JPS62253164A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enable a stable image to be rapidly formed, to dispense with rinsing, and to render dissolution and preparation of a processing solution easy and simple by processing a color photographic sensitive material composed substantially of silver chlorobromide with a specified color developing solution under specified conditions, and then executing stabilization processing after bleach-fixing processing. CONSTITUTION:The color photographic sensitive material composed substantially of silver chlorobromide is processed with the color developing solution of >=10.3 in pH containing at least one of N-sulfonamidoalkylated p-phenylenediamine type color developing agents in an amount of at least 10<-2>mol per l of the developing solution in the coexistence of a triazinylstilbene type fluorescent bleaching agent at a temperature of 30 deg.C within 120 sec. The solvent of the color developing agent is composed of water, and an nonaqueous solvent S having a log P of <=0.4 and another nonaqueous solvent S' having a log P of >=0.4 in an S'/S volume ratio of <=0.003:1. The bleach-fixing and stabilizing processings are successively executed. Linear precipitates are prevented by substantially not containing hydroxylamine in the color developing solution.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a color development processing method for silver halide color photographic light-sensitive materials (hereinafter referred to as light-sensitive materials). A rapid waterless washing stabilization processing method that can obtain images with stable dye density and excellent storage stability in a dark place, and that can be processed with a small amount of stabilizing solution without washing with water. It is related to.

[Prior art]

Processing of color light-sensitive materials basically consists of three steps: color development, desilvering, and washing with water. Desilvering consists of either a bleaching and fixing step or a bleaching and fixing step in which bleaching and fixing are performed in the same bath.

Recently, instead of the water-washing process, a waterless washing process called stabilization process has been proposed, and a process consisting of three steps of color development, bleach-fixing, and stabilization process has become popular.

In color development, the exposed silver nine halide is reduced to silver, and at the same time the oxidized aromatic primary amine developing agent reacts with the coupler to form indoaniline, indophenol, and azomethine dyes. It is well known to form color photographic images by

In these color photographic systems, a non-diffusible coupler is generally contained in the photographic emulsion layer and development is carried out using a color developing agent in a color developing solution. It is also known how to induce this in photographic materials. The coupler contained in the light-sensitive material is generally made non-diffusible by being dispersed in a water-insoluble high-boiling organic solvent. This method is extremely common, as it is more advantageous in terms of color reproducibility, color purity, and image storage stability than by introducing polymeric alkyl side chains into the coupler and making it non-diffusible. ing.

[Problem that the invention seeks to solve]

The color developing solution for processing such light-sensitive materials contains an aromatic primary amine color developing agent and a poorly soluble organic solvent (lo
It is also well known that a solvent with a gP of 0.4 or more is contained. The most well-known organic solvent of this type is a poorly soluble alcohol, which is used to enhance the efficiency of the coupling reaction that promotes the reaction between color developing agents and image-forming cassillers. This type of alcohol is often referred to as ``1 development accelerator 1 or 1 development booster'' in U.S. Pat. No. 2,304,925 or 3.8.
Benzyl alcohol is particularly effective for this purpose, as seen in US Pat. No. 14,606.

Color development is promoted by supplying a large amount of color developing agent in a short time into the oil sphere in which the coupler is dispersed, and by distributing a relatively large amount of color developing agent into the swollen gelatin film than in the bulk of the developer. The use of poorly soluble alcohols, such as benzyl alcohol, which is thought to cause a high concentration of color developing agent in the oil and gelatin in the photosensitive material during processing, results in a high residual concentration after development. This has the disadvantage of causing the storage stability of dye images to deteriorate.

What has made this problem even more obvious and emphasized is the recent rapid processing that has shortened the total processing time.Another major cause is that a large amount of washing water is supplied, and the photosensitive materials are not cleaned properly. The processing step known as water washing was removed from photographic processing, and stabilization processing, in which a small amount of replenishment was supplied, began to replace washing.

These waterless washing stabilization treatments are described in Japanese Patent Application Laid-open Nos. 57-8542, 57-8543, 58-18630, and 58
-105145, 58-134636, 59-
No. 126535, No. 59-184343, No. 59-1
No. 84344, No. 59-185336, No. 60-13
Details are described in each specification of No. 5942.

In all of these methods, it is not possible to sufficiently wash the color developing agent adsorbed to the gelatin film in the light-sensitive material or the color developing agent distributed in the coupler dispersion oil to reduce the residual concentration, resulting in poor storage stability of the dye image. This is a significant deterioration.

Furthermore, as a completely different problem, poorly soluble solvents such as benzyl alcohol with a logP of 0.4 or more have long caused separate problems due to the poor solubility of these compounds in water. For example, when preparing a developer solution, benzyl alcohol tends to dissolve very slowly, requiring extensive forced stirring and/or heating of the solution water.

If even a portion of the benzyl alcohol remains undissolved, the color developing agent will be distributed and dissolved in this portion at a high concentration, resulting in oxidation and formation of 1 tar after several days, resulting in a serious malfunction.

One solution for incorporating benzyl alcohol into a color developer is to solubilize benzyl alcohol by adding a solvent other than water with a logP of less than 0.4, such as ethylene glycol, diethylene glycol, polyethyleneimine, triethanol, etc. method is known.

This method is described in US Pat. No. 3,574,619.

Furthermore, the disadvantage of a solvent such as benzyl alcohol is that it deteriorates the solubility of the color developing agent in the solution, so the concentration of the color developing agent in the color developing solution cannot be sufficiently increased, and development is not promoted or accelerated as expected. is only half-hearted.

A particularly serious problem is that when using a developer containing benzyl alcohol, there is a limit to the amount of color developing agent that can be dissolved in the replenisher. The point is that it cannot be enriched beyond a certain level of evidence.

Further, when continuous processing was performed in the presence of a solvent with a voice of 10.3 or less and a logP of 0.4 or more, the whiteness deteriorated.

In addition, considering the problem of linear precipitates appearing near the interface between the gas phase and liquid phase in the processing tank, it has been found that in areas where liquid control cannot be performed sufficiently, such as in dispersion processing for photography, some effects may cause the photosensitive material to It has become clear that this poses a serious problem of adhesion and contamination. It has also been found that this precipitate is more likely to occur when a small amount of treatment is continued over a long period of time.

[Object of the present invention]

The object of the present invention is, firstly, to provide a method for processing color photographic materials, which allows rapid and stable dye images to be obtained;
The third objective is to provide a processing method that eliminates the need for water washing, conserves water resources, and leaves no harmful processing chemicals in the processed photographic materials, resulting in color photographs that are safe and have excellent preservation. To provide a color photographic processing method in which a processing solution can be easily adjusted.

Other objects of the invention will become apparent from the description below.

A fourth object is to provide a technique that allows photographic materials to be processed without adversely affecting photographic performance even when continuous processing is performed.

[Means to solve the problem]

The present inventors have conducted various studies to achieve the above-mentioned objects of the present invention, and as a result, they have developed a silver halide color photographic material consisting essentially of a silver chlorobromide emulsion using a poorly soluble solvent with a logP of 0.4 or more. Using a color developing solution that is a highly alkaline developer with a pH of 10.3 or higher and containing at least 1.5 x 10-2 moles of at least one color developing agent of general formula (1) or (2). It has been found that this can be achieved by processing at 30° C. or higher for 120 seconds or less in the coexistence of a triazonylstilbene type fluorescent brightener.

