JPH026954A - Processing liquid and processing method for silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve a fixing rate by using a processing liquid contg. thiosulfate as a fixer and a specific compd. and having 5-8pH value. CONSTITUTION:The processing liquid contg. the thiosulfate as the fixer and the compd. expressed by formula I and having 5-8pH value is used. In formula I, R1-R4 respectively denote a hydrogen atom or alkyl group which may have a substituent. R1 may form a heterocycle in combination with R3. For example, ammonium thiosulfate, sodium thiosulfate, potassium thiosulfate, etc., may be used for the thiosulfate as the fixer. The amt. of the thiosulfate to be added is preferably 0.5-3mol, most preferably 1.1-2.0mol per 1l processing liquid. The fixing rate is increased in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a processing solution and a processing method for silver halide color photographic materials. More specifically, silver halide color photographic materials (hereinafter referred to as "
The present invention relates to processing solutions for photosensitive materials (also referred to as "photosensitive materials") and methods for processing photosensitive materials.

[Background of the invention]

In recent years, with the development of automatic processors, rapid processing has progressed, and rapid fixing solutions containing ammonium thiosulfate as a main ingredient have come to be used in the fixing process. As the process becomes more rapid, the use of fixing accelerators has become commonplace. For example, Japanese Patent Publication No. 45-35754 describes a combination of a thiourea derivative and a potassium-containing developer, and U.S. Pat. No. 3,854,947 describes
A combination of an alkali metal salt of thiocyanate or thiosulfate and an anionic activator is described;
No. 61,958 describes N-methylpyrrolidone, No. 4,138.257 describes a pyrrolidone-containing polymer, and No. 4,126,459 describes a thioether. be. All of these methods were effective means for speeding up the fixing process, but as the speed became more rapid, they were no longer sufficient.

When a silver halide photographic material is processed with an automatic processor, when the throughput increases, the fixing solution becomes fatigued, the fixing speed is delayed, and the rapid fixing ability is eventually lost. In particular, film sensitive materials with a large amount of coating a are susceptible to this effect. Therefore, there has been a need to prevent the fixing speed from decreasing due to liquid fatigue and to improve the throughput.

Furthermore, as the concentration of the fixing agent has become higher, crystal precipitation is more likely to occur in the tank during long-term processing. Therefore, prevention of such crystal precipitation has been required.

[Purpose of the invention]

An object of the present invention is to provide a processing solution that improves the fixing speed of silver halide photographic materials.

Another object of the present invention is to provide a processing liquid that prevents crystal precipitation on the wall of a processing tank of an automatic processor.

C. Structure of the Invention] The present inventors have conducted extensive research to solve the above problems:
As a result, the above object of the present invention can be achieved by using the following components [1] and [2].
] and has a pH value of 5 to 8.

■ Thiosulfate as a fixing agent ■ Compound represented by the following general formula (A) In the formula, Rl, R2, Ri and R1 each represent a hydrogen atom or an alkyl group which may have a substituent. Also, R1
and R1 may be linked to form a heterocycle.

Further, the method for processing a photosensitive material of the present invention which achieves the above object includes using a processing liquid containing the above-mentioned components [1] and [2] and having a pH value of 5 to 8 during the processing step. It is characterized by

[Specific structure of the invention]

The present invention will be explained in more detail below.

Thiosulfate as a fixing agent used in the present invention is, for example, ammonium thiosulfate, sodium thiosulfate,
Nitrium thiosulfate, etc. can be used. The amount added is preferably 9.5 mol to 3 mol, more preferably 0.9 mol to 2.5 mol, most preferably 1 mol per 1Q of treatment liquid.
．． 1 mol to 2.0 mol.

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

RI"" R* may be the same or different, and each may be a hydrogen atom or a ζ argyl group which may have a substituent, and R4 and R3 may be connected to form a heterocycle, and may have a substituent. Examples of the alkyl group that may be present include -eu, N1m
C0NH2, -CI, CI(20H, -CH2CH2N
Examples include HCON islands. More preferably,
Hydrogen atoms, R, &R3 are linked to form a 5-membered ring, and most preferably a hydrogen atom.

Preferred specific examples of the compound represented by the general formula CA) are shown below.

(^-13IIIzCGMB.

