JPH02109044A - Processing of silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To perform processing of a photosensitive material rapidly, to reduce an amt. of processing soln. to be replenished and to retard generation of fog and silver sludge by adopting a specified bleaching agent and a specified compd. CONSTITUTION:A photosensitive material is color-developed after image- exposure, then bleached immediately, and processed with a processing soln. having fixing capacity, wherein a bleaching soln. contg. at least one ferric complex salt of a compd. expressed by the formula I or III, and having pH 2.0-5.5, and a processing soln. contg. a compd. expressed by the formula IV and having fixing capacity, are used. In the formulas, each A1-A4 is -CH2OH, -COOM, etc., M is an H, Na atom, etc., X is a 3-6C alkylene group, each B1 and B2 is a 2-5C alkylene group; (n) is 1-8; each R1-R4 is an H atom or an alkyl group, etc. A compd. expressed by the formula II may be used as the compd. expressed by the formula I, and a compd. wherein all R1-R4 are H, may be used as a compd. expressed by the formula IV.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a method for producing silver halide color photographic light-sensitive materials C (hereinafter also referred to as "photosensitive materials"), and more specifically relates to methods for producing silver halide color photographic light-sensitive materials (hereinafter also referred to as "photosensitive materials"), and more specifically, a method for producing silver halide color photographic light-sensitive materials (hereinafter also referred to as "photosensitive materials"), and more specifically, a method for producing silver halide color photographic light-sensitive materials (hereinafter also referred to as "photosensitive materials"). The present invention also relates to a method for processing a silver halide color photographic material that has improved fixing properties and can be processed quickly.

[Background of the Invention] Processing of light-sensitive materials basically consists of two steps: color development and desilvering, and desilvering consists of bleaching and fixing steps or bleach-fixing steps. In addition to this, rinsing treatment, stabilization treatment, etc. are added as additional treatment steps.

The processing solution with bleaching ability used in the desilvering process of photosensitive materials contains red blood salt, red blood salt, etc. as an oxidizing agent to bleach the image silver.
Inorganic oxidizing agents such as dichromate were widely used.

However, several serious drawbacks have been pointed out to processing solutions containing these inorganic oxidizing agents and having bleaching ability. For example, red blood salt and dichromate are relatively good in terms of bleaching blades for image silver, but they can decompose when exposed to light and produce cyanide ions and hexavalent chromium ions that are harmful to the human body, causing pollution. It has properties that are unfavorable in terms of prevention. Furthermore, treatment liquids containing these inorganic oxidizing agents have the disadvantage that it is difficult to reuse them without discarding the waste liquid after treatment.

On the other hand, metal complex salts of organic acids, such as aminopolycarboxylic acid metal complex salts, are used as oxidizing agents, as they have fewer pollution problems and meet the requirements of speeding up and simplifying treatment, and enabling the reuse of waste liquids. In recent years, treatment solutions have come to be used. However, processing solutions using metal complex salts of organic acids have a slow oxidizing power, so they have the disadvantage that the bleaching rate (oxidation rate) of image silver (metallic silver) formed in the development process is slow. . For example, iron(■) complex salt of ethylenediaminetetraacetate, which is considered to have a strong bleaching edge among aminopolycarboxylic acid metal complex salts, has been put into practical use as a bleach solution and a bleach-fix solution in some places, but silver bromide , high-sensitivity silver halide color photographic materials based on silver iodobromide emulsions, especially color papers for photography, color negative films for photography, and color reversal films that contain silver iodide as silver halide and have a high silver content. However, the bleaching blades are insufficient and the bleaching process takes a long time.

In addition, in a development method in which a large amount of silver halide color photographic light-sensitive material is continuously processed using an automatic processor, etc., in order to avoid deterioration of the performance of the bleaching solution due to changes in component concentration,
A means is required to maintain the components of the processing solution within a certain concentration range. In recent years, from economic and pollution standpoints, such methods have been adopted, such as the so-called concentrated low replenishment method in which these replenishers are concentrated and refilled in small amounts, and another method in which a regenerant is added to the 1" over 70-solution and used again as a replenisher. have also been proposed.

In particular, in bleaching solutions, organic acid ferrous rust salts produced by bleaching developed silver, such as ethylenediaminetetraacetic acid iron (II) complex salts, are converted into ethylenediaminetetraacetic acid rj1 iron (DI) complex salts, that is, organic acid ferrous salts, by aeration.
A method has been put into practical use in which iron is oxidized back to an iron complex salt, a regenerating agent is added to compensate for the missing components, and the iron is used again as a replenisher.

However, in recent years, so-called compact laboratories (also known as mini-labs) have emerged in order to shorten the processing time of silver halide color photographic materials and reduce collection and delivery costs. Also, there is a strong need to reduce the installation area of the developing machine, and recycling processing is not preferable because it requires complicated labor and management and also requires processing space.

Therefore, it is preferable to use a concentrated low replenishment method that performs low replenishment without performing regeneration processing, but if the amount of replenishment of the bleaching solution is extremely reduced, the concentration of color developer components brought into the bleaching solution will increase.
In addition, it becomes more susceptible to the effects of concentration due to evaporation, and the accumulation of color developer components increases more and more. In this way, when the concentration of color developer components in the bleaching solution increases, the proportion of reducing components such as color developing agents and sulfites adhering to and mixing with the photosensitive material increases, suppressing the bleaching reaction, and as a result. Problems include poor desilvering and poor restoration of the so-called cyan dye. A more serious problem is that bleaching blades tend to bleed. This problem with bleaching blades is particularly accentuated in recent years when bleach solutions are being refilled at low levels.

In recent years, a technique using ferric salt of propylene diaminetetraacetic acid as a new bleaching agent has become known in Japanese Patent Application Laid-open Nos. 63-65441, 63-141056, and 63-139348. However, although propylene diamine tetraacetic acid ferric complex salt has extremely excellent silver bleaching ability, it has been found that it has several drawbacks. One is that the ferrous complex salts produced by the bleaching reaction of silver and the reducing components brought in by the photosensitive materials mentioned above are extremely ferrous.
This means that it is difficult to be oxidized to iron complex salts. As a result, the ferrous complex salts generated accumulate in the bleaching solution, resulting in leucoization of the dye and poor desilvering. Another drawback is that, due to its strong oxidizing power, it oxidizes the color developing agent during the bleaching process, causing indiscriminate coupling reactions, resulting in so-called bleaching edge blur.

Furthermore, in the rapid processing of the present invention, a developing agent and a propylene diaminetetraacetic acid ferric complex salt having a strong oxidizing power are brought into the fixing solution, and fogging occurs due to the same reaction as described above. This is especially noticeable when the amount of processing is small, and becomes even more noticeable when the pH of the fixer increases. These phenomena are similar to the conventional iron ethylenediaminetetraacetate (III
) &can't be predicted with a bleach solution using salt.

It has also been found that when silver accumulates in the fixer during continuous processing, silver sludge tends to occur in the fixer due to the strong oxidizing power of the ferric salt of propylene diaminetetraacetic acid.

[Purpose of the invention]

SUMMARY OF THE INVENTION Accordingly, a first object of the present invention is to provide a method for processing silver halide color photographic materials that is rapid and has improved fogging. Furthermore, a second object is to provide a method for processing a silver halide color photographic light-sensitive material that exhibits excellent geographic stability even when processed continuously or in small quantities.

[Structure of the invention]

The object of the present invention is to subject a silver halide color photographic light-sensitive material to imagewise exposure, color development treatment, immediately bleaching treatment, and then processing it with a processing solution having fixing ability, when the bleaching solution is as follows: Contains at least one ferric complex salt of the compound represented by [A] or (B), and has a pH of 2.0 to 5.
．． 5, and the treatment liquid for improving the fixing ability has the following general formula [
The present inventors have discovered that this can be achieved by a method for processing a silver halide color photographic light-sensitive material, which is characterized by containing a compound represented by T].

As another embodiment of achieving the object of the present invention, the silver halide color photographic material in the processing method I of the silver halide color photographic light-sensitive material contains 0.5 mol % of silver iodide in at least one layer thereof. Examples of processing methods include silver halide containing the above.

[Specific structure of the invention]

First, the compound represented by the general formula (A) will be explained in detail.

A, ~A, may be the same or different, and -
CH20H, -COOM or -PO3M, M, represents
MlM and M each represent a hydrogen atom, a sodium atom, a potassium atom or an ammonium group. X represents a substituted or unsubstituted alkylene group having 3 to 6 carbon atoms (eg, trimethylene, tetramethylene, pentamethylene, etc.).

Examples of the substituent include a hydroxyl group and a lower alkyl group having 1 to 3 carbon atoms.

Preferred specific examples of the compound represented by -Fukusai (A) are shown below.

(A-1) (A (A-7) (A-3) (A-8) (A-4) (A-9) (A-5) (A-10) (A-6) (A, -11) (A-12) In addition to these compounds (A-1) to (A-12), these sodium salts, potassium salts, or ammonium salts can be similarly preferably used.

From the viewpoint of the desired effect and solubility of the present invention, ammonium salts of these ferric complex salts are preferably used.

Among the above compound examples, those particularly preferably used in the present invention are (A-1), (A-4), (A-7), and (A-9), and particularly preferred is (A-9).
-1) and (A-9).

Next, the compound represented by general formula (B) will be explained in detail.

A1 to A are synonymous with Al-A4 in the above-mentioned clothing cost (A), and n represents an integer of 1 to 8. B1 and B may be the same or different, and each represents a substituted or unsubstituted alkylene group having 2 to 5 carbon atoms (eg, ethylene, trimethylene, tetramethylene, pentamethylene, etc.).

Examples of the substituent include a hydroxyl group and a lower alkyl group having 1 to 3 carbon atoms (methyl group, ethyl group, propyl group, etc.). Preferred specific examples of the compound represented by -CB) are shown below.

(B-1) (B-2) (B-3) (B-4) (B-5) (B-6) (B-7) Compounds other than these (B-1) to (B-7) Similarly, these sodium salts, calylim salts or ammonium salts can be preferably used.

From the viewpoint of the desired effect and solubility of the present invention, ammonium salts of these ferric complex salts are preferably used.

Among the above compounds, those particularly preferably used in the present invention are (B-1), (B-4) and (B-7).
), and particularly preferred is (B-1).

One of these compounds represented by -Fukudai (A) and CB)
From the viewpoint of silver bleaching properties, the diiron complex salt is preferably used in an amount of at least 0.1 mol per bleaching solution IQ, more preferably in the range of 0.15 to 0.60 mol/Q, and most preferably 0.2 mol/Q. It is in the range of ~0.5 mol/a.

