JPH0256552A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve developing and desilvering properties by processing the photosensitive material which has silver halide emulsion layers contg. >=80mol% silver chloride and contains a specific hardening agent by using a specific color developing soln. CONSTITUTION:The photographic sensitive material which has the silver halide emulsion layers contg. >=80mol% silver chloride and contains the hardening agent expressed by formula I or formula II is processed by using the color developing soln. having <=3X10<-3>mol/l sulfite ion concn. and 3.5X10<-2> to 1.5X10<-1>mol/l chlorine ion concn. In formula, X1 denotes a halogen atom, N- methyrolamino group, glycidoxy group; Y1, Z1 denote H, halogen atom, -OH, -OM (M is an alkali metal ion), amino group, alkyl or phenylthioether group or sulfonamide, etc. The max. density is high and the desilvering is improved even if the development processing is rapidly executed.

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 more specifically, it relates to a method for processing a silver halide color photographic light-sensitive material, and more specifically, to a method for processing a silver halide color photographic light-sensitive material. The present invention relates to a development processing method with excellent desilvering properties.

(Prior Art) In recent years, in the photographic processing of color photographic materials, it has been desired to shorten the processing time due to the shortening of the finishing delivery time and the reduction of laboratory work. Common methods for shortening the time of each treatment step include increasing the temperature and increasing the amount of replenishment, but many other methods have been proposed, such as strengthening stirring or adding various accelerators.

In particular, for the purpose of speeding up color development and/or reducing the amount of replenishment, color photographic materials containing silver chloride emulsions have been developed in place of conventionally widely used silver bromide thread emulsions or silver iodide emulsions. There are known ways to treat it. for example,
International Publication WO 37104534 describes a method for rapidly processing a high silver chloride silver halide color photographic light-sensitive material with a color developer substantially free of sulfite ions and benzyl alcohol. However, if the development process is simply performed based on the above method, the minimum density after processing (D+
It was found that it had the disadvantage that it was 5 inches high and that the white background was contaminated.

Furthermore, it has been found that when a high-silver chloride color photographic light-sensitive material is rapidly desilvered, desilvering failure occurs.

As described above, in rapid processing using high-silver chloride color photographic light-sensitive materials, white backgrounds are affected due to an increase in the minimum density (Dmin) accompanying development processing, the occurrence of so-called staining, and the occurrence of desilvering defects during desilvering processing. It has become clear that there is a serious practical problem of significant contamination. JP-A-58-95345 and JP-A-59-23 as a method for suppressing the increase in minimum density (especially fog) that occurs during development in a rapid processing method using high silver chloride color photographic light-sensitive materials.
It is known to use organic antifoggants in No. 2342. However, its fog prevention effect is insufficient;
Furthermore, it has been found that the occurrence of desilvering failures due to rapid desilvering treatment is further increased.

Furthermore, in JP-A No. 61-70552, a highly chlorinated silver halide color photographic light-sensitive material is used, and during development, a replenishment amount is added in an amount that does not cause overflow into the developing bath, in order to reduce developer replenishment. The method is described in JP-A No. 63-106655.
For the purpose of stabilizing processing, the publication describes that a silver halide color photographic light-sensitive material in which the silver halide emulsion layer has a high silver chloride content is treated with a color developing solution containing a hydroxyamine compound and chloride at a predetermined concentration or higher. A method of processing is disclosed.

However, these methods were found to cause an increase in staining and poor desilvering due to the above-mentioned development treatment, and were not suitable for practical use.

(Problems to be Solved by the Invention) In the processing of conventional silver halide color photographic materials comprising high silver chloride emulsions, an increase in the minimum density after processing, ie, an increase in so-called stain, has become a problem. This is thought to be caused by the adhesion of tar particles and fog caused by oxidation of sensitizing dyes, dyes, and developing agents eluted from the light-sensitive material. In JP-A-63-106655, a special hydroxyamine compound is used as a preservative in the color developer, and the purpose is to stabilize the photographic performance even if the amount of replenishment is significantly reduced. It is still not satisfactory in terms of preventing staining.

On the other hand, if the bleaching of the silver image produced by color development is incomplete due to the formation of silver sulfide, the color of the color photograph (especially noticeable in the yellow areas) becomes blackish. It has been found that the formation of silver sulfide is particularly significant in high silver chloride photosensitive materials. Therefore, improving desilvering properties is an important issue, but
The method described in Publication No. 55 involves processing with a color developer containing chloride, which has little inhibitory effect on stabilized color development, and is not sufficient in terms of desilvering properties.

Therefore, the first object of the present invention is to provide a processing method that uses a silver halide color photographic light-sensitive material comprising a high silver chloride emulsion, is rapid, has a high maximum density, a low minimum density, and has improved developability. It is to provide.

A second object of the present invention is to provide a processing method that uses a high chloride silver halide color photographic light-sensitive material and has a reduced amount of residual silver and improved desilvering properties.

(Means for Solving the Problems) An object of the present invention is to provide a silver halide color photographic material,
A method of processing with a color developer containing at least one type of aromatic primary amine color developing agent, in which at least one layer contains a silver halide emulsion containing 80 mol% or more of silver chloride, and A silver halide color photographic light-sensitive material containing at least one hardening agent represented by formula (I) or (II) has a sulfite ion concentration of 3.
X10-3 mol/fL or less, chloride ion concentration is 3.5
This was achieved by a method for processing a silver halide color photographic light-sensitive material, which is characterized by processing using a color developer having a concentration of x10-2 to 1.5x10-1 mol/l.

(I) (I) (wherein, Xl is a halogen atom, N-methylolamino group, glycidoxy group, Yl is H, a halogen atom, -OH1
-0M (M is an alkali metal ion), amino group, substituted amino group (for example, substituents include phenyl, sulfonated phenyl, carboxylated phenyl, alkyl, sulfonated alkyl, carboxylated alkyl, hydroxyalkyl), alkyl or phenyl It represents an ether group, an alkyl or phenylthioether group, or a sulfonamide or alkylsulfonamide group.

(Z is selected from the same group as Y and may be the same as or different from Yl.) Chlorine ions are well known as one of the antifoggants, but their effect is small and even when used in large amounts, they do not increase fog. It was not possible to completely prevent the problem, but on the contrary, it had the adverse effect of delaying development and lowering the maximum density. Also,
It is known that when high chloride silver halide photosensitive materials are processed with a developer containing sulfite ions, color development deteriorates significantly due to the silver halide dissolving action of sulfite ions, but it is simply a developer that does not contain sulfite ions. There was no evidence that fog was suppressed by treatment. However, when using a high silver chloride photosensitive material using a hardening agent represented by the general formula (I) or (II), chloride ions range from 3.5xlO to 1.5x10-
The concentration is 3 mol/cross and the sulfite ion concentration is 3×1.
The fact that processing with a developing solution of 0-3 mol/M or less results in a low minimum concentration, a small amount of residual silver, and a marked improvement in developability and desilvering performance is unexpected and truly surprising. Was that.

Specific examples of hardeners represented by formulas (I) and (II) used in the present invention will be listed, but the present invention is not limited thereto.

■-1) C Dan■-2) ■-3) Be\ IN g ■-4) ■-5) I-12) [-13) I-14) ni 2 II ■ R I-9) I-10 ) 0 children l-11) NH to H20H Specific examples of the compound represented by the general formula (1) used in the present invention are given below.

l-1) fi CI+ I-3) l-4) Six groups l-5) Among the compounds represented by the general formula (I) or (II) of the present invention, particularly preferable ones are those in which xl is a chlorine atom. It is a compound.

Various Yl can be selected, and -0M (M is an alkali total ion), an alkylamino group or an arylamino group substituted with a water-soluble group such as a sulfonic acid or a carboxyl group are preferable.

Particularly preferred compounds are I-1, I-2, ■-4, l-1
It is 0.

In the present invention, the hardener may be added to the coating solution in advance, or may be mixed with the coating solution immediately before coating.

Furthermore, in the present invention, the hardening agent may be added to all of the photographic layers (for example, the light-sensitive emulsion layer, the intermediate layer 1 surface protective layer, the filter layer, etc.) coated on the support, or may be added to any layer ( −
It may be added to a layer (which may be a layer or a double image layer). The amount of hardening agent added is sufficient to harden gelatin, and is 0.5xlO to 10xlO per 100g of gelatin.
0x10-3 mol, preferably i, oxio ~30
It is preferable to use xlO-3 mol.