The present invention utilizes a specific color developing agent and a specific color developing solution.
It can only be obtained by a combination of specific silver halide emulsions, and when conventional benzyl alcohol is used, it is necessary to disperse Kaglar in order to achieve efficient color development and rapid processing. There is a trade-off relationship between increasing the concentration of developing agent in oil spacing and adding a silver solvent such as thioether or thiocyanic acid, which is a physical development accelerator, as a development accelerator, and stabilizing the dye image. It was an important discovery that the color developing reaction could be carried out quickly, the residual color developing agent could be minimized, and the storage stability of the dye image could be improved.

The present inventors have found that although general primary amino itb developing agents have better solubility as the acidity increases, the color developing agent of the present invention has a specificity in that, on the contrary, the solubility increases as the acidity increases. I discovered that.

Furthermore, when the silver halide is essentially a silver chlorobromide emulsion, the color developing agent of the present invention at a concentration above a certain level increases the development speed commensurate with the increase in the coupling speed of a conventional fogger. It has been found that extremely efficient development acceleration can be obtained, and a dye image comparable to that obtained when benzyl alcohol is added can be obtained in a rather short time. This is thought to be due to the fact that if it is above a certain level, a much higher concentration of color developing agent can be used than when benzyl alcohol is present, and this will result in an optimal increase in the coupling speed and the development speed of 710R silver oxide. It will be done.

In addition, the organic solvent with Log P 0.4 or more was present
Even though the concentration of the developing agent after processing is much higher in the developing solution of the present invention, which has a higher concentration than that used in color development, the amount of residual developing agent in the photographic light-sensitive material can be extremely reduced, and the amount of residual developing agent in the photographic light-sensitive material can be extremely reduced. An advantageous result was obtained in that even in a stabilization treatment that does not carry out oxidation, the residual amount can be extremely small. Also, the processing time is similar to benzyl alcohol.
Since processing can be done in a significantly shorter time than in the case of a low-concentration color developing agent containing a solvent with an og P of 0.4 or higher, the amount of crude drug remaining in the light-sensitive material can be further reduced.

Further, the present inventors continued their studies and found that the no-rodanized silver emulsion is silver chlorobromide, in particular, the silver bromide content is 90 molt or less, and the membrane swelling rate T1/2 of the binder of the emulsion is 20 seconds or less. and the color development process is at 30℃ or higher12
We have also discovered the surprising fact that the effects of the present invention can be achieved significantly when processing is carried out for less than 0 seconds, that is, extremely high processing speed and dye storage stability can be obtained. This is something that we have succeeded in achieving.

Also, unlike the conventional #) 10.3 or more and logP is 0
, 4 or more solvents with a tog P of 0.4 or less and in cases where the content is 0.003 or less per 1000 of water, the occurrence of staining is extremely small even when continuous processing is performed, and even more importantly, when newly adjusted Even when processing light-sensitive materials using a processing solution of A completely unexpected effect was also obtained, which did not occur even if the treatment was continued for a long period of time. Furthermore, it has been found that when continuous processing is performed without using a fluorescent brightener in the present invention, a problem arises in that image storage stability deteriorates, but this problem can also be solved by the coexistence of a fluorescent brightener. It turns out that there is a significant effect. Upon further investigation, it was discovered that the use of a fluorescent brightener (TIJ 7 dinylstilbene) has the surprising effect of stabilizing γ even in liquids where γ tends to increase.

In this specification, the term "substantially 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.

The present invention will be explained in more detail below.

The hydrophilic binder used to coat silver halide in color photographic light-sensitive materials is usually gelatin, but there are also cases where high molecular weight polymers are used, and the film swelling rate T
1/2 should be less than 30 seconds, and the membrane swelling rate T1/2 of the binder can be measured according to any method known in the art, for example A, Gr.
...n and G, I, P.

Lev@n5on, J, photo0. gel...20
．． A swellometer of the type described on pages 205 to 210 (
can be measured by using a swelling needle)
T1/2 is defined as the time it takes to reach 1/2 of the saturated film thickness, which is the maximum swollen film thickness of 90 cm when processed at 30°C for 3 minutes and 30 seconds in color development ( (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 T1/2 of 20
The lower limit is less than 2 seconds, and the smaller the better, but the lower limit is preferably 2 seconds or more, since if it is too small, the film will not be hardened and failures such as scratches will easily occur.

Particularly preferably, the time is 15 seconds or less, most preferably 10 seconds or less. If the time 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 T
1/2 can be adjusted by the amount of hardening agent used.

It is sufficient that at least one of the light-sensitive emulsion layers of the silver-free silver photographic light-sensitive material processed according to the present invention consists essentially of a silver chlorobromide emulsion; Preferably, it consists of a silver emulsion. The silver chlorobromide has a silver bromide content of preferably 90 moles or less, most preferably 70 moles or less and 40 moles or more, because the smaller the silver bromide mole, the more sufficient dye formation can be obtained even in a short color development time. result.

Further, the smaller the amount of silver coated, the more preferable it is in that sufficient dye formation can be achieved even in a short time, and the maximum effect can be obtained when the amount is less than 197 m2, particularly preferably less than 0.8177 m2, and more preferably less than 0-9i 2. Color development processing is performed at 30℃ or higher.
120 seconds or less, preferably 33°C or more, 120 seconds or less,
Particularly preferably at 33°C or higher and 90 seconds or less, most preferably at 33°C or higher and 60 seconds or less, the ib, 30
When the treatment is carried out at a temperature of 150 seconds or more at a temperature of 150 seconds or more, the storage stability of the dye deteriorates. In particular, temperature and treatment time are important; if the treatment time exceeds 150 seconds, the light brownness of the yellow dye will significantly increase, which is not preferred. The processing temperature is raised in order to finish the development in a short time rather than the storage stability of the dye.It is preferable that the processing temperature be higher than 30°C and lower than 50°C because the processing can be done in a shorter time, but the storage stability of the image is better. From the viewpoint of performance, it is better not to be too high, and it is desirable to process at a temperature of 33°C or higher and 45°C or lower.

The color photographic light-sensitive material of the present invention is a multilayer color photographic light-sensitive material having three or more layers including each of a blue-sensitive emulsion layer, a green-sensitive emulsion layer, and a red-sensitive emulsion layer. The maximum effect is exhibited when the membrane swelling rate T1/2 is 20 seconds or less, but the thickness of the gold film when dried is 14# or less, preferably 12NL or less, particularly preferably 10μm or less. In either case T1/
2 is preferably 20 seconds or less.

In the present invention, it is preferable that hydroxylamine is not substantially contained, but hydroxylamine refers to free amines as well as water-soluble salts such as sulfates, oxalates, hydrochlorides, phosphates, carbonates, and acetates. Also included are acid addition salts. Further, "substantially not containing" means that the concentration of hydroxylamine in the color developing solution is 0.007 mol or less per 1 mole, but it is most preferably 0.

In the processing method of the photographic light-sensitive material of the present invention, it is possible to use a color developing solution containing the color developing agent according to the present invention. In addition, various other methods including bath treatment,
For example, various processing methods can be used, such as a spray set in which the processing liquid is atomized, a web method using contact with a carrier impregnated with the processing liquid, or a developing method using a viscous processing liquid, but the processing steps are essentially Color development, bleach fixing,
It consists of three steps: and stabilization treatment.

Among the N-sulfonamidoalkyl-substituted p-phenylenediamine color developing agents and the N-alkoxyalkyl substituted p-phenylenediamine color developing agents used in the present invention, the compound preferably used is represented by the following formula.

