JPH0553277A - Processing method for silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a processing method for a silver halide photographic sensitive material by which changes in the gradation balance and sensitivity of each dye image are reduced even when the concn. of a color developing agent and the concn. of Br ions vary and color development time is shortened. CONSTITUTION:A color developing soln. contg. at least one kind of compd. represented by a formula L1-(A1-L2)r-A2-L3 and >=3.8X10<-2>-mol/l Br ions but not practically contg. sulfite or hydrogensulfite is used. In the formula, each of L, and L, is hydroxyalkyl, L2 is alkylene, each of A1 and A2 is -S- and r is an integer of 1-10.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide color photographic light-sensitive material which is capable of obtaining stable photographic performance even when a silver halide color photographic light-sensitive material is subjected to processing such as a low replenishment of a color developing solution and a shortened color development time. It relates to a method of processing a material.

[0002]

2. Description of the Related Art In running processing of a silver halide color photographic light-sensitive material (hereinafter simply referred to as a light-sensitive material), there is an urgent need to develop a processing method for reducing processing waste liquid in view of environmental protection. However, in order to reduce the processing waste liquid, especially the processing waste liquid of the color developing solution, even if the current photosensitive material is subjected to the color developing processing with a low replenishing amount, the sensitivity and the color density are lowered in the photographic property and the satisfactory performance is obtained. Can't get As one method for solving this problem, it has been conventionally proposed to increase the pH of the color developing solution, increase the color developing processing temperature, increase the concentration of the color developing agent, and the like. However, even if these measures are taken, the yellow, magenta, and cyan dye images are colored due to changes in the concentration of halogens and developing agents in the color developer due to fluctuations in throughput and fluctuations in evaporation due to seasons and differences in installation location. Since the densities are not balanced, there is a problem that gradations are not adjusted. In particular, this problem is large in a high-sensitivity photosensitive material for photographing.

[0003]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to obtain a yellow, magenta or cyan dye image even if the color developing agent concentration or halogen ion, especially bromine ion concentration fluctuates and the color development processing time is shortened. Another object of the present invention is to provide a processing method of a silver halide color photographic light-sensitive material which can obtain stable photographic performance by reducing the gradation balance and sensitivity fluctuation.

[0004]

Generally, the sensitivity and gradation balance of dye images of three colors of yellow, magenta, and cyan are as follows.
It is considered to be determined by the activity of the color developing solution, the diffusion speed of the color developing agent components such as the color developing agent into the light-sensitive material, and the silver halide composition of the light-sensitive material. The compounds represented by the general formula (1) among the constitutional requirements of the present invention are, for example, JP-B-37-16088, JP-B-37-5987,
38-7826, 44-12380, 45-
It is a compound known as a development accelerator or a fixing agent in 9019, US3813247 and the like. Further, the bromine ion in the color developing solution is generally about 1.6 × 10 ^-2 mol / liter, and it is known that sulfite acts as a competitive compound. On the other hand, in the present invention, when the compound represented by the general formula (1) is used when the bromine ion concentration is increased without substantially containing a sulfite or a bisulfite as a competing compound, color development is performed. It was discovered that sensitivity and gradation balance are less likely to be impaired due to changes in the concentration of the color developing agent and the bromine ion concentration, which act on the activity of the solution, and shortening of the processing time. Therefore, the above-mentioned problem is to provide a silver halide color photographic light-sensitive material with at least one compound represented by the following general formula (1):
Silver halide color photographic light-sensitive material characterized by being processed with a color developer containing bromine ions in an amount of 3.8 × 10 ^-2 mol / liter or more and containing substantially no sulfite and / or bisulfite. It could be achieved by the processing method of the material. General formula (1) L _1- (A ₁ -L ₂ ) _r -A ₂ -L _{3 In the} formula, L ₁ and L ₃ may be the same or different and each is an alkyl group, an aryl group, an aralkyl group or an alkenyl group. Or represents a heterocyclic group. However, at least one of L ₁ and L ₃ is —OM ₁ , —SO ₃ M ₁ , or —PO ₃ M.
_{2 M 3, -NR 1 (R} 2), - N + R 3 (R 4)
^{_{(R 5) · X 1 -}} , -SO 2 NR 6 (R 7), - NR 8
_{SO 2 R 9, -CONR 10 (} R 11), - NR 12 CO
_{R 13, -SO 2 R 14,} -PO (-NR 15 (R 16)) 2, -
NR ₁₇ CONR ₁₈ (R ₁₉ ), —COOM ₁ or a heterocyclic group is substituted. L ₂ represents an alkylene group, an arylene group, an aralkylene group, a heterocyclic linking group, or a linking group combining them. A ₁ and A ₂
May be the same or different and each is -S-, -O-,-.
_{NR 20 -, - CO -,} - CS -, - represents a or group any combination of the above - SO _2. However, A ₁ and A ₂
At least one of -S- represents. r represents an integer of 1 to 10. M ₁ , M ₂ and M ₃ may be the same or different and each represents a hydrogen atom or a counter cation. R _{1 to} R ₂₀
Represents respectively a hydrogen atom may be the same or different, an alkyl group, an aryl group, an aralkyl group or an alkenyl group, X ₁ ^- represents a counter anion. In the present invention, it is preferable to define the halogen composition of the silver halide emulsion. Specifically, in the processing method of the light-sensitive material of the present invention, at least one emulsion of the color-sensitive layer of the light-sensitive material is silver iodide. Is preferably 2 mol% or more and silver chloride is 10 mol% or less, and the above-mentioned silver chloroiodobromide contains substantially no silver chloride. It is more preferably silver halide.

The present invention will be described below. First, the general formula (1) will be described in detail. L ₁ and L ₃ are a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms (for example, methyl, ethyl, propyl, hexyl, isopropyl, carboxyethyl), a substituted or unsubstituted aryl group having 6 to 12 carbon atoms ( For example, phenyl, 4-methylphenyl, 3-methoxyphenyl), a substituted or unsubstituted aralkyl group having 7 to 12 carbon atoms (eg, benzyl, phenethyl), or a substituted or unsubstituted 2 carbon atom.
It represents an alkenyl group of 10 (for example, vinyl, propenyl, 1-methylvinyl) or a substituted or unsubstituted heterocyclic group having 1 to 10 carbon atoms (for example, pyridyl, furyl, thienyl, imidazolyl) and the like. However, L
_At least one of ₁ and L ₃ is —OM ₁ , —SO
_{3 M 1, -PO 3 M 2} M 3, -NR 1 (R 2) ( hydrochloride, may be in the form of salts such as acetates, for example an unsubstituted amino, methylamino, dimethylamino, N- methyl -N-
Hydroxyethylamino, N- ethyl -N- carboxyethyl _{^{amino), - N + R 3 (}} R 4) (R 5) · X 1 -
(E.g., trimethylammonio chloride), - SO ₂
NR ₆ (R ₇ ) (eg, unsubstituted sulfamoyl, dimethylsulfamoyl), —NR ₈ SO ₂ R ₉ (eg,
Methanesulfonamide, benzenesulfonamide),-
CONR ₁₀ (R ₁₁ ) [eg, unsubstituted carbamoyl, N
- methylcarbamoyl, N, N-bis (hydroxyethyl) carbamoyl], -NR ₁₂ COR ₁₃ (eg, formamide, acetamide, 4-methyl-benzoylamino), - SO ₂ R ₁₄ (e.g., methanesulfonyl, 4-
Chlorphenylsulfonyl), -PO (-NR
₁₅ (R ₁₆ )) ₂ (for example, unsubstituted phosphonamide, tetramethylphosphonamide), —NR ₁₇ CONR ₁₈ (R ₁₉ ).
(Eg, unsubstituted ureido, N, N-dimethylureido), heterocyclic group (eg, pyridyl, imidazolyl,
Thienyl, tetrahydrofuranyl), - and which is substituted by COOM _1.