As a result of further intensive research, the present inventors have unexpectedly discovered that, in addition to the compound represented by the general formula (I) or (II), a compound having at least two vinylsulfonyl groups can be used in combination to cause staining. It has been found that this method is preferable in terms of prevention of silver removal, improvement in desilvering properties, strength of the coating film, and speed of hardening.

The compound having at least two vinyl sulfone groups preferably used in the present invention is a compound represented by the following general formula (m).

General formula (III) CH=CH5O-R-5o2CH=CH2R1□ is a divalent linking group, and is an alkylene group or a substituted alkylene group (substituents include halogen, hydroxyl group, hydroxyalkyl group, and amino group). , may have an amide linkage, ether linkage, or thioether linkage between them.

In the present invention, the chloride ion concentration of the color developer is 3.
5xlO to 1.5xlO-1 mol/l, preferably 4xlO to 1.0xlO-1 mol/l. If the chloride ion concentration is more than 1.5 x 10-'' mol/cross, it has the disadvantage of slowing down the development speed and does not achieve the objectives of the present invention, such as rapid development and high maximum concentration. If the amount is less than 3.5×10 −2 mol/liter, the minimum concentration and residual silver amount will be high, and the effects of the present invention will not be sufficiently obtained.

Here, the chlorine ions may be added directly to the color developer, or may be eluted from the photosensitive material in the developer. When added directly to color developers, sodium chloride, potassium chloride, ammonium chloride,
Nickel chloride, magnesium chloride, manganese chloride, calcium chloride.

Examples include cadmium chloride, among which preferred are sodium chloride and potassium chloride.

It may also be supplied as a counter ion to a fluorescent brightener added to the developer. When eluting from a light-sensitive material in a developer, it may be supplied from a silver chloride emulsion or from a fluorescent brightener.

In the present invention, the sulfite ion concentration of the color developer is
It is not more than 3X10' mol/liter, but preferably 0 to 1.
5X10-3 mol/9. Most preferably, it contains no sulfite ions.

If the content of sulfite ions is 3 x 1 O-3 mol/i or more, staining, especially fogging, will increase significantly, and the desilvering property will also deteriorate, which does not satisfy the object of the present invention.

In the present invention, the color developer is 3XlO-5 to 1X
It is more preferable to contain bromine ions of 10-3 mol/i from the viewpoint of staining and desilvering properties.In the presence of bromine ions with a concentration of 1XlO=mol/i or more, development progress and maximum density decrease. However, the object of the present invention cannot be achieved in this respect.

The fact that the presence of a trace amount of bromine ions of 3×10 −5 to 1×10 −3 mol/fL eliminates the above-mentioned drawbacks and further improves the staining and desilvering properties was unexpected and surprising.

In the present invention, the bromine ions present in the color developer may be added directly or eluted from the color photographic material.

In the present invention, the color developer contains 3X sulfite ions.
It is necessary to contain virtually no IO-3 mol/liter or less, but in order to suppress the deterioration of the developer, do not use the developer for a long time, and use a floating pot to suppress the effects of air oxidation. , physical means such as reducing the opening degree of the developer tank, chemical means such as suppressing the temperature of the developer, adding an organic preservative, etc. can be used. Among these, the method using an organic preservative is advantageous in terms of ease of delivery.

The organic preservative described in the present invention refers to any organic compound that reduces the deterioration rate of aromatic primary amine color developing agents when added to the processing solution of color photographic light-sensitive materials. These are organic compounds that have the function of preventing oxidation by air, etc. Among them, hydroxylamine derivatives (excluding hydroxylamine; the same applies hereinafter), hydroxamic acids, hydrazines, hydrazides, phenols, α-hydroxyketones .

Particularly effective organic preservatives include α-aminoketones, sugars, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, and fused cyclic amines. It is. These are Japanese Patent Application No. 61-147823, Japanese Patent Application No. 63
-30845, 63-21647, 63-44
No. 655, Japanese Patent Application No. 197760, Japanese Patent Application No. 1983-
No. 43140, Patent Application No. 198987-1987.

No. 61-201861, JP-A No. 63-43138,
European Patent Publication No. 254280, JP 63-44657
No. 63-44658, U.S. Patent No. 3,615,5
No. 03, No. 2,494,903, JP-A-52-143
No. 020, Japanese Patent Publication No. 4-30496, etc.

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

In addition, the amounts of the following compounds added to the color developing solution are o, oo
j mol/1P-0, j mol/l, preferably 0.03
It is desirable to add it at a concentration of 71-0.1 mol/l.

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

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

General formula (IV) R11N R12 In the formula, RR represents 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. al
l and 112 cannot be hydrogen atoms at the same time, and may be linked to each other to form a petero ring together with a nitrogen atom.

The ring structure of the Peter ring is a j-membered ring, composed of carbon atoms, hydrogen atoms, halogen atoms, oxygen atoms, nitrogen atoms, sulfur atoms, etc., and may be saturated or unsaturated.

It is preferable that R11R12 is an alkyl group or an alkenyl group, and the number of carbon atoms is preferably /-10, especially /~j
is preferred. Examples of the nitrogen-containing heterocycle formed by linking R and R include lysyl group, pyrrolysilyl group for pi, silyl group for N-alkylbi, morpholyl group, indolinyl group, penztrianyl group, and the like.

(Preferred substituents for 11 and R12 are hydroxy group,
Alkoxy group, alkyl or haaryl? These are a sulfonyl group, an amide group, a carboxy group, a cyano group, a sulfo group, a nitro group, and an amide group.

Compound Examples V-1 ■-5 V-6 ■-7 ■-8 Represents an amine group, substituted or unsubstituted alkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, carbamoyl group, or amine group. As a heterocyclic group, j
It is a ~6-membered ring composed of C, H, OlN, S, and halogen atoms, and may be either saturated or unsaturated. X
3L is -COC pea hydrazine The following are preferred as the hydrazide.

General formula (V) where I(rLR represents a hydrogen atom, substituted or unsubstituted alkyl group, aryl group, or heterocyclic group, R34
represents a hydroxy group, and 11 is O or /. In particular, when n=o, 1t34 represents a group selected from an alkyl group, an aryl group, and a heterocyclic group, and R and R may jointly form a hetero yJ2.

In general formula (V), R31R32 and R33 are preferably a hydrogen atom or a C1 to C1o alkyl group, and most preferably 11.31 1 (32 is a hydrogen atom).

In general formula (V), R is preferably an alkyl group, an aryl group, an alkoxy group, a carbamoyl group, or an amino group. Particularly preferred are alkyl groups and substituted alkyl groups. Preferred substituents for the alkyl/' group include a carboxyl group, a sulfo group, a nitro group, an amine group, and a ho-delta hono group.

X31 is preferably -CO- or -5O2-, and NHN
The most preferred case is HCOCH3 -C〇-.

(Compound example) NH2NHCOOC2l-(5 NH2NI-I-←CH2zo)7-3O3HNH2NH
÷CH2+20H NI-I 2NHCONI-I 2 ■-18 NHNH303H NHNl-ICl-12CI-I2COOH ■-13 NH NH2NHCNH2 ■-14 -2O NH2NHCOCONHNH2 NHNHCH2CH2CH2S03H V-λ / ■-16 ■-22 The above general formula (■) or ( The combined use of the compound represented by V) and the amine neck represented by the following general formula (Vl) or (■) improves the stability of the color developer, and further improves the stability during continuous processing. It is more preferable in this respect.

General formula (Vl) (Compound example) T-1 N(-CH2CH20H)3 Vl-2 I-12NCH2CH20H Vl-3 HN(-CI-I 2CH20I()2 In the formula, R71R
72R73 represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, an aralkyl group, or a heterocyclic group. Here, R71 and R72R and R or R and R may be linked to form a nitrogen-containing heterocycle.

Here, R71R72 and R may have a substituent. R71R72R73 is particularly preferably a hydrogen atom or an alkyl group. Examples of the substituent include a hydroxyl group, a sulfo group, a carboxyl group, a halogen atom, a nitro group, and an amine group.