(A-3) +1 ■ (A-8) (A-9) NzNCON[1CH2CI2NICONHz(CI
! ) 2 NCONHCH3 Although the present invention shows remarkable effects in fixing solutions, favorable effects can also be obtained in bleach-fixing solutions.

When the processing solution having fixing ability according to the present invention is a bleach-fix solution, the bleaching agent used in the bleach-fix solution is preferably a ferric complex salt of aminocarboxylic acid or aminophosphonic acid. The aminocarboxylic acid and aminophosphonic acid represent an amine compound having at least two or more carboxylic acid groups and an amine compound having at least two or more phosphonic acid groups, respectively, and are preferably represented by the following general formulas CI) and (n ) is a compound represented by

In the formula, E represents a substituted or unsubstituted alkylene group, cycloalkylene group, phenylene group, Ra5ORssORas RaxZRa3-, Z represents >N Ras Aa, )NA,
R2, to Ra3 represent substituted or unsubstituted alkylene groups, A2 to A are hydrogen atoms, OH, C00M, P
OsMt is represented, and M represents a hydrogen atom or an alkali metal atom.

Next, preferred specific examples of the compounds represented by the general formulas CI) and (II) are listed below.

(Illustrative compounds) (I-1) Ethylenediaminetetraacetic acid (i-2) Diethylenetriaminepentaacetic acid (I-3) Ethylenediamine-N-(β-hydroxyethyl)-N,N
',N'-triacetic acid (1-4) 1,3-propylenediaminetetraacetic acid (I-5
) l-lyethylenetetraminehexaacetic acid (I-6) cyclohexanediaminetetraacetic acid (I-7) 1,2-diaminopropanetetraacetic acid (r-8) 1,3-diaminopropane-2-
All-tetraacetic acid (I-9) Ethyl ether diamine tetraacetic acid (I-1
0) (l-11) (I -12) (I -14) (I -15) (r -16) (I -17) (I -19) (I-20) (■ Glycol ether diamine tetranodic acid Ethylenediaminetetrapropionate Phenylenediaminetetraacetic acid Ethylenediaminetetraacetic acid disodium salt Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt Ethylenediaminetetraacetic acid tetrasodium salt Diethylenetriaminepentaacetic acid pentastrium salt Ethylenediamine-N-(β-hydroxyethyl)-N
, N',N'-triacetic acid sodium salt propylene diamine tetraacetic acid sodium salt ethylene diamine tetramethylene phosphonic acid cyclohexane diamine tetra acetic acid sodium salt diethylene triamine pentamethylene phosphonic acid (I-22) cyclohexane diamine tetramethylene phosphonic acid (n-1) ) nitrilotriacetic acid (u-2) methyliminodiacetic acid (II-3) hydroxyethyliminodiacetic acid (m-4)
Nitrilotripropionic acid (u-5) Nitrilotrimethylenephosphonic acid (If-6) Iminodimethylenephosphonic acid (n-7) Hydroxyethyliminodimethylenephosphonic acid (n-8) Nitrilotriacetic acid trisodium salt These aminocarboxylic acids and Among the aminophosphonic acids, compounds particularly preferably used from the viewpoint of the desired effects of the present invention include (I-1), (I-2), (I-4), (I-6),
(I-7), (r-10), (I-19), (n-
1) and (II-5). Among these, particularly preferred from the viewpoint of the desired effects of the present invention are (
I-4).

The ferric complex salt of an organic acid according to the present invention is a free acid (
Hydrogen salts), alkali metal salts such as sodium salts, potassium salts, lithium salts, or ammonium salts, or water-soluble amine salts such as triethanolamine salts, preferably potassium salts, sodium salts, and ammonium salts. . At least one type of these ferric complex salts may be used, but two or more types can also be used for fn.

The amount used can be arbitrarily selected and needs to be selected depending on the amount of silver and silver halide composition of the photosensitive material to be processed, but for example, it can be used in an amount of 0.01 mol or more per 1 a of bleach-fix solution, preferably 1 mol. ．． < is used in an amount of 0005 to 1.0 mol. Note that it is desirable to use the replenisher in a highly concentrated form with the highest solubility in order to achieve high concentration and low replenishment.