M ₁ , M ₂ and M ₃ are hydrogen atoms or counter cations (for example, alkali metal atoms such as sodium atom and potassium atom, alkaline earth metal atoms such as magnesium atom and calcium atom, ammonium, triethylammonium). Ammonium group, etc.).

R _{1 to} R ₃₀ are hydrogen atoms, substituted or unsubstituted alkyl groups having 1 to 10 carbon atoms (eg, methyl, ethyl, propyl, hexyl, isopropyl), substituted or unsubstituted 6 to 12 carbon atoms. Aryl group (eg, phenyl, 4-methylphenyl, 3-methoxyphenyl), substituted or unsubstituted aralkyl group having 7 to 12 carbon atoms (eg, benzyl, phenethyl), or substituted or unsubstituted 2 to 10 carbon atoms. Alkenyl groups (eg,
Vinyl, propenyl, 1-methylvinyl), X
^- represents counter anion (e.g., chloride ion, halide ions such as bromide ion, nitrate ion, sulfate ion, acetate ion, p- toluenesulfonate ion) a. L ₂
Is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms (for example, methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, 1-methylethylene, 1-hydroxytrimethylene), a substituted or unsubstituted carbon The arylene groups of the formulas 6 to 12 (for example,
Phenylene, naphthylene), a substituted or unsubstituted aralkylene group having 7 to 12 carbon atoms (for example, 1,2-xylylene), a substituted or unsubstituted heterocyclic linking group having 1 to 10 carbon atoms, for example,

[0008]

[Chemical 1]

Represents A ₁ and A ₂ are -S-, -O
—, —NR ₂₀ —, —CO—, —CS—, —SO ₂ — or a group in which they are arbitrarily combined, and examples of the optionally combined group include, for example, —CONR ₂₁ —, —NR ₂₂ CO—, —
NR ₂₃ CONR _24- , -COO-, -OCO-, -SO
₂ NR ₂₅ −, −NR ₂₆ SO ₂ −, CSNR ₂₇ −, −NR
₂₈ CS-, -NR ₂₉ CONR _30- and the like. Further, at least one of A ₁ and A ₂ represents -S-.

R represents an integer of 1 to 10.

When each of L ₁ , L ₂ , L ₃ and R _{1 to} R ₃₀ has a substituent, the substituent may be a lower alkyl group having 1 to 4 carbon atoms (eg, methyl or ethyl), or a carbon number. 6 ~
10 aryl groups (eg, phenyl, 4-methylphenyl), C7-10 aralkyl groups (eg, benzyl), C2-4 alkenyl groups (eg, propenyl), C1-4 alkoxy groups. (Eg, methoxy, ethoxy), halogen atom (eg, chlorine atom, bromine atom), cyano group, nitro group, carboxylic acid group (may be in the form of salt), hydroxy group and the like. Note that r is 2
In the above cases, A ₁ and L ₂ may be any combination of the groups listed above.

In the general formula (1), preferably L ₁ and L ₃
-OM ₁ at least one of the, -SO ₃ M _1, -PO _{3
M 2 M 3, -NR 1 (} R 2), - N + R 3 (R 4) (R
₅₎ · X ₁ ^-, represents a heterocyclic group or an alkyl group having 1 to 6 carbons substituted with -COOM _1,, L ₂ represents an alkylene group having 1 to 6 carbon atoms. A ₁ and A ₂ are -S
-, - O-or -NR ₂₀ - represent. However, at least one of A ₁ and A ₂ is —S—. R ₁ , R ₂ , R
₃ , R ₄ , R ₅ and R ₂₀ are hydrogen atoms or have 1 to 6 carbon atoms.
Represents an alkyl group, and r represents an integer of 1 to 6. In general formula (1), more preferably L ₁ and L ₃ are —O.
_{M 1, -SO 3 M 1,} -PO 3 M 2 M 3 or -CO,
Is an alkyl group having 1 to 4 carbon atoms substituted with OM ₁ ,
A ₁ and A ₂ represent -S-, and r represents an integer of 1 to 3. Specific examples of the compound of the present invention are shown below, but the present invention is not limited thereto.

[0013]

[Chemical 2]

[0014]

[Chemical 3]

[0015]

[Chemical 4]

[0016]

[Chemical 5]

[0017]

[Chemical 6]

[0018]

[Chemical 7]

[0019]

[Chemical 8]

The compound represented by the general formula (1) of the present invention is a compound of Journal of Organic Chemistry (J. Org. Chem.) 30, 2867 (196).
5), ibid. 27, 2846 (1962), Journal of American Chemical Society (J. Am.
Chem. Soc. ) 69, 2330 (1947), etc. for easy synthesis.

The amount of the compound represented by the general formula (1) of the present invention used in the color developing solution is from 1 × 10 ^-6 to 1 × 10 ^-1 mol, preferably 1
It is in the range of × 10 ^{-5 to} 5 × 10 ^-2 mol. Here, when the halogen composition of the silver halide emulsion of the color-sensitive layer in the light-sensitive material to be processed is silver iodobromide and comprises 2 mol% or more of silver iodide, the above general formula (1) The amount of the compound represented by the formula (4) used is preferably in a high concentration range and is 5 × 10 5.
^{-5 to} 5 × 10 ^-2 mol, and the silver halide emulsion of the color-sensitive layer has at least one emulsion of silver iodochlorobromide containing 10 mol% or less of silver chloride. The amount used is preferably in the low concentration range of 1 × 10 ^-5 ~
It is in the range of 1 × 10 ⁻³ mol.

