JPH02171749A - Processing method for silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To allow rapid processing and to obviate the generation of precipitate in the photosensitive material or processing liquid by incorporating the ferric complex salt of a specific compd. and thiocyanate into the processing liquid having bleachability. CONSTITUTION:The ferric complex salt of the compd. expressed by the formula I or II and at least 5X10<-2>mol/l thiocyanate are incorporated into the processing liquid having the bleachability. In the formula I, A1 to A4 denotes -CH2OH, -COOM or -PO3M1M2; M, M1, M2 respectively denote a hydrogen atom, sodium, potassium or ammonium; X denotes 3 to 6C substd. or unsubstd. alkylene group. In the formula II, (n) denotes 1 to 8 integer; B1 and B2 respectively denote 2 to 5C substd. or unsubstd. alkylene group. The rapid processing is enabled in this way and the generation of the precipitate in the photosensitive material or the processing liquid is prevented.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for processing a silver halide color photographic light-sensitive material (hereinafter referred to as a "photosensitive material" as necessary), and more specifically, a method for processing a silver halide color photographic light-sensitive material (hereinafter referred to as a "photosensitive material" as necessary), and more specifically, The present invention relates to a method for processing a photosensitive material in which no precipitate is generated in the photosensitive material or in a processing solution.

[Prior Art] In the processing of photosensitive materials, color development processing and desilvering processing are essential.

Generally, in color development processing, silver halide exposed to light is reduced by a color developing agent to produce silver, and
The oxidized color developing agent reacts with the coupler to form a dye image. In the desilvering process, metallic silver produced in the color development process is oxidized by the action of an oxidizing agent (commonly called a bleaching agent), and then dissolved and desilvered by a fixing agent.

Through this desilvering step, only the dye image remains on the photosensitive material.

This desilvering process is performed either when bleaching and fixing are performed separately, or when bleaching and fixing are performed simultaneously (herein, this process is referred to as deep fixing, and the solution used for this process is There is a bleaching ankle liquid).

Usually, in addition to the basic steps mentioned above, various auxiliary steps are included to maintain the photographic and physical quality of the image, or to improve the preservation of the image.6 For example, hardening bath, stop bath, These include processing steps using an image stabilizing bath and a water washing bath.

In the above-mentioned method of performing bleaching and fixing separately for desilvering, EIITA-Fe (ethylenediaminetetraacetic iron complex salt) is used as a bleaching agent, and thiosulfate (iron complex salt of ethylenediaminetetraacetate) is used as a fixing agent.
S2032→ is used. On the other hand, in the case of bleaching ankle treatment, EDTA-Fe or DTPA is generally used as a bleaching agent.
IIFe (diethylenetriaminepentaacetate iron complex salt) is used, and thiosulfate is used as a fixing agent.

[Problems to be Solved by the Invention] However, in the former method, thiocyanate (SCN-), which has a faster fixing speed than thiosulfate, which is a conventional fixing agent, is used.
A method using SON has been proposed, but when SON is used, there is a problem in that insoluble Rodan silver tends to precipitate on the surface of the photosensitive material.

In addition, in the latter method, the conventional fixative, thiosulfate, is weak and has strong oxidizing power, P[1TA
-If it coexists with a bleaching agent such as Fe, sulfidation will occur violently, so it is difficult to shorten the bleach-fixing completion time.Especially in the case of high-speed photosensitive materials with a large amount of silver, the bleach-fixing time will be significantly reduced. There was a problem with this.

[Object of the Invention] An object of the present invention is to provide a method for processing a photosensitive material that enables rapid processing and does not generate precipitates in the photosensitive material or processing solution.

[Means for Solving the Problems] As a result of intensive research to solve the above-mentioned problems, the inventors of the present invention conducted a treatment with a processing liquid having bleaching ability immediately after color development, and then using a processing liquid having fixing ability. In the method for processing silver halide color photographic light-sensitive material No. 4 in which processing is carried out using
a ferric complex salt of the compound represented by H3 and at least 5
The present invention was based on the discovery that the above object can be achieved by containing 10-2 mol/l of thiocyanate.

General formula [A] [In the formula, A1-A4 may be the same or different, respectively.
, -CH20H, -COOM or -PO3H+Mt
represents.

M, M+, and Ml each represent a hydrogen atom, sodium, potassium, or ammonium; X represents a substituted or unsubstituted alkylene group having 3 to 6 carbon atoms;] General formula [B] It has the same meaning as described in the general formula [A], and n represents an integer of 1 to 8. Further, B1 and B2 may be the same or different, and each represents a substituted or unsubstituted alkylene group having 2 to 5 carbon atoms.Next, the compound represented by the general formula [A] will be described in detail.

A, -A, may be the same or different, -CH
20H, -Coo)l or -P(hM+Mz), Ml and Ml each represent a hydrogen atom, sodium, potassium or ammonium, X is a substitution having 3 to 6 carbon atoms,
Unsubstituted alkylene groups (e.g. propylene, butylene,
Examples of the substituent which represent pentamethylene, etc.) include a hydroxyl group and an alkyl group having 1 to 3 carbon atoms.

Preferred specific examples of the compound represented by the general formula [A] are shown below.

(A-1) (A-7) (A-2) (A-8) (A-3) (A-9) (A-4) (A-10) (A-5) (A-11) (A-6) (A-12) For these compounds (A-1) to (A-12), in addition to the above, sodium salts, potassium salts, or ammonium salts thereof can be arbitrarily 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),
(A-9), particularly preferred is (A-9).
1), (A-9).

Next, the compound represented by the general formula [B] will be explained in detail.

A1-A4 have the same meanings as above, n represents an integer of 1 to 8, eBl and B2 may be the same or different, and each represents a substituted or unsubstituted alkylene group having 2 to 5 carbon atoms (for example, +
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).

Preferred specific examples of the compound represented by the general formula [B] are shown below.

(B-1) (B-2) (B-3) (B-4) (B-5) (B-6) (B-7) These (B-1) to (B-7) compounds are In addition to the above, sodium salts, potassium salts, or ammonium salts of these salts can be arbitrarily 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 (B-1), CB-4), and (B-7), and particularly preferred is (B-1).

These ferric complex salts of the compounds represented by the general formulas [A] and [B] are used as treatment liquids with bleaching ability! ; use of at least 0.1 mol per L is preferred, more preferably 0.1 mol;
The range is from 5 mol to 2.0 mol/i, most preferably 0
．． 2-1. It is in the range of Q mol/vertical.

The bleaching solution and the starting fixing solution of the present invention have the general formula [A]
Or, to the ferric complex salt of the compound represented by [B], other 7 ferric minoboricarboxylic acid NkjA examples include ferric ethylenediaminetetraacetic acid complex salt, diethylenetriaminepentaacetic acid ferric complex salt, 1,2-cyclohexane. It can be used in combination with diaminetetraacetic acid ferric complex salt and the like.

In the present invention, at least 50% (in terms of mole) of the organic acid ferric complex salt in the bleaching solution and bleach-fixing solution of the present invention is a ferric complex salt of a compound represented by the general formula [A] or [B]. However, in order to better achieve the desired effects of the present invention, it is preferably 70% or more, more preferably 80% or more, particularly preferably 90% or more, and most preferably It is 95% or more.

In the bleach-fix solution of the present invention, the general formula [A] or [
Preferred bleaching agents for use in combination with the compound represented by B] include the following.

[A'-1] Ethylenediaminetetraacetic acid or its salt (salt of ammonium, sodium, potassium, triethanolamine, etc.) [A'-2] ) Lance-1,2-cyclohexanediaminetetraacetic acid or its salt (〃) [ A'-3] Dihydroxyethylglycinate or its salt (ll) [A'-4] Ethylenediaminetetrakismethylenephosphonic acid or its salt (ll) [A'-5] Nitrilotrismethylenephosphonic acid or its salt (〃) [ A'-6] Diethylenetriaminepentakismethylenephosphonic acid or its salt (〃) [A'-7] Diethylenetriaminepentaacetic acid or its salt (ll) [A'-8] Ethylenediaminediorthohydroxyphenylacetic acid or its salt (// ) [A'-9] Hydroxyethylethylenediaminetriacetic acid or its salt (ll) [A'-10] Ethylenediaminedipropionic acid or its salt (ll) [A'-11] Ethylenediaminediacetic acid or its m(〃) [ A'-12] Hydroxyethyliminodiacetic acid or its salt (〃) [A'-13] Nitrilotriacetic acid or its salt (ll
) [A'-14] Nitrilotripropionic acid or its kM (//) [A'-151) Liethylenetetraminehexaacetic acid or its salt (//) [A'-18] Ethylenediaminetetrapropionic acid or its salt (// /) The above-mentioned compounds can be mentioned, but of course the compounds are not limited to these exemplified compounds.

In these compounds, especially A'-1, A'-2, A'-7
is preferred.