The processing liquid having fixing ability in the present invention is a fixing liquid or a bleach-fixing liquid, and the processing liquid that significantly exhibits the effects of the present invention is preferably a fixing liquid.

The processing liquid having fixing ability according to the present invention needs to contain a compound of general formula (T).

When the bleaching agent of the present invention is used in a bleaching solution, silver sludge is generated in a small amount of running or storage, and in the fixing solution,
It is completely unexpected that fogging occurs due to the above-mentioned reaction, and it is completely unexpected that the processing liquid of the present invention has the general formula [T
] It was surprising that the above two problems were solved by adding the compound.

Next, general formula [T] will be explained in detail.

- In clothing (T), R, , R, and R each represent a hydrogen atom, an aliphatic group, an aryl group, an acyl group, or an amino group. Furthermore, R3 and R, and R1 and R6 may be linked to each other to form a ring. Furthermore, R, and R3, and R
3 and R1 may also be linked to each other to form a ring.

Examples of the aliphatic groups represented by R1 to R include alkyl groups (e.g., methyl, ethyl, propyl, butyl, etc.), substituted alkyl groups (substituents include, for example, hydroxy, carboxylic acid, mercapto, and sulfone). (amide group, alkylamino group, amine group, sulfonic acid group, etc.), alkenyl group (eg, allyl group, etc.), and cycloalkyl group (eg, cyclohexyl group, etc.).

Examples of the aryl group represented by R3-R4 include phenyl group, substituted phenyl group (for example, substituents include halogen group (chloro group, pro-Kamihiro, etc.), alkyl group (methyl group,
(ethyl group, etc.), etc.).

Examples of the acyl group represented by R1-R1 include an acetyl group.

Examples of the amino groups represented by R1 to R include unsubstituted amino groups and substituted amino groups (substituents include aryl groups such as phenyl groups, alkyl groups such as methyl groups and ethyl groups, and thioamide groups).

In addition, examples of forming the above-mentioned polycycle include a 5-membered ring and a 6-membered ring.
It can be a membered ring, and may be a saturated ring or an unsaturated ring.

below, general formula Specific compound represented by Exemplary compounds are shown below.

C)1. cIl□OH Nll-COCH.

N.H.

- Thiourea and its derivatives represented by CT) can be synthesized by commonly known methods such as the Rodan ammonium method, the diazomethane method, and the lime nitrogen method, and some of them are commercially available as chemical products. Or Japanese Patent Application Publication No. 63-229449, US Patent No. 3,801,330, British Patent No. 931, 56
It can be synthesized by a general method such as that described in No. 0.

The amount of the compound shown in the above-mentioned - clothing cost CT) added to the Asahi Riso liquid having fixing ability can be 0.1 g/+2 or more up to the maximum dissolution amount of each compound, but preferably 0.3 to 50 g/+2.
g/Q, more preferably 0.5 to 25
It is in the range of g/12.

A so-called fixing agent is essential to the fixing solution and bleach-fixing solution according to the present invention.

As fixing agents, compounds which react with silver halides to form complex salts in aqueous solution, such as thiosulfates such as potassium thiosulfate, sodium thiosulfate and ammonium thiosulfate, potassium thiocyanate, sodium thiocyanate and ammonium thiocyanate are used. Examples include thioneanate.

In addition to these fixing agents, fixing solutions and bleach-fixing solutions include ammonium sulfite, potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite, etc. P from various salts such as sulfite, boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, etc.
It can contain one or more H buffers.

Furthermore, it is desirable to contain a large amount of a rehalogenating agent such as an alkali halide or an ammonium halide, such as potassium bromide, chlorium bromide, sodium chloride, or ammonium bromide. In addition, PO buffers such as borates, oxalates, acetates, carbonates, and phosphates, alkylamines, polyethylene oxides, and other substances known to be added to normal fixers and bleach-fixers may be added as appropriate. can do.

The Moeki fixing agent is used in an amount of 0.1 mol or more per 1a of the processing solution, and preferably 0.6 mol to 0.6 mol in terms of the desired effect of the present invention.
It is used in a range of 4 mol, particularly preferably in a range of 0.9 mol to 3.0 mol, particularly preferably in a range of 1.1 mol to 2.0 mol.

The bleaching solution of the present invention includes a ferric complex salt of the compound represented by the general formula [A] or [B], and other aminopolycarboxylic acid ferric complex salts (for example, ethylenediaminetetraacetic acid ferric complex salt, Diethylenetriaminepentaacetic acid ferric complex salt, 1
, 2-cyclohexanediaminetetraacetic acid ferric complex salt can be used in combination.

However, in order to better achieve the desired effects of the present invention, it is believed that at least 70% (in terms of moles) of the ferric complex salt in the total organic bleaching solution is represented by the general formula [A] or [B]. A bleaching solution which is a ferric complex salt of a compound is preferred, and the ratio is more preferably 80% or more, still more preferably 90% or more, even more preferably 95% or more, and most preferably a compound represented by the general formula (A). This is a bleaching solution using only the ferric complex salt of the indicated compound.

When the bleaching solution according to the present invention contains imidazole and its derivatives or at least one of the compounds shown in the following - Clothes CI) to (II), the desired effects of the present invention can be better achieved, Furthermore, the present invention has the additional effect of improving precipitation caused by silver in the bleaching solution.
More preferably used.

-Fukudai (1) In the general formula (1), A represents an atomic group necessary to form a nitrogen-containing heterocycle (including those in which 5- to 6-membered unsaturated rings are condensed). , R1 is a hydrogen atom, number of carbon atoms is 1 to 6
represents an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group (including those in which 5- to 6-membered unsaturated rings are condensed), or an amino group.

General formula (n) In the general formula CI, sR and R are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxyne group, an amino group, an acyl group having 1 to 3 carbon atoms,
Represents an aryl group or an alkenyl group.

represents a monovalent or n1-valent heterocyclic residue (including those in which 5- to 6-membered unsaturated rings are condensed), and X is -S, -0, or -
NR", where R and R' are R2 and R, respectively.
Synonymous with 1 X / is synonymous with 6 alkyl group, cycloalkyl group, aryl group, heterocyclic residue (including those in which 5- to 6-membered unsaturated rings are condensed) or amine group, na-na and m1
~m, each represents an integer from 1 to 6.

B represents an alkylene group having 1 to 6 carbon atoms, Zl represents a hydrogen atom, an alkali metal atom, an ammonium group, an amino group, a nitrogen-containing heterocyclic residue, or R4 and R2 have the same meaning as R2 and R1, respectively. However, R1 and R may each represent -B-3Z, or R8 and R3, R and R', and R4 and R6 may be bonded to each other to form a ring.

Note that the compound represented by the formula also includes enolated products and salts thereof.

General formula (III) R7 represents an integer of 1 to 6.

In general formula (IV), R and R1 are each -
In Fukudai (III), R1 and R7 are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxy group, an amine group, an acyl group having 1 to 3 carbon atoms, an aryl group, an alkenyl group, or , -B, -5-Z,
represents. However, R1 and R7 may be combined to form a ring.

, RIG is an alkyl group or -(C1(2)n,
represents so3θ. (However, R,. is -(CH,)n, 5
When o3e, Q represents 0, and when it is an alkyl group, Q represents 1. ) Go represents an anion. n represents an integer from 1 to 6.

It may be fused with a saturated or unsaturated ring.

-Fukudai [v] General formula [■] General formula (In l, QI is necessary to form a nitrogen-containing heterocycle (including those in which 5- to 6-membered unsaturated rings or saturated rings are condensed) represents an atomic group or represents an alkyl group.However, q i has the same meaning as Q□.

General formula (Vl) General formula [■] Niite, X 2 bar-C00M',
-OH.

505M', -CONHz, -5OzNHz,
-NHZ, -SH, -CN.

CO□R+a, -5O2R18, -OR+*, -NRI
IR17, -5R+s.

-5O,R,, -NHCOR,, -NH5O,R,
,, -0COR, or -5O,R,6, and Y represents D,,D! in general formula (Vl). , D and D4 each represent a simple bond, an alkylene group having 1 to 8 carbon atoms, or a vinylene group, and Q IIQ I
IQ s and q represent 0.1 or 2, respectively.

In addition, the ring formed with the sulfur atom is further 5- to 6-membered R+s
RI3 R+2 or hydrogen atom, m! and n are respectively l~
Represents an integer of IO.

Rll+Rl! +R131R141R+s, R+r and RIM each represent a hydrogen atom, a lower alkyl group, an acyl group or an acyl group, R16 represents a lower alkyl group, and R1, -NR.

R2++-0R2t or -3l? R1 and R21 each represent a hydrogen atom or a lower alkyl group, and R22 represents an atomic group necessary for bonding with Ro to form a ring. R2° or R11 may be combined with RIM to form a ring. M' is a hydrogen atom or a cation as shown in Table 4-.

General formula [■] In the general formula [■], Ar represents a divalent aryl group or a divalent organic group combining an aryl group with an oxygen atom and/or an alkylene group, and B! and B each represent a lower alkylene group, R2S, R11x R
! S and R1 each represent a hydroxy-substituted lower alkyl group, and X and y each represent 0 or l.
G I represents an anion, and 2 represents 0, ■ or 2.

General formula (II) R3 In the general formula [■], R7 and R1° each represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, R31 represents a hydrogen atom or an alkyl group, and R3
2 represents a hydrogen atom or a carboxy group.

Typical specific examples of the compounds represented by -Fukudai (I) to (I) and imidazole and its derivatives are disclosed in Japanese Patent Application No. 1983.
(■-1) to (I-10), (It-1) to (II-2) described on pages 17 to 39 of Specification No. -32501
7), (III-1) to (III-1,5), (IV
-1) ~ (rV-3), (V-1) ~ (V-23), (
■-1) ~ (Vl -17), (Vll-1) ~ (■-
15), l-1) ~ (Vll-7), (IN-1
) to (II-5) and (A-1) to (A-8).

These compounds are commonly used as bleach accelerators.

These bleach accelerators may be used alone or in combination of two or more, and good results are generally obtained when the amount added is in the range of about 0.01 to 100 g per 112 of the bleaching solution. However, in general, if the amount added is too small, the effect of promoting bleaching is small, and if the amount added is too large, precipitation may occur and contaminate the silver halide color photographic material being processed. 0.05~ per 112 liquid
The amount is preferably 50 g, more preferably 0.05 to 15 g.

When adding a bleaching accelerator, it may be added and dissolved as is, but it is common to dissolve water, alkali, etc. in acid before adding it, and add methanol, ethanol, or acetone as necessary. It can also be added after being dissolved using an organic solvent such as.