In the above formula, L2 and L4 represent a methyl group, an ethyl group, and a propyl group, respectively, and L3 represents a methine group, an ethylene group, a propylene group, and a tstyrene group.

Next, specific examples of the color developing agent represented by the above formula will be shown.

(D-1) (D-2) (D-3)
(D-4) (D-5)
(D-6) (D-7)
(D-8)H2NH2 (D-9) (o-to)(
D-11) C3H6C2H40Cf (.

H2 Among the above color developing agents, (D-2) is preferred.

(D-8), particularly preferably (D-2).

Further, the above color developing agent is preferably used as a counter salt of hydrochloric acid, sulfuric acid, p-toluenesulfonate, or the like. Also, 2
When used in combination with a color developing agent other than the present invention, the present invention agent is present in a molar ratio of 501 or more.

These color developers are hydrochloride, sulfate, phosphate, p-)
Luene sulfate salt is used in the 4th form.

- of the color developing solution of the present invention is used at a value of 10.3 or more, preferably 10.50 or more, particularly preferably 10.75 or more, and the upper limit is related to the capricity of the photographic emulsion, but in general, the higher the better.

Since the color developing agent of the present invention has extremely high solubility in water, the amount used is from 0.015 mol to 0.01 mol per 1 processing solution.
It is preferably used in a range of 1 mol, more preferably in a range of 0.015 to 0.07 mol.

The color developing solution of the present invention has a bromide ion concentration of 5 x 10-5.
It is preferable that the bromide is molar or more, but in the present invention, the higher the bromide, the lower the replenishment amount, so it is preferable. In conventional development methods, bromide suppresses the development reaction and is considered to be preferable as it is low, but in the combination of the color photographic light-sensitive material and developer of the present invention, a slight increase in bromide concentration does not impair the speed of development. It can be used without any problems.

This is the value obtained from the partition coefficient P of logPt''! and n-octatool/water according to the present invention.The P value is obtained using the following formula.The logarithm of the P value obtained in this way is the logP value. , this value has traditionally been widely used in the field of agricultural medicine as a measure of fat solubility.
It can also be known from the tag Poc in the table described in J magazine, Vol. 71, No. 6, 1971, pp. 555-613. For example, "Ecochemistry" Vol. 6, pp. 3-11
Although it can also be determined by the calculation method described on page 1, it is preferable to use actual measured values, and particularly preferably n-
It is preferable to use values measured using an octatool.

Log that is not preferable to be added to the developer in the present invention
P Q, 4 or more solvents are aliphatic alcohols, aliphatic glycol ethers, alicyclic alcohols, or aromatic alcohols, and among these, a specific example of a solvent having 5 to 20 carbon atoms is pencil alcohol Log P 1 .10
0-hydroxybenzyl alcohol logP0
．． 73 Cyclohexanol Log P 1
．． 232-benzyloxyethanol lo
gP0.41 Anisyl Alcohol Log
0.701-pentanol AogP0
．． 4 or more phenylethyl alcohol Log P
1.36p-tolylcarbinol AogPl,
36n-butanol Log 0.
4 or more phenol p-hydroxybenzyl alcohol penzolamine diethylene glycol monobutyl ether Log P
Examples include 0.41.

In addition, solvents with a Log P of less than 0.4 are mainly those with a carbon number of θ to 4, such as aliphatic alcohols and organic acids, and if highly polar functional groups are present, the Log P is less than 0.4. Although it may be less than 0.4 and is not particularly limited, specific examples include the following solvents.

The above logP values are mainly based on the values measured using the octatool described in the above-mentioned Chemical Review magazine.If the values measured using the octatool are not available, the values measured using other solvents are used as substitutes. By measuring the effectiveness of the present invention, the effects of the present invention can be utilized to the fullest.

Next, the triazinylstilbene fluorescent brightener used in the present invention will be described.

The triazinylstilbene type fluorescent brightener is preferably one represented by the following general formula.

In the formula, x , x , y and Y2 are each a hydroxyl group,
Halogen atoms such as chlorine and bromine, alkyl groups (e.g., methyl, ethyl, etc.), aryl groups (e.g., Fe) each have a hydrogen atom, an alkyl group that may have a substituent, or an aryl group that may have a substituent. , R and R4 each represent an alkylene group that may have a substituent, R5 represents a hydrogen atom, an alkyl group that may have a substituent, or an aryl group that may have a substituent, M represents a cation (eg, sodium, potassium, ammonium, etc.).

The alkyl groups represented by R, R and R5 above preferably have 1 to 6 carbon atoms, and the alkylene groups represented by R3 and R4 above preferably have 1 to 2 carbon atoms.

As the substituent for the alkyl group and aryl group represented by R1, R2 and R5 above, and the alkylene group represented by R5 and R4 above, a hydroxy group, a sulfo group, a sulfoamino group and a calgexiamino group are preferable.

Alkylamino group (e.g. methylamino, ethyla ε)
, propylamino, dimethylamino, cyclohexylamino, β-hydroxyethylamino, zo(β-hydroxyethyl)amino, β-sulfoethylamino, N-(β
-sulfoethyl) + N/ -methylamino, N-(
β-hydroxyethyl)-N'-methylamino, etc.) or arylamino groups (e.g. anilino, o-, m-, p-
-sulfoanilino, O-, m-, p-chloroanilino,
o-.

m-, p-) luidino, o-, m-, p-carboxyamino, o-, m-, p-hydroxyanilino, sulfonaphthylamino, g-, m-up-aminoanilino, 6-
, m-, p-anilino, etc.), specific examples of -〇R6 include alkoxy groups (e.g., methoxy, ethoxy, methoxyethoxy, etc.), aryloxy groups (e.g., phenoxy, p-sulfophenoxy, etc.). Can be mentioned.

Among the fluorescent brighteners represented by the above general formula, preferred compounds include all of x , x , y and Y2, and the most preferred compound is one of X and Yl and one of Xl and Y2
When one of these is =〇R2, the other is specific examples of the following compounds, but are not limited to these.

(E-1) λmax=435nm (E-2) λmax=437nm (9ft) λmax=:437nm (E-4) λmax=436nm (E-5) λmax=440nm (9Q) (E-6) λmay=442nm (E-7) λmax=437nm (E-8) λmax=440nm (E-9) λmix=436nm (E-10) λmax=437nm (E-11) λmax=439nm (E-12) λmax=440nm (E -13) λmax=442nm (E-14) λmax=440nm (FJ-15) N(C2H40H) 2 N(C2H4
0f() 2λmax=441nm (E-16) λmax=440nm (E-17) λmax”439nm (IIc-18) λmax=434nm (E-19) OCH, OCH3 λmax=436nm (E-20) λmax=442nm ( E-21) λmax=440nm (E-22) λnlax=441nm (E-23) λmix=440nm (E-24) λmax=436nm (g-25) λmax=441nm (E-26) λmax=442nm (E- 27) λrnax=444nm (g-28) λmax=441nm (E-29) λmax=442nm (E-30) λmax=444nm (E-31) λmax==443nm (g-32) λmax=440nm (E-33 ) NHC2I(5NHc2H5 λmax=441nm (E-34) (E-35) (E-36) (E-37) The triazinylstilbene-based fluorescent brightener used in the present invention is described, for example, in the Chemical Industry Association. It can be synthesized by the usual method described in "Fluorescent Brightener" (published in August 1976) 8-e-di.

The triazinylstilbene-based fluorescent whitening agent used in the present invention has a maximum fluorescence wavelength λmax of 4
The object of the present invention is most effectively achieved when the wavelength is 33 to 440 nm.