Iron aminopolycarboxylate (m)! The salts may be used in the form of complex salts or #(m) salts such as ferric sulfate, ferric chloride, ferric acetate, ferric ammonium sulfate, ferric phosphate, etc.
An iron (m) ion complex salt may be formed in a solution using iron or the like and aminopolycarboxylic acid or its salt. When used in the form of a complex salt, one type of complex salt may be used,
In addition, two or more types of complex salts may be used. On the other hand, when forming a complex salt in a solution using a ferric salt and 7-minopolycarboxylic acid, one or more types of ferric salts may be used. Furthermore, one type or two or more types of aminopolycarboxylic acids may be used, and in any case, the aminopolycarboxylic acid may be used in excess of the amount required to form the iron (m) ion complex. Aminopolycarboxylic acids and iron complex salts may be used as ammonium, sodium, potassium, or triethanolamine salts.

Two or more of these may be used in combination.

Further, the bleach-fix solution or bleaching solution containing the above-mentioned iron (m) ion complex may contain metal ion complex salts other than iron, such as cobalt, copper, nickel, and zinc.

The treatment liquid having bleaching ability of the present invention contains thiocyanate. Specific examples of thiocyanate include the following compounds.

[Exemplary Compounds] (1) NIl, 5CN (2) KSCN (3) Na5CN The amount of thiocyanate contained in the treatment solution having bleaching ability is at least 5 X 10-2 mol/l, preferably 5 X It is in the range of 10-2 to 4 mol/l, more preferably in the range of 0.1 to 2 mol/l.

Amounts lower than 5 x 10-2 mol/l will not achieve the object of the invention.

The bleaching solution and bleach-fixing solution related to the present invention are disclosed in Japanese Patent Application No. 6
When containing at least one of the imidazole and its derivatives described in Specification No. 3-48E131 or the compounds represented by the general formulas [I] to [IX] described in the same specification, the desired effects of the present invention can be better achieved. In addition, it has the additional effect of improving precipitation caused by silver in the bleaching solution, so it is more preferably used in the present invention.

In addition to the bleach accelerators mentioned above, exemplified compounds N described on pages 51 to 115 of Japanese Patent Application No. 80-283568, pages 51 to 115;
o, I-2, I-4 to 7. I-9 to 13, l-
18-21, l-23, l-24, I-28, 27,
■-30~38, ■-38, ll-2~5, II-7
~10. IT-12~20゜ll-22~25, II-
27, ll-29 to 33, ll-35, 38, ll-3
8-41, ll-43, ■l-45-55, ll-57
〜60゜ll-62~64, ll-87~71. IT
-73~79, -81~84.11-88~99, l
l-101,102, H-104~ +1゜n-112
~119. ll-121-124. ll-126,
ll-128~144, rl-+4[f, Tl-1
48-155, II-157, m-4.

l11-6~8, m-10,11, m-13, lll-
15-18, ■-20, m-22, m-23, [1-2
5, m-27, ■-29 to 32, m-35, 36, r
V-3, IV-4, V-3~6, V-8~14.
V-IS~38, V-40~42. V-44
~4B, V-48~66, ■-68~70, ■-7
2~74°V-7i (~79, V-81,82,V-
84-100, V-102-108. V-1
10, V-112, 113, V-118~119,
V-121~123. V-125~130,
V-132~144, V-148~182, V-
184-174, V-178-184, VT-
4, Vl-7, ■-10, Vl -12, 71-13°vr-te, ■-19, Vl-21, ■-22, V
l -25゜■-27~34, ■-36, ■-3, ■
-6, ■-13, ■-13, ■-20 and JP-A-1983-
17445, from page 22 to 'fs page 25, 1! Exemplary compounds (m-2) to (m-3), (m-
5) ~(m-to), (m-12) ~(m-45)
, (m-47) ~ (m-so) , (m-52) ~
(IU -54), (m-58) ~ (m -83), (
Compounds such as m-85) can also be used in the same manner.

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 11 parts of the bleach-fix 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 light-sensitive material being processed. 0.05 per sentence of liquid
~50. is preferred, more preferably a bleach-fix solution l!
The amount is 0.05 to 15 g per liter.

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

The processing temperature of the bleaching solution and bleach-fixing solution of the present invention is 20°C ~
It is used at 45°C, preferably between 25°C and 42°C.

A halide such as ammonium bromide is usually added to the bleaching solution and bleach-fixing solution of the present invention.

The bleaching solution of the present invention includes various salts such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide. narupi
(One buffering agent may be contained alone or in combination of 2!d1 or more. In addition, various optical brighteners, antifoaming agents, or surfactants may also be contained.

The preferred replenishment amount of the bleaching solution according to the present invention is from 20 m to 500 m/m of silver halide color photographic light-sensitive material.
++JL, particularly preferably 30 liters to 'J5
0 layer, more particularly preferably 40 m1 to 3
00+s sentence, most preferably 50+ml to 2
It has 50 layers.

The processing liquid having fixing ability according to the present invention is a fixing liquid and a bleach-fixing liquid, and fixing agents used in these liquids include:
A commonly used thiosulfate such as ammonium thiosulfate is used. Further, the above-mentioned thiocyanates may be used in combination.

In addition to these fixers, fixers and bleach-fixers include boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide. A pH buffering agent consisting of various salts such as the following may be contained alone or in combination.

Furthermore, alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride,
It is desirable to contain a large amount of rehalogenating agent such as ammonium bromide, and pH buffering agents such as borates, oxalates, acetates, carbonates, phosphates, alkylamines, polyethylene oxides, etc. are commonly used as fixing agents. Those known to be added to bleach-fixing solutions and bleach-fixing solutions can be added as appropriate.

In the present invention, in order to increase the activity of the bleach solution or bleach-fix solution, air or oxygen may be blown into the processing bath and processing replenisher storage tank as desired.
Alternatively, a suitable oxidizing agent such as hydrogen peroxide, bromate, persulfate, etc. may be added as appropriate.

In the present invention, even if the fixer contains a large amount of silver and iodine (for example, Ag°6g/1 or more, I-0,
6 g/1 or more), the object of the present invention can be achieved.

When carrying out the method of the present invention, silver may be recovered from the fixing solution or bleach-fixing solution by a known method.
Precipitation method (described in Japanese Patent Application Laid-Open No. 52-73037, Specification of Second Patent No. 2,331,220!Iiri), Ion exchange method (described in Japanese Patent Application Laid-Open No. 51-17114, Second Patent No. 2)
．． 548,237) and the metal replacement method (British Patent No. 1,353,805 specification a) can be effectively used.

It is particularly preferable to recover silver in-line from the tank solution, as this improves suitability for rapid processing, but it is also possible to recover silver from the overflow waste solution and reuse it.

When the fixer and t'A self-fixer according to the present invention are replenished in an amount of 1200 sJ1 or less per rn' of light-sensitive material,
The objective effects of the present invention can be better achieved. In particular, remarkable effects are obtained when the photosensitive material is 20m41 to 100hi, especially 500m to 80h, per 1 m' of photosensitive material.

A compound represented by the general formula [FA] described on page 56 of Japanese Patent Application No. 63-48931 and exemplified compounds thereof are added to the processing liquid (fixer or bleach-fixer) having fixing ability according to the present invention. Not only does the desired effect of the present invention be better achieved when used as a solution, but the sludge generated when a small amount of light-sensitive material is processed over a long period of time using a fixing solution or a bleach-fixing solution is extremely small. It is more preferably used in the present invention because the effect is enhanced.

The compound represented by the general formula [FA] described in the same specification is described in U.S. Patent No. 3,335,181 and U.S. Patent No. 3,28
It can be synthesized by a general method as described in US Pat. No. 0,718. These compounds represented by the general formula [FA] may be used alone or in combinations of 2.%i or more.

Good results can be obtained when the amount of the compound represented by the general formula [FA] ranges from 0.1 g to 200 g per treatment liquid. In particular, the range of 0.2 g to 100 g is preferable, and the range of 0.5 g to 50 g is particularly preferable.

The pH of the bleaching solution of the present invention is used in the range of 2 to 8, preferably in the range of pl+ of 2.5 to 7, particularly preferably in the range of pl+ of 113 to 6, in view of the effects of the present invention. The most preferred range is pl+3.5 to 5.8.

The pl+ of the fixing solution and bleach-fixing solution of the present invention is used in the range of 4 to 8.

Sulfites and sulfite-releasing compounds are used in the fixers and bleach-fixers of this invention. You can.

Specific examples of these compounds include potassium sulfite,
Examples include sodium sulfite, ammonium sulfite, ammonium hydrogen sulfite, potassium hydrogen sulfite, sodium hydrogen sulfite, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, and the like. Furthermore, the general formula [B-
1] or [B-2] are also included.

These sulfites and sulfite-releasing compounds are required in an amount of at least 0.1 mole as sulfite per liter of fixer or bleach-fix solution, but preferably in the range of 0.12 mol/l to 0.65 mol/l; .15 mol/cross to 0.50 mol/l
Particularly preferred is a range of 0.20 mol/l
The range of 0.40 mol/cross is preferred.