■-4 Vl-5 Vl-6 H C7I-115N (CH2CI-ICH20H) 2l-
7 1-12NCH2CH2SO□NH2 Vl-8 ■-15 Vl-9 1-12N-C(-CH20H)2 ■-16 ■-10 Vl-17 Vl-11 1(N-(-CH2COOH)2 I-12 Vl -/rii -10 Among the general formulas (■), particularly preferred ones are the general formulas (W-
These are the compounds represented by a) and (■-b).

General Formula (■) In the formula, X represents a trivalent atomic group necessary to complete the condensed ring, and R1R2 represents an alkylene group, an arylene group, an alkenylene group, or an aralkylene group.

Here, RI R2 may be the same or repeated.

In the formula, Xl represents N or CH.

/ / R1 and R2 are defined in the same way as in the general formula (■),
R3 represents the same group as R1 and R2, or l -CH2C-.

\ In the general formula (■-a), Xl is -N/ It is preferable. The number of carbon atoms in RI R2 and R3 is preferably t or less, more preferably 3 or less, and most preferably λ.

rt', R2, R3ti are preferably an alkylene group or an arylene group, and most preferably an alkylene group.

■-3 In the formula, It R is defined in the same manner as in the general formula (■).

In general formula (vII-b), it is preferable that t(1, R2c7['lL number li) be as follows. R1112 is preferably an alkylene group or an arylene group, and most preferably an alkylene group.

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

■-l ■-4 ■-5 'III [-6 ■-2 ■-7 ■-8 ■-9 ■-10 ■-15 ■-16 ■-17 ■-18 ■-J ■-11 ■-12 ■=13 ■-14 The above organic preservative can be obtained as a commercially available product, but it can also be synthesized by the method described in Japanese Patent Application No. 2-/2-20031, No. 1.2-24'J744, etc. You can also.

The dregs-developing solution 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.

D-/N, N-diethyl-p-phenylenediamine D-,2hiro-[N-ethyl-N-9 (β-hydroxyethyl)amine coaniline D-32-methyl-≠-[N-ethyl-N -(β-hydroxyethyl)amine coaniline 1) -'7 Hiro-amino-3-methyl-N-ethyl-N-(β-methanesulfonamidoethyl)-aniline In addition, these p-phenylenediamine derivatives are It may be a salt such as a salt, an acid salt, a p-1-luenesulfonate, or the like. The amount of the aromatic-grade amine developing drug used is preferably in a concentration of about O0/g-20 g per liter of developer solution, more preferably from about O0j to about 10H.

The color developer used in the present invention is preferably p I
The color developer has a value of ~/2, more preferably a value of ~//, 0, and the color developer may contain other compounds as known developer components.

In order to retain the above-mentioned H, it is preferable to use various buffering agents. 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
- and sodium droxybenzoate (sodium salicylate), potassium O-hydroxybenzoate,! Examples include sodium -sulfo-λ-hydroxybenzoate (sodium j-sulfosalicylate) and potassium j-sulfo-λ-hydroxybenzoate (potassium j-sulfosalicylate).

The amount of the buffer added to the color developer is O01 mol/1
It is preferably at least 0.1 mol/l-0.
Particular preference is given to II mol/l.

In addition, it is used as a precipitant for calcium and magnesium in color developing solutions, or as a color developing agent ('IJK1.
Various chelating agents can be used to improve the stability of.

Specific examples are shown below, but the invention is not limited to these. Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, triethylenetetraminehexaacetic acid,
N,N,N-)rimethylene/phosphonic acid, ethylenediamine-N,N,N'N'-tetramethylenephosphonic acid, /
, J = diamino-2-pro,! ! Nortetraacetic acid, transcyclohexanediaminetetraacetic acid, nitrilotripropion #i, x-diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethylenediamine/triacetic acid, ethylenediamine orthohydroxyphenylacetic acid, λ -phosphonobutane-/,,,2, tricarbonic acid, /-hydroxyethylidene-/, l-diphosphonic acid, N, N'-
Bis(2-hydroxybenzyl)ethylenediamine-N
, N'-diacetic acid, kanaml-ruJ, ≠, &-)IJ sulfonic acid, catechol-3,j-disulfo7L j-sulfosalicylic acid, Hiro-sulfosalicylic acid, These chelating agents can be used as necessary. Two or more types may be used in combination.

These chelating agents may be added in an amount sufficient to sequester metal ions in the color developer. For example /l
The current pO,/g is about θg.

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

As the development accelerator, Japanese Patent Publication No. 37-/1 Orr, No. 3
No. 7-3'917, No. 3r-7rJA, Shihirohiro-/2
No. 310, Doko 5-ta O/R, and U.S. Pat. No. 3. r/
3, 2≠7, etc., thioether compounds, JP-A-Sho! 2-l tλri issue and the same! p-phenylenediamine compound represented by No. 0-/333≠, JP-A-Sho!
No. 0-/3772, Special Publication No. 4'4'-3007μ,
Hiro-grade ammonium salts disclosed in JP-A-Sho J-A-/jAg2I, No. 2-Ko3-Ko22, etc., U.S. Patent No. 2. z/θ, No. 122 and Dohiro, //ri.

p-Aminephenol M described in '71.2, US Percentage No. 2. ≠2 Hiroshi, No. 203, same J, /21, /
l'2, same ψ, 230,796, same 3,2 evening 3゜ri/ri, Tokuko Sho≠/-//'3/, U.S. Patent No. 2
, 'AI2, jl & No., 2, 69t, ri No. 16 and same J, j! , 2, amine compounds described in J4'& etc., Japanese Patent Publication No. 37-/1,0rr,
λ-2j, No. 20/, U.S. Patent No. 3. /21,11
No. 3, special public show 'i4/-//', '3/ No., same px-2
3rgJ and US Patent No. J, s32. It is possible to add polyalkylene/oxides represented by Roi, etc., phenyl-3-pyrazolidone, hydrazines, menionic compounds, ionic compounds, imidazoles, etc. as necessary.

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

In the present invention, any antifoggant can be added if necessary. As antifoggants, alkali metals such as sodium chloride, potassium bromide, potassium iodide, etc.
Logenides and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 2
−Nitrobenzimidazole,! - To nitroindazole, j-methylbensotriazono! - Nitropensotriazole, t-40 lobenzotriazole,! Typical examples include nitrogen-containing heterocyclic compounds such as -thiazolyl-benzimidazole, λ-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine.

It is preferable that the color retaining liquid used in the present invention contains a fluorescent whitening agent. As a fluorescent brightener, Hiroshi, ≠′−
Diamin-2'-disulfostilbene compounds are preferred. The amount added is 0 to 10 g/l, preferably 0,/
-,! ; g/l.

However, 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 2O-j00C1, preferably 30-'/-00C. Processing time is 4o seconds! minutes, preferably 30 seconds to λ 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 solutions used in the present invention may contain bromides (e.g., potassium bromide, sodium bromide, ammonium bromide), or chlorides (e.g., potassium chloride, sodium chloride, ammonium chloride), or iodides. (eg, ammonium iodide).

Boric acid, borax, metaboric acid (as required), acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc. More than one type of inorganic acid, organic acid, alkali metal or ammonium salt thereof, or a corrosion inhibitor such as ammonium nitrate or guanidine 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; water-soluble such as thioether compounds and thioureas such as ethylene bisthioglycolic acid, 3,6-cythyl, and za-octanediol This is a silver halide dissolving agent, and these can be used alone or in combination of two or more. Also, Tokukai Show 1! It is also possible to use a special bleach-fixing solution consisting of a combination of the fixing agent described in No. -/jj3j and a large amount of a halide such as potassium iodide. In the present invention, thiosulfate,
Particularly preferred is ammonium thiosulfate. The amount of the fixing agent per liter is preferably in the range of 0.3 to -mol, more preferably in the range of o, r to /, 0 mol.

The pH range of the bleach-fix solution or fixer solution in the present invention is as follows:
3 to 10 are preferred, and j to 1 are particularly preferred.

If the pH is lower than this, the desilvering performance is improved, but the deterioration of the solution and the leucoization of the cyan dye are accelerated. On the other hand, if the pH is higher than this, desilvering will be delayed and staining will likely occur.

To adjust the pH, add hydrochloric acid, sulfuric acid,
Nitric acid, acetic acid, bicarbonate, ammonia, caustic potash, caustic soda, sodium carbonate, potassium carbonate, etc. can be added.

