JPH08262670A - Replenisher composition for silver halide photographic material processing, and solid processing agent for sliver halide photographic material - Google Patents

Abstract

PURPOSE: To reduce ammonium ion concentration in a processing solution without causing the precipitation of a fixing agent or the sulfurization to a transit roller by containing thiosulfates and a specified compound, and setting ammonium thiosulfate, of the thiosulfates, less than a specified value. CONSTITUTION: This replenisher composition for silver halide photographic material processing contins thiosulfates and at least one kind of compounds represented by the formula I and the formula II, wherein ammonium thiosulfate, of the thiosulfates, is less than 70 mole %. In the formula I, Q represents an atomic group necessary for forming a nitrogen-contained hetero ring (including those in which 5 to 6 membered unsaturated rings are condensed), and R1 represents a hydrogen atom, an alkyl group containing 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, a heterocyciic group (including those in which 5 to 6 membered unsaturated rings are condensed), or an amino group. In the formula II, X represents a hydrogen atom or an alkali metal, Y represents a hydrogen atom or substituted or non-substituted alkyl group, and (m) represents and integer of 1 to 6. R41 , R42 each represent a hydrogen atom or lower alkyl group.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide photographic light-sensitive material, and more particularly to a method for processing a silver halide photographic light-sensitive material capable of achieving both good processing performance and working environment.

[0002]

2. Description of the Related Art Conventionally, a fixing solution used for processing a silver halide photographic light-sensitive material and a processing solution having a fixing ability such as a bleach-fixing solution are used as a so-called fixing agent to react with silver halide to form an aqueous solution. Compounds that form a complex salt such as thiosulfates such as potassium thiosulfate, sodium thiosulfate and ammonium thiosulfate, thiocyanates such as potassium thiocyanate, sodium thiocyanate and ammonium thiocyanate, and thiourea thioethers are included. However, thiosulfates, especially ammonium thiosulfate, have been frequently used from the viewpoint of processability and handleability such as stability and solubility.

However, when the treatment liquid contains ammonium ions, it volatilizes and emits a strong ammonia odor. Therefore, in recent years, studies have been conducted to reduce the amount of ammonium salt used for the purpose of improving the working environment.

[0004]

However, when potassium thiosulfate or sodium thiosulfate is adopted instead of ammonium thiosulfate, the solubility of these is inferior to that of ammonium salt, and therefore, especially at a low treatment amount in a minilab or the like, Liquid concentration occurs, and the solubility of the fixing agent itself is low, which not only tends to cause precipitation at low temperatures, but also in low replenishment systems, processability and stability deteriorate, and it becomes necessary to increase the thiosulfate ion concentration. However, it was also found that this also causes a problem that sulfur adheres to the transport roller portion (especially the transition roller) exposed to the outside of the liquid.

The present invention has been made under the above circumstances, and an object of the invention is to halogenate a treatment liquid capable of reducing the concentration of ammonium ions without inducing deposition of a fixing agent or sulfidation to a transfer roller portion. Another object of the present invention is to provide a method of processing a silver photographic light-sensitive material.

[0006]

The above object of the present invention comprises at least one compound represented by the general formulas [I] to [V], wherein thiosulfate is ammonium thiosulfate. The replenishing composition for processing a silver halide photographic light-sensitive material having a content of 70 mol% or less, and the total weight of the compounds of the general formulas [I] to [V] with respect to the weight of thiosulfate in the composition.
0.05 wt% or more and 5 wt% or less, the silver iodide content of the silver halide emulsion used in the processed light-sensitive material is 5 mol% or more, and thiosulfates and the above-mentioned general formula [I ] To [V] at least 1
Species-containing, ammonium thiosulfate 70% of thiosulfate
It is achieved by a solid processing agent for silver halide photographic light-sensitive materials which is at most mol%.

That is, the present inventors have incorporated at least one of the compounds represented by the general formulas [I] to [V] (hereinafter, also referred to as the compound of the present invention) into the fixing solution to fix the toner. We obtained the finding that it is possible to reduce the thiosulfate concentration required to complete the reaction, and we have investigated the amount of ammonium thiosulfate and potassium thiosulfate, sodium thiosulfate, etc. without increasing the thiosulfate ion concentration related to supplementation. The inventors of the present invention have found that the processing performance can be guaranteed by optimizing the ratio with the amount.

The present invention will be described in detail below.

The first essential requirement of the present invention is that the processing solution having fixing ability contains thiosulfate and at least one compound represented by the general formulas [I] to [V].

The compounds represented by the general formulas [I] to [V] in the present invention will be described.

In the general formula [I], Q is a nitrogen-containing heterocycle (including a condensed 5- or 6-membered unsaturated ring)
(For example, an imidazoline ring, a thiazoline ring, a triazoline ring, etc.) represents an atomic group necessary for forming, and R ₁ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, a heterocyclic group. (Including those in which a 5- or 6-membered unsaturated ring is condensed) (for example, a pyridine ring group, an imidazole ring group, a thiazole ring group, etc.) or an amino group. In the general formula [II], R ₂ and R ₃ are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxy group, an amino group, an alkyl group having 1 to 3 carbon atoms (for example, a methyl group). , Ethyl group, etc.), an acyl group, an aryl group, or an alkenyl group (for example, an allyl group, a butenyl group and the like can be mentioned).