Next, color development processing of the light-sensitive material of the present invention will be described. The above-mentioned light-sensitive material of the present invention has the RD.
No. 17643, pages 28-29, ibid. 18716
Pp. 651, left column to right column and the same No. 88 of 307105
Basically, development processing can be carried out by the usual method described on pages 0 to 881, but the present invention does not carry out black and white development before color development, and in the present invention, it is used for development processing. The color developing solution is treated with a color developing solution having a bromine ion concentration of 3.8 × 10 ^-2 mol / liter or more. In order to maintain the bromine ion concentration of 3.8 × 10 ^-2 mol / liter or more, in the present invention, bromine ion may be directly added to the color developing solution, or it may be eluted from the light-sensitive material being processed. It may be. When directly added to the color developing solution, the bromine ion supplying substance may be an inorganic substance or an organic substance as long as it is a compound capable of becoming a bromine ion in the color developing solution. Preferred are inorganic compounds, such as sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide,
Cadmium bromide, cerium bromide, thallium bromide and the like can be mentioned, among which preferred compounds are potassium bromide and sodium bromide. When it is eluted from the light-sensitive material being processed and supplied, it may be supplied from a silver halide emulsion or may be supplied from an additive other than the silver halide emulsion. The bromine ion concentration of the present invention is preferably in the range of 4.0 × 10 ^{-2 to} 8.0 × 10 ^-2 mol / liter.

The color developing solution used for developing the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used, and a typical example thereof is 3-methyl-4-amino-.
N, N diethylaniline, 3-methyl-4-amino-N
-Ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N
-Ethyl-β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates, etc. may be mentioned. Of these, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline sulfate is particularly preferable. Two or more kinds of these compounds can be used in combination depending on the purpose. The content of the color developing agent is preferably 0.0002 to 1 liter per color developing solution.
The amount is 0.2 mol, and more preferably 0.001 to 0.1 mol. The color developer contains a pH buffer such as an alkali metal carbonate, borate or phosphate, a chloride salt, an iodide salt, a benzimidazole or a benzothiazole in addition to the specified amount of the bromine ion concentration of the present invention. It generally contains a development inhibitor such as a class or mercapto compound or an antifoggant. If necessary, hydroxylamines such as hydroxylamine, diethylhydroxylamine, N, N-bis (sulfonateethyl) hydroxylamine, sulfites, bisulfites, N, N-
Hydrazines such as biscarboxymethylhydrazine,
Various preservatives such as phenylsemicarbazides, triethanolamine, catechol sulfonic acids, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye formation Coupling agents, competitive couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, tackifiers, various chelating agents represented by aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, phosphonocarboxylic acids ,
For example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N,
N, N-trimethylenephosphonic acid, ethylenediamine-
Representative examples include N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof.

In the case of a color developer containing the bromide ion according to the present invention and the compound represented by the general formula (1), it is substantially a sulfite salt (for example, sodium sulfite,
It does not contain potassium sulfite, ammonium sulfite) or bisulfite (eg sodium bisulfite, potassium bisulfite, ammonium bisulfite). It is known that sulfite generally acts as a competitive compound, but it is preferable not to contain sulfite in view of the effect of the present invention, that is, stabilizing the balance of each color forming layer and shortening the color development time. In the present invention, "not substantially containing" means 1.0 g or less per liter of the color developing solution, and it is particularly preferable not to contain it at all. The color developer generally has a pH of 9 to 12. Further, the replenishment amount of the color developing solution is preferably small from the viewpoint of reducing processing waste liquid. Therefore, 600 per square meter of photosensitive material
It is preferably not more than milliliter, more preferably not more than 450 milliliter, and more preferably not more than 200 milliliter. The lower limit is preferably not less than the amount of the light-sensitive material brought into the next bath, and is about 50 to 100 ml. The contact area between the photographic processing liquid and air in the processing tank can be represented by the aperture ratio defined below. That is, aperture ratio (cm ^-1 ) = [contact area between processing liquid and air (cm
^2)] ÷ [processing solution volume (cm ^3)] The above aperture is preferably 0.1 cm ^-1 or less, more preferably 0.001~0.05cm ^-1. As a method of reducing the aperture ratio in this way, in addition to providing a cover such as a floating lid on the photographic processing liquid surface of the processing tank,
The method using a movable lid described in JP-A-1-82033 and the slit development processing method described in JP-A-63-216050 can be mentioned. Reducing the aperture ratio is preferably applied not only to color development but also to the subsequent steps, for example, all steps of bleaching, bleach-fixing, fixing, washing, stabilizing and the like. The color development processing time is usually set to 2 to 5 minutes, but in the present invention, the compound represented by the general formula (1) is used,
The processing time can be further shortened by using a high temperature and high pH and using a color developing agent at a high concentration.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed at the same time as the fixing process (bleach-fixing process) or separately. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further, treatment with two continuous bleach-fixing baths, fixing treatment before the bleach-fixing treatment, or bleaching treatment after the bleach-fixing treatment can be optionally carried out. As the bleaching agent, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. Typical bleaching agents are organic complex salts of iron (III), such as aminoamines such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid and glycol etherdiaminetetraacetic acid. Polycarboxylic acids or complex salts of citric acid, tartaric acid, malic acid and the like can be used. Of these, aminopolycarboxylic acid iron (III) complex salts including ethylenediaminetetraacetic acid iron (III) complex salts and 1,3-diaminopropanetetraacetic acid iron (III) complex salts are preferable from the viewpoint of rapid treatment and prevention of environmental pollution. .. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution. The pH of a bleaching solution or a bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 4.0 to 8, but a lower pH may be used for speeding up the processing.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath.
Specific examples of useful bleach accelerators are found in US Pat. No. 3,893,
858, West German Patents 1,290,812 and 2,0
59,988, JP-A-53-32736, JP-A-53-
No. 57831, No. 53-37418, No. 53-726.
No. 23, No. 53-95630, No. 53-95631.
No. 53-104232, No. 53-124424
No. 53-141623, No. 53-28426,
Research Disclosure No. No. 17129 (1
Compounds having a mercapto group or a disulfide group described in JP-A No. 50-140129; JP-B No. 45-8506.
No. 52-20832 and 53-32735.
Thiourea derivatives described in U.S. Pat. No. 3,706,561; West German Patent No. 1,127,715, JP-A-58.
No. 16,235, iodide salt; West German Patent No. 96
6,410, 2,748,430; polyoxyethylene compounds; JP-B-45-8836; polyamine compounds; and others, JP-A-49-40,943.
No. 49-59,644 No. 53-94,927
No. 54, 35-727, 55-26, 506.
Nos. 58-163,940; bromide ions and the like. In addition to the above compounds, the bleaching solution and the bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach stain. Particularly preferable organic acid is a compound having an acid dissociation constant (pKa) of 2 to 5, and specifically acetic acid, propionic acid, hydroxyacetic acid and the like are preferable.

Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts. Use of thiosulfates Is most commonly used, with ammonium thiosulfate being the most widely used. Further, the combined use of thiosulfate and thiocyanate, thioether compounds, thiourea and the like is also preferable. As a preservative for the fixing solution and the bleach-fixing solution, sulfites, bisulfites, carbonyl bisulfite adducts or sulfinic acid compounds described in European Patent 294769A are preferable. Further, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution and the bleach-fixing solution for the purpose of stabilizing the solution. In the present invention, the fixing solution or the bleach-fixing solution contains p for adjusting the pH.
It is preferable to add a compound having a Ka of 6.0 to 9.0, preferably 0.1 to 10 mol / liter of imidazoles such as imidazole, 1-methylimidazole, 1-ethylimidazole, and 2-methylimidazole.