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.
．． 2-0. ! The content is preferably 0 mol/l, and more preferably 0.0≠ to O3 θ mol/l.

Sulfites are commonly added as preservatives, 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 Engineering/Genius (
Journal of the 5ociety
ofMotion Picture and
'l'ervision Engineers) No. 6
It can be obtained by the method described in Hiromaki, pl, z<zza~2!3 (/rij, 3rd year j issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. The problem arises. In the processing of the color photosensitive material of the present invention, as a solution to such problems,
The method of reducing calcium urchin and magnesium described in Japanese Patent Application No. 1997/1997/3/132 can be used very effectively. In addition, chlorine-based disinfectants such as isothiazolone compounds and thiabendazole p1 chlorinated sodium incyanurate described in JP-A-7-43-1, and other benzotriazoles, "Chemistry of antibacterial and antifungal agents" by Hiroshi Horiguchi It is also possible to use the disinfectants described in ``Microorganism Sterilization, Sterilization, and Anti-Mold Technology'' by Sanitary Technology Kinsen, and ``Encyclopedia of Antibacterial and Antifungal Agents'' by Japan Antibacterial and Antifungal Science Kinsen.

The pH of the washing water in the processing of the photosensitive material of the present invention is ψ - 2, preferably j-J'. The washing water temperature and washing time can be set in various ways depending on the characteristics of the photosensitive material, its use, etc., but in general, /! Nlj'(:' selects a range of 20 seconds to IO minutes, preferably 2 evenings to 3Q seconds to j minutes.

Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water. In such stabilization treatment, Japanese Patent Application Laid-open No. 67-rJ-≠3,
/'ArJ'A, 69-/r≠34t3, AD
-2,203'lJ No. 60-2311'3.2,
Same tO-, 2J 7g≠ issue, same t.

-23 Ri 7 Buta No., same Otsu/-gu O Yuhiro No., same 2/-//
All known methods described in I'7117 and the like can be used. Especially /-hydroxyethylatene/,/
A stabilizing bath containing -diphosphonic acid, j-chloro2-methyl-4-inthiazolin-3-one, a bismuth compound, an ammonium compound, etc. is preferably used.

Further, following the water washing process, there may be cases where a further stabilization process is performed. For example, a stabilizing bath containing formalin and a surfactant, which is used as a final bath for color photosensitive materials for photography, may be further performed. When you give it up, you can make a toto.

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 stabilizing bath). The effects of the present invention can be significantly exhibited in a rapid treatment process that takes less than 30 seconds, preferably less than ψ.

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 10 molar or more, preferably J molar or more, more preferably T molar or more. From the viewpoint of rapidity, the higher the silver chloride content, the more preferable. 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 original absorption, increasing adsorption of spectral sensitizing dyes, or weakening desensitization caused by spectral sensitizing dyes.

The coating silver amount of the silver halide emulsion of the present invention is preferably 0. ♂g/m2 or less, more preferably 0.7 hirog
/m2 or less and 0.3g/m2 or more. Coated silver amount is 0,
．． When it is 1' g/m2 or less, it is very favorable in terms of rapidity and prevention of stain occurrence.

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 phase throughout the grain. It may consist of. 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 the silver halide may be fine grains of about 0,-2 microns or less, or large grains with a projected area diameter of up to about 10 microns, and may be a polydisperse emulsion or a monodisperse emulsion.

Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure (RD), Nippon/71. Group 3
(/ri7 to January/January) 1.2λ~λ3 pages, 1. Emulsion preparation and
It can be prepared using the method described in ``types''.

U.S. Patent Nos. 3,57, 62g, 3,6 and 3, and British Patent No. 1. Monodispersed emulsions such as those described in Hiroshi 73,7, etc. are also preferred.

Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described in Photographic Science and Engineering by Gutoff.

1'photographic 5science a
n4Engineerin1g), Volume 1, Volume 2, Volume 2
~2!7 pages (70 years): U.S. Patent No. μ, Hiroshi 341,
No. 22, Do Hiro, 4'/Hiro, No. 370, Do Hiro 4L, Hiro 3-
3゜o4tg No. 37,320 and British Patent No. 1. //, 2. It can be easily prepared by the method described in No./r7.

Even though the crystal structure is -like, the inside and outside are different...
It may consist of a chloride composition and 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 subject to Research Disclosure A/
7 A Ko 3 and A/J' 7/B, and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant descriptions are shown in the table below.

Additive type l Chemical sensitizer λ Sensitivity enhancer 3 Spectral sensitizer, super sensitizer G Whitening agent! Anti-fogging agents and stabilizers t Light absorbers, filter dyes UV absorbers 7 Anti-stinting agents/3 Pigment surface stabilizers Hardeners Binder plasticizers, lubricant coating aids, surfactants Static inhibitors RI )/7Agu3 p.23, 23-. 2j page, 2j page λ group 2j page, 2t~2 on page 2-evening page right column, 2j page, 2 & page 2 on page, 27 page 26-27 page 27 page RD/♂7/6 6hiro page right Column Same as above t μg Page right column - Hiro page Right column Hiro Page Right column - 2 Hi Page Right column - tSOS Left page tjo Page Left - Right column tjr / Page Left column Same as above tjO Page Right column Same as above Same as above This invention Various color couplers can be used, and specific examples are given in the Research Disclosure (
RD)A/7A4'J, ■-C-G.

Examples of yellow couplers include U.S. Patent Tube 3 and Ri 3.
3.30/No.≠, 022, 1,20, Hiromu, 3λt, No.02 Hiro, No. t, Hirooi.

No. 712, Special Publication No. 5R-to-7J, British Patent No. 11
Hiroshi, 2. t, No. 020, same No. 1. Hiro7j, 7Aθ
Preferably, those described in No.

As the magenta coupler, compounds of the Yoichi pyrazolone type and pyrazoloazole type are preferable, and US Pat.
0. A/RI No. 361゜tri No. 7, European Patent No. 73, tJA No. 3, US Patent No. 3. Ot/, ≠ No. 32,
No. 3, 7.2j, 067, Research Disclosure A 24' 220 (/rp year to month), JP-A-33112, Research Disclosure &amp;
2'lλ30 (t9rp June), JP-A-Sho tO-'13
No. 619, U.S. Patent No. 100.630,
Those listed in Yohiro, tr≠, etc. are preferable for moss.

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

062.2j No. 2, same No. Hiroshi, l≠6,32 No., same No. Hiroshi, 2.2g, No. 233, same No. G, 2ri t2.2θO,
Same No. 2,34, No. 927, Same No. 21g0/, No. 171, Same No. 1,772. /No. 1, 2, No. 2,192F, r
lt No. 3, 772, 00λ No. j, 7
31,. No. 301, No. 33'1,0//, No. ≠, No. 327.173, West German Patent Publication No. 3, 32, 7
．． No. 2, European Patent No. 12/343A, US Patent No. 3. Hiroshi 4'-A, & No. 22, Hiroshi No. 333,
Tatata-go, Dodai-Hiroshi, 4! Yui, SS No. 2, No. 1 Hiro, Hiro 27.7j No. 7, European Patent No. 11. / , &, ZJA
Preferably, those described in No.

Colored couplers for correcting unnecessary absorption of coloring dyes are available from Research Disclosure Shop/7 at Ko 3.
- Section G, U.S. Patent No. 13゜A70, Special Publication Shoyo 7
-32j13, U.S. Patent No. 11. oohiro, riλrigo,
Same No. ≠, /31. ．． ! Jg No. 7, British Patent No. 7. /Hiro A,
The one described in No. 3t♂ is preferred.

Couplers whose coloring dyes have appropriate diffusivity include U.S. Pat. /,
Preferred are those described in No. 2, No. 570, European Patent No. 570, and West German Patent (Publication) No. 3,23, No. 533.

Typical examples of polymerized dye-forming couplers are described in U.S. Patent No. 3. ≠No. 61.1.20, Hiroshi the same, Oza0,. 2/
/ No. 4', 3A7.212, British Patent No. 2,
10λ, No. 173, etc.