[0012] A is - (C = X ') - N (R) (R'), - (CH 2) n 2 -
(C = X ′) − N (R) (R ′), − (S) m ₁ − (C = X ′) − N (R)
(R ′), − (S) m ₂ − (CH ₂ ) n ₃ − (C = X ′) − N (R) (R ′), −
(S) m ₃ − (CH ₂ ) n ₄ −N (R) (R ′), − (S) m ₄ −N (R) (R ′), −
(NH) n ₅ − (CH ₂ ) m ₅ − (NH) n ₆ − (C = X ′) − N (R) (R ′), −S
-M-S- (C = X ')-N (R) (R'), -SZ or n ₁ -valent heterocyclic residue (including those in which 5- or 6-membered unsaturated ring is condensed) (For example, a pyridine ring residue, an imidazole ring residue,
A thiazole ring residue, etc.), X represents ═S, ═O or ═NR ″, where R and R ′ have the same meanings as R ₂ and R ₃ , respectively, X ′ has the same meaning as X, Z is a hydrogen atom, Alkali metal atom, ammonium group, amino group, nitrogen-containing heterocyclic residue (for example, pyridine ring residue, imidazole ring residue, etc.),
Represents an alkyl group (for example, a methyl group, an ethyl group, etc.) or --S--B--Y (R ⁴ ) (R ⁵ ), M represents a divalent metal atom, and R ″ represents a hydrogen atom or a carbon atom 1. ~ 6 alkyl groups,
Cycloalkyl group, aryl group, heterocyclic residue (5-6
Membered unsaturated rings are also condensed) (for example, a pyridine ring residue, an imidazole ring residue, etc.) or an amino group, and n _{1 to} n ₆ and m _{1 to} m ₅ are each 1 to Represents an integer of 6. B represents an alkylene group having 1 to 6 carbon atoms, Y represents -N <, = C <or -CH <, and R ₄ and R ₅
Are synonymous with R ₂ and R ₃ , respectively. However, R ₄ and R ₅ may each represent -B-SZ, and R ₂ and R ₃ ,
R and R ', R ₄ and R ₅ may be bonded to each other to form a ring.

The compound represented by the general formula [II] includes ethanolated products and salts thereof.

In the general formula [III], Q ₁ is a nitrogen-containing heterocyclic ring (including a condensed 5- or 6-membered unsaturated ring)
(For example, thiazole ring, thiadiazole ring, imidazole ring, pyrimidine ring, triazole ring, pyrazine ring,
Represents a group of atoms necessary for forming a triazine ring, an oxodiazole ring, etc., and R ₁₁ ′ is a hydrogen atom, an alkali metal atom, a group obtained by removing R ₁₁ ′ from the general formula [III], or an alkyl group (for example, , Methyl group, ethyl group, etc.).

In the general formula [IV], X ₂ is --COOM ¹ ,-
^{_{H, -OH, -SO 3 M 1}} , -CONH 2, -SO 2 NH 2, -NH 2, -SH,
−CN, −CO ₂ R ₁₆ , −SO ₂ R ₁₆ , −OR ₁₆ , −NR ₁₆ R ₁₇ , −SR
_{16, -SO 3 R 16, -NHCOR} 16, -NHSO 2 R 16, represents -OCOR ₁₆ or -SO ₂ R _16, Y ₂ is -S- _{[C (R 14) (R 15} ) - ] _n9 - N (R
₁₃₎ - _{[- C (R 11) (R} 12) - ] _{m9 -, - C (= NR} 18) (R 19) or a hydrogen atom, respectively m ₉ and n ₉ is an integer from 1 to 10 . R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₇ and R ₁₈ are each a hydrogen atom, a lower alkyl group, an acyl group or-
[-C (R ₁₁ ) (R ₁₂ )-] _m -X ₂ , R ₁₆ represents a lower alkyl group (e.g., methyl group, ethyl group, etc.), R ₁₉ represents -NR ₃₀ R ₃₁ , -NR. OR ₃₂ or —SR ₃₂ , R ₃₀ and R ₃₁ each represent a hydrogen atom or a lower alkyl group (eg, methyl group, ethyl group, etc.), and R ₃₂ is bonded to R ₁₈ to form a ring. Represents the necessary atomic group. R ₃₀ or R ₃₁ may combine with R ₁₈ to form a ring. M'represents a hydrogen atom or a cation. R ₁₁ and R ₁₂ represent a hydrogen atom or an alkyl group (for example, a methyl group, an ethyl group, etc.), and X ₂ is represented by the general formula [I
V] is the same as X ₂ .

