JPH01302352A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To reduce the replenishing amount of a color developer, and to accelerate the development processing of the title material by developing the photosensitive material comprising a silver halide emulsion contg. a sensitizing dye and silver chloride, with a specified color developer. CONSTITUTION:The photosensitive material comprises at least one layer of the silver halide emulsion contg. the sensitizing dye shown by formula I and >=80mol% silver chloride and is developed with the color developer which does not substantially contain a sulfurous acid ion, and the replenishing amount of the color developer is <=120ml per 1m<2> of the photosensitive material. In formula I, Z1 and Z2 are each an atomic group necessary for forming a benzoxazole or a naphthoxazole nucleus, etc., R1 and R2 are each alkyl group, R3 is hydrogen atom, methyl or ethyl group, X1<-> is an anion, (l) is 0 or 1. Thus, the replenishing amount of the color developer is reduced, without injuring the rapidity of the processing of the photosensitive material.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a method for processing a silver halide color photographic light-sensitive material, and in particular to a rapid silver halide color photographic light-sensitive material in which the amount of replenishment of a color developer is significantly reduced. The present invention relates to a development processing method, and at the same time, it relates to a processing method that has excellent color development and significantly reduces changes in photographic properties during continuous processing.

(Prior art) Processing of silver rodanide color photographic materials basically consists of two steps: color development (in the case of color reversal materials, the preceding monochrome first development) and desilvering. Desilvering consists of a bleach and fix step or a single bath bleach-fix step used in combination or alone. If necessary, additional processing steps may be added, such as washing with water, stopping processing, stabilizing processing, and pre-processing to accelerate development.

In color development, the exposed silver halide is reduced to silver and at the same time the oxidized aromatic primary amine developing agent reacts with the coupler to form a dye. During this process, halogen ions generated by decomposition of silver halide are eluted into the developer and accumulated. On the other hand, the color developing agent is consumed by the reaction with the above-mentioned coupler and forms a l-form. Further, other components are retained in the photographic material and taken out, and the concentration of the components in the developer decreases. Therefore, in a development method in which a large amount of silver halide photographic light-sensitive material is continuously processed using an automatic processor, etc., the components of the color developer are kept within a constant concentration range in order to avoid changes in the development finish characteristics due to changes in component concentration. We need a means to do so.

For example, if consumable ingredients such as developing drugs and preservatives are less affected by concentration, the concentration in the replenisher is generally kept high.

In addition, eluates such as halogens that have the effect of inhibiting development are
In some cases, its concentration in the replenisher may be reduced or it may not be included. Additionally, certain compounds may be included in the replenisher to eliminate the effects of eluates. Also pH
In some cases, the concentration of the alkali or chelating agent may be adjusted. As such a method, a method of replenishing a replenisher for supplementing the missing components and diluting the increasing components is usually used. However, replenishment of this replenisher inevitably generates a large amount of No. 1 bar flow liquid, which poses a major economic and pollution problem.

In recent years, there has been a strong desire to reduce the amount of developer replenishment for the purpose of speeding up the development process, saving resources, and reducing pollution. However, simply reducing the replenishment of the color developer may result in significant loss of photographic properties due to eluates from the light-sensitive material. For example, accumulation of bromide ions reduces development activity and impairs speed. Also, depending on the release and accumulation of sensitizing dye,
Photographic characteristics (gradation and minimum density) fluctuate. In particular, since the latter decomposes in the processing solution over time, the photographic characteristics vary depending on the amount of processing during continuous processing, causing serious problems in the quality of the finished product. Furthermore, during rapid processing, the latter may remain in the photosensitive material, which may increase the minimum density and cause so-called staining.

A number of techniques have been considered in the past to provide rapid processing despite low replenishment.

For example, it is known that one of the methods is to increase the pH of the developer and the processing temperature to speed up the processing. However, this method causes serious problems such as high fog, poor stability of the developer, and increased fluctuations in photographic properties during continuous processing. In addition, as another accelerating technique, a technique of adding various development accelerators is known, but the accelerating effect thereof is insufficient and unsatisfactory.

However, for the purpose of reducing the accumulation of bromide ions, which are strong development inhibitors, and speeding up the development,
4', No. j, No. j9-. 23.234tλ No. 7/
-70yo No. 52, International Publication (PC'1' Application) WOA'
No. 7-ops 3p discloses a method using a silver halide photosensitive material with a high silver chloride content, and is considered to be an effective means for reducing the amount of developer replenishment without impairing speed. However, if an attempt is made to reduce the amount of developer replenishment without sacrificing speed, the photographic properties will vary significantly during continuous processing, and floating matter, which is thought to be silver eluted from the light-sensitive material, will occur in the processing solution. New problems arose, such as contamination of the processing machine's rollers, clogging of the filter, and scratches and contamination of the photosensitive material, which proved to be impractical.

Currently, the amount of color developer replenishment varies somewhat depending on the photosensitive material to be developed, but is generally required to be about 60 to 8000 tnl/m2 of the photosensitive material to be processed. This is because, if the replenishment amount is further reduced without sacrificing speed, the extremely serious problem of large fluctuations in photographic properties and generation of floating matter in the developer will occur during continuous processing as described above. This is because there are many possible problems, and no technology has been found that can fundamentally solve these problems.

(Problems to be Solved by the Invention) Therefore, the first object of the present invention is to significantly reduce the amount of replenishment of the color developer without impairing the speed of processing, and improve the photographic properties, especially the minimum density, during continuous processing. An object of the present invention is to provide a developing processing method in which fluctuations in maximum density and gradation are small.

A second object of the present invention is to provide a development processing method that can significantly reduce the amount of replenishment of a color developer using a high silver chloride photosensitive material and that does not generate floating substances in the developer during continuous processing. be.

(Means for Solving the Problems) The objects of the present invention have been achieved by the method described below. That is, in the method of the present invention, /) a silver halide color photographic light-sensitive material is mixed with at least 7
In a method of continuous processing with a color developer containing various aromatic primary amine color developing agents, the following general formula (I
) and a silver rodanide emulsion containing a sensitizing dye represented by
A silver rodanide color photographic light-sensitive material is processed with a color developer which does not substantially contain sulfite ions and whose replenishment amount is not more than 2 dml υt per im2 of the silver rodanide light-sensitive material.・Processing method for silver rodanide color photographic material.

General formula (I) [wherein Zl and Z2 form a benzoxazole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a naphthoselenazole nucleus, a benzimidanol nucleus, a naphthimidazole nucleus represents the atomic group necessary to R1 and R2 each represent an alkyl group. R3 represents a hydrogen atom, a methyl group or an ethyl group. X□θ represents an anion, l
is O or /. ] Hereinafter, the present invention will be explained in detail.

In the S processing method, which uses a high silver chloride color photographic light-sensitive material with a silver chloride content of gO molar or higher and reduces the amount of developer replenishment, when the developer replenishment amount is reduced to 120 m1 or less per m2 of light-sensitive material, A color light-sensitive material containing a sensitizing dye of the general formula (I), a color light-sensitive material obtained by spectrally sensitizing the high silver chloride emulsion with a sensitizing dye of the general formula (I), is color developed without substantially containing sulfite ions. It was completely unexpected from the prior art that the fluctuation of photographic properties during continuous processing can be significantly improved by processing with a developing solution, and the generation of floating substances in the developing solution can be significantly prevented.

Sulfite ions usually have a function as a preservative for the developing agent, as well as a silver halide dissolving action and a reaction with the oxidized product of the developing agent, thereby reducing the dye-forming efficiency. In particular, when a photographic material containing a sensitizing dye represented by formula (I) is continuously processed with a processing solution that does not substantially contain sulfite ions, fluctuations in photographic properties and generation of floating substances are significantly reduced. This is worth noting. Because of this effect, fluctuations in the concentration of sulfite ions during continuous processing are presumed to be one of the causes of increased fluctuations in photographic properties as the developer replenisher is reduced. In addition, the floating matter that occurs specifically when a high-silver chloride photosensitive material with a high silver chloride content is continuously processed with a reduced amount of development replenishment is composed of silver eluted from the photosensitive material due to the action of sulfite ions. Presumed. However, these details are unknown.