Couplers that release all photographically useful residues upon coupling can also be preferably used in the present invention. The DIR coupler releasing the development inhibitor is described above) [)/7&≠3
, Patent stated in Section ■-F, JP-A-Shoyu, 7-, /j
/ri4t4 number, same number 57-'/J41-234,
No. 1,0-/J'4', 2Ff, US Patent No.

λ≠r, those described in No. 62 are preferred.

Couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent No. 2,017, /≠θ,
Same No. ko°, /J/, lry issue, JP-A-69-/67
1.31 issue, same! Preferred are those described in No./7DruO.

In addition, examples of couplers that can be used in the light-sensitive material of the present invention include competitive couplers described in US Pat.

21'! , No. 4'7.2, No. 41,331,32
No. 3, Hiroshi No. 3, 310. A/r, etc., multi-equivalent couplers, JP-A-Sho AO-/Zajri SO, etc., DIR redox compound releasing couplers, European Patent No. 173.30
Examples include couplers that release a dye that recovers color after separation, as described in No. 2A.

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

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat. No. 2.322.027 and the like.

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

No. 3A3, West German Percent License a (OLS) Q, z, s
<t/.

, No. 27 and No. 2. j≠/, No. 230, etc.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, A/7x Hiro3's 2g page, and Okiya/17/l's &
4'74'7 to tμg page left column.

(Effects of the Invention) According to the photographic processing method of the present invention, even if a silver halide color photographic light-sensitive material made of a high silver chloride emulsion is rapidly developed, the maximum density is high and staining is prevented. It has the excellent effect of

Furthermore, according to the processing method of the present invention, even if a silver halide color photographic light-sensitive material comprising a high silver chloride emulsion is used and rapidly processed, the amount of residual silver is low and the occurrence of desilvering defects is prevented.
Desilvering properties can be significantly improved.

According to the processing method of the present invention, silver halide color photographic light-sensitive materials can be processed very quickly (usually within 60 seconds, and even within 45 seconds).
can be developed (in seconds or less).

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

Example 1 A multilayer color photographic paper A having the following layer structure was prepared on a paper support laminated on both sides with polyethylene.

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

Preparation of coupler emulsion Add and dissolve 27.2 cc of ethyl acetate and 7.7 cc of solvent (Solv-1) to 19.1 g of yellow coupler (ExY) and 4.4 g of color image stabilizer (Cpd-1), and dissolve this solution. The mixture was emulsified and dispersed in 185 cc of a 10% gelatin aqueous solution containing 8 cc of 10x sodium dodecylbenzenesulfonate.

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

The compounds used in these emulsions are shown below.

Yellow coupler (ExYl) Magenta coupler (ExM) (EXCI) Cyan coupler (Cpd-2) Color mixture prevention agent! (EXC2) (cpci-3) (Cpd-1) Color image stabilizer (Cpd-4) (Cpd-5) Color mixing inhibitor 0H (JH (Cpd-6) 5:8':9 mixture of color image stabilizer (Weight ratio) (Solv-2) Solvent 0÷p-(-o-c8 HI3) (Solv-3:) Solvent 0-P(-0-C,H59 (1so)) 3(Sol
v-4) Solvent (cpd-7) Polymer average molecular weight 8o, oo.

(UV-1) Ultraviolet absorber (Solv-1) The following dye was added to the emulsion layer to prevent solvent irradiation.

To the red-sensitive emulsion ff1K, the following compound was added in an amount of 2.6 x 10-3 moles per mole of silver halide.

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

Blue sensitive emulsion (1 liquid) 2O aCsL gelatin (2 liquids) Sulfuric acid (IN) (3 liquids) Compound A below (1%) 000cc 5.5g 2g 4cc cc (4 liquids) Add Na0 and H2O (5 liquids) A g N O3 Add H2O and 1.7 g 00cc g 00cc (6 liquids) NaC141,3g K Ir0 sentence, (0,001$) 0,5
c Add cH2O and 600cc (7 liquids) Add 120g820 of AgN03 and heat 600cc (1 liquid) to 76℃,
(Liquid 2) and (Liquid 3) were added.

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

After another 10 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 and adjust p)l to 6.3, average particle size 1.1 μm.

Coefficient of variation (standard deviation divided by average particle size: s/
d) A monodisperse cubic chloride lamp emulsion of 0.10 was obtained.

To 1.0 kg of this emulsion, add blue spectral sensitizing dye (S-1).
26 cc of a 0.6% solution of O,OS was added, and an AgBr ultrafine grain emulsion of O,OS was added at a ratio of 0.5 mol% to the host AgCA emulsion, and mixed and aged at 58°C for 10 minutes. . After that, ThioM and sodium acid were added to optimally chemically sensitize the stabilizer (Stb-1) at 10-
4 moles and 1 mole of Ag were added.

a Sensitive emulsion (8 liquids) 2O Na0 gelatin (9 liquids) Sulfuric acid (IN) (10 liquids) Compound A (1%) (11 liquids) Add aCI H2O (12 liquids) 0001j 3.3g 2g 4ml m1 11 , OOg 00ml gNO3 Add H2O and collect 32.00g 200 (13 liquids) NaC sentence 44. OOgK
Ir0 sentence, (0,001X) 2.3m!
Add tH2O and heat 560d (14 liquids) AgN03 Add 128gH2O and heat 560d (8 liquids) to 52°C.
(Liquid 9) and (Liquid 10) were added. After that, (11 liquids)
and (liquid 12) were added simultaneously for 14 minutes. After another 10 minutes, (Liquid 13) and (Liquid 14) were added simultaneously over a period of 15 minutes.

A sensitizing dye (S-2) was added to this emulsion, and a halogenated i1mo
Add 4 x 10-4 mol per liter, and then add the following (1
5 liquid) was added over 10 minutes, and 5 minutes after the addition, the temperature was lowered and desalination was performed.

Add water and dispersed gelatin, adjust the pH to 6.2, (15 liquids) KBr 5.60gH2O
and sodium thiosulfate at 280-58°C, chemically sensitized appropriately, and the average particle size was 0.48 JLm.

Coefficient of variation (standard deviation divided by average particle size; s
/d)0.10 monodispersed cubic silver chloride emulsion was obtained.

In addition, as a stabilizer, (Stb-1) was added to silver halide 1
5 x 10-' per mol! +101 was added.

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 7.
It was prepared in exactly the same manner except that the amount was 1.5×10″'4 moles per 11 moles.

The compounds used are shown below.

(S-1) Sensitizing dye (S-2) Sensitizing dye (S-3) Sensitizing dye (Stb-1) Stabilizer (Ikakai) Below is the composition of each layer in this sample (multilayer color photographic paper). The number represents the coating amount (g/m''), and the silver halide emulsion represents the coating amount in terms of silver.

Support polyethylene laminated paper (positive ethylene on layer-1 side contains white pigment (TiO□) and bluish dye (ulmarine blue)) Layer-1 (blue-sensitive layer) Silver halide emulsion 0.25 gelatin
1.86 yellow coupler (E
xY) 0.82 color image stabilizer (Cpd-1>
0.19 solvent (Solv-1)
0.35 second layer (color mixing prevention layer) Gelatin 0.99 color mixing prevention (
Cpd-2) 0.08 Third layer (green sensitive layer) Silver halide emulsion 0.31 Gelatin
1.24 magenta coupler (
ExM) Color image stabilizer (Cpd-3) Color image stabilizer (Cpd-4) Solvent (Solv-2) Fourth layer (ultraviolet absorbing layer) Gelatin ultraviolet absorber (UV-1) Color mixing inhibitor (Cpd-5) ) Solvent (Solv-3> Fifth layer (red-sensitive layer) Silver halide emulsion gelatin cyan coupler (blend of ExCl and C2゜l:1) Color image stabilizer (Cpd-6) Polymer (Cpd-7) Solvent ( Solv-4) 6th layer (ultraviolet absorbing layer) Gelatin ultraviolet absorber (UV-1) 0, 21 1゜0゜0.21 Solvent (SoJv-J) o, oza 7th layer (
Protective layer) Gelatin /, 33 Acrylic modified copolymer of polyvinyl alcohol (denaturation degree 17%) o, t7 Fluid rough-in 0.03 Hardener (I-1) 0
．． 09 The sample obtained as above was designated as A. Next, Samples B and C were prepared in the same manner except that the hardening agent Cl-1) used in Sample A was changed as follows.

D and E were created.