In the general formula [V], X represents a hydrogen atom or an alkali metal, Y represents a hydrogen atom, a substituted or unsubstituted alkyl group, and m represents an integer of 1 to 6. R ₄₁ and R ₄₂ represent a hydrogen atom or a lower alkyl group (for example, a methyl group, an ethyl group or a nitrogen atom, an alkyl group substituted with a sulfur atom, etc.).

Specific compounds represented by the general formulas [I] to [V] of the present invention are shown below, but the compounds of the present invention are not limited thereto.

[0018]

[Chemical 7]

[0019]

Embedded image

[0020]

[Chemical 9]

[0021]

[Chemical 10]

[0022]

[Chemical 11]

[0023]

[Chemical 12]

[0024]

[Chemical 13]

[0025]

Embedded image

[0026]

[Chemical 15]

[0027]

Embedded image

[0028]

[Chemical 17]

Of the above compounds, the compounds preferably used in view of the effects of the present invention are I-2, II-6 and III.
-10, III-13, III-31, III-32, III-34, IV-
7, V-1, V-3 and V-5 are mentioned, particularly preferable ones are general formula [III] or [V], and compounds are III-10, III-13 and V-3. .

From the viewpoint of the stability of the compound of the present invention, it is preferable to apply the compound of the present invention to a fixing processing liquid.

In the present invention, it is contained in the fixing solution,
The above general formulas [I] to [V] based on the weight of thiosulfate
It is preferable that the total weight of the compound is 0.05% by weight or more and 5% by weight or less, and further 0.2% by weight or more and 2% by weight.
The following is preferred.

The fixing solution according to the present invention contains a thiosulfate represented by potassium thiosulfate, sodium thiosulfate and ammonium thiosulfate as a so-called fixing agent, and ammonium thiosulfate is 70 mol% or less in the thiosulfate. ,
It is more preferably 30 mol% or less, and the present invention is effective in such a system having a low ammonia concentration.

In the present invention, other fixing agents such as potassium thiocyanate, sodium thiocyanate,
A thiocyanate such as ammonium thiocyanate, or thiourea thioether may be used in combination.

The fixing agent is used in an amount of 0.1 mol or more per liter of the processing liquid, preferably in the range of 0.6 to 4 mol, particularly preferably in the range of 0.9 to 3.0 mol, particularly preferably.
It is used in the range of 1.1 to 2.0 mol.

In addition to these fixing agents, further fixing solutions include boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide. A pH buffer consisting of various salts such as, alkylamines, polyethylene oxides and the like which are known to be added to a fixing solution can be appropriately added.

The pH of the fixing solution of the present invention is preferably 4-8.
Used in the range of.

The fixing solution of the present invention may contain a sulfite and a sulfite-releasing compound, which include potassium sulfite, sodium sulfite, ammonium sulfite, ammonium hydrogen sulfite, potassium hydrogen sulfite, sodium hydrogen sulfite and metabisulfite. Examples thereof include potassium, sodium metabisulfite, and ammonium metabisulfite. Further, sodium formaldehyde bisulfite, sodium acetaldehyde bisulfite, sodium propionaldehyde bisulfite, sodium butyraldehyde bisulfite, sodium succinate aldehyde bisulfite, glutaraldehyde sodium bisulfite, β-methylglutaraldehyde bis sodium bisulfite, maleic acid. Dialdehyde bis sodium bisulfite and the like can also be used.

These sulfites and sulfite-releasing compounds are used as sulfurous acid in an amount of 0.1 mol or more, preferably 0.12 to 0.55 mol / l, more preferably 0.15 to 0.50 mol / l, per liter of the fixing solution.
1, especially in the range 0.20 to 0.40 mol / l.

The replenishing amount of the processing solution having fixing ability in the present invention is preferably 800 ml / m ² or less, more preferably 400 ml.
/ M ² or less, and further 100 ml / m ² or less.

The tank for fixing processing in the present invention may be one tank or a plurality of processing tanks.

In the present invention, air or oxygen may be blown in the treatment bath and the treatment replenisher storage tank, if desired, in order to increase the activity of the treatment liquid, or a suitable oxidizing agent such as peroxide may be used. Hydrogen, bromate, persulfate and the like may be added appropriately.

Examples of the silver halide of the light-sensitive material to be processed include silver chloride, silver chlorobromide, silver bromide, silver iodobromide, silver iodide, etc. The photographic light-sensitive material is preferably a photographic light-sensitive material having a relatively high silver iodide content of 5 mol% or more of that of silver halide.

It is preferable to carry out the stabilizing process immediately after the fixing process, and the time until the photosensitive material comes into contact with the stabilizing solution after the fixing process is preferably 7 seconds or less, more preferably 5.
It is preferably not more than 2 seconds, more preferably 1 to 3 seconds.