The total time of the desilvering process is preferably as short as possible so long as no desilvering failure occurs. Preferred time is 1 to 3 minutes
Minutes, more preferably 1 minute to 2 minutes. The processing temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C.
In the preferable temperature range, the desilvering rate is improved and the stain generation after the processing is effectively prevented. In the desilvering process, it is preferable that the stirring is strengthened as much as possible. As a concrete method for strengthening stirring, Japanese Patent Application Laid-Open No. 62-
No. 183460, a method of impinging a jet of a processing solution on the emulsion surface of the light-sensitive material, a method of improving the stirring effect by using the rotating means of JP-A No. 62-183461, and a wiper blade provided in the solution. Examples include a method of moving the light-sensitive material while bringing the emulsion surface into contact with the emulsion surface to make the emulsion surface turbulent, thereby further improving the stirring effect, and a method of increasing the circulation flow rate of the entire processing solution. Such a stirring improving means is effective for any of the bleaching solution, the bleach-fixing solution and the fixing solution. The automatic developing machine used for the light-sensitive material of the present invention is disclosed in JP-A-60-191257 and 60-1912.
It is preferable to have the photosensitive material conveying means described in JP-A Nos. 58 and 60-191259. JP-A-60-
As described in Japanese Patent No. 191257, such a conveying means can significantly reduce the carry-in of the treatment liquid from the front bath to the rear bath, and is highly effective in preventing the performance deterioration of the treatment liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The light-sensitive material of the present invention is generally subjected to washing and / or stabilizing steps after desilvering. The amount of rinsing water in the rinsing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), application, and further, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment system such as countercurrent, forward flow, and other various conditions. It can be set in a wide range. Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent method is described in Journal.
of the Society of Motion
Picture and Television E
nginers 64, P.N. 248-253 (19
It can be obtained by the method described in the May 55 issue).
According to the multi-stage counter-current method described in the above literature, the amount of washing water can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problems arise. In the processing of the light-sensitive material of the present invention, as a solution to such a problem, the method of reducing calcium ion and magnesium ion described in JP-A-62-288838 can be used very effectively. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8,542, chlorine-based bactericides such as chlorinated sodium isocyanurate, and benzotriazole are also described by Hiroshi Horiguchi in "Bacterial and Antifungal Agents". "Chemistry" (1986) Sankyo Publishing, edited by Sanitary Technology "Microbial sterilization, sterilization, antifungal technology" (1982) Industrial Technology Association, edited by Japan Society for Antibacterial and Antifungal "Dictionary for Antifungal Agents" (1986) It is also possible to use the bactericide described in (4).

The pH of the washing water in the processing of the light-sensitive material of the present invention is 4-9, preferably 5-8. The washing water temperature and washing time can be variously set depending on the characteristics of the light-sensitive material, the use, etc., but generally 15 to 45 ° C. for 20 seconds to 10 minutes,
A range of 30 seconds to 5 minutes at 25 to 40 ° C. is preferably selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilizing treatment, JP-A-57-8543 and 58-58 are used.
All known methods described in Nos. 14834 and 60-220345 can be used. Further, there is a case where further stabilization treatment is carried out after the water washing treatment, and an example thereof is a stabilizing bath containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photographing. be able to. Examples of dye stabilizers include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts. Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The various processing solutions used in the present invention are 10 ° C. to 50 ° C.
Used at ° C. Usually, a temperature of 33 ° C. to 38 ° C. is standard, but a higher temperature is used to accelerate the processing to shorten the processing time, and a lower temperature is used to improve the image quality and the stability of the processing liquid. be able to.

Next, the photosensitive material used in the present invention will be described. The light-sensitive material of the present invention has a blue-sensitive layer on a support,
It suffices that at least one of the silver halide emulsion layers of the green color sensitive layer and the red color sensitive layer is provided, and there is no particular limitation on the number and order of layers of the silver halide emulsion layer and the non-photosensitive layer.
As a typical example, a silver halide photographic light-sensitive material having at least one light-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. And the photosensitive layer is a unit photosensitive layer having a color sensitivity to any of blue light, green light, and red light, and in the multilayer silver halide color photographic light-sensitive material,
Generally, the unit photosensitive layers are arranged in order from the support side, that is, a red color-sensitive layer, a green color-sensitive layer and a blue color-sensitive layer. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is about 30 mol%.
Silver iodobromide, silver iodochloride, or silver iodochlorobromide, including the following silver iodides. About 2 mol% is particularly preferred.
To silver iodobromide or silver iodochlorobromide containing up to about 10 mol% of silver iodide, and at least one layer of the color-sensitive layer contains a silver iodochlorobromide emulsion containing 10 mol% or less of silver chloride. It is a photosensitive material. In particular, silver iodobromide containing no silver chloride is most preferable in terms of adjusting the balance of yellow, magenta and cyan colors. As the silver halide emulsion, those which have been physically ripened, chemically ripened and spectrally sensitized are usually used. Additives used in such a process are Research Disclosure No. 17643, the same No. 18716 and N
o. No. 307105, 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 three Research Disclosures, and the relevant portions are shown in the following table. Types of additives RD17643 RD18716 RD307105 1. Chemical sensitizer page 23 page 648 right column page 866 2. Sensitivity enhancer page 648, right column 3. Spectral sensitizer, pages 23 to 24, page 648, right column, pages 866 to 868, supersensitizer, page 649, right column 4. Whitening agent Page 24 Page 647 Right column Page 868 5. Antifoggants, pages 24 to 25, page 649, right column, pages 868 to 870, stabilizers 6. Light absorber, page 25-26, page 649, right column, page 873, filter dye, page 650, left column, ultraviolet absorber 7. 7. Anti-staining agent, page 25, right column, page 650, left column, page 872 to right column 8. Dye image stabilizer, page 25, page 650, left column, page 872 9. Hardener, page 26, page 651, left column, pages 874-875 10. Binder 26 pages 651 left column 873 to 874 11. Plasticizers and lubricants Page 27 Page 650 Right column Page 876 12. Coating aid, pages 26 to 27, page 650, right column, pages 875 to 876, surfactant 13. Static page 27, page 650, right column, pages 876-877 inhibitor 14. Matting agent pp. 878-879