In the present invention, the replenishment amount of the color developer is determined by the photosensitive material i,
In the prior art, it is unrealistic to reduce the number to 2 ornl or less due to the above-mentioned problems, but this has been made possible for the first time by the present invention. The lower limit of replenishment amount varies somewhat depending on the photosensitive material, but
The amount of replenishment of the developer may be within a range in which the amount of processing liquid taken out by the photosensitive material exceeds the amount of replenishment and the amount of processing liquid decreases, making continuous processing practically impossible. Usually, photosensitive materials/
Refill amount 1 cynl per m! is the amount at which the amount of processing liquid carried out by the photosensitive material and the amount of replenishment are approximately equal.

The replenishment amount of the color developer of the present invention is preferably 20rnl to 20rrtl, more preferably 30.1 to 80rnl per m2 of light-sensitive material. However, the amount of replenishment referred to here refers to the amount of so-called color developer replenisher to be replenished, and the amount of additives, etc. to compensate for deterioration over time and concentration is outside the replenishment amount of the present invention. . Note that the additive herein refers to, for example, water for diluting the concentrate, a preservative that easily deteriorates over time, or an alkaline agent that increases the pH.

The practice of this invention requires the use of color developers that are substantially free of sulfite ions. Here, the term "color developer substantially free of sulfite ions" refers to a processing solution containing sulfite ions of 5.0.times.10@-3 mol/l or less. j, Q x 80 mol/l means that a photosensitive material having a high chloride silver halide emulsion containing 80 mol or more of chloride is continuously processed at a developer replenishment amount of 20 ul or less per m2 of photosensitive material. This indicates the maximum value of the sulfite ion concentration within a range that does not affect photographic properties.

More preferably, it does not contain any sulfite ions. However, in the present invention, a very small amount of sulfite ion used to prevent oxidation in a processing agent kit in which the developing agent is concentrated before being mixed into a solution for use is excluded.

The developer used in the present invention needs to be substantially free of sulfite ions, and more preferably substantially free of hydroxylamine. this is,
This is because hydroxylamine acts as a preservative for the developer and at the same time has silver developing activity itself, and it is thought that fluctuations in the concentration of hydroxylamine greatly affect photographic properties.

As used herein, "substantially no hydroxylamine is contained" means that the developer contains only 80 moles/l or less of pr per liter of developer.

The method of the present invention is most effective when applied to continuous processing. Continuous processing here refers to continuous processing in which the processability is maintained constant by using means such as adding a replenisher to reduce fatigue of the processing solution due to development processing. It is necessary to have at least one layer of a high chloride silver halide emulsion consisting of silver chloride of ♂O molt or more, but if the amount of coated silver is 0#Og/rn2 or less, the development process will fail. This is very preferable in terms of speed of processing and prevention of the above-mentioned floating matter.

In the present invention, it is necessary that the color developer does not substantially contain sulfite ions, but in order to suppress the deterioration of the developer, it is necessary not to use the developer for a long time, and to suppress the influence of air oxidation, it is necessary to avoid using the developer for a long time. Physical means such as using a pig or reducing the opening of the developer tank, or chemical means such as suppressing the temperature of the developer or adding an organic preservative can be used. Among them, the method using organic preservatives is
This is advantageous in terms of simplicity.

The organic preservative according to the present invention refers to any organic compound that reduces the deterioration rate of an aromatic primary amine color developing agent when added to a processing solution for a color photographic light-sensitive material. In other words, they are organic compounds that have the function of preventing color developing agents from being oxidized by air, among others, hydroxylamine derivatives (excluding hydroxylamine; the same shall apply hereinafter), hydroxamic acids, hydrazines, hydrazides, and Fe/ -/l/, α-hydroxyketones, α
-aminoketones, sugars, monoamines, diamines,
Particularly effective organic preservatives include polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, and fused cyclic amines.

These are the patent application No. Sho t/-/≠7123, the patent application No. Sho t/-
173!9jt issue, same 6/-/Otsu! No. 62/, same J/-
11♂t/9, same t/-/9771.0, same t/-
/1661. / No. 4/-/Fr9f7 No. J/-
20/16/ issue, same A/-/It! ;! No. 4/-
/707! No. 4/-/J'J'7F, No. 2, J
/-/J'J'74! / issue, U.S. Patent No. j, t/! ,6
No. 03, Same°λ, Geta 4', No. 903, JP-A Showjλ-
/'+3020, Tokuko Sho 4#-304'ri No. 6, etc.

Regarding the preferred organic preservative, its general formula and specific compounds are listed below, but the present invention is not limited thereto.

The amounts of the following compounds added to the color developing solution are o, o
osmol/l-0,! t mol/l, preferably 0.0
3 mol/1-o1. ．． It is desirable to add it to a concentration of t mol/l.

Particularly preferred is the addition of hydroxylamine derivatives and/or hydrazine derivatives.

The hydroxylamine derivative is preferably one represented by the following general formula (II).

General formula (II) R-N-R12 H In the formula, R and R represent a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted aryl group, or a heteroaromatic group. represent. R
11 and 112 do not become hydrogen atoms at the same time, and may be linked to each other to form a trap heterocycle with a nitrogen atom. The ring structure of the Peter ring is a j-1 membered ring, and includes carbon atoms, hydrogen atoms, halogen atoms, oxygen atoms, nitrogen atoms,
It is composed of sulfur atoms, etc., and may be saturated or unsaturated.

It is preferable that R11 and R12 are an alkyl group or an alkenyl group, and the number of carbon atoms is preferably /-80, especially 7 to
j is preferred. Examples of the nitrogen-containing heterocycle formed by linking R11 and R12 include a py<lysyl group, a pyrrolysilyl group, an N-alkyl bilysyl group, a morpholyl group, an indolinyl group, and a benztriazole group.

Preferred substituents for R11 and R12 are a hydroxy group, an alkoxy group, an alkyl or polysulfonyl group, an amide group, a carboxy group, a cyano group, a sulfo group, a nitro group and an amino group.

Compound examples [-7 H [-,2 CH3QC2H4-N-C2H4-OCH3H ■-μ 1-T [-J- ■-Otsuro-7 1] -,1' The following are the hydrazines and hydrazides. preferable.

General formula (I) In the formula, R31, R32, and R33 represent a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, or a heterocyclic group, and R34 represents a hydroxy group, a hydroquinamine group, a substituted or Represents an unsubstituted alkyl group, 71J-l group, heterocyclic group, alkoxy group, aryloki7 group, carbamoyl group, or amine group. As a heterocyclic group, then! ~2
It is a membered ring, composed of C, H, OlN, S, and halogen atoms, and may be either saturated or unsaturated. X31
represents -CO-1 and is n\'io or /. Especially n
When =o, R34 represents a group selected from an alkyl group, an aryl group, and a heterocyclic group, and R and R may jointly form a heterocyclic group.

In the general formula (I[l), R, R, and R are hydrogen atoms or 01-
It is preferable that C1o is an alkyl group, especially R31
, R32 is most preferably a hydrogen atom.

In general formula (III), R is preferably an alkyl group, an aryl group, an alkoxy group, a carbamoyl group, or an amine group. Especially alkyl group 1. Substituted alkyl groups are preferred. Preferred substituents for the alkyl group here include a carboxynol group, a sulfo group, a nitro group, an amine group, a phosphono group, and the like. X is preferably -CO- or -502-, most preferably -○○-.

(Compound example) ■-/ ■-2 NH2NHmoCH2+7-8O3H NH2NH÷CH2+20H ■-g■-,t [1-7 NH2NHCONH2 ■-7 NHNHCOOC2H5 ■-r ■-ta■-80 NH2NHCONH2 1-// ■- 72 NHNH303H ■-73 NH NH2NHCNH2 ■-/ ≠ NH2NHCOCONHNH2 ■-/yoNHNHCH2CH2CH2S03I4111-/& ■-77 C4H9(n) 111-/J' NHNHCH2CH2C0OH 1-/ri[1- ,! 0 1-. 21 111-u) Use of the compound represented by the above general formula (n) or (III) in combination with the amines represented by the following general formula 1) or (V) improves the stability of the color developer. It is more preferable from the viewpoint of improving the stability during continuous processing.