The bleaching solution of the present invention can be used at a pH of 2 to 5.5, preferably at a pH of 3.0 to 5.0. The temperature of the treatment is 20°C to 45°C, preferably 25°C to 45°C.
It is 2℃.

A halide such as ammonium bromide is usually added to the bleaching solution of the present invention. In the present invention, bromide may be used in a small amount due to the strong oxidizing power of the bleaching agent of the present invention, and since it has little tarry property, it is preferably 2.0 mol/Q or less, preferably 0.5-1.5 mol/Q. / It is Q.

The bleaching solution of the present invention includes boric acid, borax, sodium hydroxide, potassium hydroxide, thorium carbonate, potassium carbonate,
pH buffering agents consisting of various salts such as sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide may be contained alone or in combination of two or more.

In the present invention, it is preferable to use acetic acid as a pH buffering agent, which reduces bleaching blade blur and is also inexpensive. The preferred amount of acetic acid is 0.1 to 2 mol/Q, particularly preferably 0.4 to 1.5 mol/Q. When the amount of acetic acid is low, the bleaching edge quality increases, and conversely, when the amount of acetic acid is high, the desilvering performance decreases.

Further, in accordance with the present invention, it is preferable to use nitrate as an embodiment. When used in combination with the bleaching agent of the present invention, the effect is particularly great, preventing the formation of ferrous complex salts and improving poor color recovery. Furthermore, it has a rust-preventing effect, which is a great cost advantage.

The nitrate is used in an amount of 0.1 to 3 mol/Q, preferably 0.3 to 2 mol/Q.

The bleaching solution according to the present invention may further contain various optical brighteners, antifoaming agents, surfactants, and antifungal agents.

The preferred replenishment amount of the bleaching solution according to the present invention is 20++Q to 500Q per lad'' of silver halide color photographic light-sensitive material.
+a12, particularly preferably 30*12 to 35
0aQ, more particularly preferably 40md to 30
0m (2, most preferably 50tsQ to 25
0all.

In the present invention, from the viewpoint of rapid processing, the material is preferably treated with a bleaching solution and then subsequently treated with a fixing solution or a bleach-fixing solution.

Preferred specific treatment steps of the treatment method according to the present invention are shown below.

(1) Color development - constant bleaching, one wash (2) color development - constant bleaching - first stable (3) color development - constant bleaching - first stable (4) color development - constant bleaching - first stable - Second stable (5
) Color development - Bleach - Bleach-fix - Wash with water (6) Color development - Bleach - Bleach-fix - 1st stability (7) Color development - Bleach - Bleach-fix - Stability (8) Color development - Bleach - Bleach-fix - 1st stability −
Second stabilization Among these steps (3), (4), (5)
.

(7) and (8) are preferred, especially (3), (
4') and (5) are preferred. Most preferred is (3).

In the present invention, in order to increase the activity of the bleach or bleach-fix solution, a desired amount of water is added in the processing bath and in the processing replenisher storage tank.
Air or oxygen may be blown through this, or a suitable oxidizing agent such as hydrogen peroxide, bromate, pericate, etc. may be added as appropriate.

When carrying out the method of the present invention, silver may be recovered from the fixer or bleach-fixer by known methods. For example, electrolysis method (described in French Patent No. 2,299,667), precipitation method (described in Japanese Patent Application Laid-Open No. 52-73037, Narrow Patent No. 2,3
31,220), ion exchange method (Japanese Unexamined Patent Publication No. 5
1-17114 publication, narrow patent 2,548,23
7) and metal substitution method (British Patent No. 1,353)
．． 805 specification) etc. can be effectively used.

It is particularly preferable to recover silver from the tank solution in-line, since the suitability for rapid processing becomes even better, but silver from the over-70% waste solution may be recovered and reused.

The fixing solution and bleach-fixing solution according to the present invention can better achieve the desired effects of the present invention when the replenishment amount is 800 mQ (l) or less per m'ffi of the light-sensitive material. In particular, it is 20 to 650 mQ per m2 of the light-sensitive material. , especially 30~
Good results are obtained for 400 m12.

Furthermore, when the fixing solution and bleach-fixing solution according to the present invention contain 0.1 to 10 g/12 of iodide (ammonium iodide, potassium iodide, sodium iodide, lithium iodide, etc.), the present invention to further promote the effects of

0.3-5g/(1, especially 0.5-3g
/12. Most preferably 0.8 to 2 g/l gives good results.

In the fixing solution and bleach-fixing solution according to the present invention, sulfite adducts are preferably used from the viewpoint of the desired effects of the present invention.

Examples of compounds that form stable sulfuric acid attachment compounds with sulfite ions include compounds having an aldehyde group, compounds containing a cyclic hemiacetal, compounds containing an a-dicarbonyl group, and nitrile groups. Among them, compounds represented by Fukudai (A-n) or CA-If) are particularly preferably used.

General formula (A-I) General formula (A-11) A! , A 3 , A + and A are hydrogen atoms,
Represents an alkyl group, formyl group, acyl group, or alkenyl group having 1 to 6 carbon atoms. The alkyl group having 1 to 6 carbon atoms includes straight chain or branched ones, such as methyl group, ethyl group, low propyl group, 1so-propyl group, n
・Butyl group, n-barrel group, s 1so-barrel group, hequinyl group, isohexyl group, etc. may be substituted, and specifically, formyl group (for example, formyl group, formylmethyl, 2-formylethyl, etc.) group), amine group (e.g., multiple groups such as aminomethyl, aminoethyl, etc.), hydroquine group (e.g., hydroxymethyl, 2-hydroxyethyl,
Substituents include substituents such as 2-hydroxypropyl, etc.), alkoxy groups (eg, methoxy, ethoxy, etc.), and halogen atoms (eg, chloromethyl, tricrocomethyl, dibromomethyl, etc.).

Examples of alkenyl groups include substituted and unsubstituted groups, examples of unsubstituted groups include polygroups such as vinyl and 2-globenyl, and examples of substituted groups include l.

Examples include groups such as 2-cyclo2-carboxyvinyl and 2-phenylvinyl.

Specific examples of compounds that form stable sulfite adducts with the sulfite ion are described below, but the present invention is not limited thereto.

(Exemplary compound) O-1 AO-5 AO-7 CH.

10 Ct(,-N+CHJ"CHOl0 CH.

A O-11 A O-12 A O-+4 A ○-21 A O-22 Formaldehyde Sodium bisulfite Acetaldehyde Sodium bisulfite Propionaldehyde Sodium bisulfite Butyraldehyde Sodium bisulfite Succinic aldehyde Sodium bisulfite Glutaraldehyde Sodium bisulfite AO-23 β-Methylglutaraldehyde Sodium bis-shield sulfite AO-24 Maleic acid dialdehyde Sodium bis-bisulfite These sulfite addition compounds are added at 0.00% per 1Q of treatment solution.
It is preferably used in a range of 1 to 80 g, more preferably in a range of 0.5 to 40 g.

The total processing time of the bleaching solution and the processing solution (fixing solution or bleach-fixing solution) having fixing ability according to the present invention is preferably 3 minutes and 45 seconds or less, and the total time is more preferably 20 seconds to 3 minutes and 20 seconds. Hereinafter, the desired effects of the present invention are best achieved when the duration is particularly preferably from 40 seconds to 3 minutes, particularly preferably from 60 seconds to 2 minutes and 40 seconds.

Further, the bleaching time can be arbitrarily selected within the range of the above-mentioned total time, but from the viewpoint of the desired effect of the present invention, it is particularly preferably 1 minute and 30 seconds or less, particularly 10 to 70 seconds, especially 20 seconds or less.
~55 seconds is preferred. The processing time of the processing liquid having fixing ability can be arbitrarily selected, but from the viewpoint of the desired effect of the present invention, it is preferably 3 minutes and 10 seconds or less, and particularly preferably 1
It is in the range of 0 seconds to 2 minutes and 40 seconds, particularly preferably in the range of 20 seconds to 2 minutes and 10 seconds.

In the processing method of the present invention, it is preferable to subject the bleaching solution, fixing solution, and bleach-fixing solution to forced liquid stirring. The reason for this is not only to better achieve the desired effects of the present invention, but also from the viewpoint of suitability for rapid processing.

Forced liquid stirring here means forcibly stirring the liquid by adding a stirring means, instead of the usual diffusion movement of the liquid.

Examples of forced stirring means include the following methods.

1. High-pressure spray treatment method or spray stirring method 2. Air bubbling treatment method 3. Ultrasonic oscillation treatment method 4. Vibration treatment method High-pressure spray treatment method refers to a discharge pressure of 0. Ikg/am”
Refers to a method in which processing is performed by spraying a processing liquid directly onto the photosensitive material from a spray nozzle under a pressure above
The blow stirring method is a nozzle discharge pressure of 0.1 kg/
It refers to a method in which processing is performed by directly spraying a processing liquid onto a photosensitive material in a geological solution under a pressure of cm2 or more, and a pressure capon or a liquid pump is generally used as a pressure sensor. Pressurized bombs include plant jar pumps, gear pumps, magfit bonzo pumps, and cascade pumps, such as the 15-LPM type, 10-BFM type, and 20-B manufactured by Kazan Seisakusho.
FM type, 25-BFij type, etc. are known as examples.

In addition, as a liquid pump, for example, MO-3 manufactured by Ikki Co., Ltd.
There are 0 type, MO-56 type, MDH-25 type, and MDK-32 type.

On the other hand, there are various types of nozzles and spray nozzles, such as straight type, fan type, circular type, full surface type, and annular type. The impact force of the spray is mainly determined by the flow rate (12/min) and the spray pressure (Xg/cm"). Therefore, a pressurizing device that can adjust the pressure in proportion to the number of spray nozzles to fully demonstrate the effect. The most preferable pressure is 0.3 to 10 kg/cm''; if the pressure is smaller than this, no effect can be obtained, and if it is too large, the photosensitive material may be scratched or damaged.

Next, the air bag ring processing method involves installing a sparger at the bottom of the lower conveyance roller in the processing liquid tank.
In this method, air or inert gas is sent to the photosensitive material, the photosensitive material is vibrated by the bubbles discharged from the port, and the processing liquid is brought into effective contact with the front, back, and side surfaces of the photosensitive material.

Suitable materials for the sparger include corrosion-resistant materials such as hard PVC, polyethylene-coated stainless steel, and sintered metal.
Drill a hole 30mm from 51 to 15
Even better effects can be obtained if the thickness is set to mm. Air can be supplied using an air compressor, such as Hitachi's Bebicon (0,4XW, BU7TL), or an air pump, such as Ikki's air pump (Ap22).
Type 0), etc.

