JPS5944626B2 - Color photo processing method - Google Patents

Description

[Detailed description of the invention] The present invention relates to photographic processing methods.

More specifically, it relates to an improved bleaching method or bleach-fixing method. In particular, it relates to the improved method or composition described above, characterized in that it uses a bleach accelerator that strengthens the bleaching blade (or bleach-fixing power). Generally, the basic steps in processing silver halide color photographic materials are a color development step and a desilvering step.

That is, the exposed silver halide color photographic material is
Enter the color development process. Here, silver halide is reduced by a color developing agent to produce silver, and the oxidized color developing agent reacts with a color former to provide a dye image. Afterwards, the color photographic material is subjected to a desilvering process. Here, the silver produced in the previous step is oxidized by the action of an oxidizing agent (commonly called a bleaching agent), and then dissolved and removed by a silver ion complexing agent, commonly called a fixing agent. Therefore, only dye images are produced in photographic materials that have undergone these steps. In addition to the two basic steps of color development and desilvering mentioned above, the actual development process includes auxiliary steps to maintain the photographic and physical quality of the image, or to improve the storage stability of the image. Contains. For example, a hardening bath to prevent excessive softening of the photosensitive layer during processing, a stopping bath to effectively stop the development reaction, an image stabilizing bath to stabilize the image, or a decoating bath to remove the backing layer of the support. Examples include bathing. In addition, the above-mentioned desilvering process may be carried out in a bleach-fixing bath containing both a bleaching agent and a fixing agent, or it may be carried out in two steps, a bleaching bath and a fixing bath, with separate baths for each. .

Generally, red blood salt is used as a bleaching agent in bleaching solutions.

However, the disadvantages of bleaching solutions using red blood salt are that the bleaching solution must be replaced after it has become exhausted, and that ferricyanide ions are emitted due to overflow during processing and carried into the washing water after bleaching. The reduced form of ferrocyanide ion undergoes photochemical oxidation to produce cyanide. These cyanide compounds are highly toxic and cause great harm. On the other hand, potassium dichromate, ferric ion complex salts, persulfates, quinones, copper salts, etc. have traditionally been used as bleaching agents other than red blood salt, but these have the drawbacks of weak oxidizing power and difficulty in handling. have.

In light of recent demands for quick and simple processing and prevention of environmental pollution in color photographic materials, ferric ion complex salts (for example, ferric ion complex salts of aminopolycarboxylic acids, etc., especially EDTA-?) complex salts have been developed. ) bleaching treatment methods are mainly used.

Ferric ion complex salts are used as bleaching agents in bleach-fix solutions for color photographic paper (German Patents No. 866,605, German Patent No. 966,410, British Patent No. 746,567, German Patent No. 933,088). No. 1,014,396, etc.).

However, since bleach-fix solutions containing ferric ion complex salts have weak oxidizing power, they contain a high concentration of silver halide, and color reversal photosensitive materials for photography using silver iodobromide (particularly so-called "inner mold") have a high concentration of silver halide. It is rarely used for ``photosensitive materials''.
Further, the ferric ion complex salt can be used as a bleaching bath by containing bromide.

However, the disadvantage of the ferric ion complex bleaching bath is that, like the bleach-fix solution, the bleaching blade is weak, so it takes a long time for bleaching. Therefore, it is desirable to increase the bleaching edge (oxidizing power) of a bleach solution (or bleach-fix solution) using a ferric ion complex salt.

The first object of the present invention is to obtain a novel bleaching accelerator that does not adversely affect photographic properties, and a color photographic processing method for bleaching using the same.

The second object is to obtain a rapid color photographic processing method using such a bleach accelerator. The third object is to obtain a method for rapidly bleaching (or bleach-fixing) color photographic materials having photographic sensitivity. The objects of the present invention are to provide a bleaching bath containing a ferric ion complex salt as a bleaching agent, a bleach-fixing bath containing a ferric ion complex salt as a bleaching agent, or a pre-bath (after color development and in a bleaching bath or a bleach-fixing bath). (Defined as the bath used until processing)
This can be achieved by containing at least one compound represented by the following general formula as a bleaching accelerator.

