JPH01244453A - Composition for silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance the preservability and rapid processing ability of a compd. for preparing a bleaching or bleach-fixing soln. by using a prescribed amt. of a specified compd. and adjusting the pH of the compsn. to a prescribed range. CONSTITUTION:This compsn. is a one-pack compsn. for preparing a bleaching or a bleach-fixing soln. for a color sensitive material, contains >=40wt.% ferric complex salt (a) of a compd. represented by the formula as a component (b) having bleaching ability and has 2.0-6.0pH. In the formula, each of A1-A4 is -CH2OH, -COOM, etc., M is H, Na, etc., and X is 3-6C alkylene. The salt (a) may be ferric ammonium 1,3-propanediaminetetraacetate monohydrate. Ferric ammonium ethylenediaminetetraacetate dihydrate may be contained as the component (b).

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide color photographic light-sensitive material composition, and more specifically, the present invention relates to a composition for a silver halide color photographic light-sensitive material, and more specifically, a halogenated silver halide composition that can be rapidly processed and has excellent long-term storage stability. This invention relates to a composition for silver color photographic materials.

[Background of the invention]

In order to obtain a color photographic image, it is necessary to perform a so-called desilvering process in which metallic silver produced together with the dye image obtained by the color development process is removed from the silver halide color photographic light-sensitive material.

Generally, this process is performed by first converting metallic silver into silver halide by treating it with a bleaching solution containing halide ions and an oxidizing agent, and then processing it in a fixing solution containing a silver halide solvent. This is done by performing various processing steps to remove silver halide generated by bleaching along with the remaining silver halide. On the other hand, there is also known a processing method in which bleaching and fixing are performed in one solution, that is, processing with a so-called bleach-fix solution.

Conventionally, compounds such as red blood salt, ferric chloride, and organic ferric lead salt have been used as bleaching agents for bleaching silver halide photosensitive discrimination after color development. .

Both red blood salt and ferric chloride are good bleaching agents because they have a strong bleaching power, a fast bleaching rate (oxidation rate), and can sufficiently restore the color of leuco compounds, which are intermediates of brown pigments. However, red blood salt is itself a cyanide compound;
Since the aqueous solution may generate free 7 anions by photolysis, it is necessary to completely detoxify the wastewater when discharging the wastewater.

In addition, bleaching solutions using ferric chloride have a very low pH and extremely high oxidizing power, so they have a strong corrosive effect on the metals that make up the processing equipment in which they are placed, and after bleaching The disadvantage is that iron hydroxide is produced in the water-washing culm, resulting in so-called staining in photosensitive materials.

Organic acid ferric complex salts are known as bleaching agents that cause fewer environmental problems and are easier to recycle than the red blood salts and ferric chloride. Cochin diamine tetraacetic acid secondary salt has been put into practical use.

In recent years, with the spread of color photography, the demand for faster processing has increased, and minilabs such as in-store processing have become prominent due to the decentralization of processing, and there is a desire for faster processing and simpler processing management. . One specific measure is to simplify the process of dissolving the processing agent. Usually, the processing agent to be treated is mixed in advance in a predetermined ratio, and when used, water is simply added to form a uniform solution at a ratio of 1:1. There is a so-called liquid type which is prepared in advance as a concentrated solution, but in order to simplify the dissolution work, the liquid type is preferable. As for liquid type kits, the question is whether the developer, bleach, fixer, bleach-fix, stabilizer, etc. are already known, and whether they can be thickened without decomposition or precipitation during storage.

For example, with bleach or bleach-fix solutions, there is a problem in which ammonium chloride halides such as ammonium bromide used in the film may crystallize when stored at low temperatures.

From the viewpoint of speeding up the processing, a method has conventionally been used in which a compound generally known as a bleach accelerator is added to the bleaching solution or bleach-fixing solution. Details of the accelerator can be found in JP-A-62-1.94615, pages 39 to 76.

However, bleach accelerators tend to react with the bleach itself,
In addition, many of them have poor solubility and often cause problems such as decomposition and precipitation.

For this reason, it is common to gift bleach accelerators and bleaching agents in separate parts.