The amount of air is 21+ per rack of automatic developing machine.
/min to 30Q/min is required, and 512/min is 20Q/min.
Even better results are obtained at Q/min. The amount of air or inert gas must be adjusted depending on the size of the processing liquid tank and the amount of photosensitive material. Preferably, an amount of active gas is delivered.

Next, the ultrasonic oscillation processing method is a method in which an ultrasonic oscillator is installed in the bottom or side wall space of the processing liquid tank of an automatic developing machine and irradiates ultrasonic waves onto the photosensitive material to increase the efficiency of development promotion. . As the ultrasonic oscillator, for example, a magnetostrictive nickel vibrator (horn type), a magnetostrictive barium titanate vibrator (Holter type), etc. manufactured by Ultrasound Kogyo Co., Ltd. are used.

The transducer frequency of the ultrasonic oscillator is 5 to 100 (I
KHz is used, especially 1O-5 (lKHz)
This is preferable in terms of the desired effect of the present invention and damage to the equipment of the automatic processor. Ultrasonic waves can be irradiated onto photosensitive materials by direct irradiation or indirect irradiation by installing a reflector, but since ultrasonic waves attenuate in proportion to the irradiation distance, direct irradiation is not recommended. It is preferable to let The irradiation time is preferably at least 1 second or more. In the case of partial irradiation, it may be applied at any of the early, middle, and late stages of the treatment process.

Further, the vibration processing method is a method in which vibration is applied to the photosensitive material between the upper roller and the lower roller in the processing liquid tank of an automatic imager to effectively perform the immersion processing. As the vibrator for the vibration source, for example, V-28 and V-4B types manufactured by Kami W4TL Machine Co., Ltd. are generally used. The method of installing the pie break is to fix the pie break to the top of the immersion processing tank of an automatic processor, and install it so that the vibrator is applied from the back side of the photosensitive material. The frequency of the vibrator is 100-100
00 times/min is preferred. The most preferred range is 500-6
000 times/min.

The amplitude of the photosensitive material to be processed is 0.2 to 30 mm, preferably 1 to 20+1101. If it is lower than this, there is no effect, and if it is too large, the photosensitive material may be damaged.

The number of vibrators to be installed varies depending on the size of the automatic processor, but if the processing tank is composed of multiple tanks, a preferable effect can be obtained by installing at least one vibrator in each processing tank.

In the present invention, the time for processing the silver halide color photographic light-sensitive material with the color developer is preferably 180 seconds or less, more preferably 150 seconds or less, even more preferably 2
It is in the range of 0 to 150 seconds, more preferably 30 to 120 seconds, and still more preferably 40 to 100 seconds.

In the present invention, by processing the above-mentioned silver halide color photographic light-sensitive material in the above-mentioned short time, surprisingly,
In addition to achieving the effects of the present invention, the graininess of the resulting dye image is also improved.

Furthermore, in the method for processing a silver halide color photographic light-sensitive material of the present invention, the color developing solution contains an aromatic primary amine color developing solution main ingredient as the processing solution IQ! - preferably 1.5X
It is a color developing solution containing 10-' mol/Q or more. More preferably 2. OX 10-' mol/Q or more, more preferably 2.5X 10-'' to 2XIl)-' mol/Q
A color developing solution containing the above-mentioned developer main ingredients is preferred. Most preferably, the content is in the range of 3XIO-'' to LX1 (1'mol/Q).

When such a color developing agent is used at a high concentration to activate the photographic light-sensitive material, an image with excellent sharpness and improved graininess can be obtained by short-time processing as described above.

This is particularly noticeable in magenta dye images.

Hereinafter, the color developing agent of the color developer that can be preferably used in the present invention will be explained.

The aromatic primary amine color developing agents used in the preferred color developing solution include known ones that are widely used in various color photographic processes. These developers include aminophenol and p-phenylenediamine derivatives. These compounds are generally used in the form of salts, such as hydrochlorides or sulfates, since they are more stable than in the free state.

Examples of amino/phenol developers include 〇-aminephenol, p-aminophenol, 5-amino-2-
Oxy-toluene, 2-amino-3-oquine-toluene, 2-oxy-3-amino-1,4-cymethyl-
Contains benzene, etc.

In the present invention, the aromatic primary amine color developer is particularly useful because it can better achieve the desired effect and improve the crystal precipitation on the inner wall of the color developer tank of an automatic processor. The agent is an aromatic primary amine color developer having an amino group having at least one water-soluble group, and particularly preferably a compound represented by the following formula [E].

NHl In the general formula (E), R1 represents a hydrogen atom, a halogen atom, or an alkyl group, and the alkyl group represents a linear or branched alkyl group having 1 to 5 carbon atoms, and may have a substituent.

R2 and R3 represent a hydrogen atom, an alkyl group, or an aryl group, and these groups may have a substituent (.).

Furthermore, at least one of R2 and R3 is an alkyl group substituted with a water-soluble group such as a hydroxyl group, a carboxylic acid group, a sulfonic acid group, an amino group, a sulfonamide group, etc.
It is 7R'. This alkyl group may further have a substituent.

In addition, R1 represents a hydrogen atom or an alkyl group, and as an alkyl group, it is a straight chain! represents a branched alkyl group having 1 to 5 carbon atoms, and p and q represent integers of 1 to 5.

Next, the compounds represented by the above-mentioned -Fukudai (E) will be listed, but the compounds are not limited thereto.

(Exemplary compound) (E N.H.

(E-4) NHt (E-5) NH2 N.H.

(E-6) (E-11) (E-7) N.H.

(E N.H.

(E-8) N)(.

Nl(.

(E-13) C2H, -N-(CH2CH,O9C,)].

(E-9) N.H.

(E-14) N)! .

(E N)■.

(E-15) N.H.

N1(.

(E-16) NH2 These p-phenylenediamine derivatives represented by [E] are organic acids and Il-free! It can be used as an acid salt, for example, a hydrochloride, a VT salt, a phosphate, a p-toluenesulfonate, a sulfite, an oxalate, a benzenedisulfonate, and the like.

In the present invention, R2 and/or R2 among the p-phenylenediamine derivatives represented by the above-mentioned
The effects of the present invention are particularly well exhibited when 3 is represented by -f'-(Ch+, U]○)goR+ (Kaiq and R' are the same as above).

Preferred compounds for use in the color developer used in the present invention include sulfites, hydroxylamine, and development inhibitors. Examples of the sulfite include sodium sulfite, sodium hydrogen sulfite, potassium sulfite, potassium hydrogen sulfite, etc., and it is preferably used in a range of 0.1 to 40 g/Q, more preferably in a range of 0.5 to log, 1. It is to be used in

The above hydroxylamine is used as a counter salt to hydrochloride, sulfate, etc., and is preferably used in a range of 0.1 to 40 g/Q, more preferably in a range of 0.5 to IOg/Q.

Further, development inhibitors preferably used in the above color developing solution include halides such as sodium bromide, potassium bromide, sodium iodide, and potassium iodide, as well as organic inhibitors, and the amount of these added is 0-005 It is preferable to use in the range of ~20gIQ, more preferably O1 old ~5g
/Q range.

Examples of the above-mentioned inhibitors preferably used in carrying out the present invention include nitrogen-containing heterocyclic compounds, compounds containing a mercapto group, aromatic compounds, onium compounds, and compounds having an iodine atom in a substituent. The following exemplified compounds are specific examples of these compounds.

However, the compounds that can be used are not limited to the following compounds.

(Exemplary compounds) (Z-1) (Z-2) (Z-8) (Z-9) (Z-3) (Z-4) (Z-10) (Z-11) (Z-5) ( z-1,2) (Z-13) (Z-6) (Z-7) (z-14) (Z-15) Furthermore, when carrying out the present invention, Japanese Patent Application No. 61-12781
The general formula [R
-I) to (R-Xllll) can be used, and the effects of the present invention can be made more effective by using the organic inhibitors described above in the present invention in combination with organic inhibitors. can be played.

Further, the organic inhibitor in the present invention is as described above, but more specifically, it is described in the above-mentioned Japanese Patent Application No. 61-127.
No. 81 Specification, page 1 to page 113 (Z-1)
(Z-3), (Z-6), (Z-8)-(Z-1
3), (Z-15) to (Z-17), (Z-19)
, (Z-22) ~ (Z -25), (z -29), (
Z-31) ~ (Z-38), (Z-40), (Z
-41), (Z-43) to (Z-64) and (Z-
66) to (Z-73).

The color developing solution used in the present invention further contains various commonly added components, such as alkaline agents such as sodium hydroxide and sodium carbonate, alkali metal thiocyanates, alkali metal halides, benzyl alcohol, and water softeners. Also, a thickening agent, a development accelerator, and the like may optionally be included.

Additives other than those mentioned above that may be added to the color developing solution include anti-stain agents, anti-sludge agents, preservatives, interlayer effect promoters, and clearing agents.

The color developing solution of the present invention has a pH of 9 or more, especially p119 to 1.
3 is preferably used.

In addition, the processing temperature of the color developing solution is preferably 35°C or higher, particularly preferably a range of 38°C to 60°C, and most preferably 40°C, in order to better achieve the effects that meet the objectives of the present invention. ~500C range.

In addition to the above, there are no particular limitations on the processing method for the photographic material of the present invention, and any processing method can be applied.

In the light-sensitive material according to the present invention, the silver iodide content of at least one of the silver halide-containing layers is 0.5 mol% or more,
The amount is preferably in the range of 1 mol % to 15 mol %, more preferably 1.5 mol % to 10 mol %. Patent Nos. 2,376.679 and 2,801.
171), as well as external development systems in which the coupler is contained in the developer (see U.S. Pat. No. 2,252,718, U.S. Pat. No. 2,592.243, U.S. Pat. No. 2,590.970).
It may be of. Moreover, any couplers generally known in the art can be used. For example, cyan couplers other than those of the present invention may be used in combination, and the cyan couplers used in combination include those based on a 7-tole or phenol structure and which form an indoaniline dye by coupling, and magenta. Couplers include those with a 5-pyrazolone ring having an active methylene group as a backbone structure and pyrazoleazole-based couplers, and yellow couplers include those with a benzoylacetanilide, bivallylacetanilide, and anruacetanilide structure having an active methylene ring. Both those with and without substituents at the coupling position can be used. In this way, as the coupler, both a so-called 2-equivalent type coupler and a 4-equivalent type coupler can be applied.

In the present invention, since the intended effects of the present invention can be better achieved, the general components CC-A) to (C-C
) are preferably used, and specific example compounds of these cyan couplers are disclosed in Japanese Patent Application No. 6
(C-1) to (C-46) described on pages 159 to 173 of the specification of No. 3-32501 and (C-51) to (c-118) described on pages 178 to 196 of the same specification.
).