In the general formula, R1 and R2 each represent a hydrogen atom, a methyl group or an ethyl group.

Alternatively, R1 and R2 together with the nitrogen atom to which they are bonded represent a 1-pyrrolidinyl group, a piperidino group or a hexamethyleneimino group. A represents acid. R
As the acid represented by /X, both so-called inorganic acids and organic acids can be used.
such as nitric acid, phosphoric acid or carbonic acid; oxalic acid as an organic acid;
A water-soluble carboxylic acid (for example, acetic acid) represented by R3COOH (R3 represents an alkyl group having 1 to 3 carbon atoms), R4SO3H (R4 has a substituent such as an alkyl group having 1 to 3 carbon atoms or a methyl group) A water-soluble sulfonic acid (for example, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, valatoluenesulfonic acid, etc.) represented by a phenyl group (which can represent a phenyl group) is used.

The compound of the general formula of the present invention is an excellent bleach accelerator in any of bleaching solutions, bleach-fixing solutions, and pre-baths containing ferric ion complex salts.

A method for synthesizing the compound represented by this general formula is described, for example, by R. M.
Pinder;K. Brewster；D●W●Swa
Written by nstOn Chim●Ther. Volume 5 (4), 261
-263 (1970), etc., and compounds not specifically described can also be synthesized according to the synthesis methods described in these documents. Specific examples of the compounds of the general formula used in the present invention include the following (1) to (self), but the present invention is not limited to these exemplified compounds. The compound of the above general formula, which is the bleach accelerator used in the present invention, can be added to any of the bleach bath, bleach-fix bath, and pre-bath at any concentration depending on the type of compound and purpose, but approximately It is best to use 2 x 10-6 to about 2 x 10-1 mol, preferably 1 x 10-4 to about 2 x 10-1 mol.
It is used in a range of 5 x 10-2 mol.

The complex salt of ferric ion used as a bleaching agent preferably uses an organic compound as a ligand, especially an organic chelating agent such as aminopolycarboxylic acid, aminopolysulfonic acid, or a salt thereof. Those using polycarboxylic acids or salts thereof are preferred because they are inexpensive and have relatively little risk of causing pollution.

These bleaching solutions are superior because they do not have the disadvantages of red blood salt bleaching solutions, such as: In other words, bleaching solutions using red blood salts have two drawbacks: firstly, the bleaching solution must be replaced when it is worn out, and secondly, there is a problem with Felician complexes, which are discharged as a result of overflow during processing or carried into the washing water after bleaching. The drawback is that the ions and ferrocyanide complex ions undergo photochemical oxidation to produce highly toxic cyanide compounds, which can cause great harm. Examples of these aminopolycarboxylic acids and aminopolyphosphonic acids or salts thereof are listed below.

Namely, ethylenediaminetetraacetic acids (ethylenediaminetetraacetic acid and its disodium salt, diammonium salt, tetra(trimethylammonium) salt, tetrapotassium salt, tetrasodium salt, trisodium salt, etc.), diethylenetriaminepentaacetic acid (diethylenetriaminepentaacetic acid, etc.) its pentasodium salt, etc.),
Ethylenediamine-N-(β-oxyethyl)-N,N
/, N' Monotriacetic acids (this acid and its trisodium salts, triammonium salts, etc.), peropylenediaminetetraacetic acids (this acid and its disodium salts, etc.), nitrilotriacetic acids (this acid and its trisodium salts, etc.) salt, etc.)
Cyclohexanediaminetetraacetic acids (this acid, its disodium salt, etc.), other iminodiacetic acids, dihydroxyethylglycines, ethyl etherdiaminetetraacetic acids, glycol etherdiaminetetraacetic acids, ethylenediaminetetrapropionic acids, phenylenediaminetetraacetic acids 1,3 diaminoprobanol-N,
N,N',N'-tetramethylenephosphonic acids, ethylenediamine-N,N,N',N'-tetramethylenesulfonic acids, 1,3-propylenediamine-N,N,Nl
, N'-tetramethylenephosphonic acids, etc. Examples of bases that form salts with aminopolycarboxylic acids and aminopolyphosphonic acids include caustic alkali (alkali metal hydroxide), ammonia, and amines.