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, German Patent No. 2,3
31.220), ion exchange method (Japanese Unexamined Patent Publication No. 5
1-17114, German patent 2,548,23
7) and metal substitution method (British Patent No. 1,353)
, 3Q5 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 may also be recovered from the overflow waste solution and recycled.

The fixing solution and bleach-fixing solution according to the present invention exhibit the desired effect W of the present invention better when the replenishment amount thereof is 800+off or less per m 2 of light-sensitive material. Especially photosensitive material 1
20m4-65 per m2 (bd, especially 30m
(Remarkable effects are obtained from 2 to 400 m+2.

It is necessary that the processing time of the fixer according to the present invention is 3 minutes 10 seconds or less in total, and the total time is preferably 20 seconds to 3 minutes 20 seconds or less, particularly preferably 40 seconds to 3 minutes, especially Preferably, the desired effects of the present invention can be achieved within a range of 60 seconds to 2 minutes and 10 seconds. Further, the processing time of the bleach-fix solution is preferably 3 minutes 45 seconds or less, more preferably 20 seconds to 3 minutes 20 seconds, particularly preferably 40 seconds to 3 minutes. Good effect.

In the processing method of the present invention, it is preferable that the bleaching solution, the fixing solution, and the bleach-fixing solution be forcibly stirred. 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.

Forced stirring means and 1. Here are some 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/cm2
Refers to a method in which processing is performed by spraying processing liquid directly onto photosensitive materials in geological liquid from a spray nozzle while applying the above pressure.
When spraying using a stirring method, the discharge pressure from the nozzle is 0□1kg/
A method of spraying the processing solution directly onto the photosensitive material in the processing solution by applying a pressure of e+m''tL is used.The pressure source and L2 are generally a pressure pump. Plunger pump, garbo:
There are pumps, magnet pumps, and cascade pumps, such as Maruyama's 15-LPM type, 10-BFM type, and 2
0-BFM type, 25-BFM type, etc. are known as examples.

In addition, as a liquid pump, for example, MD-8 manufactured by Ikki Co., Ltd.
Type, MD-10 type, MD-20R type, MD-30R type,
There are MD55R type, MDK-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 (Q/win) and the spray pressure (kg/cm2). Therefore, there is a need for a pressurizing device whose pressure can be adjusted in proportion to the number of spray nozzles so that the effect is concentrated on the upper needle. n is also preferred 1
．． The pressure is 0.3 - 10 kg/c, 2. If it is 1 - smaller, no effect can be obtained, and if it is too large, it will cause damage to the photosensitive material (yI).
& Damaged 1-,! Sometimes it makes me nervous.

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. Furthermore, this is a method in which 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. These are 5mm to 15mm
Even better results can be obtained by setting the value to wm. Air can be supplied using an air compressor, such as Bebicon (0.4KW, BU7TL) manufactured by Hitachi, or an air pump, such as the Ikki Air Pump (Ap22).
Type 0), etc. The amount of air is 212/min to 30i2/win per transport rack of automatic developing machine.
is necessary, and more favorable results can be obtained from 5127w1n to 20Q/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. It is preferable to send an amount of

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 Ultrasound Kogyo Co., Ltd. are used.

The transducer frequency of the ultrasonic oscillator is 5 to 1000K.
Hz is used, and a frequency of 10 to 50 KHz is particularly preferable in terms of the desired effects 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 longer. In the case of partial irradiation, it may be applied at any of the initial, intermediate, or 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 solution tank of an automatic processor to effectively perform immersion processing. As a vibrator as a vibration source, for example, V manufactured by Shinko Electric Co., Ltd.
-28, V-4B types, etc. are generally used. The vibrator is installed by fixing a pie break to the top of the immersion processing tank of an automatic processor and installing the vibrator so that it is applied from the back side of the photosensitive material. The frequency of the vibrator is 100 to 1000
0 times/win is preferable. The most preferable range is 500~
6000 times/min. The amplitude of the photosensitive material to be processed is from 0.2+nm to 30mm, preferably l mm-20
It is mm.

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.

The color developing solution according to the present invention contains alkaline agents commonly used in developing solutions, such as sulfur/lium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate, borax, etc. Furthermore, various additives such as benzyl alcohol, alkali metal silver halides such as potassium bromide or potassium chloride, development regulators such as nthrazic acid, preservatives such as hydroxylamine or sulfites, etc. May contain.