In order to prevent deterioration of photographic performance due to formaldehyde gas, US Pat. No. 4,411,98
It is preferable to add a compound capable of being immobilized by reacting with formaldehyde described in No. 7 and No. 4,435,503 to the light-sensitive material. The light-sensitive material of the present invention can be incorporated into U.S. Pat.
JP-A-62-18539, JP-A-1-28355
It is preferable that the mercapto compound described in No. 1 is contained. A compound described in JP-A No. 1-106052, which releases a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof, to the light-sensitive material of the present invention, irrespective of the amount of developed silver produced by the development processing. Is preferably contained. In the light-sensitive material of the present invention, the international publication WO88 / 04
It is preferable to incorporate the dyes dispersed by the method described in JP-A No. 794, 1-502912 or the dyes described in EP317,308A, US Pat. No. 4,420,555, and JP-A-1-259358. . Various color couplers can be used in the present invention, and specific examples thereof include Research Disclosure No. 176
43, VII-C to G, and the same No. 307105, V
It is described in the patents described in II-C to G. Examples of yellow couplers include US Pat. No. 3,933,5
No. 01, No. 4,022,620, No. 4,326,
No. 024, No. 4,401,752, No. 4,24
8,961, Japanese Patent Publication No. 58-10739, British Patent Nos. 1,425,020, 1,476,760, U.S. Pat. Nos. 3,973,968, 4,314,02.
3, No. 4,511,649, European Patent 249,
Those described in No. 473A and the like are preferable.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619 and 4,351,897 are preferred.
No., EP 73,636, US Pat. No. 3,06
1,432, 3,725,067, Research
Disclosure No. 24220 (June 1984)
Mon.), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, 61-72238 and 60.
-35730, 55-118034, 60-1
No. 85951, U.S. Pat. Nos. 4,500,630, 4,540,654, 4,556,630, and International Publication WO88 / 04795 are preferable, and branched directly to the mother nucleus. A pyrazolotriazole type coupler to which an alkyl group is bonded is particularly preferable. Examples of cyan couplers include phenol-based and naphthol-based couplers, and US Pat. Nos. 4,052,212 and 4,1.
No. 46,396, No. 4,228,233, No. 4,
No. 296,200, No. 2,369,929, No. 2,801,171, No. 2,772,162, No. 2,895,826, No. 3,772,002,
No. 3,758,308, No. 4,334,011
No. 4,327,173, West German Patent Publication No. 3,3
29,729, European Patents 121,365A, 249,453A, and U.S. Pat. No. 3,446,622.
No. 4,433,999, 4,775,61
No. 6, No. 4,451,559, No. 4,427,7
No. 67, No. 4,690, 889, No. 4,254.
212, 4,296,199, JP-A-61-4
Those described in No. 2658 and the like are preferable. Furthermore, JP-A 64-533, 64-554, 64-555.
And the imidazole-based couplers described in U.S. Pat. No. 4,818,672 can also be used. Typical examples of polymerized dye-forming couplers are described in US Pat.
451,820, 4,080,211, 4,367,282, 4,409,320, 4,576,910, and British Patent 2,102,137.
And European Patent No. 341,188A.

Examples of couplers in which the color forming dye has an appropriate diffusibility include US Pat. No. 4,366,237, British Patent 2,125,570, European Patent 96,570,
Those described in West German Patent (Publication) No. 3,234,533 are preferable. Colored couplers to correct unwanted absorption of colored dyes are available from Research Disclosure N.
o. 17643, Item VII-G, ibid. 307105, Section VII-G, U.S. Pat. No. 4,163,670, Japanese Patent Publication No. 57-39413, U.S. Pat. No. 4,004,929.
No. 4,138,258, British Patent No. 1,14.
Those described in No. 6,368 are preferable. Further, a coupler described in US Pat. No. 4,774,181 for correcting unnecessary absorption of a coloring dye by a fluorescent dye released upon coupling, and a reaction with a developing agent described in US Pat. No. 4,777,120. It is also preferable to use a coupler having a dye precursor group capable of forming a dye as a leaving group. Compounds that release a photographically useful residue upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors are described above in RD1764.
3, VII-F section and No. No. 307105, Patents described in VII-F, JP-A-57-151944,
7-154234, 60-184248, 63
The compounds described in U.S. Pat. Nos. 37346, 63-37350, and U.S. Pat. Nos. 4,248,962 and 4,782,012 are preferable. R. D. No. The bleaching accelerator releasing couplers described in 11149, 24241, JP-A-61-201247 and the like are effective in shortening the processing time having a bleaching ability, and particularly, the tabular silver halide grains described above. The effect is great when it is added to the photosensitive material using. Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent No. 2,0
97,140, 2,131,188, JP-A-5
Those described in 9-157638 and 59-170840 are preferable. Further, JP-A-60-107029,
Compounds releasing a fog, a development accelerator, a silver halide emulsion, etc. by an oxidation-reduction reaction with an oxidized product of a developing agent described in JP-A-60-252340, JP-A-1-44940 and JP-A-1-45687. Is also preferable.

Other compounds that can be used in the light-sensitive material of the present invention include US Pat. No. 4,130,427.
Couplers described in U.S. Pat. No. 4,283,4
No. 72, No. 4,338,393, No. 4,310,
No. 618 and the like, multiequivalent couplers, JP-A-60-18.
5950, DI described in JP-A-62-24252, etc.
R redox compound-releasing coupler, DIR coupler-releasing coupler, DIR coupler-releasing redox compound or DIR redox-releasing redox compound, coupler releasing a dye that recolors after separation described in European Patent Nos. 173,302A and 313,308A , A ligand releasing coupler described in U.S. Pat. No. 4,555,477, a coupler releasing a leuco dye described in JP-A-63-75747, and a fluorescent dye described in U.S. Pat. No. 4,774,181. Examples thereof include releasing couplers.

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. 2,322,222.
No. 027 and the like.

In the light-sensitive material of the present invention, phenethyl alcohol, JP-A-63-257747 and JP-A-62-272 are used.
248, and 1, described in JP-A No. 1-80941.
2-benzisothiazolin-3-one, n-butyl p
-Hydroxybenzoate, phenol, 4-chloro-
It is preferable to add various preservatives or antifungal agents such as 3,5-dimethylphenol, 2-phenoxyethanol, and 2- (4-thiazolyl) benzimidazole.
The present invention can be applied to various color light-sensitive materials, but color negative films for general use or movies are particularly preferable. Suitable supports that can be used in the present invention include, for example:
The RD. No. 17643, page 28, ibid. 18
716, page 647, right column to page 648, left column, and ibid.
o. 307105, page 879. In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 23 μm or less, more preferably 18 μm or less, particularly preferably 16 μm or less. The film swelling speed T _1/2 is preferably 20 seconds or less. The film thickness is 25
Means the film thickness measured under a humidity condition of 55 ° C. and a relative humidity of 55% (2 days), and the film swelling rate T _1/2 can be measured according to a method known in the art. For example, Photographic Science and Engineering (Photo) by A. Green et al.
gr. Sci. Eng. ), Volume 19, Issue 2, 124-1
It can be measured by using a swellometer (swelling meter) of the type described on page 29, and T _1/2 is 30 in a color developer.
The maximum swollen film thickness reached when treated at 3 ° C for 15 minutes
The saturation film thickness is defined as 0%, and is defined as the time required to reach 1/2 of the saturation film thickness. The film swelling speed T _1/2 can be adjusted by adding a film hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling rate is preferably 150 to 400%. Swelling rate, from the maximum swollen film thickness under the conditions described above,
It can be calculated according to the formula: (maximum swollen film thickness-film thickness) / film thickness. The light-sensitive material of the present invention is preferably provided with a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer. This back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, surface active agent and the like. The swelling ratio of this back layer is 150 to 500.
% Is preferred. Coated silver amount of the light-sensitive material of the present invention, in particular 6.0 g / m ² or less is preferable ku, 4.5 g / m ² or less is most preferred.