The number of stabilizing tanks may be one, but the number of tanks can be increased up to about 2 to 10, and the replenishing amount of the stabilizing solution can be reduced by increasing the number of tanks. Considering downsizing of the developing machine, about 2 to 6 tanks are preferable. The replenisher may be replenished in several places, but preferably it is replenished to a subsequent tank in view of the processing flow of the light-sensitive material and its overflow (the tanks are communicated with each other by a pipe located below the liquid surface). In such a case, it is preferable to adopt a system in which the solution flows through the pipe) into the previous tank of the tank, that is, a countercurrent system (multistage countercurrent system), and a cascade system is included in one of them. More preferably, in the stabilizing tank of two or more tanks, the last stabilizing tank is supplemented with the replenishing solution, and the overflow solution is sequentially transferred and poured into the preceding tank.

The replenishing amount of the stabilizing solution is preferably 900 ml or less, and more preferably 50 to 100 m @ ^{2 of the} light-sensitive material to be processed.
800 ml, more preferably 100-650 ml, especially 150-
It is 500 ml. By introducing the processing liquid pumped out from the stabilizing tank into the fixing liquid in the fixing processing step, the amount of the replenishing liquid can be effectively reduced.

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

(1) Color development → bleaching → fixing → washing (2) Color developing → bleaching → fixing → washing → stable (3) Color developing → bleaching → fixing → stable (4) Coloring development → bleaching → fixing → first Stable → Second stability (5) Color development → Bleach → Bleach fixing → Washing (6) Color development → Bleach → Bleach fixing → Washing → Stable (7) Color developing → Bleach → Bleach fixing → Stable (8) Color developing → Bleach → Bleach-fixing → 1st stability → 2nd stability (9) Color development → Bleach → Bleach fixing → Fixing → Washing → Stable (10) Color development → Bleach → Bleach fixing → Fixing → 1st stability → 2nd stability (11) Color development → bleaching → bleach-fixing → washing with water (12) Color development → bleaching → bleach-fixing → stability In these steps, (3), (4), (7), (10),
(12) is preferable, and (3), (4) and (12) are particularly preferable.

In order to effectively bring out the effects of the present invention,
For the replenishment of the treatment liquid, it is preferable to use a solid treatment agent such as a powder, a granular treatment agent or a tablet, preferably a granular treatment agent and a tablet, and further a tablet.

The powder mentioned here is an aggregate of fine crystal grains. Granules refer to granules having a particle size of 50 to 5000 μm, and preferably granulated powder. A tablet refers to a powder or granule compression-molded into a certain shape. As a tablet molding method, the method of granulating the powder or granule and then forming into a tablet is effective because it can maintain more stable processing performance. Is preferred.

As the granulation method for forming tablets, known methods such as rolling granulation, extrusion granulation, compression granulation, crushing granulation, stirring granulation, fluidized bed granulation and spray drying granulation can be used. Can be done.
For tablet formation, the average particle size of the obtained granules is 100 to 2000 μm in terms of non-uniformity of components when mixing and granulating the granules, so-called segregation is unlikely to occur. It is preferable to use one, more preferably 200 to 1500 μm
Is. Furthermore, the particle size distribution is ± 20 for 50% or more of the granulated particles.
Those within a deviation of 0 to 250 μm are preferred. The obtained granulated product is used as it is as granules. When compressing the obtained granulated product under pressure, a known compressor such as a hydraulic press, a single-shot tableting machine, a rotary tableting machine, or a preketching machine can be used. Further, tableting may be carried out by mixing the granulated product prepared by the above-mentioned granulating method and the commercially available raw material crystal as it is.

The solid processing agent obtained by compression under pressure can take any shape, but from the viewpoint of productivity and handleability, or from the problem of dust when used on the user side, a cylindrical type, So-called tablets are preferred.

The solid processing agent of the present invention contains at least one compound selected from polyethylene glycols, polyvinylpyrrolidones, polyvinyl alcohols and saccharides to prevent decomposition of thiosulfate due to storage over time and The effect of preventing generation of powder of the solid processing agent due to friction after storage with time is further enhanced.

[0053]

The present invention will be described in detail below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 A color negative film processor (L-KP-50QA) having the following processing steps was prepared using the following starting solution and replenishing solution.
Then, the Konica Color Super DD film (manufactured by Konica Corporation) exposed by a conventional method was continuously treated for 3 weeks at a rate of 10 rolls per day for evaluation.

(Color development starter) Potassium carbonate 30 g Sodium hydrogen carbonate 2.5 g Potassium sulfite 3.0 g Sodium bromide 1.2 g Potassium iodide 0.6 mg Hydroxylamine sulfate 2.5 g Sodium chloride 0.6 g 4-Amino-3-methyl-N -Ethyl-N- (β-hydroxyethyl) aniline sulfate 4.6g Diethylenetriamine pentaacetic acid 3.0g Potassium hydroxide 1.2g Add water to make 1 liter, and adjust to pH 10.0 with potassium hydroxide or 20% sulfuric acid. .

(Color development replenisher) potassium carbonate 40 g sodium hydrogen carbonate 3 g potassium sulfite 7 g sodium bromide 0.5 g hydroxylamine sulfate 3.1 g 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) Aniline sulfate 6.5 g Diethylenetriamine pentaacetic acid 3.0 g Potassium hydroxide 2 g Add water to make 1 liter, and adjust to pH 10.12 with potassium hydroxide or 20% sulfuric acid.