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 preferably 7 or more, 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 ethyl etc. may be contained.

Moreover, various chelating agents can be used in combination as metal ion sequestering agents in the color developing solution according to the present invention.

For example, as the chelating agent, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid,
Organic phosphonic acids such as l-hydroxyethylidene-1,1-diphosphonic acid, aminopolyphosphonic acids such as aminotri(methylenephosphonic acid) or ethylenediaminetetraphosphonic acid, oxycarboxylic acids such as citric acid or gluconic acid, 2-phosphonobutane-1 , phosphonocarboxylic acids such as 2,4-tricarboxylic acid, polyphosphoric acids such as tripolyphosphoric acid or hexametaphosphoric acid, and the like.

The amount of replenishment of the stabilizer according to the present invention is 1 to 1 of the amount brought in from the pre-bath per unit area of the color photographic light-sensitive material to be processed.
It is preferably 80 times, and particularly preferably 2 to 60 times, but in the present invention, the concentration of the pre-bath component (bleach-fix solution or fixer) in the stabilizing solution is lower than that in the final tank of the stabilizing solution tank. It is more preferably 1500 or less, particularly preferably 1/1000 or less. Furthermore, from the viewpoint of low pollution and liquid storage stability, 11500 to 100000 is preferable,
More preferably, the treatment tank of the stabilization tank is configured to have a ratio of l/2000 to 1150000.

The stabilization treatment tank is preferably composed of a plurality of tanks, and the number of the plurality of tanks is preferably 2 or more and 6 or less.

This is a case where the number of stabilization treatment tanks is 2 or more and 6 or less, and it is preferable to use a countercurrent method (a method in which the material is supplied to the after bath and over-70% from the front bath). 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 on the surface of the photosensitive material, etc., in the case of normal color film (roll film for photography), the amount of carry-on is usually 50 tQ/n'' to 15 (laff
/i'', and the replenishment amount, which is more remarkable than the effect of the present invention on this amount brought in, is 50m+2/m'' to 4.0 (1/
w” range, and the most effective replenishment amount is 200 m
12/m" and 1500 mQ/m".

The treatment temperature for the treatment with the stabilizing liquid is preferably from 5 to 60°C, more preferably from 20 to 45°C.

The silver halide emulsion that can be used in the present invention is preferably a tabular silver halide emulsion, but in addition to this,
Any silver halide such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, and silver chloroiodobromide may be used. Furthermore, as protective colloids for these silver halides, in addition to natural products such as gelatin, various synthetically obtained colloids can be used. The silver halide emulsion may contain conventional photographic additives such as coupler stabilizers, sensitizers, hardeners, sensitizing dyes, and surfactants.

As the photosensitive material used in the present invention, color negative film, color paper, color reversal film, color reversal paper, etc. can all be used.