General Formula (IV) In the formula, R, R, and R represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a heterocyclic group. Here, R and R, R71 and R73, or R72 and R73 may be linked to form a nitrogen-containing heterocycle.

Here, R, R and R may have a substituent. R7
1, R72, and R73 are particularly preferably a hydrogen atom or an alkyl group. Examples of the substituent include a hydroxyl group, a sulfo group, a carboxyl group, a rhodane atom, a nitro group, an amine group, and the like.

(Compound example) ■-7 N+CH2CH20H)3 ■-, 2 H2NCH□CH20H ■-J HN(-CH2CH20H)2 ■−μ OH C7■(I5N(CH2CH2I(20)■)2■-Evening ■－＝ ■-7 ■-f ■-7 IV-i.

(HOCH2CH2 Rikiu C■ (2CH2SO□CH3■
-// To■N(-CH2COOH)2 ■-72 ■-73 HNCHCH5O8NH2 ■-7tA ■-/j H2N-CHCH20H)2 ■-/6 ■-77 ■-/J' ■-/ri■-20 General Formula (■) In the formula, X represents a trivalent atomic group necessary to complete the condensed ring, R1 and R2 are an alkylene group, an arylene group,
Represents an alkenylene group or an aralkylene group.

Here, R1 and R2 may be the same or different.

Among general formulas (V), particularly preferred are general formulas (V-
These are compounds represented by a) and (V-b).

＼　　　＼ In the formula, X represents -/N or FCH.

R1 and R2 are defined as in general formula (V),
R represents the same group as R%R or l -CH2C-.

In the general formula (■-.), Xl is preferably N. The number of carbon atoms in R1, R2, and R3 is preferably 6 or less, more preferably 3 or less,
The most preferred case is .

R' and R1R are preferably an alkylene group or a 71J-vn group, most preferably an alkylene group.

In the formula, R and R are defined as in general formula (V).

In the general formula (■-b), the number of carbon atoms in R1 and R2 is preferably 6 or less. R1 and R2 are preferably an alkylene group or an arylene group, most preferably an alkylene group.

Among the compounds of general formulas (V-a) and (V-b), the compound represented by general formula (V-a) is particularly preferred.

V-/ ■−λ ■-Hiroshi −j ■-g ■-ta V-/.

■-/ / \par-/2 ■-/3 I, T 7 p ■-/s V-/A ~ r-77 ■-/I The above organic preservatives can be obtained commercially, but Other special neck A2-/u≠03g issue, same otsuko, 2≠
374 can also be synthesized by the method described in No. 374.

Next, details of the sensitizing dye represented by the general formula (+) will be explained.

In particular, it is noteworthy that by using the sensitizing dye of general formula (I), fluctuations in photographic properties during continuous processing due to low replenishment were significantly improved, and residual color was also reduced even during rapid processing. Worth it.

The sensitizing dye represented by the general formula ([) is preferably used in the green-sensitive emulsion layer.

The sensitizing dye represented by formula (I) is preferably used in the blue-sensitive emulsion layer.

In the general formula (I), the heterocyclic nucleus represented by Zl and Z2 is preferably a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, or a naphthoselenazole nucleus, and further a benzothiazole nucleus or a benzoselenazole nucleus. Preferred and most preferred are benzothiazole nuclei.

These nuclei may be substituted with various substituents,
Preferred substituents include a halogen atom, a hydroxyl group, a cyano group, an aryl group, an alkyl group, an alkoxy group, or an alkoxycarbonyl group. More preferred substituents include a halogen atom, a cyan group, an aryl group, an alkyl group or an alkoxy group having a carbon atom number of 1 to 3, and particularly preferred substituents are a halogen atom, a cyano group, a methyl group, an ethyl group, a methoxy group, and an ethoxy group. It is the basis.

R1 and R2 represent an alkyl group, and the alkyl group represented by R1 and R2 is preferably an alkyl group having a carbon atom number of 1 to 2, and an ethyl group, a propyl group, and a butyl group are particularly preferable. This alkyl group may be substituted with various substituents, and the preferred substituents are carboxyl and sulfo groups. In this case, a salt may be formed with an alkali metal ion, quaternary amines or ammonium ion. R
At least one of □ and R2 is preferably an alkyl group substituted with a sulfo group.

R3 represents a hydrogen atom, a methyl group, or an ethyl group (represented by f-, preferably a hydrogen atom).

Xθ represents an anion. Chloride ions, bromide ions, iodide ions, and lyluenesulfone are preferably ions.

l is an integer of O or l. Note that when at least one of R1 and R2 is a group that itself has a negative character, such as a carboxyl group or a sulfo group, l is 0.

Specific examples are shown below, but the invention is not limited to these.

CI-/　　　) (I-, 2) (I-j) (I-≠) <1-4) (I-A) ([-r) (I-2) CI-/fl)) (I-//) (CH2)3SO3■(・NET3 (I-/1 (I-/4') (J-it) (I-/4) (I-/7) (I-/J’) (I-/ri) (I-, 2/) (I-ko3) (C112) 4S (J3H・M compensation.

(I--2j) (l-16) (■-λ7) (I-=t) CI-,2F) (I-j/) (■-32) (I-3μ) (I-1j) (I -jA) (I-3Ir) (I-32) (I-3) (I-4'ko) (I-≠3) (I-4'4') (■-・zri General of the present invention Sensitizing dyes of formula (I) are described, for example, in British Patent No. tAOAOr and US Pat.
Gu280! It can be easily synthesized by the method described in the specification.

7.' / / /' / Usually, in order to spectral sensitize a silver halide emulsion, a method is used in which a spectral sensitizing dye is adsorbed onto the surface of the grains after the grains are completely formed. In contrast, U.S. Patent No. 2,73! , 7Al.

The issue discloses a method of adding a merocyanine dye during the precipitation formation of Rodan ratio particles, and states that it is possible to reduce the amount of dye that is not adsorbed. Also, Tokukai Akira! jr-, 2t! No. R discloses a method in which a spectral sensitizing dye is added and adsorbed during addition of an aqueous silver salt solution and a halogen salt aqueous solution to form silver halide crystal grains. In this way, the spectral sensitizing dye may be added during the formation of silver rhodanide crystal grains, after the formation is completed, or even before the formation begins.

Specifically, "before the start of grain formation" means that a spectral sensitizing dye is introduced into the reaction vessel in advance (7) before starting the reaction to form silver rhodanide crystals, and "during grain formation" means that the The term "after grain formation" refers to the method described in the patent of 1999, and "after grain formation" means adding and adsorbing after the substantial grain formation process has ended. is chemically sensitized after the completion of grain formation, but addition of a spectral sensitizing dye after the completion of grain formation does not result in chemical sensitization, whether before or during chemical sensitization. It does not matter whether the 7-layer emulsion is coated even after the completion of the printing process. In the present invention, it is preferable that the above-mentioned spectral sensitizing dye is added and adsorbed in at least one step after the step in which the formation of silver rhodanide grains is substantially completed. It is also possible to add it in portions over two or more processes. Further, within one step, the addition may be carried out intensively over a short period of time, or may be added continuously over a period of time. It is also possible to combine several such addition methods.

The spectral sensitizing dye to be added may be added as it is in the form of crystals or powder, but it is preferable to dissolve it by some method or disperse it. For dissolution, a water-soluble solvent such as an alcohol having from 3 to 3 carbon atoms, acetone, pyridine, methyl cellulose, or a mixed solvent thereof may be used. It is also possible to perform micelle dispersion or other dispersion using a surfactant.

The amount of spectral sensitizing dye added depends on the purpose of spectral sensitization and the content of the silver halide emulsion, but it is usually from /X80-6 mol to 1 xio-
2 mol, more preferably /x80-5 mol to J-X8
0-3 mol is added.

The spectral sensitizing dye used in the present invention may be used alone, but
Two or more compounds may be used in combination.

Along with the spectral sensitizing dye, it contains a dye that itself does not have a spectral sensitizing effect, or a supersensitizer that has no substantial absorption in the visible region but enhances the sensitizing effect of the spectral sensitizing dye. Good too.

The color developer used in the present invention will be explained below.

The color developer used in the present invention contains a known aromatic primary amine color developing agent. A preferred example is p-phenylenediamine, and representative examples are shown below, but the invention is not limited thereto.