Alkali metals include sodium, potassium, lithium, etc.; amines include alkyl amines such as methylamine, diethylamine, triethylamine, and butylamine; ring amines such as cyclohexylamine;
These are arylamines such as aniline and m-toluidine, and heterocyclic amines such as pyridine, morpholine and piperidine. The ferric ion complex salt may be added to the bleach bath in the form of a complex.

Also, ferric salts (e.g. ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate, etc.)
and a chelating agent such as aminopolycarboxylic acid or aminopolyphosphonic acid are added to the bleach bath to form a second
An iron ion complex salt may be formed. When added in the form of a complex, one type of complex salt or two or more types of complex salts may be used. On the other hand, when forming a complex in a solution using a ferric salt and a chelating agent, one or more types of ferric salts may be used. Furthermore, one type or two or more types of chelating agents may be used. Further, in either case, the chelating agent may be used in excess of the amount required to form a complex of ferric ions. In this case, the amount of ferric ion complex per bleach bath 11 is from about 0.1 to about 2 moles.

The pH of the bleaching bath is approximately 3.0 to approximately 8.0 during use.
In particular, it is desirable that it be 4.0 to 7.0. In addition to the ferric ion complex and the novel bleach accelerator, the bleach bath used in the present invention contains halides [for example, ammonium and alkali metal (e.g., sodium and potassium) bromides, chlorides, and iodides. be.

Among these, bromides are particularly preferred. ] is preferably included. The amount of halide is about 50 to 300 per 11 parts of bleaching solution.
9 is appropriate. The bleaching solution of the present invention further includes P such as boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, and tartaric acid.
One or more types of inorganic acids, organic acids, and salts thereof having H buffering ability, and further sulfites (eg, sodium sulfite, potassium sulfite, ammonium sulfite, etc.), etc. can be added. When using ferric ion complexes in the bleach-fixing bath, the usual fixing agents, such as thiosulfates such as sodium thiosulfate, ammonium thiosulfate, sodium ammonium thiosulfate, potassium thiosulfate; sodium thiocyanate, ammonium thiocyanate, Use of one or more water-soluble silver halide solubilizers such as thiocyanate salts such as potassium thiocyanate; thioether compounds such as ethylene bisthioglycolic acid and 3,6-dithia-1,8-octanediol. can do. The amounts of each component in the bleach-fix bath are as follows:
The amount of the ferric ion complex is about 0.1 to 2 mol, and the amount of the fixing agent is about 0.2 to 4 mol. The bleach-fixing bath can contain the aforementioned additives and sulfites (eg, sodium sulfite, potassium sulfite, ammonium sulfite), etc. that can be added to the bleach solution.

Furthermore, compounds already known to have bleach-fix accelerating properties (for example, polyamine compounds described in Japanese Patent Publication No. 45-8836, thiourea derivatives described in Japanese Patent Publication No. 45-8506, German Patent No. 1,127,715) Iodides described in the specification, polyethylene oxides described in German Patent No. 966,410, German Patent No. 1,290,8
The nitrogen-containing zero-ring compound described in Specification No. 12, etc.
It is also possible to contain more than one type. In addition, the bleach-fix solution P
In use, H generally has to be about 4.0 to 8.0, particularly preferably about 5.0 to 7.0. The present invention can be applied to the processing of all color light-sensitive materials using silver halide, such as color pavers, color negative films, color reversal films, and color positive films, and can improve the effect of promoting desilvering.

Particularly remarkable effects can be achieved on color reversal photosensitive materials. When the compound of the above general formula, which is a bleach accelerator of the present invention, is added to a bleach solution, a bleach-fix solution, or a prebath (e.g., second stop solution), it can remove silver in a short time and in a sufficient amount. Can be bleached.

The halide composition of silver halide in the silver halide color photographic light-sensitive material used in the present invention may be any one of C2, Br, and I.

In the color photographic processing method of the present invention, the silver halide color photographic light-sensitive material has at least one silver halide photographic emulsion layer on a support, and the silver halide emulsion preferably has a low iodine content. A remarkable effect is obtained in the case of silver iodobromide emulsions containing about 1 to 8 mol %, particularly preferably 3 to 7 mol %.