[Example] Next, the present invention will be explained 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 1.2 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 (HG-1) Black colloidal silver...0.22 Ultraviolet absorber (UV
-1) ・0.20 colored coupler (cc-
1) ...0.06 colored coupler (CM-2
)...0.05 high boiling point solvent (oil-1)
-0-19 gelatin...1
．． 3 Second layer: Intermediate layer (IL-1) Ultraviolet absorber (UV-1) -0.01 High boiling point solvent (Oil-1) ...0.01 Gelatin ...1.4 Third layer: Low Sensitivity Red-sensitive emulsion layer (RL) Silver iodobromide emulsion (Em-1)
...1.1 Silver iodobromide emulsion (Em-2)
...0.5 sensitizing dye (S-1) ...2.
5X 10-' (mol/silver amount mol) Sensitizing dye (5-2)...2.5X 10-1 (mol/silver amount mol) Sensitizing dye (5-3) -o, 5x lo''( mole/silver amount mole) Cyan coupler (C-4')...1.1 uncoupler (C-2')...0.07 Colored cyan coupler (CC-1)...0.05 DIR compound (D-1) -0,002 High boiling point solvent (oi 1-1) -0,5 Gelatin...1.3 4th layer: High sensitivity red-sensitive emulsion layer (RH) Silver iodobromide emulsion (Em- 3) Sensitizing dye (S-1) ...2.0 ...2.OX 10-' (mol/silver amount mole) Sensitizing dye (5-2) = -2, Ox 10-'
'(Mole/silver amount mole) Sensitizing dye (5-3) -0, I X 10-'
(mol/silver amount mole) Cyan coupler (C-1')...0.15 cyan coupler (C-2')...0.02 cyan coupler (C-3')...1.15 colored Cyan coupler (CC-1)...0.02 DIR compound (D-2) -0,05 High boiling point solvent (oil-1) -0,5 Gelatin...1.4 5th layer: Intermediate layer ( I
L-2) Gelatin 6th layer: Low-sensitivity green-sensitive emulsion layer (GL) Silver iodobromide emulsion (E+a-1) Sensitizing dye (5-4) ...0.4 ...1.1 ...・5-Ox 1O-4 (mol/silver amount mol) ...1. OX 10-' Sensitizing dye (S-5) DIR compound (D-3) DIR compound (D-4) High boiling point solvent (Oil-2) Gelatin intermediate layer (IL-3) Gelatin high boiling point solvent (Oil-1 ) 8th layer: High-sensitivity green-sensitive emulsion layer (GH) Silver iodobromide emulsion (Em-3) Sensitizing dye (5-6) 7th layer: Sensitizing dye (5-7) Sensitizing dye (5- 8) Magenta coupler (M-2) (mol/mol of silver) ...0.5 - (CM-1) ...0.05 ...0.015 ...0.020 ...0 .5...1,0 Magenta coupler (M-1) Colored magenta coupler...0.9...0.2...1.2...1.5X 10-' (mol/mole of silver ) ...2.5X 10-' (mol/mole of silver amount) ...0.5X 10-' (mole/mole of silver amount) ...0.06 DIR compound (D-3) High boiling point solvent ( oi 1-3) Gelatin 9th layer: Yellow filter layer Yellow colloid silver stain inhibitor (SC-1) High boiling point solvent (oil-3) Gelatin 10th layer: Low sensitivity blue-sensitive emulsion layer (BL) Silver iodobromide emulsion(
Em-1) Silver iodobromide emulsion (Em-2) Sensitizing dye (S-10) (YC) Yellow coupler (Y-1) Yellow coupler (Y-2) DIR compound (D-2) High boiling point solvent ( oi 1-3) Magenta coupler (G3) Colored magenta coupler...0.18 - (CM-2)...0.05...o, oi...0.5...1.0 ...0.1 ...0.1 ...0.1 ...0.8 ...0.25 ...0.25 ...7. OX 10-' (mole/mole of silver amount) ...0.6 ...0.12 ...0.015 ...0.14 Gelatin 11th layer: High sensitivity blue-sensitive emulsion layer (Bl-1 ) Silver iodobromide emulsion (Em-4) Silver iodobromide emulsion (Em-1) Sensitizing dye (5-9) Sensitizing dye (S-10) Yellow coupler (Y-1) Yellow coupler (Y-2) ) High boiling point solvent (oil3) Gelatin 12th layer: 1st protective layer (pro-1) Fine grain silver iodobromide emulsion (average grain size 0.08 μm, AgI Ultraviolet absorber (UV-1) Ultraviolet absorber (UV- 2) High boiling point solvent (oil-1) High boiling point solvent (oil-4) Formalin scavenger...1.1...0.53...0.20...1.OX 10-' ( mole/1 mole of silver)...3.OX 10-' (mol/1 mole of silver)...0.36...o, i.

...0.07 ...1.1 ...0.4 2 mol%) ...0.10 ...0.05 ...0.15 ...0.1 - (Is- 1) ...0.5 (H3-2) ...0.2 Gelatin ...0.9 Second protective layer (Pro-2) Surfactant (Su-1) -0,005 Soluble in alkali Matting agent (average particle size 2μIl)...0. lO cyan dye (AIC-1) ...0.01 macenta dye (A rM-1) -0.02 slip agent (WAX-1) ...0.04 gelatin ...0.9 In addition, each layer In addition to the above composition, Coating aid 5u-2, Dispersion aid 5u-3, Hardeners H-1 and H-2, Preservative DI-1° Stabilizer 5ta
b-1, and antifoggants AF-1 and AF-2 were added.