])-/N,N-)Ethyl-p-22-2-diamine])-24Z-(N-ethyl-N-(β-hydroquinethyl)aminecoaniline D-32-methyl-gu[N- Ethyl-N-(β-hydroquinether)amino]aniline Du lI-amino-3-methyl-N-ethyl-N
-(β-methanesulfonamidoethyl)-aniline These p-phenylene diamino derivatives may also be in the form of salts such as sulfates, hydrochlorides, p-toluenesulfonates, and the like. The amount of aromatic-grade amine developing agent used is preferably about O1/g-20 g per liter of developer solution, more preferably at a concentration of about o, r to about log.

The color developer used in the present invention is preferably r+H
The color developer has a value of ~/λ, more preferably a value of ~//, 0, and the color developer may contain other known developer component compounds.

In order to maintain the above pH, it is preferable to use various buffers. Buffers include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate,
Sodium tetraborate (borax), potassium tetraborate, 0
- Sodium hydroxybenzoate (sodium salicylate), potassium 0-hydroxybenzoate, sodium j-sulfo-hydroxybenzoate (sodium S-sulfosalicylate), potassium j-sulfo-2-hydroxybenzoate (!-potassium sulfosalicylate) etc. can be mentioned.

The amount of the buffer added to the color developer is 0.7 mol/1
It is preferably at least 0.1 mol/l-0, particularly 0.1 mol/l-0,
Particularly preferred is ≠mol/l.

In addition, various chelating agents can be used in the color developer as an agent for preventing precipitation of calcium or magnesium, or to improve the stability of the color developer.

Specific examples are shown below, but the invention is not limited to these. Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, triethylenetetraminehexaacetic acid,
N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N'.

N'-tetramethylenephosphonic acid, /, 3-diamino-
2-propatoltetraacetic acid, transcyclohexanediaminetetraacetic acid, nitrilotripropionic acid, /1.2-diaminopronoξanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethylenediaminetriacetic acid, ethylenediamine orthohydroxyphenyl Acetic acid, -monophosphonobutane/I2. ≠-tricarboxylic acid, /-hydroxyethylidene-/, /-diphosphonic acid, NIN'-bis(-monohydroxybenzyl)ethylenediamine-N, N'-diacetic acid, catechol-3,! , t-) lysulfonic acid, catechol-3,
! -Disulfonic acid,! -sulfosalicylic acid, Hiro-sulfosalicylic acid, Two or more of these chelating agents may be used in combination as necessary.

These chelating agents may be added in an amount sufficient to sequester metal ions in the color developer. For example /l
It is about 0.7g to 80g per serving.

Any development accelerator may be added to the color developer, if necessary.

Examples of development accelerators include Tokko Sho 37-/1.01# and Sho 37-! ;917, 3g-7ff,! J issue, same 1.
tμ-/23g0, 4tj-taO/ri, and U.S. Patent No. 3,1/3,2≠7, etc.; ;0
-/j! p-phenylenediamine compound represented by No. J'1, JP-A No. 60-/3772, JP-A No. 4T4
No. t-3007, JP-A No. 4-/J & 12A, and No. f2-4L31i2, etc., and US Patent No. 2. A80. /-2 and the same≠
,//the law of nature.

p-Abataphenols described in US Pat. No. 1,762, US Pat. Hirori≠, ri03, same 3. /21. /8'2 No. 4t, 230, 7ri No. 6, No. 3, 233.

No. ri/ri, Special Publication No. 4'/-//4'3/, U.S. Patent No. j, 4'12, j! A, J, jlP [
, No. 92, No. 3, J12, Jμ No. 6, etc., Japanese Patent Publication No. 37-/1.01#, No. ≠λ-, 2! , No. 20/, U.S. Patent No. 3. /21,11
No. 3, Special Public Akihiro/-//413/ No. 4tλ-23r
♂ No. 3 and US Patent No. 3,! Polyalkylene oxides represented by No. 3.2, 60/, etc./-phenyl-3-pyrazolidones, hydrazines, methionic compounds, ionic compounds, imidazoles, etc. can be added as necessary.

Preferably, the color developer is substantially free of benzyl alcohol. Substantially means color developer/l per F)
2.0 ml or less, more preferably not at all. When it is not substantially contained, fluctuations in photographic properties during continuous processing are smaller and more favorable results can be obtained.

In the present invention, any anti-capri agent can be added as required. As anti-capri agents, alkali metal halides such as sodium chloride, potassium bromide, potassium iodide and organic anti-capri agents can be used. Examples of organic anti-capri agents include benzotriazole, 6-
Nidropenzimidazole, j-nitroinindazole,! -Methylbenzotriazole, j-nitropensotriazole, j-chlorobenzotriazole, cortiazolyl-benzimidazole, λ-teazolylmethylpenzimidazole, in'dandol, hydroxyazaindolizine, adenine Typical examples include nitrogen-containing heterocyclic compounds such as:

The color developer used in the present invention preferably contains a fluorescent brightener. As the fluorescent brightener, p,l-diamino-2,2'-disulfostilbene compounds are preferred. The amount added is 0-80g/l, preferably o, i
~6g/l.

Furthermore, various surfactants such as alkylsulfonic acids, arylphosphonic acids, aliphatic carboxylic acids, and aromatic carboxylic acids may be added as necessary.

The processing temperature of the color developer of the present invention is jO-j00C1, preferably 30 to 00C. Processing time is 20 seconds ~
j minutes, preferably 30 seconds to 2 minutes.

In the present invention, desilvering treatment is performed after color development. The desilvering step generally consists of a bleaching step and a fixing step, but it is particularly preferable that they are carried out simultaneously.

The bleach or bleach-fix solution used in the present invention may contain bromides (e.g., potassium bromide, sodium bromide, ammonium bromide), chlorides (e.g., potassium chloride, sodium chloride, ammonium chloride), or iodine. Rehalogenating agents such as ammonium iodide (eg, ammonyl iodide) can be included.

If necessary, one or more inorganic substances having pH buffering ability such as boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc. Acids, organic acids and alkali metal or ammonium salts thereof, or corrosion inhibitors such as ammonium nitrate, guanidine, etc. can be added.

The fixing agent used in the bleach-fixing solution or fixing solution according to the present invention is a known fixing agent, namely sodium thiosulfate,
Thiosulfates such as ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; ethylene bisthioglycolic acid; 3. These are water-soluble silver halide dissolving agents such as thioether compounds such as t-dithia-i and r-octanediol, and thioureas, and these can be used alone or in combination of two or more. Also, Tokukai Showtz-ijjt3! lI
Such as the fixing agent described in the issue and a large amount of potassium iodide...
A special bleach-fix solution consisting of a combination of rhodanides and the like can also be used. In the present invention, preference is given to using thiosulfates, especially ammonium thiosulfates. /
The amount of fixing agent per liter is preferably 0.3 to 2 mol, more preferably O0! ~/, in the range of 0 mol.

The pH range of the bleach-fix solution or fixer solution in the present invention is as follows:
3 to 80 is preferable, and 5 to 5 is particularly preferable.

If the pH is lower than this, the step-out property will be improved, but the deterioration of the liquid and the leucoization of the cyan dye will be promoted. On the other hand, if the pH is higher than this, desilvering is delayed and staining is more likely to occur.

In order to adjust the pH, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, bicarbonate, ammonia, caustic potash, caustic soda, sodium carbonate, potassium carbonate, etc. can be added as necessary.

The bleach-fix solution may also contain various other fluorescent brighteners, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol.

The bleach-fix solution and fixer solution used in the present invention contain sulfites (e.g., sodium sulfite, potassium sulfite,
ammonium sulfite, etc.), bisulfites (e.g. ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.), metabisulfites (e.g. potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.) ) and other sulfite ion-releasing compounds. These compounds are approximately 0.0 in terms of sulfite ion.
The content is preferably 0.60 mol/l, more preferably O0θhiro~o,t,to mol/l.

As a preservative, sulfites are commonly added, but other preservatives include ascorbic acid, carbonyl bisulfite adducts,
Sulfinic acids, carbonyl compounds, sulfinic acids, etc. may be added.

Furthermore, buffering agents, fluorescent brighteners, chelating agents, antifungal agents, etc. may be added as necessary.