Next, examples of magenta couplers preferably used in the present invention include magenta couplers represented by the general formula CM-r) described on pages 197 to 207 of Japanese Patent Application No. 63-32051, and specific examples of these magenta couplers. Exemplary compounds include (M-1) - described on pages 208 to 227 of the specification of Japanese Patent Application No. 1983-325.
(M-76), and specification of patent application Akiguchi-9791, 66
No. I to No. on page 122.

223 magenta coupler.

The silver halide color photographic light-sensitive material used in the present invention contains a compound (hereinafter referred to as BAR) which reacts with an oxidized form of a color developing agent to release a bleaching accelerator in at least one of the silver halide emulsion layers.
The desired effects of the present invention are better achieved when the present invention contains a compound (referred to as a compound).

Preferably used BAR compounds include those disclosed in Japanese Patent Application No. 1983.
Compounds represented by the general formulas [:BAR-A) and (BAR-B) described in the specification of May 32, 2013, pages 233 to 252 are mentioned, and specific examples of these BAR compounds include 63-32501 Specification 252
Examples include compounds (1) to (77) described on page 274.

In the method for processing a silver halide color photographic light-sensitive material of the present invention, the silver halide emulsion used is silver halide grains composed of two or more phases having different silver iodide contents; Preferably, the emulsion is a silver halide emulsion containing silver halide grains having a silver iodide content higher than the silver iodide content of the outer edge phase of the grains.

In the method for processing the silver halide color photographic light-sensitive material of the present invention, whether the average silver iodide content of the grains is higher than the silver iodide content of the outer edge phase of the grains can be determined by the following method.

When the silver halide emulsion of the present invention contains halogen grains having an average value of grain size/grain thickness of less than 5,
Average silver iodide content (J,
) and the silver iodide content (J2) on the grain surface determined by X-ray photoelectron spectroscopy, the relationship jl>J2 is satisfied.

The particle size referred to here is the diameter of the circumscribed circle of the surface where the projected area of the particle is maximum.

X-ray photoelectron spectroscopy will be explained.

Prior to measurement by X-ray photoelectron spectroscopy, the emulsion is pretreated as follows. First, a pronase solution is added to the emulsion and stirred at 40°C for 1 hour to decompose gelatin. Next, the emulsion particles are sedimented by centrifugation, and after removing the supernatant, an aqueous pronase solution is added and gelatin decomposition is performed again under the above conditions. This sample is centrifuged again, the supernatant liquid is removed, distilled water is added to redisperse the emulsion particles in the distilled water, the sample is centrifuged, and the supernatant liquid is removed. After repeating this water washing operation three times, the emulsion particles are redispersed in ethanol. A thin layer of this was applied onto a mirror-polished silicon wafer and used as a measurement sample.

For measurements by X&I photoelectron spectroscopy, an ESCA/SAM560 model manufactured by P Corporation was used as an apparatus, and excitation X-rays were Mg-Ka rays, X-rays were 1TLHI5KV, and X-ray IT flow was 40
The test was carried out under the conditions of mA and bus energy of 50eV.

Ag5d to determine the surface halide composition.

Br5d, I Detect 3d3/2 electrons.

The composition ratio is calculated by the relative sensitivity coefficient method using the integrated intensity of each peak. Ag5d, Br5d.

+3d3/2 relative sensitivity coefficient each 5.10°0
．． 81.4.592 gives the composition ratio in atomic percent.

When the silver halide emulsion used in the present invention contains grains having an average value of grain size/grain thickness of less than 5, it is preferable that the grain size distribution is monodisperse. A monodisperse silver halide emulsion has an average grain size of γ centered around 120
% grain size range is 60% or more of the total silver halide grain weight, preferably 70% or more, more preferably 80% or more.

Here, the average particle size γ is the frequency n of particles having particle size γi
The particle size γi is defined as the maximum value of the product niXγ11 of i and 111 (3 significant digits, the minimum digit is rounded down to 4 to 5).

In the case of spherical silver halide grains, the grain size referred to here means the diameter thereof, and in the case of grains having shapes other than spherical, the diameter when its projected image is converted into a circular image of the same area.

For example, the particle size can be determined by photographing the particle with an electron microscope magnified 10,000 to 50,000 times and measuring the particle diameter or projected area on the print. (The number of particles to be measured shall be 1,000 or more indiscriminately.) A particularly preferable highly dispersed emulsion of the present invention is defined by the standard deviation "H x 100 - Width of distribution (%)" The width of the distribution is 20% or less, more preferably 15% or less.

Here, the average particle size and particle size standard deviation are determined from the γ group defined above.

When the silver halide emulsion used in the present invention is a tabular silver halide emulsion in which the average value of grain size/grain thickness is 5 or more, the average silver iodide content determined by the above-mentioned fluorescent X-ray analysis method (Jl) and the average value of the silver iodide content measured on silver halide crystals that are 80% or more away from the center in the grain diameter direction of the silver halide grains using the X-ray microanalysis method ( When comparing J,), the relationship Jl>Jl is satisfied.

The X-ray microanalysis method will be explained.

Silver halide particles were dispersed in an electron microscope observation grid equipped with an energy dispersive X-ray analyzer attached to an electron H-microscope, and the magnification was set so that one particle entered the field of view of the CRT using liquid nitrogen cooling, and the particles were exposed for a certain period of time. AgLα.

Integrate the intensity of ILα rays. The silver iodide content can be calculated using the intensity ratio of ILσ/AgLσ and a previously prepared calibration curve.

In tabular silver halide emulsions in which the average value of grain size/grain thickness is 5 or more, the average value of grain size/grain thickness is more preferably 6 or more and 100 or less, particularly preferably 7 or more and 50 or less.

In the silver halide emulsion of the present invention in which the average value of grain size/grain thickness is less than 5, the silver iodide content (J,) on the grain surface as determined by X-ray photoelectron spectroscopy is found to be 6 to 0 mol. It is preferably 5 to 0 mol%, particularly preferably 4 to 0.01 mol%.

In the tabular silver halide emulsion of the present invention in which the average value of grain size/grain thickness is 5 or more, the silver halide grains are separated from the center by 80% or more in the grain diameter direction as determined by the X-ray microanalysis method. The average value (J) of the silver iodide content measured on silver halide crystals is preferably 6 to 0 mol%, more preferably 5 to 0 mol%, and particularly preferably < is 4 to 0.01 mol%. Average thickness of tabular halogenated, Ia grains is 0.5-0.01
it m is preferred, particularly preferably 0.3 to 0.05
It is μm. The average grain size of the silver halide grains contained in the tabular silver halide emulsion is preferably 0.5 to 30 μm,
More preferably, it is 1.0 to 20 μm.

The silver halide emulsion preferably used in the present invention and having an average value of grain size/grain thickness of less than 5 is preferably monodisperse, and is preferably of core/shell type. The tabular silver halide emulsion preferably used in the present invention and having an average value of grain size/grain thickness of 5 or more preferably has silver iodide localized in the center of the grains.

A core/shell type silver halide emulsion with an average value of grain size/grain thickness of less than 5 has a grain structure composed of two or more phases with different silver iodide contents. The phase having the highest content (referred to as the core) consists of silver halide grains other than the outermost layer (referred to as the shell).

The inner phase (core) having the highest silver iodide content may preferably have a silver iodide content of 6 to 40 mol%, more preferably 8 to 30 mol%, particularly preferably 10 to 20 mol%.
It is mole%. The content of silver gold iodide in the outermost layer is preferably less than 6 mol%, more preferably 0 to 4.0 mol%.

The ratio of the shell portion of the core/shell type silver halide grains is preferably 10 to 80% by volume, more preferably 1
It is 5 to 70%, particularly preferably 20 to 60%.

In addition, the core portion accounts for 10 to 80% of the total particle volume.
%, more preferably 20 to 50%.

In the present invention, the content difference between the core portion with a high silver iodide content and the shell portion with a low silver iodide content of the silver halide grains may have a sharp boundary, or may have a continuous boundary that is not necessarily clear. It may be something that changes. Further, those having an intermediate phase between the core and the shell having a silver iodide content between the core and the shell are also preferably used.

In the case of core/shell type silver halide grains having the intermediate layer, the volume of the intermediate layer is preferably 5 to 60%, more preferably 20 to 55%, of the entire grain. The difference in silver iodide content between /L and the intermediate layer, and between the intermediate layer and the core is preferably 3 mol% or more, and the difference in silver iodide content between the shell and the core is preferably 6 mol% or more.

The core/shell type silver halide emulsion is preferably silver iodobromide, and its average silver iodide content is preferably 4 to 20 mol%, more preferably 5 to 15 mol%. Further, silver chloride may be contained within a range that does not impair the effects of the present invention.

Core/shell type silver halide emulsion is disclosed in JP-A-59-177.
535, 60-138538, 59-52238,
80-143331, 60-35726 and 60
It can be manufactured by a known method disclosed in Japanese Patent No.-258536 and the like.

When a core/shell type silver halide emulsion is grown starting from seed grains as in the method described in the Examples of JP-A-60-138538, the center of the grains may have a halogen composition region different from that of the core. sell.

In such cases, the halogen composition of the seed grains may be of any composition such as silver bromide, silver iodobromide, silver chloroiobromide, silver chlorobromide, silver chloride, etc., but if the silver iodide content is Silver iodobromide or silver bromide of 10 mol % or less is preferred.

The proportion of the seed grains in the total silver halide is 50% by volume.
% or less is preferable, and 10% or less is particularly preferable.

The distribution state of silver iodide in the above-mentioned core/shell type silver halide grains can be detected by various physical measurement methods. This can be investigated by measuring luminescence at low temperatures or using X-ray diffraction.

The core/shell type silver halide grains may be normal crystals such as cubes, tetradecahedrons, and octahedrons, may be composed of twin crystals, or may be a mixture of these, but it is preferable that they be normal crystals. preferable.

In a tabular silver halide emulsion in which the average value of grain size/grain thickness is 5 or more and silver iodide is localized in the center of the grain, the high iodine-containing phase in the center is the entire grain. It is preferably 80% or less of the product, particularly preferably 60% to 10%. The silver iodide content in the center is preferably 5 to 40 mol%, particularly 10 to 40 mol%.
30 mol% is preferred. The low iodine content phase (periphery) surrounding the high iodine content phase in the center has a silver iodide content of 0 to 10.
Preferably it consists of silver iodobromide in mole %, more preferably from 0.1 to 6.0 mole %.

A tabular silver halide emulsion in which silver iodide is localized in the center can be obtained by a known method as disclosed in JP-A-59-99433.