[0040]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited thereto.

Example 1 On a subbed cellulose triacetate film support,
Multi-layer color light-sensitive material 101 was prepared by coating each layer having the following composition in multiple layers. (Photosensitive layer composition) The numbers corresponding to the respective components indicate the coating amount expressed in g / m ² , and for silver halide and colloidal silver, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer.

First layer (antihalation layer) Black colloidal silver 0.20 Gelatin 1.50 UV-1 0.20 CC-1 0.05 CM-1 0.05 Solv-1 0.20 Second layer (intermediate) Layer) Gelatin 1.50 UV-1 0.01 Solv-1 0.01

Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Monodisperse silver iodobromide emulsion (average silver iodide content 7.5 mol%, average grain size 0.46 μ) 0.84 monodisperse silver iodobromide Emulsion (average silver iodide content 2.0 mol%, average grain size 0.32 μ) 0.42 gelatin 1.50 ExS-1 2.5 × 10 ⁻⁴ ExS-2 2.5 × 10 ⁻⁴ ExS− 3 5.0 × 10 ^-5 ExC-1 1.00 ExC-4 0.05 CC-1 0.05 ExD-1 0.002 Solv-1 0.50 Fourth layer (high-sensitivity red-sensitive emulsion layer) Single Dispersed silver iodobromide emulsion (average silver iodide content 6.0 mol%, average grain size 0.78 μ) 1.40 gelatin 1.50 ExS-1 2.0 × 10 ⁻⁴ ExS-2 2.0 × 10 ⁻⁴ ExS-3 1.0 × 10 ⁻⁵ ExC-2 0.015 ExC-3 0.25 CC-1 0.015 ExD-2 0.05 S olv-1 0.50 Fifth layer (intermediate layer) Gelatin 0.50 ExC-5 0.03 Solv-4 0.01

Sixth Layer (Low Sensitivity Green Sensitive Emulsion Layer) Monodisperse silver iodobromide emulsion (average silver iodide content 7.5 mol%, average grain size 0.46 μ) 0.84 gelatin 1.00 ExS- 4 5.0 × 10 ⁻⁴ ExS-5 1.0 × 10 ⁻⁴ ExM-1 0.49 CM-1 0.05 ExD-3 0.015 ExD-4 0.02 Solv-2 0.50 7th Layer (intermediate layer) Gelatin 0.80 Solv-1 0.20 Eighth layer (high sensitivity green emulsion layer) Monodisperse silver iodobromide emulsion (average silver iodide content 6.0 mol%, average grain size 0) 0.78 μ) 1.00 Gelatin 1.00 ExS-6 1.5 × 10 ⁻⁴ ExS-7 2.5 × 10 ⁻⁴ ExS-8 5.0 × 10 ⁻⁵ ExM-2 0.05 ExM-30 .15 CM-2 0.05 ExD-3 0.01 Solv-3 0.50 9th layer (yellow filter layer) Yellow Colloidal silver 0.10 Gelatin 0.80 Cpd-1 0.10 Solv-3 0.10

Layer 10 (low-sensitivity blue-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (average silver iodide content 7.5 mol%, average grain size 0.46 μ) 0.25 monodisperse silver iodobromide Emulsion (average silver iodide content 2.0 mol%, average grain size 0.32 μ) 0.25 gelatin 1.00 ExS-10 7.0 × 10 ^-4 ExY-1 0.50 ExY-2 0.10 ExD-2 0.01 Solv-3 0.15 11th layer (high-sensitivity blue-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (average silver iodide content 8.0 mol%, average grain size 0.95 μ) 0.50 Monodisperse silver iodobromide emulsion (average silver iodide content 7.5 mol%, average grain size 0.46 μ) 0.20 gelatin 1.10 ExS-9 1.0 × 10 ⁻⁴ ExS-10 ^{3.0 × 10 -4 ExY-1 0.30} ExY-2 0.05 Solv-3 0.07 12th layer (first protective layer) fine Silver iodobromide emulsion (silver iodide content 2.0 mol%, average grain size 0.08 μ) 0.40 gelatin 1.00 UV-1 0.10 UV-2 0.05 Cpd-2 0.50 Cpd -3 0.20 Solv-1 0.10 Solv-4 0.10 13th layer (2nd protective layer) Gelatin 0.60 Alkali-soluble matting agent (average particle size 2μ) 0.10 Sliding agent 0.04 ExF -1 0.005 ExF-2 0.01 W-1 0.005 In each layer, in addition to the above compounds, a coating aid W-2, a dispersion aid W-3, a hardener H-1 and H-. 2, preservative Cpd-
4, stabilizer Cpd-5, antifoggant Cpd-6 and C
pd-7 was added. The structural formulas of the compounds used above are as follows.

[0046]

[Chemical 9]

[0047]

[Chemical 10]

[0048]

[Chemical 11]

[0049]

[Chemical formula 12]

[0050]

[Chemical 13]

[0051]

[Chemical 14]

[0052]

[Chemical 15]

[0053]

[Chemical 16]

[0054]

[Chemical 17]

[0055]

[Chemical 18]

[0056]

[Chemical 19]

[0057]

[Chemical 20]

[0058]

[Chemical 21]

[0059]

[Chemical formula 22]

[0060]

[Chemical formula 23]

The processing steps and processing recipes for processing the above samples are shown below. Processing process Processing time Processing temperature Color development 3 minutes 15 seconds 38 ℃ Bleach 6 minutes 30 seconds 38 ℃ Water wash 2 minutes 10 seconds 24 ℃ Settlement 4 minutes 20 seconds 38 ℃ Water wash (1) 1 minute 05 Second 24 ℃ Washing with water (2) 1 minute 00 seconds 24 ℃ Stability 1 minute 05 seconds 38 ℃ Dry 4 minutes 20 seconds 55 ℃

Next, the composition of the treatment liquid will be described. (Color developer) Diethylenetriamine pentaacetic acid 1.0 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 Sodium sulfite 4.0 Potassium carbonate 37.0 Potassium bromide (see Table A) Potassium iodide 1.5 mg Hydroxyl Amine sulfate 2.4 3-methyl-4-amino-N-ethyl-N- (β-hydroxyethyl) aniline sulfate [developing agent] (see Table A) Compound represented by the general formula (1) of the present invention (See Table A) Add water 1.0 liter pH 10.25