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

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (the number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. this house,
The relationship between the number of flushing tanks and the amount of water in the multistage countercurrent method is described in the Journal of the Society of Motion.
Picture and Television Engineers (
Journal of the 5ociety
ofMotion Picture and
It can be obtained by the method described in Terevision Engineers, Vol. 6, p. 24'J', jt3 (J month issue, 1993!).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but this increases the residence time of water in the tank, causing bacteria to propagate and the resulting suspended matter to adhere to the photosensitive material. Problems such as In the processing of the color photosensitive material of the present invention, as a solution to such problems,
The method for reducing calcium and magnesium described in Japanese Patent Application Sho A/-/, 3/l=3.2 can be used very effectively. Also, Tokukai Akira! 7-♂! Intiazolone compounds and thiabendazoles described in No. λ, tf
Chlorine-based disinfectants such as fi-X sodium isocyanurate, other benzotriazole, etc., Hiroshi Horiguchi, "Chemistry of antibacterial and antifungal agents," Sanitary technology wire mesh "Sterilization, sterilization, and antifungal technology of microorganisms," Nihon Bo It is also possible to use the fungicides described in the "Encyclopedia of Antibacterial and Antifungal Agents" published by Kinryu.

In the processing of the photosensitive material of the present invention, p)-1 of the washing water is t~ri, preferably j-g'''C.The washing water temperature and washing time can also be set variously depending on the characteristics of the photosensitive material, the use, etc. Generally, /j-≠tOC for 20 seconds to 10 minutes, preferably 1
Actually 2! ~3θ seconds at ~riθ0C~! A range of minutes is selected.

Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water. In such stabilization treatment, Japanese Patent Application Laid-Open Nos. 37-4341!3 and 61-61
-/4tza 341, same Tata/g'134t3, same 6Q-2203 Hiroj, same to-23!132, same Otsu 0-. 23ri No. 711A, same t.

-! 377-digit number, same 1. /-480414' No. 2
All known methods described in /-//za74L7 etc. can be used. In particular, /-hydroxyethythelene-/, /-diphosphonic acid, j-chloro-λ-methyl-
A stabilizing bath containing isoteazolin-3-one, a bismuth compound, an ammonium compound, etc. is preferably used.

Furthermore, following the water washing process, a further stabilization process may be carried out; an example of this is a stabilizing bath containing phor-7rin and a surfactant, which is used as a final bath for color photosensitive materials for photography. I can do it.

The processing time of the present invention is defined as the time from when the photosensitive material comes into contact with the color developer until it exits the final bath (generally water washing or stable specific gravity). The effects of the present invention can be significantly exhibited in a rapid processing type in which the processing time is 30 seconds or less, preferably less than μ.

Next, details of the silver halide color photographic material used in the present invention will be explained.

The silver halide emulsion of the present invention consists essentially of silver chloride.

Here, "substantially" means that the content of silver chloride based on the total amount of silver halide is at least go mole, preferably at least j mole, more preferably at least j mole. From the viewpoint of rapidity, culms with a high silver chloride content are preferred. Further, the high silver chloride composition of the present invention may contain a small amount of silver bromide or silver iodide. This may have many useful benefits in terms of photosensitivity, such as increasing the amount of light absorption, strengthening the adsorption of spectral sensitizing dyes, or weakening desensitization caused by spectral sensitizing dyes. Furthermore, regarding the halogen composition of other emulsion layers that do not contain the sensitizing dye of general formula (I), the above-mentioned silver chloride
A molar coefficient or higher is preferable.

The coating silver amount of the silver halide emulsion of the present invention is preferably 0.1 g/m or less, more preferably 0.76 g/m or less and 3 g/m or more. Coated silver amount is 0. g/m or less is very preferable in terms of rapidity and prevention of the occurrence of staining.

The silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention may have different phases inside and on the surface, may have a multiphase structure such as a bonded structure, or may have a uniform grain structure as a whole. It may consist of phases. Moreover, they may be mixed.

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

The grain size of silver rhodanide may be fine grains of about 00.2 microns or less or large grains with a projected area diameter of about 80 microns, and may be a polydisperse emulsion or a monodisperse emulsion.

Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure 1. D), &/7 A
'l 3 (/97g year/-month) 1.2. ! ~
23 pages, '■, Emulsion pre
It can be prepared using the method described in "Paration and Types".

U.S. Patent No. 3.574t, Aλg, 3. Otsu! j, 3
Tag number and British patent cylinder 1. Monodisperse emulsions such as those described in II/3, 7 μg are also preferred.

Also, the aspect ratio is approx. Tabular grains such as those described above can also be used in the present invention. Tabular grains are described in ``Photographic Science and Engineers'' by Gutoff.
7f (Gutoff.

Photographic 5science an
dEngineering), Volume 1μ, 2'lr
~2!7 pages (/70 years); US patent tube≠, '13! I
, Koλ1, Dogu, ≠/≠, 380, ≠, Ko 33゜ot, tr, 4', 4'J, 320, and British Patent No. 1, /12,117, etc. It can be easily prepared by the method described.

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

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

The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening and spectral sensitization. Additives used in such processes are available from Research Disclosure Shop/
74≠3 and A/J' 7/6, and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in one of the research disclosures mentioned above, and the relevant descriptions are shown in the table below.

Additive type RD/7A! JRD/17/l
/ Chemical sensitizer page 23 page 8 right column λ
Sensitivity enhancer Same as above 3 Spectral sensitizer, pages 23-24L +lI, right column on page r ~ supersensitizer t≠right column on page ≠ brightener
-24' page j Antifoggant,! q ~ Coj page t≠Page right column ~ and stabilizer t Light absorber, 2j-jA page 6 wide page right column ~ Filter dye Tro page left column Ultraviolet absorber 7 Stain inhibitor Page 2j right column 630 Left to right column g Dye image stabilizer page 2j ta Hardener page 2 tri page left column 8
0 Binder, 24 pages Same as above//
Plasticizer, lubricant Page 17 tjO page right column/, 2
Coating aids, Tables 2t to λ7 Pages Same as above Surface activator/3 Static prevention Page 27 Same as above Stop agent Various color couplers can be used in the present invention, and specific examples thereof can be found in the above-mentioned research, disc o-ja (
RD) A/7A44J, ■-C-G.

As a yellow coupler, for example, U.S. Pat.
3. No. 601, No. 601, No. 022, No. t20, No. ψ,
3 pieces A, 02≠ issue, same issue μ, '40/.

7j No. 2, Tokko Akira! r-80732, British patent cylinder 1.
≠2, those described in No. 020, No. i, A7A, No. 760, etc. are preferable.

As magenta couplers, pyrazolone and pyrazoloazole compounds are preferred, and U.S. Pat.
0. t/ri No. 311゜niri No. 7, European Patent No. 73.636, U.S. Patent No. J, Ot/, 't3λ,
Same No. 3,726. OA7, Research Disclosure A24'-λ0 (/91≠June), JP-A-Sho-tO-
33J'! λ, Research Disclosure &2'
A230 (/98” June 1), JP-A-1.0-'A3
6!2, U.S. Patent No. 300.1i30, U.S. Patent No. μ
, jμo, tz4 are particularly preferred.

Cyan couplers include phenolic and naphthol couplers, as disclosed in the US patent.

Oj, 2, 1 no, 2, same no. ≠, /4'A, 3 ri no., same no. μ, -1, 233, same no.
2Qo issue, m 2nd. JA Ri, Tata issue, same No. 2. rO/
, No. 771, No. 2, 77, / & 2, No. r, t
9s, IsA No. 3,772,002, IsA No. J
, 7! r, No. 30&', No. v, 33μ, θ//
No., Hiroshi, 3 Core, No. 7.3, West German Patent Application No. 3,
3 Kota, 7 Kota No. 1, European Patent No. 1j/, 31tA, U.S. Patent No. 3, 4Z44J, t2 Kota, same No. 3
No. 33.922, No. 4, 4t! /,! ! No. ri, No. a
, <t, x7,717, European patent cylinder 16/, core lzA
Preferably, those described in No.