(Bleaching Start Solution) 1,3-Propylenediaminetetraacetic acid Ammonium ferric acid 133 g Ethylenediaminetetraacetic acid disodium 10 g Ammonium bromide 100 g Succinic acid 30 g Maleic acid 70 g Ammonium nitrate 40 g Water was added to make 1 l and aqueous ammonia was used. Adjust to pH 4.4.

(Bleach Replenisher) 1,3-Propylenediaminetetraacetic acid Ammonium ferric acid 175 g Ethylenediaminetetraacetic acid disodium 2 g Ammonium bromide 120 g Succinic acid 40 g Maleic acid 80 g Water was added to make 1 l, and ammonia water or glacial acetic acid was added. Adjust to pH 3.4 using.

(Fixing starter / replenisher) Sodium thiosulfate Listed in Table 1 Ammonium thiosulfate Listed in Table 1 Sodium sulfite 18 g Potassium carbonate 2 g Ethylenediaminetetraacetic acid disodium salt 2 g Compound of the invention (listed in Table 1) 1 g Water In addition, finish to 1 liter.

(Stable starter / replenisher) m-Hydroxybenzaldehyde 1.5 g Sodium lauryl sulfate 0.2 g Ethylenediaminetetrasodium acetate 0.6 g Lithium hydroxide monohydrate 0.7 g Water is added to make 1 liter.

(Processing step) Processing time Processing temperature Replenishment amount Color development 3 minutes 15 seconds 38 ° C 520 ml / m ² Bleach 45 seconds 38 ° C 100 ml / m ² Fixing-1 45 seconds 38 ° C fixing-2 45 seconds 38 ° C 510 ml / M ² Stable -1 20 sec 38 ℃ Stable-2 20 s 38 ℃ Stable -3 20 s 38 ℃ 860ml / m ² Dry 80 s 38 ℃ Fixing from 2 to 1, Stability from 3 to 2, 2 It is a countercurrent method to 1.

<< Evaluation Items >> (Amount of Residual Silver) After continuous processing, the unexposed light-sensitive material was processed, and the amount of residual silver was measured by the fluorescent X-ray method.

(Observation of Presence or Absence of Deposited and Sticking Substances on Transition Roller) Observation of rollers in the transition rack from the first fixing tank to the second fixing tank and from the second fixing tank to the stable first tank after continuous processing The evaluation was performed according to the following criteria.

⊚: The crystals attached to the roller are few and can be easily removed by wiping with a hand. ◯: Even if the crystals attached to the roller are wiped by hand, some crystals remain, but there is no problem. Δ: Roller The crystals may remain on the film even if they are wiped off by hand, and scratches may occur on the film. ×: Many crystals adhere to the roller and cannot be wiped off by hand (adhesion may occur). There is a great risk that

(Low Temperature Precipitability) The fixing treatment liquid after continuous treatment was separated and stored at 0 ° C.

◯: Crystal precipitation was not observed. Δ: Crystals were slightly accumulated at the bottom of the container. ×: Large amount of large crystalline material was generated.

The above results are shown in Table 1.

[0068]

[Table 1]

As is clear from Table 1, by using the compound of the present invention, the thiosulfate concentration can be reduced even if the molar ratio of ammonium thiosulfate in the thiosulfate used is 70 mol% or less. Therefore, it is possible to prevent the phenomenon of sticking of the rollers in the transfer rack and the precipitation of crystals during low temperature storage of the treatment liquid, and to maintain good fixing performance.

Example 2 Of the thiosulfate salts of the fixing replenisher used in Example 1, the molar ratio of ammonium salt was fixed at 10 mol%, and the thiosulfate concentration of the whole fixing replenisher and the compound of the present invention were fixed. Was changed as shown in Table 2 and treated in the same manner as in Example 1 and evaluated.

The results are shown in Table 2.

[0072]

[Table 2]

As a result, by using the compound of the present invention, the thiosulfate concentration can be reduced even if the molar ratio of ammonium thiosulfate in the thiosulfate to be used is 70 mol% or less. Of the formula (III) or (V) among the compounds of the present invention, which can prevent the sticking phenomenon of the roller and crystal precipitation during storage of the treatment liquid at low temperature and can maintain good fixing performance. It can be seen that the compound is particularly effective.

Example 3 In the fixing replenisher, the molar ratio of ammonium salt to thiosulfate was fixed to 10 mol%, and the compound of the present invention was fixed to III-10,
The thiosulfate concentration of the entire fixing replenisher and the use weight ratio of the compound of the present invention to the thiosulfate were changed as shown in Table 3, and the same treatment as in Example 1 was carried out and evaluated.

[0075]

[Table 3]

From this, it can be seen that it is effective to set the weight of the compound of the present invention to be used in the range of 0.05 to 5.0 based on the weight of thiosulfate.