(Bleach) Ethylenediaminetetraacetic acid sodium ferric trihydrate 100.0 Ethylenediaminetetraacetic acid disodium salt 10.0 Ammonium bromide 140.0 Ammonium nitrate 30.0 Ammonia water (27%) 6.5 ml Water In addition 1.0 liter pH 6.0

(Fixer) Ethylenediaminetetraacetic acid disodium salt 0.5 Sodium sulfite 7.0 Sodium bisulfite 5.0 Ammonium thiosulfate aqueous solution (700 g / liter) 170.0 ml Water is added to 1.0 liter pH 6.7

(Stabilizer) Formalin (37%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 Ethylenediaminetetraacetic acid disodium salt 0.05 Water was added to 1.0 Liter pH 6.5

The sample 101 was subjected to gradation exposure with a B-G-R3 color separation filter for processing. The sample obtained by the treatment was subjected to measurement of the respective densities of yellow, magenta and cyan, which are the coloring dyes of the B, G and R layers, and the characteristic curves thereof were obtained. From this characteristic curve, the minimum density (Dmin)
The logarithm of the reciprocal of the exposure amount at the point giving a density of +0.2 was taken, and this was taken as the sensitivity (S), and the fluctuation of the sensitivity was examined. On the other hand, on the other hand, a point giving a density of Dmin +0.5 (A
The density value of the point (point B) at the exposure amount of logE = 1.0 is calculated from the exposure amount of point
The gradient of the straight line connecting the points B and B was defined as the gradation (G). These sensitivities and gradations are based on the processing 101 and the processing 107, and each processing No. And the difference ΔS and ΔG were calculated. The smaller the difference between the yellow, magenta, and cyan color images, the better the sensitivity balance due to changes in the bromine ion concentration and the color developing agent concentration in the color developing solution, and the smaller the gradation variation, the better the color balance. The results are shown in Table A.

[0067]

[Table 1]

[0068]

[Table 2]

As is clear from the table, when the bromine ion concentration in the color developing solution is high (+8 mmol / l), the development inhibition is increased, the sensitivity is lowered and the gradation is softened, and these are yellow. Processes 101 to 103 may cause the sensitivity and gradation to be out of balance due to different influences depending on the color images of magenta, cyan, and cyan.
And a comparison between 107 and 109. Further, even in a color developing solution containing the compound represented by the general formula (1) of the present invention, if the bromine ion concentration is low, the above-mentioned processing 1
In the case of the processings 104 to 106 from 01 to 103, although a slight improvement is observed, variations in sensitivity and gradation are still observed, and the balance among the three colors of yellow, magenta and cyan is poor. However, in the case of the treatment 110 containing the compound represented by the general formula (1) of the present invention and increasing the bromine ion concentration to the concentration range of the present invention, both sensitivity and gradation are significantly improved, Moreover, the balance among the three colors is good. Further, even if the bromine ion concentration becomes slightly high, or the concentration of the color developing agent is increased, these sensitivity and gradation variations are small, and the balance among the three colors of yellow, magenta, and cyan is good. It is clear from the processing of comparisons between ~ 112 and other comparisons. On the other hand, the compound (1) represented by the general formula (1) of the present invention is replaced with other compounds (5), (13), (19), (6), (18),
It can be seen that even in the treatments 113 to 118 in which the equimolar amount is replaced with (51), the results are as good as those of the treatment 111.

Example 2 Using the sample 101 prepared in Example 1, exposure under the same conditions as in Example 1 was performed, and the same processings 101 to 114 were used, the processing temperature for color development was set to 39.5 ° C., and color development was performed. The time was changed as shown in Table 3 and the treatment was carried out without changing the others. Table B shows the fluctuations in the photographic properties at that time and the gradations of the yellow, magenta, and cyan dye images. In addition,
Gradation method, standard, etc. were in accordance with Example 1.

[0071]

[Table 3]

As is clear from Table B, the color developer treatments 110 to 110 in the region where the compound represented by the general formula (1) of the present invention is contained in the color developer and the bromine ion concentration is high.
Even though 114 is slightly softened even if the color development time is shortened, it is smaller than the comparative processing, and yellow
The gradation balance of the three colors of magenta and cyan is in order,
It shows that the processing time can be shortened. On the other hand, in the comparative processes 101 to 109, the softening is large and the balance of the three colors is poor.

Example 3 Using the sample 105 of JP-A-2-89045, the sensitivity and gradation of B, G, and R3 colors and variations in gradation were changed in the same manner as in Example 1 with the following processing steps and processing solution compositions. Was carried out using. The treatment was carried out by using an automatic developing machine until the cumulative replenishing amount of the replenisher for the color developing solution became three times the volume of the mother liquor tank, and then separately subjecting the sample imagewise exposed to running treatment to the above evaluation.

Processing process Processing time Processing temperature Replenishment amount Tank capacity Color development 3 minutes 05 seconds 39.5 ℃ 80ml 5 liters Bleach 50 seconds 38.0 ℃ 140ml 3 liters Bleach fixing 50 seconds 38.0 ℃ -3 liters Fixed 50 seconds 38.0 ℃ 420ml 3L Water wash 30 seconds 38.0 ℃ 980ml 2L Stability (1) 20 seconds 38.0 ℃ −2L Stability (2) 20 seconds 38.0 ℃ 560ml 2L Dry 1 minute 60 ℃ ＊ Replenishment amount is for photosensitive material Amount per 1 m ² The washing water was a countercurrent system from (2) to (1), and the overflow of washing water was all introduced into the fixing bath. To replenish the bleach-fixing bath, connect the upper part of the bleaching tank of the automatic processor and the lower part of the bleach-fixing tank and the upper part of the fixing tank and the lower part of the bleach-fixing tank with a pipe, and supply the replenisher to the bleaching tank and the fixing tank. All of the overflow liquid generated by the supply was introduced into the bleach-fixing bath. The amount of developing solution brought into the bleaching process, the amount of bleaching solution brought into the bleach-fixing process, the amount of bleach-fixing solution brought into the fixing process, and the amount of fixing solution brought into the water washing process are respectively per 1 m ² of the light-sensitive material. 65ml, 50ml,
It was 50 ml and 50 ml. The crossover time is 5 seconds in each case, and this time is included in the processing time of the previous step.

The composition of the processing liquid is shown below. (Color developer) Mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 2.0 3.0 1-Hydroxyethylidene-1,1-diphosphonic acid 3.3 3.3 Potassium carbonate 37.5 40.0 Odor Potassium iodide 6.0 (50.4 mmol) -potassium iodide 1.3 mg-hydroxylamine sulfate 2.4 5.0 3-methyl-4-amino-N-ethyl-N-4.5 11.5 (β- Hydroxyethyl) aniline sulfate Compound of general formula (1) (see Table C) Add water 1.0 liter 1.0 liter pH 10.25 10.95

(Bleach) Mother liquor (g) Replenisher (g) 1,3-Propylenediaminetetraacetic acid Ferric ammonium monohydrate 144.0 206.0 Ammonium bromide 84.0 120.0 Ammonium nitrate 17. 5 25.0 Hydroxyacetic acid 63.0 80.0 Acetic acid 54.2 80.0 Add water 1.0 liter 1.0 liter pH (adjusted with ammonia water) 3.80 3.60

(Bleach-fixing solution mother liquor) 15:85 mixture of the bleaching-fixing mother liquor and the fixing liquor mother-liquor described below.