However, the number of moles of these sulfites and sulfite-releasing compounds are shown in values converted to sulfite.

The total processing time of the processing liquid having bleaching ability and the processing liquid having fixing ability according to the present invention is preferably 3 minutes 45 seconds or less, and more preferably the total time is 20 seconds to 3 minutes 20 seconds.
The objective effects of the present invention are well achieved when the time is within a range of seconds, 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 seconds to 70 seconds, particularly 2 minutes or less.
The processing time of the processing liquid having fixing ability, which is preferably 0 seconds to 55 seconds, can be arbitrarily selected within the above-mentioned total range, but from the viewpoint of the desired effect of the present invention, it is preferably 3 minutes and 10 seconds or less, and particularly The time period is preferably from 10 seconds to 2 minutes and 40 seconds, particularly preferably from 20 seconds to 2 minutes and 10 seconds.

In the processing method of the present invention, it is preferable to apply forced liquid agitation to the bleaching solution, fixing solution, and bleach-fixing solution. This is from the perspective of

The term "forced liquid stirring" as used herein means adding a stirring means to forcibly stir the liquid, rather than the usual diffusion and movement of the liquid.

Examples of forced stirring means include the following methods.

1. High-pressure spray treatment method or spraying is a stirring method 2. Air bubbling treatment method 3. Ultrasonic oscillation treatment method 4. Vibration treatment method High-pressure spray treatment method is a discharge pressure of 0.1 kg/crn.
This refers to a method in which processing is performed by directly spraying a processing liquid onto a photosensitive material from a spray nozzle while applying a pressure of 0.0 or more. Ik
It refers to a method in which processing is carried out by directly spraying a processing liquid onto a photosensitive material under a pressure of g/crn' or more, and a pressure pump or a liquid pump is generally used as the pressure source. Pressure pumps include plunger pumps, gear pumps, magnet pumps, and cascade pumps, such as 15-LPM type, 10-BFM type, and 20 type manufactured by Kazan Seisakusho.
-BFM type, 25-BFM type, etc. are known as examples.

In addition, as a liquid pump, for example, M[]- manufactured by Iwaki Co., Ltd.
8 type, MO-10 type, 11! []-20R type, MD-3
0R type, NO-35R type, MDK-25 type, MDK-3
There are two types.

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 (win/win) and the spray pressure (kg/cgo). Therefore, a pressurizing device is required that can adjust the pressure in proportion to the number of spray nozzles in order to fully exhibit the effect. The most preferable pressure is 0.3~]Okg/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, in the air bubbling processing method, a sparger is installed at the bottom of the lower transport roller of the processing liquid tank, air or inert gas is sent to the sparger, and the air bubbles discharged from the sparger's mouth vibrate the photosensitive material. In this method, 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 holes from 1 to 3 hm, and then from 5 to 1
Even better results can be obtained if the ratio is set to 5II11. An air compressor such as Bebicon (0.4KW, BU7TL, manufactured by Hitachi, Ltd.) can be used to send air.
) and air pumps, such as Ikki air pumps (
AP220 type), etc.

The amount of air is 21 per rack of automatic developing machine.
301 /ll1n is required from /win, and 51
/win to 20Jl /+*in gives a more favorable result.

The amount of air or inert gas must be adjusted depending on the size of the processing liquid tank and the seedlings of the photosensitive material. Preferably, the amount of 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 processor 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 (holder type), etc. manufactured by Ultrasonic T Co., Ltd. are used.

The transducer frequency of the ultrasonic oscillator is 5 to 1000K.
Hz is used, but ultrasonic waves of 10 to 50 KHz are particularly preferable in terms of the desired effect of the present invention and damage to the equipment of automatic processors. Direct irradiation or indirect irradiation by providing a reflector may be used, but as the ultrasonic waves attenuate in proportion to the irradiation distance, direct irradiation is preferable, and the irradiation time should be at least 1 second. 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 processor to effectively perform immersion processing. As the vibrator for the vibration source, for example, V-28 and V-4B types manufactured by Shinko Electric Co., Ltd. are generally used. The method of installing the vibrator is to fix the vibrator to the upper part 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 to 100
00 times/sin is preferable, and the most preferable range is 500 times/sin.
~6000 times/win. The amplitude of the photosensitive material to be processed is from 0.2 mm to 30+ am, preferably from 1 mm to 2
It is 0mm. 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.

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

(1) Color development → bleaching → fixing → washing with water (2) color development → bleaching → fixing → washing → stabilization (3) color development → bleaching → ankle → stabilization (4) color development → bleaching → fixing → first stable → first stabilization 2 stable (5
) Color development → bleaching → bleach ankle → washing with water (5) color development → bleaching → bleach-fixing → washing → stabilization (7) color development → bleaching → bleaching ankle → stable (8) color development → bleaching → gain white fixing → first Stability → Second Stability (9) Color Development → Bleach-Fixing → Fixing → Stability Among these steps, (3), (4), (7), and (8) are particularly preferred, and especially (3) and (4). ) is preferred.

The color developing solution according to the present invention includes alkaline agents commonly used in developing solutions, such as sodium hydroxide, potassium hydroxide,
ammonium hydroxide, sodium carbonate, potassium carbonate,
It may contain sodium sulfate, sodium metaborate, borax, etc., and may further contain various additives, such as benzyl alcohol, alkali metal silver halides, such as potassium bromide or potassium chloride, or a developing tA moderating agent, such as citradinic acid. , hydroxylamine or ordinary m-salt may be contained as a preservative.

Furthermore, various antifoaming agents, surfactants, and organic solvents such as methanol, dimethylformamide or dimethyl sulfoxide can be appropriately contained.

Further, the pH of the developer according to the present invention is usually 7 or more, preferably about 9-13.

The color developer used in the present invention may optionally contain antioxidants such as hydroxylamine, tetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone, aromatic secondary alcohol, hydroxamic acid, pentose, or Hexose, pyrogallol-1,3
- Dimethyl ether etc. may be contained.

Furthermore, in the color developing solution according to the present invention, various chelating agents can be used together as metal ion chaining agents. For example, the chelating agents include ethylenediaminetetraacetic acid,
Aminopolycarboxylic acids such as diethylenetriaminepentaacetic acid; organic phosphonic acids such as l-hydroxyethylidene-1,1-diphosphonic acid;

7minobolyphosphonic acid such as aminotri(methylenephosphonic acid) or ethylenediaminetetraphosphoric acid, oxycarboxylic acid such as citric acid or gluconic acid, phosphonocarboxylic acid such as 2-phosphonobutane-1,2,4-tricarboxylic acid, tripolyphosphoric acid Alternatively, polyphosphoric acids such as hexametaphosphoric acid may be mentioned.

In the present invention, when processing with a stabilizing solution subsequent to a fixing solution or a bleach-fixing solution, the desired effects of the present invention, especially the staining of unexposed areas during storage over time, are improved.

The amount of replenishment of the stabilizer according to the present invention is 1 of the amount brought in from the pre-bath per unit area of the color photographic light-sensitive material to be processed.
The concentration of the pre-bath component (bleach-fix solution or fixer) in the stabilizing solution is 1 to 80 times, preferably 2 to 60 times, but in the present invention, the concentration of the pre-bath component (bleach-fix solution or fixing solution) in the final stabilizing solution tank is /
More preferably 500 or less, particularly preferably I/10
00 or less.

Furthermore, from the viewpoint of low pollution and liquid storage stability, the
100000 is preferable, more preferably 1/20
The processing tank of the stabilization tank is configured so that the number is 00 to 1,150,000.

Stabilization treatment tank! The tank is preferably composed of the same number of Bt tanks, and the plurality of tanks is preferably 2 or more and 6 or less.

When the number of stabilization treatment tanks is 2 or more and 6 or less, and a countercurrent method (a method in which the supply is supplied to the rear bath and overflows from the front bath) is used, the effects of the present invention, especially low pollution and image preservation, can be obtained. It is preferable from the viewpoint of improvement. Particularly preferably 2 to 3 tanks, more preferably 2 tanks.

The amount brought in depends on the type of photosensitive material, the conveyance speed of the automatic processor,
Although it varies depending on the transportation method, squeezing method for the surface of the photosensitive material, etc., color photosensitive materials for photography usually use color film (
In the case of roll film), the usual carry-on amount is 50m1
/rn' to 150 m1/rn', and the replenishment amount at which the effect of the present invention is more remarkable for this carry-in amount is in the range of 50 m1/m' to 4.01/rn', and the replenishment amount where the effect is particularly remarkable. The amount is 200 rin/m1
~1500 m sentences/ml.

The treatment temperature for the treatment with the stabilizing solution is preferably in the range of 15 to 60°C, preferably 20 to 45°C.

The p)I value of the stabilizer of the present invention is preferably in the range of pH 4.0 to 9.0, more preferably pH 4.5 to 9.0, for the purpose of improving image storage stability in addition to the effects of the present invention. The pH range is particularly preferably 5.0 to 8.5.