QI-1 Average grain size 0.46 μm 1 Average silver iodide content 7.5% Monodisperse surface paper silver iodide-containing emulsion m-2 Formalin scavenger 13th layer: Average grain size 0.32 μm 1 Average iodide Silver iodide content: 2.0% Monodisperse, uniform composition emulsion E+n-3 Average grain size: 0678μ11 Average silver iodide content: 6.0% Monodisperse, surface paper Silver iodide-containing emulsion m-4 Average grain The emulsions En+-1, Em-3 and Em-4, which have a diameter of 0.95μ and an average silver iodide content of 8.0% and are monodisperse and contain silver iodide on the surface, are manufactured by JP-A-60-13.
It is a silver iodobromide emulsion mainly composed of octahedrons and has a multilayer structure adjusted with reference to publications No. 8538 and No. 61-245151.

Furthermore, for both Em-1 and Em-4, the average value of particle size/particle thickness was 1.0, and the width of particle distribution was 14%, 10%, and 12%, respectively.

-t ■ Shit Shiμ ■ 2 'C-3' C ■ M-1 CM-2 D - V ■ ■ ■ Shiμ ■ CC00CH2(C)2CF'zJsllV u-2 NaOs S CC00Cs H+ vCH2COC
00C+y AX H ■ υi AIM-1 0i! 3 1l-4 s tab -1 F-1 F-2 The sample thus prepared was exposed to white light using a wedge, and then subjected to the following development process.

[Experimental treatment]

Processing process Processing time Processing temperature Color development (1 tank) 3 minutes 15 seconds 38°C bleaching (Ill)
45 seconds 35℃ fixation (2 baths) 1 minute 30 seconds 35℃ (2 bath cascade) Stabilization 1 minute 35℃ (3 bath cascade) Drying 45 seconds (40℃~8
0°C) The composition of the treatment liquid used is as follows.

[Color developer]

Potassium carbonate 30g Sodium bicarbonate 2.5g Potassium sulfite
4g sodium bromide 1.
3g potassium iodide 1.0111g
Hydroxylamine sulfate 2.5g Sodium chloride 0.6g 4-Amino-3-methyl-N-ethyl-N-(β-hydroxylethyl)aniline sulfate 4.8g Potassium hydroxide
Add 1.2 g of water to make up to 1Q, and adjust the pH to 10.06 using potassium hydroxide or 1150% sulfuric acid.

[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-ethyroot (β-hydroxylethyl) aniline sulfate m salt 6.0g potassium hydroxide 2g Add water to make IQ, hydration power 1 m (pH 1O using 120% sulfuric acid,
Adjust to 12.

[Bleach solution]

1.3 Diaminoglopane-N,N,N',N'-tetranodic acid ferric ammonium salt 0.23 mol Ethylenediamine-N,N,N',N'-tetranodic acid ferric ammonium salt 0. 25M hydroxyethylethylenediaminetriacetic acid 0g Ammonium bromide 150g Glacial acetic acid
30mα ammonium nitrate
Add 30 g of water to make 2, and adjust the pH to 5.3 using aqueous ammonia or glacial acetic acid.

[Bleach replenisher]

1.3 Diaminoglopane-N,N,N',N'-tetranodic acid ferric ammonium salt 0.33 mol Ethylenediamine-N,N,N',N'-tetranodic acid ferric ammonium salt 0. 36M hydroxyethylethylenediaminetriacetic acid 1F Ammonium bromide 178g Glacial acetic acid
21+nQ ammonium nitrate
Add 35 g of water to set lα, and adjust to p[(5,0) using ammonia water or glacial acetic acid.

[Fixer]

Ammonium thiosulfate 250g Ammonium sulfite 20g Ethylenediaminetetraacetic acid 0.5g Exemplary compound A (listed in Table 1) Add water and 112. ! : and adjust to p) 17.0 using acetic acid and aqueous ammonia.

[Fixer replenisher]

Ammonium thiosulfate 250g Ammonium sulfite 20g Ethylenediaminetetraacetic acid 0.5g Exemplary compound A (listed in Table 1) Add water to make IQ and adjust pH to 7.0.