Example 4 The replenishing device section of the color negative film processor CL-KP-50QA (manufactured by Konica Corp.) was modified as shown in FIG. 1 and replenished by using the solid processing agent supplying (charging) device shown in FIG. . Konica Color Super DD100 film (manufactured by Konica Corporation)
After imagewise exposure, the columnar container containing the tablets was set in the tablet loading section and treated at a rate of 20 tablets per day.

FIG. 1 shows a solid processing agent replenishing apparatus 2A,
2B, 2C, 2D to KP-50QA (automatic developing machine (hereinafter,
FIG. 3 is a view showing a mounting position of the solid processing agent replenishing device 2A, 2B, 2C, 2 attached to the automatic processing machine).
D is attached to the upper part of the color developing tank 1A, the bleaching tank 1B, the fixing tank 1C, and the stabilizing tank 1D at the positions shown by the diagonal lines. FIG. 2 shows the solid processing agent replenishing (feeding) devices 2A, 2
In the configuration diagram showing one embodiment of B, 2C, and 2D, a dissolution chamber 106 for introducing the solid processing agent 111 is provided on the side of each tank.

In FIG. 2, a solid processing agent (hereinafter also referred to as a tablet or a tablet chemical) 111 is housed in a container (cartridge) 101 divided into a plurality of chambers and sealed by a slide type cap 102. When this cartridge is set on the cartridge support base 103 of the solid processing agent automatic supply device installed on the processing tank of the automatic processor, the cap 102 is opened, and the tablet is cut from the cartridge fixed obliquely and the rotary cylinder 104 is cut. Rolls into mouth 105.
The slits 105 of the rotary cylinder 104 are staggered so that a plurality of tablets stored in different chambers of the cartridge do not roll down at the same time.

The processing steps are shown below.

Treatment process Treatment time Treatment temperature Replenishment water amount Color development 3 minutes 15 seconds 38.0 ° C. 520 ml / m ² Bleach 45 seconds 38.0 ° C. 100 ml / m ² Fixing-1 45 seconds 38.0 ° C. fixing-2 45 seconds 38.0 ° C. 510 ml / m the ^bistable -1 20 sec 38.0 ° C. stable -2 20 seconds 38.0 ° C. stable -3 20 sec 38.0 ° C. 860 ml / m ² drying 80 sec 55 ° C. fixing from 2 to 1, stable to the 3 2,2 1 The replenishing water for the second fixing tank was made to flow into the second fixing tank by a pump for the stable first tank liquid.

Evaporation correction is 10 ml, 6.5 ml, 7 ml, and 7 ml per hour in color development, bleaching, fixing-1, fixing-2, stable-1, stable-2, and stable-3 tanks during temperature control. , 8.6ml, 8.6ml, 9.3
Evaporation correction was performed by a program that replenishes the water by evaporation.
In addition, when not in operation, the non-operation time is added up for color development, bleaching,
Fixing-1, Fixing-2, Stable-1, Stable-2, Stable-3 with evaporative correction water of 7.5 ml, 5 ml, 6 ml, 6 ml and 5 ml per hour respectively
Water of 5 ml and 5 ml was collectively replenished at the start of operation. The tank solution at the start was prepared by using a replenisher solution and a starter of the processing agent CNK-4-52 (manufactured by Konica Corporation) for Konica color negative film.

Next, the following color negative treating agent was prepared.

1) Color development replenishing tablet operation for color negative film (1) Developing agent CD-4 [4-amino3-methyl-N-ethyl-N- [β
-(Hydroxy) ethyl] aniline sulphate] 60 g is ground in a commercial hammer mill to an average particle size of 10 μm. This fine powder is placed in a commercially available stirrer for about 7 minutes at room temperature for 10 minutes.
After granulating by adding ml of water, the granulated product is dried in a fluidized bed dryer at 40 ° C. for 2 hours to almost completely remove the water content of the granulated product, and color development replenishing granules for color negative (1)
It was created.

Operation (2) 69.4 g of hydroxylamine sulfate and 4 g of Pine Flow (manufactured by Matsutani Chemical Co., Ltd.) were pulverized in the same manner as in the operation (1), and then mixed and granulated. The amount of water added was 3.5 ml, and after granulation,
The granules were dried for 0 minutes to remove almost completely the water content, to prepare granules (2) for color development replenishment for color negative.

Operation (3) 1-hydroxyethane-1,1-diphosphonate disodium 15
g, potassium sulphite 72.8g, potassium carbonate 350g, sodium hydrogen carbonate 3g, sodium bromide 3.7g and mannite 22g, polyethylene glycol 6000 5.0g are crushed and mixed in the same manner as in the operation (1), and the amount of water added is 40 ml. And granulate. After the granulation, the granulated product was dried at 70 ° C. for 60 minutes to almost completely remove the water content of the granulated product to prepare color development replenishing granules (3) for color negative.