In the method for processing a silver halide color photographic material of the present invention, the average silver iodide content of all the silver halide emulsions in the silver halide photographic material is preferably 0.1 to 15 mol%, More preferably 0.5 to 12 mol%, particularly preferably 1 to 6 mol%. In the method for processing a silver halide color photographic material of the present invention, the average grain size of all the silver halide emulsions in the silver halide color photographic material is preferably 2.0 μm or less, more preferably 0.0 μm or less.
．． 1 to 1.0 μm or less, particularly preferably 0.2 to 0.6
It is μm.

In the method for processing a silver halide color photographic material of the present invention, the total dry film thickness of all hydrophilic colloid layers of the silver halide color photographic material (hereinafter referred to as the film thickness on the emulsion side)
There is a lower limit depending on the silver halide emulsion, coupler oil, additives, etc. contained, and the preferred film thickness on the emulsion surface is 5 to 18 μm, more preferably 10 to 16 μm.
It is m.

Further, the distance from the outermost surface of the emulsion surface to the lower end of the emulsion layer closest to the support is preferably 14 μm or less, and the distance from the emulsion layer to the lower end of the emulsion layer that is the next closest to the support is 14 μm or less.
It is preferably 0 μm or less.

As a method for thinning the photosensitive material according to the present invention, a method for reducing the amount of hydrophilic colloid as a binder can be used. It retains small oil droplets of coupler dissolved in silver halide and high boiling point solvents, prevents fog from increasing due to mechanical stress, and prevents color turbidity due to diffusion of oxidized developing agent between layers. Since hydrophilic colloids are added for these purposes, the amount can be reduced within a range that does not impair those purposes.

As another method for thinning the layer, a method using a highly color-forming coupler can be used.

Other methods for thinning the layer include reducing the amount of high-boiling solvent;
A method of thinning the intermediate layer by adding a scavenger of an oxidized developing agent to the intermediate layer between the eyebrows having different color sensitivity can be used.

In the method for processing a silver halide color photographic light-sensitive material of the present invention, the total fl of the silver halide color photographic light-sensitive material, the total amount of silver halide contained in the light-sensitive silver decagenide emulsion contained in the agent layer. is preferably 6.5 g/m" or less, more preferably 2.5 to 6.0 g/m", more preferably 3.0 to 5.5 g/m", particularly preferably 3.5
~5.0 g/m''.

In the method for processing a silver halide color photographic light-sensitive material of the present invention, the swollen film thickness during development of the entire hydrophilic protective colloid layer coated on the emulsion layer side on the support of the silver halide color photographic light-sensitive material is reduced by drying. It is preferably 180 to 350%, particularly preferably 200 to 300%, of the original film thickness.

Techniques for adjusting the swollen film thickness are well known to those skilled in the art, and can be carried out, for example, by appropriately selecting the amount and type of hardening agent.

Hardening agents include aldehyde-based, aziridine-based (for example, PB Report 19,921, U.S. Patent 2,950,1
No. 97, No. 2,964,404, No. 2,983,31
Specifications of No. 1 and No. 3,271,175, Special Publication No. 1973
-40898 and JP-A-50-91315), inoxazole systems (for example, those described in U.S. Pat. No. 331,609), epoxy/based systems (such as those described in US Pat. No. 331,609),
For example, US Patent No. 3,047,394, West German Patent No. 1,0
85,663, the specifications of British Patent No. 1,033,518, and those described in Japanese Patent Publication No. 48-35495),
Vinyl sulfone type (e.g. PB Revo-1-19,9
20, West German Patent No. 1,100,942, West German Patent No. 2,337.
No. 412, No. 2,545゜722, No. 2,635,5
No. 18, No. 2,742,308, No. 2,749゜26
No. 0, British Patent No. 1,251.091, Patent Application No. 1973-5
No. 4236, No. 48-110996, U.S. Patent No. 3,5
39.644 and 3,490°911), acryloyl type (for example, Japanese Patent Application No. 1973-
No. 27949, U.S. Pat. No. 3,640.720), carbodiimides (e.g., U.S. Pat. No. 2,938.892, U.S. Pat. No. 4,043,818, U.S. Pat. No. 4,061,499) Specifications, Tokkosho, 16-38
No. 715, those described in Japanese Patent Application No. 49-15095), triazine-based (for example, West German Patent No. 2, 4),
No. 0.973, No. 2553.915, U.S. Patent No. 3,3
25,287, those described in JP-A-52-12722), polymer type (for example, British Patent No. 82-12722),
2.06], U.S. Pat. No. 3,623.878, U.S. Pat.
Specifications of No. 396,029 and No. 3,226,234, Japanese Patent Publication No. 47-18578, No. +857'1, No. 4
7-48896), maleimide-based, acetylene-based, methanesulfonic acid ester-based, and (N-methylol-based) hardening agents can be used alone or in combination. Useful combination techniques include, for example, West German Patents No. 2.447,587, West German Patent No. 2,505.746, West German Patent No. 2
, 514.245, U.S. Pat. No. 4,047,957,
Specifications of No. 3,832.181, No. 3,840゜370, JP-A-48-43319, No. 50-6306
No. 2, No. 52-127329J+, Special Publication No. 48-323
Examples include the combinations described in each publication of No. 64.

In the present invention, the swollen film thickness during development is defined as the thickness after being immersed for 3 minutes in the following solution kept at 38°C.

Swelling degree measurement solution 4: Amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniline, sulfate 4.75g Anhydrous sodium sulfite 4.25g Hydroxylamine, 1/2 sulfate 2.0g Anhydrous potassium carbonate 37.5 g Sodium bromide
Add 1.3 g nitrilotriacetic acid trisodium salt (l hydrate) 2.5 g potassium hydroxide 1.0 g water; Let it be Q.

The swelling film thickness can be measured, for example, by A. Green and G. I. B. Levenson, Journal of Photographic Science (J.

Photogr, Sci, ), 20.205 (197
2) Can be measured by the method described.

The dry film thickness in this specification means the film thickness measured at 23° C. and under 55% humidity control. Also, regarding each film thickness,
A cross-section of the dried sample is taken under magnification using an operating electron microscope, and the thickness of each layer is measured.

The above-mentioned total hydrophilic protective colloid layer includes at least one blue-sensitive, green-sensitive, and red-sensitive silver halide emulsion layer, as well as a protective layer coated as necessary;
It includes an antihalation layer, a yellow filter layer, an intermediate layer, etc.

The layer structure of a silver halide color photographic light-sensitive material that can particularly exhibit the effects of the present invention is as follows: from the support, the colloidal silver antihalation layer (intermediate layer), the red-sensitive layer (intermediate layer), the green-sensitive layer (intermediate layer), and the amount of colloidal silver. Color filter layer, blue-sensitive layer (intermediate layer), coated with a protective layer, and a colloidal silver antihalation layer (intermediate layer), red-sensitive FJ (intermediate layer), green-sensitive layer (intermediate layer), and blue-sensitive layer (intermediate layer). Layer) Red-sensitive layer (intermediate layer) Green-sensitive layer (colloidal silver yellow filter layer) Blue-sensitive layer (intermediate layer) It has a layer structure coated with a protective layer.

Note that the layers in parentheses may be omitted. It is preferable that each of the red-sensitive layer, green-sensitive layer and blue-sensitive layer is divided into a low-sensitivity layer and a high-sensitivity layer.

In addition, at least one of a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer as described in Japanese Patent Publication No. 49-15495 is
A layer structure divided into two partial layers, a layer structure separated into a high-sensitivity emulsion layer unit and a low-sensitivity emulsion layer unit as described in Japanese Patent Application Laid-Open No. 51-49027, and West German Publication No. 2,622
．． No. 922, No. 2,622.923, No. 2,622,
No. 924, No. 2,704.826 and No. 2,704,
Examples include the layer structure described in No. 797.

In addition, in the present invention, JP-A No. 57-177551,
It is also possible to apply the layer configurations described in the respective publications of No. 59-177552 and No. 59-180555.

These silver halide emulsions contain: activated gelatin; sulfur sensitizers such as allylthiocarbamide, thiourea, cystine; selenium sensitizers; reduction sensitizers such as stannous salts, thio Urea, polyamines, etc.; noble metal sensitizers, such as gold sensitizers, specifically potassium aurithiocyan-1, potassium chloroaurate, 2-rothio-3-methylbenzothiazolium chloride, etc.; For example, sensitizers with water-soluble groups such as ruthenium, palladium, platinum, rhodium, iridium, etc., specifically ammonium chlorovaladate, potassium chloroplatinate, and sodium chloroparadate (the species consisting of Depending on the size, it acts as a sensitizer or a fog suppressant. (May be chemically sensitized.

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

The silver halide used in the present invention is mixed with an appropriate sensitizing dye in a ratio of 5X 10-' to 3X 10-' per mole of silver halide in order to impart photosensitivity in the desired wavelength range.
Optical sensitization may be achieved by adding 3 moles.

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

That is, as sensitizing dyes used in blue-sensitive silver halide emulsions, for example, West German Patent No. 929,080 and U.S. Pat.
, No. 231,658, No. 2,493,748, No. 2,
No. 503,776, old No. 2,519.0, No. 2,91
No. 2,329, No. 3,656.959, No. 3,672
, No. 897, No. 3,694,217, No. 4,025°349, No. 4,046,572, British Patent No. 1,24
No. 2,588, Special Publication No. 44-14030, No. 52.2
Examples include those described in No. 4844 and the like.

Sensitizing dyes used in green-sensitive silver halide emulsions include, for example, U.S. Pat.
No. 072,908, No. 2,739゜149, No. 2,9
Representative examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. 45,763, British Patent No. 505,979, and the like. Furthermore, the sensitizing dye used in red-sensitive silver halide emulsions is disclosed in, for example, US Pat. No. 2,269,234.
cyanine dyes, melon-anine dyes, etc., as described in No. 2,270,378, No. 2,442.710, No. 2,454,629, No. 2,776.280, etc. Cyanine dyes can be cited as a typical example.

Furthermore, U.S. Patent Nos. 2,213,995 and 2,493
, No. 748, Old No. 2,519.0, West German Patent No. 929,
Cyanine dyes, melonanine dyes, or composite cyanine dyes such as those described in No. 080 can be advantageously used in green-sensitive/10 silver-genide emulsions or red-sensitive silver halide emulsions.

These sensitizing dyes may be used alone or in combination.

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

Typical particularly preferred spectral sensitization methods include, for example,
Japanese Patent Publication No. 43-4936 concerning the combination of benzimidazolocarpocyanine and benzoxazolocarbocyanine
No. 43-22884, No. 45-18433, No. 47-37443, No. 48-28293, No. 49-
No. 6209, No. 53-12375, JP-A-52-23
No. 931, No. 52-51932, No. 54-80118
No. 58-153926, No. 59-116646, No. 59-116647, and the like.