(Fixer) Mother liquor (g) Replenisher (g) Ammonium sulfite 19.0 57.0 Ammonium thiosulfate aqueous solution (700 g / liter) 280 ml 840 ml Imidazole 28.5 85.5 Ethylenediaminetetraacetic acid 12.5 37. 5 Water was added to 1.0 liter 1.0 liter pH (adjusted with aqueous ammonia and acetic acid) 7.40 7.45

(Washing water) Common to mother liquor and replenisher tap water is prepared by using H type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas Co.) and OH type strongly basic anion exchange resin (Amberlite IRA-type). Four
00) packed in a mixed bed column to treat calcium and magnesium ions at a concentration of 3 mg / liter or less, followed by 20 m of sodium diisocyanurate dichloride.
g / l and 150 mg / l sodium sulfate were added. The pH of this liquid was in the range of 6.5-7.5.

(Stabilizer) Mother liquor and replenisher common (unit: g) Formalin (37%) 1.2 ml Sodium p-toluenesulfinate 0.3 g Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0 .2 Disodium salt of ethylenediaminetetraacetic acid 0.05 Water was added to 1.0 liter pH 7.2

In the above processing, the change in the concentration of bromine ion as shown in Table C was given by controlling the daily evaporation correction amount to the color developing solution. At the end of the running process, a characteristic curve was obtained in the same manner as in Example 1, and changes in sensitivity and gradation were evaluated. The results are shown in Table C.

[0082]

[Table 4]

As is clear from Table C, when the bromine ion concentration is high (5.04 × 10 ^-2 mol / liter), the bromine ion concentration varies ± 1.0 × 10 ^-2 mol / liter. However, the running color developer containing the compound represented by the general formula (1) of the present invention [Processes 304 to 3]
06 (invention)], its photographic properties (sensitivity and gradation)
Variation is small, and yellow, magenta, and cyan 3
Processing 301-that the difference between colors is small and well balanced
It is clear from comparison with 303 (comparative example). Further, the treatments 307 to 309 in which the compound (8) represented by the general formula (1) of the present invention is changed to other compounds of the present invention (25), (30) and (2) are the same as the above treatment 304. It is also clear that they show almost the same good photographic properties. In addition, in any of the treatments 304 to 309 (invention) treated with a color developer containing the compound represented by the general formula (1) of the present invention, the sensitivity of photographic property is 3 of yellow, magenta and cyan.
Balanced by color and processing for all three colors 301
It can be seen that there is another advantage that the sensitivity is slightly higher than that of.

Example 4 The sample of Example 3 was exposed to the same light, and then the sample of Example 3 was used.
The color developing solution used in the continuous processing in (Processing Nos. 301 to 3
09) was used as it was, and the color development time was set to 2 minutes and 30 seconds as shown in Table D by adjusting the transporting part of the processed sample of the automatic developing machine for processing. However, processing steps after color development,
The time and the like are the same as in Example 3. The sample obtained by the treatment is subjected to concentration measurement, and from the characteristic curve thereof, treatments 401 to 4 are performed.
03, processing 401, and processings 404 to 409, processing 4
The difference was obtained with reference to the color development time of No. 04 of 3 minutes 05 seconds. The results are summarized in Table D.

[0085]

[Table 5]

From Table D, the compound represented by the general formula (1) of the present invention is contained in the color developing solution, and the bromine ion concentration of the color developing solution is as high as 5.04 × 10 ^-2 mol / liter. In this case, even if the bromine ion concentration fluctuates by 1.0 × 10 ^-2 mol / liter, the fluctuations in photographic properties (sensitivity and gradation) in the processing in which the color development time is shortened are noticeable. Processes 404 to 406 show that although the image quality is low and the gradation is low, the variation among the three colors of yellow, magenta, and cyan is small and well balanced, and the color development processing time can be shortened sufficiently. ing. Also,
The compound represented by the general formula (1) is converted from (8) to (2
It is clear from the processes 407 to 409 that the same results are obtained in the processes changed to 5), (30) and (2). On the other hand, in the comparison processes 401 to 403, it can be seen that the variation of the photographic property is large and the balance of the three colors is largely lost, and the variation of the gradation balance is particularly large.

[0087]

According to the embodiments of the present invention, stable photographic performance (sensitivity and gradation) is exhibited even when the concentration of the color developing agent or the bromine ion concentration varies, and the balance of the three colors of yellow, magenta and cyan is obtained. Provided is a processing method of a silver halide color photographic light-sensitive material, which gives excellent photographic performance, and further provides balanced photographic performance of three colors even when processing is performed with the color developing solution for a shortened color development time. can do.

Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material comprising at least one compound represented by the following general formula (1):
Silver halide color photographic light-sensitive material characterized by being processed with a color developer containing bromine ions in an amount of 3.8 × 10 ^-2 mol / liter or more and containing substantially no sulfite and / or bisulfite. Material processing method. General formula (1) L _1- (A ₁ -L ₂ ) _r -A ₂ -L _{3 In the} formula, L ₁ and L ₃ may be the same or different and each is an alkyl group, an aryl group, an aralkyl group or an alkenyl group. Or represents a heterocyclic group. However, at least one of L ₁ and L ₃ is —OM ₁ , —SO ₃ M ₁ , or —PO ₃ M.
_{2 M 3, -NR 1 (R} 2), - N + R 3 (R 4)
^{_{(R 5) · X 1 -}} , -SO 2 NR 6 (R 7), - NR 8
_{SO 2 R 9, -CONR 10 (} R 11), - NR 12 CO
_{R 13, -SO 2 R 14,} -PO (-NR 15 (R 16)) 2, -
NR ₁₇ CONR ₁₈ (R ₁₉ ), —COOM ₁ or a heterocyclic group is substituted. L ₂ represents an alkylene group, an arylene group, an aralkylene group, a heterocyclic linking group, or a linking group combining them. A ₁ and A ₂
May be the same or different and each is -S-, -O-,-.
_{NR 20 -, - CO -,} - CS -, - represents a or group any combination of the above - SO _2. However, A ₁ and A ₂
At least one of -S- represents. r represents an integer of 1 to 10. M ₁ , M ₂ and M ₃ may be the same or different and each represents a hydrogen atom or a counter cation. R _{1 to} R ₂₀
Represents respectively a hydrogen atom may be the same or different, an alkyl group, an aryl group, an aralkyl group or an alkenyl group, X ₁ ^- represents a counter anion.