As the pHrA adjuster that can be contained in the stabilizer preferably used in the present invention, any commonly known alkaline agents or acid agents can be used.

The stabilizing solution in the present invention preferably contains a metal salt in combination with a chelating agent.

Such metal salts include Ha, Ca, Ce, G
o, In.

La, Mn, old, Bi, Pb, Sn, Zn,
It is a metal salt of Ti, Zr, Mg, An, or Sr, and can be supplied as an inorganic salt such as a halide, hydroxide, sulfate, carbonate, phosphate, or acetate, or as a water-soluble chelating agent. The amount used is 1 stabilizing solution IX 10
-4 to IX 10 to 1 mol, preferably 4X 10-4 to 2X 10-2 mol.

The stabilizer of the present invention includes organic salts (citric acid, acetic acid, amber acid, oxalic acid, benzoic acid, etc.), pH adjusters (phosphates, borates, hydrochloric acid, sulfates, etc.), and surfactants. , preservatives, etc. can be added.

The amount of these compounds to be added may be determined in any combination that is necessary to maintain the pH of the stabilizing bath according to the present invention and that does not adversely affect the stability of color photographic images during storage and the occurrence of precipitation. It is safe to use.

Anti-spill agents preferably used in the stabilizer of the present invention include hydroxybenzoic acid ester compounds, phenolic compounds,
Thiazole compounds, pyridine compounds, guanidine compounds, carbamate compounds, morpholine compounds,
These include quaternary phosphonium compounds, ammonium compounds, urea compounds, inxazole compounds, propanolamine compounds, sulfamide compounds, amino acid compounds, active halogen-releasing compounds, and penttriazole compounds.

The hydroxybenzoic acid ester compound includes methyl ester, ethyl ester, propyl ester, butyl ester, etc. of hydroxybenzoic acid, preferably n-butyl ester, isobutyl ester, propyl ester of hydroxybenzoic acid, and more preferably This is a mixture of three types of hydroxybenzoic acid esters.

The phenolic compound preferably used as the anti-spill agent of the present invention is a compound which may have an alkyl group, a halogen atom, a nitro group, a hydroxyl group, a carboxylic acid group, an amine group, a phenyl group, etc. as a substituent, and is preferably a compound. are ortho phenylphenol and orthocyclohexyphenol,
These are phenol, nitrophenol, chlorophenol, cresol, guaiacol, and aminephenol. Particularly preferably, ortho-phenylphenol exhibits remarkable anti-spiking properties in combination with bisulfite adducts of aldehyde derivatives.

The thiazole compound is a compound having a nitrogen atom and a sulfur atom in a five-membered ring, and is preferably 1,2-pentwinthiazolin-3-one, 2-methyl-4-thiazolin-3-one, or 2-octyl-4. -inthiazoline 3-one, 5-chloro-2-methyl-4-inthiazoline 3-
2-chloro-4-thiazolyl-penzimidazole.

Specifically, the pyridine-based compounds include 2,6-dimethylpyridine, 2,4,6-)limethylpyridine, and radium-
Examples include 2-pyridinethiol-1-oxide, but radium-2-pyridinethiol-1-oxide is preferred.

Specifically, guanidine compounds include cyclohexidine,
Examples include polyhexamethylene biguanidine hydrochloride, dodecylguanidine hydrochloride, etc., and dodecylguanidine and its salts are preferred.

Specific examples of carbamate compounds include methyl-1-(butylcarbamoyl)-2-benzimidazole carbamate and methylimidazole carbamate.

Specific examples of morpholine compounds include 4-(2-nitrobutyl)morpholine and 4-(3-nitrobutyl)morpholine.

Quaternary phosphonium compounds include tetraalkylphosphonium salts, tetraalkoxyphosphonium salts, etc.
Preferred are tetraalkylphosphonium salts, and more specific preferred compounds are tri-n-butyl-tetradecylphosphonium chloride and triphenyl-nitrophenylphosphonium chloride.

Specific examples of quaternary ammonium compounds include benzalkonium salts, benzethonium salts, tetraalkylammonium salts, alkylpyridium salts, and specific examples include dodecyldimethylbenzylammonium chloride, dodecyldimethylammonium chloride, and laurylpyridinium chloride. etc.

Specifically, the urea-based compounds include N-(3,4-dichlorophenyl)-N'-(4-chlorophenyl)urea, N-(
Examples include 3-)lifluoromethyl)-N'-(4-chlorophenyl)urea.

Specific examples of inxazole compounds include 3-hydroxy-5-methyl-isoxazole.

Propatur amino compounds include n-propaturs and inpropaturs, specifically 0L-2-benzylamino-1-propatur, 3-diethylamino-
1-propanol, 2-dimethylamine-2-methyl-
1-propaturamine, 3-amino-1-propaturamine, idopropaturamine, diimpropaturamine, N
, N-dimethyl-isopropanolamine, and the like.

Examples of sulfamide compounds include 0-nitrobenzenesulfamide, p-aminebenzenesulfamide F, 4-
Chloro-3,5-dinitrobenzenesulfamide, α-
Examples include amino-p-)luenesulfamide.

A specific example of the amino acid compound is N-lauryl-β-alanine.

Active halogen-releasing compounds include primary sodium hypochlorite, chloramine T dichloroisocyanurate, chloramine B, dichlorodimethylhydantoin, and chlorobromodimethylhydantoin, while sodium hypochlorite, sodium dichloroisocyanurate, trichloroisocyanurate Acids are preferred.

Among the anti-spill agents mentioned above, compounds preferably used in the present invention are phenolic compounds, thiazole compounds, pyridine compounds, guanidine compounds, quaternary ammonium compounds, active halogen-releasing compounds, and penttriazole compounds. Furthermore, from the viewpoint of liquid storage properties, phenolic compounds, thiazole compounds,
These are active halogen-releasing compounds and penztriazole compounds.

The amount of anti-piping agent added to the stabilizing liquid is 0.0 per liter of stabilizing liquid.
If it is less than 0.01 g, the desired effect of the present invention will not be achieved, and if it is less than 50 g.
If the amount exceeds 0.001 g, it is not preferable in terms of cost and the storage stability of the dye image deteriorates.
Used in the range of 50g, preferably 0.005 to 10
It is used in the range of g.

In the treatment of the present invention, silver may also be recovered from the stabilizing solution by the method described above8.Also, the treatment of bringing the stabilizing solution of the present invention into contact with an ion exchange resin, the electrodialysis treatment (see Japanese Patent Application No. 59-98352) It is also possible to use reverse osmosis treatment (see Japanese Patent Application No. 5!]-98532).

Further, it is preferable to use water that has been previously deionized in the stabilizing solution of the present invention, since this improves the anti-spill properties of the stabilizing solution, the stability of the stabilizing solution, and the image storage stability. As a means of deionization treatment, the dielectric constant of the washing water after treatment is set to 50 islands s/c11 or less, or Ca and g ions are added to
Any material may be used as long as it has a pp+w or less, but it is preferable to use an ion exchange resin or a reverse osmosis membrane alone or in combination. Regarding ion exchange resins and reverse osmosis membranes, see Technical Report No. 87-1984. Although described in detail, it is preferable to use a strongly acidic Hg cation exchange resin and a strongly basic oH type anion exchange resin.

In the present invention, the salt concentration in the stabilizing solution is 11,000 ppm or less, preferably 800 ppm or less, which enhances the washing effect and is good for improving the white background and preventing pimples.

The processing time for the stabilizing solution in the present invention is 2 minutes or less, preferably 1 minute and 30 seconds or less, particularly preferably 1 minute or less, in order to achieve the effects of the present invention, particularly for the processing stabilizing solution.

In the present invention, the inclusion of a surfactant in the stabilizing liquid is particularly preferably used from the viewpoint of preventing the formation of precipitates on the surface of the photosensitive material and improving the surface properties.

As the surfactant, compounds represented by the general formulas [I] to [II] and water-soluble organic siloxane compounds described in JP-A-62-250449 are particularly preferably used from the viewpoint of the effect on the object of the present invention. .

Next, the photosensitive material to be processed in the present invention will be explained.

The photosensitive material is developed using an internal development method in which a coupler is contained in the photosensitive material (U.S. Pat. No. 2, No. 76,679, No. 2,801).
, 171), as well as external development methods in which the coupler is contained in the developer (see U.S. Pat. No. 2.252.7+8,
2,592,243 and 2,590,970). Further, as the coupler, any coupler generally known in the industry can be used. For example, cyan couplers include those based on a naphthol or phenol structure and form indoaniline dyes through a coupling link, while magenta couplers include those having a 5-pyrazolone ring with an active methylene group as a backbone structure, and pyrazole azole-based couplers. As yellow couplers, those having penzoylacetanilide, bivalylacetanilide, or acylacedoanilite structures having an active methylene ring, with or without a substituent at the coupling position, can be used. In this way, couplers include so-called 2-equivalent couplers and 4-equivalent couplers.
Any of our shop type couplers can be applied.