Further, regarding the combination of carbocyanine having a benzimidazole nucleus with other cyanine or merocyanine, for example, Japanese Patent Publication Nos. 45-25831 and 47-
No. 11114, No. 47-25379, No. 48-384
No. 06, No. 48-38407, No. 54-34535, No. 55.1569, JP-A No. 50-33220, No. 50-38526, No. 51-107127, No. 51
-115820, 51-135528, 52-
No. 104916, No. 52-104917, and the like.

Further, regarding combinations of benzoxazolocarbocyanine (oxa-carbocyanine) and other carbocyanines, for example, Japanese Patent Publications Nos. 44-32753 and 46-
11627, JP-A No. 57-1483, and regarding merocyanine, for example, JP-A-48-38408, JP-A-48-41204, JP-A-5.0-40662, JP-A-56-25728, JP-A-58-10753. No. 5
No. 8-C11445, No. 59-116645, No. 50
-33828 etc. are mentioned.

Furthermore, regarding combinations of thiacarbocyanin and other carbocyanins, for example, Japanese Patent Publication No. 43-4932
No. 43-4933, No. 45-26470, No. 4
No. 6-18107, old issue No. 47-87, JP-A No. 59-1
No. 14533, etc., and the method described in Japanese Patent Publication No. 49-6207, which uses zeromethine or dimethine merocyanine, monomethine or trimethine cyanine, and styryl dye, can be advantageously used.

In order to add these sensitizing dyes to the silver halide emulsion according to the present invention, a dye solution such as methyl alcohol, ethyl alcohol, acetyl alcohol, dimethyl filmamide, or fluorinated dye as described in Japanese Patent Publication No. 50-40659 is prepared in advance. It is used by dissolving it in a hydrophilic organic solvent such as alcohol.

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

The photographic constituent layer of the silver halide color photographic light-sensitive material according to the present invention contains a dye (A
The AI dyes include oxonol dyes, hemioxonol dyes, melonanine dyes and azo dyes. Among them, oxonol dyes, hemioxonol dyes, merocyanine dyes, and the like are useful. Examples of AI dyes that can be used include British Patent Nos. 584, 609, 1,277.429, JP-A-48-85130, JP-A-49-99620, and JP-A-49.
-114420, 49-129537, 52-
No. 108115, No. 59-25845, No. 59-11
No. 1640, No. 59-111641, U.S. Patent No. 2,2
No. 74,782, No. 2.533,472, No. 2,95
No. 6,079, No. 3.125,448, No. 3,148
．． No. 187, 3. ! , No. 77.078, 3,247
．． No. 1.27, No. 3.260601, No. 3,540,
No. 887, No. 3,575,704, No. 3,653゜9
No. 05, No. 3,718,472, No. 4,070,35
Examples include those described in No. 2.

These AI dyes are generally used at a concentration of 2 per mole silver in the emulsion layer.
It is preferable to use X 10-' to 5X 10-' moles.

A DIR compound can be used in the photosensitive material according to the present invention.

Typical examples of DIR compounds include DIR couplers in which a group capable of forming a compound having a development-inhibiting effect when separated from the active site is introduced into the active site of the coupler; for example, British Patent No. 935.454; US Patent 3,2
No. 27,554, No. 4,095,984, No. 4゜14
9.886 etc.

When the above DIR coupler undergoes a coupling reaction with an oxidized color developing agent, the coupler core forms a dye,
On the other hand, it has the property of releasing a development inhibitor. Moreover, in the present invention, US Pat. No. 3,652.345 and US Pat.
No. 41, No. 3,958.993, No. 3,961,95
No. 9, No. 4.052.213, JP-A-53-1105
No. 29, No. 54-13333, No. 55-161237
Also included are compounds that undergo a coupling reaction with oxidized forms of color developing agents such as those described in No. 1, etc., and sometimes release development inhibitors, but do not form dyes.

Furthermore, JP-A-54-145135 and JP-A-56-11
When reacted with oxidized color developing agents such as those described in No. 4946 and No. 57-154234, the mother nucleus forms a dye or a colorless compound, while the released timing group undergoes an intramolecular nucleophilic substitution reaction. Or so-called timing D, which is a compound that releases a development inhibitor through an elimination reaction.
IR compounds can also be used in the present invention.

Also, Japanese Patent Publication No. 160954, No. 58-16294
Timing DI in which a timing group as described above is bonded to a coupler core that produces a completely diffusible dye when reacted with an oxidized color developing agent described in No. 9.
R compounds can also be used.

The amount of the DIR compound contained in the photosensitive material is preferably in the range of 10-' mol of IX to 10-' mol of IOX per 1 mol of silver.

Furthermore, in addition to DIR(t) compounds, compounds that release development inhibitors during development can also be used in the present invention; for example, U.S. Pat. No. 3,297,445 and U.S. Pat.
No. 29, West German Patent Application (OL S) 2,417.91
4, and those described in JP-A-52-15271, JP-A-53-9116, JP-A-59-123838, and JP-A-59-127038.

The silver halide color photographic light-sensitive material used in the present invention may contain various other photographic additives. For example, antifoggants, stabilizers, ultraviolet rays, absorbers, color stain inhibitors, optical brighteners, color image fading inhibitors, antistatic agents, hardeners, and surfactants described in Research Disclosure No. 17643. Agents, plasticizers, wetting agents, etc. can be used.

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

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

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

〔Example〕

Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

Example 1 In all Examples, the amount added in the silver halide photographic light-sensitive material is 9 per lm2 unless otherwise specified. In addition, silver halide and colloidal silver are expressed in terms of silver.

A sample of a multilayer color photographic material was prepared by sequentially forming each layer having the composition shown below on a triacetyl cellulose film support from the support side.

1st layer: Antihalation layer Black colloidal silver ...0.18 Ultraviolet absorber (UV-1) -0,20 Colored coupler (cc-1) ...0.05 Colored coupler (GL2) ...0 .06 High boiling point solvent (
Oil-1) ...0.20 gelatin
...1.5 Second layer: Intermediate layer ultraviolet absorber (LIV-1) ・0.01 High boiling point solvent (Oil-1) ...0. Old gelatin...1.5 3rd layer:
Low sensitivity red-sensitive emulsion layer silver iodobromide emulsion (Em-1)...1. Ot
t (E m -2)...0.5 Sensitizing dye (S-1)...2.2XIO-' (mol/1 mole of silver)tt (S-2)...2.5X 10- '(
/l)tt, (S-3)...0.5x
10-'(tt) Cyan coupler (C'-4)
...1.2tt (C'-2)
...0.06 colored cyan coupler (CC
-1)...0,05DLR compound (D-1)
...0.002 high dregs point solvent (Oi 11)
...0.5 gelatin
...1.4 Fourth layer: High sensitivity red-sensitive emulsion layer Silver iodobromide emulsion (E-3) ...2.0 Sensitizing dye (S-1) 2.2xlO-'(-t -ru/1 mole of silver) tt (S -2) ... 2. OXl
, O-'()l) Sensitizing dye (S-3)
...0.1XIO-' (mol/silver 1 mole) cyan coupler (C'-1) ...0415//
(C'-2) ...0.018t
t (C”3)...1.
15 colored cyan turnip-y-(cc-1)-=0
．． 015DIR compound (D-2)...
・0.05 high boiling point solvent (Oil-1) ・
...0.5 gelatin ...1.
5 5th layer: Intermediate layer gelatin ... 0.5th layer (5th layer: low-sensitivity green-sensitive emulsion layer (GL) silver iodobromide emulsion (Em-1
)...1.0 Sensitizing dye (S-4)-5x
lO-' (mol/mol silver) tt (s-5)-1
, ylo” (tt) magenta coupler (M'
-1) ...0.5 Colored Magenta Cabra =
(CM-1)...0.05DIR compound CD-3>
...0.015// (D -4
)...0.020 High sludge point solvent (Oi
l-2) ...0.5 gelatin
...1.0 Seventh layer: Intermediate layer gelatin ...0.8 High boiling point solvent (0th -1) ...0.2 Eighth layer: Highly sensitive green-sensitive emulsion layer Silver iodobromide emulsion ( Em-3) ... Bow, 3 sensitizing dye (S-6)-1,5X10-' (mol/silver 1 mol)
// (S-7)-2,5XlO-'(// )
// (S-8)-0,5XIO-'(// )
Magenta Cobra (T2) ...0.06/
/ (M-3) ...0.18
Colored magenta coupler (CIJ-2)...0.0
5 DIR compound (D-3)...0.0
1 High-temperature solvent (Oil-3)...0.
5 Gelatin °゛1.0 51st layer: Yellow filter yellow colloid silver stain inhibitor (sc-1) High boiling point solvent (Oi 1-3) Gelatin 10th layer: Low sensitivity blue-sensitive emulsion layer...0.1 ...0.1 ...0.1 ...0.8 Layered silver iodobromide emulsion (Effl-1) ...0.
25// (E m -2)
...0.25 sensitizing dye (S-10)...7X10-
'(Mole/1 mole of silver) Yellow coupler (Y-1)
...0.6// (Y -2)
...0.12DIR compound (D-2)
...0.01 high boiling point solvent (Oil-3)
...0.15 gelatin
...1.0 11th layer: Highly sensitive stomach-sensitive emulsion layer Silver iodobromide emulsion (Em-4)"・0.50t
t (E tr+ -1) ...0
．． 20 Sensitizing dye (S-9)...lXl0"' (mol/
1 mole of silver) // (S-1,0)-3X10-4(
// ) Yellow coupler (Y-1)
...0.36tt (Y -2)
...0.06 high boiling point solvent (O11-3)
・・・0.07 gelatin ・・・
1.1 12th N: First protective layer fine grain silver iodobromide emulsion...0.4 (average grain size 0.08 μm Ag + 2 mol%) ultraviolet absorber (
[I V -1'I...0. lO//
(11V -2) ...0.
05 High boiling point solvent (0th -1) ...0.1
tt (Oil-4)...
0.1 formalin scavenger (H5-1)...0
．． 5// (HS -2)...0.
2 Gelatin °゛1.0 13th F
I! 3: Second protective layer surfactant (Sun) -0,005 Alkali-soluble matting agent...0.10 (average particle size 2
μlI+) Dian dye (AIG-1)...0.0
05 Magenta dye (AIM-1)...0
．． Old Schheli agent (WAX-1) -0,0
4 Gelatin °0・6 In addition to the above composition, each layer includes a coating aid of 5 u-2 and a dispersing aid of 5 u.
-3, hardeners H-1 and H-2, preservative D1-1, stabilizer 5tab-L, antifoggant AF-1 and 8F2 were added.