The processing steps for color reversal sensitive materials are usually, for example, black and white development (bath) → stop (bath) → washing with water → fogging (bath) → color development (bath) → stop (bath) → (hardening film (bath)) → washing with water. → Bleaching (bath) →
The order is washing with water → fixing (bath) → washing with water → stabilizing (bath) → drying.

Furthermore, a pre-bath, a pre-hardening bath, a neutralization bath, etc. can be provided during these steps. On the other hand, a stabilizing bath, washing with water before and after bleaching, etc. can be omitted from the above steps. When the so-called pre-bath of the present invention is provided, it is preferably provided immediately before the bleaching bath during the above steps. Add a fogging bath to t-butylamine borane, sodium borohydride, or Sn.
(2) As a processing bath containing the complex, color development can be carried out after being covered with a treatment bath before color development.

Also, by adding a fogging agent (eg, t-butylamine borane, sodium borohydride, etc.) to the color developer, the fogging bath can be omitted. Also, re-exposure can be used instead of a fogging bath. The treatment temperature in each treatment step can be about 200 to 70°C, preferably 300 to 60°C. Color photosensitive materials suitable for processing, especially reversal color photosensitive materials,
It may be an "internal type" sensitive material containing a coupler in the photographic emulsion, or
It may also be an "external type" photosensitive material containing a coupler in a color developing solution (in short, the present invention is particularly applicable to reversal color photosensitive materials of any practical design).

As the color developer, black and white developer (for color reversal processing), stop solution, fixer, etc., commonly used ones can be used.

For example, as a color developing solution for color reversal processing, those mentioned in the examples are typical, but in addition to this, for example, ethylenediamine can also be added to this developer.

In addition, regarding photographic silver halide emulsions and other hydrophilic colloid liquids that can be used in color sensitive materials processed by the color processing method of the present invention, their preparation methods, and photographic additives (or photographic materials), etc. , Research Disclosure
Those described in re) Shisho 92 (December 1971), pages 107 to 110, can be used as appropriate.

EXAMPLE A color reversal photographic material was prepared by coating each layer on a triacetate film base in the following order.

1st layer (red-sensitive emulsion layer) Coating solution: red-sensitive silver iodobromide emulsion (silver iodide: 1-hydroxy-4-chloro-2-n-dodecylnaphthamide as J■■-, dibutyl phthalate as coupler solvent) )
and are mixed so that the silver/coupler molar ratio is 8.0.

Coated silver amount: 1.59Ag/m''.

Second layer (intermediate layer) A gelatin intermediate layer containing di-t-amyl hydroquinone dispersed therein.

3rd layer (green-sensitive emulsion layer) Coating solution: Green-sensitive silver iodobromide emulsion (silver iodide: 6 mol%)
and magenta coupler emulsion (1 as magenta coupler)
-(2,4,6-trichlorophenyl)-3-[3-(
2,4-di-t-amylphenoxyacetamido)benzamide]-5-pyrazolone and tricresyl phosphate as a coupler solvent are mixed so that the silver/coupler molar ratio is 9.5.

Coated silver amount: 1.59Ag/M2.

4th layer (yellow filter layer) A single layer of filter consisting of yellow colloidal silver and gelatin.

5th layer (blue-sensitive emulsion layer) Coating solution: Blue-sensitive silver iodobromide emulsion (silver iodide: 6 mol%)
, yellow coupler emulsion (α as yellow coupler)
- pivaloyl-2-chloro-5-[γ-(2,4-di-t-amylphenoxy)butanamide] acetanilide and dibutyl phthalate as a coupler solvent are mixed so that the silver/coupler molar ratio is 8.0. do.

Coated silver amount: 1.89Ag/M2.

6th layer (protective layer) A protective layer consisting mainly of gelatin.

After this color reversal film was exposed to light (1/100 second exposure through a light wedge using a tungsten lamp as a light source), the following reversal process was performed.