However, by using two or more Kira l- liquids, the following coexistence occurs. In other words, from the manufacturer's perspective, it takes a lot of time to create the kit, extra containers are required, and if the PT of each part (or PT) is likely to fluctuate, it is necessary to contain the appropriate Hanwha agent for each part, etc. Cost increase. From the user's perspective, it is less convenient to use than liquids.

In addition to the method of using a bleaching accelerator, in order to further enhance and speed up the bleaching, 1,4-butanediaminetetraacetic acid iron complex salt or 1,3-propaneammitetraacetic acid iron complex salt can be used instead of ethylenediminetetraacetic acid hexa-iron complex salt. It has also been proposed to use ferric complex salts of aminopolycarboxylic acids with large molecular weights as bleaching agents.

However, as a result of research conducted by the present inventors, it has been found that in these compounds, the formation of ferrous complex salts is greater than that of ethylenediammytetraacetic acid iron complex salts.

If ferrous complex salts are present in the bleaching solution or bleach-fixing solution, the bleaching performance will deteriorate.Secondly, dyes, especially cyan dyes, may be reduced to leuco dyes, resulting in a so-called double color failure, which is a fatal drawback. It is.

[Purpose of the invention]

An object of the present invention is to provide a composition for preparing a bleaching or bleach-fixing solution, which is a one-component composition that has greater advantages than two or more components, and has excellent long-term solution storage stability and rapid processing ability. .

[Structure of the invention]

The object of the present invention is to contain 40% by weight of a ferric complex salt of a compound represented by general formula [A] among the components having bleaching ability.
This is achieved by a one-liquid silk composition containing the above and having a pH of 2.0 to 60.

General formula [A] In the formula, A, , A2. A3 and A may be the same or different, and -CH20H, -COOM or P0
3MIM2. M, M and M2 each represent a hydrogen atom, a sodium atom, a potassium atom or an ammonium group.

X represents a substituted or unsubstituted alkylene group having 3 to 6 carbon atoms.

Next, the compound represented by the general formula [A] will be described in detail.

Examples of the substituted or unsubstituted alkylene group having 3 to 6 carbon atoms represented by X include propylene, butylene, 1-rimethylene, tetramethylene, pentamethylene, etc., and examples of the substituent include a hydroxyl group. Preferred specific examples of the compound represented by the general formula (All) are shown below.

(A-1) (A-2) (A-3) (A-4) (A-5) (A-6) (A-7) (A-8) 1'lLI These (A-1)~ For the compound (A-8), any of these salts, potassium salts, or ammonium salts can be used in addition to the above.

From the viewpoint of the desired effects 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-2), and (A-4).
), (A-7), and particularly preferred is (A-1).

As components having bleaching ability other than general formula (A), compounds generally known as bleaching agents can also be used, such as ethylenediaminetetracomplex acid ferric complex salt, ethylenetriamine Aminopolycarboxylic acid ferric complex salts such as ferric pentaacetic acid complex salt, 1.2-/chlorohegysancyaminetetraacetic acid ferric complex salt, glycol ether diamine tetraacetic acid ferric complex salt are used from an economic point of view and bleaching fog. It is preferable because it is less.

Among the components having bleaching ability, the compound represented by the general formula [A] must be contained in an amount of 40% by weight or more, preferably 45% by weight or more, and particularly preferably 5% by weight or more.
If it is 0% or more, the effects of the present invention can be fully exhibited.

Further, the pH of the kit is required to be 2.0 to 6.0, preferably po is 2.5 to 5.5, and more preferably p+11;I: 2.5 to 50.

In addition, it is an effective means from the viewpoint of liquid preservation to include a buffer in the kit for the purpose of keeping pl+ constant. Buffers include sulfur hydroxide, potassium hydroxide, D(+) tartaric acid, citric acid, cacodylic acid, phthalic acid, greenin, aconitic acid, phosphoric acid, phthalic acid, 3.3-
Dimethylglutaric acid, phenylacetic acid, acetic acid, maleic acid, phosphoric acid, and their storium or potassium salts can be used alone or in combination of two or more.

Further, a halide such as ammonium bromide is usually added, but various optical brighteners, antifoaming agents, surfactants, and anti-scaling agents can also be added.

Furthermore, the bleaching accelerator mentioned above can also be added as long as it does not impair the storage stability of the solution.