Em-1 average grain size 0.46μ, average silver iodide content 7.
5 mol % Monodisperse surface paper silver iodide-containing emulsion Em-2 Average grain size 0.32 μm 1 Average silver iodide content 2.
0 mol % Monodisperse emulsion with uniform composition Em-3 Average grain size: 0.78 μm, average silver iodide content: 6.
0 mol % Monodisperse surface paper silver iodide-containing emulsion Em-4 Average grain size 0.95 μm, average silver iodide content 8.
0 mol % monodisperse surface paper silver iodide-containing emulsions E m -1+ E m -38 and E+a-4 were prepared with reference to JP-A-60-138538 and JP-A-61-245151. It is a silver iodobromide emulsion that has a multilayer structure and mainly consists of octahedrons. Maf: E+o-1-
For all Em-4, the average value of particle size/particle thickness is 1.
0, and the width of the particle distribution is 14% and 10%, respectively.
, 12% and 12%.

Margin, white---, I (CHris">Or" (CHx), SO+'+1 ・(C,)I,), NH"C' Q Q1 M-1 Ct Hs AlC-1 [(CHz = CH3OzCH1)xccHasOz(
Ctlz)z] J(CHz)tsOJC-C00CH
z (CFICFt) Ta.

<Experimental processing> Processing process Processing time Processing temperature Color development (
1 bath) 3 minutes 15 seconds 38°C bleaching (t
t) 45 seconds 38°C fixation (/l) 1 minute 30 seconds 38°C stabilization (3W! Cascade) 1 minute 38°C drying
Drying 1 minute 40℃～80℃
Composition 1 of the color developing solution used is as follows.

Potassium carbonate 30B Sodium bicarbonate 2.5g Potassium sulfite 5.0g Sodium bromide
1.3g potassium iodide
! , 2mg hydroxylamine sulfate
2.5g sodium chloride
0.6g4-amino-3-methyl-N-ethyl-N-(
β-Hydroxylethyl) Aniline sulfate 4.8g Diethylenetriaminepentaacetic acid 3.0g Potassium hydroxide 1.2g Add water and boil for 10 minutes.
pH 0,06 using potassium hydroxide or 20% sulfuric acid
Adjust to.

The bleaching solution used was as follows.

Organic acid ferric complex salt (listed in Table 1) 0.3 mol Disodium ethylenediamontetraacetic acid 10 g Ammonium bromide 150 g Glacial acetic acid
50yrQ color developer
Add 200m+2 water to make In and adjust pH to 4.4 using aqueous ammonia or glacial acetic acid.

The composition of the fixer used is as follows.

Ammonium thiosulfate 150g Anhydrous sodium bisulfite 12g Sodium metabisulfite 2.5g Disodium ethylenediaminetetraacetate 0.5g Sodium carbonate 1Og - Compound for clothing (T) The bleaching solution listed in Table 1
], 00 m Q Add water 1.12
and adjust the pH to 7.0 using acetic acid and aqueous ammonia.

The composition of the stabilizing liquid used is as follows.

Formaldehyde (37% solution 1) 2ml125
-Chloro-2-methyl-4-isothiazolin-3-one 0.05g Emulgen 8
10 1 m (1,1: lumaldehyde bisulfite adduct sodium 2 g) Water was added to make IR, and the pH was adjusted to 7.0 with aqueous ammonia and 50% sulfuric acid.

As shown in Table 1 below, development was performed using varying bleaching agents and compounds of general formula [T], and the green light density of the unexposed areas of the processed film samples was measured.

8.0g IQ of silver ions and 0.8g IQ of iodide ions, which are thought to accumulate after continuous processing, were dissolved in the treated solution and stored in a constant temperature bath at 50"C for 2 weeks to observe the formation of silver sludge. The results are shown in Table 1.

In the table, ○ means that no silver sludge is generated, △ means that some amount of silver sludge is generated, × means that silver sludge is clearly observed, and the higher the number of ×, the more serious it is. .

When the thiourea derivative represented by formula (T) is added, fog caused by bleaching agents is suppressed and the generation of silver sludge is also reduced. General formula CA other than A-1, B-1,
) or CB), similar results were obtained.

Example 2 An experiment similar to Example 1 was conducted using the color negative film used in Example 1 and using ammonium thiocyanate instead of ammonium thiosulfate in the fixing solution of Example I.

As is clear from Table 1 above, the fixing solution generally contains Table 2 above.
As is clearer, when the thiourea derivative represented by the general formula (T) is added to the fixing solution, fog caused by bleaching agents is suppressed and the generation of silver sludge is also reduced.

Similar results were obtained for bleaching agents represented by general formula (A) or [B) other than A-1 and B-1.

Example 3 The same type of experiment as in Example I was conducted using the color negative film used in Example 1 and changing the pH of the fixing solution in Example 1.

The results are shown in Table 3.

As is clear from Table 3 above, the general formula (T) in the fixer
If a thiourea derivative represented by is added, fog can be kept low even if 9H is increased. A-1,
Similar results were obtained for compounds of general formula (A) other than B-1 or [BJ] before bleaching.

Example 4 Using the car negative film prepared in Example 1, the type and amount of the compound of general formula (T) in the composition of the fixer were as shown in Table 4 above, and the running rule was carried out using the following replenisher. The same experiment as in actual test No. 1-13 of Example 1 was conducted except for the following.

The composition of the color developer replenisher used is as follows.

Potassium carbonate Sodium bicarbonate Potassium sulfite Sodium bromide Hydroxylamine sulfate 4-Amino-3-methyl-N=ethyl 0g 3g 3g 0.5g 3.1g -N-(β-hydroxyethyl) Aniline sulfate 6.0g Diethylenetriamine Pentaacetic acid 3.0g Potassium hydroxide 2g Add water to 10 liters, close and adjust to pH 10.1 using potassium hydroxide or 2096 sulfuric acid.
Adjust to 2.

The composition of the bleach replenisher used is as follows.

Organic acid ferric complex salt listed in Table 4 0.32 mole ethyl
Nondiaminetetraacetic acid disodium 2g ammonium bromide 178g ammonium nitrate
50g water #acid
Add 71 mC water to make IQ, and adjust to pH 3.5 using aqueous ammonia or glacial acetic acid.

The composition of the fixing replenisher used is as follows.

Ammonium thiosulfate 200g Anhydrous sodium bisulfite 15g Sodium metabisulfite 3g Disodium ethylenediaminetetoacetate 0.8g - Compounds with CTE listed in Table 4 Add water to prepare 1a. The pH was adjusted to 7.5.

As the stabilizing replenisher, the stabilizing solution of Example 1 was used. The processing steps, processing time, processing temperature, and replenishment amount of the running treatment were as follows.

Running geography was performed until the bleach tank tank was refilled with twice the volume of bleach replenisher. After the running process was completed, the green light density (transmission) of the unexposed area was measured to check the occurrence of silver sludge.

The results are summarized in Table 4.

From Table 4, the fixer has the general formula (T) 5-/
It can be seen that the use of O-base derivatives is quick, requires low replenishment, and, despite being brittle, there is little capri formation in unexposed areas and no silver sludge formation. Example 5 The average silver iodide content of the silver iodobromide emulsions used in the third and fourth layers of the film sample used in Example 1 was varied as shown in Table 5 above, and the experimental film samples were It was created. Except for using this sample, the treatment was carried out in the same manner as in Example 1, Experiment No. 1-4, and the green light density of the unexposed area was measured. The results are shown in Table 5. From Table 5, it can be seen that fogging is good when the average silver iodide content is 0.5 mol % or more.

Example 6 Example 1, except that cyan couplers C'-2 and C'-3 used in Example 1 were replaced with cyan couplers listed in Table 6 having the same mole as C'-2 and C'-3. No, 1-
Perform the same process as in 4 (but face direction processing for 145 seconds),
The density of the unexposed area of the film sample after processing was determined as sr. Furthermore, the highest cyanide concentration of the processed film sample was measured, and then treated with 120g/Q#7 solution (pH 6.0) of ferric ammonium ethylenediaminetetraacetate for 6 minutes to produce a leucocyan dye (!euco-cyan dy
e) was completely oxidized to cyan dye, the cyan dye density at the highest density portion was measured again, and the difference was determined by calculation. However, the cyan coupler used is patent application No. 63-3250.
The material described on pages 159 to 196 of Specification No. 1 was used.

Cyan couplers (C-1) to (C-96) in Table 6 have the same meanings as the cyan coupler numbers described in Japanese Patent Application No. 63-32501, pages 159 to 196.

The results are summarized in Table 6.

As is clear from the arrangement 6 on the cyan coupler of I2 R-6 H, when using the cyan coupler indicated by the above-mentioned - Clothes [C-A:] to CC-C), rapid processing is required. Despite this, there is little bleaching edge blur due to cyan dye, and there is little generation of leucocyan dye, which is good.

〔Effect of the invention〕

According to the present invention, there is provided a method for processing a silver halogen color photographic light-sensitive material, which enables quick and low replenishment while improving fogging and generation of silver sludge.

Claims (2)

[Claims] (1) After imagewise exposure of the silver halide color photographic light-sensitive material,
When processing with a processing solution having fixing ability after color development processing and immediate bleaching processing, the bleaching solution contains at least a ferric complex salt of a compound represented by the following general formula [A] or [B]. a silver halide having a pH of 2.0 to 5.5, and wherein the processing liquid having fixing ability contains a compound represented by the following general formula [T]. A method of processing color photographic materials. General formula [A] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, A_1 to A_4 may be the same or different, -CH_2OH, -COOM or -PO_3M_
Represents 1M_2. M, M_1 and M_2 each represent a hydrogen atom, a sodium atom, a potassium atom or an ammonium group. X represents a substituted or unsubstituted alkylene group having 3 to 6 carbon atoms. ] General formula [B] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, A_1 to A_4 may be the same or different, and -CH_2OH, -COOM or -PO_3M_
Represents 1M_2. M, M_1 and M_2 each represent a hydrogen atom, a sodium atom, a potassium atom or an ammonium group, and n is 1
Represents an integer between ~8. Further, B_1 and B_2 each represent a substituted or unsubstituted alkylene group having 2 to 5 carbon atoms, and may be the same or different. ] General formula [T] ▲ Numerical formulas, chemical formulas, tables, etc. Represents a good aryl group, amino group, acetyl group, allyl group or cycloalkylene group. However, R_1 and R
_2, R_3 and R_4 may each form a nitrogen-containing heterocycle, and R_1 and R_3, R_2 and R_4 may also each form a ring. ] (2) The silver halide color photographic light-sensitive material described in item 1 has a silver halide containing silver iodide in at least 0.5 mol% or more in at least one layer. Processing method for silver color photographic materials.