Sample B I-2 Sample CI-4 Sample D Formaldehyde sample E Dimethylol urea Samples A, B, C, D, and E were heated at 40°C 70% immediately after application.
It was stored in an RH atmosphere for 16 hours. In addition, samples B, C, and D were prepared so that the swollen film thickness at that time was almost the same as that of sample A.
, the amount of hardener added in E was adjusted.

In addition, the hardener used in the present invention was applied at
It was added directly to the coating solution kept at 0°C.

In order to examine the photographic properties of these coated samples, the following experiment was conducted.

First, using a photosensitive needle (FWH type manufactured by Fuji Photo Film Co., Ltd., color temperature of light source 3200K) on the coated sample,
Provided gradation exposure for sensitometry. The exposure at this time was carried out so that the exposure time was 1/10 second and the exposure amount was 250 CMS.

The above sample was processed using the following processing steps and the following processing composition. However, the composition of the color developer was changed as shown in Table 1.

Treatment process temperature Color development 3 Bleach fixing 30-36 Rinse ■ 3Q~37 Rinse ■ 3Q~37 Rinse ■ 30-37 Drying 7ONff0 time 'c 4!5 seconds 00 ≠ 3 seconds 'C3o seconds 'Cio seconds 'C3o seconds 00 40 seconds The composition of each treatment liquid is as follows.

color developer water Ethylenediamine-N.

N,N,N-tetramethylenephosphonic acid organic preservative A (I'1r-1) Sodium chloride Potassium carbonate N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-Hiroshi-Aminoaniline sulfuric acid Salt J, Og Triethanolamine 10.0g Fluorescent brightener (Hiroshi, q'-diaminostilbene type) Add sodium sulfite water and adjust pH (2j'c)? 00m1 J, Og O, OJmol See Table 1 3g 2.0g See Table 1 7000m1 io, or Bleach-fixing solution water 4t
001nl Ammonium thiosulfate (70%) l
o O,1 Sodium sulfite /
7g Iron ethylenediaminetetraacetate (■) Ammonium YomagDisodium ethylenediaminetetraacetate tgAmmonium bromide HiroOg Glacial acetic acid
Add 2g water
1000mlpH100OoC)
J-, Hiro 0 rinse solution (tank solution and refill solution are the same) Ion exchange water (calcium, magnesium each jppm
Below) Blue (B), fi color (G) of the above sensitometry,
The minimum density of red (R) (Din) and the maximum density of blue (B) (in Drxa) were measured using a Macbeth densitometer and the results are shown in Table 1.

At the same time, the light-sensitive material is uniformly exposed so as to obtain developed silver of 90% of the amount of silver coated, and then processed,
The amount of developed silver and the amount of residual IR were measured using fluorescent X-rays, and the results are shown in Table 1.

According to Table tjIJ1, sample A using the hardening agent of the present invention
Experiment No. 1 using the treatment of the present invention in ,B,C
As seen from 6 to 6, the maximum density is high and the minimum density is very low, and the amount of residual silver is also small.

In particular, one of the effects of the present invention is that the sulfite ion concentration in the developer is 3.0xlO-2 mol/9. It can be seen from the following that this is remarkable when the chlorine ion concentration is 4X10=~lXl0-1 mol/l.

Example 2 Same as Sample A of Example 1, except that hardener I-3
When changed to I-6, I-8, ll-1, ll-3 and processed with the developer of experiment No. 1 of the same example, the maximum density was high, the minimum density was low, and the amount of residual silver was small. Good results were obtained.

Example 3 Using Samples A and D of Example 1, the developability and desilvering properties were tested in the same manner as in Example 1.

The composition and treatment steps of each treatment liquid are as follows.

However, the chloride ion concentration and bromide ion concentration in the color developer were changed as shown in Table 2.

Processing process color development bleach fixing Rinse ■ Rinse■ Rinse ■ drying temperature r0c 30～JJ’C 30~J 7”C 30~37°0 30-37°C 7O-rOoC time pt seconds Gu! seconds 30 seconds 30 seconds 30 seconds to seconds color developer J’00m1 water Ethylenediamine-N.

N,N,N-tetramethylenephosphonic acid organic preservative A (1'V-1) Sodium chloride Potassium bromide Potassium carbonate N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-V- Aminoaniline sulfate triethanolamine fluorescent brightener (Hiroshi, San'-diaminostilbene type) Add water to pH (2j'c) ooomt 2.0g j, 0g 1o, oyo10, Og 3, Og 0 .03mol See Table 2See Table 2 3g Bleach-fix water 4'00 ml Ammonium thiosulfate (70%) 100ml
Sodium sulfite / 7g Iron ethylenediaminetetraacetate (■) Ammonium Disodium ethylenediaminetetraacetate 5g Ammonium bromide Glacial acetic acid
Add tag water
1000rnlpH(,2j'C)
s, ≠0 Rinse liquid (tank liquid and refill liquid are the same) Ion exchange water (calcium, magnesium each jppm
Below) The above color developer is applied to the aperture ratio (area of contact with air (cm)
)/Volume Ta (cm) ) 0.02cm-1c
7) Place it in a container and leave it at room temperature for one month, and measure the change in minimum concentration before and after aging, the maximum concentration after aging, and the amount of residual silver in the same manner as in Example 1, and the results are shown in the m2 table. Ta.

According to Table 2, as can be seen from Experiment Nos. 2 to 7 using the treatment of the present invention in Sample A using the hardener of the present invention, the minimum density difference before and after aging of the color developer is very large. , the maximum density was high, and the developability was improved. Furthermore, the amount of residual silver is small and the desilvering property is improved.

Among the present invention, when the bromide ion concentration in the color developer is 5xlO-5 to 4x10-' mol/JIL,
It can be seen that this is particularly preferable in terms of preventing staining and reducing the amount of residual silver.

(Example 4) Samples E~ were prepared in the same manner as Samples A and D of Example 1, except that the halogen composition of the emulsion was changed as shown in Table 3.

As in Example 1, the amount of hardener added to Sample J was adjusted so that the swollen film thickness was approximately the same as Sample E.

These coated samples were subjected to gradation exposure for sensitometry in the same manner as in Example 1.

The above sample was processed using an automatic vapor processing machine using the following processing steps and the following processing composition.

The composition of each treatment liquid is as follows.

color developer water Ethylenediamine-N.

N,N,N-tetramethylenephosphonic acid 3.0g Organic preservative A (V-19) 0. OJmoI Sodium chloride 3.0g Potassium carbonate 23g N-ethyl-N-(β-methanesulfonamidoethyl)-3-methylguamine aniline sulfate triethanolamine fluorescent brightener (Hiroshi, Hiro'-diaminostilbene type) Add sodium sulfite water and pH (λyo'c) j, Og 00ml io,og λ,og See Table 4 000mg 1o, os Bleach-fix solution water Hiroo
ammonium thiosulfate (7 (7%)
100ml sodium sulfite
/7g ethylenediaminetetraacetic acid iron (■) Ammonium jjgethylenediaminetetraacetic acid thorium acetate 5g ammonium bromide 4tOg glacial acetic acid
Add 7g water
1000 pH (-25OC)
s, Hiro O rinse solution (tank solution and refill solution are the same) Ion exchange water (calcium, magnesium, each jpp
m or less) The maximum concentration of blue (B) in the above sensitometry (Dma
x), the minimum density (Dmin) was measured using a Macbeth densitometer, and the results are shown in Table 4.

At the same time, the light-sensitive material was uniformly exposed so as to obtain developed silver of 90% of the coated silver amount, and then processed, and the developed silver amount and residual silver amount were measured using fluorescent X-rays. are shown in Table 4.

According to Table 4, in samples E to G using the C content and hardening agent of the present invention, Experiment No. 1 using the treatment of the present invention,
As seen from Nos. 1 to 6, the maximum density is high and the minimum density is low, showing good photographic performance, and furthermore, the amount of residual silver is small, and no desilvering failure is observed at all.

It can be seen that samples E and F, which have a carbon content of 95 mol % or more, have the highest concentration among the present invention, and are particularly preferable.

Example 5 Same as Sample E of Example 4, except that the hardener f-3 was changed to I-5, I-7, 1-12, 11-5, and experiment No. 1 of the same example was used. When processed with a developer, good photographic properties such as high maximum density, low minimum density, and small amount of residual silver were obtained.