〔Example〕

The present invention will be described in detail below, but the present invention is not limited thereby.

Example 1 An organic acid ferric complex and ammonium bromide were dissolved in water in the proportions shown below, and each p)I was 1.8 to 7 as shown in Table 1.
Adjust to 5°C and place in a polyethylene container at 5°C.
The composition (treatment liquid kit) was left to stand for a period of 1 month, and the crystal precipitation property of the composition (processing liquid kit) was examined.

The results are shown in Table 1.

■ Ethylenediaminetetraacetic acid Fe(1) ammonium
Dihydrate salt 240g/Q■
Ethylenecyaminetetraacetic acid Fe(III) ammonium
dihydrate salt], 68g/121
．． 3-Propanecyaminetetraacetic acid Fe(TII) ammonium monohydrate 72g/Q■ Ethylenediaminetetraacetic acid Fe(In) ammonium 2
Water salt 156g/41.3
-Propanediaminetetraacetic acid Fe(lI[) ammonium monohydrate 84. g/(1■"
-Thyrenaminetetraacetic acid Fe(III) ammonium
Dihydrate salt 144g/(11,
3-propanecyaminetetraacetic acid Fe(1) ammonium
1 hydrate 96g/Q■ Ethylenecyaminetetraacetic acid Fe (ITI) ammonium dihydrate
132g/(11,3-propanediaminetetraacetic acid Fe(III) ammonium 1
Water salt 108g/(1■ Ethylenediaminetetraacetic acid Fe(II[) ammonium dihydrate)
120g/Q.

1.3-propanediaminetetraacetic acid Fe(III) ammonium l hydrate 120g/(+
■ Ethylenediaminetetraacetic acid Fe(I[+) ammonium dihydrate 108g #2
1.3-Propanediaminetetraacetic acid Fe(TII) ammonium monohydrate 132g#! ■
Ethylenediaminetetraacetic acid Fe (ITJ) ammonium dihydrate 96g/Q1.
3-Propanediaminetetraacetic acid Fe(III) ammonium monohydrate 144 g/(ammonium monobromide ('') 300 g#!

The proportions of the ferric complex salt of 1,3-propanediaminetetraacetic acid in the compositions of ■ to ■ are 30% by weight, 35% by weight, 40% by weight, 45% by weight, and 50% by weight, respectively, based on the total bleaching components.
, 55% by weight, and 60% by weight.

Table 2 shows the results when 2-hydroxy-1,3-glopanaminetetraacetic acid (nl) Fe ammonium monohydrate was used instead of 1.3-propaneaminetetraacetic acid Fe(III) ammonium monohydrate. Table 3 shows the results when 1,4-butanediaminetetraacetic acid Fe(III) ammonium monohydrate was used.

In Tables 1 to 3, ○ indicates that no crystal precipitation is observed, Δ indicates that some crystals are observed, X indicates that crystal precipitation is clearly observed, and × indicates that crystal precipitation is clearly observed. The higher the number, the worse the degree.

Example 2 The same composition as in Example 1 was placed in a polyethylene container for 50 min.
The composition was allowed to stand for 2 weeks at °C, and the concentration of ferrous complex salt in the composition was determined by the ol-I-phenan[·lorin method]. The results are shown in Table 4.

The numerical values in the table are the production rates of ferrous complex salts. r) H is Table 4
It was adjusted to the range of 20 to 10.0 shown in . 1,3-propanecyaminetetraacetic acid Fe(III) ammonium 1
Table 5 shows the results when 2-Hil~roxy-1,3-propanediaminetetraacetic acid Fe(lit) ammonium monohydrate was used instead of the hydrate salt. ) Table 6 shows the results when ammonium monohydrate was used.

Example 3 The same composition as in Example 1 was added with 50 g of thurium acetate as a buffering agent, and p+( was adjusted to the range of 18 to 75 shown in Table 7, and these were designated as ■' to ■'. ■～■、■′～■′
The compositions were placed in a polyethylene container and left to stand at 25°C for one month, and the l)H change of each composition was investigated.

The results are shown in Table 7.

In Table 7, ○ marks are changes in I)H or ±0, those below 2nd place are marked △ (or ±0.2 to ±0.4, and X marks are ±0.4).
〜±0.6, XX mark l: j±06 and above''2, all not shown.