In the present invention, since the intended effects of the present invention can be better achieved, Japanese Patent Application No. 148
Cyan couplers represented by the general formula [C-A col [C-C] described on pages 196 to 196 are preferably used, and specific examples of these cyan couplers include Japanese Patent Application No. 63-1:
(C-1) described in Specification No. 2501, pages 159 to 173
-(C-46) and (C-51) to (C-118) described on pages 178 to 196 of the same specification.

Next, as a magenta coupler preferably used in the present invention, Japanese Patent Application No. 197-32051
Examples include magenta couplers represented by the general formula [M-I] described on pages 207 to 207, and specific examples of these magenta couplers include ( M-1) ~ (M-76)
and magenta couplers No. 31 to No. 223 described on pages 66 to 122 of Japanese Patent Application No. 51-9791.

The silver halide color photographic light-sensitive material used in the present invention is a compound (hereinafter referred to as B
When containing an AR compound), the desired effects of the present invention can be better achieved.

Preferably used BAR compounds include those disclosed in Japanese Patent Application No. 1983.
-32501 Specification, pages 233 to 252, compounds represented by the general formulas [BAR-A and [BAR-Bl] are mentioned, and specific examples of these BAR compounds include No. Specification Nos. 252-274
Compounds (1) to (77) described on p.

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

When the silver halide emulsion used in the present invention contains silver halide grains having an average grain size/grain thickness of less than 5, the average silver iodide content determined by X-ray fluorescence analysis When (J, ) is compared with the silver iodide content (J2) on the grain surface determined by X-ray photoelectron spectroscopy, the relationship J,>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.

xi 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. This is applied thinly onto a mirror-polished silicon wafer to obtain a Δlft constant sample.

For measurements by X-ray photoelectron spectroscopy, the device as a Pl+1
ESCA/SAM5 [i05 manufactured by Co., Ltd. was used, Mg-Ka ray was used as the excitation X-ray, X-ray source voltage was 15 KV, and X-ray source current was 4.
This is carried out under the conditions of 0 uA and bus energy of 50 eV.

Ag5d, Br5d to determine the surface halide composition
.

Detect ld3/2 electrons.

The composition ratio is calculated by the relative sensitivity coefficient method using the integrated intensity of each peak. Ag:ld, Br5d, 13d
5 respectively as a 3/2 relative sensitivity coefficient. +0.0.81
．． By using 4.592, the composition ratio can be given in atomic percent.

When the silver halide emulsion used in the present invention contains grains whose average value of grain size/grain thickness is less than 5, it is preferable that the grain size distribution is monodisperse. Emulsion means ±20% around the average grain size of 7.
The weight of silver halide contained within the grain size range is 60% or more of the total weight of the silver halide grains, preferably 70% or more, and more preferably 80% or more.

Here, the average particle size T is the frequency n of particles having a particle size ri of 1
The particle size ri is defined as the product nix ri3 of i and ri3 (3 significant digits, the minimum digit is rounded down to 5 decimal places).

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.

The particle size can be obtained, for example, by photographing the particles with an electron microscope at a magnification of 10,000 to 50,000 times, and actually measuring the particle diameter or projected area of Print-E (the number of particles measured is (assumed to be at least 1000 indiscriminately)
.

Particularly preferred highly monodisperse emulsions of the present invention have a distribution width defined by 20% or less, more preferably 15% or less.

Here, the average particle diameter and particle diameter standard deviation shall be determined from ri defined above.

In the case of a tabular silver halide emulsion used in the present invention, 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 ( J3), it satisfies the relationship J1>J's.

The X-ray microanalysis method will be explained.

Energy dispersive X-ray analyzer for electronics! Silver halide grains were dispersed in a tallit for electron microscopy equipped with one mirror, and the magnification was set so that only one grain fell into the field of view of the CRT by cooling with liquid nitrogen. Accumulate the intensity. The silver iodide content can be calculated using the intensity ratio of ILα/AgLα 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 (J2) on the grain surface measured by X-ray photoelectron spectroscopy is preferably 6 to 0 mol. , more 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 distance from the center of the silver halide grains by 80% or more in the grain diameter direction is determined by the X-ray microanalysis method. The average value (J3) of the silver iodide content measured on silver halide crystals is preferably 6 to 0 mol%, more preferably 5 to 0 mol%, particularly preferably 4 to 0 mol%. It is 0.01 mol%. The average thickness of tabular silver halide grains is 0.5 to 0.01 g.
ta is preferred, particularly preferably 0.3 to 0.05
g m. The average grain size of the silver halide grains contained in the tabular silver halide emulsion is preferably 0.5 to 3 (Igm), more preferably 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 preferably core/shell type. The tabular silver halide emulsion which is preferably used has silver iodide localized in the center of the grains, and has an average value of grain size/grain thickness of 5 or more.

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. It consists of silver halide grains in which the phase with the highest content (referred to as the core) is other than the outermost surface (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 silver iodide content in the largest phase is preferably less than 6 mol %, more preferably ON 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. Those having an intermediate phase between the core and shell having a silver iodide content intermediate between those of 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 80%, more preferably 20 to 55%, of the entire grain. The silver iodide content difference between the shell and the core is preferably 3 mol% or more, and the silver iodide content difference between the shell and the core is 6 mol%.
It is preferable that it is above.

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.

The core/shell type silver halide emulsion is disclosed in Japanese Patent Application Laid-Open No. 59-17
No. 7535, No. 80-138538, No. 59-522
No. 38, No. 80-143331, No. 80-35728
No. 59-52238 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-138538, the center of the grains may have a halogen composition region different from that of the core. obtain.

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

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

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 content phase in the center covers the entire grain volume. The silver iodide content in the center is preferably 80% or less, particularly preferably 60 to 10%, and the silver iodide content in the center is preferably 5 to 40 mol%, particularly 10 to 3%.
The low iodine content phase (periphery) surrounding the high iodine content phase in the center, which is preferably 0 mol%, has a silver iodide content of 0 to 10 mol%, more preferably 0.1 to 6.0 mol%. % of silver iodobromide.

A tabular silver halide emulsion in which silver iodide is localized in the center can be obtained by a known method such as that 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 pm or less, more preferably 0.1 to 1.0 pm. g m or less, particularly preferably from 0.2 to 0.8 g m.

In the method for processing a silver halide color photographic light-sensitive material of the present invention, the lower limit of the total dry film thickness of all the woody colloid layers of the silver halide color photographic light-sensitive material (hereinafter referred to as the film thickness on the emulsion side) is: There are limits depending on the silver halide emulsion, couplers, oils, additives, etc. contained, and the preferred film thickness on the emulsion side is 5 to 18 mm, more preferably 10 to 187 mm.
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 pLm or less.

The distance from the emulsion layer to the lower end of the emulsion layer that is next to the support and which is different in color sensitivity from the emulsion layer is preferably 10 gm or less.

As a method for thinning the color light-sensitive material of the present invention, there is a method of reducing the amount of hydrophilic colloid as a binder. It retains coupler minute oil droplets dissolved in silver halide and high-temperature point solvents, prevents fog from increasing due to mechanical stress, and prevents color turbidity due to diffusion of oxidized developing agent between layers. Hydrophilic colloids are added for this purpose.

The amount can be reduced within a range that does not impair the purpose.

Another method for thinning the layer is to use highly chromogenic couplers.

Other methods for thinning the layer include reducing the amount of high S point solvent;
Examples include a method of thinning the intermediate layer by adding a scavenger of oxidized developing agent to the intermediate layer of the living room having different color sensitivity.

In the method for processing a silver halide color photographic light-sensitive material of the present invention, the total amount of silver halide contained in the light-sensitive silver halide emulsion contained in all emulsion layers of the silver halide color photographic light-sensitive material is 8.5 g/ rn' or less, more preferably 2.5 to 8.0 g/rn', more preferably 3.0 to 5.5 g/rn', particularly preferably 3.5 N
There is 5.0g/rn'te.

In the method for processing a silver halide color photographic light-sensitive material of the present invention, the total hydrophilic protective colloid layer coated on the emulsion layer side on the support of the silver halide color photographic light-sensitive material during development has a swollen film thickness when dried. The film thickness is preferably 180 to 350%, particularly preferably 200 to 300%.

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.