Granules (1) to (3) for color development for color negative described above are mixed, and 2 g of sodium N-myristoylalanine is added to the granules thus prepared, and the mixture is kept at 25 ° C. and 40% RH or less. Mix evenly for 10 minutes using a mixer in a conditioned room. Next, mix the mixture with Kikusui Seisakusho KK
Using a tableting machine modified from Tough Press Collect CO., Ltd. 1527HU, compression filling was performed with a filling amount of 10 g per tablet, and a diameter of 30 mm.
A color development replenishing tablet for color negative was prepared.

2) Bleaching Replenishing Tablet for Color Negative Operation (4) 1,3-Propanediamine 4 ferric ammonium acetate monohydrate
175 g, 1,3-propanediamine tetraacetic acid 2 g, and Pine Flow (Matsuya Chemical Co., Ltd.) 17 g were pulverized and mixed in the same manner as in the operation (1), and the amount of water added was 8 ml to perform granulation. After the granulation, the granulated product is dried at 60 ° C for 30 minutes to almost completely remove the water content of the granulated product.

Operation (5) 133 g of succinic acid, 200 g of ammonium bromide and pine flow
10.2 g is crushed, mixed and granulated in the same manner as in the operation (H). The amount of water added was 17 ml, and after granulation, the granules were dried for 60 minutes at 70 ° C to almost completely remove water.

Operation (6) In the same manner as in the operation (H), 66.7 g of potassium sulfate, 60 g of potassium hydrogen carbonate and 8 g of mannite are pulverized, mixed and granulated. The amount of water added is 13 ml, and after granulation, the granules are dried at 60 ° C for 60 minutes to almost completely remove water.

The granules prepared by the above operations (4) to (6) are uniformly mixed for 10 minutes using a mixer in a room where the humidity is controlled to 25 ° C. and 40% RH or less. Next, 6 g of sodium N-lauroyl sarcosine is added to this mixed granulated product, and they are mixed for 3 minutes. Next, the mixture was compressed into tablets with a tableting machine modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. with a filling amount of 10 g per tablet, and a bleaching replenishing tablet for a color negative having a diameter of 30 mm and a thickness of 10 mm. And

3) Fixing replenishing tablet for color negative (7) Sodium thiosulfate / ammonium thiosulfate = 1700 g /
180 g, sodium sulfite 180 g, potassium carbonate 20 g, ethylenediaminetetraacetic acid disodium salt 20 g, pine flow (Matsuya Chemical Co., Ltd.) 70 g, and the compound 25 g shown in Table 2 were pulverized in a commercially available bandam mill until the average particle size became 30 μm, and this powder 50 ml of water is added in a stirring granulator for about 10 minutes at room temperature to granulate. After granulation, granulate at 12 ° C in a fluid bed dryer for 12
Dry for 0 minutes to remove almost completely the water of the granulate. Next, the dried granules were made to have an average particle size of 800 μm so that 50% or more of the particles were within a deviation of ± 200 to ± 250 μm.

Operation (8) 30 g of N-lauroyl sarcosine sodium is mixed with the above fixing replenishing granules in a room conditioned at 25 ° C. and 45% RH or less for 5 minutes using a mixer. Next, mix the mixture with Kikusui Seisakusho KK
The filling amount was set to 10 g by a tableting machine modified from Tough Press To Correct 1527HU, and a color negative fixing replenishing tablet having a diameter of 30 mm and a thickness of 10 mm was prepared.

4) Stable replenishing tablet operation for color negative (9) m-Hydroxybenzaldehyde 150 g, sodium lauryl sulfate 20 g, ethylenediamine tetrasodium acetate 60
g, 65 g of lithium hydroxide monohydrate and 10 g of pine flow are pulverized, mixed and granulated in the same manner as in the operation (1). How much water is added
After granulating to 10 ml, the granulated product is dried at 50 ° C. for 2 hours to almost completely remove the water content of the granulated product.

The granules prepared by the above operation were treated at 25 ° C. and 40% R
In a room whose humidity was controlled to H or less, compression tableting was performed with a tableting machine modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. with a filling amount of 10 g per tablet and a diameter of 30 mm and a thickness of 10
mm stable negative refill tablets for color negatives were made.

The color negative replenishing tablets were placed in the processing tank at the intervals shown in the following table.

[0097]

[Table 4]

The replenishment form using these tablets was set to form 2, the replenishment form using the replenisher up to Example 3 was set to form 1, and the composition of the fixing processing liquid was changed as shown in Table 5 and evaluated in the same manner. did.

[0099]

[Table 5]

Thus, by using the compound of the present invention and adopting the replenishing form using tablets, the phenomenon of sticking to the rollers in the transfer rack and the precipitation of crystals during the low temperature storage of the treatment liquid were prevented, and it was even better. It can be seen that excellent fixing performance can be maintained.

[0101]

EFFECTS OF THE INVENTION According to the present invention, even if the amount of ammonium salt used is reduced, the phenomenon of sticking to the rollers in the rack and the precipitation of crystals during storage of the treatment liquid at low temperature are prevented, and good fixing performance is maintained. It is possible to provide a good working environment.

[Brief description of drawings]

FIG. 1 is a configuration diagram showing a mounting position of a solid processing agent replenishing device to an automatic developing machine.