The amount of triazinylstilbene-based fluorescent whitening agent added to the water-washing alternative stabilizing solution is 0.0511 to 100 g per 1 part of the solution.
The range is preferably 0.11, more preferably 0.11
7-20g range, most preferably 0.2g-l
og range.

Next, the general formulas CI), [11) and [
The chelating agent represented by [2] will be explained.

General formula [1) A-COOM General formula (If) B-P-82 General formula (■) M C-OH In the formula, ABB and B2 each represent a monovalent group or atom, and may be an inorganic substance. However, it may also be an organic substance. D represents an atomic group necessary to form an aromatic ring or heterocycle which may have a substituent, and M represents a hydrogen atom or an alkali metal atom.

Among the chelating agents represented by the general formula (1), [n) or (1) added to the present invention, preferred chelating agents for the present invention are represented by any of the following general formulas [IV] to [w]. The compound shown is

General formula [■] yLmPm03m General formula [■] Mn+2Pno3n+1 General formula 1: ■) A, -R', -Z-R', -COO
H general formula [■] In the formula, E is a substituted or unsubstituted alkylene group, cycloalkylene group, phenylene group, -R', -0-R', -.

<-oR'7oR', -, -m', zR'7-,
2 represents N-”7-A61 cytoA6, Ry, ~R/
, represents a substituted or unsubstituted alkylene group, A1 to A6
is hydrogen, -OH, -COOM.

-PO, M2, M represents hydrogen or an alkali metal atom, m represents an integer of 3 to 6, and n represents an integer of 2 to 2o.

General formula (W) R'8N(CH2PO,M2)2 In the formula, R'8 is a lower alkyl group, an aryl group, an aralkyl group, a nitrogen-containing 6-membered ring group [as a substituent 10H1-OR'-C
OOM ), and M represents a hydrogen atom or an alkali metal atom. (R1 is an alkyl group) General formula (DO B, 82B5 In the formula, R1, to R', 1 are hydrogen atoms, -〇H9 lower alkyl (unsubstituted or as a substituent -OH, -COOM
.

-PO,M2), 81 to B3 are hydrogen atoms, -〇H
9-COOM, -PO3M2. -Nl2, J is a hydrogen atom, lower alkyl, C2H4OH, -PO,M
2, M represents a hydrogen atom or an alkali metal, n, m
represents O or 1.

General formula [X] 0M ■ In the formula, R11□ and R'1s are hydrogen atoms, alkali metals,
Represents an alkyl group, alkenyl group, or cyclic alkyl group of 01 to C12.

General formula CXI) 1Q2 In the formula, R' is an alkyl group of C,
1-12 1-1
2 alkoxy group, C monoalkylamino group, 1-12 02-, 2 dialkylamino group, amino group, C1-2
4 represents an aryloxy group, C an arylamino group, and 6-24 amyloxy7 groups, Q and ~Q5 are -OH, C1-2
4 represents an alkoxy group, an aralkyloxy group, an allyloxy group, -0M3 (M is a cation), an amino group, a morpholino group, a cyclic amino group, an alkylamino group, a sialkylamino group, an arylamino group, and an alkyloxy group.

General formula (XI It represents an alkyl group of numbers 1 to 18.

General formula (XIV) 1'24 In the formula, R'23 and R'24 represent a hydrogen atom, a halogen atom, or a sulfonic acid group.

General formula [XV] In the formula, R' and s o are a hydrogen atom, a phosphoric acid group, a carnoic acid group, -CH2COOH, -CH2PO,
R2 or a salt thereof; Xl represents a hydroxyl group or a salt thereof; W, Z, and Yl each represent a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a carboxylic acid group, a phosphoric acid group, a sulfonic acid group or a salt thereof, an alkoxy group or an alkyl group. Also, ml is 0 or 1, nl is 1
An integer of ~4, tl is 1 or 2. pl is an integer from O to 3, q
l represents an integer of 0 to 2.

Specific examples of the chelating agents represented by the general formulas [■] to [X■] include the following.

[Exemplary chelating agent]

(1) Na4P40,2 (2) Na, P3O.

(3) H4P2O, (4) H4F, 01° (5
) Na4P40. .

IAri) (15) (HOC2I(4), NCH2C00H(
Lkl) COOf (HOOC-CH2 HO-C-HHO-C-COOH 1 (00C-C-HH-C-COOH PO, HI ) (52)
(52suOH2 0sH2 CH2Coot( OH H2O, P-C-PO, ■2 HOCH2CH(OH) -CH2O-P-(ON&
) 2HOCH2CH20-P-(OH) 2OH20
H HOCH2C-CH2-0-P-(OH)2HO-CH
2-OH-CH2-0-P-(OH)2OH Cζ Takashi) OH2 COOK C00HH
2N-CH2CH2-0-P-(OH)2H2N-CO
O-P-(OK)2Hc-coo-p-(of()2CI(.

;1 OH OH NaOONm OHOH OHOHOH OHOH0H OF(OH0H OCR30CH6 0H0H S0.HC00CH3 CH2C00H(0H2Coot( Cf(2COOI(CH2C00H COOHC00H CHCoot(CH2 C0OH Qoo) CH2P03Na2 CH2COONa CH2C0ONaCH2COO
HCH2C00H CH2COONa CH3COONa CH2C00N In the present invention, the general formula ('lV), [V), [V
I).

It is effective to use the chelating agents shown by [■], [circle], [IX), [■] and [XV]. Preferably, the general formula [■], [■), (IX), (XI
I), (XV) are preferred, more preferably the number of chelates with iron (IV) ions is 6 or more, and particularly preferred are specific examples (7),
(11), (13), (22).

(44), (46), (52), (81)
, (82), (83), (88).

(89), (93), (97), (101
).

The chelating agent represented by any of the above general formulas (]) to (nl) used in the present invention is the stabilizer 1! It's true plXlo
It can be added in the range of "-' mole - 1 mole, preferably in the range of 2 x 10 to I x 10" mole, and more preferably in the range of 5 x 10" to 5 x
It can be added in a range of 10-2 mol.

The color developing solution used in the present invention further contains various commonly added components, such as alkaline agents such as sodium hydroxide and sodium carbonate, alkali metal sulfites,
Alkali metal bisulfites, alkali metal thiocyanates, alkali metal norodanides, polystyrene sulfonic acid, water softeners, thickeners, development accelerators, and the like may optionally be included.

Examples of additives other than the above added to the color developing solution include bromides such as potassium bromide and ammonium bromide;
Compounds for quick processing liquids such as alkali iodide, nitrobenzimidazole, mercagutopenzimidazole, 5-methyl-benzotriazole, 1-phenyl-5-mercaptotetrazole, as well as anti-stain agents, anti-sludge agents, and preservatives. agents, interlayer effect promoters, chelating agents, etc.

Aminopolycal is a bleaching agent used in bleaching solution thickening. Generally known are those in which metal ions such as iron, cobalt, copper, etc. are coordinated with organic acids such as phosphoric acid, oxalic acid, and citric acid. And the aminopolycal mentioned above? Examples of substitutes for phosphoric acid include the following:

Ethylenediaminetetraacetic aciddiethylenetriaminepentaacetic acidpropylene diaminetetraacetic acidnitrilotriacetic acidiminodiacetic acid glycol ether diaminetetraacetic acidethylenediaminetetrazolobionic acidethylenediaminetetraacetic acid disodium saltdiethylenetriaminepentaacetic acid pentansodium saltnitrilotriacetic acid sodium saltThe bleach solution is used together with the above bleaching agent. It may contain various additives.