As a hardening agent, aldehyde type, aziridine type (for example, PR Report 1f3,921, U.S. Patent No. 2.950,
No. 197, No. 2,8134.404, No. 2,983
, No. 311, No. 3,271,175, Japanese Patent Publication No. 48-40898, Japanese Patent Application Laid-open No. 91315-1983), isoxazole type (e.g.
(as described in U.S. Pat. No. 331.809), epoxy systems (e.g., U.S. Pat. No. 3,047,394, West German Patent No. 1.085,663, British Patent No. 1,033,51)
No. 8 specifications, those described in Japanese Patent Publication No. 48-35495), vinyl sulfone type (for example, PR Revo)
19920, West German Patent No. 1,100,942, 2 and 3
No. 37,412, No. 2.545,722, No. 2.8
No. 35,518, No. 2,742,308, No. 2,74
No. 9,280, British Patent No. 1,251,091, Japanese Patent Application No. 45-54236, Japanese Patent Application No. 48-110998, and US Patent No. 3,539,644, and US Patent No. 3,490,911. acryloyl type (e.g., those described in Japanese Patent Application No. 48-27949 and US Pat. No. 3,840,720), carbodiimide type (e.g., US Pat. No. 2,938,892, 4,043,81
No. 8, specifications of No. 4.061,499, Special Publication No. 4B
-38715, those described in Japanese Patent Application No. 49-150135, triazine-based (for example, West German Patent No. 2,
410,973, 2.553,915, U.S. Pat. No. 3.125,287, JP-A-52-127
22), polymer type (for example, the specifications of British Patent No. 822.0ff1, U.S. Patent No. 3,823,878, U.S. Patent No. 3,398,029, and U.S. Patent No. 3,228,234) , Special Publication No. 47-18578, No. 47-185
No. 79 and No. 47-48898)
, and other maleimide-based, acetylene-based, methanesulfonic acid ester-based, (N-methylol-based) hardening agents can be used alone or in combination. As a useful combination technique,
For example, West German Patent No. 2,447,587, West German Patent No. 2,505,
No. 748, No. 2,514,245, U.S. Patent No. 4.04
No. 7,957, No. 3,832,181, No. 3,840
, No. 370, 4. Sho 48-43319, Sho 5O-fi3082, Sho 52-127329,
Examples include combinations described in Japanese Patent Publication No. 48-32384.

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, a colloidal silver antihalation layer (intermediate layer), a red-sensitive layer (intermediate layer), a green-sensitive layer (intermediate layer), and a colloidal silver yellow layer. Filter layer, blue-sensitive layer (intermediate layer) coated with a protective layer, and further sequentially from the support: colloidal silver antihalation layer (intermediate layer), red-sensitive layer (intermediate layer), green-sensitive layer (intermediate layer), 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. -15
A layer structure in which at least one of a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer is divided into three partial layers as described in Japanese Patent Application Laid-open No. 49027/1983; The layer structure in which high-speed emulsion layer units and low-speed emulsion layer units are separated, as well as West German Published Publication Nos. 2,822,922 and 2,8
No. 22,923, No. 2.622,924, No. 2,70
Examples include layer structures such as those described in No. 4,826 and No. 2,704.7!37.

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. 5!3-180555.

These silver halide emulsions contain activated gelatin; sulfur sensitizers such as allylthiocarocamide, thiourea, cystine; selenium sensitizers; reduction sensitizers such as primary
tin salts, thiourea dioxide, polyamines, etc.; noble metal sensitizers, such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-aurothio-3-methylbenzothiazolium chloride, etc.; or e.g. Sensitizers with water-soluble groups such as ruthenium, palladium, platinum, rhodium, and iridium, specifically ammonium chloroparadate, potassium chlorooleate, and sodium chloroparadate (these types may It acts as a sensitizer or a fog suppressant.

), etc. alone or in combination as appropriate (for example, a combination of a gold sensitizer and a sulfur sensitizer, a combination of a gold sensitizer and a selenium sensitizer, etc.)
It may also be chemically sensitized.

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

The silver halide used in the present invention is mixed with an appropriate sensitizing dye in an amount of 5 x 10-3 to 3
Optical sensitization may be achieved by adding o-3 moles.

Various sensitizing dyes can be used, and each sensitizing dye can be used singly or in combination of two or more types. Examples of the sensitizing dyes advantageously used in the present invention include the following: I can list things like:

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. 231,858, No. 2,493,748, No. 2.
503.77E1, 2,519,001, 2,
No. 912,329, No. 3,658,959, No. 3,6
72.8!37, 3.8114.217, 4
, No. 025,349, No. 4,048,572, British Patent No. 1,242,588, Japanese Patent Publication No. 14030/1973,
Examples include those described in No. 52-24844. Further, as sensitizing dyes used in green-sensitive silver halide emulsions, for example, U.S. Pat. Typical examples include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in British Patent No. 505,979. Further, as sensitizing dyes used in red-sensitive silver halide emulsions, for example, U.S. Pat.
, No. 234, No. 2,270,378, No. 2.442,
No. 710, No. 2,454,829, No. 2,776.2
Typical examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. 80 and the like. Furthermore, U.S. Patent 2,213
, No. 995, No. 2,483,748, No. 2,519,
No. 001, West German Patent No. 92!9,080, etc., such as xianine dyes, merocyanine dyes or composite cyanine dyes can be advantageously used in green-sensitive silver halide emulsions or red-sensitive silver halide emulsions.

These sensitizing dyes may be used alone or in combination.

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

A typical example of a particularly preferred spectral sensitization method is, for example, Japanese Patent Publication No. 43-4938 concerning the combination of benzimidazolocarbocyanine and benzoxazolocarbocyanine.
No. 43-22884, No. 45-18433, No. 47-37443, No. 4B-28293, No. 49-
No. 8209, No. 53-12375, JP-A-52-23
No. 931, No. 52-51932, No. 54-80118
No. 58-15H2B, No. 5i11-11 [18
4e, No. 59-11H47, and the like.

In addition, regarding the combination of carbocyanine containing a benzimidazole nucleus with other cyanine or merocyanine, for example, Japanese Patent Publication Nos. 45-25831 and 47
-11114, 47-25379, 48-38
No. 408, 48-3840? No. 54-34535
No. 55-15H, JP-A-50-33220, JP-A No. 50-38528, JP-A No. 51-107127, JP-A No. 51
-115820, 51-135528, 52-
No. 104916, No. 52-10491? For example, the number etc.

Furthermore, regarding combinations of benzoxazolocarbocyanine C oxa e carbocyanine) with other carbocyanines, for example, Japanese Patent Publication Nos. 32753/1986 and 4
B-11827, JP-A-57-1483.

Regarding merocyanine, for example, Tokuko Sho 4B
-38408, 4B-41204, 5G-40
61112, JP-A No. 513-25728, JP-A No. 58-
No. 10753, No. 58-91445, No. 58-118
No. 845, No. 50-33828, and the like.

Regarding combinations of thiacarbocyanin and other carbocyanins, for example, Japanese Patent Publication No. 43-493
No. 2, No. 43-4933, No. 45-28470, No. 4B-18107, No. 47-8741, JP-A No. 1973
1-114533, etc., and Japanese Patent Publication No. 49-6207 using zeromethine or dimethine merocyanine, monomethine or trimethine cyanine, and styryl dye.
The method described in No.

In order to add these sensitizing dyes to the silver halide emulsion according to the present invention, a dye solution such as methyl alcohol, ethyl alcohol, acetone, dimethylformamide, or fluorinated alcohol as described in Japanese Patent Publication No. 50-40859, etc. is added in advance. It is used by dissolving it in a hydrophilic organic solvent.

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

A dye (AI dye) that is water-soluble or decolorable with a color developer can be added to the photographic constituent layer of the silver halide color photographic light-sensitive material used in the present invention. Examples of the AI dye include oxonol dye, hemi- Included are oxonol dyes, merocyanine dyes and azo dyes. Among them, oxonol dyes.

Hemioxonol dyes and merocyanine dyes are useful. Examples of AI dyes that can be used include British Patent 584
, No. 808, No. 1,277.42f3, Japanese Unexamined Patent Publication No. 1977-
No. 85130, No. 49-fa11820, No. 49-
No. 114420, No. 48-129537, No. 52-1
No. 08115, No. 59-25845, No. 59-111
No. 840, No. 59-111841, U.S. Patent No. 2.27
No. 4,782, No. 2,533,472, No. 2. E1
No. 56,079, No. 3,125,448, No. 3,14
No. 8,187, No. 3.177.078, No. 3,24
No. 7,127, No. 3,280,801, No. 3,540
, No. 887, No. 3,575,704, No. 3.853,
No. 905, No. 3,718,472, No. 4,070,3
Examples include those described in No. 52.

These AI dyes are generally used at a concentration of 2 per mole silver in the emulsion layer.
It is preferable to use X 10-3 to 5 X 10-1 mol.

Furthermore, in addition to DIR compounds, compounds that release development inhibitors during development can also be used in the present invention; for example, U.S. Pat.
No., West German Patent No. 116'i (OLS) 2,417,9
No. 14, JP-A-52-15271, JP-A No. 53-9118
No. 59-123838, No. 59-127038, and the like.

The DIR compound used in the present invention is a compound capable of reacting with an oxidized form of a color developing agent to release a development inhibitor.

A typical example of such an IR compound is a DIR coupler 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. 454, U.S. Patent No. 3,227,554, U.S. Patent No. 4,095,984,
4,149.88E1 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. Further, in the present invention, US Pat. No. 3,852,345 and US Pat.
No. 41, 3,958. H3 No. 3,961,959
No. 4,052,213, JP-A-53-11052
No. 9, No. 54-13333, No. 55-181237, etc., there are compounds that release a development inhibitor but do not form a dye when subjected to a coupling reaction with an oxidized color developing agent. included.