[Stabilizing liquid and stabilizing replenisher]

Formaldehyde (37% solution) 2m (25-
Chloro-2-methyl-4-inthiazolin-3-one 0
．． 05g Emulgen 810 1m12 Sodium formaldehyde bisulfite adduct Add 2g water and 1
The pH was adjusted to 7.0 using aqueous ammonia and 50% sulfuric acid.

However, the amount of replenishment for each photosensitive material is ll11! per color developer replenisher 650ml 12. A running test was conducted using bleaching replenisher 140a+Q, fixing replenisher 815mff, and stabilizing replenisher 1000+o12.

The running process is carried out every day until the fixer replenisher is replenished in an amount twice the capacity of the fixer tank.

After the running was completed, the fixing processing time was changed in units of lθ seconds until 6 minutes, and the time at which derailment was completed (the amount of residual silver in the Da + ax part and the Dn + in part was 0.51 g/100 cm in the fluorescent X-ray silver amount analysis) Table 1 shows the time at which the condition was below 100%.After the running, the degree of crystal precipitation on the inner wall of the fixing tank of the tank was observed and evaluated in 3 stages: good ○, somewhat good △, and poor ×. did.

Table 1 *Example 2 shown in g/Q A sample prepared in the same manner as in Example 1 was wedge exposed using white light, and then subjected to the following development treatment.

[Experimental treatment]

Processing process Processing time Processing temperature Color development (1 tank) 3 minutes 15 seconds 38℃ bleach fixing (2 tanks) 2
Minutes 30 seconds 35°C (2 tank cascade) Stabilization 1 minute 35°C (3 tank cascade) Drying 45 seconds (40°C ~
(80°C) The composition of the treatment liquid used is as follows.

[Color developer]

Potassium carbonate 30g Sodium bicarbonate 2.5g Potassium sulfite
4g sodium bromide 1.
3g Potassium iodide 1.0mg Hydroxylamine sulfate 2.5g Sodium chloride 0.6g 4-Amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)aniline sulfate 4.8g Potassium hydroxide
Add 1.2 g of water and adjust the pH to 1O.06 using IQ, binder, potassium hydroxide or 50% sulfuric acid.

[Color developer replenisher]

Potassium carbonate 40g Sodium bicarbonate 3g Potassium sulfite
7g Sodium Bromide 0.5
g Hydroxylamine sulfur am 3.1g4-7
” Mi/-3-methyl-N-ethyl=N-(β-hydroxylethyl)aniline sulfate 6.0 g Potassium hydroxide Add 2 g water and I
ff and p using potassium hydroxide or 20% sulfuric acid.
Adjust to H10,12.

[Bleach-fix solution and bleach-fix replenisher]

Exemplified Compound I -40,25M Hydroxyethylethylenediaminetriacetic acid 0g Glacial acetic acid 30n++2 Ammonium thiosulfate 200g Ammonium sulfite 20g Exemplified Compound A (listed in Table 1) Water was added to make 1Q, and the pH was adjusted using acetic acid and aqueous ammonia.
Adjust to 7.0.

[Stabilizing solution and stabilizing replenisher] Formaldehyde (37% solution) 2mQ5-chloro-2-methyl-4-inthiazolin-3-one 0.
05g Emulgen 810 1mQ Formaldehyde bisulfite adduct sodium Add 2g water and 1
(pH 7.0 with ammonia water and 50% sulfuric acid)
Adjusted to.

However, the running test was conducted with each replenishment amount being 650 m (2) of color developing replenisher, 1000 m4 (2) of bleach-fixing replenisher, and 775 m (2) of stabilizing replenisher per 1 m2 of light-sensitive material.

The running process was continued for 10 days until the bleach-fix tank was replenished with twice the capacity of the bleach-fix replenisher.

After the running, the same evaluation as in Example 1 was carried out in Table 2.

Claims (1)

[Claims] (1) Contains the following ingredients [1] and [2], and 5 to 8
A processing liquid for silver halide color photographic materials, characterized in that it has a pH value of . [1] Thiosulfate as a fixing agent [2] Compound represented by the following general formula (A) General formula (A) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_1, R_2, R_3 and R_4 are Each represents a hydrogen atom or an alkyl group which may have a substituent. Moreover, R_1 and R_3 may be connected to form a heterocycle. (2) A method for processing a silver halide color photographic material, which comprises using the processing solution according to claim 1.