Furthermore, a solution containing a silver halide fixing agent is applied. The whitening solution may also contain further halogen compounds, such as potassium bromide, and, as in the case of the bleaching solution mentioned above, various other additives, such as - buffering agents, fluorescent Brighteners, antifoaming agents, surfactants, preservatives, chelating agents, stabilizers, organic solvents, etc. may be added or contained.

In addition, as a silver halide fixing agent, for example, thiosulfate)
List of compounds that react with silver halides to form water-soluble silver salts, such as ammonium thiosulfate, potassium thionanate, sodium thiocyanate, or thioureas, thioethers, etc., as used in conventional fixing processes. I can do it.

Regarding the processing temperature of various processing steps other than color development, such as bleach-fixing and stabilization processing of the silver herodanide color photographic light-sensitive material of the present invention, it is preferable to carry out the processing at a temperature of 25° C. or higher from the viewpoint of rapid processing. Not particularly limited.

The stabilization treatment of the present invention is disclosed in JP-A-58-14834 and JP-A-58-14834.
No. 8-105145, No. 58-134634 and No. 5
Water washing alternative stabilization treatments as shown in No. 8-18631 and Special Application No. 58-2709 and No. 59-89288 are mainly used.

A water-soluble dye or a dye (AI dye) that is decolorized by a color developing solution can be added to the photographic constituent layer of the silver halide color photosensitive material of the present invention. Included are nol dyes, merocyanine dyes and azo dyes. 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, 6
No. 09, No. 1,277.429, Japanese Unexamined Patent Publication No. 48-85.
No. 130, No. 49-99, 620, No. 49-114.
No. 420, No. 49-129.537, No. 52-108
．． No. 115, No. 59-25,845, No. 59-111
．． No. 640, No. 59-111,641, U.S. Patent No. 2.
No. 274,782, No. 2.533.472, No. 2.9
No. 56.879, No. 3,125,448, No. 3,14
No. 8,187, No. 3,177,078, 1HJ3,2
No. 47,127, No. 3,260,601, No. 3,54
No. 0.887, No. 3,575,704, No. 3,653
．． No. 905, No. 3,718,472, No. 4,071,
Examples include those described in No. 312 and No. 4,070,352.

These AI dyes are generally present in the emulsion layer @52 per mole.
It is preferable to use X10-3 to 5X10-' moles,
More preferably, 1×10′″2 to I×10−′ mol is used.

The crystals of the silver halide grains may be normal crystals, twin crystals, or other crystals, and any ratio of [1,0,0) planes to (1,1,1) planes can be used. Furthermore, the crystal structure of these silver halide grains may be uniform from the inside to the outside, or may have a specific layered structure (core-shell type) between the inside and the outside. , these silver halides are of the type that mainly forms latent images on the autumn surface;
It may also be of a type formed inside the particles. Furthermore, tabular silver rhodanide grains (see JP-A-58-113934 and Japanese Patent Application No. 59-170070) can also be used.

In the present invention, non-rodanized silver particles are particularly preferably used in terms of rapid processing and improved stabilization of image dyes.
A core-shell emulsion that is substantially monodisperse is preferable.

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 grown by an acidic method or grown to a predetermined size by an ammonia method, which has a fast growth rate. When growing 710 silver halide grains, the noise in the reaction vessel, pAg, etc. are controlled, and the amount of silver 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 ions and halide ions sequentially and simultaneously.

Preferably, the silver halide grains according to the present invention are prepared as described above. Compositions containing commercially available silver halide grains are referred to herein as silver halide emulsions.

These silver halide emulsions contain activated gelatin; sulfur sensitizers such as allylthiocarbamide, thiourea, cystine; selenium sensitizers; reduction sensitizers such as stannous salts, thiourea dioxide, 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 chloroparadate, potassium chlorooleate and sodium chloroparadate (these Depending on the amount, they act as sensitizers (70) or capri inhibitors, etc., either alone or in combination as appropriate (e.g., a combination of gold sensitizers and sulfur sensitizers, gold sensitizers, etc.). Chemical sensitization may be carried out by using a combination of a sensitizer and a selenium sensitizer, etc.).

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. At least one type of telocyclic compound may be included.

The silver halide used in the present invention is mixed with a suitable sensitizing dye in an amount of 5 x 10-8 to 3 x 1 per mole of silver halide in order to impart photosensitivity to a desired wavelength range.
Optical sensitization may be achieved by adding 0 to 3 moles.

Various sensitizing dyes can be used, and each sensitizing dye 'ff can be used alone or in combination of two or more. Examples of sensitizing dyes that can be advantageously used in the present invention include the following.

That is, as sensitizing dyes used in blue-sensitive silver halide emulsions, for example, West German Patent No. 929,080 and U.S. Pat.
, No. 231,658, No. 2,493,748, No. 2,
No. 503,776, No. 2,519,001, No. 2,9
No. 12,329, No. 3,656,959, No. 3,67
No. 2,897, No. 3,694.217, No. 4,025
, No. 349, No. 4,046,572, British Patent 1.
No. 242,588, Special Publication No. 44-14030, No. 52
-24844 etc. can be mentioned. In addition, examples of sensitizing dyes used in green-sensitive silver halide emulsions include, for example, U.S. Pat.
．． No. 072.908, No. 2,739,149, No. 2,
Representative examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. 945,763, British Patent No. 505,979, and the like. Further, as sensitizing dyes used in red-sensitive silver halide emulsions, for example, U.S. Patent No. 2,269,23
No. 4, No. 2,270.378, No. 2,442,710
Typical examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in Japanese Patent Application No. 2,454,629, and Japanese Patent No. 2,776,280. Furthermore, U.S. Patent 2,213.99
No. 5, No. 2,493,748, No. 2,519,001
Cyanine dyes, merocyanine dyes or composite cyanine dyes such as those described in German Patent No. 929.080 and others can be advantageously used in green-sensitive silver halide emulsions or red-sensitive silver halide emulsions.

These sensitizing dyes may be used alone or in combination.

The photographic material of the present invention may be optically sensitized in a desired wavelength range by a spectral sensitization method using cyanine or merocyanine dyes alone or in combination, if necessary.

A typical particularly preferred spectral sensitization method is 111J
, t, Japanese Patent Publication No. 1973- Concerning the combination of benzimidazocal with cyanine and benzoxazolocarbocyanine
No. 4936, No. 43-22884, No. 45-1843
No. 3, No. 47-37443, No. 48-28293,
No. 49-6209, No. 53-12375, JP-A-5
No. 2-23931, No. 52-51932, No. 54-8
No. 0118, No. 58-153926, No. 59-116
Examples include methods described in No. 646 and No. 59-116647.

Further, regarding combinations of Cal cyanine with a penzi-ξdazole nucleus and other cyanines or merocyanine, for example, Japanese Patent Publication Nos. 45-25831 and 47-11
No. 114, No. 47-25379, No. 48-38406
No. 48-38407, No. 54-34535, No. 55-1569, JP-A-50-33220, No. 50
-38526, 51-107127, 51-
No. 115820, No. 51-135528, No. 52-1
No. 04916, No. 52-104917, and the like.