Colored couplers for correcting unnecessary absorption of coloring dyes are disclosed in Research Disclosure /71sμ3■-G section, U.S. Patent No.≠, /Otsu3゜A70, Special No.
No. 7-37'713, U.S. Patent Tube 4t, oop, 72
No. F, No. 'A, /31,2! No. R, British patent cylinder 1. /
4t1. ．． The one described in No. 3!1 is preferred.

Examples of couplers in which coloring dyes have appropriate diffusivity include U.S. Pat.
, 2! , No. 370, European Patent No. 370, West German Patent (Publication) No. 3. ．． 23μ, No. 533 is preferred.

Typical examples of polymerized dye-forming couplers are U.S. Patent No. J, 416/,! 2θ issue, same issue μ, orO,
Co//No., No. 3, No. 7, 2♂, British Patent Tube, 2
, 80, No. 73, etc.

Couplers that release photographically useful residues upon camping may still be preferably used in the present invention. The DIR coupler releasing the development inhibitor is the aforementioned RD/7Aψ3,
■-Patent described in Section F, JP-A No. 7-/jt/ri≠V, same! 7-/jftl 3'A, same to-ir
a, μg issue, US patent cylinder≠.

, 2≠g, those described in Ri No. 62 are preferred.

Couplers that release a nucleating agent or a development accelerator image-wise during development include British Patent No. Tar 1s7t3r, same! Those described in No./701≠0 are preferred.

In addition, examples of couplers that can be used in the photosensitive material of the present invention include competitive couplers described in U.S. Pat.

213, ≠ No. 72, Hiroshi No. 331, No. 3, No. 3, 380, 1. long-equivalent couplers described in JP-A No. 70-/IJ Reso, etc.; DIR redox compound-releasing couplers described in JP-A No. 173.30JA; couplers that release dyes that change color after separation as described in European Patent No. 173.30JA; etc.

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

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat.

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

JAj, West German Patent Application (OLS) No. 2. Yo4'/.

No. 274: and No. 2 of the same. ! It is described in G/, Ko 3o, etc.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, A/7 t'l J's λr page, and wholesaler/
and 7/B are listed from the right column on page A1+7 to the left column on page &4'J'.

Next, preferred embodiments of the present invention will be described below.

(I) The processing method according to claim 1, wherein the color developer does not substantially contain hydroxylamine.

(2) The amount of coated silver on the photosensitive material is 0, r Og/m
The processing method according to claim 1, characterized in that:

(3) A processing step in which a color development step is followed by a bleach-fixing treatment, followed by washing and/or stabilization treatment, and the total processing step time is ≠ minutes and 30 seconds or less. 2. A method for processing a silver halide color photographic material according to item 1.

(Examples) Examples of the present invention will be specifically shown below, but the present invention is not limited thereto.

(Effects of the Invention) According to the method of the present invention, the amount of color developer replenishment can be significantly reduced without impairing processing speed, and fluctuations in photographic properties, especially minimum density, maximum density, and gradation, are small during continuous processing. It has the excellent effect of being able to perform development processing. Further, according to the method of the present invention, the amount of replenishment of color developer can be significantly reduced by using a high silver chloride photosensitive material, and development processing can be performed without generating floating substances in the developer during continuous processing.

(Example) Examples of the present invention will be specifically shown below, but the present invention is not limited thereto.

Example 1 Multilayer color photographic paper A having the following N configuration was prepared on a paper support laminated on both sides with polyethylene.

The coating solution is prepared by mixing and dissolving an emulsion, various chemicals, and an emulsified dispersion of a coupler, and the respective preparation methods are shown below.

Preparation of coupler emulsion 27.2 cc of ethyl acetate and 7.7 cc of solvent (So 1v-1) were added to 19.1 g of yellow coupler (ExY) and 4.4 g of color image stabilizer (Cpd-1) and dissolved.
This solution was emulsified and dispersed in 185 cc of an 80% gelatin aqueous solution containing 8 cc of 80% sodium dodecylbenzenesulfonate.

Thereafter, emulsions for magenta, cyan, and intermediate layers were prepared according to this method.

The compounds used in each emulsion are shown below.

Yellow coupler (ExYl) Magenta coupler (EXM) CBHH7 (tj (ExQ) Cyan coupler (ExC2) Zero bar (Cpd-1) Color image stabilizer (Cpd 2) Color mixture prevention agent OH OH (Cpd ”) ((p d - 4) (Cpd-5) Color mixing inhibitor OH (cpd-6) 5:8:9 warm mixture of color image stabilizer (weight ratio) (cpd-7) Polymer-tl-CH2-CH+7 CONHC4Hgit) Average molecular weight 80 .000 (UV-1) Ultraviolet absorber"C<H9[2:9:8 mixture of UV (M ratio) (so+v-1) solvent (Solv-2) solvent 0=P-+0-C3H17) 3 (so+v-3) solvent o=p-(o-CgH19(iso))3(so+v-
4) The following dyes were added to the emulsion layer to prevent solvent irradiation.

To the red-sensitive layer, green-sensitive layer, and red-sensitive emulsion layer, the following compound was added in an amount of 2.6.times.80@-3 mol per mol of silver rodanide.

Next, a method for preparing the emulsion used in this example will be described.

Blue sensitive emulsion (liquid I) H2O8000CC NaC 5.5g gelatin
32g (2 liquids) Sulfuric acid (IN) 24cc (3 liquids) The following compound A (I%) 3cc (4 liquids) 11.7g NaC Add H2O 200cc (5 liquids) 35g AgNO Add H2O 200cc (6 liquids) NaC141, 3g K Ir0 sentence 6 (0,001%) 0,5
Add c cH2O, 600 c c
(7 liquids) A g N 03 120 gH2
(Liquid I) was heated to 76°C, and Liquid (2) and (Liquid 3) were added.

Thereafter, (liquid 4) and (liquid 5) were added simultaneously for 10 minutes.

After a further 80 minutes, (Liquid 6) and (Liquid 7) were added simultaneously over a period of 35 minutes. After 5 minutes of addition, the temperature was lowered and desalted.

Add water and dispersed gelatin to adjust the pH to 6.3, and form monodisperse cubic mounds with an average particle size of 1.1 gm and a coefficient of variation (standard deviation divided by average particle size: s/d) of 0.80. An emulsion was obtained.

To 1.0 kg of this emulsion, add blue spectral sensitizing dye (S-1).
Add 26cc of 0.6% solution of
The AKBr ultrafine grain emulsion was added at a ratio of 0.5 mol % to the host AgC1 emulsion, and mixed and aged at 58°C for 80 minutes. After that, sodium thiosulfate was added to optimally chemically sensitize the stabilizer (Stb-1) to 80-4
One mole of Ag was added. ' Green-sensitive emulsion (8 liquids) H2O8000Tnili NaC 3.3g gelatin
32g (9 liquids) Sulfuric acid (IN) 24d (I0 liquid) Compound A (I%) 3ml (I1 liquid) NaC 111,00g Add H2O 200 rubs (I2 liquid) AgNO332,00g Add H2O 200ml (I3 liquid) Na0 sentence 44. OOg
K I rcl (0,001$)
2. Added 3TngH2O and added 560ml (I4 liquid). Added 128g AgNo3 and H2O. 560ml (8 liquids) was heated to 52°C, and (9th liquid) and (I0 liquid) were added. Thereafter, (Liquid I1) and (Liquid I2) were added simultaneously for 14 minutes. After a further 80 minutes, (Liquid I3) and (Liquid I4) were added simultaneously for 15 minutes.

A sensitizing dye (S-2) was added to this emulsion in an amount of 1 mo of silver halide.
Add 4 x 80-4 mol per liter, and then add the following (I
5) was added over 80 minutes, and 5 minutes after the addition, the temperature was lowered and desalted.

Add water and dispersed gelatin, adjust the pH to 6.2, (liquid I5), add 5.60 g of KBr, and mix at 280 m at 158°C with Thio-FtMi.
Sodium was added and chemically sensitized appropriately, with an average particle size of 0.48 pm.

Coefficient of variation (standard deviation divided by average particle size; s/
d) A 0.80 monodisperse cubic silver chloride emulsion was obtained.

In addition, (Stb-1) was used as a stabilizer for 1s of silver halide.
Added 5 x 80-4+ol per ol.

