 4.

Margin Table 4 Below: From this, it was found that the bleach-fixing temperature is preferably 15 to 55°C, particularly preferably 25 to 55°C.

Example 5 The paper samples obtained in Example 1 were processed using varying color development and bleach-fixing steps as shown in Table 5. The contamination of the unexposed area after treatment was measured in the same manner as in Example 1, and is shown in Table 5.

If the pH value of the color developer is 10.5 or more,
It has been found that more preferable effects of the present invention can be obtained when the color development time is 120 seconds or less and the bleach-fixing time is 60 seconds or less.

Example 6 In Experiment No. 6 of Example 1, hydroxylamine sulfate was added to the color developing solution in varying amounts as shown in Table 6, and bleaching accelerators were also added as shown in Table 6. The only difference was that .

As in Example 1, the contamination of the unexposed area after processing was measured,
The results are shown in Table 6.

The color development time was 45 seconds, the bleach fixing time was 40 seconds, and the water washing alternative stabilization time was 45 seconds (15 seconds x 3 tanks).

Table 6 As is clear from Table 6, the effect of the present invention is better when the amount of hydroxylamine sulfate (an example of a composition whose redox potential is nobler than -:100 mV) added to the color developer is smaller. It turned out that.

Example 7 In Experiment No. 006 of Example 1, the only difference was that the amount of replenishment of the washing substitute stabilizing solution was changed as shown in Table 7, and the experiment was conducted in the same manner as in Example 1. However, the test was carried out in the case where no bleaching additive was used in the bleach-fix solution and in the case where 1.0 gel of ■-6 was used.

As in Example 1, the contamination of the unexposed area after treatment was measured, and the results are shown in Table 7.

Note that the water washing alternative stabilization or water washing was performed at 33°C.

Table 7 As is clear from Table 7, it was found that the effects of the present invention can be obtained even if the amount of replenishment of the washing substitute stabilizing solution is reduced to 500 mJL/m' or less.

Example 8 In Experiment No. 6 of Example 1, the type and amount of color developing agent added were changed as shown in Table 8, but the experiment was conducted in the same manner as in Example 1.

As in Example 1, the contamination of the unexposed area after processing was measured,
The results are shown in Table 8.

Table 8 As is clear from Table 8, the effects of the present invention were observed only in the color developing solution using the color developing agent (exemplary compound) of the present invention, and in the other color developing agents No. 5, No. 5, No.
It was found that treatment with a color developing solution using No. 7 could not prevent contamination of unexposed areas after treatment.

In addition, when the same experiment was conducted using Exemplary Compounds-2, 3, 4, and 5 instead of Exemplary Compound-1 as the color developing agent used in No. 79.80, similar results were obtained.

NI(2 NH2

[Brief explanation of drawings]

FIG. 1 is a graph showing the membrane swelling rate T1/2 of the binder.

Claims (5)