Yet again. JP-A No. 54-145135, 5B-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. Alternatively, a so-called timing DIR compound, which is a compound that releases a development inhibitor through an elimination reaction, can also be used in the present invention.

Also, JP-A-58-160954, JP-A No. 5B-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 1X10-' mol to IOX 10-1 mol per 1 mol of silver.

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

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

Supports for the silver halide color photographic light-sensitive material used in the present invention include, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, a transparent support 1 with a reflective layer or a reflector, such as a glass plate, Examples include cellulose acetate, cellulose nitrate, polyester films such as polyethylene terephthalate, polyamide films, polycarbonate films, polystyrene films, and other common transparent supports.

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

[Effects of the Invention] According to the present invention, since the processing solution having bleaching ability contains a specific ferric complex salt and at least 5 x 10-2 mol/cross of thiocyanate, rapid processing is possible and photosensitive processing is possible. It is an object of the present invention to provide a method for processing a photosensitive material in which no precipitate is generated in the material or in a processing solution.

[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 expressed in grams per 1 m'' unless otherwise specified.

In addition, silver halide and colloidal silver are shown in terms of silver.

Sample 1 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.

Sample 1 (Comparison) 1st layer: Antihalation layer (HC-1) black colloidal silver...0.22 Ultraviolet absorber (UV, -1
) -0,20 colored coupler (C:C-1)
...0.05 colored coupler (CX-2)
...0.08 high boiling point solvent (oil-1) ...
0.20 Gelatin...1.2 Second layer: Intermediate layer (IL-1) Ultraviolet absorber (tlV-1) -0.01 Takayanagi point solvent (oil-1)...0.01 Gelatin
...1.3 Third layer: Low sensitivity red-sensitive emulsion layer (RL) Silver iodobromide emulsion (El-1) ... Bow, 0 silver iodobromide emulsion (Ea-2) ...05 sensitization Dye (S-1
) ...2.5 Xl0-4 (T-nyl/silver 1
mol) Sensitizing dye (S-2)...2.5 X10= (mol/17 silver) Sensitizing dye (S-3)...0.5 Xl0-4 (mol/1 mol silver) Cyan coupler (C'-4)...1.2 Cyan coupler (C'-2)...0.10 Colored cyan coupler (CG-1)...0.05 DIR compound ([1-1) ...0.002 High boiling point solvent (oil-1) ...0.5 Gelatin ...1.4 4th layer: High sensitivity red-sensitive emulsion layer (RH) Silver iodobromide emulsion (Es-3) Sensitizing dye (S-1) Sensitizing dye (S-2) Sensitizing dye (S-3) Cyan coupler (C'-1) Cyan coupler (C'-2) Cyan coupler (C'-3) Colored cyan Coupler...2,0...2. OXl0-4 (mol/silver 1 mol)...2. OXl0-4 (mol/silver IEL)...0. I Xl0-4 (mol/silver 1 mol) ...0.15 ...0.03 ...1.15 (CC-1) ...0.015 DIR compound (D-2) ... 0.05 high point solvent (oil-1)...0.5 gelatin
... Bow, 4 5th layer: Intermediate layer (IL-2) Gelatin ...0.4 6th layer: Low-sensitivity green-sensitive emulsion layer (GL) Silver iodobromide emulsion (Es-1) ...1 , 1 sensitizing dye (S-4)...5. OXl0-4 (mol/silver 1 mol) Sensitizing dye (S-5)...1. OXl0 (mol/silver 1 mol) Magenta coupler (T1)...0.5 Colored magenta coupler (CM-1)...0.05 DIR compound (D-3) DIR compound (11-4) Takashi Point solvent (oil-2) Gelatin 7th layer: Intermediate layer (IL-3) Gelatin high-row single point solvent (oil-1) 8th layer: High-sensitivity green-sensitive emulsion layer (GH) Silver iodobromide emulsion (Ea -3) Sensitizing dye (S-6) Sensitizing dye (S-7) Sensitizing dye (S-8) ...0.015 ...0.020 ...0.5 ...1. 1...0.9...0.2...1.2...1.5XIO (mol/1 mole of silver)...2.5XIO (mol/1 mole of silver)...0. 5 Xl0-4 (Mole/1 mole of silver) Magenta coupler (T2)...0.08 Magenta coupler (T3)...0,18 Colored magenta coupler (C:M-2)...0, 05 DIR compound (D-3)...0.01 high S
1-point solvent (oi 1-3) -・0.5 Gelatin... Bow, O 9th layer: Yellow filter layer (YC) Yellow colloidal silver...0.15 Color stain inhibitor (SC-1)
...0.1 high point solvent (oil-3)
...0.1 Gelatin ...0.8 10th layer: Low-speed blue-sensitive emulsion (BL) Silver iodobromide emulsion (E
Oni-1) ...0.25 silver iodobromide emulsion (Ea-2
)...0.25 sensitizing dye (S-IQ)
...7. OXl0-4 (mol/silver 1 mol) Yellow coupler (Y-1) Yellow coupler (Y-2) DIR compound (D-2) Takaura point solvent (oil-3) Gelatin...0.6... 0.12 ...0.01 ...0.15 ...1.1 11th layer: High-sensitivity blue-sensitive emulsion layer (BH) silver iodobromide emulsion (
Ea-4) Silver iodobromide emulsion (Ea-1) Sensitizing dye (S-9) Sensitizing dye (S-10) ...0.48 ...0.20 ...1. OXI.

(Mole/1 mole of silver)...3.0XIO (Mole/1 mole of silver) Yellow coupler (Y-1)...0.36 Yellow coupler (Y-2)...0.08 High point solvent (
oil-3) ...0.07 gelatin
... Tsukasa, 2 12th layer: First protective layer (Pro-1) Fine grain silver iodobromide emulsion ...0.4 (average grain size 0.4)
08 p-m, Agl 2 mol%) ultraviolet absorber (UV
-1) -0,10 ultraviolet absorber (UV-2)
・0.05 high point solvent (oil-1) ・
...0.1 high Buddha point solvent (oi 1-4) ...
0.1 formalin scavenger ()Is-1)...
0.5 Formalin scavenger (H3...0.2 Gelatin...4.0 13th layer: 2nd protective layer (Pro-2) Surfactant (Su-1) -0,007 Soluble in alkali Matting agent (average particle size 2 lm)...0.10 cyan dye (
A [knee 1) ...0.005 magenta dye (
AIM-1) ...0.01 SHE IJ agent (WAX
-1) -0,04 gelatin
...0.8 In addition to the above composition, each sound contains coating aid 5u-2, dispersion aid 5u-3, hardening agent H-1 and H-
2. Preservative DI-1, stabilizer Sta b-1, and antifoggant AF-IAF-2 were added.

E-Row 1 Average grain size Q, 46 pm, average silver iodide content 7.5% Monodisperse surface paper Silver iodide-containing emulsion m-2 Average grain size 0.32 pm, average silver iodide content 2. Emulsion Em-3 with 0% monodispersity and uniform composition, average grain size 0.78 ars, average silver iodide content 6.
0% monodisperse surface paper silver iodide-containing emulsion m-4 Average grain size 0.95 g m, average silver iodide content 80%
Monodisperse surface paper silver iodide-containing emulsions Em-1, Em-3 and Em-4 are disclosed in Japanese Patent Application Laid-Open No. 1983-1999.
It is a silver iodobromide emulsion mainly composed of octahedrons and has a multilayer structure adjusted with reference to the publications No. 38538 and No. 61-245151.

Further, for all of Ea-1 to Em-4, the average value of particle size/lion thickness was 1.0, and the width of particle distribution was 14%, 10112%, and 12%, respectively.

C. lI.

C. lI.

C-1 c'-2 σ-3 C-1 M-1 ll Cρ Q Q Q 01! r]-4 u-1 l Na0zS-c-C00CI+, (CI!, CFri11
1C-COOC11, (CF, CF,), +111゜u-2 NaO*5-C-COoC, II, t Cll+ C00Cell+7 u V-2 To1 ((CI+1=CIISO, C11f) accll, s
o! (CIll),)tll(CI+,),SO,K c-1 IC-1 IM-1 S [ab AP-1 DI-1 1l-3 F-2 1l-4 The sample prepared in this way was After wedge exposure using white light, the following development process was performed.

Experimental processing> Rissho Koso] Processing time Processing temperature Color development (1 tank) CD 3 minutes 15 seconds 38°C bleaching (1 tank) IIL 30 seconds 38°C constant
Fix (1 tank) Fix 1 minute Stabilize at 38℃ (3
Tank cascade) 1 minute 38°C drying (710°
C ~ 80℃) 45 seconds random - 2 plates (Processing time Processing temperature Color development (1 tank) CD 3 minutes 15 seconds 38℃
Bleach-fixing (1 tank) [1L 30 seconds 38
°C fixation (14y3) Fix 1 minute 38
°C stabilization (3 tank cascade) 1 minute 38 °C drying
Repeat (40°C to 80°C) for 45 seconds The composition of the processing solution used is as follows.