More penzoxaglocal? Examples of combinations of cyanine (oxa-cardocyanin) and other cardocyanins include Japanese Patent Publications Nos. 44-32753 and 46.
-11627, Japanese Unexamined Patent Publication No. 1483/1983, and Japanese Patent Publication No. 38408/1983 regarding merocyanine.
No. 48-41204, No. 50-40662, JP-A No. 56-25728, No. 58-10753, No. 5
No. 8-91445, No. 59-116645, No. 50-
No. 33828 etc. are mentioned.

Regarding combinations of thiacarbocyanin and other carbocyanins, for example, Japanese Patent Publications Nos. 43-4932, 43-4933, 45-26470, and 46
-18107, No. 47-8741, JP-A-59-1
The method described in Japanese Patent Publication No. 14533 and the like, and further using zeromethine or dimethine merocyanine, monomethine or trimethine cyanine, and nutiryl dye, can be advantageously used.

In order to add these sensitizing dyes to the silver halide emulsion according to the present invention, a dye solution such as methyl alcohol, ethyl alcohol, acetone, dimethylformamide, or fluorinated alcohol described in Japanese Patent Publication No. 40659/1984 is used in advance. It is used by dissolving it in a hydrophilic organic solvent.

The addition may be made at any time such as at the start of chemical ripening of the silver halide emulsion, during ripening, or at the end of ripening, and in some cases, it may be added at a step immediately before coating the emulsion.

Each of the silver halide emulsion layers according to the present invention can contain a coupler, that is, a compound capable of reacting with an oxidized product of a color developing agent to form a dye.

As the above-mentioned couplers that can be used in the present invention, various yellow couplers, magenta couplers and cyan couplers can be used without particular limitation. These couplers may be of the so-called 2-equivalent type or 4-equivalent type of kazoler, and it is also possible to use a diffusible dye-releasing coupler or the like in combination with these couplers.

The yellow coupler includes an open-chain ketomethylene compound and an active point compound called a so-called 2-equivalent type canoler.
〇-aryl substituted coupler, active point -〇-acyl substituted coupler, active point hydantoin compound substituted coupler, active point urazole compound substituted coupler, and active point succinimide compound substituted camera-1 active point fluorine substitution force f-1
+, active point chlorine or bromine substituted couplers, active point -0-sulfonyl substituted cassoles, etc. can be used as effective yellow couplers. Specific examples of yellow couplers that can be used include U.S. Pat.
, No. 551,155, No. 3,582,322, No. 3,
No. 725,072, No. 3,891,445, West German Patent No. 1,547,868, West German Patent Application No. 2,219,91
No. 7, No. 2,261,361, No. 2,414,006
No., British Patent No. 1,425,020, Special Publication No. 1984-10
No. 783, JP-A-47-26133, JP-A No. 48-731
No. 47, No. 51-102636, No. 50-6341, No. 50-123342, No. 50-130442,
No. 51-21827, No. 50-87650, No. 52
-82424, 52-115219, 58-9
Examples include those described in No. 5346 and the like.

Further, examples of the magenta coupler used in the present invention include pyrazolone-based, pyrazolotriazole-based, pyrazolinopenzimidazole-based, and indasilone-based compounds. These magenta couplers, like the yellow couplers, may be not only 4-stroke type canolas but also 2-stroke type canolas. Specific examples of magenta couplers include U.S. Patent Nos. 2,600.788 and 2,983.
, No. 608, No. 3,062,653, No. 3,127,
No. 269, No. 3,311,476, No. 3,419,3
No. 91, No. 3,519,429, No. 3,558,31
No. 9, No. 3,582,322, No. 3,615,506
No. 3,834,908, No. 3,891,445, West German Patent No. 1,810,464, West German Patent Application (OL
S) No. 2,408,665, No. 2,417,945, No. 2,418,959, No. 2,424,467,
Special Publication No. 40-6031, Japanese Patent Publication No. 51-20826,
No. 52-58922, No. 49-129538, No. 4
No. 9-74027, No. 50-159336, No. 52-
No. 42121, No. 49-74028, No. 50-602
Examples include those described in No. 33, No. 51-26541, No. 53-55122, and Japanese Patent Application No. 110943/1983.

Further, useful cyan couplers used in the present invention include, for example, phenol couplers, naphthol couplers, and the like. These cyan couplers may be not only 4-equivalent type couplers but also 2-equivalent type couplers like the yellow couplers. Specific examples of cyan couplers include U.S. Pat. Nos. 2,369,929 and 2,434,2.
No. 72, No. 2,474,293, No. 2,521,90
No. 8, No. 2,895,826, No. 3,034,892
No. 3,311,476, No. 3,458,315, No. 3,476,563, No. 3,583,971,
No. 3,591,383, No. 3,767,411, No. 3,772,002, No. 3,933,494, No. 4
, No. 004,929, West German Patent Application (OLS) 2,4
No. 14,830, No. 2,454,329, Japanese Unexamined Patent Publication No. 1973
-59838, 51-26034, 48-50
No. 55, No. 51-146827, No. 52-69624
No. 52-90932, No. 58-95346, Japanese Patent Publication No. 49-11572, etc. can be used.

Couplers such as non-diffusible DIR compounds, colored magenta or cyan couplers, polymer canolers, 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. 59-193611 by the applicant, and polymer canolers are described in Japanese Patent Application No. 1987-1 by the applicant.
The descriptions in No. 72151 can be referred to.

The method of adding the above coupler that can be used in the present invention to the photographic constituent layer of the present invention is conventional, and the amount of the above coupler added is not limited, but it is within the range of 1 mole of silver! IIIX
IO~5 mol is preferable, more preferably 1×10~5 mol
×10.

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, Color stain inhibitors, fluorescent whitening agents, color image fading inhibitors, antistatic agents, hardeners, surfactants, plasticizers, wetting agents, and the like can be used.

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

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, Holicar, l? N) film, polystyrene film, etc., and other ordinary transparent supports may also be used. These supports are appropriately selected depending on the intended use of the photosensitive material.

For coating the silver halide emulsion layer and other photographic constituent layers used in the present invention, various coating methods such as dipping coating, air doctor coating, curtain coating, and Hotno 9-coating can be used. Also, U.S. Patent 2.76
It is also possible to use a simultaneous coating method of two or more layers by the method described in No. 1.791 and No. 2,941,898.

In the present invention, the coating thickness of each emulsion layer can be set arbitrarily. For example, in the case of a full-color photosensitive material for photographic paper, 1 may be arranged in order from the support side as a light-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer. preferable. Each of these photosensitive silver halide emulsion layers may be composed of two or more layers, and the effects of the present invention are greatest when all of these photosensitive emulsion layers are substantially composed of silver chlorobromide emulsion. It is.

The light-sensitive material of this section has an appropriate thickness depending on the purpose. The J layer may be provided optionally, and various layers such as a filter layer, an anti-curl layer, a protective layer, and an antihalation layer may be used in appropriate combinations as constituent layers. In these +14 layers, a hydrophilic colloid y that can be used in the emulsion layer as described above can be similarly used as a binder, and can also be contained in the emulsion layer as described above. Various photographic additives can be included.

〔Example〕

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 silver halide color photographic light-sensitive material samples A1 to A24.

Layer 1...L2p/- gelatin, 0.32 p/ln
A blue-sensitive silver halide gelatin emulsion (silver halide composition and average grain size are shown in Table 1).

), a blue-sensitive silver halide emulsion layer containing a yellow coupler (y-1) of 0.80j'/- dissolved in 0.5097 m'' of dioctyl phthalate.

Layer 2-0.70917m” Noceratin, 10m97m
” anti-irradiation dye (AI-1), 5Tv/
- an intermediate layer consisting of (AI=2).