Example 6 Silver halide emulsion (1) of the fg silver halide emulsion layer was prepared as follows.

(/liquid) NaCt j, J' g Sulfuric acid (/N) (3 liquids) The following compound (1%) +20cc CC (Horizontal liquid) (J liquid) (6 liquids) Add 20 (7 liquids) , 2 ff jcc (liquid 1) is heated by J (7'CK), (liquid 2) and (liquid 3)
was added. Thereafter, (≠liquid) and (liquid J) were added simultaneously for t0 minutes. (≠liquid) and (liquid J) addition completed 70
Minutes later, (solution 7) and (solution 7) were added simultaneously over a period of 2≠ minutes. Addition! The diameter and temperature were lowered and desalted. Add water and dispersed gelatin, adjust the pH to t, o, average particle size 1.0 μm coefficient of variation (standard deviation divided by average particle size; s/K) 0, / / , silver bromide 1 mol A monodisperse cubic silver chlorobromide emulsion with stripes was obtained. Triethylthiourea was added to this emulsion to perform optimal chemical sensitization.

Furthermore, thereafter, the following spectral sensitizing dye (Sen -/) was added to the silver halide emulsion (1 mol Schiff x 10' mol).

Silver halide emulsion in green-sensitive silver halide emulsion layer (2)
and the silver halide emulsion in the red-sensitive silver halide emulsion layer (
3) was also prepared in the same manner as above by changing the amount of chemicals, temperature and addition time.

A spectral sensitizing dye (Sen) was added to silver halide emulsion (2).
-2) was added at 5xlO-' mol per 1 mol of the emulsion, and for silver halide emulsion (3), a spectral sensitizing dye (Sen-
3) was added in an amount of 0.9×10 −3 mol per mol of emulsion.

Mol added.

The shapes, average grain sizes, halogen compositions and coefficients of variation of silver halide emulsions (1) to (3) are as shown below.

Emulsion Shape Average Grain Halogen - Coefficient of Variation Size
Composition (μm) (Br mol%) (1) Cubic /, 00 /, 0 0. ///
(k) Cube O2ψr i, o o, ori (3) Cube 0.3≠ /, 1 0,10 (S
en-/) (Sen-J) Using the prepared silver halide emulsions (1) to (3), a multilayer color X-sensitive material having the layer structure shown below was prepared.

The coating solution was prepared as follows.

1st layer coating liquid preparation Yellow coupler (ExY)/g, acetic acid solution J-
27, 2QC and solvent (Solv-/)j.

Add the mark ♂ and dissolve, and add this solution to an aqueous IO gelatin solution containing 70% sodium dodecylbenzenesulfonate sea urchin c/r! It was emulsified and dispersed in cc. On the other hand, 1 mole of silver was added to the silver halide emulsion (1) with a blue-sensitive sensitizing dye (Sen-/)! , 0x10' moles were prepared. The above emulsified dispersion and this emulsion layer were mixed and dissolved to prepare a first layer coating solution having the composition shown below.

The coating liquids for the second to seventh layer phases were also prepared in the same manner as the coating liquid for the first layer.

For the red-sensitive emulsion layer, 1 mole of silver halide was added to the following compound.1. x l0-3 mol was added.

Further, to the blue-sensitive emulsion layer, ≠-hydroxy-6-mether/, J, Ja, 7-titrazaindene was added in an amount of υ1.0×10 mol per mol of silver halide.

Furthermore, t-(t
-methylureidophenyl)-yo-mercaptotetrazole was added to 1 mol of silver chloride, respectively.pi, oxi
o mol, /, jxlO-3 mol was added.

Furthermore, for the red-sensitive emulsion layer, 2-amino-! -Mercap)-/, 3. 'I-thiadiazole was added at p2, jX/0 moles per mole of silver halide.

The composition of each layer is shown below.

(Layer structure) Paper support laminated on both sides with polyethylene support [white pigment: T r O2 (2.7 g/
-2) Contains dark dye (ulmarine blue)] -th layer (blue-sensitive layer) Silver halide emulsion (1) ol, 2A gelatin /, /3 Yellow coupler (ExY) 0.1. A solvent (SOIV
-/) o,, 2r second layer (color mixing prevention layer) Gelatin color mixing prevention agent (Cpd-/ Solvent (Solv-/) Solvent (Solv-, 2) Dye (T-/) Hardener (1-1) ,Ir?,or,,2 Q,20.00! Third layer (green-sensitive layer) Silver halide emulsion (2) Gelatin magenta coupler (ExM-/) Color image stabilizer (cpa-2) Color image stabilizer (cpa-3) Color image stabilizer (Cpd-≠) Color image stabilizer (Cpd-yo) Solvent (Solv-x) Solvent (Solv-J) Fourth layer (ultraviolet absorbing layer) Gelatin ultraviolet absorber (UV- /) Color mixture prevention agent (Cpd-/) Solvent (Solv-Hiroshi) Dye (T-, 2) Fifth layer (red-sensitive layer) Silver halide emulsion (3) See Table 2 O, Tata 0, +26 0. 10 o, or O,07 0,01 0,l O0/! ≠2 t λ 6 l j 0.22 Gelatin cyan coupler (ExC-/) (ExC--2) Color image stabilizer (cpct-x) Color image stabilizer (Cpd-7) Solvent (Solv-F) Solvent (Solv-j) Solvent (Solv-A) /, 06 o, it Q, / 3 Q, 3ko0, /1 0.10 0. 10 0, l 1 (ExY) Yellow coupler 6th layer (ultraviolet absorption layer) Gelatin ultraviolet absorber (UV-/) Solvent (Solv-μ) Dye (T-2) O, Hiroto o, ir o, or o , oar (ExM-/) Magenta coupler seventh layer (protective layer) Acrylic modified copolymer of gelatin polyvinyl alcohol (degree of modification! 7%) Liquid paraffin hardener (I-1), 33 o, or 0.03 Ol (ExC-/) Cyan coupler (Cpd-co) color image stabilizer α (ExC-u) cyan coupler (Cpd-j) color image stabilizer α The structures of the compounds used are as follows.

(Cpd-g) Pigment stabilizer (Cpd-/) Color mixing prevention agent (Cpd-yo) Color image stabilizer (S.

■-3) Solvent ■-Hiro) Solvent (cpct-1 Color Image Stabilizer (Sol) Solvent Average Molecular Weight: Q O0 (So 1 V -/) Solvent 2H5 (S01 ■-2) Solvent (Cpd-7) Color Image Stabilizer (S o 1 V-t) Solvent (T-/4t of C4H9(+): λ! Mixture (heavy metal ratio) /2 of (T-,2): 10:3 Mixture C weight ratio) Hard Samples 201 to 205 were created by changing the film agent as shown in the table below.

The above sample, 201-. After imagewise exposure of 20J, continuous processing (running test) was carried out using a paper processing machine in the following processing steps until twice the tank capacity for color development was replenished.

Color development JJ”Clo seconds JOmt bleach fixing 3
0~3J℃＜ztsec2/jml stable ■30~37℃2Q
Stable for seconds ■ 30-37℃, 20 seconds - Stable ■ 30-37℃, 20 seconds - Stable 030-37℃ for 30 seconds! 0go drying 'yo-rz°C to seconds * Photosensitive material 7rn2 per υ replenishment amount (stable ■→■ Hiro tank countercurrent method was used.

4(J Hiroshi Co1 λ1 The composition of each treatment liquid is as follows.