[Color developer] Potassium carbonate 30g Sodium bicarbonate 2.5g Potassium sulfite 4g Sodium bromide
1. :1g potassium iodide
], 2B hydroxylamine sulfate
2.5g sodium chloride
0.6g4-amino-3-methyl-N-ethyl-N-
(β-Hydroxylethyl)aniline sulfur butyrate 4.8g Potassium hydroxide 1.2g Add water to make IJI, use potassium hydroxide or 50% sulfuric acid to prepare pl+
Adjust to 10.06.

[Bleach solution] Bleach agent Ni1.
SCN
NoI ammonium bromide
150g glacial acetic acid
101 Ammonium Nitrate 3
Add 0 g of water to make LM, and adjust to )I+ 5.8 using aqueous ammonia or glacial acid.

[Bleach-fix solution] Bleach agent listed in Table 1 N11. S
CN ammonium hornothiosulfate (70% solution) 150g Prepare skin 1 with potassium carbonate or glacial acid at pl+7.1 and add water to make 11.

[Fixer ammonium cothiosulfate (70% solution) 150g ethylenecyaminetetrabutyrate disodium 0.5g sodium carbonate 10g Add water to make 1fL, use acetic acid and aqueous ammonia to make pl+ 7
．． Adjust to 0.

[Stabilizing liquid] Hexamethylenetetramine 0.2g 5-chloro-2-methyl-4-inthiazolin-3-one 0.05g Sodium formaldehyde sulfite adduct 2g Sodium sulfite 0.5g Add water and lf
pl+ with ammonia water and 50% sulfuric acid.7.
Adjusted to 0.

As shown in Table 1 below, t':! Experiments were conducted by changing the amount of organic acid ferric acid in the bleach-fix solution and the fix solution.

Measurements were made using the fluorescent X-ray method, which is a residual recording of the highest intensity region.

The results are summarized in Table 1 below.

In the margin table below, I,:l PDT8・Fc・Exemplary compound
Δ-11,4 RO DTA-Fc: I
I A-4NPTDTA-Fe:n
A-9 GEDTA-Fe:II [1-1 As is clear from Table 1 above, when the specific organic acid ferric complex salt according to the present invention is used in the bleaching solution, and 0.05 mol/liter or more of thiocyanine 1 When using %I salt, no abnormalities such as precipitation RI1 were observed in the fixing solution, and the desilvering reaction was roughly completed, indicating suitability for rapid processing.

However, it can be seen that even if any of these conditions is lacking, the above-mentioned effects are lost and the product cannot be put to practical use.

Example 2 In Example 1, NIl and SCN were changed to Na5CN and S
As a result of conducting the same experiment as in Example 1 in place of CN and thiocyanocatecol, the same effects as in Example 1 were obtained.

Example 3 Using the bleach-fix solution of Experiment No. 1F-1-5 in Example 1, the same treatment as in Example 1 was carried out according to the following treatment steps. The results are shown in Table 2.

``Reco l Yu D L Fix Mizurin Unisou] D BF Fix Stabilization (3 tanks) Processing lI! p 1if1 3 minutes 15 seconds 30 seconds 1 minute 1 minute Processing time 3 minutes 15 seconds 30 seconds 1 minute 1 minute Table 2 As is clear from the table above, it can be seen that fixing performance is improved by providing a stabilizing bath. .

Example 4 The same treatment as in Example 1 was performed using experiment No. BF-1-5 of Example 1 as BF, adding the compounds shown in Table 3 to the stabilizing bath, and using the following fixer as Fix. .

[Fixer] (NIl4) JJz 0.9 mol/lNi1
43CN 1.5 mol/treatment results are shown in Table 3.
Shown below.

Table 3 Call+tpeF C:, l+,, -Q- 0(C211,0), ,+1 0 (C211, O), SO, Na Regarding the surface precipitation of sensitive materials ○, No precipitation observed △: Slight precipitation is observed ×: Considerable precipitation is observed.

As is clear from the above table, even if the above Fix is used, the generation of precipitates on the surface of the sensitive material can be suppressed by adding the compounds shown in A to D to the stabilizing bath.

Example 5 Experiment No. ItF-1-5 of Example 1 was used as OF.

The same treatment as in Example 1 was carried out according to the following treatment steps, using the ankle fluid of Example 1 as a fix with the addition of 8g'', l-1Br- shown in Table 4-1.4-2. Ta.

Ward 1 Tech Mutual 4 Processing time CD 3 minutes 15 seconds 81, : IO seconds Fix 1 minute Stb 1 minute ward Onkooka j Processing time CD 3 minutes 15 seconds [IF : IO seconds Fix
Stabilization for 1 minute (3 tanks) 1 minute As is clear from the above batter 4-1.2, the BF of the present invention,
By using the Fix treatment method, the accumulated Ag' concentration and ■-concentration in Fix were reduced to 6 g/fL and 0, respectively.
．． It can be seen that good desilvering performance is shown up to 8 g/l.

Example 6 Experiment No. BF-r-5 of Example 1 was used as 8F, and a running treatment was performed using the same treatment solution as in Example 1 and the following replenisher according to the following treatment steps, Residual silver (■) was measured on the sensitive material after running treatment.

The composition of the replenisher used is as follows.

[Color developer replenisher] Potassium carbonate 40g Sodium bicarbonate 3g Potassium sulfite
7g sodium bromide
0.5g hydroxylamine sulfate 3.1g 4-amino-3-methyl-N-ethyl-N-(β-hydroxylethyl)aniline sulfate 6.0g potassium hydroxide 2g Add water to make 11, potassium hydroxide or pH 10,12 using 20% sulfuric acid
Adjust to.

[Bleach replenisher] 1.3 PDTA-Fe
0.3vsNH4SCN
'
0.5M ammonium bromide
178g ice vinegar m
21 tal ammonium nitrate
Add 35 g of water to make one layer, and adjust the pH to 5.8 using aqueous ammonia or glacial acetic acid.

[Bleach-fix replenisher] 1.3 PDTA-Fe
O, 3 mo ANH4SCN

O,5 mol ammonium thiosulfate (
70%) Adjust the pH to 7.1 with 180 mJl potassium carbonate or glacial acetic acid, and add water to make one sentence.

[Fixer replenisher] Ambinium thiosulfate (70%) +80u+
Add 14g of Sodium Sodium Water to make one sentence, and use ammonia water and acetic acid to make ldl 6
．． Adjust to 5.

As the stabilizing replenisher, the stabilizing solution of Example 1 was used.

Processing process ■ Processing time CD 3 minutes 15 seconds n L 311 seconds Fi
x 1 minute 30 seconds Stb 1 minute processing process ■ Processing time CD 3 minutes 15 seconds 11F: 10 seconds Fix
1 minute Stb The replenishment amount for the 1 minute running process was as shown in Table 5.

Note that the replenishment amount is a value per 1 m' of photosensitive material.

The running process takes 2 times the capacity of the bleach tank for 40 days.
This was done until double the amount of bleach replenisher was added. As in Example 1, the amount of residual silver in the highest density portion of the film sample after the running process was determined by Jull.

The results are shown in Table 5.

From the table above, it can be seen that according to the processing method of the present invention, Fix has good desilvering properties even with low replenishment.

Example 7 The same treatment as in Example 1 was carried out on the sensitive materials shown in Table 6 using Experiment No. BF-1-5 of Example 1 as the BF.

For magenta couplers MR-1 to Ml-3, magenta couplers 1 to 3 used in Example 1 were replaced,
Cyan couplers CR-1 to Cl1-: l are the cyan couplers C'-1 to C'-4 used in Example 1, with each ///total amount replaced. However, the total number of moles was kept the same.

The magenta and cyan couplers for comparison are each /iM-:l
, all m 33 were changed to C'-3.

table R-1 -Hs R-2 C,H.

R-3 H α) C, Il, 0CONH R-1 R-2 R LJL+etl+7Lri Above table MR-1 to 3 CR-1~3 as coupler By using G of unexposed area Above R concentration can be suppressed.

Claims (1)

[Scope of Claims] A method for processing a silver halide color photographic light-sensitive material, which immediately after color development is processed with a processing solution having a bleaching ability, and subsequently processed with a processing solution having a fixing ability. The treatment liquid is a ferric complex salt of a compound represented by the following general formula [A] or [B] and at least 5 x 10^
- A method for processing a silver halide color photographic material, characterized in that it contains 2 mol/l of thiocyanate. 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_1
Represents M_2. M, M_1, M_2 are hydrogen atoms, sodium,
Represents potassium or ammonium. X represents a substituted or unsubstituted alkylene group having 3 to 6 carbon atoms. ] General formula [B] ▲ Numerical formulas, chemical formulas, tables, etc. are included. Also B_1 and B_
2 may be the same or different, and each has 2 to 2 carbon atoms.
5 represents a substituted or unsubstituted alkylene group. ]