FIG. 2 is a configuration diagram of a solid processing agent supply (input) device.

[Explanation of symbols]

 1A to 1E Processing tank 2A to 2D Solid processing agent replenishing device 101 Cartridge 102 Sliding cap 103 Cartridge support 104 Rotating cylinder 105 Notch opening 106 Dissolution chamber 107 Filter 108 Shutter 109 Processing tank 110 Canopy 111 Solid processing agent (tablets)

Claims (4)

[Claims] 1. A thiosulfate and at least one compound represented by the following general formulas [I] to [V] are contained, and ammonium thiosulfate in the thiosulfate is 70 mol% or less. Replenishing composition for processing silver halide photographic light-sensitive material. Embedded image [In the formula, Q represents an atomic group necessary for forming a nitrogen-containing heterocycle (including a condensed 5- or 6-membered unsaturated ring), and R ₁ represents a hydrogen atom or a carbon atom having 1 to 1 carbon atoms. 6 alkyl groups, cycloalkyl groups, aryl groups, heterocyclic groups (5
A 6-membered unsaturated ring is condensed) or an amino group. ] [Chemical 2] [In the formula, R ₂ and R ₃ are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxy group, an amino group, an acyl group having 1 to 3 carbon atoms, an aryl group, or an alkenyl group; Represent A is-(C = X ')-N (R)
(R ′), − (CH ₂ ) n ₂ − (C ＝ X ′) − N (R) (R ′), − (S) m ₁ − (C
= X ′) − N (R) (R ′), − (S) m ₂ − (CH ₂ ) n ₃ − (C = X ′) − N
(R) (R ′), − (S) m ₃ − (CH ₂ ) n ₄ −N (R) (R ′), − (S) m ₄ −N
(R) (R ′), − (NH) n ₅ − (CH ₂ ) m ₅ − (NH) n ₆ − (C = X ′) − N
(R) (R '), -S-MS- (C = X')-N (R) (R '), -SZ or n ₁ -valent heterocyclic residue (5- or 6-membered unsaturated (Including condensed rings), X represents ═S, ═O or ═NR ″, wherein R and R ′ are synonymous with R ₂ and R ₃ , respectively, and X ′ is synonymous with X. , Z is a hydrogen atom, an alkali metal atom, an ammonium group, an amino group, a nitrogen-containing heterocyclic residue,
Alkyl or -S-B-Y, (R 4) (R 5), M is 2
Represents a valent metal atom, R ″ represents a hydrogen atom or a carbon atom of 1 to 6
Represents an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic residue (including those in which a 5- to 6-membered unsaturated ring is condensed) or an amino group, and is n _{1 to} n ₆ and m _{1 to} m. ₅ represents an integer of 1 to 6, respectively. B represents an alkylene group having 1 to 6 carbon atoms, Y is -N <, = C <or represents -CH <, R ₄ and R ₅ have the same meanings as R ₂ and R _3, respectively.
However, R ₄ and R ₅ may each represent -B-SZ,
R ₂ and R ₃ , R and R ′, R ₄ and R ₅ may be bonded to each other to form a ring. The compound represented by the general formula [II] also includes an ethanolated product and a salt thereof. ] [Chemical 3] [Chemical 4] Alternatively, it represents a hydrogen atom, and m ₉ and n ₉ each represent an integer of 1 to 10. R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₇ and R
₁₈ is a hydrogen atom, a lower alkyl group, an acyl group or R ₁₆ represents a lower alkyl group, R ₁₉ represents —NR ₃₀
R ₃₁ represents —OR ₃₂ or —SR ₃₂ , R ₃₀ and R ₃₁ each represent a hydrogen atom or a lower alkyl group, and R ₃₂ represents a group of atoms necessary to combine with R ₁₈ to form a ring. . R ₃₀ or R ₃₁ may combine with R ₁₈ to form a ring. M'represents a hydrogen atom or a cation. R _11, R ₁₂ represents a hydrogen atom, a lower alkyl group, an acyl group, X ₂ is X ₂ in the general formula [IV]
Is synonymous with ] [Chemical 6] [In the formula, X represents a hydrogen atom or an alkali metal, Y represents a hydrogen atom, a substituted or unsubstituted alkyl group, and m represents an integer of 1 to 6. R ₄₁ and R ₄₂ are a hydrogen atom, a lower alkyl group,
Represents an acyl group] 2. The total weight of the compounds of the above formulas [I] to [V] is 0.05% by weight or more and 5% by weight or less with respect to the weight of thiosulfate in the composition.
A replenishing composition for processing a silver halide photographic light-sensitive material described in 1. 3. The silver halide photographic light-sensitive material processing according to claim 1, wherein the silver iodide content of the silver halide emulsion used for the light-sensitive material to be processed is 5 mol% or more. Replenishing composition. 4. A thiosulfate and at least one compound represented by the above general formulas [I] to [V] are contained, and ammonium thiosulfate is 70 mol% or less in the thiosulfate. Solid processing agent for silver halide photographic light-sensitive materials.