Composition of the first developer: 1 portion each of the above bleaching solution and the above compound of the general formula of the present invention (with the above compound number).
Bleaching was carried out for 6 minutes using the solution added at 9/l.

The amount of silver remaining in the film after processing (at two locations, the highest density area and the lowest density area) was determined by fluorescent X-ray analysis, and the results are shown in Table 1. From this result, the bleaching solution according to the present invention (1-
It can be seen that when B) to (1-D) are used, bleaching is accelerated compared to Comparative Example (1-A) which does not contain the compound of the present invention.

The fogging solution of this example was removed, and a fogging agent, such as sodium borohydride (0.5%) was added to the color developing solution.
A similar bleaching accelerating effect was observed when the treatment was carried out with the addition of 1 g/l).

EXAMPLE A color reversal film similar to that in Example 1 was exposed in the same manner as in Example 1 and subjected to the following treatments.

That is, in the processing step, instead of the second stop bath after color development, a pre-bath containing the accelerator of the present invention is used as described below for 2 minutes before bleaching, and then bleaching is performed without washing with water. bath(
The same treatment as in Example 1 was carried out, except that the treatment was carried out for 6 minutes with (no particular addition of the accelerator of the present invention). After the treatment, the amount of silver remaining in the film was determined in the same manner as in Example 1. The results are shown in the table. These results show that bleaching was significantly accelerated in the pre-baths (2-B) to (2-F) containing the bleach accelerator of the present invention compared to the pre-bath (2A) containing no additives. I understand that.

Example 1 In the processing step of Example 1, a bleach-fixing bath having the following formulation was provided as a single bath instead of a bleaching bath and a fixing bath, and each of the compounds of the general formula of the present invention was added to 1.59% of each bath in this bath. The same reversal process as in Example 1 was carried out except that 1 was added (however, the bleach-fixing times were 4 minutes and 6 minutes).

The amount of silver remaining in the film was determined in the same manner as in Example (1). The results are shown in the table. As is clear from this experimental result, the bleach-fix solution using the compound of the present invention has a greater desilvering promoting effect than (3-B) using the compound described in US Pat. No. 3,893,858. It turns out that it has.

Preferred embodiments of the present invention are described below.

1) A color photographic processing method according to the claims, wherein the complex salt of ferric ion is a ferric aminopolycarboxylic acid complex salt.

2) A color photographic processing method according to the claims, wherein the color photographic processing method is a color photographic reversal processing method.

3) The silver halide photosensitive material has at least one silver halide photographic emulsion layer on the support, and the silver halide emulsion layer has an iodine content of about 1 to 8 mol%. A color photographic processing method as claimed in the claims, comprising a silver bromide emulsion.

4) The content of the compound represented by the above general formula in the bleach bath, bleach-fix bath, or pre-bath is 2 x 10-6 to 2 x 1
A color photographic processing method as claimed in the claims, wherein the concentration is 0-1 mol/l.

5) The content of the compound represented by the above general formula in the bleach bath, bleach-fix bath, or pre-bath is 0-4 to 5×10
-2 mol/l color photographic processing method according to the claims.

6) The color photographic processing method according to claim 1, wherein the content of the ferric ion complex salt in the bleach bath or bleach-fix bath is about 0.1 to 2.0 m01/l.

7) The color photographic processing method according to the claims, which is carried out at 30 to 60°C.

Claims (1)

[Scope of Claims] 1. In a color photographic processing method in which an exposed silver halide color photographic light-sensitive material is subjected to at least a color development treatment and a desilvering treatment, a bleaching bath containing a ferric ion complex salt as a bleaching agent; In at least one of the bleach-fix baths or pre-baths (defined as the baths used after color development and before processing with the bleach bath or bleach-fix bath) containing ferric ion complex salts, the following bleach accelerators may be added: A color photographic processing method characterized by containing a compound represented by the general formula. General formula▲There are numerical formulas, chemical formulas, tables, etc.▼ In the formula, R_1 and R_2 each represent a hydrogen atom, a methyl group, or an ethyl group. Alternatively, R_1 and R_2 together with the nitrogen atom to which they are bonded represent a 1-pyrrolidinyl group, a piperidino group or a hexamethyleneimino group. A represents acid.