Layer 3...1.25p/- gelatin, 0.28p/-
green-sensitive silver halide gelatin emulsion (silver halide composition and average grain size are shown in Table IK), containing 0.6297 m'' of magenta cobra (M-1) dissolved in 0.3097 m'' of dioctyl 7 tallate. green-sensitive silver halide emulsion layer.

Layer 4: Intermediate layer consisting of 1.2P/- gelatin.

Layer 5 ・1.4 P/- gelatin, 0.2697 m"
red-sensitive silver halide gelatin emulsion (silver halide composition and average grain size are shown in Table 1), 0.201! A red-sensitive silver halide emulsion layer containing 0.45717 m'' of cyan cuff''2- (C-1) dissolved in /m'' of dioctyl phthalate.

Layer 6: Protective layer containing 0.50 p/- of 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 a general sensitizing dye with an increased color.

(AI-2) (Y-1) t Cノ(C-1) ShiL In addition, as a hardening agent, 2.4-dichloro-6-hydroxy-8-) riazine sodium was added to layers 2.4 and 6. inside,
Each gelatin film was added at a concentration of 0.02 F per gelatin IP, and after drying, the gelatin film swelling rate T1/2 was measured at 30° C. using the following color developing solution, and the result was about 7 seconds.

The measurement was carried out using a Lepenson type swelling meter.

Each of the photosensitive material samples A1-25 shown in Table 1 was exposed to light through an optical camera and then processed in the following steps.

Processing steps (38℃) Color development 60 seconds bleach-fixing 60 seconds stabilization 60 seconds drying 60-80℃ 12
The composition of each treatment solution for 0 seconds is as follows.

[Color developer] (Tank liquid) Pure water 800M Hydroxyamine sulfate 2.OF Potassium bromide 0.6F Sodium chloride 1.OF Potassium sulfite 2.OF Triethanolaone-2, Op Magnesium chloride 0.3F Potassium carbonate 40jl Pure Add water to make 11 and 20% potassium hydroxide or 10%
Adjust to m=11 with dilute sulfuric acid.

[Bleach-fix solution] (tank solution) Pure water 550++ J Thio (j
lt [Ammonium (70% aqueous solution) 85P Sodium hydrogen sulfite 10P Sodium metabisulfite 2F Ethylene sif'mintetraacetic acid-disodium 5F Add pure water to make 11, and adjust to -=7.0 with aqueous ammonia or dilute sulfuric acid .

A triazinyl stilbene type fluorescent whitening agent (listed in Table 1) was added to the tank solution of the color developer at 2F per liter of the color developer, and the color developing agent was set as CD-3. 151n of color developer per paper 100-
! , replenish 3 d of bleach-fix solution and 4.5 d of stabilizing solution to prepare the E version of the color paper (95.9 m”).
600 sheets were processed. The replenisher at this time is shown below.

At this time, a comparative fluorescent whitening agent (2) was used as a comparative example.

[Color developer replenisher]

Add pure water to make 11, 48% potassium hydroxide or 10
Adjust pli=12 with dilute #L acid.

[Bleach fixation replenisher]

[Stabilization treatment liquid] (tank liquid) (5-chloro-2-methyl-4-inthiazoline-3-
On 1.0PpF48.3 (adjusted with ammonia water and sulfuric acid) [Stabilizing replenisher] pH 8.4 (adjusted with ammonia water and sulfuric acid) The white background after continuous treatment was measured as the reflectance at 440 nm using Hitachi's 330 ultraviolet - Determined using a visible spectrophotometer. Also, 8
Table 1 shows the fading rate of the magenta dye after storage for 20 days at 0° C. and 70 RH.

[Color developing agent]

(CD-3): 3/2 H2SO4・H2O Comparative fluorescent whitening agent (1) According to the results in Table 1, there is no deterioration of the white background even with continuous processing or using triazinylstilbene type fluorescent whitening agent. It can be seen that compounds having -0R2 and -0R2, respectively, on the triazine ring are particularly preferable. It was also found that the whiteness of the solution was significantly improved even when the solution was carefully prepared.

(Example 2) Tank liquid voice 10.1 benzyl alcohol 15P/l
and 2.0 yl of exemplified compound (E-4) as a fluorescent brightener.
10.6 of the replenisher and 19 of benzyl alcohol.
V, 2.5 y/l of fluorescent brightener (Exemplary Compound E
-4) and processed 6000 8-size sheets continuously as in Example 1, the reflection temperature (440 nm) changed from 0.08 to 0.120 compared to the case of -11,0 continuous processing in Example 1, resulting in a white background. Deterioration and magenta fading rate from 24 to 52
%. Other E-17, E-18, E-24, E
Similar results were obtained with the exemplified compounds -30, E-34, E-35, E-36, and E-37. 1 yo voice 10, 1 yo 5
10.2 Perform continuous processing (at this time, the replenisher...
10.7) Similar results were obtained. However, p) 410.5
．． During the continuous treatment of 10.8, the same results as in Example 1 were obtained.

The above results indicate that when the pH is less than 10.3 and contains benzyl alcohol, white background deterioration is likely to occur due to continuous processing, whereas when the pH is 10.3 or higher, deterioration of white background deterioration and image storage stability can be prevented. found.

(Example 3) Continuous processing was performed in the same manner as in Example 1. Then, by changing the tank liquid of the color developer and the - of the replenisher, 8 size (1
02cm”) for a total of 600 pieces over 12 days.
A second person summarized the results of investigating the occurrence of linear precipitates near the wall of the liquid interface in the tank when zero sheets were processed. The fluorescent brightener used was E-4.

The precipitates in Table 2 represent the situation shown below.

Precipitates on the interface are +10 when more than ~1ml of precipitates are found on the liquid interface of the tank, +0 when less than ~1rnl,
There are times when you can barely detect it, but you can barely tell it's there, and times when it's completely absent.

m28 result, benzyl alcohol log
It has become clear that precipitation occurs during running, depending on whether P contains a solvent larger than 0.4 or whether it is a liquid.

(Example 4) Example 3 using E-17 in place of exemplified compound E-4
An experiment was conducted in the same manner. As a result, the same results as in Example 3 were obtained. E-18, E-24, E-30, E-3
Using the exemplified compounds of No. 4, E-35, E-36, and E-37, the same results as E-4 and E-17 were obtained.

Therefore, as long as a triazinyl stilbene type fluorescent brightener is used and benzyl alcohol is used at a pH of less than 10.3, linear precipitates seen on the liquid interface will not disappear; It has also been found that the use of a triazinylstilbene fluorescent brightener without alcohol has the effect of eliminating precipitates.

(Example 5) Continuous treatment was carried out in the same manner as in Example 3 using solvents with different HP values instead of benzyl alcohol. The results are shown in Table 3. @Photobrightener is Exemplified Compound E-4
was used.

As a result, the solvents with bgP of 0.4 or more were water and bgP0.
It was found that when the volume of the solvent is less than 4 liters, no precipitates are generated when the amount is 0.003 or less, but when it is more than 0.03, the generation of precipitates is likely to occur. . However, it has been found that the absence of a solvent with a log P of less than 0.4 is more effective in that linear precipitates do not appear.

(Example 6) In place of exemplified compound E-4 in Example, E-17, E-1
8, E-24, E-30, E-35, E-36, E-3
An experiment was conducted in the same manner as in Example 5 using Example 7. When an experiment was conducted in the same manner as in Example 5, Example 5
obtained similar results. From this, it was found that klgP had similar effects in different solvents. However, E-4, E-34, E-35, E-36, E-3
No. 7 seemed to generate slightly less precipitates.