Water Ethylenediaminetetraacetic acid j, 4-dihydroxybenzene-72μm Trisulfonic acid triethanolamine J' 00rttl I 00m1j, Og
j, Og 0.3g r, og 0, Jg 1.0g Sodium chloride 1. Hirog potassium carbonate jig 2yogN
-Ethyl-N-(β-methanesulfonamide ether)-3-methyl Kazuhiro-aminoaniline sulfate j, Og /j, Og Organic preservative A (see Table 4) 0.03mof 0.08
mol Sodium sulfite See Table 4 Fluorescent brightener (IIL, 4''-diaminostilbene type) 2.0g j, add 0g water 1ooo go, 1000 gop
H (2yo'C) lo, oyo //, 00 Bleach-fix solution (Bleach solution and replenisher are the same water Ammonium thiosulfate (70%) Sodium sulfite Nislene diamine Tetraacetate Iron (III) Ammonium aooml 00ml / 7g 11g Disodium ethylenediaminetetraacetic acid Add glacial acetic acid water to pH (jj'c) Stabilizing solution (tank solution and replenisher are the same) Formalin (37%) Formalin-sulfite adduct-chloro-λ-methyl-glucinte Azolin-3-one λ-methyl-inteazolin-3-one Copper ammonia sulfate water (2 g head) Add water to pH (λjo() 5 g 5 g 000 ml, IIL 0 0, 7 g 0.7 g 0.0 + 2 g o, oig 0.00g 2, Oml 000me g, 0 Similarly to Example 1, the coating sample was heated with a photosensitive needle (FWH type manufactured by Fuji Photo Film Co., Ltd., color temperature of light source 320
0K) was used to provide gradation exposure for sensitometry. The exposure at this time was 250C with an exposure time of 1710 seconds.
The exposure amount was adjusted to be that of MS.

The sensitometry was processed at the start and end of the running test, and the blue (B), green (G), red (R
) The amount of change in the minimum concentration due to continuous treatment was measured using a Macbeth densitometer, and the results are shown in Table 5.

At the same time, the amount of remaining silver at the end of the running was measured in the same manner as in Example 1, and the results are shown in Table 5.

In Table 5, the replenishment amount of the color developer is 30 d per 1 m'' of the photosensitive material, and the chlorine ion concentration in the developer is only the amount eluted from the photosensitive material and may vary somewhat depending on the amount of silver coated.
The amount is approximately 1.0 to 1.4 x 10' mol/liter.

According to Table 5, as can be seen from Experiments Nos. 001 to 7 in which the hardener of the present invention was used and the treatment of the present invention was used, the increase in Dmin due to running was small and the amount of residual silver was small.

In particular, when the organic preservative is V-19 or IV-1, the effect is remarkable.

Example 7 Same as Sample 201 of Example 6, but.

When the hardener I-1 was applied in parts to all layers without changing the amount applied, favorable results similar to those in Example 6 were obtained.

Example 8 Same as Sample 201 of Example 6, but.

When the hardener I-3 was changed to I-5, l-10, l-12, and ■-4, and a running test was conducted using the developer of Experiment No. 1 in the same example, it was found that the minimum density increase due to running was Good results were obtained with a small amount of residual silver.

Example 9 In Experiment No. 1 of Example 6, the organic preservative A of the developer was IV-2, IV-7, IV-8, V-6, ■-17.
．． V-18, V-21, triethanolamine Vl
-3, ■-10, ■-12, ■-1゜■-4, ■-8 and ran a running test, the minimum density increase due to running was small, the amount of residual silver was small, and the results were good. was gotten.

Agent Gabushi Tori 165・-L'14" 4) □ Procedure Qj Seisho (spontaneous) 2. Name of invention Processing method for silver halide color photographic light-sensitive materials 3. Relationship with the person making the amendment Patent Applicant Address: 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name (52
0) Fuji Photo Film Co., Ltd. Representative: Minoru Ohnishi 4, Agent address: 3-7-3-6 Shinbashi, Minato-ku, Tokyo 105, Column 7 of "Detailed Description of the Invention" of the specification to be amended, Amendment Contents (1) Next to the third line of page 65 of the specification, a new line is written [In the present invention, in addition to the above-mentioned couplers, the following compounds are used as 9! It is preferable to use Particularly preferred is the combination with a pyrazoloazole coupler.

That is, a compound (F) that chemically bonds with the aromatic amine developing main system remaining after color development and *I# processing to produce a chemically inert and substantially colorless compound and/or color development treatment. A compound that chemically bonds with the oxidized product of the aromatic amine-based color-forming fjt acupuncture drug that remains afterward to form a chemically inert and substantially colorless compound (Gi can be used simultaneously or alone, for example, during treatment. This is preferable in that it completely prevents staining and other side effects due to the formation of coloring pigments due to the reaction between the color developing agent or its oxidized product remaining in the film during subsequent storage and Kabuji.

A preferred compound (F) has a second-order reaction rate constant with p-aningine in which 2 (in trioctyl phosphate of IrOoC) is /, 01/rnol·5ec-/X
It is a compound that reacts within a range of 10 1/mol-sec. In addition, the second-order reaction rate constant is JP-A-3-/11r.
μ! It can be measured by the method described in No.

When k2 is larger than this range, the compound itself becomes unstable and may react with gelatin and water and decompose. On the other hand, if k2 is smaller than this range, the reaction with the remaining aromatic amine developing agent will be slow, and as a result, it may not be possible to prevent the side effects of the remaining aromatic amine developing agent, which is the objective of the present invention.

A more preferable compound (F) can be represented by the following formula (FI) or (Fn).

Monofunctional formula (Fl) R1-(Person)nX-Final formula (Fil) R2-C=Y In the formula, R1 and R2 each represent an aliphatic group, an aromatic group, or a heterocyclic group 'Ik. n represents/or Of. X represents a group that reacts with an aromatic amine developer to form a chemical M association, and X represents a group that reacts with an aromatic amine developer and leaves the group. B is a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group; represents a group that promotes Here R1 and X.

Y and R2-ff1 or B may be bonded to each other to form a cyclic structure.

Among the methods of chemical V3 interaction with the residual aromatic amine-based active agent, the typical ones are substitution reaction and addition reaction.

Specific examples of compounds represented by formulas (Fl) and (Fn) are described in JP-A No. 3-/j13413, A, 2-
Preferably, those described in specifications such as No. 21r3331r, Tokatsuki Akira &, 2-/J-za3≠2, and FF Gansho 63-7♂ Ko 37 are preferred.

-More preferred compounds (G) that chemically combine with the blackened aromatic amine developing agent remaining after color development to produce a chemically inert and colorless compound are as follows- It can be expressed by the role formula (Gl).

Monofunctional formula (Gl) -Z In the formula, R represents an aliphatic group, an aromatic group, or a heterocyclic group. Z represents a nucleophilic group or a group that decomposes in the photosensitive material to release a nucleophilic group. - Compounds of the formula (Gl) in which 2 is Pearson's nucleophilic nCH3I [(
R.G. Pearson, et al.

J, Am, Chem, Soc,, ヱo, 3iy</yt
r)> is! The above groups or groups derived therefrom are preferred.

For specific examples of compounds represented by the monofunctional formula (GI), see European Patent Publication No. 211722, JP-A-62-7-30
Hiroshi No. 12-2221≠j, Patent Wdl, J-/
l'<tjY, same j j-/J l 7.2g,
Same A2-2/U&JR/No., Same T2-iz
Those described in t3 Kou No. 2 are preferred.

For details on the combination with the above-mentioned compound (G) and compound (F), please see ¥! It is described in F.Gan Sho 43-/I Hiroshi 32. (2) Experiment No. 9.10 in Table 2, page 95 of the same book.
11. Each photosensitive material rCJ corresponding to 12 is rDJ
will be corrected.

(3) "See Table 4" in lines 8 and 9 of page 122 of the same book have been amended to "see Table 5," respectively.

(that's all)

Claims (1)

[Claims] (1) In a method of processing a silver halide color photographic light-sensitive material with a color developer containing at least one aromatic primary amine color developing agent, a silver halide emulsion containing 80 mol% or more of silver chloride is used. A silver halide color photographic light-sensitive material comprising at least one hardening agent represented by the following general formula (I) or (II) in at least one layer has a sulfite ion concentration of 3× 10＾-
^3 mol/l or less, and the chloride ion concentration is 3.5 x 1
A method for processing a silver halide color photographic light-sensitive material, characterized in that the processing is carried out using a color developer having a concentration of 0^-^2 to 1.5 x 10^-^1 mol/l. ▲There are mathematical formulas, chemical formulas, tables, etc.▼▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (II) (In the formula, X_1 is a halogen atom, N-methylolamino group, glycidoxy group, Y_1 is H, halogen Atom, -
OH, -OM (M is an alkali metal ion), amino group,
substituted amino groups, alkyl or phenyl ether groups,
It represents an alkyl or phenylthioether group or a sulfonamide or alkylsulfonamide group. Z_1 is selected from the same group as Y_1 and may be the same or different from Y_1. )