For the red-sensitive emulsion, the sensitizing dye used was changed to (S-3) in the preparation method of the green-sensitive emulsion, and the amount added was changed to halogenated #
! A product was prepared in exactly the same manner except that the ratio was 1;5XiO-' mole per mole.

The compounds used are shown below.

(S-/) Sensitizing dye (compound ■-co0) (Stb-/)
Stabilizer (layer structure) The composition of each layer in this sample (multilayer color photographic paper) is shown below. The numbers represent the coating amount (g/m2). Silver halide emulsions represent coating amounts in terms of silver.

Support polyethylene laminated paper (white pigment (T i O2) on the polyethylene on the first layer side
and bluish dye (ulmarine blue)) Layer (blue-sensitive layer) Silver halide emulsion 0#J gelatin
'°t6 yellow coupler (Ex
Y) 0.12 color image stabilizer (cpa-/)
0. / solvent (So 1v-/)
o, 3j 2nd layer (color mixing prevention layer) Gelatin O, Tata color mixing prevention (
cpct-2) o, or third layer (green-sensitive layer) silver halide emulsion O,3t gelatin
/・24′ magenta coupler (
ExM) o, b0 color image stabilizer (cpa-J)
0.2! Pigment stabilizer (Cpd-≠) θ
, /2 Solvent (Solv-λ) θ, Hiroko Fourth layer (UV absorbing layer) Gelatin i, rr Ultraviolet absorber (UV-/) θ, 7u Color mixing inhibitor (Cpd
-j) 0.01 solvent (Solv-J)
0.2u 5th layer (red sensitive layer) Silver halide emulsion 0,2/gelatin
7.3 Gusian coupler (Ex
Blend of C/ and C2°/:/) θ, 34 is a dye stabilizer (Cpd-A) 0. /7 polymer (Cpd-
7) o, 30 Solvent (Solv-1) (I),, 2J Sixth layer (ultraviolet absorbing layer) Gelatin O1!3 Ultraviolet absorber (UV-/) 0.2/Solv
J) 0.61 Seventh layer (protective layer) Gelatin l/33 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 77%) o, i7 Liquid paraffin 0.0! The hardening agent for each layer is l-oxy-3,! -dichloroS-) using riazine sodium salt.

The nine samples obtained as described above were used as humans.

Next, the sensitizing dye (S
Samples B, C%D, E, and F were prepared in the same manner except that -/, I-,2(7) was changed as follows.

Sample Bl-/7 Sample Cl-2≠ Sample DI-≠! t Sample F The following central experiment was conducted to investigate the photographic properties of these coated samples.

First, using a sensitometer (FWH model manufactured by Fuji Photo Film Co., Ltd., color temperature of light source 3200K) on the coated sample,
A 14th floor corridor was provided for sensitometry. The exposure at this time was performed with an exposure time of //io seconds so that the amount of waste light was 0.000000000000 seconds.

After imagewise fogging, the above photosensitive material was subjected to continuous processing (running test) using the following processing steps and the following processing composition until twice the tank capacity of the color developer was replenished. However, the composition of the color developer was changed as shown in Table 1, and a running test was conducted for each of them.

Process the sensitometry at the start and end of the running test and determine the minimum concentration of blue (B) (Dmin).
Using a Macbeth densitometer, we measured the amount of change in maximum density (I) max ) and gradation (density difference from the point representing density 0.5 to the density point on the high exposure side of 0.3 at 80 gE) due to continuous processing. The results are shown in Table 1.

At the same time, the presence or absence of floating substances in the colored liquid was visually confirmed at the end of the run. The results are shown in Table 1.

Color phenomenon 1 phenomenon 3g”Cat! seconds FOxl r
l Bleach fixing 30~3AcC≠j seconds/Anal Il Rinse ■ 30~37℃ 30 seconds -4tl Rinse■
30~37℃ 30 seconds -IIL rinse■ 30
~37℃ 30 seconds -ooxl μl dry 7%J
Amount of replenishment per '0°C to second*photosensitive material/m2 (Rinse ■→■ Tank countercurrent method was adopted.) The composition of each processing solution is as follows.

Water rθOml
f 00ml ethylenediamine-N.

N,N,N-tetramethylenephosphonic acid, 3.0g Otsu, og organic preservation AIIA (7th uniform) 0.03mol
0.07mo1 sodium chloride Hiroshi, 2g
= Potassium carbonate 2 oz
λyogN-ethyl-N-(β-methanesulfona is doethyl)-3-methyl-≠-aminoaniline sulfate 6.0g //, 0g triethanolamine 80. Og 80.0g optical brightener (≠,≠'-cyabanosterbene type), 2. og ≠, Og sulfite) IJum See Table 1 Add water
/ 000rd / 000r11pH
(λj'c) 80.0o 80.1! Bleach-fix solution (tank solution and refill solution are the same) water
Ammonium thiosulfate (70%) 800 tl Sodium sulfite / 7 g Iron(III) ethylenediaminetetraacetate Ammonium 5g Ammonium bromide ≠Og Glacial acetic acid
Add tag water
1ooorttpH(2t'C)
r, 4t.

Rinse solution (tank solution and refill solution are the same) Ion exchange water (calcium, magnesium each jppm
Below) According to Table 1, samples A, B using the sensitizing dye of the present invention,
In cases C and D, by using the processes ①, ②, and ② of the present invention, changes in photographic properties during continuous processing are significantly small, stable photographic performance can be obtained, and at the same time color development is possible. There is also less generation of suspended matter in the liquid.

The effect is particularly remarkable in treatments (1) and (2) using the organic preservative of the present invention.

(Example 2) In Example/, in treatment ■, organic preservative [-/ is ■-λ,
When Sample A was processed in the same manner as in Example/, except for changing to 1ll-J-1ll-/j, lll-/A, and ■-27, good results were obtained with small changes in photographic properties during continuous processing. was gotten.

(Example 3) Silver halide emulsion (I) of a blue-sensitive silver halide emulsion layer was prepared as follows.

(Liquid L) (Liquid 2) Sulfuric acid (/N) 2o Kaku (Liquid 3) The following compound (7%) 3cc H3 (Liquid J) (Liquid J) (Liquid) (Liquid 7) (Liquid) ≦ It was heated to θ0C, and (liquid 1) and (liquid 3) were added. Thereafter, (liquid T/-) and (liquid J) were added simultaneously over a period of 60 minutes. (Hori liquid) and (! liquid) addition completed 70
After a minute, add (6 liquid) and (7 liquid) 2! It was added at the time of opening. After j minutes of addition, the temperature was completely lowered and desalination was performed. Water and dispersed gelatin whole eggs, pn set to 12.0, average particle size 1.0 μm coefficient of variation (standard deviation divided by total average particle size: s/d) 0. //A monodispersed cubic silver chlorobromide emulsion containing 1 mole of silver bromide was obtained. Triethylthiourea was added to this emulsion to perform optimal chemical sensitization.

Thereafter, the following spectral sensitizing dye (see Table 1) was added in an amount of υ7×80 mol per mol of silver halide emulsion. Further, the amount of applied S was changed as shown in Table 2.

Green-sensitive silver halide emulsion layer...Silver rhodanide emulsion (2)
And for the red-sensitive silver rhodanide emulsion (3) in the red-sensitive silver rhodanide emulsion layer, the same method as above was applied, the amount of chemicals,
By changing the temperature and addition time, v! 4 were made.

Spectral sensitizing dye (Sen) for silver halide emulsion (co)K
-2) is more than 1 mole of emulsion! ×80-' mol, and for silver halide emulsion (3), a spectral sensitizing dye (Sen
-J) was added to the emulsion in an amount of 1 mol and a pO of 6 ×/Q mol.

The shapes, average grain sizes, halogen compositions and coefficients of variation of silver halide emulsions (I) to (3) are as shown below.

Emulsion Shape Average grain No. Rodan Coefficient of variation Size Composition (μrrL) (Br molar ratio) (I) Cubic /, 00 /, 0 0. ///
(J) Cube O1≠j / , 0 0.0ヂ (3) Cube 0.3≠ /, 1 0.80 (S
en -/) Table 2 Sen-2 (Sen-J) Using the prepared silver halide emulsions (I) to (3), a multilayer color photographic material having the layer structure shown below was exploded. .

The coating solution was prepared as follows.