(Example 7) When performing continuous processing in the same manner as in Example 2, the processing time 'fe
When the time was set to 180 seconds, exemplified compounds E-4 and E-17E
-18, E-24, E-30, E-34, E-35, E
-36 and E-37 both have a magenta dye fading rate of 25-3
It went from just 5% to 45-50%.

Although it was found from the above results that a longer processing time was not favorable for image preservation, it was also found that no major dye fading occurred if the processing time was 120 seconds or less.

(Example 8) Using silver chlorobromide shown in Table 4 among the samples of Example 1,
Samples were prepared by using silver halide markers such that the silver coating thickness of the blue, green, and red light-sensitive emulsions was the same as in Example 2, and using various hardening agent additives. The film swelling rate T1/2 of the sample after drying was measured using the above-mentioned color developing solution (processing temperature: 35° C.) using a Repenn/type swelling meter. Membrane swelling rate T1/2 is approximately 2 seconds, 5 seconds, 10 seconds, 20 seconds, 30 seconds,
A sample that took 40 seconds was selected and used in the experiment. This sample was treated in the same manner as in Example 1 by applying four lights and using the same treatment solution as in Example 1. The fluorescent whitening agent used at this time was E-4.

At this time, a fourth person summarized the fading rate of the cyan dye when the plant remained under sunlight irradiation for 30 days.

Table 4 From the results, it was found that the faster the membrane swelling rate, the better the photobleaching property of the cyan dye.

(Example 9) The amount of silver in the emulsion of Example 1 was the same, and AgBr, Ag
C no.

Example 1 of changes in the amount of benzyl alcohol and pH when continuously processing 6,000 8-size sheets by changing the abundance ratio of AgI
The fading rate of the magenta dye of the Canbeno matrix used in 20 days at 80 DEG C., 70 RH, and the maximum density obtained by developing with the solution immediately after preparation were determined and shown in Table 5.

From the fifth coating, when the silver iodide-containing emulsion was contained, the maximum linearity could not be obtained and the fading rate of the magenta dye was large.

(Example 10) When about 2000 sheets were processed in the same manner as in Example 9, the same results as in Example 9 were obtained. At this time, each component in the fifth coating was replenished at a concentration 1.25 times that of the tank liquid. As for the replenisher, -10.5 was used for -10.1, and -12 was used for pi-111.

(Example 11) Exemplary compound D-2 was used as the color developing agent in the same manner as in Example 9.
An experiment was conducted in the same manner as in Example 9 using Exemplified Compound D-8 instead of (CD-3), and almost the same results were obtained.

(Example 12) In the same manner as in Example 9, the concentration of the color developing agent was changed to 0. oos
mole //, 0.01 mole/1.0.02 mole/! When I changed it to 0. γ2 when o o smol/l
Although a decrease in Dm□ was observed and a slight decrease in Dm□, the results were almost the same as in Example 9 in other respects.

Furthermore, when Exemplified Compound (D-5) was used, the magenta dye faded significantly upon storage, which indicates that it is preferable to use D-2 and D-8 as herbal medicines.

It can also be seen that the crude drug concentration is preferably 0.01 mol/1 or more.

(Example 13) Continuous processing was performed in the same manner as in Example 1, but 12,000 sheets were processed.

At this time, a comparison was made between those containing hydroxylamine sulfate and those containing no hydroxylamine sulfate as in Example 1.

The results were shown to the 6th party.

As is clear from Table 6, white background 9 does not deteriorate only when it does not contain hydroxylamine sulfate. Even if hydroxylamine hydrochloride is used instead of hydroxylamine sulfate, the sixth
Similar results were obtained using hydroxylamine sulfate in the table. This result shows that the absence of hydroxylamine has the effect that deterioration of the white background does not occur even during long-term continuous processing. - (Example 14) Continuous processing was performed in the same manner as in Example 3, but the number of sheets processed was 12,000.

At this time, a comparison was made between those containing hydroxylamine sulfate and those containing no hydroxylamine sulfate as in Example 3.

The results are shown in Figure 7. The precipitation situation in this table is the same as in Table 2.

As is clear from the results in Table 7, it is clear that in the presence of a fluorescent brightener and in the absence of a hydroxylamine compound, the generation of linear precipitates does not occur even during long-term continuous treatment. .

Even when hydroxylamine hydrochloride was used instead of hydroxylamine sulfate, linear precipitates were observed, similar to when hydroxylamine cisulfate was present. Therefore, it has become clear that no linear precipitates are observed when hydroxylamine is not contained.

Patent applicant Roku Konishi Photo Industry Co., Ltd. Procedural amendment (method) % formula %] 2. Name of the invention Processing method for silver halide color photographic light-sensitive materials 3. Person making the amendment Relationship with the case Patent applicant address Tokyo 1-26-2 Nishi-Shinjuku, Shinjuku-ku Contact address: Konishiroku Photo Industry Co., Ltd., 1 Sakura-cho, Hino-shi, Tokyo 191 (0425-83-1521)
Patent Department 4, date of amendment order, May 20th, 1986 (shipping port), with a lot of insults)
- 〉 5. Description of the subject of amendment 6, engraving of the description of the contents of the amendment

Claims (8)

[Claims] (1) In a processing method in which a silver halide color photographic light-sensitive material consisting essentially of silver chlorobromide is processed in three steps: color development, bleach-fixing, and stabilization treatment, the color developer has a pH of 10.
3 or more, at least one of an N-sulfonamidoalkyl-substituted p-phenylenediamine color developing agent and an N-alkoxyalkyl substituted p-phenylenediamine color developing agent per 1 liter of color developing solution, at least 1.0 ×10
^-^ Contains 2 moles and the solvent is water and log P0.4
It is composed of a solvent in which the ratio of the volume of a solvent with a log P of 0.4 or more to the volume of a solvent with a log P of 0.4 or less is 0.003 or less, development is performed at 30° C. or higher and within 120 seconds, and a triazinylstilbene-based fluorescent brightener is used. 1. A method for processing a silver halide color photographic material, characterized in that the processing is carried out in the coexistence of a silver halide color photographic material. (2) If the color developer is water or a solvent other than water, the log P0
．． Claim 1, characterized in that it consists of less than 4 solvents and does not substantially contain any solvent with a log P of 0.4 or more.
Treatment method described in section. (3) The film swelling rate T1/2 of the emulsion film (binder) of the silver halide color photographic material is 15 seconds or less, and the color development treatment is performed at 30°C or higher for 20 seconds or more and 90 seconds or less. A method for processing a silver halide color photographic material according to any one of claims 1 to 2. (4) A silver halide color photograph according to any one of claims 1 to 3, characterized in that the total processing time of color development, bleach-fixing, and stabilization treatment is within 5 minutes. How to process photosensitive materials. (5) The halogen according to any one of claims 1 to 4, characterized in that a replenishing solution to a stabilizing solution during continuous processing of a color photographic light-sensitive material is carried out at a rate of 500 ml/m^2 or less. Processing method for silver chemical color photographic materials. (6) The method for processing a silver halide color photographic material according to any one of claims 1 to 5, wherein the color developer has a pH of 10.5 or more. (7) The method for processing a silver halide color photographic material according to any one of claims 1 to 6, wherein the color developer has a pH of 10.75 or more. (8) The method for processing a silver halide color photographic material according to any one of claims 1 to 7, wherein the color developing solution does not substantially contain hydroxylamine.