Similar results were obtained when thorium phosphate was used instead of thorium acetate.

Example 4 1) The same composition as in Example 1 in which H was adjusted to 18 to 7.5 was left at 50°C for two weeks. A bleach solution was prepared by diluting 500 mC of this composition to IQ and adjusting the pH to 6.0.

Using this bleaching solution, perform the following treatment steps as shown below.
Processing was carried out using a sample of the photosensitive +A material exposed to Wesson light, and the amount of residual silver in the highest density part of the sample after processing was determined using fluorescent X-rays.

The results are shown in Table 8.

[Processing process] Time Temperature light color development 3 minutes 15 seconds 38°C bleaching
White 45 seconds 38°
C fixation 3 minutes 15 seconds
Wash with water at 35°C for 3 minutes
30-34°O female 1 minute 20 seconds 30-34°C I drying The following color developing solution, fixing solution and stabilizing solution were used.

[Color developer] Potassium carbonate 30.0g I-lium sulfite 2. Oghi]・Loki/ruamine sulfate 2.0g Potassium bromide 1.2g Storium hydroxide
3.4g 3-Methyl-4-amino-N-ethyl-N-β-hydroxydiylaniline sulfate 4.6g water was added to make a solution of 1a, and the pH was adjusted to 10.1 with strontium hydroxide and 50% sulfuric acid. Adjusted to.

[Fixer ammonium cothiosulfate (725%) aqueous solution 250 mQ Ammonium sulfite 20 g water was added and the solution was adjusted to IQ, and the pH was adjusted to 7.0 with ammonia and acetic acid.

U stabilizer] Formalin (35% aqueous solution) 7.0mQ
Add water to make H.

A photosensitive old material 1 - rear acetate 1 - A anti-reaction layer and a gelatin layer are provided on the film, and a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a yellow colloid I to silver A filter layer and a blue-sensitive silver halide emulsion layer were coated to give a total silver content of 62 mg per 100 cm 2 . The emulsion layer contains 7% or about 48% silver iodide.
% of silver iodobromide, and in this case, the blue-sensitive silver halide emulsion layer contained α-(4-2l・lofoenoki/)-α-pyharyl-5-[γ-(2°4-so) as a yellow coupler. Using t-aminophenoxy)phthylamito]-2-chloroacetanilide, 1. -(2,,1,,6-1-lichlorophenyl)-3-([α-(2,4-N-L-amylphenoxy/)-acetamide 1hensamiF13-pyranolone and 1-(2,4,6 - Dolichlorophenyl)
-3-([α-(2,4-・/'-t-amylphenoxy/)-ace1~amiF ]]benzami Fl-4-1-
Me1-quinphenylaso-5-pyranolone was used, and the following (
C-1), and conventional additives such as sensitizing dyes and hardeners were added to each emulsion layer according to conventional methods.

＞7Nnonozolar (C-], ) Table 4 Table 5 Table 6 -23~ From the test results, 40% of the ferric salt of the compound represented by the general formula [A] among the components with bleaching ability Contains at least % by weight, and p+12. It can be seen that the composition having a range of o to 60 has excellent storage stability, and the bleaching solution prepared from this composition has excellent rapid processability.

〔Effect of the invention〕

According to the present invention, -liquid chira l- has excellent storage stability,
Furthermore, a composition for preparing a bleaching solution or a bleach-fixing solution for silver halide photographic materials, which has excellent rapid processing ability, is provided.

Claims (1)

[Scope of Claims] It has a one-component form, contains 40% by weight or more of a ferric complex salt of a compound represented by the following general formula [A] among the components having bleaching ability, and has a pH of 2.0. 1. A composition for a silver halide color photographic light-sensitive material, characterized in that the silver halide color is in the range of 6.0 to 6.0. General formula [A] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, A_1, A_2, A_3 and A_4 may be the same or different, -CH_2OH, -COO
Represents M or -PO_3M_1M_2. M, M_1 and M_2 each represent a hydrogen atom, a sodium atom, a potassium atom or an ammonium group. X represents a substituted or unsubstituted alkylene group having 3 to 6 carbon atoms. ]