1st layer coating liquid preparation Yellow coupler (ExY) / ig, acetic acid x-J-
k27, 2CC and Solv-/)J.

rcc was added and dissolved, and this solution was emulsified and dispersed in a 1Q multi-gelatin aqueous solution/IICE containing 1 ozb of sodium dodecylbenzenesulfonate. P4 was prepared by adding r, oxio' moles of blue-sensitive sensitizing dye (Sen-/) per mole of silver to silver rhodide emulsion (I). The above emulsified dispersion and this emulsion layer were mixed and dissolved to prepare a first layer coating solution 94 having the composition shown below.

The coating solutions for the second to seventh layers were also subjected to vI4 splitting in the same manner as the coating solution for the first layer.

The gelatin hardening agent for each layer is l-oxy-3,j-
Dichloro-S-triazine sodium salt was used.

To the red-sensitive emulsion layer, the following compound was added in an amount of 80 moles per mole of silver halide.

In addition, to the blue-sensitive emulsion layer, Hi, oxio mol of hydroxyl-methyl-, J, 3a, 7-titrazaindey was added per mol of silver halide.

Also, for the blue-sensitive emulsion layer and the green-sensitive emulsion layer /-(j
-) tylureidophenyl) -yo-mercaptotetrazole per 7 moles of silver halide, respectively #) 1. ox
io mol, /, j×/0 mol was added.

Further, to the red-sensitive emulsion layer, zXio mol of core mercap)-/,j,≠-thiadiazole was added per mol of silver halide.

The composition of each layer is shown below.

(Layer structure) Paper support laminated on both sides with polyethylene support [white pigment on polyethylene on the first layer side: T r 02 (J, 7
g/rn2) Contains W taste dye (ulmarine blue)] Layer (blue sensitive layer) Silver halide emulsion (I) See Table λ Gelatin /, /J yellow coupler (ExY) 0. AA solvent (Solv-/
) 0.21 Second layer (color mixing prevention layer) Gelatin O, R Color mixing prevention agent (Cpd-/) 0, Or Solvent (S
QIV-/) o, 2° Solvent (Solv
-Co) O,Co0 dye (T-/)
0,003;'Third layer (green-sensitive layer) Silver halide emulsion (2) 0.30 Gelatin 06 Tatama magenta coupler (ExM-/) 0,25 Color image stabilizer (Cpd-
2) 0,80 color image stabilizer (Cpd-j)
o, or color image stabilizer (cpct-≠)
0.07 color image stabilizer (Cpd-z)
o, ol solvent (Sol v-2)
O1/Solv-J
0. /jt Fourth layer (ultraviolet absorption layer) Gelatin 1. ≠2 Ultraviolet absorber (UV-/) o, r, 2 Color mixing inhibitor (Cpd-/) 0.06 Solvent (Sol
v-4') 0.26 dye (T--2)
o, olj Fifth layer (red-sensitive layer) Silver halide emulsion (J) o, x2 Seratin /, Ot/Uncoupler (EXC-/) o, /A (ExC-,!
) o, i: Color f-image stabilizer (Cpd-1)
o, J, two-color image stabilizer/Cpd-7)
o, ir solvent (Solv-+)
o,/.

Solvent (Solv-s) o, i.

Solvent (Solv-&) 0. //Sixth layer (ultraviolet absorbing layer)
lv-4t) o, ox dye ('r
-2) o, oos 7th layer (protective layer) Gelatin 7.33 Horihini real alcohol ac-11-modified co-M combination (denaturation degree 77%) o, os flow fluidizing buff 1'0, OJ (EχY) yellow Coupler (ExM-/) Magenta Coupler 〇/ (Lxu/) Noan Coupler (I) Shima C-, 2) Noah/Coupler α The structure of the compound used is as follows.

(Cpd-/) Color mixing prevention agent H (Cpd-, color image stabilizer (Cpd-1) Color image stabilizer (Cpd-1) Stable dye reduction (Cpd-5) Color image stabilizer (Cp d-t) Color image stabilizer Average molecule two: to, oo.

(SOIV-/) Solvent (Solv-, 2) Solvent (Solv-J) Solvent (Solv-Hiroshi) Solvent (Solv-J) Solvent (CPD-7) Color Image Stabilizer C4H9(t) 4Z:, 2: j mixture (weight ratio) /2:80:3 mixture (weight ratio) (Solv-j) solvent (T-/) (T-2) The sensitizing dye and coating silver amount of the blue-sensitive layer are as shown in the table below. sample 20/, λθ-1,2Q3.20','.

and 201 were created.

Table 2 The above sample KO/~20! After imagewise fogging, the following process is carried out using a paper processing machine to reduce the capacity of the color developing tank to 2
Continuous processing (running test) was carried out until double replenishment.

Color current glI JI'Cto seconds 3Q resistance 1I-
l Bleach-fix 30~3A 'C4Lj seconds 2/! ml
+' l Stable 030~37℃ 20 seconds -2Z Stable ■ 30~37℃ θ seconds -, 21 Stable ■ 30~37℃ - Q seconds -21 Stable ■ 30~37℃ 30 seconds, 25O shoulder 1 21W Dry 70 -46'C 40 seconds This photosensitive material/, 26 times the light supplementing lid (stable ■→■ ≠ tank countercurrent system) The composition of each processing solution is as follows.

Water 80 (hxl
100ml ethylenediaminetetraacetic acid j, Og
! , Ogj, 4-dihydroxybenzene-72gutrisulfonic acid 0.3g 0.3g triethanolamine 1. Ogl, Og sodium chloride! , Hirog potassium carbonate 2'g 2! gN
-Ethyl-N-(β-methanesulfonamidoethyl)-3-methyl≠-Amineaniline sulfate j, Og /j, 0g Diethylhydroxylamine Hiroshi, 2g 80.0g Optical brightener (≠, San'- Diamino stilbene type) 2. Og j, add 0g water 7000112 8000xl
pH (2j 0C) 80.0! //,
00 bleach-fix solution (tank solution and refill solution are the same) water
≠00*1 Ammonium thiosulfate (70%) 800x! Sodium sulfite / 7g Ethylenediaminetetraacetate Iron (III) Ammonium! ! g ethylenediaminetetraacetic acid thorium acetate 5 g glacial acetic acid
Add tag water
8000rnlpH (jj'c)
Yo, ≠ O stable solution (tank solution and replenisher are the same) Formalin (37%) 0.1 g formalin-sulfite adduct 0.7 g
-Methyl-Hiroshi-Isotheazolin-3-one 0.02gλ-Methyl-Hiro-Isotheazolin-3-one 0.0Ig Sulfuric acid steel
0.006g ammonia water (2f
f%), 2. Add water
8000rrtlpH (ko!0C)
Gu,.

In the same manner as in Example/, Dmin associated with running processing
The changes in are shown in Table 3.

Table 3 According to the present invention, there is little increase in pmin (increase in stain) due to running, especially when the amount of coated silver is O8Ig/m2
The effect is remarkable in the following samples Ko≠ and 20j.

(Example 4) A running test was carried out in the same manner as in Example 3 except that the diethylhydroxylamine in the color developer in Example 3 was changed to an equimolar compound [[-/-. Excellent results were obtained in which the increase in Dmin was significantly small for O3 and λO!.

Claims (1)

[Scope of Claims] A method of continuously processing a silver halide color photographic light-sensitive material with a color developer containing at least one aromatic primary amine color developing agent, which comprises the following general formula (I):
A silver halide color photographic light-sensitive material having at least one layer a sensitizing dye represented by the formula and a silver halide emulsion containing 80 mol% or more of silver chloride, which substantially does not contain sulfite ions and whose replenishment amount is Silver halide photosensitive material 1m^
1. A method for processing a silver halide color photographic light-sensitive material, comprising processing with a color developer of 120 ml or less per color developer. General formula (I) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, Z_1 and Z_2 are benzoxazole nuclei,
Represents the atomic group necessary to form a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a naphthoselenazole nucleus, a benzimidazole nucleus, and a naphthoimidazole nucleus. R_1 and R_
2 each represents an alkyl group. R_3 is a hydrogen atom,
Represents a methyl group or an ether group. X_1^■ represents an anion, and l is 0 or 1. ]