[Claims] (1) After imagewise exposure, a silver halide color photographic light-sensitive material in which the silver halide contained in the light-sensitive emulsion layer is substantially silver chlorobromide is treated with halogen by at least a color development step and a bleach-fixing step. In the method for processing a silveride color photographic light-sensitive material, [1] The color developer used in the color development step is p-phenylenediamine having at least one alkylsulfonamide alkyl group on the benzene ring and/or in the amino group. [2] A solvent is contained in the color developing solution in a volume ratio range expressed by the following formula [A], and the formula [A] (logP is 0.4). Capacity of (solvent above) / (water) + Capacity of (solvent other than water with logP less than 0.4) ≦
0.003 [3] The bleach-fix solution used in the bleach-fixing step has organic acid ferric complex salt and thiosulfate as main components, [4] The bleach-fix solution has the following general formulas [I] to [VIII] ]
1. A method for processing a silver halide color photographic material, which comprises at least one compound represented by: General formula [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [III] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [IV] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [V] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [VI] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [VII] ▲ Mathematical formulas, chemical formulas, Tables etc. are available▼ [In the above general formula, Q is a heterocycle containing one or more N atoms (
Represents the atomic group necessary to form a 5- to 6-membered unsaturated ring (including those with at least one fused ring), and A is ▲Mathematical formula, chemical formula, table, etc.▼, ▲Mathematical formula, chemical formula ,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, -SZ' or n_1-valent heterocyclic residue (including those with at least one 5- to 6-membered unsaturated ring fused to it) represents,
B represents an alkylene group having 1 to 6 carbon atoms, M represents a divalent metal atom, and X and X″ are =S, =O or =NR″
R'' represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, a heterocyclic residue (
(including those with at least one 5- to 6-membered unsaturated ring condensed thereto) or an amino group, Y represents >N- or >CH-, Z represents a hydrogen atom, an alkali metal atom,
Ammonium group, amino group, nitrogen-containing heterocyclic residue or ▲
There are mathematical formulas, chemical formulas, tables, etc. Represents ▼, Z' represents Z or an alkyl group, R^1 is a hydrogen atom, and 1 carbon number
~6 alkyl groups, cycloalkyl groups, aryl groups,
Represents a heterocyclic residue (including those to which at least one 5- to 6-membered unsaturated ring is fused) or an amino group,
R^2, R^3, R^4, R^5, R and R' are each
Hydrogen atom, alkyl group having 1 to 6 carbon atoms, hydroxy group,
represents a carboxyl group, an amino group, an acyl group having 1 to 3 carbon atoms, an aryl group, or an alkenyl group, provided that R^4 and R^5 may represent -B-SZ, and R, R', R
^2 and R^3, R^4 and R^5 each cyclize with each other to form a heterocyclic residue (including those to which at least one 5- to 6-membered unsaturated ring is fused). It's okay. R^6 and R^7 each have ▲mathematical formula, chemical formula, table, etc.▼, ▲mathematical formula, chemical formula,
There are tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ , where R^9 is an alkyl group or -(CH_2)n_■
Represents SO^-_3 (however, R^8 is -(CH_2)n_
■When SO^-_3, l represents 0 or 1. )G＾−
are anions, m_1 to m_4 and n_1 to n_
■ represents an integer from 1 to 6, and m_5 represents an integer from 0 to 6. R^6 represents a hydrogen atom, an alkali metal atom, a numerical formula, a chemical formula, a table, etc., or an alkyl group. However, Q' has the same meaning as Q above. D represents a simple bond, an alkylene group or vinylene group having 1 to 8 single primes, and q represents an integer of 1 to 10. A plurality of D's may be the same or different, and the ring formed together with the sulfur atom may be further fused with a 5- to 6-membered unsaturated ring. X' is -COO
M', -OH, -SO_3M', -CONH_2, -S
O_2NH_2, -NH_2, -SH, -CN, -CO
_2R^1^6, -SO_2R^1^6, -OR^1^
6, -NR^1^6R^1^7, -SR^1^6, -S
O_3R^1^6, -NHCOR^1^6, -NHSO
_2R^1^6, -OCOR^1^6 or -SO_2R
It represents ^1^6, and Y' is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲mathematical formulas, chemical formulas,
There are tables, etc. ▼ Or represents a hydrogen atom, and m and n each represent an integer from 1 to 10. R^1^1, R^1^2, R^1^4, R^
1^5, R^1^7 and R^1^8 represent a hydrogen atom, a lower alkyl group, an acyl group, or ▲a mathematical formula, a chemical formula, a table, etc.▼, and R^1^5 is a lower alkyl group represents. R^1
^9 represents -NR^2^0R^2^1, -OR^2^2 or -SR^2^2, and R^2^0 and R^2^1 represent a hydrogen atom or a lower alkyl group. Represents R^2^2 is R^
Represents an atomic group necessary to connect with 1^8 to form a ring. R^2^0 or R^2^1 and R^1^6 may be connected to form a ring. M' represents a hydrogen atom or a cation. The compounds represented by the above general formulas [I] to [V] include enolized compounds and salts thereof. ] General formula [XVIII] ▲Mathematical formulas, chemical formulas, tables, etc.▼ (In the above general formula, Ar is an aromatic linking group, B^1 and B^
2 each represents a lower alkylene group. R^2^3,
R^2^4, R^2^5 and R^2^6 each represent a hydroxy-substituted lower alkyl group. G' is an anion,
x and y each represent an integer of 0 or 1, and z represents an integer of 0, 1 or 2. ) 2. Replace pages 29 and 95 with separate sheets. (2) The method for processing a silver halide color photographic material according to claim 1, wherein the color developing solution has a pH of 10.3 or more. (3) The method for processing a silver halide color photographic light-sensitive material according to claim 1 or 2, wherein the capacity ratio of the formula [A] is 0 to 0.001. (4) The method for processing a silver halide color photographic light-sensitive material according to any one of claims 1 to 3, wherein the bleach-fix solution has a pH in the range of 5 to 9. . (5) The silver halide photographic light-sensitive material is subjected to a water-washing alternative stabilization treatment after being processed in a color development step and a bleach-fixing step. A method for processing a silver halide color photographic material according to any one of the above.